阅读说明：本技术 一种在超双疏表面制备高分子微球的方法 (Method for preparing polymer microspheres on super-amphiphobic surface ) 是由 邓旭 范岳 于 2020-06-16 设计创作，主要内容包括：本发明提供了一种在超双疏表面制备高分子微球的方法,包括以下步骤：在基底上制作超双疏表面；采用高分子材料配置高分子纺丝溶液,通过微流体纺丝的方法,在超双疏表面上纺丝高分子纤维阵列；使用激光热切割剪裁高分子纤维阵列,得到若干段高分子短纤维；将附着有高分子短纤维的基底加热至高分短纤维熔融,形成球形结构,然后降温,制得。该方法可有效解决现有的方法存在的制备设备价格昂贵,制得的高分子微球结构形貌难以满足要求的问题,并可灵活控制目标高分子微球的尺寸。(The invention provides a method for preparing polymer microspheres on a super-amphiphobic surface, which comprises the following steps: manufacturing a super-amphiphobic surface on a substrate; preparing a polymer spinning solution by adopting a polymer material, and spinning a polymer fiber array on the super-amphiphobic surface by a microfluid spinning method; cutting the polymer fiber array by laser thermal cutting to obtain a plurality of sections of polymer short fibers; heating the substrate attached with the high molecular short fiber to melt the high molecular short fiber to form a spherical structure, and then cooling to obtain the high molecular short fiber-containing glass. The method can effectively solve the problems that the preparation equipment is expensive and the structure and the shape of the prepared polymer microsphere are difficult to meet the requirements in the existing method, and can flexibly control the size of the target polymer microsphere.)

1. A method for preparing polymer microspheres on a super-amphiphobic surface is characterized by comprising the following steps:

(1) manufacturing a super-amphiphobic surface on a substrate;

(2) preparing a polymer spinning solution by using a polymer material, and spinning a polymer fiber array on the super-amphiphobic surface prepared in the step (1) by using a microfluid spinning method;

(3) cutting the polymer fiber array by laser thermal cutting to obtain a plurality of sections of polymer short fibers;

(4) and (4) heating the substrate attached with the high polymer short fibers in the step (3) until the high polymer short fibers are melted to form a spherical structure, and then cooling to obtain the high polymer short fiber composite material.

2. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the super-amphiphobic surface in the step (1) is prepared by the following steps:

a: placing the glass sheet in candle flame to move and collecting black carbon nano particles until the glass sheet is completely opaque;

b: b, placing the glass sheet treated in the step a and a beaker filled with tetraethyl orthosilicate and ammonia water respectively in a vacuum dryer;

c: pumping the vacuum drier to a vacuum state, and maintaining sealing for 20-28 h;

d: and d, taking out the glass sheet treated in the step c, carrying out ion surface treatment on the surface of the glass sheet, then placing the treated glass sheet and the beaker filled with the fluoridizing reagent into a vacuum drying container, continuously vacuumizing the vacuum drying container, and maintaining the vacuum drying container for sealing for 1-4 hours to obtain the glass.

3. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the polymer material in the step (2) is polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polycarbonate, polyvinyl acetate, polyethylene oxide, polylactic acid, polyurethane, polyvinyl chloride, polycaprolactone or cellulose acetate.

4. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the diameter of the polymer fibers in the step (2) is 1-30 μm.

5. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the method for cutting the polymer fiber array by laser thermal cutting in the step (3) is as follows:

a: focusing light spots on the contact surface of the polymer fiber array-super-amphiphobic surface in the step (2) by using an infrared laser and a micro-slit mask plate;

b: driving an infrared laser through an electric displacement platform, so that laser emitted by the infrared laser is guided along the gaps on the micro-gap mask plate to cut the polymer fiber array;

c: and controlling the distance between two adjacent hot cutting processes to obtain a plurality of sections of high-molecular short fibers.

6. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 5, wherein the width of the gap on the mask plate in the step (3) is 1-30 μm.

7. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the heating rate in the step (4) is 10-50 ℃/min.

8. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the cooling rate in the step (4) is less than 60 ℃/min.

9. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the minimum diameter of the polymer microspheres prepared in the step (4) is 10 μm, and the maximum diameter is the capillary length of the polymer material.

10. The method for preparing polymer microspheres on the super-amphiphobic surface according to claim 1, wherein the contact angle of the melt of the molten high-molecular short fibers in the step (4) on the super-amphiphobic surface is not less than 150 degrees.

Technical Field

The invention belongs to the technical field of preparation of polymer microspheres, and particularly relates to a method for preparing polymer microspheres on a super-amphiphobic surface.

Background

In recent years, due to the characteristics of micron-sized size, spherical structure, good size uniformity, extremely large specific surface area and the like, the polymer microsphere is widely concerned by people and shows wide application prospect in the fields of drug delivery, drug slow release, chemical sensing, material modification, optical imaging and the like. The traditional method for synthesizing the macromolecular microspheres mainly adopts a strategy from bottom to top, and synthesizes the macromolecular microspheres by polymerization reaction based on small molecules, wherein the polymerization modes comprise dispersion polymerization, seed polymerization, emulsion polymerization, microemulsion polymerization and the like. In order to obtain the polymer microspheres with required size, structure and function, the chemical synthesis method usually needs to finely control the reaction conditions, and a universal and simple synthetic route does not exist. Meanwhile, in the process of preparing the polymer microspheres by chemical synthesis, the use amount of organic solutions such as a solvent, a surfactant, an emulsifier and the like is very large, and great pressure is also exerted on the environment. Recently, new methods for preparing polymer microspheres by physical means, such as solvent evaporation, microfluidics, 3D microprinting, etc., have been developed. However, such methods still have disadvantages for the actual industrial production at present. The equipment is expensive and can not completely meet the requirement of the industry on the structural morphology of the polymer microsphere. For example, the surface of the microsphere prepared by 3D micro-printing is not in a smooth spherical shape and has a certain roughness; the technology of preparing the high molecular weight high molecular microspheres by adopting the microfluidic method still needs to be further developed.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for preparing polymer microspheres on a super-amphiphobic surface, which can effectively solve the problems that the preparation equipment is expensive and the structural morphology of the prepared polymer microspheres is difficult to meet the requirements in the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:

a method for preparing polymer microspheres on a super-amphiphobic surface comprises the following steps:

(1) manufacturing a super-amphiphobic surface on a substrate;

(2) preparing a polymer spinning solution by using a polymer material, and spinning a polymer fiber array on the super-amphiphobic surface prepared in the step (1) by using a microfluid spinning method;

(3) cutting the polymer fiber array by laser thermal cutting to obtain a plurality of sections of polymer short fibers;

(4) and (4) heating the substrate attached with the high polymer short fibers in the step (3) until the high polymer short fibers are melted to form a spherical structure, and then cooling to obtain the high polymer short fiber composite material.

Further, the method for cutting the polymer fiber array by laser thermal cutting in the step (3) is as follows:

a: focusing light spots on the contact surface of the polymer fiber array-super-amphiphobic surface in the step (2) by using an infrared laser and a micro-slit mask plate;

b: driving an infrared laser through an electric displacement platform, so that laser emitted by the infrared laser is guided along the gaps on the micro-gap mask plate to cut the polymer fiber array;

c: and controlling the distance between two adjacent hot cutting processes to obtain a plurality of sections of high-molecular short fibers.

