CN112481644B - Flower-shaped graphene, melt-blown cloth, preparation methods of flower-shaped graphene and melt-blown cloth and mask - Google Patents
Flower-shaped graphene, melt-blown cloth, preparation methods of flower-shaped graphene and melt-blown cloth and mask Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- 239000004744 fabric Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 8
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims abstract description 6
- 239000002356 single layer Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 44
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- 238000007664 blowing Methods 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000004743 Polypropylene Substances 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- 229920001155 polypropylene Polymers 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 19
- -1 polypropylene Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920001410 Microfiber Polymers 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002788 crimping Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000000805 cytoplasm Anatomy 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 150000003904 phospholipids Chemical class 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to the field of graphene preparation and application, and particularly relates to flower-like graphene based on electrochemical treatment, a preparation method thereof and application thereof in melt-blown products. The flower-like graphene is composed of a plurality of mutually independent graphene aggregates, wherein the graphene aggregates are formed by curling single-layer or multi-layer ultrathin two-dimensional nano materials, and the size of each single graphene aggregate is between 50 and 200 nm. The flower-like graphene material can effectively improve the air permeability of the filtering performance of the composite melt-blown cloth, and endows the composite melt-blown cloth with excellent antibacterial performance and mechanical performance. The melt-blown cloth prepared from the flower-shaped graphene has excellent performances of oleophylic and hydrophobic properties, antibacterial and bacteriostatic properties, strong adsorption capacity and the like, and the prepared mask has a large practical application value in epidemic situation resistance.
Description
Technical Field
The invention belongs to the field of graphene preparation and application, and particularly relates to flower-like graphene based on electrochemical treatment, a preparation method thereof and application thereof in melt-blown products.
Background
The melt-blown cloth is formed by unordered accumulation of micron-sized fibers, extremely fine particles are formed to filter narrow gaps and detention spaces, and electrostatic charges loaded on the fibers can capture the fine particles through coulomb force after residence treatment, so that the manufactured mask is suitable in respiratory resistance and comfortable to wear. Since the outbreak of a new crown epidemic situation in 2020, the mask becomes a necessary article for life, work and travel of people, and higher requirements are also put forward for the filtering performance, the air permeability, the service life and even the antibacterial effect of the mask.
The graphene is an ultrathin two-dimensional nanomaterial with the thickness of only 0.34nm, has excellent chemical stability and mechanical property, super-strong heat conduction property and electric conductivity, and also has strong ion exchange property and adsorption property, and can be widely applied to the fields of air purification, water treatment, energy storage, catalysis and the like. Similarly, graphene can play an important role in meltblown and mask. The graphene nano sheets are assembled into a certain three-dimensional structure and uniformly dispersed into the melt-blown cloth, so that the advantage of large specific surface area of the graphene nano sheets can be exerted, and particles in the air can be fully adsorbed, and the air permeability is greatly improved while the filtering performance is maintained.
In the related preparation technology of graphene/polypropylene composite master batch and melt-blown cloth thereof, for example, CN202010580101.6 is a recyclable graphene composite melt-blown cloth with high filterability and a preparation method thereof, although the graphene melt-blown cloth is also described, the method is limited to introducing the components of the melt-blown cloth, and the effect of the structural characteristics of graphene on the melt-blown cloth is not developed in deep research by utilizing a graphene material. Meanwhile, a large number of various auxiliary agents and additives are used for meeting the uniformity requirement of the product, so that the residues of the various auxiliary agents and additives in the product reduce the performance of the product. For example, in the existing graphene/polypropylene composite master batch, the mass fraction of the auxiliary agent is as high as 1-5%, which affects the processing performance of the graphene/polypropylene composite master batch to a certain extent and causes the quality of the melt-blown cloth product to be reduced and the performance to be reduced.
Disclosure of Invention
The purpose of the invention is that: the flower-shaped graphene with controllable structure, oleophilic, hydrophobic, antibacterial, bacteriostatic and strong adsorption capacity, and melt-blown cloth and mask adopting the graphene are provided.
In addition, the invention also provides a preparation method of the flower-shaped graphene and melt-blown cloth.
