CN115110306A - Preparation method of aramid nanofiber based on ball-milling assisted deprotonation - Google Patents
Preparation method of aramid nanofiber based on ball-milling assisted deprotonation Download PDFInfo
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- 238000000498 ball milling Methods 0.000 title claims abstract description 69
- 230000005595 deprotonation Effects 0.000 title claims abstract description 36
- 238000010537 deprotonation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000004760 aramid Substances 0.000 title claims abstract description 26
- 239000002121 nanofiber Substances 0.000 title claims abstract description 23
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 41
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 25
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 22
- 239000012046 mixed solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
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- 238000001757 thermogravimetry curve Methods 0.000 description 3
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- 238000000089 atomic force micrograph Methods 0.000 description 2
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- 238000002834 transmittance Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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Abstract
The invention belongs to the technical field of preparation of aramid nano-fibers, and discloses a preparation method of an aramid nano-fiber based on ball-milling assisted deprotonation. The method comprises the following steps: (1) adding aramid fiber and potassium hydroxide into a mixed solvent consisting of dimethyl sulfoxide and water; (2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls, performing planetary ball milling at room temperature, and taking out the ball milling solution when no fiber remains; wherein, when the ball milling is carried out by the planet, the revolution speed is 200 plus 800 rpm, and the rotation speed is 50 percent of the revolution speed; (3) and (3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining the Aramid Nano Fiber (ANF). According to the invention, the diameter of the ANF prepared by using ball milling assisted deprotonation is significantly reduced compared with that of the ANF prepared by using the traditional method, and compared with the traditional method, the preparation efficiency and the quality of the prepared ANF are significantly improved, so that the method is expected to become a mainstream method for large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of preparation of aramid nano-fibers, and particularly relates to a preparation method of an aramid nano-fiber based on ball-milling assisted deprotonation.
Background
One-dimensional (1D) Aramid Nanofibers (ANF) prepared by deprotonating and stripping aramid fibers not only keep excellent mechanical properties and high temperature resistance of macroscopic aramid fibers, but also show nanomaterial characteristics such as nanoscale, large length-diameter ratio and high specific surface area. In the application field of composite materials, ANF is used as a base material, has structural characteristics which are comparable to those of Carbon Nanotubes (CNTs), Cellulose Nanofibers (CNF) and the like, and can be used for preparing a high-performance shell-like laminated structure composite film with multi-dimensional nano functional fillers (such as carbon nanotubes, graphene, boron nitride, MXene and the like); on the other hand, the ANF serving as the organic nano reinforcing filler has the advantages of strong interface interaction, excellent reinforcing effect and the like in the aspect of reinforcing polymer matrix materials (such as epoxy resin, polyolefin materials and the like). Meanwhile, the ANF film based on the ANF layer-layer assembly has the characteristics of high strength, high transparency, thermal/chemical stability, high flame retardance and the like, and has a great application prospect in the fields of flexible electronics, biomedicine, energy sources and the like.
Nicholas et al, USA, first reported a deprotonation preparation method of ANF (ACS Nano, 2011, 5(9): 6945-54), namely, obtaining an ANF/DMSO dispersion by deprotonation dissolution of aramid fibers in a dimethyl sulfoxide (DMSO) solvent with the aid of potassium hydroxide (KOH); the method has the greatest characteristic of simple and convenient operation process, but has the defect of overlong preparation time (stirring for 7-10 days), and greatly influences the large-scale preparation efficiency of ANF. In recent years, Yan bin and the like (Chinese patent, CN 110055797A; ACS Nano 2019, 13, 7886-7897) of Shanxi science and technology university report a series of methods for shortening the preparation time of ANF and improving the preparation efficiency, and concretely comprises the steps of carrying out microfibrillation treatment, ultrasonic-assisted deprotonation stripping and proton donor-assisted deprotonation stripping on aramid fibers by adopting mechanical action; wherein, a small amount of H is added into a DMSO solvent 2 Providing substance of OThe sub-donor assists in the deprotonation process of the aramid fiber, so that the preparation time of the ANF can be greatly shortened to 4 hours, and the ANF film obtained by the obtained ANF through a layer-by-layer self-assembly method has similar performance to that of the ANF obtained by the traditional method in the aspects of transparency, mechanical property, thermal/chemical stability and the like. Nevertheless, the improved process produces high concentrations of>20 mg/mL) ANF dispersion still required a longer time, limiting further extension of the method. Therefore, it is desired to develop a more rapid, efficient and highly concentrated ANF dispersion preparation method.
