CN113969427A - Aramid micro-nanofiber with net-shaped structure and preparation method and application thereof - Google Patents
Aramid micro-nanofiber with net-shaped structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an aramid fiber micro-nanofiber with a net-shaped structure and a preparation method and application thereof. The preparation method of the aramid micro-nano fiber comprises the following steps: (1) adding an aramid polymer into a dispersion solvent, and uniformly stirring and dispersing to obtain an aramid polymer dispersion liquid; (2) directly spraying the aramid polymer dispersion liquid into the dispersion liquid after air-jet atomization treatment, continuously stirring to obtain aramid micro-nano dispersion liquid, and then carrying out ultrasonic treatment and freeze drying to obtain the aramid micro-nano fiber with a net structure; wherein, the conditions of the gas spray atomization treatment are as follows: the spinneret orifices are an inner air inlet hole and an outer liquid inlet hole, the aperture range of the atomizer is 0.1-8.0 mm, and the gas pressure range is 0.1-1.2 MPa. The micro-nano fiber prepared by the method has a unique net-shaped structure and a larger specific surface area, can obviously improve the bonding strength of the fiber interface in the aramid paper, and effectively improves the mechanical strength and the dielectric property of the aramid paper.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to aramid micro-nanofibers with a net-shaped structure, and a preparation method and application thereof.
Background
The aramid fiber micro-nano fiber has the advantages of micro-nano aramid fiber, high length-diameter ratio, high specific surface area, excellent strength modulus, outstanding chemical and thermal stability and the like, and is widely applied to various fields. Since 2011, it was considered one of the most promising nano-building materials and thus received increasing attention. At present, the technology for preparing the aramid nano-fiber is relatively short, and the technology for industrial production is more scarce. According to different paths, the method is mainly summarized into two schemes of top-down scheme and bottom-up scheme; wherein the 'top-down' strategy mainly comprises electrostatic spinning, rotary jet spinning, alkali-synergetic mechanical milling and hydrolysis, an alkali dissolution method and the like; the "bottom-up" strategy refers primarily to a polymerization-dispersion process.
At present, an alkali fusion method is commonly used for preparing aramid micro-nanofibers, but due to the unique molecular structure of the aramid fibers, the aramid fibers have the defects of high molecular chain rigidity, high degree of crystal orientation, smooth surface, low content of active groups, extremely low surface energy and the like, so that the preparation strategy of the alkali fusion method needs to use a large amount of chemicals, the energy consumption is high, the preparation concentration is low, and the production process is complex. For example, chinese patent application 202011304031.8 discloses a method for preparing an aramid nanofiber dispersion, which is mainly prepared from a strong alkali solution and dimethyl sulfoxide, and has harsh reaction conditions. Chinese patent 201810141423.3 discloses a method for preparing aramid nano-fiber by a mechanical coupling chemical alkali dissolution method, which comprises the steps of carrying out mechanical fibrillation coupling homogenization treatment on aramid chopped fiber, and then carrying out deprotonation treatment by using KOH/DMSO, and has the advantages of complex process and high energy consumption. Chinese patent 201910340388.2 discloses a method for preparing aramid nano-fiber, which comprises treating para-aramid fiber with KOH/DMSO, performing ultrasonic treatment in ice water bath, titrating with cation standard solution by colloid, judging reaction, and performing displacement washing for multiple times to obtain aramid nano-fiber dispersion. The conventional jet spinning technology mostly adopts an inner liquid inlet pipe and an outer gas inlet pipe, the diameter of the prepared aramid fiber is large, the length of the aramid fiber cannot be regulated, the size distribution range is wide, the production efficiency of the electrostatic spinning technology is low, and the regulation difficulty is high.