The beneficial effect that above-mentioned technical scheme produced does: the super-amphiphobic surface can repel water and oil, and has higher anti-adhesion capability; the polymer material is a thermoplastic polymer which can be spun and has a glass transition temperature, a polymer fiber array is spun on the super-amphiphobic surface, then an infrared laser is driven to move by an electric displacement platform, the polymer fiber array is cut into a plurality of sections of polymer short fibers by laser emitted by a laser emitter, the displacement accuracy of the electric displacement platform is extremely high, therefore, the volume of each section of the cut polymer short fibers is basically the same, then the substrate is heated, the heating temperature is higher than the melting temperature of the polymer material, the polymer short fibers are gradually melted along with the rise of the temperature, the surface energy of the fiber melt is minimized under the action of the super-amphiphobic surface, a melt with a spherical structure is formed, then the temperature is reduced, the melt is cooled and solidified, the target polymer microsphere is obtained, and the anti-adhesion capability of the super-amphiphobic surface is strong, the polymer microspheres are easy to fall off from the substrate, and the collection of the polymer microspheres is realized.

The device can calculate the length of the polymer short fiber according to the size of the target polymer microsphere and the diameter of the polymer fiber formed by spinning, then the polymer short fiber with the required length is prepared by adjusting the spacing distance between two adjacent laser cutting processes, and finally the polymer microsphere with the required size is prepared.

Further, the infrared laser in the step (3) is an optical fiber coupling infrared laser with adjustable power of 1mW-10W, and the excitation wavelength of the infrared laser is 808 nm.

The beneficial effects produced by adopting the scheme are as follows: the power of the infrared laser can be adjusted according to the diameter of the polymer fiber so as to improve the cutting effect.

Further, the width of the gap on the mask plate in the step (3) is 1-30 μm.

Further, the width of the slit on the mask plate in the step (3) is 15 μm.

The beneficial effects produced by adopting the scheme are as follows: the 1-20 μm wide slit can effectively focus and improve the cutting effect.

Further, the displacement precision of the electric displacement platform in the step (3) is at least micron-scale.

The beneficial effects produced by adopting the scheme are as follows: the displacement precision of the electric displacement platform is at least micron-sized, the moving distance of the laser emitter can be accurately controlled, the length of the polymer short fibers generated by cutting is accurately controlled, and the uniformity of the prepared polymer microspheres is improved.

Further, the preparation process of the super-amphiphobic surface in the step (1) is as follows:

a: placing the glass sheet in candle flame, uniformly and slowly moving to collect black carbon nano particles until the glass sheet is completely opaque;

b: b, placing the glass sheet treated in the step a and a beaker filled with tetraethyl orthosilicate and ammonia water respectively in a vacuum dryer;

c: pumping the vacuum drier to a vacuum state, and maintaining sealing for 20-28 h;

d: taking out the glass sheet, carrying out plasma surface treatment on the surface of the glass sheet, then placing the treated glass sheet and a beaker filled with a fluorination reagent perfluorooctyl trichlorosilane into a vacuum drying container, continuously vacuumizing the vacuum drying container, and maintaining the vacuum drying container for sealing for 1-4 hours to obtain the product.

The beneficial effects produced by adopting the scheme are as follows: placing a glass sheet on a flame to move, collecting black carbon nanoparticles in the flame and enabling the black carbon nanoparticles to be uniformly deposited on the glass sheet, placing the glass sheet, tetraethyl orthosilicate and ammonia water in a vacuum environment, reacting to generate silicon dioxide nanoparticles, covering the upper parts of the carbon nanoparticles on the surface of the glass sheet through vapor deposition, then carrying out plasma surface treatment on the surface of the glass sheet, placing a fluorination reagent and the treated glass sheet in the vacuum environment, volatilizing the fluorination reagent and carrying out fluorination on a silicon dioxide layer on the surface of the glass sheet to obtain the glass sheet with the super-amphiphobic surface.

Further, the polymer material in step (2) is polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polycarbonate, polyvinyl acetate, polyethylene oxide, polylactic acid, polyurethane, polyvinyl chloride, polycaprolactone or cellulose acetate.

Further, the diameter of the polymer fiber in the step (2) is 1-30 μm.

Further, the diameter of the polymer fiber in the step (2) is 5 μm.

