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Preparation method of micrometer-sized silicon dioxide microspheres
Description
translated from Chinese
技术领域technical field
本发明涉及球状粉体材料制备技术领域，特别是涉及一种微米尺寸的二氧化硅微球的制备方法。The invention relates to the technical field of preparation of spherical powder materials, in particular to a method for preparing micron-sized silica microspheres.
背景技术Background technique
目前，亚微米和微米球形二氧化硅微球在机械、电子、日用化工及生物医药领域有着广泛的应用。At present, submicron and micron spherical silica microspheres are widely used in the fields of machinery, electronics, daily chemical industry and biomedicine.
1968年stober等人首次采用溶胶-凝胶法，在氨水催化下将四乙氧基硅烷水解缩合成纳米级单分散性二氧化硅微球。后来基于此化学途径的溶胶一凝胶法湿法制备二氧化硅微球引起了许多学者极大的关注。然而在该体系中，由于反应后期的成核生长阶段，中间体Si(OH)4的消耗速率低于其生成速率，使得制备出的二氧化硅颗粒尺寸只有几百纳米，很难突破1μm。因此，利用单独的stober方法制备微米级二氧化硅微球十分困难。In 1968, Stober et al. used the sol-gel method for the first time to hydrolyze and condense tetraethoxysilane into nano-scale monodisperse silica microspheres under the catalysis of ammonia water. Later, the sol-gel method wet preparation of silica microspheres based on this chemical route has attracted great attention of many scholars. However, in this system, due to the nucleation and growth stage in the later stage of the reaction, the consumption rate of the intermediate Si(OH) 4 is lower than its production rate, so that the size of the prepared silica particles is only a few hundred nanometers, and it is difficult to break through 1 μm. Therefore, it is very difficult to prepare micron-sized silica microspheres by a single stober method.
目前制备微米级尺寸的球形氧化硅的方法主要有两种：第一种方法是基于stober方法改进的种子法。即将利用stober方法制备的小尺寸的SiO2作为种子，然后向该种子的分散液中加入水解液和硅前驱体，新形成的中间体Si(OH)4水解缩合后，在SiO2种子表面生长，制备微米级的SiO2颗粒。因此，二次成核现象的发生以及苛刻实验条件的要求使其难以大规模产业化生产。第二种方法是乳液法。即在油水两相体系中引入表面活性剂，形成类似微乳液体系中的液滴反应池，来制备微米级SiO2。例如：在含有Na2SiO3的水相和柴油、四氯化碳的油相两相体系中，引入表面活性剂司盘和吐温，加入硫酸溶液制备5～40μm的SiO2微球。在该方法中，由于乳液的形成需要大量的表面活性剂以及乳液的不稳定性，可控性差，难以大量制备SiO2微球。At present, there are mainly two methods for preparing spherical silica with micron-scale size: the first method is the improved seed method based on the Stober method. The small-sized SiO 2 prepared by the stober method is used as a seed, and then the hydrolyzed solution and silicon precursor are added to the seed dispersion, and the newly formed intermediate Si(OH) 4 grows on the surface of the SiO 2 seed after hydrolysis and condensation , to prepare micron-sized SiO 2 particles. Therefore, the occurrence of the secondary nucleation phenomenon and the requirements of harsh experimental conditions make it difficult for large-scale industrial production. The second method is the emulsion method. That is, the surfactant is introduced into the oil-water two-phase system to form a droplet reaction pool similar to that in the microemulsion system to prepare micron-sized SiO 2 . For example: in the water phase containing Na 2 SiO 3 and the oil phase two-phase system of diesel oil and carbon tetrachloride, the surfactant Span and Tween are introduced, and sulfuric acid solution is added to prepare SiO 2 microspheres of 5-40 μm. In this method, it is difficult to prepare SiO2 microspheres in large quantities due to the large amount of surfactant required for the formation of the emulsion and the instability of the emulsion, which has poor controllability.
发明内容Contents of the invention
基于此，有必要提供一种工艺简单的微米尺寸的二氧化硅微球的制备方法，以大规模制备微米尺寸的二氧化硅微球。Based on this, it is necessary to provide a method for preparing micron-sized silica microspheres with a simple process, so as to prepare micron-sized silica microspheres on a large scale.
