CN112776436A

CN112776436A - Composite polymer functionalized fiber, preparation method thereof and pressure spraying equipment used for preparing composite polymer functionalized fiber

Info

Publication number: CN112776436A
Application number: CN201911077736.8A
Authority: CN
Inventors: 牛琳; 李秀双
Original assignee: Beijing Zhongke Aijia Technology Co ltd
Current assignee: Beijing Zhongke Aijia Technology Co ltd
Priority date: 2019-11-06
Filing date: 2019-11-06
Publication date: 2021-05-11

Abstract

The invention discloses a composite polymer functionalized fiber, a preparation method thereof and pressure spraying equipment for preparing the same. The composite polymer functionalized fiber comprises a protective layer, a spinning layer and a supporting layer which are arranged in sequence; the spinning layer comprises composite high-molecular fibers, and the composite high-molecular fibers comprise polymers and nano materials doped in the polymers; the protective layer is selected from a setting yarn and/or a pattern plain cloth; the support layer is selected from fibers having a network structure. The fiber has a sandwich structure of a supporting layer, a spinning layer and a protective layer, is stable in structure, uniform in fiber and controllable in size, and can be used for a filter screen of atmospheric haze particles or a sewage filtering membrane and the like.

Description

Composite polymer functionalized fiber, preparation method thereof and pressure spraying equipment used for preparing composite polymer functionalized fiber

Technical Field

The invention belongs to the field of fiber materials, and particularly relates to a composite polymer functionalized fiber, a preparation method thereof and pressure spraying equipment for preparing the same.

Background

The electrostatic spinning technology has become one of the main approaches for effectively preparing nanofiber materials due to the advantages of simple manufacturing device, low spinning cost, various spinnable substances, controllable process and the like. By regulating and controlling the nozzle structure of the spinning equipment, controlling the experimental conditions and the like, the fiber membranes with different structures and different sizes can be obtained. At present, a wide variety of functionalized fibers with controllable sizes, including organic, organic/inorganic composite and inorganic nanofibers, can be prepared by utilizing an electrospinning technology. However, there are still some limitations to the preparation of functionalized fibers by electrospinning. Firstly, the natural polymer varieties which can be used for electrostatic spinning are very limited, secondly, the research on the structure and the performance of the product obtained by electrostatic spinning is not perfect, most of the applications of the final product are only in the experimental stage, and especially, the time consumption and the cost for preparing the polymer fiberization material by the electrostatic spinning technology are high, and the industrial production of the products has a great problem.

With the aggravation of atmospheric haze pollution, water pollution and the like in recent years, the demand for the functionalized fiber filtering membrane is increased rapidly, so that the demand for the functionalized fiber in industrial batch production cannot be met completely only by the electrostatic spinning technology. At present, the functionalized three-dimensional non-woven fabric is prepared by mainly utilizing a method of melting and spraying polypropylene and other materials in industry. The melt-blowing method is a spinning method in which a melt of a polymer just extruded is rapidly drawn, solidified and formed at a high magnification by means of a high-speed hot gas stream. Its advantages are short technological route, direct spinning to obtain non-woven fabric, and high speed and productivity. However, the equipment and fittings required for the melt-blowing process are expensive and consume a lot of energy. And a manual pressure spraying method can be adopted, the method can form filaments without generating bead knots, but the filament thickness is not uniform, and the influence on wind resistance is large.

Disclosure of Invention

The invention provides a composite polymer functionalized fiber, which comprises a protective layer, a spinning layer and a supporting layer which are sequentially arranged;

the spinning layer comprises composite polymer fibers, and the composite polymer fibers comprise polymers and nano materials doped in the polymers; for example, the polymer may be selected from one, two or more of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyacrylonitrile, polysulfone, polyimide, polyethylene glycol, and other conductive polymers. For example, the morphology of the nanomaterial may be inorganic nanoparticles, nanoplates, or nanotubes; preferably, the nano material may be selected from one, two or more of ferroelectric, pyroelectric and piezoelectric inorganic nanoparticles such as barium titanate, lithium niobate and lithium tantalate, carboxyl modified graphene oxide nanosheets and multi-walled carbon nanotubes.

According to the polymer functionalized fiber of the present invention, the protective layer may be selected from a set yarn and/or a patterned flat; for example, the material of the sizing yarn may be one, two or more selected from chemical fibers such as nylon, terylene, acrylic fiber, and the like.