Further, the heating rate in the step (4) is 10-50 ℃/min.

Further, the temperature increase rate at the time of heating in step (4) was 30 ℃/min.

The beneficial effects produced by adopting the scheme are as follows: the heating rate is too high, so that the Ruili of the fiber melt is unstable and breaks, and the forming rate of the polymer microspheres is reduced.

Further, the cooling rate in the step (4) is less than 60 ℃/min.

Further, the cooling rate in the step (4) is 30 ℃/min.

The beneficial effects produced by adopting the scheme are as follows: the temperature reduction rate is too fast, and cracks can appear on the surfaces of the microspheres.

Further, the minimum diameter of the polymer microsphere prepared in the step (4) is 10 μm, and the maximum diameter is the capillary length of the polymer material.

Further, the contact angle of the fused mass of the high molecular short fiber in the step (4) on the super-amphiphobic surface is more than or equal to 150 degrees.

The beneficial effects produced by the invention are as follows:

the preparation method has the advantages of environmental protection, low preparation cost, simplicity and feasibility, and can be used for preparing the polymer microspheres with various materials and sizes in a customized manner according to the needs. The preparation method can be used for preparing most thermoplastic polymer microspheres, can prepare polymer microspheres which are difficult to synthesize by a chemical method, and the prepared microspheres have good morphological structures, and can also be used for preparing polymer microspheres with high molecular weight (molecular weight is more than 100000 g/mol).

Drawings

FIG. 1 is a SEM image of a super-amphiphobic surface;

FIG. 2 is a schematic view of a microfluidic spinning apparatus;

FIG. 3 is a microscopic image of a 4. + -. 0.2 μm diameter polymethylmethacrylate fiber array on the super-amphiphobic surface of example 2;

FIG. 4 is an SEM topography of various sizes of polymethylmethacrylate fibers prepared on the super-amphiphobic surface of examples 1-3;

FIG. 5 is a schematic view of a fiber array infrared laser thermal cutting apparatus;

FIG. 6 is a microscopic view of the laser trimming effect of the PMMA fiber array of example 2;

FIG. 7 is a schematic illustration of the process of heating fibers on a super-amphiphobic surface to form microspheres;

FIG. 8 is a microscopic image of the polymethyl methacrylate microspheres formed by heating the fibers on the super-amphiphobic surface in example 2;

FIG. 9 is an SEM photograph of the PMMA microspheres prepared in example 2;

FIG. 10 is a graph showing the effect of the polymethyl methacrylate microspheres of various sizes prepared in examples 1, 3 and 4;

FIG. 11 is a normalized size distribution diagram of the polymethylmethacrylate microsphere prepared in example 2.

Detailed Description

The following detailed description of embodiments of the invention refers to the accompanying drawings.

The preparation of the super-amphiphobic surfaces in the following examples is as follows:

a: taking the specification of 1-100cm²The smooth transparent glass sheet uniformly and slowly moves in the burning candle flame for 1min, and black carbon nano particles in the candle flame are collected and uniformly deposited on the glass sheet;

b: placing a glass sheet with deposited carbon nano-particles in a vacuum dryer with the bottom diameter of 240mm, respectively placing 3mL of tetraethyl orthosilicate and 3mL of ammonia water in two separate beakers, and placing the two beakers in the dryer;

c: vacuumizing the dryer to-0.08 MPa, maintaining the sealing state for 24h, and covering the silicon dioxide nanoparticles obtained by the reaction in the dryer on the carbon nanoparticles on the surface of the glass sheet through vapor deposition;

d: and taking out the glass sheet, carrying out ion surface treatment for 8-10min, placing the glass sheet in a dryer, placing 0.1mL of fluorinated reagent in a beaker and in the dryer, vacuumizing the dryer to-0.08 MP, maintaining the sealed state for 2h, and volatilizing the fluorinated reagent to perform fluorination with the silicon dioxide layer on the surface to obtain the super-amphiphobic surface glass sheet.