一种微米尺寸的二氧化硅微球的制备方法，包括如下步骤：A preparation method of micron-sized silica microspheres, comprising the steps of:
制备含有硅前驱体的溶液；及preparing a solution containing a silicon precursor; and
将所述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，搅拌反应30分钟～5小时，分离纯化并干燥得到所述微米尺寸的二氧化硅微球。The solution containing the silicon precursor is added to the solution containing the electrolyte and the catalyst, stirred and reacted for 30 minutes to 5 hours, separated, purified and dried to obtain the micron-sized silicon dioxide microspheres.
在其中一个实施例中，所述搅拌反应30分钟～5小时后，还包括静置陈化的步骤，然后再进行分离纯化并干燥。In one embodiment, after the stirring reaction for 30 minutes to 5 hours, a step of standing and aging is also included, and then separation, purification and drying are carried out.
在其中一个实施例中，所述将所述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中的步骤是用蠕动泵以1～100转/分的速度将所述含有硅前驱体的溶液滴加入到含有电解质和催化剂的溶液中。In one of the embodiments, the step of adding the solution containing the silicon precursor to the solution containing the electrolyte and the catalyst is to use a peristaltic pump to pump the solution containing the silicon precursor at a speed of 1 to 100 rpm The solution is added dropwise to the solution containing the electrolyte and catalyst.
在其中一个实施例中，所述硅前驱体选自正硅酸四甲酯、正硅酸四乙酯、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷及γ-巯丙基三甲氧基硅烷中的至少一种。In one embodiment, the silicon precursor is selected from tetramethyl orthosilicate, tetraethyl orthosilicate, γ-(2,3-glycidoxy)propyltrimethoxysilane, γ- At least one of (methacryloyloxy)propyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane.
在其中一个实施例中，所述含有硅前驱体的溶液的溶剂选自无水乙醇、丙醇、异丙醇及无水丁醇中的至少一种。In one embodiment, the solvent of the solution containing the silicon precursor is at least one selected from absolute ethanol, propanol, isopropanol and absolute butanol.
在其中一个实施例中，所述含有硅前驱体的溶液中的硅前驱体的浓度为0.20～2.0mol/L。In one of the embodiments, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.20˜2.0 mol/L.
在其中一个实施例中，所述电解质选自氯化钠、氯化钾、氯化钙、氯化铵、十六烷基三甲基溴化铵、十二烷基苯磺酸钠及聚丙烯酰胺中的一种。In one of the embodiments, the electrolyte is selected from sodium chloride, potassium chloride, calcium chloride, ammonium chloride, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate and polypropylene One of the amides.
在其中一个实施例中，所述催化剂选自氨水、尿素、二乙胺、三乙胺、赖氨酸及精氨酸中的至少一种。In one embodiment, the catalyst is at least one selected from ammonia water, urea, diethylamine, triethylamine, lysine and arginine.
在其中一个实施例中，所述含有电解质和催化剂的溶液中，所述电解质的浓度为0.1～10mmol/L。In one embodiment, in the solution containing the electrolyte and the catalyst, the concentration of the electrolyte is 0.1-10 mmol/L.
在其中一个实施例中，所述含有电解质和催化剂的溶液中，所述催化剂的浓度为0.05～10mol/L。In one embodiment, in the solution containing the electrolyte and the catalyst, the concentration of the catalyst is 0.05˜10 mol/L.
在其中一个实施例中，所述搅拌反应30分钟～5小时是于20℃～60℃下搅拌反应30分钟～5小时。In one embodiment, the stirring reaction for 30 minutes to 5 hours is stirring the reaction at 20° C. to 60° C. for 30 minutes to 5 hours.
上述微米尺寸的二氧化硅微球的制备方法通过向stober体系中引入合适浓度电解质就可以实现微米尺寸的二氧化硅微球的制备，这种方法不仅工艺简单，而且同时避免了种子法的二次成核和耗时长以及乳液法使用大量表面活性剂的缺点，能够大规模制备，满足实际应用需求。The preparation method of micron-sized silica microspheres mentioned above can realize the preparation of micron-sized silica microspheres by introducing an appropriate concentration of electrolyte into the stober system. This method is not only simple in process, but also avoids the secondary Due to the shortcomings of secondary nucleation and long time-consuming and the use of a large amount of surfactants in the emulsion method, it can be prepared on a large scale to meet the needs of practical applications.