The polymer functionalized fiber according to the present invention, the support layer may be selected from fibers having a network structure; for example, the fiber may be selected from one, two or more of polyamide, glass fiber, polypropylene (PP), polyethylene terephthalate (PET), PP non-woven fabric, PET spunbonded fabric, and the like.

According to the polymer functionalized fiber, in the spinning layer, the polymer accounts for 1-20% of the mass of the spinning layer, such as 2-15%, 5-10%; exemplary are 3%, 6%, 8%, 12%, 14%.

In the spinning layer, the nanomaterial comprises 0.1% to 2%, for example 0.12% to 0.18%, illustratively 0.14%, 0.16%, 0.19% by mass of the spinning layer.

According to the polymer functionalized fiber of the present invention, the thickness of the spinning layer may be several hundred nanometers to several hundred micrometers, for example, the thickness is 100nm-900 μm, 300nm-500 μm, 1-100 μm.

According to the polymer functionalized fiber of the present invention, the diameter spun in the spinning layer is 0.1 μm to 5 μm, such as 0.5 μm to 4 μm, 1 μm to 3 μm.

According to the polymer functionalized fiber of the present invention, the thickness of the protective layer may be 0.3 to 1.5mm, such as 0.5 to 1mm, and by way of example, the thickness of the protective layer may be 0.6mm, 0.7mm, 0.75mm, 0.8mm, 0.9 mm.

According to the polymer functionalized fiber, the protective layer can have a hollow-out pattern structure; preferably, the mesh size of the hollow pattern structure may be 100-.

According to the polymer functionalized fiber of the present invention, the thickness of the support layer may be 0.3-1.5mm, such as 0.5-1mm, and by way of example, the thickness of the support layer may be 0.6mm, 0.7mm, 0.75mm, 0.8mm, 0.9 mm.

According to the polymer functionalized fiber of the present invention, the mesh size of the support layer may be 100-.

The invention also provides a preparation method of the composite polymer functionalized fiber, which comprises the following steps:

(1) spraying the polymer nano composite solution in a mist form, collecting the polymer nano composite solution on a supporting layer in a polymer nano composite fiber form, and heating, drying at high temperature and curing the supporting layer to obtain the supporting layer with the polymer nano composite fiber spinning layer;

(2) and (2) compounding the protective layer with the supporting layer with the spinning layer in the step (1) in an ultrasonic point pressing, hot pressing or gluing mode, so that the spinning layer is positioned between the protective layer and the supporting layer, and the composite polymer functionalized fiber is obtained.

According to the preparation method of the present invention, in the step (1), the polymer nanocomposite solution includes a polymer, a nanomaterial, and a solvent. Preferably, the polymer and nanomaterial have the meaning as described above. Further, the polymer is present in an amount of 1-20%, such as 3-15%, 5-10%, by mass of the polymer nanocomposite solution, and illustratively 6%, 8%, 12% by mass of the polymer nanocomposite solution. For example, the solvent may be selected from one, two or more of N, N' -Dimethylformamide (DMF), N-methylpyrrolidone (NMP), acetone, ethanol, ethyl ester, butyl ester, water, and dimethyl sulfoxide (DMSO), and the like. For example, the nanomaterial comprises 1-5% by mass of the polymer nanocomposite solution, such as 1.5-4%, illustratively 2%. Further, the preparation process of the polymer nanocomposite solution may include: ultrasonically dispersing a polymer and a nano material in the solvent, centrifuging, and collecting supernatant to obtain the polymer nano composite solution; preferably, the time of the ultrasonic dispersion may be 1 to 10 hours, for example 3 to 8 hours.

According to the preparation method of the present invention, in the step (1), the mist form is obtained by pressing or spraying the polymer nanocomposite solution by a pressure formed by compressed air. Wherein the pressure may be 10-60Pa (e.g., pressure of 15-50Pa, 20-45 Pa; as an example, pressure of 25Pa, 30Pa or 35Pa), and the flow rate of the extruding or ejecting is 0.5-5ml/min (e.g., flow rate of 1-4ml/min, 1.5-3.5 ml/min; as an example, flow rate of 2ml/min, 2.5ml/min or 3 ml/min). Preferably, the polymer nanocomposite solution is extruded or sprayed from a spray head having a diameter dimension of 0.1 to 2mm, such as 0.2 to 0.3 mm.