Disclosure of Invention
In order to overcome the defects of low preparation efficiency, low ANF concentration, difficulty in large-scale preparation and the like in the traditional deprotonation preparation of ANF dispersion liquid, the invention aims to provide a preparation method of aramid nano-fiber based on ball-milling assisted deprotonation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of aramid nano-fiber based on ball-milling assisted deprotonation comprises the following steps:
(1) adding aramid fiber and potassium hydroxide into a mixed solvent consisting of dimethyl sulfoxide and water;
(2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls (zirconia microspheres with the diameter of 1-10 mm) to perform planetary ball milling at room temperature, taking out a sample every 5-30 min to observe whether fiber residues exist or not so as to judge whether a deprotonation process is finished or not, and taking out the ball milling solution when no fiber residues exist; wherein, when the ball milling is carried out by the planet, the revolution speed is 200 plus 800 rpm, and the rotation speed is 50 percent of the revolution speed;
(3) and (3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining the dispersion liquid of the aramid nano-fibers.
Preferably, in the step (1), in the mixed solvent, the mass ratio of dimethyl sulfoxide to water is = (1-10) to (0-1); every 500 mL of mixed solvent contains 1-20 g of aramid fiber and 1.5-30 g of potassium hydroxide.
Preferably, in the mixed solvent, the mass ratio of dimethyl sulfoxide to water is = (20-30): (1).
Preferably, in step (3), the centrifugation speed is 8000-11000 rpm, and the centrifugation time is 5-30 min.
In the method, the strong mechanochemical action in the ball milling process accelerates the dissolving process of KOH in the mixed solvent on one hand and provides enough OH rapidly - The ions are used for weakening the hydrogen bond action among molecular chains in the aramid fiber and increasing the proton exchange speed. More importantly, the zirconia microspheres collide with each other and rotate to generate strong impact force and shearing force in the ball milling process to tear aramid fibers, so that the permeation and dissolution of solvents and ions to the inside of the fibers are accelerated, the solvents and ions permeating into the fibers further swell the fibers, and the stripping and tearing of the microfibers are further accelerated under the action of the ball milling shearing force. Therefore, the deprotonation process of the aramid fiber is greatly accelerated, and the preparation period of the ANF is greatly shortened (the shortest time can be shortened to 30 min, which is far shorter than 7-10 days reported by the traditional technology). Meanwhile, compared with mechanical stirring used in the traditional technology, the high-concentration fiber solution can be effectively stirred and dispersed in the ball milling process, so that the high-concentration ANF dispersion liquid (the concentration can reach 40mg/mL, and the ball milling time is only 1 h) can be prepared.
Has the advantages that:
(1) the diameter of the ANF prepared by the deprotonation assisted by ball milling is obviously reduced compared with that of the ANF prepared by the traditional method due to the tearing microfibrillation of the aramid fiber under the strong shearing action of the ball milling;
(2) the lower fiber diameter leads the nano-fibers to be more compactly stacked and assembled in the suction filtration process, so that the prepared ANF film is superior to the ANF film prepared by the traditional technology in the aspects of tensile strength (271.6 MPa), transparency (75.1%), thermal stability (586.2 ℃) and the like;
(3) compared with the technology (ultrasonic pretreatment, proton solvent addition and stirring deprotonation) reported in the patent CN 110055797A, the invention realizes the one-pot preparation of the ANF dispersion liquid, namely, the ANF dispersion liquid is obtained by adding reaction raw materials into one pot and performing one-step ball milling; in contrast, the preparation efficiency and the quality of the prepared ANF are both remarkably improved, and the method has the advantages of simplified process, easiness in operation and the like, and is expected to become a mainstream method for large-scale preparation.
Drawings
FIG. 1: schematic flow chart of preparation of ANF by ball milling assisted deprotonation.
FIG. 2: physical representation of the ANF dispersion obtained in example 1.
FIG. 3: and (3) an undissolved substance of the aramid fiber obtained in the comparative example.
FIG. 4: atomic force microscopy images of the ANF dispersions obtained in example 1.
FIG. 5: tensile stress strain curves for ANF films prepared using the ANF dispersions obtained in example 1 and comparative example 1.
FIG. 6: transmittance spectra of ANF films prepared using the ANF dispersions obtained in example 1 and comparative example 1.
FIG. 7: thermogravimetric analysis curves of ANF films prepared using the ANF dispersions obtained in example 1 and comparative example 1.
