CN106178974A - A kind of nano modification enhancement type hollow fiber film and preparation method thereof - Google Patents
A kind of nano modification enhancement type hollow fiber film and preparation method thereof Download PDFInfo
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- CN106178974A CN106178974A CN201610708136.7A CN201610708136A CN106178974A CN 106178974 A CN106178974 A CN 106178974A CN 201610708136 A CN201610708136 A CN 201610708136A CN 106178974 A CN106178974 A CN 106178974A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to a kind of high flux, resistant to pollution reinforced type polyvinylidene fluoride hollow fiber film and preparation method thereof, described hollow-fibre membrane has hollow pipe and stratum disjunctum, described hollow pipe is through nano-titanium dioxide modified hollow fiber conduit, and described stratum disjunctum comprises the Kynoar of 10 20 weight portions, the solvent of 50 80 weight portions and the porogen of 5 30 weight portions；Stratum disjunctum is positioned at the surface of hollow pipe；In preparation, in hollow fiber conduit surface-coated after feed liquid, during entering coagulating bath, the butyl titanate of its surface graft modification starts hydrolysis, the hydrophilic nano titanium dioxide granule that hydrolysis obtains, to film surface migration, enhances the adhesive force between film layer and hollow pipe.In transition process, contributing to through membrane pore structure, improve membrane flux, make fenestra evenly simultaneously, porosity improves, and hydrophilic and anti-fouling performance improve, and this method of modifying is simple to operate, and production cost is relatively low, promotes the use of the most on a large scale.
Description
[technical field]
The invention belongs to membrane material and manufacture field, relate to a kind of high flux, resistant to pollution enhancement type polyvinylidene fluoride hollow
Fibrous membrane and preparation method thereof.
[background technology]
In water technology application, increasing consideration uses high-precision membrane separation technique, and membrane separation technique has often
The lower operation of temperature, without phase-state change, energy-efficient, the most do not produce the features such as pollution, at drink water purifying, Industry Waste
The aspects such as water processes, and food, water for beverages purify, degerming, and bioactive substance reclaims, refined are used widely.But it is actual
During use, film strength and resistance tocrocking are most important indexs, and particularly, hollow-fibre membrane is relatively thin due to film silk, intensity
Poor, due to the disturbance of aeration in MBR waste water processes, the phenomenon of fracture of wire often occurs, causes deteriorating water quality；Simultaneously because film
The hydrophobic property of material itself, causes fenestra and the pollution on film surface during use, makes permeability rate decline, cause membrane lifetime to subtract
Little, operating cost increases, and in order to expand the application of film, controls fouling membrane and has become the Main way of research.
For the issue of improvement of film silk intensity, use Thermal inactive, fusion drawn and liner enhancing etc. all around this side
Face is launched, and above technology all can be substantially improved film strength.In recent years, patent CN102219969A " Kynoar-polyether sulfone
Blend hollow fiber membrane and Thermal inactive preparation method " etc. all be use thermic phase method improve film silk intensity；Fusion drawn skill
Art is limited and be difficult to be widely used in sewage disposal due to membrane material kind；United States Patent (USP) US5472607 discloses one
Liner PVDF hollow-fibre membrane, but this kind of film hydrophilic is poor, easily pollutes, and the adhesive force between film layer and liner is poor.