In summary, the currently reported methods for preparing the aramid micro-nanofibers include electrostatic spinning, rotary jet spinning, alkali-assisted mechanical milling and hydrolysis, an alkali dissolution method, a polymerization dispersion method, and the like. The electrostatic spinning method has low production efficiency and difficult size regulation; the alkali fusion method needs to dissolve aramid fiber and then redisperse, and the process is complicated; the mechanical method has high energy consumption and large power consumption; the existing jet spinning technology adopts an inner liquid inlet pipe and an outer gas inlet pipe, and the prepared aramid fiber has large diameter, uncontrollable length and wide size distribution range; the technical defects limit the industrialization process and the application range of the aramid micro-nano fiber.
Therefore, the search for a rapid and effective aramid fiber micro-nanofiber preparation technology has important significance for realizing functionalization and high performance of the aramid fiber micro-nanofiber and cross diversified application of the aramid fiber micro-nanofiber in various fields such as reinforced materials, battery diaphragms, electric insulation nano-paper, flexible electronic devices, adsorption filter media and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of aramid micro-nanofibers with a net-shaped structure.
The invention also aims to provide the aramid micro-nano fiber with the net-shaped structure prepared by the method.
The invention further aims to provide application of the aramid micro-nanofiber with the net-shaped structure.
The purpose of the invention is realized by the following technical scheme:
a preparation method of aramid micro-nanofibers with a net-shaped structure comprises the following steps:
(1) adding an aramid polymer into a dispersion solvent, and uniformly stirring and dispersing to obtain an aramid polymer dispersion liquid;
(2) directly spraying the aramid polymer dispersion liquid obtained in the step (1) into the dispersion liquid after air-jet atomization treatment, continuously stirring to obtain aramid micro-nano dispersion liquid, and then performing ultrasonic treatment and freeze drying to obtain the aramid micro-nano fiber with a net structure; wherein, the conditions of the gas spray atomization treatment are as follows: the spinneret orifices of the atomizer are an inner air inlet hole and an outer liquid inlet hole (namely, a mode of inner air inlet flow and outer liquid inlet flow is adopted), the aperture range is 0.1-8.0 mm, and the gas pressure range is 0.1-1.2 MPa.
The aramid polymer in the step (1) is at least one of poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide) and polyamide polymer containing a heterocyclic ring structure; preferably polyisophthaloyl metaphenylene diamine, piperazine aromatic polyamide, piperazine aromatic ring nylon and polyquine
At least one of a quinolinedione amide; more preferably polyisophthaloyl metaphenylene diamine.
The dispersing solvent in the step (1) is one or a mixture of N, N-dimethylacetamide, N-dimethylformamide (dimethylformamide), dimethyl sulfoxide and acetone; n, N-dimethylacetamide is preferred.
The concentration of the aramid polymer dispersion liquid in the step (1) is 1-20% by mass; preferably 10-20% by mass; more preferably 12 to 20 mass%.
The stirring in the step (1) is performed by adopting a magnetic stirrer (stirring by using a magnetic rotor) or a blade type stirrer; preferably, the stirring is carried out using a paddle stirrer.
The stirring conditions in the step (1) are as follows: the rotating speed is 50-10000 rpm, and the stirring time is 1-60 min; preferably: the rotating speed is 500-1000 rpm, and the stirring time is 1-30 min; more preferably: the rotation speed is 1000rpm, and the stirring time is 20 min.
The dispersion liquid in the step (2) is a solution with a curing effect; preferably at least one of N, N-dimethylacetamide, ethanol and water; further preferably at least one of an aqueous solution of N, N-dimethylacetamide, an aqueous solution of ethanol, and water; further preferably selecting an N, N-dimethylacetamide solution with the mass percent of 0-90%; more preferably, the N, N-dimethylacetamide solution is 40-60% by mass.
The aperture range of the atomizer in the step (2) is preferably 2.0-8.0 mm; more preferably 2.0 to 5.0 mm.
The gas pressure range in the step (2) is preferably 0.7-1.2 MPa; further preferably 0.7 to 0.8 MPa; more preferably 0.7 MPa.
The gas source for the gas-jet atomization treatment in the step (2) is at least one of air, nitrogen and argon; preferably air.
The continuous stirring in the step (2) is carried out by adopting a magnetic stirrer (stirring by using a magnetic rotor), a blade type stirrer or a high-speed emulsifying machine; preferably by means of a high-speed emulsifying machine.