According to the production method of the present invention, in the step (1), the temperature of heating may be 40 to 80 ℃, for example, 50 to 70 ℃, and as an example, the temperature may be 55 ℃, 60 ℃ or 70 ℃. The heating time may be 10s to 5min, for example 20s-60s, as an example 30s, 40s, 50 s.

According to the preparation method of the present invention, in the step (2), the power of the ultrasonic spot pressure is 10-20kw, for example, 10-15kw, and as an example, the power may be 12kw, 13kw, 16 kw. The pressure of the ultrasonic spot pressure is 0.5 to 2MPa, such as 0.5 to 0.8MPa, and the pressure may be 0.5MPa, 0.6MPa, 0.7MPa, as an example. The ultrasonic spot pressing has a spot pressing compounding time of 0.5-2s, such as 0.5-1s, and as an example, the spot pressing compounding time is 0.5s, 0.6s or 0.8 s. The ultrasonic spot pressing has a spot pressing delay time of 0.5-2s, such as 0.5-1s, as an example, 0.5s, 0.6s, 0.7s, 0.8s, or 1 s.

According to the exemplary technical scheme of the invention, the preparation method of the composite polymer functionalized fiber specifically comprises the following steps:

(1) firstly, a polymer nano composite solution containing a polymer, a nano material and a solvent is extruded or sprayed out of a spray head through pressure formed by compressed air to form a fog shape, the fog shape is collected on a supporting layer in the form of polymer nano composite fibers, then the supporting layer is heated and dried and solidified at high temperature to obtain the supporting layer with a polymer nano composite fiber spinning layer;

According to an exemplary technical scheme of the invention, the preparation method of the composite polymer functionalized fiber specifically comprises the following steps:

(1) the supporting layer is placed on the supporting layer rolling shaft and is conveyed to the position of the pressure spraying device by using the conveying belt;

(2) extruding and spraying the polymer nano composite solution in a mist form by using a pressure spraying device, volatilizing the solvent to form nano polymer composite fibers, and collecting the nano polymer composite fibers on a supporting layer;

(3) the supporting layer with the nano-scale polymer composite fiber attached to the surface obtained in the step (2) is continuously conveyed to a heating and drying part through a conveyor belt, and is dried and solidified at high temperature to obtain the supporting layer with the nano-scale polymer composite fiber spinning layer;

(4) and (4) compounding the protective layer with the support layer with the nano-scale polymer composite fiber spinning layer in the step (3) in an ultrasonic point pressing mode, so that the spinning layer is positioned between the protective layer and the support layer, and the composite polymer functionalized fiber is obtained.

The invention provides application of the composite polymer functionalized fiber in air purification or water purification. For example, a filter screen as atmospheric haze particles, a sewage filter membrane, or the like.

The invention also provides a production device of the composite polymer functionalized fiber, namely pressure spraying equipment, wherein the pressure spraying equipment comprises the following components in sequence: supporting layer roller, adjusting device, pressure spraying device, drying device, ultrasonic point pressing device, rolling roller and conveying device.

According to the pressure spraying equipment of the invention, the adjusting device is used for adjusting the conveying position and the stability of the supporting layer. For example, the adjustment device may be selected from an automatic adjustment device or a manual adjustment device, preferably a manual adjustment device.

According to the pressure spraying equipment of the invention, the pressure spraying device can be selected from automatic pressure spraying devices known in the field, for example, a spray gun, an air compressor, a sample cavity, an adjusting mechanism and a driving mechanism can be included, and the components are connected in a manner known in the field. Wherein, the spray gun can adopt an air pressure spray gun, such as a paint spray gun.

According to the pressure spraying equipment, the drying device with the temperature control function can be selected from drying devices with the temperature control function and known in the field.

According to the pressure spraying equipment of the invention, the ultrasonic point-pressing device can be selected from devices known in the field, and can comprise a solid-state relay, an ultrasonic generator, a pressure device and a pressing die, and the components are connected in a manner known in the field.

According to the pressure spraying equipment, the conveying device is used for conveying the supporting layer in the preparation process and the supporting layer with the spinning layer; the rolling roller is used for collecting the composite polymer functional fiber.

According to the pressure spraying apparatus of the present invention, the conveying means may be a conveyor belt for conveying the support layer and the support layer with the spinning layer.

According to the pressure spraying equipment, when the pressure spraying equipment is in a working state, materials (such as fiber cloth serving as a supporting layer) on the supporting layer roller are adjusted by the manual adjusting device through the conveying device, then are sequentially conveyed to the pressure spraying device for pressure spraying, then are dried through the drying device, are subjected to ultrasonic point pressing through the ultrasonic point pressing device, and finally are conveyed to the winding roller for collection.