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of aramid nano-fiber based on ball-milling assisted deprotonation is shown in a schematic flow diagram in figure 1 and comprises the following steps:
(1) adding 5g of aramid fiber and 7.5g of potassium hydroxide (KOH) into 500 mL of solution prepared from dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is mixed in a mixed solvent composed of 25: 1 according to the mass ratio;
(2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls (zirconia microspheres with the diameter of 5 mm) and carrying out planetary ball milling at room temperature; taking out the sample every 5min to observe whether fiber residue exists or not, judging whether the deprotonation process is finished or not, and taking out the reaction solution when no fiber residue exists; the planetary ball milling is carried out, wherein the revolution speed is 500rpm, and the rotation speed is 50% of the revolution speed;
(3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining a dispersion liquid of ANF (shown in a real object diagram in figure 2); during the centrifugal treatment, the centrifugal speed is 8000rpm, and the centrifugal time is 5 min; the concentration of the resulting ANF dispersion was 10 mg/mL.
Example 2
A preparation method of aramid nano-fiber based on ball-milling assisted deprotonation comprises the following steps:
(1) 10g aramid fiber and 7.5g potassium hydroxide (KOH) were added to 500 mL solution prepared from dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is mixed in a mixed solvent composed of 25: 1 according to the mass ratio;
(2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls (zirconia microspheres with the diameter of 5 mm) and carrying out planetary ball milling at room temperature; taking out the sample every 5min to observe whether fiber residue exists or not, judging whether the deprotonation process is finished or not, and taking out the reaction solution when no fiber residue exists; the planetary ball milling is carried out, wherein the revolution speed is 500rpm, and the rotation speed is 50% of the revolution speed;
(3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining an ANF dispersion liquid; during the centrifugal treatment, the centrifugal speed is 8000rpm, and the centrifugal time is 5 min; the concentration of the resulting ANF dispersion was 20 mg/mL.
Example 3
A preparation method of aramid nano-fiber based on ball-milling assisted deprotonation comprises the following steps:
(1) 20g of aramid fiber and 30g of potassium hydroxide (KOH) are added into 500 mL of solution prepared from dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is mixed in a mixed solvent composed of 25: 1 according to the mass ratio;
(2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls (zirconia microspheres with the diameter of 5 mm) and carrying out planetary ball milling at room temperature; taking out the sample every 5min to observe whether fiber residue exists or not, judging whether the deprotonation process is completed or not, and taking out the reaction solution when no fiber residue exists; the planetary ball milling is carried out, wherein the revolution speed is 800 rpm, and the rotation speed is 50% of the revolution speed;
(3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining an ANF dispersion liquid; during the centrifugal treatment, the centrifugal speed is 8000rpm, and the centrifugal time is 5 min; the concentration of the resulting ANF dispersion was 40 mg/mL.
Example 4
A preparation method of aramid nano-fiber based on ball-milling assisted deprotonation comprises the following steps:
(1) adding 5g of aramid fiber and 7.5g of potassium hydroxide (KOH) into 500 mL of solution prepared from dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is mixed in a mixed solvent with the mass ratio of 1: 0;
(2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls (zirconia microspheres with the diameter of 5 mm) and carrying out planetary ball milling at room temperature; taking out the sample every 10 min to observe whether fiber residue exists or not, judging whether the deprotonation process is finished or not, and taking out the reaction solution when no fiber residue exists; the planetary ball milling is carried out, wherein the revolution speed is 500rpm, and the rotation speed is 50% of the revolution speed;
(3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, thus obtaining DMSO dispersion liquid of ANF; during the centrifugal treatment, the centrifugal speed is 8000rpm, and the centrifugal time is 5 min; the concentration of the resulting ANF dispersion was 10 mg/mL.
Comparative example 1
The conventional 7-day method for preparing an ANF dispersion comprises the following steps:
(1) adding 5g of aramid fiber and 7.5g of potassium hydroxide (KOH) into 500 mL of solution prepared from dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is mixed in a mixed solvent with the mass ratio of 1: 0;
(2) magnetically stirring the dispersion liquid obtained in the step (1) at room temperature, wherein the stirring speed is 100rpm, and the stirring time is 7 days;
(3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining an ANF dispersion liquid; performing centrifugal treatment, wherein the centrifugal speed is 8000rpm, and the centrifugal time is 5 min; the concentration of the resulting ANF dispersion was 10 mg/mL.
Comparative example 2
The traditional method for preparing the ANF dispersion by adding the protic solvent comprises the following steps:
(1) adding 5g of aramid fiber and 7.5g of potassium hydroxide (KOH) into 500 mL of solution prepared from dimethyl sulfoxide (DMSO) and deionized water (H) 2 O) is mixed in a mixed solvent composed of 25: 1 according to the mass ratio;
(2) magnetically stirring the dispersion obtained in the step (1) at room temperature, wherein the stirring speed is 100 rpm; taking out the sample every 5min to observe whether fiber residue exists or not, judging whether the deprotonation process is finished or not, and taking out the reaction solution when no fiber residue exists;
(3) centrifuging the stirred solution obtained in the step (2) to remove impurities, and obtaining an ANF dispersion liquid; performing centrifugal treatment, wherein the centrifugal speed is 8000rpm, and the centrifugal time is 5 min; the concentration of the resulting ANF dispersion was 10 mg/mL.
