CN106621563A - Gelatin/polyetherimide compound electret fiber filtration material prepared through electrostatic spinning and preparation method thereof - Google Patents
Gelatin/polyetherimide compound electret fiber filtration material prepared through electrostatic spinning and preparation method thereof Download PDFInfo
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- CN106621563A CN106621563A CN201610998783.6A CN201610998783A CN106621563A CN 106621563 A CN106621563 A CN 106621563A CN 201610998783 A CN201610998783 A CN 201610998783A CN 106621563 A CN106621563 A CN 106621563A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0028—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions provided with antibacterial or antifungal means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/0216—Bicomponent or multicomponent fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Filtering Materials (AREA)
- Multicomponent Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a gelatin/polyetherimide compound electret fiber filtration material prepared through electrostatic spinning. The gelatin/polyetherimide compound electret fiber filtration material is prepared from, by weight, 65-80 parts of polyetherimide, 10-18 parts of gelatin, 6-11 parts of silicon oxide, 9-16 parts of powdery activated carbon, 1-3 parts of 3-aminopropyl triethoxy silane coupling agent, 0.8-2 parts of glacial acetic acid, a proper amount of ionized water, 3-6 parts of metatitanic acid, 0.6 mol/L AgNO3 solution, a proper amount of N-methylpyrrolidone and 0.8-2 parts of acetic acid. Alpha-quartz-containing silicon nanowires are prepared by adopting the material, the gelatin/polyetherimide compound electret fiber filtration material is prepared through an electrostatic spinning technology and has excellent charge storage stability, and the filtering efficiency of the filtration material is greatly improved. In addition, nano silver is added and nano titanium dioxide is loaded to improve the antimicrobial persistence performance of the filtration material and to achieve a long-term and efficient filtration effect.
Description
Technical field
The invention belongs to field of air filtration, and in particular to a kind of electro-spinning is for the compound electret of gelatin/PEI
Body fiber filter material and preparation method thereof.
Technical background
With going deep into and fast-developing for process of industrialization, the dust granules thing being discharged in air is sharply increased, wherein
PM2.5（Particulate pollutant of the particle diameter less than 2.5 m）The health of the mankind can be caused serious injury, it is inhaled into meeting after human body
Bronchus is directly entered, causes the diseases such as asthma, bronchitis, pneumoconiosis and cardiovascular disease, this is to cause China's patients with lung cancer urgency
Increase severely the one of the main reasons for adding.Therefore air filter unit becomes study hotspot, the research of its core filtering material and opens
Send out to be even more and become the most important thing.
Through electret process, electric charge makes it have higher filtration effect to traditional melt-blown non-woven electret material in surface band
Rate, but its charge stability is easily affected by environment, and charge decay rate is very fast, filter efficiency declines to a great extent therewith.Additionally, staying
Pole process also increased to a certain extent production cost as a necessary aftertreatment technology.
Electrostatic spinning process needs to apply high pressure, the inorganic electret of excellent performance is added in spinning solution, by quiet
Electrospun, makes fiber and inorganic electret all take electric charge, and using Electrostatic Absorption Static Spinning/electret bluk recombination can be greatly enhanced
The filter efficiency of tunica fibrosa, and resistance pressure drop is reduced, PM2.5 can effectively be protected.
Li little Qi, high crystalline substance pair et al. exist《Electret PEI-silica nano fibrous membrane answering in air filtration
With》Electrostatic spinning technique is adopted in one text, first with PEI（PEI）For raw material, the PEI for preparing variable concentrations is molten
The electrets such as liquid, addition silica, silicon nitride, barium titanate, the addition of electret makes big quantity space on electrostatic spinning fiber film band
Electric charge so as to which filter efficiency is greatly improved.
The present invention is added to silicon nanowires as inorganic electret in PEI spinning solution, prepares PEI
Composite fibre filtering material, adds the antimicrobial form that Ag-carried nanometer titanium dioxide improves composite fibre filtering material, improves electret
The strainability of filtering material.