At the doping of film hydrophilically modified aspect main organic/inorganic nano particle, the modification of organic polymer bulk graft and hydrophilic
Material is blended, wherein nano-TiO2Owing to having good chemical stability, chemical resistance, uvioresistant ability and huge
Specific surface area be widely used in the modification of membrane material.But owing to the surface of nano material can be high, it be susceptible to reunite, be formed
Offspring, is difficult to the shortcoming such as infiltration and dispersion stabilization difference, it is impossible to show gratifying effect in organic facies.China
Application for a patent for invention CN102091540A " sulfonated polyether sulfone/TiO2Nano combined ultrafiltration membrane preparation method " by self assembly mode
Hydrophilic nano titanium dioxide is firmly attached to sulfonated polyether sulfone film surface, obtains that there is hydrophilic nano combined ultrafiltration
Film, but it still has deficiency in terms of hydrophilic and permeability；Further for Pvdf Microporous Hollow Fiber Membrane, as existing skill
Chinese invention patent application CN201310309928.0 of art discloses Kynoar, composite thinning agent and amphipathic polymerization
Thing engrafted nanometer oxide particle is blended preparation casting solution, so prepares hydrophilia polyvinylidene fluoride hollow fiber membrane；
CN201210552806.2 discloses a kind of Kynoar/Pd nano particle hydridization hollow-fibre membrane, be the most also prepare poly-
Compound gel/Pd nano particle hybrid dispersion liquid, i.e. prior art prepares corresponding hollow at modified this kind of Kynoar
During fibrous membrane, being all to be mixed with nano-particle by Kynoar, solution causes uneven, the nano-particle skewness of mixing
Problem, and then the hydrophilic of the hollow-fibre membrane of final impact and permeability.
The method of the present invention abandons the existing technology direct for nano-particle and Kynoar casting solution being blended, but will
Hydrolyzable is that the organic polymer of nano-particle is grafted on hollow pipe surface so that it is utilize dimethyl methyl during surface coating
The organic base effect of amide is hydrolyzed, thus avoids the problem that nano-particle is easily reunited.Between reinforcing membrane layer and hollow pipe
Adhesive force, and then the hollow-fibre membrane that prepared hydrophilic, permeability and contamination resistance are excellent.
[summary of the invention]
It is an object of the invention to overcome the Pvdf Microporous Hollow Fiber Membrane hydrophilic obtained by prior art and infiltration
Property not enough shortcoming, simultaneously in order to improve its contamination resistance, the hollow-fibre membrane especially for sewage disposal provides one
Plant reinforced type polyvinylidene fluoride hollow fiber film, and the preparation method of this Pvdf Microporous Hollow Fiber Membrane.
A kind of reinforced type polyvinylidene fluoride hollow fiber film, described hollow-fibre membrane is divided into hollow pipe and stratum disjunctum, described
Hollow pipe is through nano-titanium dioxide modified hollow fiber conduit；Described stratum disjunctum comprises the poly-inclined fluorine of 10-20 weight portion
Ethylene, the solvent of 50-80 weight portion and the porogen of 5-30 weight portion；Described stratum disjunctum is positioned at the surface of hollow pipe.
Described solvent is N, N dimethyl acetamide, dimethylformamide and N-Methyl pyrrolidone, dimethyl sulfoxide, phosphorus
In triethylenetetraminehexaacetic acid ester at least one or multiple；It is preferably N, N dimethyl acetamide；
Described porogen is polyvinylpyrrolidone, Polyethylene Glycol, diethylene glycol, ethylene glycol；It is preferably Polyethylene Glycol and gathers
The vinylpyrrolidone mixture with weight ratio as 5:6；
Preferably, described stratum disjunctum comprises the Kynoar of 18 weight portions, the N of 60 weight portions, N dimethyl acetamide,
The Polyethylene Glycol of 10 weight portions, the polyvinylpyrrolidone of 12 weight portions.
Described hollow pipe can also is that through nano silicon, cerium oxide or alumina modified macromolecule terylene fine
Dimension hollow pipe.