The technical scheme of the invention is as follows: the flower-shaped graphene consists of a plurality of mutually independent graphene aggregates, wherein the graphene aggregates are formed by curling single-layer or multi-layer ultrathin two-dimensional nano materials, the size of each single graphene aggregate is between 50 and 200nm, the structure is uniform and stable, and the independence of each aggregate can be effectively maintained without secondary aggregation, so that the external contact area is increased.
The graphene aggregate single structure body is provided with a reel center, and is curled by a strip-shaped ultrathin two-dimensional nano material around the reel center to form a flower-shaped structure.
The number of the curling layers of the graphene aggregate is 2-20, and the special adsorption performance and sterilization performance of graphene can be effectively exerted.
The preparation method of the flower-like graphene comprises the following steps:
(1) A graphite rod is adopted as an anode, and a metal electrode is adopted as a cathode;
(2) Preparing KOH/H 2O2 water solution as electrolyte;
(3) The graphite rod and the metal electrode are used as electrodes of an electrolytic cell, the electrodes are placed in the electrolytic cell, the positions of the electrodes are adjusted, the electrodes are immersed in electrolyte, the graphite rod and the metal electrode are connected with a direct current power supply through wires, the anode is connected with the positive electrode of the direct current power supply, the cathode is connected with the negative electrode of the direct current power supply, and electrolytic reaction is carried out after the direct current voltage is applied by the direct current power supply;
(4) In the electrolysis process, bubbles are continuously generated on the anode graphite rod, and the color of the electrolyte is changed from colorless to black;
(5) After the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(6) And drying the cleaned black powder to obtain the flower-like graphene.
The concentration of KOH in the step (2) is 0.1-10M, and the concentration of H 2O2 is 10 mM-1M, so that a proper reaction speed is achieved, the structural stability and consistency of the flower-like graphene can be ensured, and the yield is stable.
In the step (3), the purity of the graphite rod is not lower than 99.9%, so that excessive impurity components are prevented from being contained in the flower-like graphene, the filtering or antibacterial performance is reduced, and the performance requirement or the chemical component requirement of a final product cannot be met. The metal anode adopts a platinum electrode, the distance between the cathode and the anode is 3-10 cm, and the unstable structure of the flower-like graphene due to insufficient electrolysis is avoided.
In the step (3), the direct current voltage is 0.1-20V, the temperature of an electrolysis reaction system is not higher than 50 ℃, and the peeling reaction acceleration caused by overhigh temperature is prevented, so that the structure of the flower-like graphene material is unstable.
The melt-blown fabric comprises the flower-like graphene, wherein the mass content of the flower-like graphene in the melt-blown fabric is 0.001% -1%, the phenomenon of uneven dispersion caused by overhigh content is avoided, and evidence shows that the beneficial synergy of the melt-blown fabric product by the excessive content of the flower-like graphene is very limited.
A method of making a meltblown web according to the present invention, comprising:
(1) Preparation of composite master batches: respectively weighing a certain amount of flower-like graphene, a dispersing agent and a polypropylene resin material, uniformly mixing and stirring the three raw materials, adding the mixture into a double-screw extruder, setting the temperature of each section of the extruder, starting the extruder to extrude filaments, and then cooling, granulating and drying to obtain the composite master batch;
(2) And (3) melt-blowing process treatment: taking a certain amount of the composite master batch prepared in the step (1) and a polypropylene resin material, uniformly mixing the two materials, feeding the mixture into a melt-blowing device for melt-blowing spinning, leading a melt to a spinning component through a screw rod, and then spraying the melt to a spinneret plate, and drawing the melt by high-temperature high-speed airflow to prepare melt-blowing ultrafine fibers;
(3) And (3) carrying out electret treatment: and (3) winding the melt-blown superfine fiber prepared in the step (2), carrying out static electrode residence, slitting and winding to obtain the melt-blown product taking the flower-like graphene as the filler.
In the step (1), the mass ratio of the flower-like graphene, the dispersing agent and the polypropylene resin material is 0.01-10: 0.1-1:99.89-89; in the step 1, the extrusion temperature is 150-250 ℃.