The content of the invention
Not enough for prior art, it is fine for gelatin/PEI composite electret that the present invention provides a kind of electro-spinning
Dimensional filter material and preparation method thereof.
A kind of electro-spinning for gelatin/PEI composite electret fiber filtering material, by the original of following weight portion
Material component：PEI 65-80 parts, gelatin 10-18 parts, silicon monoxide 6-11 parts, Powdered Activated Carbon 9-16 parts, 3- aminopropyls
Triethoxysilane coupling agent 1-3 parts, glacial acetic acid 0.8-2 parts, appropriate deionized water, metatitanic acid 3-6 parts, 0.6mol/L's
AgNO3Appropriate solution, appropriate 1-METHYLPYRROLIDONE, acetic acid 0.8-2 parts.
Comprise the following steps that：
（1）The preparation of Ag-carried nanometer titanium dioxide：
Metatitanic acid is added in deionized water, in 0.4-0.7mol/L, be heated to 105-125 DEG C maintains it to control solution concentration
, there is hydrolysis and generate white metatitanic acid precipitation in boiling, centrifugal filtration, wash into precipitation and no longer detect SO4 2-Ion, leaching
AgNO of the stain in 0.6mol/L3In solution, 1-2 hours are calcined at 460-490 DEG C after drying at 70-90 DEG C, obtain carrying silver
Nano titanium oxide；
（2）The preparation of silicon nanowires：
The little porcelain boat that will be equipped with silicon monoxide powder is placed horizontally in the middle of alumina tube, then the pipe is placed on into high temperature process furnances
In, vacuumize in 80-100Pa, then temperature is increased to respectively 100-200,800-1100 DEG C and 50-70 is incubated respectively and is divided
Clock, is warmed up to afterwards 1300-1400 DEG C of insulation 3-5 hour；Cool to 550-650 DEG C with the speed of 1-3 DEG C/min afterwards and protect
Warm 20-40 minutes, while blasting air to furnace chamber with 50sccm, room temperature is naturally cooled to, obtain silicon nanowires, it is standby；
（3）The preparation of activated carbon supported silicon nanowires：
1., 3- aminopropyl triethoxysilane coupling agents are added to into deionized water, and pH to 4 is adjusted with a small amount of glacial acetic acid,
Stir 20-40 minutes under room temperature, step is added afterwards（1）The silicon nanowires for obtaining is little in 80-100 DEG C of back flow reaction 11-13
When, suction filtration, washing, drying obtain silicon amide nanowire composite；
2., the silicon amide nanowire composite for obtaining, Powdered Activated Carbon are added to into deionized water, with ultrasonic wave 40 DEG C,
20-40 minutes are mixed under conditions of 150W, static aging 24 hours under room temperature, during deionized water cleaning is in repeatedly to efflux
Property, 110-120 DEG C of drying 10-14 hour is to constant weight, then is placed in 380-420 DEG C of roasting 3-5 hour in Muffle furnace, cools down, is dried,
Activated carbon supported silicon nanowires is obtained；
（4）The preparation of spinning solution：
1., by step（1）Obtain Ag-carried nanometer titanium dioxide, step（3）Activated carbon supported silicon nanowires is obtained and adds N- methyl
In pyrrolidones, ultrasound 1-3 hours in ultrasonic cleaner are placed on, are set to solution A；
2., at ambient temperature, by PEI and 1-METHYLPYRROLIDONE with 1:3-4 ratio mixing, add gelatin after
It is continuous to stir to being well mixed, add acetic acid to stir to transparent afterwards, use ParafilmTM bottleneck, be placed in oil bath 55-65 DEG C plus
Hot 18-22 hours, are set to solution B, are placed on magnetic stirring apparatus and stir, and are slowly added to above-mentioned solution A, continue to stir 7-9 hours,
It is configured to the spinning solution of good fluidity；
（5）Above-mentioned spinning solution is carried out into electrostatic spinning, electrostatic spinning nano fiber electret filtering material is obtained.
