阅读说明：本技术 一种三尺度微纳米聚合物粒子及其制备方法和应用 (Three-scale micro-nano polymer particle and preparation method and application thereof ) 是由 胡继文 李志华 林树东 涂园园 魏彦龙 肖运彬 尚颖超 黄振祝 欧明 于 2018-09-11 设计创作，主要内容包括：本发明属于聚合物粒子领域,公开了一种三尺度微纳米聚合物粒子及其制备方法和应用。该方法使用乙醇和甲苯作为混合溶剂,以聚乙烯吡咯烷酮作为稳定剂,以AIBN为引发剂,以甲基丙烯酸缩水甘油酯为单体,以乙二醇二甲基丙烯酸酯为交联剂,通过分散聚合一步反应制备三尺度微纳米聚合物粒子。该方法工艺简单,成本低廉,得到的三尺度微纳米聚合物粒子为非球形树莓状结构,整体粒子直径在3.6～4.2μm左右,上面有910～1000nm左右的二级结构,然后二级结构上面有190～400nm左右的三级结构。可应用于超双疏涂料、药物载体、磁性材料、生物材料和光电材料等领域。(The invention belongs to the field of polymer particles, and discloses a three-scale micro-nano polymer particle and a preparation method and application thereof. The method uses ethanol and toluene as mixed solvents, polyvinylpyrrolidone as a stabilizer, AIBN as an initiator, glycidyl methacrylate as a monomer and ethylene glycol dimethacrylate as a cross-linking agent, and prepares the three-scale micro-nano polymer particles through one-step reaction of dispersion polymerization. The method is simple in process and low in cost, the obtained three-scale micro-nano polymer particles are of non-spherical raspberry-shaped structures, the diameter of the whole particle is about 3.6-4.2 mu m, a secondary structure with the size of about 910-1000 nm is arranged on the whole particle, and a tertiary structure with the size of about 190-400 nm is arranged on the secondary structure. Can be applied to the fields of super-amphiphobic coatings, drug carriers, magnetic materials, biological materials, photoelectric materials and the like.)

1. A preparation method of three-scale micro-nano polymer particles is characterized by mainly comprising the following steps: ethanol and toluene are used as mixed solvents, polyvinylpyrrolidone is used as a stabilizer, AIBN is used as an initiator, glycidyl methacrylate is used as a monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, and three-scale micro-nano polymer particles are prepared through one-step reaction of dispersion polymerization.

2. The preparation method of the three-dimensional micro-nano polymer particles according to claim 1, which is characterized by comprising the following steps;

(1) dissolving polyvinylpyrrolidone in a mixed solvent of ethanol and toluene to prepare a polyvinylpyrrolidone/ethanol-toluene mixed solution;

(2) dissolving azobisisobutyronitrile, glycidyl methacrylate and ethylene glycol dimethacrylate in a mixed solvent of ethanol and toluene to prepare a precursor mixed solution of azobisisobutyronitrile/glycidyl methacrylate/ethylene glycol dimethacrylate/ethanol-toluene;

(3) and (3) introducing nitrogen into the mixed solution obtained in the steps (1) and (2), removing water and oxygen, then dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under the condition of heating and stirring, then keeping the temperature and stirring for reaction, continuing the reaction for 10-21 h after the color of the reaction solution turns from transparent to turbid and finally turns into milky white, then stopping the reaction, and purifying the obtained reaction solution to obtain the three-scale micro-nano polymer particles.

3. The method for preparing the three-dimensional micro-nano polymer particles according to claim 2, wherein the method comprises the following steps:

in the mixed solvent of ethanol and toluene in the step (1), the volume ratio of the ethanol to the toluene is 32: 6-34: 4;

the amount of the mixed solvent of ethanol and toluene in the step (1) is such that 4-6 mL of toluene is added to each 0.75g of polyvinylpyrrolidone;

the molecular weight of the polyvinylpyrrolidone in the step (1) is 40000-58000, and the K value is more than 30.

