阅读说明：本技术 一种不对称的氨基化二氧化硅/酚醛树脂复合粒子的制备方法 (Preparation method of asymmetric aminated silicon dioxide/phenolic resin composite particles ) 是由 马士禹 任东方 许嘉琼 李晓峰 叶子昕 陈宁 相雪晨 陈喆 陈启明 李自成 于 2019-11-09 设计创作，主要内容包括：本发明公开了一种不对称的二氧化硅/酚醛树脂复合粒子的制备方法,在醇-水体系中,以硅源、间苯二酚和甲醛作为原料,在碱源条件下反应得到不对称的二氧化硅/酚醛树脂复合粒子。本发明通过简单调控间苯二酚和甲醛的用量以及原料的添加方式,可以实现对复合粒子形貌的有效调控。本发明在无需加入其它的碱作为催化剂的条件下,仅使用三氨丙基三乙氧基硅烷作为碱源即可制得单分散不对称的氨基化二氧化硅/酚醛树脂复合粒子。本发明合成方法简单,是一种环境友好的合成工艺。(The invention discloses a preparation method of asymmetric silicon dioxide/phenolic resin composite particles, which comprises the step of reacting silicon sources, resorcinol and formaldehyde serving as raw materials under the condition of an alkali source in an alcohol-water system to obtain the asymmetric silicon dioxide/phenolic resin composite particles. According to the invention, the shape of the composite particles can be effectively regulated and controlled by simply regulating and controlling the use amounts of resorcinol and formaldehyde and the addition mode of the raw materials. Under the condition of not adding other alkali as a catalyst, only triaminopropyltriethoxysilane is used as an alkali source to prepare the monodisperse asymmetric aminated silicon dioxide/phenolic resin composite particles. The synthetic method is simple and is an environment-friendly synthetic process.)

1. A method for preparing asymmetric aminated silica/phenolic resin composite particles, characterized in that the method comprises the following steps: in an alcohol-water system, a silicon source, resorcinol and formaldehyde are used as raw materials, and the asymmetric aminated silicon dioxide/phenolic resin composite particles are obtained by reaction under the condition of an alkali source.

2. The method for preparing according to claim 1, comprising the following specific steps:

(1) adding a silicon source into ethanol and uniformly mixing;

(2) adding an alkali source into the uniformly mixed solution obtained in the step (1) and uniformly mixing;

(3) adding deionized water into the solution obtained in the step (2) for mixing;

(4) and (4) adding resorcinol and formaldehyde into the solution obtained in the step (3) to react to obtain the asymmetric aminated silica/phenolic resin composite particles.

3. The preparation method according to claim 1, wherein in the step (1), the silicon source is added into ethanol and mixed under ultrasonic or stirring conditions, the ultrasonic power is 99%, and the stirring speed is 400-600 rpm; and/or the mixing time is 1-3 min.

4. The method according to claim 1, wherein in the step (1), the volume of the ethanol is 10 to 12 ml; and/or the silicon source is one or two of tetraethyl orthosilicate and propyl orthosilicate; and/or the volume of the silicon source is 0.6-1.0 ml.

5. The preparation method according to claim 1, wherein in the step (2), the mixing mode is ultrasonic or stirring, the power of the ultrasonic is 99%, and the rotating speed of the stirring is 400-600 rpm; and/or the mixing time is 1-3 min.

6. The method according to claim 1, wherein in the step (2), the alkali source is triaminopropyltriethoxysilane; and/or the volume of the alkali source is 0.06-0.1 ml.

7. The preparation method according to claim 1, wherein in the step (3), the mixing manner is ultrasonic or stirring, the power of the ultrasonic is 99%, and the rotation speed of the stirring is 400-600 rpm; and/or the mixing time is 1-3 min; and/or the volume of the deionized water is 8.0-10 ml.

8. The method according to claim 1, wherein in the step (4), the temperature of the reaction is-18 to-10 ℃; the reaction time is 12-36 h.

9. The method according to claim 1, wherein in the step (4), the mass of the resorcinol is 0.05 to 0.2 g; the volume of the formaldehyde is 0.07-0.28 ml.

10. Asymmetric aminated silica/phenolic resin composite particles prepared according to the process of any one of claims 1-9.

Technical Field

The invention belongs to the technical field of sol-gel, and relates to a preparation method of asymmetric aminated silicon dioxide/phenolic resin composite particles.

