CN103933903B - The method of preparation hollow-core construction nano-organosilicon microsphere - Google Patents

Abstract

The invention discloses a kind of method preparing hollow-core construction nano-organosilicon microsphere, the method includes: silane coupler is mixed by (1) with water, in order to obtain silane coupled agent dispersing liquid；(2) in the described silane coupled agent dispersing liquid that step (1) obtains, ammonia is added, in order to obtain single dispersing organosilicon medicine ball；And the described organosilicon medicine ball that step (2) is obtained by (3) carries out hydrothermal treatment consists, in order to obtain described hollow-core construction nano-organosilicon microsphere.The method of preparation hollow-core construction nano-organosilicon microsphere according to embodiments of the present invention can keep the complete of hollow-core construction nano-organosilicon microsphere surface morphology.

Description

Method for preparing hollow-structured nano-organosilicon microspheres

technical field

The invention belongs to the field of materials, in particular, the invention relates to a method for preparing hollow-structured nano-organosilicon microspheres.

Background technique

In recent years, hollow spherical nanostructured materials have attracted widespread attention because of their special structure and morphology, and the research on this kind of hollow microspheres has achieved remarkable results in terms of different sizes, shapes, structures, and surface properties. the results. Hollow spheres have the characteristics of low density, high specific surface area, and low expansion coefficient, so they have great application potential in catalysts, refractive surface coatings, rechargeable batteries, lithium batteries, and drug delivery and sustained release. For example, micelles, vesicles, hydrogels, etc. prepared from functional polymers, and inorganic nanoparticles such as SiO ₂ , Fe ₃ O ₄ , Au, etc. Due to good biocompatibility, good monodispersity, large specific surface area, modifiable surface hydroxyl groups and natural slow-release properties of drugs, mesoporous silica nanoparticles have become a research hotspot in drug smart carriers in recent years. Hollow silicon nanoparticles have a higher drug-carrying capacity and thus have a greater advantage. To load macromolecules such as DNA and RNA, silicon particles need to have larger pores on the surface. Therefore, it is of great significance to develop hollow silicon spheres with large pore diameters and high loading rates.

The main preparation methods of hollow silicon spheres include hard template method, soft template method, spray method, no template method and other methods. The hard template method mainly uses various methods to control the deposition or reaction of precursors on the surface of monodisperse polystyrene and carbon spheres to form a shell, and then remove the core by calcination or dissolution to obtain a hollow structure, the size of which is determined by The size of the template is determined. For example, the layer-by-layer coating technology based on the hard template method uses the electrostatic interaction between different materials, and the obtained colloidal particles are coated layer by layer, and the thickness of the shell layer can be controlled by the number of times of coating. This method is currently widely used. Chen et al modified the template with the method of atom transfer free radicals, introduced functional groups, functional groups and monomers polymerized at the interface to form shell materials, and synthesized SiO ₂ hollow microspheres. The soft template method is widely used, that is, microemulsion droplets can be used as templates to form a microcapsule structure by growing shell materials on the surface of the droplets, and then the liquid droplets in the shells can be treated with the corresponding organic solvent by the dissolution method. Dissolving, and then using high-temperature sintering to remove excess surfactants and organic solvents, the corresponding hollow microspheres can be obtained. At the same time, because the capsule core is removed by dissolving, mesopores are formed on the surface of the spherical shell. Barbe et al. synthesized SiO ₂ hollow microspheres in the emulsion, and the microreactor used was the droplet. Using CTAB as a template, by adjusting the concentration and pH value of the solution, TEOS can be used to prepare nano-sized SiO ₂ hollow microspheres in a microsolution. Bubbles can also be used as soft templates. First, bubbles are formed, and nanoparticles attach to the gas/liquid interface of the bubbles, and then gather around the bubbles to form a dense shell. The most commonly used sonochemical synthesis of hollow structures is the bubble soft template. The bubbles come from the collision of the sonic vortex. With the help of ultrasonic facilities, SiO ₂ hollow spheres can be synthesized in an aqueous solution containing tetraethyl orthosilicate and surfactants, submicron, and The shell has mesopores.