The invention has the beneficial effects that:

the invention provides pressure spraying equipment capable of efficiently, quickly and massively preparing composite polymer functionalized fibers. The equipment mainly comprises supporting layer rolling shafts, a manual adjusting mechanism, a conveying system, a pressure spraying device, a drying mechanism, an ultrasonic point pressing mechanism, a rolling shaft and the like. The transmission system transmits the gridding cloth or non-woven fabric (namely a supporting layer) with the collecting substrate at a certain speed, the polymer nano-composite solution is sprayed on the gridding cloth or non-woven fabric supporting layer of the collecting substrate at the lower end of the spray head at a set spraying speed and pressure to form a spinning layer on the supporting layer, the gridding cloth or non-woven fabric with the spinning layer is transmitted to a drying mechanism for heating, drying and curing, the dried and cured supporting layer with the spinning layer is transmitted to an ultrasonic point pressing device part, and the ultrasonic point pressing technology is utilized to point-press and compound the protective layer and the supporting layer with the spinning layer; and collecting the processed fiber composite grid cloth or non-woven fabric with the sandwich structure into a roll through a collecting roller so as to be practical for the subsequent process. Compared with processing equipment and processing methods such as electrostatic spinning and 3D printing, the pressure spraying equipment can be used for realizing rapid and batch production of polymer materials such as PVDF. When the non-woven fabric is prepared by spinning PVDF and other solutions through electrostatic spinning, the preparation efficiency is low, the processing cost is high, and the defects of string beads and the like are easy to occur. When the pressure spraying equipment is utilized, the fiber structure with uniform structure, less defects and controllable size can be rapidly and massively prepared due to controllable spraying pressure, high processing speed and low requirement on environmental parameters. Compared with processing methods such as electrostatic spraying and melt-blowing, the method utilizing pressure spraying not only eliminates the need for expensive equipment and accessories, but also can realize batch production. The pressure spraying equipment has simple structure, low processing cost and low energy consumption.

The method for preparing the polymer functionalized fiber based on the pressure spraying equipment provided by the invention takes polymers such as PVDF and the like which can be dissolved in a certain solvent as spraying raw materials, takes a reticular structure such as nylon, glass fiber, PP, PET or PP non-woven fabric, PET spunbonded fabric and the like as a receiving end substrate (namely a supporting layer), and forms a multilayer composite non-woven fabric with controllable size and uniform structure on the substrate of a collecting end by adjusting parameters such as pressure, spraying flow, nozzle size and the like. The non-woven fabric prepared by the method not only solves the problem of fiber defects such as beading of electrostatic spinning, but also can realize large-scale preparation. During the spraying process, the polymer solution with certain viscosity is pressed out or sprayed out of the container by the pressure formed by the compressed air and forms a mist which is collected on the grid cloth at the collecting end. One of the advantages of the method is that the polymer which can be dissolved in a certain solvent can be sprayed by adjusting parameters, which avoids the requirement on the polarity of the solution in electrostatic spinning to a certain extent and also avoids the requirement on the parameters such as melting point, viscosity and the like of the polymer in equipment such as melt blowing and the like. The polymer functionalized fiber provided by the invention has a sandwich structure, and after the sprayed spinning is collected on the supporting layer, a grid protective layer needs to be covered on the spinning layer due to the small diameter and flexibility of the spinning layer to form the supporting layer-spinning-protective layer sandwich structure. The protective layer can play a protective role in the spinning fiber structure, so that the spinning structure is not damaged in the using and cleaning processes to influence the filtering efficiency. This stable in structure, fibre are even, and the size is controllable, can be used to the filter screen of atmosphere haze particulate matter or sewage filtration membrane etc..

Drawings

Fig. 1 is an overall configuration diagram of a spray coating device of embodiment 1.

Fig. 2 is a side view structural diagram of a spray coating device of embodiment 1.

Reference numerals: the device comprises a gauze rolling shaft 1, a manual adjusting device 2, a conveying belt 3, a pressure spraying device 4, a sample cavity 5, a drying device 6, an ultrasonic point pressing device 7 and a rolling shaft 8.

FIG. 3 is a schematic view of the sandwich structure of the composite polymer functionalized fiber obtained in example 2.

