CN113622191B

CN113622191B - Special surface structure fiber and preparation method and application thereof

Info

Publication number: CN113622191B
Application number: CN202111190042.2A
Authority: CN
Inventors: 陈书铖; 吴鑫娣; 张楠楠
Original assignee: Carbon Good Beijing Technology Co ltd
Current assignee: Carbon Good Beijing Technology Co ltd
Priority date: 2021-10-13
Filing date: 2021-10-13
Publication date: 2022-02-08
Anticipated expiration: 2041-10-13
Also published as: CN113622191A

Abstract

The invention relates to a special surface structure fiber and a preparation method and application thereof, belonging to the technical field related to filtration and purification. The preparation method comprises the following steps: preparing an organic mixed solution; soaking a fiber raw material in the organic mixed solution; and carrying out polymerization reaction at a preset temperature in an oxygen-free environment, and then taking out the fiber raw material to obtain the fiber with the special surface structure. The invention also discloses a special surface structure fiber and application thereof. The fiber raw material is contacted with the organic mixed solution in a soaking mode, solute reactants in the organic mixed solution are chemically polymerized to form high polymer materials which are uniformly coated on the surface of the fiber through chemical reaction, a surface coating is formed on the surface of the fiber, the surface of the fiber is enabled to be rough from smooth on the premise that the total weight of the fiber is increased by less than 20wt%, the specific surface area is increased, and the same or different surface properties are given to the fiber raw material through the adhesion materials.

Description

Special surface structure fiber and preparation method and application thereof

Technical Field

The invention relates to the technical field related to filtration and purification, in particular to a special surface structure fiber and a preparation method and application thereof.

Background

The mask is a sanitary product, is generally worn at the mouth and nose part and is used for filtering air entering the mouth and nose, and can prevent harmful gas, smell and spray from entering and exiting the mouth and nose of a wearer, so that aerosol generated by the patient is prevented from escaping outwards, and harmful airborne particles are prevented from being transported inwards.

Filters used in modern surgical masks and respirators are considered "fibrous" in nature and are made from flat, non-woven mats of fine fibers. Fiber diameter, porosity (i.e., ratio of open space to fiber), and filter thickness all have an effect on the ability of the filter to collect particulates.

Along with the gradual emphasis on health and safety, the demand of the mask is increased rapidly, and the requirement on the performance and quality of the mask is also improved. The melt-blown cloth is composed of fibers with the diameter range of 0.5-10 microns, and the melt-blown cloth of the fiber raw materials can effectively utilize static electricity to adsorb virus dust and spray. However, the existing melt-blown fibers are usually smooth in surface, and although the diameter is small, the surface area is also small, so that the adsorption performance of the particles is influenced; at the same time, the fiber density must not be too high to ensure air circulation. In order to improve the performance, the electrostatic spinning nanofiber membrane technology is applied to the mask by various enterprises and research institutes in the recent period, so that the specific surface area can be increased, and the filtering efficiency can be improved. But compared with the current universal mature simple production mode and cheap raw materials, the technology has greatly increased cost, generally has higher air resistance than that of melt-blown materials, and has great limitation on wide popularization and use in industry. Therefore, it is necessary to invent a method for greatly increasing the specific surface area of the fiber without affecting the existing production mode and the overall cost, so that when the method is applied to masks and related products, the mask not only has more efficient adsorption and blocking performance, but also can realize better air permeability and user experience.

Disclosure of Invention

The invention aims to provide a preparation method of a fiber, in particular to a preparation method of a fiber with a special surface structure.

The technical scheme for solving the technical problems is as follows: a method for preparing a special surface structure fiber comprises the following steps: preparing an organic mixed solution; soaking a fiber raw material in the organic mixed solution; and carrying out polymerization reaction at a preset temperature in an oxygen-free environment, and then taking out the fiber raw material to obtain the fiber with the special surface structure.

The special surface structure of the special surface structure fiber obtained by the invention is the fiber with increased specific surface area and roughness, and the special surface structure of the special surface structure fiber can be seen in figures 1b and 1c, namely, a rough, clustered and petal-like sheet structure form is formed.

The preparation method of the special surface structure fiber has the beneficial effects that:

the preparation method comprises the steps of contacting the fiber raw material with an organic mixed solution in a soaking mode, carrying out chemical reaction on the organic mixed solution at a preset temperature in an oxygen-free environment, carrying out chemical polymerization on solute reactants in the organic mixed solution to form high polymer materials, uniformly coating the high polymer materials on the surface of the fiber, and forming a surface coating on the surface of the fiber, so that a layer of coating material formed by polymerization is uniformly adhered to the surface of the fiber raw material, on the premise that the total weight of the fiber is increased by less than 20wt%, the surface of the fiber is roughened from smooth, the specific surface area is increased, and the same or different surface properties are provided for the fiber raw material through the adhering material.