附图说明Description of drawings
图1为一实施方式的微米尺寸的二氧化硅微球的制备方法的流程图；Fig. 1 is the flow chart of the preparation method of the micron-sized silica microsphere of one embodiment;
图2为实施例1制备的微米尺寸的二氧化硅微球的SEM图；Fig. 2 is the SEM picture of the silica microspheres of micron size prepared in embodiment 1;
图3为实施例2制备的微米尺寸的二氧化硅微球的SEM图；Fig. 3 is the SEM picture of the silica microspheres of micron size prepared in
图4为实施例3制备的微米尺寸的二氧化硅微球的SEM图；Fig. 4 is the SEM figure of the silica microspheres of micron size prepared in embodiment 3;
图5为实施例4制备的微米尺寸的二氧化硅微球的SEM图。5 is an SEM image of micron-sized silica microspheres prepared in Example 4.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。In order to make the above objects, features and advantages of the present invention more comprehensible, specific implementations of the present invention will be described in detail below in conjunction with the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described here, and those skilled in the art can make similar improvements without departing from the connotation of the present invention, so the present invention is not limited by the specific implementations disclosed below.
请参阅图1，一实施方式的微米尺寸的二氧化硅微球的制备方法，包括如下步骤S110和步骤S120。Please refer to FIG. 1 , a method for preparing micron-sized silica microspheres according to one embodiment includes the following steps S110 and S120.
步骤S110：制备含有硅前驱体的溶液。Step S110: preparing a solution containing silicon precursor.
硅前驱体为含有硅的有机物或无机物。优选地，硅前驱体选自正硅酸四甲酯、正硅酸四乙酯、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷及γ-巯丙基三甲氧基硅烷中的至少一种。Silicon precursors are organic or inorganic substances containing silicon. Preferably, the silicon precursor is selected from tetramethylorthosilicate, tetraethylorthosilicate, γ-(2,3-glycidoxy)propyltrimethoxysilane, γ-(methacryloxy ) At least one of propyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane.
将硅前驱体溶于溶剂中，制备含有硅前驱体的溶液。优选地，溶剂选自无水乙醇、丙醇、异丙醇及无水丁醇中的至少一种。The silicon precursor is dissolved in a solvent to prepare a solution containing the silicon precursor. Preferably, the solvent is at least one selected from absolute ethanol, propanol, isopropanol and absolute butanol.
优选地，含有硅前驱体的溶液中硅前驱体的浓度为0.20～2.0mol/L。Preferably, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.20˜2.0 mol/L.
步骤S120：将含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，搅拌反应30分钟～5小时，分离纯化并干燥得到微米尺寸的二氧化硅微球。Step S120: adding the solution containing the silicon precursor to the solution containing the electrolyte and the catalyst, stirring and reacting for 30 minutes to 5 hours, separating, purifying and drying to obtain micron-sized silica microspheres.
将电解质和催化剂溶解于醇和水的混合溶剂中，制备得到含有电解质和催化剂的混合溶液。The electrolyte and the catalyst are dissolved in a mixed solvent of alcohol and water to prepare a mixed solution containing the electrolyte and the catalyst.
优选地，电解质选自氯化钠、氯化钾、氯化钙、氯化铵、十六烷基三甲基溴化铵、十二烷基苯磺酸钠及聚丙烯酰胺中的一种。Preferably, the electrolyte is selected from one of sodium chloride, potassium chloride, calcium chloride, ammonium chloride, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate and polyacrylamide.
优选地，催化剂选自氨水、尿素、二乙胺、三乙胺、赖氨酸及精氨酸中的至少一种。Preferably, the catalyst is at least one selected from ammonia water, urea, diethylamine, triethylamine, lysine and arginine.
醇为无水乙醇、丙醇、异丙醇或无水丁醇。水优选为超纯水。The alcohol is absolute ethanol, propanol, isopropanol or absolute butanol. Water is preferably ultrapure water.
优选地，醇和水的体积比为30～240:5～15。Preferably, the volume ratio of alcohol to water is 30-240:5-15.