Further, the present invention relates to the preparation method of a kind of reinforced type polyvinylidene fluoride hollow fiber film, its feature exists
In, described preparation method comprises the steps:
Step one, the nano modification of hollow fiber conduit
(1) pretreatment: after hollow fiber conduit decocting in water, supersound washing in acetone solvent, subsequently baking oven is dried；
(2) hollow fiber conduit of 1-10 weight portion is placed in flask, subsequently by the third of initiator dibenzoyl peroxide
Ketone solution adds in flask, and the consumption of initiator is 0.5-3 weight % of hollow pipe；Mix homogeneously, puts into mixture subsequently
In 50-70 DEG C of water-bath, logical nitrogen protection, causes 15min in advance；Subsequently the butyl titanate of 1-10 weight portion is dissolved in deionized water
In, adding to after stirring in flask, under nitrogen is protected, react 20-80min, reaction takes out hollow pipe after terminating, and uses water logging
Bubble 5min, dissolution unreacted monomer, prepare the hollow pipe through preliminary nano modification；
Step 2, prepare enhancement type hollow fiber film
(1) hollow pipe that step one prepares is passed sequentially through coating device and gel groove, be then around on wire drawing wheel；
(2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and feed liquid is added in reactor, feed liquid
Consist of: the Kynoar of 10-20 weight portion, the solvent of 50-80 weight portion and the porogen of 5-30 weight portion；Then to instead
Answer in still and pressurize, make feed liquid lead to charge tube and carry to coating device；
(3) after above-mentioned hollow pipe coating feeding, coagulation bath is entered, about its a length of 2-10 rice, on hollow pipe outer surface
Feed liquid gel sizing, formed film silk, collection membrane silk；
(4) film silk is sheared and is bound, and puts into immersion 24h in tank, displaces solvent and additive (such as unreacted initiation
Agent, butyl titanate, porogen etc.)；It is subsequently dried process, prepares reinforced type polyvinylidene fluoride hollow fiber film.
Described hollow pipe is the hollow pipe made selected from nylon, dacron polyester or polyurethane fiber.
Preferably, the consumption of initiator is 1 weight % of hollow pipe；The consumption of initiator dibenzoyl peroxide is should
Control, but the concentration that dibenzoyl peroxide is in acetone soln is without impact reaction.
Preferably, in step one, the water-bath of (2nd) step is 60 DEG C.
Principle about the present invention: the first step is to be the organic polymer of nano material by hydrolyzable to the modification of hollow pipe
Tetrabutyl titanate ester is grafted on the hollow pipe of PET material, in case hydrolyzing dispersion in later stage film forming procedure uniformly.Meanwhile, right
Nano titanium oxide will be produced, therefore in the present invention after the preliminary nano modification of step one, butyl titanate hydrolysis itself
The first step is that hydrolyzable is become the organic polymer of nano-size titania to be grafted on PET material by the method utilizing glycerol polymerization
Hollow pipe surface, utilize the weak organic bases effect of dimethyl acetylamide to be hydrolyzed into nano titanium oxide in later stage film forming procedure
Granule, dispersed in film；The most existing document (Hybrid organic/inorganic Reverse osmosis (RO)
Membrane for bactericidal anti-fouling.1.preparation and characterization of
tio2nanopariticle self-assembled aromatic polyamide thin-film-composite(TFC)
Membrane.ENVIRON.SCI Technol 2001,35,2388-2394) in i.e. have similar collosol and gel hydrolytic process.
Compared with prior art, the invention have the benefit that the nano modification hollow pipe of the present invention, the present invention can water
Solve the organic polymer for nano-particle and be grafted on hollow pipe surface so that it is during surface coating, utilize dimethylformamide
Organic base effect be hydrolyzed, and in coagulating bath in film forming phase process, hydrophilic titanium dioxide nanoparticle is to film
Outer surface migrates, and can improve the hydrophilic on film surface, simultaneously because the addition of inorganic material makes film strength increase.Enhance
Adhesive force between film layer and hollow pipe.In transition process, contribute to through membrane pore structure, improve membrane flux, make film simultaneously
Evenly, porosity improves in hole, and hydrophilic and anti-fouling performance improve, and this method of modifying is simple to operate, and production cost is relatively low,
Suitably promote the use of on a large scale.Directly being mixed with nano-particle by Kynoar in compared to existing technology, the pure water at film leads to
In amount, the aspect such as doughnut film-strength be improved, finally make the hydrophilic of doughnut and permeability be improved.
[accompanying drawing explanation]
The nano modification liner of Fig. 1: the present invention strengthens the mechanism of modification figure of hollow-fibre membrane.