The fiber with the increased specific surface prepared by the preparation method can be used in the general application of the fiber, and the application comprises the fields of mask materials, air or liquid filtering materials, isolating materials, absorbing materials, heat-insulating materials, wiping cloths and the like, but has better or more unique performance than the original fiber raw materials.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, the preparation method of the organic mixed solution comprises the following steps: dissolving a high molecular monomer and an initiator into an organic solvent.

The beneficial effect of adopting the further scheme is that: the high molecular monomer can be chemically polymerized to form a high molecular material which is uniformly coated on the surface of the fiber to form a surface coating with a special structure. In the chemical polymerization reaction process, the formed polymer and the fiber surface have similar polarity, and interfacial polymerization can occur due to the affinity among chemical functional groups and the like, the polymer can grow on the fiber surface firstly, and then the polymer can continue to form and coat the fiber surface, and the steps are repeated until the reaction is finished.

Further, in the organic mixed solution, the concentration of the high molecular monomer is 5wt% -50wt%, and the concentration of the initiator is 0.1wt% -1 wt%.

Further, the addition amount of the cross-linking agent in the organic mixed solution is 0-10 wt% of the weight of the high molecular monomer.

The beneficial effect of adopting the further scheme is that: the addition of the cross-linking agent can improve the diversity of the fiber surface coating structure and adjust the pore size distribution more widely.

Further, the crosslinking agent is divinylbenzene.

The beneficial effect of adopting the further scheme is that: can react and crosslink with the polymer material formed by the polymer monomer and the initiator to form a three-dimensional structure.

Further, the high molecular monomer comprises at least one of styrene, methyl methacrylate, acrylonitrile and butyl acrylate; the initiator includes at least one of azobisisoheptonitrile and azobisisobutyronitrile.

The beneficial effect of adopting the further scheme is that: special structures can be formed on the surface of the fiber and the surface properties can be modified.

Further, the organic solvent includes at least one of acetonitrile, ethanol, propanol, acetone, and N-methyl-2-pyrrolidone.

The beneficial effect of adopting the further scheme is that: ensure that the high molecular monomer can be dissolved in the organic solution for reaction, and simultaneously, the high molecular monomer can be precipitated from the solution and coated on the surface of the fiber after being formed.

Further, the fiber raw material includes polypropylene fiber or carbon fiber.

Further, the preset temperature is 60-90 ℃, the anaerobic environment comprises a nitrogen or argon environment, and the polymerization reaction time is 2-6 hours.

The beneficial effect of adopting the further scheme is that: the high molecular monomer and the initiator can react to form the high molecular polymer by adopting proper temperature and oxygen-free environment.

The second purpose of the invention is to provide the special surface structure fiber prepared by the method.

The technical scheme for solving the technical problems is as follows: the special surface structure fiber is prepared by the preparation method.

The special surface structure fiber has the beneficial effects that: according to the special surface structure fiber, the surface of the fiber forms a rough, clustered and petal-like sheet-shaped structure, and the structure enables the fiber to have better adsorption performance.

The third purpose of the invention is to provide the application of the special surface structure fiber prepared by the method.

The technical scheme for solving the technical problems is as follows: the special surface structure fiber prepared by the preparation method is applied to mask materials, isolation materials, absorption materials, heat-preservation materials, wiping cloth and filtering materials. The filter material may be used to filter air or liquid, etc.

The application of the special surface structure fiber has the beneficial effects that:

the special surface structure fiber, namely the fiber with increased specific surface area and roughness, can be used in any field needing barrier protection, has higher fiber surface roughness and larger specific surface area, and has better or more unique performance compared with fiber raw materials.

Drawings

FIG. 1a is a schematic representation of the structure of a meltblown fiber prepared using the process of the present invention in a comparative example;

FIG. 1b is a schematic structural diagram of a meltblown fiber prepared by the method of example 1 of the present invention;

FIG. 1c is an enlarged schematic view of the particular surface structure of FIG. 1 b;

FIG. 2 is a nitrogen isothermal adsorption and desorption curve of different fiber materials of example 1 of the present invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.