The mass ratio of the composite master batch to the polypropylene resin in the step (2) is 0.1-10: 99.9 to 90; in the step (2), the extrusion temperature is 160-280 ℃ and the receiving distance is 7-25 cm.
A mask which adopts the melt-blown cloth.
The invention has the beneficial effects that: the flower-like graphene prepared by the method has the advantages that the flower-like graphene has a large number of curled aggregate structures inside, so that the content of functional groups on the surface of the graphene is low, the graphene is high in hydrophobicity, aggregation of molecules in the breathing process can be effectively avoided, meanwhile, the flower-like graphene can physically damage bacteria by utilizing sharp edges of the flower-like graphene, phospholipid in cell membranes of the flower-like graphene is extracted to damage the integrity of the flower-like graphene, and finally cytoplasm flows out; graphene can also generate reactive oxygen species, thereby inducing oxidative stress, causing destruction of microbial activity by oxidizing cellular structures or components. Therefore, the melt-blown cloth containing the flower-shaped graphene has the characteristics of high filtering performance, good air permeability, excellent antibacterial and bacteriostatic properties, long service life and the like, and the stretch resistance of the melt-blown cloth added with the graphene is improved, which means that the graphene melt-blown cloth is stronger, and correspondingly, the manufactured mask is stronger and durable, so that the comprehensive performance is superior to that of the common melt-blown cloth and the conventional graphene melt-blown cloth. In addition, the preparation process of the melt-blown cloth adopting the flower-shaped graphene is simple, the mass production can be realized, the cost is low, and the manufactured mask has extremely high practical application value in a quite certain period of time after epidemic situation or even epidemic situation.
Drawings
FIG. 1 is a schematic diagram of the preparation electrolysis of flower-like graphene according to the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of flower-like graphene prepared in example 1;
fig. 3 is a Transmission Electron Microscope (TEM) picture of the flower-like graphene prepared in example 2.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) A high-purity graphite rod is adopted as an anode, and a platinum electrode is adopted as a cathode; an aqueous KOH/H 2O2 solution was prepared as an electrolyte, wherein the concentration of KOH was 5M and the concentration of H 2O2 was 20mM.
(2) Referring to fig. 1, a high purity graphite rod and a platinum electrode are placed in an electrolytic cell, the electrode spacing is adjusted to be 5cm, the high purity graphite rod and the platinum electrode are immersed in electrolyte, a lead is used for connecting the high purity graphite rod and the platinum electrode with a direct current power supply, an anode is connected with the positive electrode of the direct current power supply, a cathode is connected with the negative electrode of the direct current power supply, and after the direct current voltage is applied to the direct current power supply for 15V, electrolytic reaction is performed at room temperature; after the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(3) The cleaned black powder was dried in a drying oven to obtain flower-like graphene, please refer to fig. 2, which is a Transmission Electron Microscope (TEM) picture of the flower-like graphene prepared in this example, and from the figure, it can be seen that the prepared graphene was rolled into a rose shape with a size of about 100 nm. The flower-like graphene is formed by curling 10 layers of ultrathin two-dimensional nano materials with the thickness not exceeding 1nm, has less surface functional group content and high hydrophobicity, can effectively avoid aggregation of molecules in the breathing process, has sharp edges, can be used for physically damaging bacteria, and can extract phospholipid in cell membranes to damage the integrity of the bacteria, so that cytoplasm can flow out, and the flower-like graphene has good antibacterial property.
(4) Weighing flower-like graphene, a dispersing agent and a polypropylene resin material according to the mass ratio of 0.01: and (3) mixing and stirring uniformly, adding the mixture into a double-screw extruder, setting the temperature of each interval of the extruder to be 150 ℃, starting the extruder to extrude the strand silk, and then cooling, granulating and drying to obtain the composite master batch.