The method described above, no matter through the soft template or the hard template, needs to prepare the template, and then remove the template by calcination and dissolution. The template preparation process inevitably wastes some material, and there is always damage to the hollow structure when the template is removed. This hinders the further application of hollow spheres to a certain extent. Moreover, some template preparation methods must go through extremely cumbersome steps. Because of this, the research community has been exploring template-free preparation methods. The basis of the template-free method is the mechanism of "Ostwald ripening". The process of the mechanism is completely spontaneous, that is, due to the accumulation of energy, small particles accumulate into large particles. Lou et al. implemented a one-step template-free method and successfully synthesized a polycrystalline SnO ₂ hollow structure. During the reaction, potassium stannate (K ₂ SnO ₃ 3H ₂ O) was added to the mixed solution of ethanol-water as Precursor. In the initial stage of the reaction, potassium stannate was hydrolyzed to form amorphous solid particles. As the reaction progressed, the surface nanoparticles in contact with the surrounding solution first crystallized, therefore, inside the solid particles, a The tendency to diffuse and dissolve large crystallized particles on the surface provides a driving force for spontaneous "Ostwald ripening" from the inside out. The dissolution of solid particles originating from the surface or near the center takes advantage of the gradual maturation of nanoparticles to produce hollow microspheres or core-shell particles.

Although the theoretical support of the template-free method is not perfect, many researchers have used this method to synthesize a wide variety of oxide hollow microspheres.

To sum up, in the research on the preparation of hollow silicon spheres, it is often grown on the surface of a certain template, and then the substance of the capsule core is removed by dissolution, sintering, etc., so as to obtain hollow microspheres. For multilayer hollow microspheres with more than two layers, more complex methods are often required, such as etching or continuous volume shrinkage. In this process, not only the preparation process is complicated, but also the shell material will inevitably be damaged to varying degrees.

Therefore, the method for preparing nano-organosilicon microspheres with hollow structures needs further study.

Contents of the invention

The present invention aims to solve one of the above-mentioned technical problems at least to a certain extent. Therefore, an object of the present invention is to provide a method for preparing hollow-structure nano-organosilicon microspheres, which can maintain the integrity of the surface morphology of hollow-structure nano-organosilicon microspheres.

In one aspect of the present invention, the present invention proposes a method for preparing hollow structure nano-organosilicon microspheres, the method comprising:

(1) Mix the silane coupling agent with water to obtain a silane coupling agent dispersion;

(2) adding ammonia water to the silane coupling agent dispersion obtained in step (1), so as to obtain monodisperse silicone solid spheres; and

(3) Hydrothermally treating the silicone solid spheres obtained in step (2), so as to obtain the hollow nano-structure silicone microspheres.

The method for preparing nano-organosilicon microspheres with a hollow structure according to an embodiment of the present invention uses a silane coupling agent as a raw material. During the preparation process, by using a hydrothermal method, a multilayer hollow microsphere can be formed at one time without adding a template, thereby It avoids the material waste and cumbersome process of eroding the template, and at the same time, there is no need to add an emulsifier in the system, so the residual problem of the emulsifier in the subsequent treatment is avoided. In addition, the structure of the silicon microsphere can be adjusted by adjusting the experimental conditions, and the obtained hollow Structural nano-organosilicon microspheres can meet the needs of various purposes.

In addition, the method for preparing hollow-structure nano-organosilicon microspheres according to the above-mentioned embodiments of the present invention may also have the following additional technical features:

In some embodiments of the present invention, in step (1), the silane coupling agent is selected from tetraethyl orthosilicate, silane coupling agent A151, silane coupling agent KH550, silane coupling agent KH580, silane coupling agent At least one of coupling agent KH792 and silane coupling agent KH602. Thereby, nano-organosilicon microspheres with hollow structures can be efficiently prepared.

In some embodiments of the present invention, in step (1), based on the total weight of the silane coupling agent dispersion, the content of the silane coupling agent is 1-65% by mass. Thereby, the nano-organosilicon microspheres with hollow structure can be further effectively prepared.

In some embodiments of the present invention, in step (1), the silane coupling agent is mixed with water with stirring, wherein the stirring speed is 200-8000 rpm. Thus, the silane coupling agent is uniformly dispersed in water.

In some embodiments of the present invention, in step (1), before mixing the silane coupling agent with water, the emulsifier is pre-dispersed in water.

In some embodiments of the present invention, the emulsifier is selected from polyvinylpyrrolidone, block polyether, polyvinyl alcohol, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, Span 60, and emulsifier At least one of temperature 60.