Fig. 4 is an optical photograph and a scanning electron microscope photograph of the support layer and the protective layer in example 2:

in fig. 4, a is an optical photograph and a scanning electron microscope photograph of the support layer, and b is an optical photograph and a scanning electron microscope photograph of the protective layer.

Fig. 5 includes a scanning electron microscope image (a) of a spun fiber obtained by electrospinning according to comparative example 1, a scanning electron microscope image (b) of a spun fiber obtained by manually spraying according to comparative example 1, and a scanning electron microscope image (c) of a spun fiber obtained by mechanically and automatically pressure spraying according to example 2.

Fig. 6 includes a scanning electron microscope picture (a) of adsorbing and filtering haze particles of the spun fiber obtained by electrostatic spinning in comparative example 1, a scanning electron microscope picture (b) of adsorbing and filtering haze particles obtained by manual spraying in comparative example 1, a scanning electron microscope picture (c) of adsorbing and filtering haze particles of the spun fiber obtained by mechanical automatic pressure spraying in example 2, and a comparison (d) of the filtering efficiencies of the three polymer fibers.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

The Graphene Oxide nanoplatelets used in the following examples are carboxylated Graphene Oxide nanoplatelets, which are publicly sold by the institute of sciences, china, organic chemistry ltd, and have the trade name Graphene Oxide.

Example 1 composite Polymer functionalized Web processing Equipment

As shown in fig. 1 and 2, the present embodiment provides a composite polymer functionalized fiber web processing apparatus, which includes, in sequence: a gauze rolling shaft 1, a manual adjusting device 2, a pressure spraying device 4, a sample cavity 5, a drying mechanism 6, an ultrasonic point pressing mechanism 7, a rolling shaft 8 and a conveying belt 3. The pressure spraying device is an automatic pressure spraying device known in the art.

The supporting layer is placed on the gauze rolling shaft 1, the manual adjusting device 2 is used for adjusting the gauze conveying position and stability, the left side and the right side of the supporting layer are not fixed, and the gauze rolling shaft 1, the conveying belt 3 and the winding rolling shaft 8 are used for forward conveying movement and winding after processing and forming. Firstly, conveying the polymer nano composite solution to the position of a pressure spraying device 4, extruding and spraying the polymer nano composite solution contained in a sample cavity 5 in a fog form by utilizing the pressure spraying device 4 through the set spraying pressure, spraying amount and spraying speed, and volatilizing a solvent to form nano polymer composite fibers and collecting the nano polymer composite fibers on a gauze support layer; the supporting layer with the nano-scale polymer composite fibers attached to the surface is continuously conveyed to a heating and drying mechanism 6 through a conveyor belt 3, and the nano-scale polymer composite fibers are dried and cured at high temperature; and further compounding the protective layer with the supporting layer with the nano-scale polymer composite fiber spinning layer by using an ultrasonic point pressing mechanism 7 in an ultrasonic point pressing mode, so that the nano-scale polymer composite fiber spinning layer is positioned between the protective layer and the supporting layer, and the composite polymer functionalized fiber is obtained.

Polyvinylidene fluoride nanocomposite solution, support layer and protective layer used in example 2

1. Preparation of polyvinylidene fluoride nano composite solution

Dissolving a graphene oxide sheet layer (GO) with surface carboxyl modification and polyvinylidene fluoride with molecular weight of 50-55 ten thousand g/mol in N, N' -dimethylformamide, performing ultrasonic dispersion for 4h, centrifuging, and collecting supernatant.

Wherein the graphene oxide sheet layer with the surface carboxyl modified accounts for 2.0 wt% of the total mass of the polyvinylidene fluoride nano composite material.

2. Selection of support layer

The nylon-made supporting grid framework is selected, the thickness of the supporting grid framework is 0.6mm, the supporting grid cloth is 20-100-mesh nylon or glass fiber grid cloth, and 20-mesh grid cloth is selected in the embodiment.

An optical photograph and a scanning electron micrograph of the support layer are shown in fig. 4 a.

3. Selection of protective layer

The nylon setting yarn is used as a protective layer, the thickness of the protective layer of the setting yarn is 0.6mm, and the protective layer has a hollow pattern structure with the mesh size of 500 mu m.

An optical photograph and a scanning electron micrograph of the protective layer are shown in fig. 4 b.