Wherein, described electrostatic spinning process parameter is：Voltage is 1-50KV, and syringe needle is 0.1- to template distance is received
2m, spinnerette diameters are 1 μm of -2mm, and spinning speed is 0.1-20mL/h, and the spinning time is 8-10 hours, and environment temperature is 20-
60 DEG C, envionmental humidity is 20-80%.
Compared with prior art, the present invention has advantages below：
（1）The present invention prepares the silicon nanowires containing alpha-quartz, because the volumetric expansion in alpha-quartz forming process is by outer layer
Amorphous silica limit and make alpha-quartz generate piezo-electric effect, while by the electric charge of generation be stored in outer layer have it is good
In the amorphous silica layer of good electric charge storge quality, so as to show good electret behavior, by electrostatic spinning skill
The step of art one prepares Static Spinning/electret composite fibre filtering material, have that aperture is little, porosity is high when PM2.5 particles are purified,
The advantages of low-drag, and with excellent Charge Storage Stability energy, greatly improve the filter efficiency of filter material.
（2）Activated carbon has the chemical functional group of abundant pore structure and uniqueness, is environmentally friendly superior adsorbent,
The present invention improves load of the activated carbon to silicon nanowires using the activated carbon supported silicon nanowires Jing after silane coupler process
Amount, both compounding uses improve absorption of the filter material to harmful substance in air.
（3）Surface is carried out using Nano Silver loading nano titanium oxide to be modified, can expand to the utilization scope of light can
See light, the harmful substances such as the micronic dust in the air of filtering material Long-Term Sorption are decomposed in the realization under conditions of visible light catalytic, and
And the microorganism such as bacterium, virus for growing on filtering materials is decomposed in both collaborations, improves self-cleaning performance, the antibacterial of filtering material
Enduring quality, reaches long-term efficient filter effect.
（4）The fibre diameter of the prepared gelatin/PEI composite nano fiber of the present invention is little, with excellent obstruct,
Strainability and good mechanical property.Phase just can be fast and efficiently solved by adding a small amount of cheap acetic acid in solution
Separation problem, and the acetic acid for being added can quickly volatilize in spinning process, not affect the chemical constitution of fiber composition material
And performance.
Specific embodiment
A kind of electro-spinning for gelatin/PEI composite electret fiber filtering material, by the original of following weight portion
Material component：PEI 75, gelatin 16, silicon monoxide 8, Powdered Activated Carbon 13,3- aminopropyl triethoxysilane coupling agents
2, glacial acetic acid 1.5, appropriate deionized water, metatitanic acid 5, the AgNO of 0.6mol/L3Appropriate solution, appropriate 1-METHYLPYRROLIDONE,
Acetic acid 1.
Comprise the following steps that：
（1）The preparation of Ag-carried nanometer titanium dioxide：
Metatitanic acid is added in deionized water, in 0.6mol/L, be heated to 115 DEG C makes it maintain boiling to control solution concentration, sends out
Raw hydrolysis generates white metatitanic acid precipitation, centrifugal filtration, washs into precipitation and no longer detects SO4 2-Ion, is immersed in
The AgNO of 0.6mol/L3In solution, calcine 1 hour at 480 DEG C after drying at 80 DEG C, obtain Ag-carried nanometer titanium dioxide；