In some embodiments of the present invention, based on the total weight of the silane coupling agent dispersion, the content of the emulsifier is 4% by mass or less.

In some embodiments of the present invention, in step (2), the concentration of the ammonia water is 0.1-5% by mass. Thereby, the nano-organosilicon microspheres with hollow structure can be further effectively prepared.

In some embodiments of the present invention, in step (2), ammonia water is added dropwise to the silane coupling agent dispersion liquid, wherein, the drip rate of the ammonia water is 0.5-5 ml/min, and the total amount of dripping is 0.5-20ml. Thereby, the nano-organosilicon microspheres with hollow structure can be further effectively prepared.

In some embodiments of the present invention, in step (3), the hydrothermal treatment is performed at a temperature of 120-200 degrees Celsius for 12-24 hours. Thereby, the nano-organosilicon microspheres with hollow structure can be further effectively prepared.

In some embodiments of the present invention, the particle size of the hollow-structure nano-organosilicon microspheres is 0.02-100 microns. Thus, the needs of various uses can be met.

Additional aspects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Description of drawings

The above and/or additional aspects and advantages of the present invention will become apparent and comprehensible from the description of the embodiments in conjunction with the following drawings, wherein:

Fig. 1 is a schematic flow chart of a method for preparing hollow-structure nano-organosilicon microspheres according to an embodiment of the present invention;

Fig. 2 is a schematic flow chart of a method for preparing hollow nano-organosilicon microspheres according to yet another embodiment of the present invention;

Fig. 3 is the electron micrograph of the hollow structure nano-organosilicon microsphere prepared by the method for preparing the hollow-structure nano-organosilicon microsphere according to an embodiment of the present invention;

Fig. 4 is the electron micrograph of the hollow structure nano-organosilicon microsphere prepared according to the method for preparing the hollow-structure nano-organosilicon microsphere according to another embodiment of the present invention;

Fig. 5 is the electron micrograph of the hollow structure nano-organosilicon microsphere prepared according to the method for preparing the hollow-structure nano-organosilicon microsphere according to another embodiment of the present invention;

6 is an electron micrograph of a hollow nano-organosilicon microsphere prepared by a method for preparing a hollow-structure nano-organosilicon microsphere according to another embodiment of the present invention;

Fig. 7 is an electron micrograph of hollow nano-organosilicon microspheres prepared by the method for preparing hollow-structure nano-organosilicon microspheres according to another embodiment of the present invention.

detailed description

Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.

In one aspect of the present invention, the present invention proposes a method for preparing nano-organosilicon microspheres with hollow structures. The method for preparing hollow-structure nano-organosilicon microspheres according to the embodiment of the present invention will be described in detail below with reference to FIGS. 1-2 . According to an embodiment of the invention, the method includes:

S100: Preparation of silane coupling agent dispersion

According to an embodiment of the present invention, the silane coupling agent is mixed with water to prepare a silane coupling agent dispersion. According to an embodiment of the present invention, the specific type of silane coupling agent is not particularly limited. According to a specific embodiment of the present invention, the silane coupling agent can be selected from tetraethyl orthosilicate, silane coupling agent A151, silane coupling agent At least one of coupling agent KH550, silane coupling agent KH580, silane coupling agent KH792 and silane coupling agent KH602. It should be explained that the silane coupling agent A151 is vinyltriethoxysilane, the silane coupling agent KH550 is 3-aminopropyltriethoxysilane, and the silane coupling agent KH580 is γ-mercaptopropyltrimethoxy Silane, silane coupling agent KH792 is N-(β-aminoethyl)-γ-aminopropyltrimethyl(ethyl)oxysilane, silane coupling agent KH602 is N-β-(aminoethyl)-γ-ammonia Propylmethyldimethoxysilane. According to an embodiment of the present invention, the amount of the silane coupling agent is not particularly limited. According to a specific embodiment of the present invention, based on the total weight of the silane coupling agent dispersion, the content of the silane coupling agent can be 1 to 65% by mass %. The inventors have found that if the content of the silane coupling agent is too high, the overall viscosity will be too high, resulting in a wide particle size distribution, which will result in an uneven particle size distribution of the obtained hollow silicon microspheres. According to an embodiment of the present invention, mixing the silane coupling agent with water is accompanied by stirring. According to a specific embodiment of the present invention, the stirring rate is not particularly limited. According to a specific example of the present invention, the stirring rate can be 200 ~8000 rpm. Thereby, the silane coupling agent can be uniformly dispersed in the water phase.