Preparation of composite electrostatic anti-haze composite mesh fabric with sandwich structure

Utilize the pressure spraying equipment of preparation polymer functional fiber grid structure in embodiment 1, will have the polyvinylidene fluoride nano-composite of piezoelectricity effect and attach to the supporting layer, through high temperature stoving solidification to with the compound of stereotyping yarn protective layer ultrasonic wave point pressure complex, make the compound static of "sandwich" structure prevent haze compound net cloth (the schematic structure is shown in figure 3), including protective layer, nanometer polymer composite fiber spinning layer and supporting layer.

The specific preparation process of the composite electrostatic haze-preventing composite mesh cloth is as follows: (a) the supporting layer is placed on the gauze rolling shaft, the gauze conveying position and the stability are adjusted by using a manual adjusting mechanism, the left side and the right side of the supporting layer are not fixed, and the supporting layer is conveyed to the position of the pressure spraying device by using the conveying belt. And extruding and spraying polyvinylidene fluoride nano composite solution (containing 2.0 wt% of GO) in a fog form by using an automatic pressure spraying device, volatilizing a solvent in the spraying process to form nano polymer composite fibers, and collecting the nano polymer composite fibers on a gauze support layer. Specifically, the polyvinylidene fluoride nanocomposite solution was ejected from the head (ejection flow rate 2ml/min) by a pressure (pressure 30Pa) formed by compressed air.

(b) Conveying the nylon supporting layer with the polyvinylidene fluoride nano-composite polymer fibers collected in the step (a) to a drying mechanism through a conveying belt, accurately controlling the drying temperature to be 60 ℃, and drying for 40s, wherein in the process of passing through the drying mechanism, the polyvinylidene fluoride nano-composite polymer fibers sprayed to the surface of the mesh cloth are subjected to high-temperature curing.

(c) The nylon supporting layer which is combined with the polyvinylidene fluoride nano composite polymer fiber on the surface and is solidified at high temperature in the step (b) is conveyed to an ultrasonic point pressing mechanism through a conveying belt, the nylon supporting layer which is combined with the polyvinylidene fluoride nano composite polymer fiber is combined with a protective layer through an ultrasonic pressing mode by an ultrasonic pressing component, and the ultrasonic point pressing is combined together to form the composite static haze-proof composite mesh fabric with a sandwich structure.

Ultrasonic point pressure parameters: the ultrasonic voltage power is 15kW, the pressure is 0.8MPa, the point pressure compounding time is 1s, and the point pressure delay time is 1 s.

(d) And (c) conveying the composite static anti-haze composite gridding cloth with the sandwich structure in the step (c) to a rolling roller through a conveying belt, and collecting the composite gridding cloth with the sandwich structure into a roll through the rolling roller.

The SEM photograph of the spun layer prepared in this example is shown in FIG. 5c, and it can be seen that the obtained electrostatic fibers have controllable size (about 500nm in diameter) and uniform distribution, and the thickness of the spun layer is about 1 μm.

Comparative example 1 comparison of the morphology of fibers prepared by electrospinning, hand spraying and example 2

The process of preparing the fiber by electrostatic spinning comprises the following steps: the nylon mesh cloth (20 meshes) on the roller is used as a substrate of a receiving end, the temperature of the receiving end is 50 ℃, and the roller motor rotates at a constant speed of 200 r/min. The polyvinylidene fluoride nanocomposite solution used in example 2 was placed in a needle tube at a voltage of 15KV and a distance of 10cm between the conductive needle and the receiving end of the needle tube. When the stepping motor drives the end of the needle tube to advance (the advancing speed is 1mL/h), the polymer solution forms jet flow between the needle head and the receiving end, the jet flow is uniformly spread on the receiving end, and the PVDF fiber is formed after solidification. The morphology of the PVDF fiber prepared by electrostatic spinning is shown in FIG. 5a, and beads exist in the fiber, so that uniform fiber is difficult to prepare. The reason is that beading is easy to occur and the prepared fiber is not uniform under the influence of factors such as environmental humidity, electrostatic force, concentration and the like in the spinning process, especially under the influence of some solvents which volatilize rapidly. In addition. The electrostatic spinning also has the problems of high equipment cost, slow processing process and low processing efficiency.