Background

The silicon dioxide nano material has the characteristics of large specific surface area, low density, easy control of morphology, good biocompatibility and the like, and the characteristics endow the silicon dioxide nano material with irreplaceable roles in the fields of catalysis, adsorption, drug delivery and the like. The sol-gel method is an important method for preparing silica nanoparticles. Stober successfully prepared monodisperse spherical silica nanoparticles in 1968 under the conditions of alcohol as a cosolvent and ammonia water as a catalyst. Since then, the process has progressed rapidly, with many improvements to the stober process for silica production. In addition, the phenolic resin is not only widely used for preparing various nano carbon materials, but also has a structure similar to silane.

Compared with the stober method for preparing silicon dioxide, the phenolic resin can be successfully synthesized under the same system. More importantly, through the simple and ingenious design of the synthesis scheme, the silica/phenolic resin composite particles (such as yolk-shell structures, bowl-shaped particles and bottle-shaped particles) with different structural types can be prepared in the stober system. In addition, in order to obtain silica/phenol resin composite particles with aminated surfaces, a two-step process is generally employed: firstly, preparing silicon dioxide/phenolic resin composite particles; and performing amination modification on the surface of the prepared silicon dioxide/phenolic resin composite particle. The modification method has complicated steps, and the surface of the obtained nano-particle is generally spherical, so that the application of the nano-particle is limited. Compared with spherical particles, the non-spherical asymmetric particles have a wide application prospect in biomedicine, particularly cancer treatment and the like.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a preparation method of asymmetric aminated silica/phenolic resin composite particles, which is prepared by taking a silicon source, an alkali source (also used as an amination reagent), resorcinol and formaldehyde as raw materials and performing sol-gel reaction in an alcohol-water system. During preparation, the shape of the composite particles can be effectively regulated and controlled by simply regulating and controlling the use amounts of resorcinol and formaldehyde and the addition mode of raw materials. The target product obtained by the invention is an asymmetric aminated silicon dioxide/phenolic resin composite particle.

In order to achieve the above purpose, the invention adopts the technical scheme that:

the invention provides a preparation method of asymmetric aminated silica/phenolic resin composite particles, which comprises the step of reacting silicon sources, resorcinol and formaldehyde serving as raw materials under the condition of an alkali source in an alcohol-water system to obtain the asymmetric aminated silica/phenolic resin composite particles.

The method specifically comprises the following specific steps:

(1) adding a silicon source into ethanol and uniformly mixing;

(2) adding an alkali source into the uniformly mixed solution obtained in the step (1) and uniformly mixing;

(3) adding deionized water into the solution obtained in the step (2) for mixing;

(4) and (4) adding resorcinol and formaldehyde into the solution obtained in the step (3) to react to obtain the asymmetric aminated silicon dioxide/phenolic resin composite particles.

The adding sequence of the silicon source, the alkali source and the ethanol can also be as follows: firstly, mixing a silicon source and an alkali source to obtain a mixed solution, and then adding the mixed solution into ethanol.

In the step (1), the mixing mode is ultrasonic or stirring; preferably, ultrasound.

The power of the ultrasound was 99%.

The stirring speed is 400-600 rpm; preferably, it is 600 rpm.

In the step (1), the mixing time is 1-3 min; preferably, it is 2 min.

In the step (1), the volume of the ethanol is 10-12 ml; preferably, it is 12 ml.

In the step (1), the silicon source is one or more of tetraethyl orthosilicate, propyl orthosilicate and the like; preferably tetraethyl orthosilicate.

In the step (1), the volume of the silicon source is 0.6-1.0 ml; preferably, it is 1.0 ml.

In the step (2), preferably, an alkali source is rapidly added to the uniformly mixed solution in the step (1).

In the step (2), the alkali source is rapidly added to better dissolve in the mixed solution of the silicon source and the ethanol.

In the step (2), the mixing mode is ultrasonic or stirring; preferably, ultrasound.

The power of the ultrasound was 99%.

The stirring speed is 400-600 rpm; preferably, it is 600 rpm.

In the step (2), the mixing time is 1-3 min; preferably, it is 2 min.

In the step (2), the alkali source is triaminopropyltriethoxysilane.

In the step (2), the volume of the alkali source is 0.06-0.1 ml; preferably, it is 0.1 ml.

In step (3), deionized water is preferably added rapidly to the solution of step (2).