The invention relates to a preparation method of a special surface structure fiber, which comprises the following steps: preparing an organic mixed solution; soaking a fiber raw material in the organic mixed solution; and carrying out polymerization reaction at a preset temperature in an oxygen-free environment, and then taking out the fiber raw material to obtain the fiber with the special surface structure. The preset temperature is 60-90 ℃, the oxygen-free environment comprises a nitrogen or argon environment, and the polymerization reaction time is 2-6 hours. The preparation method of the organic mixed solution comprises the following steps: dissolving a high molecular monomer and an initiator into an organic solvent. The high molecular monomer reactant can be chemically polymerized to form a high molecular material which is uniformly coated on the surface of the fiber to form the fiber surface coating with increased specific surface area.

Wherein, the fiber raw material can be selected from polypropylene fiber or carbon fiber.

In a specific embodiment of this embodiment, in the organic mixed solution, the concentration of the polymer monomer is 5wt% to 50wt%, and the concentration of the initiator is 0.1wt% to 1 wt%.

In a preferred embodiment of this embodiment, the addition amount of the cross-linking agent in the organic mixed solution is between 0% and 10% by weight of the high molecular monomer. The crosslinking agent is divinylbenzene.

The weight of the fiber raw material in this embodiment is 0.2 to 5 times of the weight of the polymer monomer added to the organic mixed solution.

An alternative of this embodiment is that the high molecular monomer comprises at least one of styrene, methyl methacrylate, acrylonitrile, and butyl acrylate; the initiator includes at least one of azobisisoheptonitrile and azobisisobutyronitrile.

An alternative to this embodiment is that the organic solvent comprises at least one of acetonitrile, ethanol, propanol, acetone, N-methyl-2-pyrrolidone.

The fiber with a special surface structure, namely the fiber with increased specific surface area and roughness, is prepared by adopting the preparation method.

The special surface structure fiber prepared by the preparation method is applied to mask materials, isolation materials, absorption materials, heat-preservation materials, wiping cloth and filtering materials. The filter material may be used to filter air or liquid, etc.

The preparation method of the invention contacts the fiber raw material with the organic mixed solution in a soaking mode, and chemically polymerizes solute reactants in the organic mixed solution through a chemical reaction to form a high polymer material which is uniformly coated on the surface of the fiber to form a surface coating with a special structure, so that a thin layer of organic material is uniformly adhered on the surface of the fiber raw material, the surface of the fiber is changed from smooth to rough on the premise of small increase of the total weight of the fiber, the specific surface area is increased, and the same or different surface properties are given to the original fiber material through the adhering material. The special surface structure fiber prepared by the preparation method can be used in the general application of the fiber, and the application comprises the fields of mask materials, air or liquid filtering materials, isolating materials, absorbing materials, heat-insulating materials, wiping cloths and the like, but has better or more unique performance than the original fiber raw materials.

Example 1

47.5mL of methyl methacrylate and 2.5mL of styrene monomer were dissolved in 450mL of acetone solution.

200mg of azobisisobutyronitrile and 4g of divinylbenzene were dissolved in the above solution to obtain an organic mixed solution.

10g of polypropylene fiber was soaked in 100mL of acetone solution for 20 minutes by sonication, and then taken out to be completely immersed in the organic mixed solution.

And reacting the organic mixed solution soaked with the polypropylene fibers at 70 ℃ for 2 hours under the nitrogen protection environment.

And after the reaction is finished, taking out the polypropylene fiber, washing the polypropylene fiber by using plasma water, and drying the polypropylene fiber in an oven at 70 ℃ for 4 hours to obtain a polypropylene fiber product with increased specific surface area.

The performance parameters of the polypropylene fibers used in this example as raw materials when they were not reacted and the performance parameters of the polypropylene fibers having an increased specific surface area obtained after the reaction are shown in Table 1.

Example 2:

5mL of methyl methacrylate and 95mL of acrylonitrile monomer were dissolved in 300mL of acetonitrile and n-methyl-2-pyrrolidone 1: 1 volume of mixed solution.

100mg of azobisisobutyronitrile and 4g of divinylbenzene were dissolved in the above solution to obtain an organic mixed solution.

2g of carbon fiber was soaked in 200mL of propanol solution for 2 hours, and then taken out to be completely immersed in the organic mixed solution.

And reacting the organic mixed solution soaked with the carbon fibers at 65 ℃ for 4 hours under the nitrogen protection environment.

And after the reaction is finished, taking out the carbon fiber, washing the carbon fiber by using plasma water, and drying the carbon fiber in an oven at 70 ℃ for 4 hours to obtain a carbon fiber product with increased specific surface area.

The performance parameters of the carbon fiber used in this example as a raw material when it was not reacted and the performance parameters of the polypropylene fiber having an increased specific surface area obtained after the reaction are shown in Table 1.

Example 3:

15mL of styrene monomer and 5mL of butyl acrylate were dissolved in 380mL of ethanol solution.