The continuous stirring conditions in the step (2) are as follows: the rotating speed is 500-30000 rpm, and the stirring time is 1-60 min; preferably: the rotating speed is 10000-20000 rpm, and the stirring time is 5-10 min.
The ultrasonic treatment conditions in the step (2) are as follows: the power is 200-3000W, and the time is 1-60 min; preferably: the power is 500-3000W, and the time is 1-30 min.
The aramid micro-nano fibers in the step (2) are in a net shape, and the width of the aramid micro-nano fibers is less than 200 nm.
The aramid micro-nanofiber with the net-shaped structure is prepared by any one of the methods.
The aramid micro-nano fiber with the net structure is applied to the preparation of aramid paper.
The aramid fiber paper is manufactured by the aramid fiber micro-nano fiber with the net-shaped structure.
The quantitative amount of the aramid paper is 40g/m2The above.
The aramid fiber micro-nanofiber with the net-shaped structure and/or the aramid fiber paper can be applied to composite reinforced materials, battery diaphragm materials, adsorption filtering materials, electric insulating materials or flexible electronic devices.
The electric insulating material comprises electric insulating nano paper and the like.
The flexible electronic device comprises a flexible electrode and the like.
The utility model provides a be used for preparing above-mentioned aramid fiber micro-nanofiber's atomizer that has network structure, includes negative pressure production device and the inlet pipe that is used for carrying the polymer, negative pressure production device one side is located to the inlet pipe, and the inlet pipe is equipped with the discharge gate, and negative pressure production device is equipped with the nozzle, and nozzle one side is located to the discharge gate, and discharge gate and nozzle syntropy set up.
The nozzle of the negative pressure generating device penetrates through the feeding pipe, and the cross section of the discharge port is larger than that of the nozzle.
The inlet pipe include first body and second body, first body and second body intercommunication each other, contained angle is less than 180 between first body and the second body, the second body is located to the discharge gate, the second body is worn to locate by the nozzle of negative pressure production device.
The first tube is preferably perpendicular to the second tube.
The negative pressure generating device comprises an air compressor, an air pipe and a pressure regulating valve, one end of the air pipe is connected to the air compressor, the other end of the air pipe is arranged on the nozzle, the pressure regulating valve is connected to the air pipe, the air pipe penetrates through the second pipe body, and the air pipe is parallel to the second pipe body.
The nozzle is a nozzle with an adjustable caliber.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention adopts the injection technology of internal air inlet flow and external liquid inlet flow to prepare the aramid micro-nanofibers with the average diameter less than 200nm and controllable and adjustable sizes; the liquid substances are scattered and dispersed by the high-speed flowing compressed gas entering the device, the aramid fiber micro-nanofibers are collected by the collecting device and subjected to double diffusion in a reagent with a solidification effect to be initially solidified, dimethylacetamide aqueous solution or ethanol aqueous solution or water and the like can be selected, then the aramid fiber micro-nanofibers are obtained through ultrasonic treatment, and the size of the micro-nanofibers can be controlled and adjusted by adjusting the concentration of the liquid flow entering the device and the pressure of the compressed gas.
2. The micro-nanofiber prepared by the method has a unique net-shaped structure and a larger specific surface area, can remarkably improve the bonding strength of the fiber interface in the aramid paper, effectively improves the mechanical strength and dielectric property of the aramid paper, and can be widely applied to the field of new high-end insulating materials.
3. The preparation method of the aramid fiber micro-nano fiber is simple to operate, convenient and easy to implement, has high production efficiency compared with the conventional preparation method at present, is suitable for industrial continuous production, can replace the existing fibrid production technology, and can obviously improve the dielectric property and the interface bonding property of aramid fiber paper.
4. The aramid micro-nanofiber efficient preparation technology can also increase the functionalization and high performance of the aramid polymer by adding functional elements (such as functional nano particles, conductive polymers, heat-conducting fillers and the like) into the aramid polymer, and can be applied to various fields or cross diversified fields of composite reinforcement (reinforced materials), battery diaphragms, adsorption filtration, electrical insulation (such as electrical insulation nano paper), flexible electronic devices (such as flexible electrodes), adsorption filtration media and the like.