(5) Uniformly mixing the composite master batch and the polypropylene resin material according to the mass ratio of 2:98, feeding the mixture into melt-blowing equipment for melt-blowing spinning, leading the melt to a spinning component through a screw rod, then leading the melt to a spinneret plate for spraying, and preparing melt-blowing ultrafine fibers after high-temperature high-speed airflow traction;
(6) And (3) winding, electrostatic electret, slitting and rolling the melt-blown superfine fiber to obtain the melt-blown cloth taking the flower-like graphene as the filler.
Example 2
(1) A high-purity graphite rod is adopted as an anode, and a platinum electrode is adopted as a cathode; an aqueous KOH/H 2O2 solution was prepared as an electrolyte, wherein the concentration of KOH was 5M and the concentration of H 2O2 was 20mM.
(2) Placing a high-purity graphite rod and a platinum electrode into an electrolytic cell, adjusting the electrode spacing to be 6cm, immersing the high-purity graphite rod and the platinum electrode into electrolyte, connecting the high-purity graphite rod and the platinum electrode with a direct current power supply by using a lead, connecting an anode with the positive electrode of the direct current power supply, connecting a cathode with the negative electrode of the direct current power supply, and carrying out electrolytic reaction at room temperature after the direct current voltage of 15V is applied by the direct current power supply; after the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(3) The black powder after cleaning was dried in a drying oven to obtain flower-like graphene, please refer to fig. 3, which is a Transmission Electron Microscope (TEM) picture of the flower-like graphene prepared in this example, and its shape and structure are similar to those of example 1, and its size is also similar, which indicates that the product stability of the method of the present invention is better, the manufacturability is better, and the quality is better.
(4) Weighing flower-like graphene, a dispersing agent and a polypropylene resin material according to the mass ratio of 0.01: and (3) mixing and stirring uniformly, adding the mixture into a double-screw extruder, setting the temperature of each interval of the extruder to be 150 ℃, starting the extruder to extrude the strand silk, and then cooling, granulating and drying to obtain the composite master batch.
(5) Uniformly mixing the composite master batch and the polypropylene resin material according to the mass ratio of 2:98, feeding the mixture into melt-blowing equipment for melt-blowing spinning, leading the melt to a spinning component through a screw rod, then leading the melt to a spinneret plate for spraying, and preparing melt-blowing ultrafine fibers after high-temperature high-speed airflow traction;
(6) And (3) winding, electrostatic electret, slitting and rolling the melt-blown superfine fiber to obtain the melt-blown cloth taking the flower-like graphene as the filler.
Example 3
(1) A high-purity graphite rod is adopted as an anode, and a platinum electrode is adopted as a cathode; an aqueous KOH/H 2O2 solution was prepared as an electrolyte, wherein the concentration of KOH was 10M and the concentration of H 2O2 was 100mM.
(2) Placing a high-purity graphite rod and a platinum electrode into an electrolytic cell, adjusting the electrode spacing to be 5cm, immersing the high-purity graphite rod and the platinum electrode into electrolyte, connecting the high-purity graphite rod and the platinum electrode with a direct current power supply by using a lead, connecting an anode with the positive electrode of the direct current power supply, connecting a cathode with the negative electrode of the direct current power supply, and carrying out electrolytic reaction at room temperature after the direct current voltage of 15V is applied by the direct current power supply; after the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(3) And drying the cleaned black powder in a drying oven to obtain the flower-like graphene.
(4) Weighing flower-like graphene, a dispersing agent and a polypropylene resin material according to the mass ratio of 0.01: and (3) mixing and stirring uniformly, adding the mixture into a double-screw extruder, setting the temperature of each interval of the extruder to be 150 ℃, starting the extruder to extrude the strand silk, and then cooling, granulating and drying to obtain the composite master batch.
(5) Uniformly mixing the composite master batch and the polypropylene resin material according to the mass ratio of 2:98, feeding the mixture into melt-blowing equipment for melt-blowing spinning, leading the melt to a spinning component through a screw rod, then leading the melt to a spinneret plate for spraying, and preparing melt-blowing ultrafine fibers after high-temperature high-speed airflow traction;
(6) And (3) winding, electrostatic electret, slitting and rolling the melt-blown superfine fiber to obtain the melt-blown cloth taking the flower-like graphene as the filler.