The purpose of the rapid addition of deionized water in step (3) is to prevent the silicon source from reacting at room temperature.

In the step (3), the mixing mode is ultrasonic or stirring; preferably, ultrasound.

The power of the ultrasound was 99%.

The stirring speed is 400-600 rpm; preferably, it is 600 rpm.

In the step (3), the mixing time is 1-3 min; preferably, it is 2 min.

In the step (3), the volume of the deionized water is 8.0-10 ml; preferably, it is 10 ml.

In the step (4), the temperature of the reaction is-18 to-10 ℃; preferably, it is-10 ℃ or-18 ℃; further preferably-18 ℃.

In the step (4), the reaction time is 12-36 h; preferably, it is 22 h.

In the step (4), the mass of the resorcinol is 0.05-0.2 g; preferably 0.1 and 0.2 g.

In the step (4), the volume of the formaldehyde is 0.07-0.28 ml; preferably 0.14 and 0.28 ml.

The method also comprises a post-treatment step after the step (4): and centrifuging, washing with alcohol, washing with water, and drying to obtain the asymmetric aminated silica/phenolic resin composite particles.

Wherein the rotation speed of the centrifugal separation is more than 8000 rpm; preferably 10000 rpm.

Wherein the centrifugal separation time is 2-5 min; preferably, it is 3 min.

In a specific embodiment, the method specifically comprises the steps of:

(1) adding a silicon source into a beaker filled with ethanol and uniformly mixing;

(2) quickly adding a certain amount of alkali source into the solution obtained in the step (1) to uniformly mix the alkali source and the solution;

(3) rapidly adding a certain volume of deionized water into the solution obtained in the step (2) for mixing;

(4) adding a certain amount of resorcinol and formaldehyde into the solution obtained in the step (3) and uniformly mixing;

(5) standing the solution obtained in the step (4) at a low temperature for reaction;

(6) and (4) centrifuging, washing with alcohol, washing with water, and drying the product obtained in the step (5) to obtain the asymmetric aminated silicon dioxide/phenolic resin composite particles.

The invention also provides the asymmetric aminated silicon dioxide/phenolic resin composite particle prepared by the method.

The composite particles have a bowl-like or multi-directionally concave spherical structure, and the particle size is usually 1 to 3 μm.

The innovation points of the invention are as follows: according to the invention, no extra alkali is required to be added as a catalyst, the triaminopropyltriethoxysilane is used as an amination reagent and an alkali source, so that an alkaline environment is provided for a system, and meanwhile, the system is subjected to phase separation at a low temperature to generate oil drops, so that the obtained product does not have a symmetrical spherical shape any more, but forms a sunken bowl-like composite particle; the effective regulation and control of the appearance can be realized by simply regulating and controlling the use amounts of the resorcinol and the formaldehyde and the adding mode of the raw materials. When a silicon source and an alkali source are sequentially added into ethanol, the obtained composite particles have a spherical structure with a plurality of concave directions; when the silicon source and the alkali source are mixed firstly and then the mixed solution is added into the ethanol, the composite particles with the bowl-shaped structure are obtained.

The invention has the beneficial effects that: compared with the existing preparation method, the preparation method of the aminated silicon dioxide nano particle with the rough surface provided by the invention has the following advantages:

(1) no additional base is required to catalyze the reaction;

(2) the obtained sample has asymmetric appearance;

(3) the appearance can be effectively regulated and controlled only by changing the adding sequence of the raw materials;

(4) the amination of the surface of the sample is realized in one step;

(5) the preparation method is simple and has good monodispersity.

Drawings

Fig. 1 is a transmission electron microscope image of a lower magnification and fig. 1b is a transmission electron microscope image of a higher magnification of the silica/phenolic resin composite particle prepared in example 1 of the present invention.

Fig. 2 is a graph of a silica/phenolic resin composite particle prepared in example 2 of the present invention, in which fig. 2c is a transmission electron microscope graph with a lower magnification, and fig. 2d is a transmission electron microscope graph with a higher magnification.

Fig. 3 is a graph of a silica/phenolic resin composite particle prepared in example 3 of the present invention, in which fig. 3e is a transmission electron microscope graph with a lower magnification, and fig. 3f is a transmission electron microscope graph with a higher magnification.

Detailed Description

The invention is further illustrated by the following examples. The specific examples are all carried out on the premise of the technical scheme of the invention, and the purpose is to better study the contents of the invention.