Drawings
Fig. 1 is a schematic diagram of a preparation process of the aramid micro-nanofibers in the present invention.
Fig. 2 is a schematic diagram of the atomizer device (in the figure: 1, air compressor; 2, air pipe; 3, pressure regulating valve; 4, compressed gas flow; 5, feed pipe; 6, polymer; 7, nozzle).
FIG. 3 is a schematic view of the process of the present invention using an atomizer device for gas atomization.
Fig. 4 is an atomic force microscope measurement result diagram of the aramid micro-nanofibers prepared in example 4.
Fig. 5 is a diameter frequency histogram distribution diagram of the aramid micro-nanofibers prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The following examples are given without reference to specific experimental conditions, and are generally in accordance with conventional experimental conditions. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
The starting materials for the preparation process of the present invention are commercially available or may be prepared according to prior art methods.
In the present example, aramid polymer (polyisophthaloyl metaphenylene diamine), aramid staple fiber, and aramid pulp were provided by Ganzhou Longbang materials science and technology, Inc.
The performance detection standard of the aramid paper related in the embodiment of the invention is as follows:
thickness (GB/T20628.2-2006); tensile strength (GB/T453-2002); tear strength (GB/T455-2002); electrical strength (GB/T1408.1-2016); dielectric constant and dielectric loss factor (GB/T1409-.
In the present invention, the gas-spray atomization treatment may be performed using an atomizer device that can be realized in the art; in the examples, the following atomizer devices (fig. 2) were used for the gas-jet atomization process:
the atomizer comprises a negative pressure generating device and a feeding pipe 5 for conveying a polymer 6, the feeding pipe 5 is arranged on one side of the negative pressure generating device, the feeding pipe 5 is provided with a discharge port, the negative pressure generating device is provided with a nozzle 7, the discharge port is arranged on one side of the nozzle, and the discharge port and the nozzle 7 are arranged in the same direction;
the nozzle 7 of the negative pressure generating device is arranged in the feeding pipe 5 in a penetrating way, and the cross section of the discharge port is larger than that of the nozzle 7;
the feeding pipe 5 comprises a first pipe body and a second pipe body, the first pipe body and the second pipe body are mutually communicated, an included angle between the first pipe body and the second pipe body is less than 180 degrees, the discharging port is arranged on the second pipe body, and a nozzle of the negative pressure generating device penetrates through the second pipe body; preferably, the first pipe body is perpendicular to the second pipe body;
the negative pressure generating device comprises an air compressor 1, an air pipe 2 and a pressure regulating valve 3, one end of the air pipe 2 is connected to the air compressor 1, a nozzle 7 is arranged at the other end of the air pipe 2, the pressure regulating valve 3 is connected to the air pipe 2, the air pipe 2 penetrates through a second pipe body, and the air pipe 2 is parallel to the second pipe body;
the nozzle 7 is a nozzle with an adjustable caliber.
A schematic diagram of the air-jet atomization process using the atomizer device is shown in fig. 3. During operation, the aramid polymer is subjected to air-jet atomization treatment in a mode of internal air flow and external liquid flow, and the method specifically comprises the following steps: the gas forms a compressed gas flow 4 through an air compressor 1 and a pressure regulating valve 3, the compressed gas flow 4 is ejected from a nozzle 7, a negative pressure gas flow area is formed at the nozzle, and when the polymer 6 passes through a feeding pipe 5, the polymer 6 is disturbed and dispersedly sprayed in the dispersion liquid (the aperture size of the nozzle 7 and the pressure of the pressure regulating valve 3 can be regulated to achieve the optimal atomization effect); wherein the gas is one or a mixture of two or more of air, nitrogen and argon (preferably air).