[detailed description of the invention]
Below in conjunction with the accompanying drawings and embodiment, the detailed description of the invention of invention is described in further detail.Following example
For the present invention is described, but it is not limited to the scope of the present invention.
Embodiment 1:
By hollow fiber conduit decocting in water 1h, taking-up is dried, and places into and uses supersound washing 30min in acetone solvent, to remove a good appetite suddenly appearing in a serious disease
The oil stain on blank pipe surface and other impurity, be finally putting in the baking oven of 80 DEG C drying, obtain the hollow fiber conduit of pretreatment.
The hollow fiber conduit of 5g pretreatment is placed in the there-necked flask of 500ml, and 0.05g initiator (BPO) is dissolved in
In 50ml acetone, it is subsequently adding in there-necked flask, mix homogeneously, puts it in 70 degree of water-baths, logical nitrogen protection, causes in advance
15min.5g butyl titanate is dissolved in 20ml deionized water, is rapidly added after stirring in there-necked flask, continue at nitrogen
Reacting 40min under gas shielded, reaction takes out hollow pipe after terminating, and be soaked in water 5min, dissolution unreacted monomer etc., naturally dries
Standby.
Take polyvinylidene fluoride resin: dimethylacetamide solvent: Polyethylene Glycol additive: polyvinylpyrrolidone additive
By weight 18:60:10:12 mix, use machine mixer to stir, then use the mode of negative pressure to take off
Bubble, the casting solution made after deaeration is positioned in batch can, 70 degree of insulations；It is the dimethyl acetylamide of 10:90 with mass ratio: water mixes
Bonding solvent is that coagulating bath is circulated, then according to following method prepares nano modification lining-reinforced hollow-fibre membrane:
1) the nona modified fiber hollow pipe pulled in fiber roller is passed sequentially through coating device and gel groove, be then around
On wire drawing wheel；
2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and the speed of the two is 15 ms/min, will
Casting solution adds in reactor, then pressurizes in reactor, makes casting solution lead to charge tube and carries to coating device；
3) modified fibre hollow pipe is under the traction receiving silk machine, enters coagulation bath after coating device coating feeding, in
Feed liquid generation immersion precipitation inversion of phases on blank pipe outer surface and gel sizing, lose flowability, form film silk, pass through wire drawing wheel
Collect.
4) a number of film silk will be collected and shear binding, put into immersion 24h in tank, thoroughly to displace solvent and to add
Add agent.
5) film is dried process, obtains described lining-reinforced hollow membrane.
Above-mentioned film is carried out following performance measurement:
1) the average of the obtained hollow-fibre membrane of solution-air and the double method of testing pore-size distribution analysis-e/or determining of liquid liquid is used
Aperture is 0.3 micron, and internal diameter is 1.0 millimeters, and external diameter is 2.0 millimeters.
2) the doughnut film-strength using universal tensile machine to measure is 150N.
3) use the described hollow-fibre membrane that flux detector measures under 0.1MPa pressure under 25 DEG C and 1 atmospheric pressure
Pure water flux is 3000L/m2.h。
4) the described hollow-fibre membrane contact angle size using dynamic contact angle analyzer to measure is 38 degree.
Embodiment 2
Except the addition of initiator is in addition to 0.1g, and remaining is with embodiment 1；
Test result be doughnut film-strength be 155N；Pure water flux is 2550L/m2.h；Contact angle size is 42.5
Degree.
Embodiment 3
Except the addition of initiator is in addition to 0.03g, and remaining is with embodiment 1；
Test result be doughnut film-strength be 160N；Pure water flux is 2410L/m2.h；Contact angle size is 45 degree.
Embodiment 4
Except the bath temperature in step one is 70 DEG C, remaining is with embodiment 1；
Test result be doughnut film-strength be 158N；Pure water flux is 2550L/m2.h；Contact angle size is 46 degree.