（2）The preparation of silicon nanowires：
The little porcelain boat that will be equipped with silicon monoxide powder is placed horizontally in the middle of alumina tube, then the pipe is placed on into high temperature process furnances
In, vacuumize in 90Pa, then temperature is increased to respectively 200,900 DEG C and 60 minutes is incubated respectively, 1350 are warmed up to afterwards
DEG C insulation 4 hours；Cool to 600 DEG C with the speed of 2 DEG C/min afterwards and be incubated 30 minutes, while blast air with 50sccm arriving
Furnace chamber, naturally cools to room temperature, obtains silicon nanowires, standby；
（3）The preparation of activated carbon supported silicon nanowires：
1., 3- aminopropyl triethoxysilane coupling agents are added to into deionized water, and pH to 4 is adjusted with a small amount of glacial acetic acid,
Stir 30 minutes under room temperature, step is added afterwards（1）The silicon nanowires for obtaining, in 95 DEG C of back flow reactions 12 hours, suction filtration, washes
Wash, be dried, obtain silicon amide nanowire composite；
2., the silicon amide nanowire composite for obtaining, Powdered Activated Carbon are added to into deionized water, with ultrasonic wave 40 DEG C,
Mix 30 minutes under conditions of 150W, static aging 24 hours under room temperature, deionized water cleaning is in repeatedly neutrality to efflux,
115 DEG C of drying 12 hours are to constant weight, then are placed in Muffle furnace 400 DEG C of roastings 4 hours, cooling, are dried, and activated carbon supported silicon is obtained
Nano wire；
（4）The preparation of spinning solution：
1., by step（1）Obtain Ag-carried nanometer titanium dioxide, step（3）Activated carbon supported silicon nanowires is obtained and adds N- methyl
In pyrrolidones, ultrasound 2 hours in ultrasonic cleaner are placed on, are set to solution A；
2., at ambient temperature, by PEI and 1-METHYLPYRROLIDONE with 1:4 ratio mixing, adds gelatin to continue
Stir to being well mixed, add acetic acid to stir to transparent afterwards, use ParafilmTM bottleneck, be placed on 60 DEG C of heating 20 in oil bath little
When, solution B is set to, it is placed on magnetic stirring apparatus and stirs, above-mentioned solution A is slowly added to, continue to stir 8 hours, it is configured to flowing
The good spinning solution of property；
（5）Above-mentioned spinning solution is carried out into electrostatic spinning, electrostatic spinning nano fiber electret filtering material is obtained.
Wherein, described electrostatic spinning process parameter is：Voltage is 12KV, and syringe needle is 20cm to template distance is received, and is sprayed
Silk a diameter of 0.5mm, spinning speed is 0.6mL/h, and the spinning time is 9 hours, and environment temperature is 25 DEG C, envionmental humidity
For 55%.
Properties of product test result：
Gas permeability：185.67L/m2S, porosity：>80%, pressure drag：<20Pa, can to the filter efficiency of 0.006-1 μm of particle
Up to more than 99.999%.
Claims (3)
1. a kind of electro-spinning is for gelatin/PEI composite electret fiber filtering material, it is characterised in that by following heavy
The raw material components of amount part：PEI 65-80 parts, gelatin 10-18 parts, silicon monoxide 6-11 parts, Powdered Activated Carbon 9-16 parts,
3- aminopropyl triethoxysilane coupling agent 1-3 parts, glacial acetic acid 0.8-2 parts, appropriate deionized water, metatitanic acid 3-6 parts,
The AgNO of 0.6mol/L3Appropriate solution, appropriate 1-METHYLPYRROLIDONE, acetic acid 0.8-2 parts.