Example 4
(1) A high-purity graphite rod is adopted as an anode, and a platinum electrode is adopted as a cathode; an aqueous KOH/H 2O2 solution was prepared as an electrolyte, wherein the concentration of KOH was 5M and the concentration of H 2O2 was 20mM.
(2) Placing a high-purity graphite rod and a platinum electrode into an electrolytic cell, adjusting the electrode spacing to be 5cm, immersing the high-purity graphite rod and the platinum electrode into electrolyte, connecting the high-purity graphite rod and the platinum electrode with a direct current power supply by using a lead, connecting an anode with the positive electrode of the direct current power supply, connecting a cathode with the negative electrode of the direct current power supply, and carrying out electrolytic reaction at room temperature after the direct current voltage of 15V is applied by the direct current power supply; after the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(3) And drying the cleaned black powder in a drying oven to obtain the flower-like graphene.
(4) And weighing flower-like graphene, a dispersing agent and a polypropylene resin material according to a mass ratio of 1:1:98, uniformly mixing and stirring, adding into a double-screw extruder, setting the temperature of each section of the extruder to be 150 ℃, starting the extruder to extrude the strand silk, and then cooling, granulating and drying to obtain the composite master batch.
(5) Uniformly mixing the composite master batch and the polypropylene resin material according to the mass ratio of 5:95, feeding the mixture into melt-blowing equipment for melt-blowing spinning, leading the melt to a spinning component through a screw rod, then spraying the melt to a spinneret plate, and drawing the melt by high-temperature high-speed airflow to prepare melt-blowing ultrafine fibers;
(6) And (3) winding, electrostatic electret, slitting and rolling the melt-blown superfine fiber to obtain the melt-blown cloth taking the flower-like graphene as the filler.
Example 5
(1) A high-purity graphite rod is adopted as an anode, and a platinum electrode is adopted as a cathode; an aqueous KOH/H 2O2 solution was prepared as an electrolyte, wherein the concentration of KOH was 5M and the concentration of H 2O2 was 20mM.
(2) Placing a high-purity graphite rod and a platinum electrode into an electrolytic cell, adjusting the electrode spacing to be 5cm, immersing the high-purity graphite rod and the platinum electrode into electrolyte, connecting the high-purity graphite rod and the platinum electrode with a direct current power supply by using a lead, connecting an anode with the positive electrode of the direct current power supply, connecting a cathode with the negative electrode of the direct current power supply, and carrying out electrolytic reaction at room temperature after the direct current voltage of 15V is applied by the direct current power supply; after the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(3) And drying the cleaned black powder in a drying oven to obtain the flower-like graphene.
(4) And weighing flower-like graphene, a dispersing agent and a polypropylene resin material according to a mass ratio of 1:1:98, uniformly mixing and stirring, adding into a double-screw extruder, setting the temperature of each section of the extruder to be 150 ℃, starting the extruder to extrude the strand silk, and then cooling, granulating and drying to obtain the composite master batch.
(5) Uniformly mixing the composite master batch and the polypropylene resin material according to the mass ratio of 10:90, feeding the mixture into melt-blowing equipment for melt-blowing spinning, leading the melt to a spinning component through a screw rod, then spraying the melt to a spinneret plate, and drawing the melt by high-temperature high-speed airflow to prepare melt-blowing ultrafine fibers;
(6) And (3) winding, electrostatic electret, slitting and rolling the melt-blown superfine fiber to obtain the melt-blown cloth taking the flower-like graphene as the filler.
Comparative example 1
(1) Feeding polypropylene resin material into melt-blowing equipment for melt-blowing spinning, and making melt into melt-blown superfine fiber after the melt is fed into a spinning component through a screw rod and then sprayed out by a spinneret plate and drawn by high-temperature high-speed air flow;
(2) And (5) winding, electrostatic electret, slitting and rolling the melt-blown superfine fibers to obtain the melt-blown fabric.
