阅读说明：本技术 粗糙表面结构纳米纤维及其制备方法 (Nano fiber with rough surface structure and preparation method thereof ) 是由 祝国成 王琰 肖远香 姚菊明 于 2019-10-28 设计创作，主要内容包括：本发明公开了一种粗糙表面结构纳米纤维的制备方法,包括如下步骤：将聚合物材料干燥,然后加入至有机溶剂中,搅拌至干燥后聚合物材料溶解,接着于室温下静置脱泡6～8小时；将所得的静置脱泡后的聚合物溶液采用静电纺丝,将制取获得的纳米纤维干燥,得粗糙表面结构纳米纤维。本发明简化了制备粗糙纤维表面的工艺流程,且由于纤维表面粗糙颗粒与纤维是一体化的,因此,本发明永久性的制备了纤维的粗糙表面。(The invention discloses a preparation method of a nanofiber with a rough surface structure, which comprises the following steps: drying the polymer material, adding the dried polymer material into an organic solvent, stirring until the dried polymer material is dissolved, and standing and defoaming at room temperature for 6-8 hours; and (3) performing electrostatic spinning on the obtained polymer solution after standing and defoaming, and drying the prepared nanofiber to obtain the nanofiber with the rough surface structure. The invention simplifies the process flow for preparing the rough fiber surface, and the rough particles on the fiber surface are integrated with the fiber, so the invention permanently prepares the rough surface of the fiber.)

1. The preparation method of the nanofiber with the rough surface structure is characterized by comprising the following steps of:

1) drying the polymer material at 60-90 ℃ to constant weight to obtain a dried polymer material;

2) adding the dried polymer material into an organic solvent, stirring until the dried polymer material is dissolved, wherein the mass concentration of the dried polymer material in the obtained polymer solution is 10-18%;

standing and defoaming the polymer solution at room temperature for 6-8 hours;

3) electrostatic spinning is adopted for the polymer solution obtained in the step 2) after standing and defoaming, and nano fibers are obtained;

4) drying the nano-fibers at 35-60 ℃ to constant weight; obtaining the nanofiber with the rough surface structure.

2. The method for preparing the nano fiber with the rough surface structure according to claim 1, wherein: the polymer material is polyvinylidene fluoride.

3. The method for preparing the nano fiber with the rough surface structure according to claim 2, wherein: the organic solvent is at least one of polymethyl formamide, polymethyl acetamide, dichloromethane, acetic acid and acetone.

4. The method for preparing the nanofiber with the rough surface structure according to any one of claims 1 to 3, wherein the method comprises the following steps: the stirring in the step 2) is magnetic stirring, the rotating speed of the magnetic stirring is 300-2000 r/min, and the stirring time is 6-12 hours.

5. The method for preparing the nanofibers with a rough surface structure according to any one of claims 1 to 3, wherein in the step 3), the voltage of electrostatic spinning is 12 to 28kv, the distance between electrodes is 12 to 24cm, the spinning supply amount is 0.3 to 1 ml/hour, the ambient temperature is 25 to 40 ℃, and the ambient relative humidity is 35 to 50%.

6. The method of claim 5, wherein the receiving substrate used in the step 3) of preparing the nanofibers by electrospinning is aluminum foil, release paper, non-woven fabric, or glass fiber mesh.

7. The nanofiber with rough surface structure prepared by any one of the methods of claims 1 to 6, wherein: the diameter of the fiber is 200-1000 nanometers, the particle size of the rough particles on the surface is 40-150 nanometers, the rough particles are uniformly distributed on the surface of the fiber, and the specific surface area is 18-40 square meters per gram.

Technical Field

The invention relates to preparation of nano fibers, in particular to a preparation method of electrostatic spinning nano fibers with rough surface structures.

Background

The regular rough fiber surface structure can endow the fiber with more excellent characteristics, such as higher specific surface area and a bionic multistage micro-nano structure, so that the fiber can be applied to the fields of super hydrophobicity, oleophobicity, high adsorption, cell adsorption and proliferation and the like.

Although the surface function of the fiber can be modified by ozone treatment, plasma treatment, ion beam sputtering, surface grafting and other technologies, a multi-stage structure with a regular and obvious surface structure is not manufactured. Patent CN105887469A discloses a method for compounding nanoparticles on the surface of a fiber, which comprises placing the fiber in a dopamine buffer solution containing nanoparticles to obtain a nanoparticle-coated fiber, and forming a multilevel structure on the surface of the fiber. However, the method has a complex process flow, and the bonding fastness of the nanoparticles and the fibers is still to be improved.

Disclosure of Invention

The invention aims to solve the technical problem of providing a nanofiber with a rough surface structure, a preparation method and application thereof.

In order to solve the technical problems, the invention provides a preparation method of a nanofiber with a rough surface structure, which comprises the following steps:

1) drying the polymer material at 60-90 ℃ to constant weight (about 6-8 hours) to obtain a dried polymer material;

2) adding the dried polymer material into an organic solvent, stirring (magnetically stirring) until the dried polymer material is dissolved, wherein the mass concentration of the dried polymer material in the obtained polymer solution (homogeneous solution) is 10-18% (preferably 12-14%);

standing and defoaming the polymer solution at room temperature (10-25 ℃) for 6-8 hours;

3) electrostatic spinning is adopted for the polymer solution obtained in the step 2) after standing and defoaming, and nano fibers are obtained;

4) drying the nano-fiber at 35-60 ℃ to constant weight (so that the solvent is completely volatilized for about 6-12 hours); obtaining the nanofiber with the rough surface structure.