4. The preparation method of the three-dimensional micro-nano polymer particles according to claim 3, characterized in that:

in the mixed solvent of the ethanol and the toluene in the step (1), the volume ratio of the ethanol to the toluene is 33: 5;

the amount of the mixed solvent of ethanol and toluene used in the step (1) is such that 5mL of toluene is added per 0.75g of polyvinylpyrrolidone.

5. The method for preparing the three-dimensional micro-nano polymer particles according to claim 2, wherein the method comprises the following steps:

the mass ratio of the glycidyl methacrylate to the ethylene glycol dimethacrylate in the step (2) is 84: 16-90: 10;

the dosage of the azobisisobutyronitrile in the step (2) meets the condition that the mass of the azobisisobutyronitrile is 1.00-1.50% of the mass sum of glycidyl methacrylate and ethylene glycol dimethacrylate;

in the mixed solvent of the ethanol and the toluene in the step (2), the volume ratio of the ethanol to the toluene is 5: 1; the amount of the mixed solvent of ethanol and toluene used in the step (2) was such that 10mL of ethanol was added per 2.61g of glycidyl methacrylate.

6. The preparation method of the three-dimensional micro-nano polymer particles according to claim 5, characterized in that:

the mass ratio of the glycidyl methacrylate to the ethylene glycol dimethacrylate in the step (2) is 87: 13;

the dosage of the azobisisobutyronitrile in the step (2) meets the condition that the mass of the azobisisobutyronitrile is 1.28 percent of the mass sum of the glycidyl methacrylate and the ethylene glycol dimethacrylate.

7. The method for preparing the three-dimensional micro-nano polymer particles according to claim 2, wherein the method comprises the following steps:

the use amount of the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) in the step (3) is such that the mass of the polyvinylpyrrolidone in the mixed solution obtained in the step (1) is 25% of the mass sum of the glycidyl methacrylate and the ethylene glycol dimethacrylate in the mixed solution obtained in the step (2).

8. The method for preparing the three-dimensional micro-nano polymer particles according to claim 2, wherein the method comprises the following steps:

the dropwise adding in the step (3) means that the dropwise adding speed is 4.5-5.0 mL/h;

the heating and stirring in the step (3) is stirring at a stirring speed of 200-400 rpm when the temperature is heated to 70-80 ℃;

and (3) purifying, namely cooling the obtained reaction solution to room temperature, centrifuging, soaking the obtained precipitate in tetrahydrofuran at room temperature for 5-10 hours, centrifuging again, washing with ethanol for three times, and freeze-drying to obtain white powder of the purified three-scale micro-nano polymer particles.

9. A three-dimensional micro-nano polymer particle prepared according to the method of any one of claims 1 to 8.

10. The application of the three-dimensional micro-nano polymer particles according to claim 9 in the fields of super-amphiphobic coatings, drug carriers, magnetic materials, biological materials and photoelectric materials.

Technical Field

The invention belongs to the field of polymer particles, and particularly relates to a three-scale micro-nano polymer particle and a preparation method and application thereof.

Background

Polymer particles, particularly multi-scale polymer particles having a micro-nano composite structure, are receiving increasing attention for their unique physical, chemical, optical and catalytic properties. The multi-scale polymer particles are widely applied to the fields of preparation of super-amphiphobic coatings, drug carriers, biological materials, magnetic materials, photoelectric materials and the like.