The process for preparing the fiber by manual pressure spraying comprises the following steps: nylon mesh cloth (20 meshes) is fixed on the support to be used as a substrate of a receiving end, the polyvinylidene fluoride nano composite solution used in the embodiment 2 is placed into a sample cavity of a spray gun, the spray gun is connected with an air compressor, the switch of the spray gun is manually controlled, and the air compressor is used for spraying under the pressure of 0.3 MPa. In the manual spraying process, the spray gun is 10cm away from the receiving end, the spray gun is moved left and right at a constant speed of 1m/s by the handheld spray gun, the solution spraying amount is about 0.5mL/s, the polymer solution forms jet flow between the gun mouth of the spray gun and the receiving end, the jet flow is uniformly spread on the receiving end, and the PVDF fiber is formed after curing. With the manual pressure spraying method, a fiber structure with a certain regularity can be rapidly obtained for the PVDF polymer solution, as shown in fig. 5 b. However, in the manual spraying process, the pressure, the moving speed of the spray head and the flow rate are completely completed manually, so that the uniformity and the stability of the spraying are difficult to maintain, and the better spraying effect is difficult to control, so that the unevenness of fibers and the uncontrollable size are easily caused.

As shown in fig. 5c, the scanning electron micrograph of the spinning layer prepared in example 2 shows that, since the pressure, the moving speed of the nozzle, and the flow rate can be precisely controlled during the automatic mechanical spraying process, an electrostatic fiber spinning layer with a controllable size and uniform distribution can be obtained.

Comparative example 2 static anti-haze composite mesh cloth haze adsorption effect and haze filtration efficiency of sandwich structure prepared through electrostatic spinning, manual spraying and embodiment 2

(1) Haze adsorption test process: attached in the window outside with the compound net cloth of "sandwich" structure static of electrostatic spinning, manual spraying and embodiment 2 preparation, arrange in the outdoor that has haze weather, vibration prevents the piezoelectricity effect that the compound net cloth effect of haze produced to static and comes the haze particulate matter in the static absorption atmosphere when utilizing wind to blow. The electrostatic spinning and manual spraying under the wind blowing deformation and the electrostatic haze-preventing composite mesh fabric with the sandwich structure prepared in the embodiment 2 have charges on the surface, have a strong coulomb effect and show a strong adsorption effect on haze.

Fig. 6 a-c are scanning electron microscope images of electrostatic spinning, manual spraying and electrostatic haze adsorption of the sandwich-structured electrostatic haze-preventing composite mesh fabric prepared in example 2. As can be seen from fig. 6, although the electrostatic anti-haze composite mesh cloth prepared by the three methods can effectively adsorb particles with various sizes in the air in the haze weather, including dust, PM10, PM2.5 and submicron particles, the electrostatic anti-haze composite mesh cloth with the sandwich structure prepared by electrostatic spinning, manual spraying and the embodiment 2 has obvious difference in the ability of effectively adsorbing haze particles (PM0.3, PM1.0, PM2.5 and PM10) in the atmosphere due to the difference in fiber density, size and uniformity.

(2) Haze filtration efficiency test process: referring to GB/T6165-2008, the DEHS dust source is used for testing the filtering efficiency of electrostatic spinning, manual spraying and the electrostatic haze-preventing composite mesh fabric with the sandwich structure prepared in the embodiment 2 on particles with the particle size of more than 300 nm.

D in fig. 6 is an adsorption efficiency diagram of electrostatic spinning, manual spraying and the sandwich-structured electrostatic haze-preventing composite mesh cloth prepared in embodiment 2 for adsorbing haze particles in the air. Under the same piezoelectric condition, the first group from left to right is the filtering efficiency of the static anti-haze composite mesh cloth of different preparation processes for PM10, and the three components from left to right in the group of filtering efficiency histograms are respectively: electrostatic spinning, manual spraying, the compound net cloth of haze is prevented to "sandwich" structure static of embodiment 2 mechanical automatic spraying preparation can be reachd from it, the compound net cloth of haze is prevented to "sandwich" structure static of embodiment 2 mechanical automatic spraying preparation because pressure, shower nozzle translation rate, flow can obtain accurate control, can obtain the controllable and dense, the even electrostatic fiber spinning layer of distribution of size, consequently static filtration efficiency and electrostatic spinning, the net cloth of manual spraying compares and obviously risees. In d in fig. 6, turn right the second group of histogram from a left side, the compound net cloth of haze is prevented for static respectively to third group of histogram and fourth group of histogram, and to PM2.5, PM1.0, PM 0.3's filtration efficiency, the compound net cloth of haze is prevented to "sandwich" structure static of preparing through embodiment 2 mechanical automatic spraying equally, and filtration efficiency is showing the improvement equally. D data in fig. 6 show that the electrostatic anti-haze composite mesh cloth with the piezoelectric effect can effectively adsorb haze particles in filtered air, and along with the improvement of the processing technology, the electrostatic anti-haze composite mesh cloth with the sandwich structure prepared by mechanical automatic spraying in the embodiment 2 has the highest filtering efficiency.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The composite polymer functionalized fiber is characterized by comprising a protective layer, a spinning layer and a supporting layer which are sequentially arranged;