S200: Preparation of monodisperse silicone solid spheres

According to an embodiment of the present invention, ammonia water is added to the silane coupling agent dispersion liquid obtained above, so as to obtain monodisperse silicone solid spheres. According to the embodiment of the present invention, the concentration of the ammonia water added is not particularly limited, and according to a specific embodiment of the present invention, the concentration of the ammonia water may be 0.1-5% by mass. According to the embodiments of the present invention, the way of adding ammonia water is not particularly limited. According to specific embodiments of the present invention, the dripping rate of ammonia water can be 0.5-5 ml/min, and the total amount of dripping can be 0.5-20 ml. Specifically, ammonia water can be used as a catalyst to promote the formation of monodisperse silicone solid spheres.

S300: Preparation of hollow silica microspheres

According to an embodiment of the present invention, the obtained organic silicon solid spheres are subjected to hydrothermal treatment, so that nano-organic silicon microspheres with hollow structures can be obtained. According to the embodiments of the present invention, the conditions of the hydrothermal treatment are not particularly limited. According to specific embodiments of the present invention, the hydrothermal treatment may be performed at a temperature of 120-200 degrees Celsius for 12-24 hours. According to the embodiment of the present invention, the particle size of the obtained hollow nano-organosilicon microspheres is not particularly limited. According to a specific embodiment of the present invention, the particle size of the hollow-structure nano-organosilicon microspheres can be 0.02-100 mm . Thus, the obtained organosilicon microspheres can meet the needs of various purposes. Specifically, the hydrothermal method is in a closed system, using an aqueous solution as a solvent, at a certain temperature (100-1000 ° C), and under the pressure (1-100 MPa) generated by the water itself, in subcritical, critical, supercritical In the state, the process of synthesizing new compounds by using the chemical reaction of the substances in the solution. Since the reaction process of the hydrothermal method is in a state of non-ideal equilibrium, it often has relatively simple operability and adjustability, and it is easier to obtain chemical reactions that cannot be obtained by ordinary reactions under relatively mild conditions. Therefore, new products with metastable structures and condensed states can be obtained. For example, this principle is used to study the formation process of TiO _2. TiF ₄ with different concentrations is placed in the reactor. The small particles in the inner core of the particle will have a higher surface energy than the outer layer, thus promoting the formation of small particles. Continuously escaping from the inside, forming a hollow structure.

The method for preparing nano-organosilicon microspheres with a hollow structure according to an embodiment of the present invention uses a silane coupling agent as a raw material. During the preparation process, by using a hydrothermal method, a multilayer hollow microsphere can be formed at one time without adding a template, thereby It avoids the material waste and cumbersome process of eroding the template, and at the same time, there is no need to add an emulsifier in the system, so the residual problem of the emulsifier in the subsequent treatment is avoided. In addition, the structure of the silicon microsphere can be adjusted by adjusting the experimental conditions, and the obtained hollow Structural nano-organosilicon microspheres can meet the needs of various purposes.

Referring to Fig. 2, the method for preparing hollow nano-organosilicon microspheres according to an embodiment of the present invention further includes:

S400: pre-dispersed emulsifier in water

According to an embodiment of the present invention, before mixing the silane coupling agent with water, the emulsifier is dispersed in water in advance. According to embodiments of the present invention, the specific type of emulsifier is not particularly limited. According to specific embodiments of the present invention, the emulsifier can be selected from polyvinylpyrrolidone, block polyether, polyvinyl alcohol, lauryl sulfate At least one of sodium, sodium dodecylbenzenesulfonate, Span 60 and Tween 60. According to the embodiment of the present invention, the amount of the silane coupling agent is not particularly limited, and based on the total weight of the silane coupling agent dispersion, the content of the emulsifier may be 4% by mass or less. Specifically, due to the emulsification effect of the emulsifier, the monomer droplets can be more uniformly dispersed, so that monodisperse silicon spheres with smaller particle sizes can be obtained, and the particle size can be adjusted by adjusting the amount of the emulsifier.

The present invention will be described below with reference to specific embodiments. It should be noted that these embodiments are only illustrative and do not limit the present invention in any way.