Compared with the nano-polymer spherical particles, the three-scale micro-nano polymer particles are unique in that the three-scale micro-nano polymer particles have a micro-nano multistage composite structure, and the structure is closely related to the performance of the three-scale micro-nano polymer particles. The micro-nano polymer particles have a micro-nano multistage composite structure and excellent optical and chemical properties, so that the micro-nano polymer particles can be used as basic units to form colloidal crystals by self-assembly and can be applied to the fields of photonic crystals, optical switches, ordered porous materials and the like. However, the size and morphology of the multi-scale micro-nano polymer particles have a great influence on the performance of the multi-scale micro-nano polymer particles, for example, the size and morphology influence the surface roughness of the micro-nano polymer particles and the reaction degree of further functionalization of the micro-nano polymer particles. Therefore, the method can be used for controllably synthesizing micro-nano polymer particles with different sizes and shapes. At present, the main synthesis methods of micro-nano polymer particles include a polymerization method, a layer-by-layer self-assembly method, a microfluid method, a template method, a mechanical stretching method and the like, but the methods for preparing the three-scale micro-nano polymer particles are complex in process or high in cost, or uneven in size and shape. Therefore, the invention synthesizes micro-nano polymer particles with proper size and morphology in one step by a dispersion polymerization method, and can be further applied to the preparation of super-amphiphobic surfaces.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of three-scale micro-nano polymer particles. According to the method, ethanol and toluene are used as mixed solvents, and three-scale micro-nano polymer particles are synthesized through one-step reaction. The method has simple process (one-step reaction), low cost and high product yield. The invention researches the influence of parameters such as the ratio of ethanol to toluene, the dosage of a cross-linking agent, the reaction time, the stirring speed, the temperature and the like on reaction products in detail in the reaction process, and realizes the controllable synthesis of the three-scale micro-nano polymer particles.

The invention also aims to provide the three-scale micro-nano polymer particles prepared by the method.

The invention further aims to provide application of the three-scale micro-nano polymer particles. The three-scale micro-nano polymer particles have obvious structures in all scales, have larger roughness on the surface and have a plurality of potential applications.

The purpose of the invention is realized by the following scheme:

a preparation method of three-scale micro-nano polymer particles mainly comprises the following steps: the three-scale micro-nano polymer particles are prepared by using ethanol and toluene as mixed solvents, polyvinylpyrrolidone (PVP) as a stabilizer, AIBN as an initiator, Glycidyl Methacrylate (GMA) as a monomer and Ethylene Glycol Dimethacrylate (EGDMA) as a cross-linking agent through dispersion polymerization and one-step reaction.

The preparation method of the three-scale micro-nano polymer particles specifically comprises the following steps:

(1) dissolving polyvinylpyrrolidone (PVP) in a mixed solvent of ethanol and toluene to prepare a polyvinylpyrrolidone/ethanol-toluene mixed solution;

(2) dissolving Azobisisobutyronitrile (AIBN), Glycidyl Methacrylate (GMA) and Ethylene Glycol Dimethacrylate (EGDMA) in a mixed solvent of ethanol and toluene to prepare a precursor mixed solution of Azobisisobutyronitrile (AIBN)/Glycidyl Methacrylate (GMA)/Ethylene Glycol Dimethacrylate (EGDMA)/ethanol-toluene;

(3) introducing nitrogen into the mixed solution obtained in the steps (1) and (2), removing water and oxygen, dropwise adding the precursor mixed solution obtained in the step (2) into the polyvinylpyrrolidone/ethanol-toluene mixed solution obtained in the step (1) under the condition of heating and stirring, carrying out heat preservation and stirring reaction, continuing the reaction for 10-21 h after the color of the reaction solution changes from transparent to turbid and finally changes into milky white, stopping the reaction, and purifying the obtained reaction solution to obtain the three-scale micro-nano polymer particles.

In the step (1), in the mixed solvent of ethanol and toluene, the volume ratio of ethanol to toluene is 32: 6-34: 4, preferably 33: 5; the dosage of the mixed solvent of the ethanol and the toluene meets the requirement that 4-6 mL of toluene is added to each 0.75g of polyvinylpyrrolidone, and preferably 5mL of toluene is added to each 0.75g of polyvinylpyrrolidone;

the molecular weight of polyvinylpyrrolidone (PVP) in the step (1) is 40000-58000, and the K value is more than 30;