Example 1
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps (figure 1):
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide (N, N-dimethylacetamide and DMAC) at room temperature according to mass percent, stirring by a mechanical blade type stirrer at the rotating speed of 500rpm for 20min, and continuously stirring, dispersing and filtering to obtain 20% of aramid polymer dispersion liquid;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 8.0mm, air is used as an air source, and the air pressure is 1.2 MPa; directly spraying the mixture into a dimethylacetamide aqueous solution (the concentration of the dimethylacetamide aqueous solution is 40 mass percent), and adopting high-speed emulsification and dispersion, wherein the rotating speed is 30000rpm, and the stirring time is 1 min; processing the aramid fiber micro-nano dispersion liquid for 30min under the ultrasonic power of 1000W to obtain aramid fiber micro-nano dispersion liquid, and freeze-drying to obtain aramid fiber micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: aramid micro-nanofiber (5): 3.5: 1.5, and the thickness of the aramid paper prepared by hot pressing at 200 ℃ is 0.05 mm.
Example 2
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps:
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide at room temperature according to the mass percentage, stirring by a paddle type stirrer at the rotating speed of 1000rpm for 1min, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 12%;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 5.0mm, air is used as an air source, and the air pressure is 0.8 MPa; directly spraying the mixture into a dimethylacetamide aqueous solution (the concentration of the dimethylacetamide aqueous solution is 60 mass percent), and emulsifying and dispersing at a high speed of 10000rpm for 5 min; processing for 5min under ultrasonic power of 3000W to obtain aramid fiber micro-nano dispersion liquid, and freeze-drying to obtain aramid fiber micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: aramid micro-nanofiber (5): 3: and 2, the thickness of the aramid paper prepared by hot pressing at 200 ℃ is 0.05 mm.
Example 3
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps:
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide at room temperature according to the mass percentage, stirring by a paddle type stirrer at the rotating speed of 1000rpm for 30min, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 12%;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 3.0mm, air is used as an air source, and the air pressure is 0.7 MPa; directly spraying the mixture into a dimethylacetamide aqueous solution (the concentration of the dimethylacetamide aqueous solution is 60 mass percent), and emulsifying and dispersing at a high speed of 10000rpm for 5 min; processing for 10min under the ultrasonic power of 2000W to obtain aramid fiber micro-nano dispersion liquid, and freeze-drying to obtain aramid fiber micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: the thickness of the aramid fiber paper prepared by hot pressing the aramid fiber micro-nano fiber at 200 ℃ is 0.05mm, wherein the aramid fiber micro-nano fiber is 5:2: 3.
Example 4
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps:
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide at room temperature according to the mass percentage, stirring by a paddle type stirrer at the rotating speed of 1000rpm for 10min, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 12%;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 2.0mm, air is used as an air source, and the air pressure is 0.7 MPa; directly spraying into dimethylacetamide aqueous solution (the concentration of dimethylacetamide aqueous solution is 60% by mass), and emulsifying and dispersing at high speed at 20000rpm for 10 min; processing for 20min under the ultrasonic power of 2000W to obtain aramid fiber micro-nano dispersion liquid, and freeze-drying to obtain aramid fiber micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: the thickness of the aramid fiber paper prepared by hot pressing the aramid fiber micro-nano fiber at 200 ℃ is 0.05mm, wherein the aramid fiber micro-nano fiber is 5:1: 4.
Example 5
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps:
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide at room temperature according to the mass percentage, stirring by a paddle type stirrer at the rotating speed of 500rpm for 10min, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 10%;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 3.0mm, air is used as an air source, and the air pressure is 0.1 MPa; directly spraying the mixture into a dimethylacetamide aqueous solution (the concentration of the dimethylacetamide aqueous solution is 50 mass percent), and stirring and dispersing by adopting a magnetic rotor at the rotating speed of 500rpm for 60 min; processing for 1min under 500W of ultrasonic power to obtain aramid fiber micro-nano dispersion liquid, and freeze-drying to obtain aramid fiber micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: the thickness of the aramid fiber paper prepared by hot pressing the aramid fiber micro-nano fiber at 200 ℃ is 0.05mm, wherein the aramid fiber micro-nano fiber is 5:4: 1.