优选地，含有电解质和催化剂的溶液中，电解质的浓度为0.1～10mmol/L。催化剂的浓度为0.05～10mol/L。Preferably, in the solution containing the electrolyte and the catalyst, the concentration of the electrolyte is 0.1-10 mmol/L. The concentration of the catalyst is 0.05-10 mol/L.
选用0.1～10mmol/L的电解质浓度，有利于控制所生成微米尺寸二氧化硅微球的粒径。Selecting the electrolyte concentration of 0.1-10 mmol/L is beneficial to control the particle size of the micron-sized silica microspheres produced.
选用浓度为0.05～10mol/L的催化剂浓度，能够较好地催化生成微米尺寸二氧化硅微球的反应，提高制备效率。The catalyst concentration of 0.05-10 mol/L is selected, which can better catalyze the reaction of forming micron-sized silica microspheres and improve the preparation efficiency.
优选地，将含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中是用蠕动泵以1～100转/分的速度将所述含有硅前驱体的溶液滴加入到含有电解质和催化剂的溶液中。通过控制含有硅前驱体的溶液的滴加速度，有利于控制最终生成的微米尺寸二氧化硅微球的粒度。Preferably, adding the solution containing the silicon precursor to the solution containing the electrolyte and the catalyst is to use a peristaltic pump to add the solution containing the silicon precursor dropwise to the solution containing the electrolyte and the catalyst at a speed of 1 to 100 rpm middle. By controlling the drop rate of the solution containing the silicon precursor, it is beneficial to control the particle size of the finally produced micron-sized silica microspheres.
优选地，搅拌反应30分钟～5小时是于20℃～60℃下搅拌反应30分钟～5小时。在20℃～60℃下进行反应，有利于生成粒度均匀性较好的微米尺寸的二氧化硅微球。Preferably, the stirring reaction for 30 minutes to 5 hours is stirring the reaction at 20° C. to 60° C. for 30 minutes to 5 hours. The reaction is carried out at 20°C to 60°C, which is conducive to the formation of micron-sized silica microspheres with better particle size uniformity.
优选地，搅拌反应30分钟～5小时后，还包括静置陈化的步骤，从而有利于控制二氧化硅微球的尺寸的均一，静置陈化后再进行分离纯化。Preferably, after the stirring reaction for 30 minutes to 5 hours, a step of standing and aging is also included, which is beneficial to control the uniform size of the silica microspheres, and separation and purification are carried out after standing and aging.
静置陈化的时间优选为1～5小时。The time for static aging is preferably 1 to 5 hours.
分离纯化的方法具体为：将反应物进行抽滤分离，然后依次用乙醇和水洗涤多次。The separation and purification method is specifically as follows: the reactant is separated by suction filtration, and then washed with ethanol and water for several times in sequence.
上述分离纯化的方法较为简单，且对设备和试剂要求低。用乙醇和水就能够将电解质除去，制备得到高纯度的微米尺寸的二氧化硅微球。可以理解，在其他实施方式中，分离纯化的方法不限于此，任何可以分离纯化微米尺寸的二氧化硅微球的方法均可应用。The above separation and purification method is relatively simple, and has low requirements for equipment and reagents. The electrolyte can be removed with ethanol and water, and high-purity micron-sized silica microspheres can be prepared. It can be understood that in other embodiments, the separation and purification method is not limited thereto, and any method that can separate and purify micron-sized silica microspheres can be applied.
由于二氧化硅的等电点在2左右，所以在pH大于2的体系中，其表面带负电荷，进而形成了稳定的双电层结构。在普通的stober方法中，当SiO2的尺寸达到1μm左右时，SiO2表面的双电层结构会阻碍中间体Si(OH)4在SiO2表面的沉积反应速率，使得SiO2的生长速率越来越慢，而此时中间体Si(OH)4向SiO2表面的扩散反应速率不变，导致中间体Si(OH)4的扩散速率大于沉积速率，当其浓度积累达到临界过饱和浓度后，就会有SiO2新核生成继而生长，因此普通的stober方法制备SiO2时，其粒径很难突破1μm。Since the isoelectric point of silicon dioxide is around 2, its surface is negatively charged in a system with a pH greater than 2, thereby forming a stable electric double layer structure. In the common stober method, when the size of SiO 2 reaches about 1 μm, the electric double layer structure on the surface of SiO 2 will hinder the deposition reaction rate of intermediate Si(OH) 4 on the surface of SiO 2 , making the growth rate of SiO 2 faster. Slower and slower, while the diffusion reaction rate of the intermediate Si(OH) 4 to the SiO 2 surface remains unchanged, resulting in the diffusion rate of the intermediate Si(OH) 4 being greater than the deposition rate, when its concentration accumulates to the critical supersaturation concentration , there will be new nucleation and subsequent growth of SiO 2 , so when SiO 2 is prepared by the ordinary stober method, its particle size is difficult to break through 1 μm.