Example 1

1) Preparation of silane coupling agent dispersion: mix 5g of silane coupling agent A151 with 300ml of deionized water, stir with a homogenizer, set the stirring speed at 200r/min, so that silane coupling agent A151 is evenly dispersed in the water phase neutralized and hydrolyzed for 2 hours to obtain a silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.1wt%, the dropping rate of ammonia water is 0.5ml/min, and the total amount of dropping is 0.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 180°C for 12 hours, and cool naturally to obtain hollow nano-structure silicone microspheres (such as image 3).

Example 2

1) Preparation of silane coupling agent dispersion: mix 10g of silane coupling agent A151 with 300ml of deionized water, and stir with a homogenizer, set the stirring speed to 400r/min, so that the silane coupling agent A151 is evenly dispersed in the water phase neutralized and hydrolyzed for 2 hours to obtain a silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.5wt%, the dropping rate of ammonia water is 0.8ml/min, and the total amount of dropping is 1.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 190°C for 12 hours, and cool naturally to obtain hollow nano-structure silicone microspheres (such as Figure 4).

Example 3

1) Preparation of silane coupling agent dispersion: mix 15g of silane coupling agent A151 with 300ml of deionized water, and stir with a homogenizer, set the stirring speed at 1000r/min, so that the silane coupling agent A151 is evenly dispersed in the water phase neutralized and hydrolyzed for 2 hours to obtain a silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.15wt%, the dropping rate of ammonia water is 1.5ml/min, and the total amount of dropping is 2.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 190°C for 24 hours, and cool naturally to obtain hollow nano-organic silicon microspheres (such as Figure 5).

Example 4

1) Preparation of silane coupling agent dispersion: mix 20g of silane coupling agent A151 with 300ml of deionized water, and stir with a homogenizer, set the stirring speed at 1200r/min, so that silane coupling agent A151 is evenly dispersed in the water phase neutralized and hydrolyzed for 2 hours to obtain a silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.25wt%, the dropping rate of ammonia water is 1.75ml/min, and the total amount of dropping is 7.0ml, then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion to a hydrothermal reaction kettle, react at 200°C for 15 hours, and cool naturally to obtain hollow nano-structure silicone microspheres (such as Figure 6).

Example 5

1) Preparation of silane coupling agent dispersion: mix 20g of silane coupling agent A151 with 300ml of deionized water, and stir with a homogenizer, set the stirring speed at 1500r/min, so that silane coupling agent A151 is evenly dispersed in the water phase neutralized and hydrolyzed for 2 hours to obtain a silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.15wt%, the dropping rate of ammonia water is 2.5ml/min, and the total amount of dropping is 9.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 220°C for 16 hours, and cool naturally to obtain hollow nano-organic silicon microspheres (such as Figure 7).

Example 6

1) Preparation of silane coupling agent dispersion: Dissolve 0.5wt% polyvinylpyrrolidine copper in 300ml deionized water in advance, then add 5g of silane coupling agent KH550, and stir with a homogenizer, set the stirring speed to 500r /min, the silane coupling agent KH550 was evenly dispersed in the water phase and hydrolyzed for 2 hours to obtain the silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.05wt%, the dropping rate of ammonia water is 0.5ml/min, and the total amount of dropping is 10.0ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 200°C for 12 hours, and cool naturally to obtain hollow nano-structure silicone microspheres.

Example 7

1) Preparation of silane coupling agent dispersion: Dissolve 0.5wt% sodium lauryl sulfate in 300ml deionized water in advance, then add 10g of silane coupling agent KH580, and stir with a homogenizer, set the stirring speed to 800r/min, the silane coupling agent KH580 is uniformly dispersed in the water phase and hydrolyzed for 2 hours to obtain the silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.5wt%, the dropping rate of ammonia water is 1.5ml/min, and the total amount of dropping is 12.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 200°C for 24 hours, and cool naturally to obtain hollow nano-structure silicone microspheres.

Example 8

1) Preparation of silane coupling agent dispersion: Dissolve 1wt% sodium lauryl sulfate in 300ml deionized water in advance, then add 5g of silane coupling agent KH792, and stir with a homogenizer, set the stirring speed to 800r /min, the silane coupling agent KH792 was uniformly dispersed in the water phase and hydrolyzed for 2 hours to obtain the silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.15wt%, the dropping rate of ammonia water is 0.8ml/min, and the total amount of dropping is 15.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 220°C for 24 hours, and cool naturally to obtain hollow nano-structure silicone microspheres.