Comparative example 1
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps:
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide at room temperature according to the mass percentage, stirring by a magnetic rotor at the rotating speed of 50rpm for 60min, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 0.1%;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 8mm, air is used as an air source, and the air pressure is 0.1 MPa; directly spraying into water solution, and stirring and dispersing with mechanical blade at 50rpm for 1 min; processing the aramid fiber micro-nano dispersion liquid for 60min under 100W of ultrasonic power to obtain aramid fiber micro-nano dispersion liquid, and freeze-drying to obtain aramid fiber micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: aramid micro-nano fiber (5: 4.5: 0.5) and hot pressing at 200 deg.CThe thickness of the prepared aramid paper is 0.05 mm.
Comparative example 2
An efficient preparation method and application of aramid micro-nanofibers are disclosed, wherein the preparation method comprises the following steps:
(1) preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in dimethylacetamide at room temperature according to the mass percentage, stirring by a magnetic rotor at the rotating speed of 50rpm for 60min, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 5%;
(2) preparing aramid micro-nano fibers: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal air inlet flow and external liquid inlet flow by adopting an atomizer, wherein the size of an atomization hole is 7mm, air is used as an air source, and the air pressure is 0.05 MPa; directly spraying into water solution, and stirring and dispersing with mechanical blade at 500rpm for 10 min; processing for 10min under 500W of ultrasonic power to obtain aramid micro-nano dispersion liquid, and freeze-drying to obtain aramid micro-nano fibers; the size and the specific surface area of the prepared aramid micro-nanofibers are characterized;
(3) the prepared aramid micro-nano fiber is made into micro-nano fiber with the quantitative of 40g/m2The aramid fiber paper comprises aramid chopped fibers in mass proportion: aramid pulp: the thickness of the aramid fiber paper prepared by hot pressing the aramid fiber micro-nano fiber at 200 ℃ is 0.05mm, wherein the aramid fiber micro-nano fiber is 5:4.5: 0.5.
Effects of the embodiment
The sizes and specific surface areas of the aramid micro-nanofibers prepared in examples 1 to 5 and comparative examples 1 to 2 were characterized, and the performance tests of the aramid papers prepared in examples 1 to 5 and comparative examples 1 to 2 were performed (a blank control was set, aramid chopped fibers: aramid pulp: 5 in mass ratio, and base paper (basis weight of 40 g/m) was manufactured by kesai method sheet making (basis weight of 40 g/m)2) Then, a base paper having an aramid paper thickness of 0.05mm prepared after hot pressing at 200 ℃ was used as a control (blank).
An atomic force microscope measurement result of the aramid micro-nanofiber prepared in example 4 is shown in fig. 4, and a diameter frequency histogram is shown in fig. 5; other test results are shown in table 1.
Table 1 summary table of testing results of aramid micro-nanofiber and aramid paper
As can be seen from table 1, in comparative examples 1 and 2, the pressure is lower, the pore size is larger, effective disturbance of air flow is insufficient, the polymer concentration is lower, and the solidification rate in water is higher, so that the aramid micro-nanofiber is comprehensively in a large-particle spherical structure.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of aramid micro-nanofibers with a net-shaped structure is characterized by comprising the following steps:
(1) adding an aramid polymer into a dispersion solvent, and uniformly stirring and dispersing to obtain an aramid polymer dispersion liquid;
(2) directly spraying the aramid polymer dispersion liquid obtained in the step (1) into the dispersion liquid after air-jet atomization treatment, continuously stirring to obtain aramid micro-nano dispersion liquid, and then performing ultrasonic treatment and freeze drying to obtain the aramid micro-nano fiber with a net structure; wherein, the conditions of the gas spray atomization treatment are as follows: the spinneret orifices of the atomizer are an inner air inlet hole and an outer liquid inlet hole, the aperture range is 0.1-8.0 mm, and the gas pressure range is 0.1-1.2 MPa.