Comparative example 3
The difference from example 1 is that: in the step (2), the revolution speed of the planetary ball mill is 100rpm, and the rotation speed is 50 percent of the revolution speed; however, the aramid fiber is still insoluble after 10h of ball milling, and the picture of the real object is shown in figure 3. The reason for this analysis is that a weak shearing force is provided at this rotation speed, tearing damage cannot be caused to the aramid fiber, and the solvent and ions are difficult to permeate and dissolve the interior of the fiber.
In order to verify the basic performance of the ANF prepared by the ball-milling assisted deprotonation, the high-transparency and high-strength ANF layered film is prepared by adopting a vacuum-assisted suction filtration method, and the method comprises the following steps:
(1) taking the ANF dispersion liquid with the solid content of 30mg, adding DMSO to dilute to 1 mg/mL, adding H 2 Removing the DMSO solvent through multiple times of suction filtration washing after O stirring;
(2) adding H into the filter cake obtained in the step (1) under the condition of high-speed shearing emulsification 2 Diluting to 0.5 mg/mL by using O;
(3) carrying out suction filtration on the surface of the filter membrane by vacuum assistance on the ANF diluent obtained in the step (2);
(4) and (4) naturally airing the suction filtration membrane obtained in the step (3), and peeling from the surface of the filtration membrane to obtain the high-transparency high-strength ANF membrane.
The atomic force microscope images of the ANF dispersions obtained in example 1 and comparative example 1 are shown in fig. 4. As can be seen from fig. 4: the ANF prepared by using the ball milling assisted deprotonation has the advantages that the tearing microfibrillation of the aramid fiber is realized under the strong shearing action of the ball milling, the diameter (1-5 nm) of the obtained ANF fiber is obviously reduced compared with the diameter (10-15 nm) of the ANF prepared by the traditional 7-day method, and the average diameter is 2.09 nm.
The tensile stress strain curve, transmittance spectrum, thermogravimetric analysis curve of the ANF films prepared using the ANF dispersions obtained in examples 1 to 4 and comparative examples 1 to 2 were respectively tested, wherein the tensile stress strain curve, transmittance spectrum, thermogravimetric analysis curve of the ANF films prepared using the ANF dispersions obtained in example 1 and comparative example 1 are respectively shown in fig. 5, 6 and 7. The data are compared in table 1.
By comparing example 1 with comparative examples 1 and 2, it can be seen that: the preparation efficiency of the aramid nanofiber can be remarkably improved by adopting a ball-milling assisted deprotonation method; even if the addition amount of the aramid fiber is increased (example 2), the preparation efficiency is obviously improved compared with that of the traditional 7-day method (comparative example 1) and the proton solvent adding method (comparative example 2); compared with the performance of the ANF film, the ANF film prepared by the ball-milling assisted deprotonation method is improved in transmittance, mechanical strength and decomposition temperature compared with the ANF film prepared by the traditional method.
Claims (4)
1. A preparation method of aramid nano-fiber based on ball-milling assisted deprotonation is characterized by comprising the following steps:
(1) adding aramid fiber and potassium hydroxide into a mixed solvent consisting of dimethyl sulfoxide and water;
(2) adding the mixed solution obtained in the step (1) into a ball milling tank, adding ball milling balls, performing planetary ball milling at room temperature, taking out a sample every 5-30 min to observe whether fiber residues exist or not, judging whether a deprotonation process is finished or not, and taking out the ball milling solution when no fiber residues exist; wherein, when the ball milling is carried out by the planet, the revolution speed is 200 plus 800 rpm, and the rotation speed is 50 percent of the revolution speed;
(3) and (3) centrifuging the ball-milling solution obtained in the step (2) to remove impurities, and obtaining a dispersion liquid of the aramid nano-fibers.
2. The preparation method of the aramid nanofiber based on ball-milling assisted deprotonation as claimed in claim 1, wherein: in the step (1), in the mixed solvent, by mass ratio, dimethyl sulfoxide and water = (1-10) to (0-1); every 500 mL of mixed solvent contains 1-20 g of aramid fiber and 1.5-30 g of potassium hydroxide.
3. The preparation method of the ball-milling assisted deprotonation-based aramid nanofiber as claimed in claim 2, characterized in that: in the mixed solvent, the mass ratio of dimethyl sulfoxide to water is = (20-30) to 1.
4. The preparation method of the ball-milling assisted deprotonation-based aramid nanofiber as claimed in claim 1, wherein: in the step (3), the centrifugation speed is 8000-11000 rpm, and the centrifugation time is 5-30 min.
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