Example 9

1) Preparation of silane coupling agent dispersion: Dissolve 1.5wt% sodium dodecylbenzenesulfonate in 300ml deionized water in advance, then add 5g of silane coupling agent KH792, and stir with a homogenizer, set stirring The speed is 1000r/min, so that the silane coupling agent KH792 is uniformly dispersed in the water phase and hydrolyzed for 2 hours to obtain the silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.35wt%, the dropping rate of ammonia water is 2.5ml/min, and the total amount of dropping is 18.5ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 220°C for 24 hours, and cool naturally to obtain hollow nano-structure silicone microspheres.

Example 10

1) Preparation of silane coupling agent dispersion: Dissolve 2wt% sodium dodecylbenzenesulfonate in 300ml deionized water in advance, then add 5g of silane coupling agent KH602, and stir with a homogenizer, set the stirring speed 1500r/min, the silane coupling agent KH602 is uniformly dispersed in the water phase and hydrolyzed for 2 hours to obtain the silane coupling agent dispersion;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.45wt%, the dropping rate of ammonia water is 2.5ml/min, and the total amount of dropping is 19.0ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 230°C for 16 hours, and cool naturally to obtain hollow nano-structure silicone microspheres.

Example 11

1) Preparation of silane coupling agent dispersion: Dissolve 3wt% sodium dodecylbenzenesulfonate in 300ml deionized water in advance, then add 5g of silane coupling agent KH580, and stir with a homogenizer, set the stirring speed The silane coupling agent KH580 is uniformly dispersed in the water phase and hydrolyzed for 2 hours to obtain a silane coupling agent dispersion at 1800r/min;

2) Preparation of monodisperse silicone solid spheres: add ammonia water to the obtained dispersion liquid, wherein the concentration of ammonia water is 0.45wt%, the dropping rate of ammonia water is 2.5ml/min, and the total amount of dropping is 20.0ml, and then After 20 minutes of reaction, monodisperse silicone solid balls can be formed;

3) Preparation of hollow silicon microspheres: Transfer the obtained silicone solid sphere dispersion into a hydrothermal reaction kettle, react at 220°C for 16 hours, and cool naturally to obtain hollow nano-structure silicone microspheres.

In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be construed as limitations to the present invention. Variations, modifications, substitutions, and modifications to the above-described embodiments are possible within the scope of the present invention.

Claims (7)

1. A method for preparing hollow-structure nano organic silicon microspheres is characterized by comprising the following steps:

(1) mixing a silane coupling agent with water to obtain a silane coupling agent dispersion liquid;

(2) adding ammonia water into the silane coupling agent dispersion liquid obtained in the step (1) so as to obtain a monodisperse organic silicon solid sphere; and

(3) carrying out hydrothermal treatment on the organic silicon solid sphere obtained in the step (2) so as to obtain the hollow-structure nano organic silicon microsphere,

wherein,

in the step (1), the content of the silane coupling agent is 1 to 65 mass% based on the total weight of the silane coupling agent dispersion liquid,

the silane coupling agent is silane coupling agent A151, silane coupling agent KH550, silane coupling agent KH580, silane coupling agent KH792 or silane coupling agent KH602,

in the step (2), the dropping speed of the ammonia water is 0.5-5 ml/min, the total dropping amount is 0.5-20 ml,

in the step (3), the hydrothermal treatment is carried out at a temperature of 120-200 ℃ for 12-24 hours.

2. The method according to claim 1, wherein in the step (1), the silane coupling agent is mixed with water with stirring, wherein the stirring rate is 200 to 8000 rpm.

3. The method according to claim 1, wherein in the step (1), an emulsifier is dispersed in water in advance before the silane coupling agent is mixed with the water.

4. The method according to claim 3, wherein the emulsifier is at least one selected from the group consisting of polyvinylpyrrolidone, block polyether, polyvinyl alcohol, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, span 60 and tween 60.

5. The method according to claim 3, wherein the content of the emulsifier is 4% by mass or less based on the total weight of the silane coupling agent dispersion liquid.

6. The method according to claim 1, wherein the concentration of the aqueous ammonia in the step (2) is 0.1 to 5 mass%.

7. The method of claim 1, wherein the particle size of the hollow-structure nano-organosilicon microspheres is 0.02-100 μm.