TABLE 1 melt-blown properties with flower-like graphene added
Note that: the particulate matter filtration efficiency and pressure difference were tested according to standard YY 0469-2011. The antibacterial rate was tested according to standard GB/T20944.3-2008.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (11)
1. The flower-shaped graphene is characterized by being composed of a plurality of mutually independent graphene aggregates, wherein the graphene aggregates are formed by curling single-layer or multi-layer ultrathin two-dimensional nano materials, and the size of each graphene aggregate is between 50 and 200 nm;
The graphene aggregate single structure body is provided with a reel center, and is curled by a strip-shaped ultrathin two-dimensional nano material around the reel center to form a flower-shaped structure.
2. The flower-like graphene of claim 1, wherein the number of graphene agglomerate crimping layers is between 2 and 20.
3. A method for preparing the flower-like graphene according to claim 1 or 2, comprising the steps of:
(1) A graphite rod is adopted as an anode, and a metal electrode is adopted as a cathode;
(2) Preparing KOH/H 2O2 water solution as electrolyte;
(3) The graphite rod and the metal electrode are used as electrodes of an electrolytic cell, the electrodes are placed in the electrolytic cell, the positions of the electrodes are adjusted, the electrodes are immersed in electrolyte, the graphite rod and the metal electrode are connected with a direct current power supply through wires, the anode is connected with the positive electrode of the direct current power supply, the cathode is connected with the negative electrode of the direct current power supply, and electrolytic reaction is carried out after the direct current voltage is applied by the direct current power supply;
(4) In the electrolysis process, bubbles are continuously generated on the anode graphite rod, and the color of the electrolyte is changed from colorless to black;
(5) After the electrolysis is completed, filtering the electrolyte to obtain a black product, and cleaning the black product by using distilled water;
(6) And drying the cleaned black powder to obtain the flower-like graphene.
4. The method for producing a flower-like graphene according to claim 3, wherein the concentration of KOH in the step (2) is 0.1M to 10M and the concentration of H 2O2 is 10mM to 1M.
5. The method for preparing flower-like graphene according to claim 3, wherein the graphite rod in the step (3) has a purity of not less than 99.9%, the metal electrode is a platinum electrode, and the distance between the cathode and the anode is 3-10 cm.
6. The method for preparing flower-like graphene according to claim 3, wherein the direct current voltage in the step (3) is 0.1 to 20V, and the temperature of the electrolysis reaction system is not higher than 50 ℃.
7. A meltblown fabric, characterized in that the meltblown fiber contains the flower-like graphene according to claim 1 or 2, and the mass content of the flower-like graphene in the meltblown fiber is 0.001% -1%.
8. A method of making the meltblown web according to claim 7, characterized by the process of:
(1) Preparation of composite master batches: respectively weighing a certain amount of flower-like graphene, a dispersing agent and a polypropylene resin material, uniformly mixing and stirring the three raw materials, adding the mixture into a double-screw extruder, setting the temperature of each section of the extruder, starting the extruder to extrude filaments, and then cooling, granulating and drying to obtain the composite master batch;
(2) And (3) melt-blowing process treatment: taking a certain amount of the composite master batch prepared in the step (1) and a polypropylene resin material, uniformly mixing the two materials, feeding the mixture into a melt-blowing device for melt-blowing spinning, leading a melt to a spinning component through a screw rod, and then spraying the melt to a spinneret plate, and drawing the melt by high-temperature high-speed airflow to prepare melt-blowing ultrafine fibers;
(3) And (3) carrying out electret treatment: and (3) winding the melt-blown superfine fiber prepared in the step (2), carrying out electrostatic electret, slitting and winding to obtain the melt-blown product taking the flower-shaped graphene as a filler.
9. A method of making a meltblown web according to claim 8, wherein: in the step (1), the mass ratio of the flower-like graphene, the dispersing agent and the polypropylene resin material is 0.01-10: 0.1-1:99.89-89; in the step (1), the temperature of each section of the extruder is 150-250 ℃.
10. A method of making a meltblown web according to claim 8, wherein: the mass ratio of the composite master batch to the polypropylene resin in the step (2) is 0.1-10: 99.9 to 90.
11. A mask employing the meltblown web of claim 7.
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