当向体系中引入合适浓度的电解质后，电解质溶于水中发生电离，阳离子会优先吸附在SiO2的表面，进而压缩SiO2表面的双电层，减小Si(OH)4缩聚体向SiO2表面的扩散生长阻力，有效增大其粒径至微米尺寸。一般来说，电解质的阳离子的粒径越大，与周围水分子的水合能力越弱，就越容易在二氧化硅微球表面发生吸附，从而使其表面电势能降低得越多，形成更大的颗粒，从而制备得到微米尺寸的二氧化硅微球。When an appropriate concentration of electrolyte is introduced into the system, the electrolyte is dissolved in water and ionized, and the cations will be preferentially adsorbed on the surface of SiO 2 , thereby compressing the electric double layer on the surface of SiO 2 and reducing the tendency of Si(OH) 4 polycondensate to SiO 2 Diffusion growth resistance on the surface, effectively increasing its particle size to micron size. Generally speaking, the larger the particle size of the cation of the electrolyte, the weaker the hydration ability with the surrounding water molecules, and the easier it is to adsorb on the surface of the silica microsphere, so that the surface potential energy is reduced more and the formation of larger particles to prepare micron-sized silica microspheres.
上述微米尺寸的二氧化硅微球的制备方法通过向stober体系中引入合适浓度的电解质就可以实现微米尺寸的二氧化硅微球的制备，这种方法不仅工艺简单，而且同时避免了种子法的二次成核和耗时长以及乳液法使用大量表面活性剂的缺点，能够大规模制备，满足实际应用需求。The preparation method of the above-mentioned micron-sized silica microspheres can realize the preparation of micron-sized silica microspheres by introducing an appropriate concentration of electrolyte into the stober system. This method not only has a simple process, but also avoids the disadvantages of the seed method. Due to the disadvantages of secondary nucleation and time-consuming and the use of a large amount of surfactants in the emulsion method, it can be prepared on a large scale to meet the needs of practical applications.
并且，微米尺寸的二氧化硅微球的粒度可以由电解质的浓度进行调控，可控性较好。Moreover, the particle size of the micron-sized silica microspheres can be regulated by the concentration of the electrolyte, and the controllability is good.
采用上述方法制备的微米尺寸的二氧化硅微球适合用于超大规模集成电路的封装材料制备，也可以用于、机械、电子、日用化工及生物医药领域。The micron-sized silica microspheres prepared by the above method are suitable for the preparation of packaging materials for ultra-large scale integrated circuits, and can also be used in the fields of medicine, machinery, electronics, daily chemical industry and biomedicine.
以下通过具体实施例进一步阐述。Further elaborate below by specific embodiment.
实施例1Example 1
（1）将17ml的正硅酸四乙酯溶于150ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 17ml tetraethyl orthosilicate in 150ml absolute ethanol to prepare a solution containing silicon precursor;
（2）将22.6ml氨水（质量分数25%）、11ml超纯水、0.017g NaCl和267ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 22.6ml ammonia water (mass fraction 25%), 11ml ultrapure water, 0.017g NaCl and 267ml absolute ethanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以1rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于30℃下反应2h；静置陈化1小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, use a peristaltic pump at a speed of 1 rpm to add the above solution containing the silicon precursor to the solution containing the electrolyte and the catalyst, and react at 30°C for 2 hours; after standing and aging for 1 hour, the The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
所得到的微米尺寸的二氧化硅微球的SEM图如图2所示。由图2可看出，实施例1制备的微米尺寸的二氧化硅微球的粒径约为1.1μm，且粒度的均一性较好。The SEM image of the obtained micron-sized silica microspheres is shown in FIG. 2 . It can be seen from FIG. 2 that the particle size of the micron-sized silica microspheres prepared in Example 1 is about 1.1 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体的溶液中硅前驱体的浓度为0.46mol/L，电解质的浓度为0.97mmol/L，催化剂的浓度为1.05mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.46 mol/L, the concentration of the electrolyte is 0.97 mmol/L, and the concentration of the catalyst is 1.05 mol/L.