2. a kind of electro-spinning according to claims 1 is for gelatin/PEI composite electret fiber filter material
The preparation method of material, it is characterised in that comprise the following steps that：
（1）The preparation of Ag-carried nanometer titanium dioxide：
Metatitanic acid is added in deionized water, in 0.4-0.7mol/L, be heated to 105-125 DEG C maintains it to control solution concentration
, there is hydrolysis and generate white metatitanic acid precipitation in boiling, centrifugal filtration, wash into precipitation and no longer detect SO4 2-Ion, leaching
AgNO of the stain in 0.6mol/L3In solution, 1-2 hours are calcined at 460-490 DEG C after drying at 70-90 DEG C, obtain carrying silver
Nano titanium oxide；
（2）The preparation of silicon nanowires：
The little porcelain boat that will be equipped with silicon monoxide powder is placed horizontally in the middle of alumina tube, then the pipe is placed on into high temperature process furnances
In, vacuumize in 80-100Pa, then temperature is increased to respectively 100-200,800-1100 DEG C and 50-70 is incubated respectively and is divided
Clock, is warmed up to afterwards 1300-1400 DEG C of insulation 3-5 hour；Cool to 550-650 DEG C with the speed of 1-3 DEG C/min afterwards and protect
Warm 20-40 minutes, while blasting air to furnace chamber with 50sccm, room temperature is naturally cooled to, obtain silicon nanowires, it is standby；
（3）The preparation of activated carbon supported silicon nanowires：
1., 3- aminopropyl triethoxysilane coupling agents are added to into deionized water, and pH to 4 is adjusted with a small amount of glacial acetic acid,
Stir 20-40 minutes under room temperature, step is added afterwards（1）The silicon nanowires for obtaining is little in 80-100 DEG C of back flow reaction 11-13
When, suction filtration, washing, drying obtain silicon amide nanowire composite；
2., the silicon amide nanowire composite for obtaining, Powdered Activated Carbon are added to into deionized water, with ultrasonic wave 40 DEG C,
20-40 minutes are mixed under conditions of 150W, static aging 24 hours under room temperature, during deionized water cleaning is in repeatedly to efflux
Property, 110-120 DEG C of drying 10-14 hour is to constant weight, then is placed in 380-420 DEG C of roasting 3-5 hour in Muffle furnace, cools down, is dried,
Activated carbon supported silicon nanowires is obtained；
（4）The preparation of spinning solution：
1., by step（1）Obtain Ag-carried nanometer titanium dioxide, step（3）Activated carbon supported silicon nanowires is obtained and adds N- methyl
In pyrrolidones, ultrasound 1-3 hours in ultrasonic cleaner are placed on, are set to solution A；
2., at ambient temperature, by PEI and 1-METHYLPYRROLIDONE with 1:3-4 ratio mixing, add gelatin after
It is continuous to stir to being well mixed, add acetic acid to stir to transparent afterwards, use ParafilmTM bottleneck, be placed in oil bath 55-65 DEG C plus
Hot 18-22 hours, are set to solution B, are placed on magnetic stirring apparatus and stir, and are slowly added to above-mentioned solution A, continue to stir 7-9 hours,
It is configured to the spinning solution of good fluidity；
（5）Above-mentioned spinning solution is carried out into electrostatic spinning, electrostatic spinning nano fiber electret filtering material is obtained.
3. a kind of electro-spinning according to claims 2 is for gelatin/PEI composite electret fiber filter material
The preparation method of material, it is characterised in that described electrostatic spinning process parameter is：Voltage is 1-50KV, and syringe needle is to reception template
Distance is 0.1-2m, and spinnerette diameters are 1 μm of -2mm, and spinning speed is 0.1-20mL/h, and the spinning time is 8-10 hours, environment
Temperature is 20-60 DEG C, and envionmental humidity is 20-80%.
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| CN201610998783.6A CN106621563A (en) | 2016-11-14 | 2016-11-14 | Gelatin/polyetherimide compound electret fiber filtration material prepared through electrostatic spinning and preparation method thereof |
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| CN201610998783.6A CN106621563A (en) | 2016-11-14 | 2016-11-14 | Gelatin/polyetherimide compound electret fiber filtration material prepared through electrostatic spinning and preparation method thereof |
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Cited By (2)
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| CN111139594A (en) * | 2020-03-11 | 2020-05-12 | 昆明理工大学 | Preparation method of composite porous material for bone repair |
| CN113068903A (en) * | 2021-03-26 | 2021-07-06 | 莆田市协诚鞋业有限公司 | Antifouling and antibacterial upper material and preparation method thereof |
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| CN105920919A (en) * | 2016-05-17 | 2016-09-07 | 华南理工大学 | Preparation and activation methods for super-hydrophobic electret filter material for purifying PM2.5 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139594A (en) * | 2020-03-11 | 2020-05-12 | 昆明理工大学 | Preparation method of composite porous material for bone repair |
| CN113068903A (en) * | 2021-03-26 | 2021-07-06 | 莆田市协诚鞋业有限公司 | Antifouling and antibacterial upper material and preparation method thereof |
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Application publication date: 20170510 |