2. The preparation method of the aramid micro-nanofibers with the net-shaped structure according to claim 1, characterized in that:
the aramid polymer in the step (1) is at least one of poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide) and polyamide polymer containing a heterocyclic ring structure;
the dispersing solvent in the step (1) is one or a mixture of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and acetone;
the concentration of the aramid polymer dispersion liquid in the step (1) is 1-20% by mass;
the dispersion liquid in the step (2) is at least one of N, N-dimethylacetamide, ethanol and water;
the aperture range of the atomizer in the step (2) is 2.0-8.0 mm;
the gas pressure range in the step (2) is 0.7-1.2 MPa.
3. The preparation method of the aramid micro-nanofibers with the net-shaped structure according to claim 2, characterized in that:
the aramid polymer in the step (1) is poly (m-phenylene isophthalamide);
the dispersing solvent in the step (1) is N, N-dimethylacetamide;
the concentration of the aramid polymer dispersion liquid in the step (1) is 12-20% by mass;
the dispersion liquid in the step (2) is an N, N-dimethylacetamide solution with the mass percent of 40-60%;
the aperture range of the atomizer in the step (2) is 2.0-5.0 mm;
the gas pressure range in the step (2) is 0.7-0.8 MPa.
4. The preparation method of the aramid micro-nanofibers with the net-shaped structure according to claim 1, characterized in that:
the stirring conditions in the step (1) are as follows: the rotating speed is 50-10000 rpm, and the stirring time is 1-60 min;
the gas source for the gas-jet atomization treatment in the step (2) is at least one of air, nitrogen and argon;
the continuous stirring conditions in the step (2) are as follows: the rotating speed is 500-30000 rpm, and the stirring time is 1-60 min;
the ultrasonic treatment conditions in the step (2) are as follows: the power is 200-3000W, and the time is 1-60 min.
5. The utility model provides an aramid fiber micro-nanofiber with network structure which characterized in that: prepared by the method of any one of claims 1 to 4.
6. The application of the aramid micro-nano fiber with the net-shaped structure in preparing aramid paper, disclosed by claim 5.
7. An aramid paper, its characterized in that: the aramid micro-nano fiber with the net structure is manufactured by the aramid micro-nano fiber with the net structure of claim 5.
8. The use of the aramid micro-nanofibers with a network structure of claim 5 and/or the aramid paper of claim 7 in composite reinforcement materials, battery separator materials, adsorption filtration materials, electrical insulation materials or flexible electronic devices.
9. An atomizer for preparing the aramid micro-nanofibers with the net-shaped structure of claim 5, characterized in that: the device comprises a negative pressure generating device and a feeding pipe for conveying polymers, wherein the feeding pipe is arranged on one side of the negative pressure generating device and is provided with a discharge port, the negative pressure generating device is provided with a nozzle, the discharge port is arranged on one side of the nozzle, and the discharge port and the nozzle are arranged in the same direction;
the nozzle of the negative pressure generating device penetrates through the feeding pipe, and the cross section of the discharge port is larger than that of the nozzle;
the feeding pipe comprises a first pipe body and a second pipe body, the first pipe body and the second pipe body are mutually communicated, an included angle between the first pipe body and the second pipe body is less than 180 degrees, the discharging port is arranged on the second pipe body, and a nozzle of the negative pressure generating device penetrates through the second pipe body;
the negative pressure generating device comprises an air compressor, an air pipe and a pressure regulating valve, one end of the air pipe is connected to the air compressor, the other end of the air pipe is arranged on the nozzle, the pressure regulating valve is connected to the air pipe, the air pipe penetrates through the second pipe body, and the air pipe is parallel to the second pipe body.