实施例2Example 2
（1）将5.7ml的正硅酸四乙酯溶于50ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 5.7ml tetraethyl orthosilicate in 50ml absolute ethanol to prepare a solution containing silicon precursor;
（2）将7.5ml二乙胺、13.3ml超纯水、0.017g KCl和78ml丙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 7.5ml of diethylamine, 13.3ml of ultrapure water, 0.017g of KCl and 78ml of propanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以2rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于36℃下反应1h；静置陈化2小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, use a peristaltic pump at a speed of 2rpm to add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 36°C for 1h; after standing for 2 hours, put The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
所得到的微米尺寸的二氧化硅微球的SEM图如图3所示。由图3可看出，实施例2制备的微米尺寸的二氧化硅微球的粒径约为2.0μm，且粒度的均一性较好。The SEM image of the obtained micron-sized silica microspheres is shown in FIG. 3 . It can be seen from FIG. 3 that the particle size of the micron-sized silica microspheres prepared in Example 2 is about 2.0 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体的溶液中硅前驱体的浓度为0.46mol/L，电解质的浓度为2.3mmol/L，催化剂的浓度为0.74mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.46 mol/L, the concentration of the electrolyte is 2.3 mmol/L, and the concentration of the catalyst is 0.74 mol/L.
实施例3Example 3
（1）将20ml的γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷溶于30ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 20ml of γ-(2,3-glycidoxy)propyltrimethoxysilane in 30ml of absolute ethanol to prepare a solution containing silicon precursor;
（2）将10ml三乙胺、5ml超纯水、0.055g十六烷基三甲基溴化铵（CTAB）和30ml无水丁醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 10ml of triethylamine, 5ml of ultrapure water, 0.055g of cetyltrimethylammonium bromide (CTAB) and 30ml of anhydrous butanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以5rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于32℃下反应2h；静置陈化3小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, using a peristaltic pump at a speed of 5 rpm, add the above solution containing the silicon precursor to the solution containing the electrolyte and the catalyst, and react at 32°C for 2 hours; after standing and aging for 3 hours, the The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
所得到的微米尺寸的二氧化硅微球的SEM图如图4所示。由图4可看出，实施例3制备的微米尺寸的二氧化硅微球的粒径约为1.5μm，且粒度的均一性较好。The SEM image of the obtained micron-sized silica microspheres is shown in FIG. 4 . It can be seen from FIG. 4 that the particle size of the micron-sized silica microspheres prepared in Example 3 is about 1.5 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前驱体的浓度为1.81mol/L，电解质的浓度为3.4mmol/L，催化剂的浓度为1.54mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 1.81 mol/L, the concentration of the electrolyte is 3.4 mmol/L, and the concentration of the catalyst is 1.54 mol/L.
实施例4Example 4
（1）将17ml的γ-（甲基丙烯酰氧）丙基三甲氧基硅烷溶于180ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 17ml of γ-(methacryloyloxy)propyltrimethoxysilane in 180ml of absolute ethanol to prepare a solution containing silicon precursor;
（2）将2g赖氨酸、11ml超纯水、0.017g十二烷基苯磺酸钠（SDS）和267ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 2g of lysine, 11ml of ultrapure water, 0.017g of sodium dodecylbenzenesulfonate (SDS) and 267ml of absolute ethanol to prepare a solution containing electrolytes and catalysts;
（3）在机械搅拌下，利用蠕动泵以1rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于20℃下反应5h；静置陈化4小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, use a peristaltic pump at a speed of 1 rpm to add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 20°C for 5 hours; after standing for 4 hours, put The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
所得到的微米尺寸的二氧化硅微球的SEM图如图5所示。由图5可看出，实施例4制备的微米尺寸的二氧化硅微球的粒径约为1.2μm，且粒度的均一性较好。The SEM image of the obtained micron-sized silica microspheres is shown in FIG. 5 . It can be seen from FIG. 5 that the particle size of the micron-sized silica microspheres prepared in Example 4 is about 1.2 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前躯体的浓度为0.36mol/L，电解质的浓度为0.18mmol/L，催化剂的浓度为0.05mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.36 mol/L, the concentration of the electrolyte is 0.18 mmol/L, and the concentration of the catalyst is 0.05 mol/L.