200mg of azobisisoheptonitrile was dissolved in the above solution to obtain an organic mixed solution.

1g of polypropylene fiber was completely immersed in the organic mixed solution.

And reacting the organic mixed solution soaked with the polypropylene fibers at 80 ℃ for 2 hours under the argon protection environment.

Comparative example:

this comparative example differs from example 1 in that the high-molecular polymer formed by reacting methyl methacrylate and styrene monomer was used directly: polymethyl methacrylate-b-polystyrene to prepare an organic mixed solution. The rest are the same, and the details are as follows:

47g of polymethyl methacrylate-b-polystyrene was ultrasonically dispersed in 450mL of acetone solution to obtain a mixed organic solution.

And after the reaction is finished, taking out the polypropylene fiber, washing the polypropylene fiber by using plasma water, and drying the polypropylene fiber in an oven at 70 ℃ for 4 hours to obtain a polypropylene fiber product.

The performance parameters of the polypropylene fiber used in this comparative example, which was not reacted as a raw material, and the polypropylene fiber having an increased specific surface area obtained after the reaction, are shown in Table 1.

TABLE 1

Polypropylene fiber product obtained in example 1

Example 2 carbon fiber

Example 3 Polypropylene fiber product

Comparative example the resulting polypropylene fiber product

Polypropylene fiber raw material

Carbon fiber raw material

Specific surface area

8 m²/g

4.3 m²/g

7.6 m²/g

4 m²/g

0.9 m²/g

Adsorption capacity of nitrogen

35 cm³/g

3.8 cm³/g

32 cm³/g

2.9 cm³/g

1.3 cm³/g

The morphology of the fibers of example 1 and comparative example above was obtained by FEI XL30 silicon scanning electron microscopy. In the comparative example, the polypropylene fiber surface treated by the comparative example method was still smooth as shown in FIG. 1 a. In example 1, the surface of the polypropylene fiber treated by the above method can be uniformly modified into a rough surface, forming a rough, clustered, petal-like sheet structure, as shown in fig. 1b and fig. 1 c.

The fiber materials obtained in examples 1 to 3 and comparative example were subjected to a nitrogen adsorption test. The nitrogen adsorption experiment was performed using an Autosorb iQ2 (Quantachrome) low pressure gas adsorption analyzer with a nitrogen concentration of 99.999%, 77K. Surface area measurements were obtained by the BET method at pressures ranging from P/Po = 0.05-0.25. The specific surface area of the polypropylene fiber in the comparative example was 4 m²The specific surface area of the fiber with the special surface structure in the embodiment 1 is increased by 1 time and can reach 8 m²(ii) in terms of/g. As shown in FIG. 2, the nitrogen adsorption amount of the polypropylene fiber in the comparative example was 2.9 cm³Per g, the nitrogen adsorption capacity of the fiber with the special surface structure in example 1 can reach 35 cm³The/g is more than 10 times of that of the common fiber.

In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. The preparation method of the special surface structure fiber is characterized by comprising the following steps of: preparing an organic mixed solution; soaking a fiber raw material in the organic mixed solution; carrying out polymerization reaction at a preset temperature in an oxygen-free environment, and then taking out the fiber raw material to obtain a cluster of special surface structure fibers in a petal-type flaky structure form, wherein the special surface structure fibers are used for mask materials, isolating materials, heat-insulating materials and filtering materials;

the preset temperature is 60-90 ℃, the oxygen-free environment comprises a nitrogen or argon environment, and the polymerization reaction time is 2-6 hours;

the preparation method of the organic mixed solution comprises the following steps: dissolving a high molecular monomer and an initiator into an organic solvent; the high molecular monomer comprises at least one of styrene, methyl methacrylate, acrylonitrile and butyl acrylate; the initiator comprises at least one of azobisisoheptonitrile and azobisisobutyronitrile; the organic solvent comprises at least one of acetonitrile, ethanol, propanol, acetone and N-methyl-2-pyrrolidone; the fiber raw material is selected from polypropylene fiber or carbon fiber.

2. The method for producing a fiber having a special surface structure according to claim 1, wherein the concentration of the polymer monomer in the organic mixed solution is 5 to 50wt%, and the concentration of the initiator is 0.1 to 1 wt%.

3. The method for preparing the special surface structure fiber according to claim 1, wherein the amount of the crosslinking agent added to the organic mixed solution is 0 to 10wt% of the weight of the high molecular monomer.

4. The method for producing the special surface structure fiber according to claim 3, wherein the crosslinking agent is divinylbenzene.

5. The special surface structure fiber produced by the production method according to any one of claims 1 to 4.