10. The nebulizer of claim 9, wherein:
the first pipe body is vertical to the second pipe body;
the nozzle is a nozzle with an adjustable caliber.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115275504A (en) * | 2022-06-28 | 2022-11-01 | 陈克复 | Aramid fiber diaphragm and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX155527A (en) * | 1980-05-13 | 1988-03-24 | Lonza Ag | IMPROVEMENTS IN SCATTERED SYSTEMS |
| WO2016119693A1 (en) * | 2015-01-27 | 2016-08-04 | 昆明纳太科技有限公司 | Air filter paper and preparation method therefor |
| CN106189577A (en) * | 2016-06-30 | 2016-12-07 | 嘉兴市高正高分子材料有限公司 | A kind of preparation method of high dispersive type water system carbon nanotube conducting slurry |
| CN108276588A (en) * | 2018-02-11 | 2018-07-13 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber water-dispersed/nano-cellulose compound system and ultraviolet shielded type transparent membrane |
| CN108912350A (en) * | 2018-06-13 | 2018-11-30 | 中科广化（重庆）新材料研究院有限公司 | A kind of spherical shape aramid fiber nano material and preparation method thereof |
| CN110205862A (en) * | 2019-06-10 | 2019-09-06 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber self-reinforcing aramid fiber mica paper |
| CN112609493A (en) * | 2020-12-28 | 2021-04-06 | 山东聚芳新材料股份有限公司 | Composite papermaking nano reinforced aramid fiber paper and preparation method thereof |
| CN112726283A (en) * | 2020-12-25 | 2021-04-30 | 烟台民士达特种纸业股份有限公司 | Poly (p-phenylene benzobisoxazole) fiber paper base material for high-temperature-resistant honeycomb core material and preparation method thereof |
| CN112912564A (en) * | 2018-08-14 | 2021-06-04 | 杜邦安全与建筑公司 | High tensile strength paper suitable for use in electrochemical cells |
| CN113293640A (en) * | 2021-06-28 | 2021-08-24 | 山东聚芳新材料股份有限公司 | Para-aramid nanofiber and high-performance carbon fiber composite paper and preparation method thereof |
-
2021
- 2021-09-07 CN CN202111047123.7A patent/CN113969427B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX155527A (en) * | 1980-05-13 | 1988-03-24 | Lonza Ag | IMPROVEMENTS IN SCATTERED SYSTEMS |
| WO2016119693A1 (en) * | 2015-01-27 | 2016-08-04 | 昆明纳太科技有限公司 | Air filter paper and preparation method therefor |
| CN106189577A (en) * | 2016-06-30 | 2016-12-07 | 嘉兴市高正高分子材料有限公司 | A kind of preparation method of high dispersive type water system carbon nanotube conducting slurry |
| CN108276588A (en) * | 2018-02-11 | 2018-07-13 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber water-dispersed/nano-cellulose compound system and ultraviolet shielded type transparent membrane |
| CN108912350A (en) * | 2018-06-13 | 2018-11-30 | 中科广化（重庆）新材料研究院有限公司 | A kind of spherical shape aramid fiber nano material and preparation method thereof |
| CN112912564A (en) * | 2018-08-14 | 2021-06-04 | 杜邦安全与建筑公司 | High tensile strength paper suitable for use in electrochemical cells |
| CN110205862A (en) * | 2019-06-10 | 2019-09-06 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber self-reinforcing aramid fiber mica paper |
| CN112726283A (en) * | 2020-12-25 | 2021-04-30 | 烟台民士达特种纸业股份有限公司 | Poly (p-phenylene benzobisoxazole) fiber paper base material for high-temperature-resistant honeycomb core material and preparation method thereof |
| CN112609493A (en) * | 2020-12-28 | 2021-04-06 | 山东聚芳新材料股份有限公司 | Composite papermaking nano reinforced aramid fiber paper and preparation method thereof |
| CN113293640A (en) * | 2021-06-28 | 2021-08-24 | 山东聚芳新材料股份有限公司 | Para-aramid nanofiber and high-performance carbon fiber composite paper and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 井晶等: "喷雾干燥法制备水分散聚酰亚胺", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115275504A (en) * | 2022-06-28 | 2022-11-01 | 陈克复 | Aramid fiber diaphragm and preparation method and application thereof |
| CN115275504B (en) * | 2022-06-28 | 2023-10-27 | 陈克复 | Aramid fiber diaphragm and preparation method and application thereof |
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