The step 4) is specifically as follows: putting the prepared nanofiber membrane and a receiving substrate of the nanofiber into an oven, and drying at 35-60 ℃ to constant weight; then separating the nano-fiber receiving substrate to obtain the nano-fiber with the rough surface structure.

As an improvement of the preparation method of the rough surface structure nanofiber of the present invention: the polymer material is polyvinylidene fluoride.

As a further improvement of the preparation method of the rough surface structure nanofiber of the present invention: the organic solvent is at least one of polymethyl formamide, polymethyl acetamide, methylene dichloride, acetic acid and acetone.

The above organic solvent, preferably dimethylformamide, or preferably dimethylformamide: dichloromethane ═ 9:1 mixed solvent.

As a further improvement of the preparation method of the rough surface structure nanofiber of the present invention: the stirring in the step 2) is magnetic stirring, the rotating speed of the magnetic stirring is 300-2000 r/min, and the stirring time is 6-12 hours.

As a further improvement of the preparation method of the rough surface structure nanofiber of the present invention: in the step 3), the voltage of electrostatic spinning is 12-28 kv, the distance between electrodes is 12-24 cm, the spinning supply amount is 0.3-1 ml/h, the ambient temperature is 25-40 ℃, and the ambient relative humidity is 35-50%.

As a further improvement of the preparation method of the rough surface structure nanofiber of the present invention: in the step 3), the receiving base materials used for preparing the nano-fibers by electrostatic spinning are aluminum foil, release paper, non-woven fabrics and glass fiber grids.

The invention also provides the rough surface structure nanofiber prepared by any one of the methods: the diameter of the fiber is 200-1000 nanometers, the particle size of the rough particles on the surface is 40-150 nanometers, the rough particles are uniformly distributed on the surface of the fiber, and the specific surface area is 18-40 square meters per gram.

In the step 3), a medical sterile 10 ml syringe can be used for extracting a solution with a certain mass, and the nano-fiber is prepared by adopting an electrostatic spinning process; in the step 3), the electrostatic spinning adopts a needle electrode.

Compared with the existing method for modifying the fiber surface by using the nano particles, the method has the following technical advantages:

(1) the invention simplifies the process flow for preparing the rough fiber surface;

(2) because the rough particles on the surface of the fiber are integrated with the fiber, the invention permanently prepares the rough surface of the fiber;

(3) by setting the electrostatic spinning process and environmental parameters, the solution is drawn from the needle electrode to the receiving substrate by using the high-voltage electric field force, and the nano-fiber with nano-particles uniformly distributed on the surface is obtained.

The diameter of the prepared nano fiber is 200-1000 nanometers, the particle size of the rough particles on the surface is 40-150 nanometers, the rough particles are uniformly distributed on the surface of the fiber, and the specific surface area can reach 18-40 m²/g。

The nanofiber with the rough surface structure can be prepared into a fiber aggregate and applied to the fields of super-hydrophobic and oleophobic materials, high-adsorption-performance materials, cell adsorption and proliferation and the like.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 is a scanning electron microscope image of a nanofiber with a rough surface structure prepared in example 1 by using 12% by mass of polyvinylidene fluoride as a raw material;

FIG. 2 is a scanning electron microscope image of the nanofibers with rough surface structure prepared from example 2 using 14% by mass of polyvinylidene fluoride as a raw material;

fig. 3 is a scanning electron microscope image of the coarse structured nanofiber prepared in example 3 by using 12% by mass of polyvinylidene fluoride as a raw material and using dimethylformamide and dichloromethane as a mixed solvent.

Fig. 4 is a scanning electron microscope image of the coarse structured nanofiber prepared in example 4 by using 14% by mass of polyvinylidene fluoride as a raw material and using dimethylformamide and dichloromethane as a mixed solvent.

FIG. 5 is a scanning electron microscope image of nanofibers prepared from comparative example 1 using 6% by mass of polyvinylidene fluoride as a raw material;

FIG. 6 is a scanning electron microscope image of nanofibers prepared from 8% by mass of polyvinylidene fluoride as a raw material in comparative example 2;

FIG. 7 is a scanning electron microscope image of nanofibers prepared in comparative example 3 under conditions of an ambient spinning temperature of 25 ℃ and a humidity of 30%;

FIG. 8 is a scanning electron microscope image of the nanofibers prepared in comparative example 4 with a dimethylformamide to dichloromethane content ratio of 7: 3.

Detailed Description

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.

In the following examples:

in the step 3), a medical sterile 10 ml syringe is used for extracting a solution with a certain mass, and the nano-fiber is prepared by adopting an electrostatic spinning process; electrostatic spinning uses a needle electrode, the nanofiber take-up distance, i.e., the distance between the needle and the receiving substrate. The receiving substrate is in close proximity to the negative electrode.