实施例5Example 5
（1）将17ml的γ-巯丙基三甲氧基硅烷溶于180ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 17ml of γ-mercaptopropyltrimethoxysilane in 180ml of absolute ethanol to prepare a solution containing silicon precursor;
（2）将2g尿素、11ml超纯水、0.017g聚丙烯酰胺和267ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 2g of urea, 11ml of ultrapure water, 0.017g of polyacrylamide and 267ml of absolute ethanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以1rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于60℃下反应3h；静置陈化5小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, use a peristaltic pump at a speed of 1 rpm to add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 60°C for 3 hours; after standing and aging for 5 hours, the The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
实施例5制备的微米尺寸的二氧化硅微球的粒径约为1.2μm，且粒度的均一性较好。The particle size of the micron-sized silica microspheres prepared in Example 5 is about 1.2 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前驱体的浓度为0.46mol/L，电解质的浓度为0.86mmol/L，催化剂的浓度为0.12mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.46 mol/L, the concentration of the electrolyte is 0.86 mmol/L, and the concentration of the catalyst is 0.12 mol/L.
实施例6Example 6
（1）将8.5mL的γ-巯丙基三甲氧基硅烷和8.5mL正硅酸四乙酯溶于180mL体积比为1:1的无水乙醇和丙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 8.5mL of γ-mercaptopropyltrimethoxysilane and 8.5mL of tetraethylorthosilicate in 180mL of absolute ethanol and propanol with a volume ratio of 1:1 to prepare silicon precursor-containing solution;
（2）将4g尿素、2g赖氨酸、11ml超纯水、0.017g聚丙烯酰胺、0.017g氯化钠和109ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 4g urea, 2g lysine, 11ml ultrapure water, 0.017g polyacrylamide, 0.017g sodium chloride and 109ml absolute ethanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以10rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于60℃下反应30min；静置陈化5小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, use a peristaltic pump at a speed of 10rpm to add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 60°C for 30min; after standing for 5 hours, put The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
实施例6制备的微米尺寸的二氧化硅微球的粒径约为2.2μm，且粒度的均一性较好。The particle size of the micron-sized silica microspheres prepared in Example 6 is about 2.2 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前驱体的浓度为0.41mol/L，电解质的浓度为4.4mmol/L，催化剂的浓度为0.67mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.41 mol/L, the concentration of the electrolyte is 4.4 mmol/L, and the concentration of the catalyst is 0.67 mol/L.
实施例7Example 7
（1）将8.5mL的γ-巯丙基三甲氧基硅烷和8.5mL正硅酸四甲酯溶于200mL体积比为1:1的异丙醇和丙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 8.5mL of γ-mercaptopropyltrimethoxysilane and 8.5mL of tetramethylorthosilicate in 200mL of isopropanol and propanol with a volume ratio of 1:1 to prepare a solution containing silicon precursors ;
（2）将10g赖氨酸、12g精氨酸、11ml超纯水、0.017g十二烷基苯磺酸钠、0.017g氯化钠和189ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 10g of lysine, 12g of arginine, 11ml of ultrapure water, 0.017g of sodium dodecylbenzenesulfonate, 0.017g of sodium chloride and 189ml of anhydrous ethanol to prepare a solution containing electrolytes and catalysts. solution;
（3）在机械搅拌下，利用蠕动泵以20rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于50℃下反应45min；静置陈化5小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, use a peristaltic pump at a speed of 20rpm to add the above solution containing silicon precursor to the solution containing electrolyte and catalyst, and react at 50°C for 45min; after standing and aging for 5 hours, put The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
实施例7制备的微米尺寸的二氧化硅微球的粒径约为1.8μm，且粒度的均一性较好。The particle size of the micron-sized silica microspheres prepared in Example 7 is about 1.8 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前驱体的浓度为0.47mol/L，电解质的浓度为1.70mmol/L，催化剂的浓度为0.69mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.47 mol/L, the concentration of the electrolyte is 1.70 mmol/L, and the concentration of the catalyst is 0.69 mol/L.