the mass ratio of Glycidyl Methacrylate (GMA) to Ethylene Glycol Dimethacrylate (EGDMA) in the step (2) is 84: 16-90: 10, preferably 87: 13; the dosage of the Azobisisobutyronitrile (AIBN) in the step (2) meets the requirement that the mass of the Azobisisobutyronitrile (AIBN) is 1.00-1.50%, preferably 1.28% (mass percentage) of the mass sum of Glycidyl Methacrylate (GMA) and Ethylene Glycol Dimethacrylate (EGDMA);

in the mixed solvent of the ethanol and the toluene in the step (2), the volume ratio of the ethanol to the toluene is 5: 1; the dosage of the mixed solvent of ethanol and toluene in the step (2) meets the requirement that 10mL of ethanol is added for every 2.61g of Glycidyl Methacrylate (GMA);

the use amount of the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) in the step (3) meets the condition that the mass of polyvinylpyrrolidone (PVP) in the mixed solution obtained in the step (1) is 25 percent (mass percentage) of the mass sum of Glycidyl Methacrylate (GMA) and Ethylene Glycol Dimethacrylate (EGDMA) in the mixed solution obtained in the step (2);

the dropping in the step (3) is performed at a dropping speed of 4.5-5.0 mL/h, preferably by using a peristaltic pump.

The heating and stirring in the step (3) is to heat the mixture to 70-80 ℃, preferably 75 +/-1 ℃, and the stirring speed is 200-400 rpm, preferably 250 rpm;

and (3) purifying, namely cooling the obtained reaction solution to room temperature, centrifuging, soaking the obtained precipitate in tetrahydrofuran at room temperature for 5-10 hours, centrifuging again, washing with ethanol for three times, and freeze-drying to obtain white powder of the purified three-scale micro-nano polymer particles.

The room temperature in the invention is 20-25 ℃.

The three-scale micro-nano polymer particles prepared by the method.

The three-scale micro-nano polymer particles have a micro-nano multilevel structure, so the three-scale micro-nano polymer particles have excellent chemical and optical properties, and can be applied to the fields of super-amphiphobic coatings, drug carriers, magnetic materials, biological materials, photoelectric materials and the like.

The mechanism of the invention is as follows:

the invention uses a mixed solvent of ethanol and toluene, synthesizes three-scale micro-nano polymer particles by adjusting the proportion and adopting one-step reaction, the overall particle diameter of the three-scale micro-nano polymer particles is about 3.6-4.2 mu m, a secondary structure with the size of about 910-1000 nm is arranged on the three-scale micro-nano polymer particles, and then a tertiary structure with the size of about 190-300 nm is arranged on the secondary structure. In the method, if toluene is not added or the proportion of the cross-linking agent is not proper, three-scale micro-nano polymer particles cannot be synthesized.

Compared with the prior art, the invention has the following advantages and beneficial effects:

the preparation method provided by the invention is simple in process and low in cost, and the polymer particles with the three-scale micro-nano structure can be prepared through one-step reaction, and are of non-spherical raspberry-shaped structures, the diameter of the whole particles is about 3.6-4.2 mu m, secondary structures of about 910-1000 nm are arranged on the particles, and then tertiary structures of about 190-300 nm are arranged on the secondary structures. Can be applied to the fields of super-amphiphobic coatings, drug carriers, magnetic materials, biological materials, photoelectric materials and the like.

Drawings

Fig. 1 is a scanning electron microscope image of the three-dimensional micro-nano polymer particles prepared in example 1.

Fig. 2 is a scanning electron microscope image of the three-dimensional micro-nano polymer particles prepared in example 2.

Fig. 3 is a scanning electron microscope image of the three-dimensional micro-nano polymer particles prepared in example 3.

Fig. 4 is a scanning electron microscope photograph of the white powder prepared in comparative example 1.

Fig. 5 is a scanning electron microscope photograph of the white powder prepared in comparative example 2.

Fig. 6 is a scanning electron microscope photograph of the white powder prepared in comparative example 3.

Fig. 7 is a scanning electron microscope photograph of the white powder prepared in comparative example 4.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.