the spinning layer comprises composite polymer fibers, and the composite polymer fibers comprise polymers and nano materials doped in the polymers;

preferably, the polymer is selected from one, two or more of polyvinylidene fluoride, polyvinyl alcohol, polyacrylonitrile, polysulfone, polyimide, polyethylene glycol and other conductive polymers;

preferably, the morphology of the nanomaterial is an inorganic nanoparticle, a nanosheet, or a nanotube;

preferably, the nanomaterial is selected from one, two or more of ferroelectric, pyroelectric, piezoelectric inorganic nanoparticles, carboxyl-modified graphene oxide nanoplatelets and multi-walled carbon nanotubes.

2. The composite polymer functionalized fiber according to claim 1, wherein the protective layer is selected from a set yarn and/or a patterned flat cloth;

preferably, the support layer is selected from fibers having a network structure; preferably one, two or more of polyamide, glass fiber, polypropylene, polyethylene terephthalate, PP nonwoven fabric and PET spunbonded fabric;

preferably, in the spinning layer, the polymer accounts for 1-20% of the mass of the spinning layer;

preferably, in the spinning layer, the nano material accounts for 0.1-2% of the mass of the spinning layer;

preferably, the thickness of the spinning layer is several hundred nanometers to several hundred micrometers;

preferably, the diameter of the spun yarn in the spinning layer is 0.1-5 μm;

preferably, the thickness of the protective layer is 0.3-1.5 mm;

preferably, the protective layer has a hollowed-out pattern structure;

preferably, the thickness of the support layer is 0.3-1.5 mm;

preferably, the mesh size of the support layer is 100-1200 μm.

3. A method for preparing the composite polymer functionalized fiber according to claim 1 or 2, wherein the method comprises the steps of:

4. The method according to claim 3, wherein in the step (1), the polymer nanocomposite solution comprises a polymer, a nanomaterial, and a solvent,

wherein the dosage of the polymer accounts for 1 to 20 percent of the mass of the polymer nano composite solution,

the solvent is one or two or more selected from N, N' -dimethylformamide, N-methylpyrrolidone, acetone, ethanol, ethyl ester, butyl ester, water and dimethyl sulfoxide;

the nano material accounts for 1-5% of the mass of the polymer nano composite solution.

5. The production method according to claim 3 or 4, wherein in the step (1), the mist form is obtained by pressing or spraying the polymer nanocomposite solution by pressure of compressed air;

preferably, the pressure is 10-60Pa, and the flow rate of the extrusion or the ejection is 0.5-5 ml/min;

preferably, the polymer nanocomposite solution is extruded or sprayed from a spray head having a diameter size of 0.1 to 2 mm.

6. The production method according to any one of claims 3 to 5, wherein in the step (1), the heating temperature is 40 to 80 ℃ and the heating time is 10s to 5 min;

preferably, in the step (2), the power of the ultrasonic point pressure is 10-20kw, the pressure of the ultrasonic point pressure is 0.5-2MPa, and the point pressure compounding time of the ultrasonic point pressure is 0.5-2 s;

preferably, the point pressure delay time of the ultrasonic point pressure is 0.5-2 s.

7. The method for preparing according to any one of claims 3 to 6, characterized in that it comprises the steps of:

8. Use of the composite polymer-functionalized fiber according to claim 1 or 2 for air purification or water purification.

9. The composite polymer functionalized fiber production apparatus according to claim 1 or 2, a pressure spraying apparatus, wherein the pressure spraying apparatus comprises, in order: supporting layer roller, adjusting device, pressure spraying device, drying device, ultrasonic point pressing device, rolling roller and conveying device.

10. A pressure spraying device according to claim 9, characterized in that the adjusting means is selected from automatic adjusting means or manual adjusting means, preferably manual adjusting means;

preferably, the pressure spraying device comprises a spray gun, an air compressor, a sample cavity, an adjusting mechanism and a driving mechanism, and the components are connected in a manner known in the art; preferably, the spray gun is an air pressure spray gun;

preferably, the ultrasonic point pressing device comprises a solid-state relay, an ultrasonic generator, a pressure device and a pressing die, and the components are connected in a manner known in the art.