实施例8Example 8
（1）将17ml的正硅酸四甲酯溶于150ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 17ml of tetramethyl orthosilicate in 150ml of absolute ethanol to prepare a solution containing silicon precursor;
（2）将20g精氨酸、11ml超纯水、0.017g NaCl和89ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 20g of arginine, 11ml of ultrapure water, 0.017g of NaCl and 89ml of absolute ethanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以30rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于28℃下反应4h；静置陈化1小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, using a peristaltic pump at a speed of 30rpm, add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 28°C for 4h; after standing and aging for 1 hour, the The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100°C to obtain micron-sized silica microspheres.
实施例8制备的微米尺寸的二氧化硅微球的粒径约为1.6μm，且粒度的均一性较好。The particle size of the micron-sized silica microspheres prepared in Example 8 is about 1.6 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前驱体的浓度为0.68mol/L，电解质的浓度为2.91mmol/L，催化剂的浓度为1.15mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.68 mol/L, the concentration of the electrolyte is 2.91 mmol/L, and the concentration of the catalyst is 1.15 mol/L.
实施例9Example 9
（1）将17ml的γ-巯丙基三甲氧基硅烷溶于180ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 17ml of γ-mercaptopropyltrimethoxysilane in 180ml of absolute ethanol to prepare a solution containing silicon precursor;
（2）将45.2ml二乙胺、11ml超纯水、0.034g CaCl2和189ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 45.2ml of diethylamine, 11ml of ultrapure water, 0.034g of CaCl 2 and 189ml of absolute ethanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以40rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于38℃下反应2.5h；静置陈化2小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, using a peristaltic pump at a speed of 40rpm, add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 38°C for 2.5h; after standing and aging for 2 hours, The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100° C. to obtain micron-sized silica microspheres.
实施例9制备的微米尺寸的二氧化硅微球的粒径约为1.7μm，且粒度的均一性较好。The particle size of the micron-sized silica microspheres prepared in Example 9 is about 1.7 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前躯体的浓度为0.46mol/L，电解质的浓度为1.25mmol/L，催化剂的浓度为1.79mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.46 mol/L, the concentration of the electrolyte is 1.25 mmol/L, and the concentration of the catalyst is 1.79 mol/L.
实施例10Example 10
（1）将17ml的γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷溶于180ml无水乙醇中，制备得到含有硅前驱体的溶液；(1) Dissolve 17ml of γ-(2,3-glycidoxy)propyltrimethoxysilane in 180ml of absolute ethanol to prepare a solution containing silicon precursor;
（2）将22.6ml三乙胺、11ml超纯水、0.060g十六烷基三甲基溴化铵和139ml无水乙醇混合均匀，配制成含有电解质和催化剂的溶液；(2) Mix 22.6ml of triethylamine, 11ml of ultrapure water, 0.060g of cetyltrimethylammonium bromide and 139ml of absolute ethanol to prepare a solution containing electrolyte and catalyst;
（3）在机械搅拌下，利用蠕动泵以80rpm的转速，将上述含有硅前驱体的溶液加入到含有电解质和催化剂的溶液中，于45℃下反应3.5h；静置陈化3小时后，将反应物进行抽滤，取白色沉淀，并用依次用乙醇和水反复洗涤至中性，100℃下干燥，得到微米尺寸的二氧化硅微球。(3) Under mechanical stirring, using a peristaltic pump at a speed of 80rpm, add the above solution containing the silicon precursor to the solution containing the electrolyte and catalyst, and react at 45°C for 3.5h; after standing and aging for 3 hours, The reactant was suction-filtered, and the white precipitate was taken, washed repeatedly with ethanol and water until neutral, and dried at 100° C. to obtain micron-sized silica microspheres.
实施例10制备的微米尺寸的二氧化硅微球的粒径约为2.3μm，且粒度的均一性较好。The particle size of the micron-sized silica microspheres prepared in Example 10 is about 2.3 μm, and the particle size uniformity is good.
在本实施例中，含有硅前驱体溶液中硅前驱体的浓度为0.39mol/L，电解质的浓度为0.95mmol/L，催化剂的浓度为0.91mol/L。In this embodiment, the concentration of the silicon precursor in the solution containing the silicon precursor is 0.39 mol/L, the concentration of the electrolyte is 0.95 mmol/L, and the concentration of the catalyst is 0.91 mol/L.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.