Embodiment 5
In addition to porogen uses the polyvinylpyrrolidone of same weight ratio and replaces polyvinylpyrrolidone and Polyethylene Glycol,
Remaining is with embodiment 1；
Test result be doughnut film-strength be 165N；Pure water flux is 2450L/m2.h；Contact angle size is 48 degree.
Embodiment 6
Except polyvinylidene fluoride resin: dimethylacetamide solvent: Polyethylene Glycol additive: polyvinylpyrrolidone weight ratio
Outside for 15:55:14:10, remaining is with embodiment 1；
Test result be doughnut film-strength be 170N；Pure water flux is 2150L/m2.h；Contact angle size is 56 degree.
As can be seen here, it is Polyethylene Glycol and the polyvinylpyrrolidone mixture with weight ratio as 5:6, separation when porogen
Each component of being comprised of layer is preferable amount ratio, and in 1 weight % that the consumption of initiator is hollow pipe and step one (2nd)
The water-bath of step be 60 DEG C be the application technical scheme in highly preferred scheme, obtained hollow-fibre membrane is in intensity, pure
Water flux and contact angle aspect best performance.
Comparative example 1
Except the consumption of initiator is 0.01g, remaining is with embodiment 1；
Test result be doughnut film-strength be 170N；Pure water flux is 2230L/m2.h；Contact angle size is 58 degree.
Comparative example 2
Except the consumption of initiator is 0.3g, remaining is with embodiment 1；
Test result be doughnut film-strength be 165N；Pure water flux is 2350L/m2.h；Contact angle size is 60 degree.
Comparative example 3
Except the bath temperature in step one is 45 DEG C, remaining is with embodiment 1；
Test result be doughnut film-strength be 169N；Pure water flux is 2250L/m2.h；Contact angle size is 50 degree.
Comparative example 4
Disclosed Kynoar, composite thinning agent and amphipathic nature polyalcohol grafting of CN201310309928.0 is used to receive
Rice oxide particle is blended preparation casting solution, prepares hydrophilia polyvinylidene fluoride hollow fiber membrane according to corresponding method；
Test result be doughnut film-strength be 140N；Pure water flux is 1850L/m2.h；Contact angle size is 68 degree.
Comparative example 5
Method disclosed in CN201210552806.2 is used to prepare Pvdf Microporous Hollow Fiber Membrane.
Test result be doughnut film-strength be 167N；Pure water flux is 1980L/m2.h；Contact angle size is 70 degree.
The above is only the preferred embodiments of the invention, it is noted that for the ordinary skill people of the art
For Yuan, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and modification, these improve and modification
Also should be regarded as protection scope of the present invention.
Claims (10)
1. a reinforced type polyvinylidene fluoride hollow fiber film, it is characterised in that described hollow-fibre membrane is divided into hollow pipe and divides
Absciss layer, described hollow pipe is through nano-titanium dioxide modified hollow fiber conduit；Described stratum disjunctum comprises 10-20 weight portion
Kynoar, the solvent of 50-80 weight portion and the porogen of 5-30 weight portion；Described stratum disjunctum is positioned at the table of hollow pipe
Face.
Hollow-fibre membrane the most according to claim 1, it is characterised in that described solvent is N, N dimethyl acetamide, diformazan
At least one in base Methanamide and N-Methyl pyrrolidone, dimethyl sulfoxide, triethyl phosphate or multi-solvents.
Hollow-fibre membrane the most according to claim 1, it is characterised in that described porogen is polyvinylpyrrolidone, gathers
Ethylene glycol, diethylene glycol and/or ethylene glycol.
Hollow-fibre membrane the most according to claim 3, it is characterised in that described porogen is Polyethylene Glycol and polyethylene pyrrole
The pyrrolidone mixture with weight ratio as 5:6.
Hollow-fibre membrane the most according to claim 1, it is characterised in that described stratum disjunctum comprises the poly-inclined fluorine of 18 weight portions
Ethylene, the N of 60 weight portions, N dimethyl acetamide, the Polyethylene Glycol of 10 weight portions, the polyvinylpyrrolidone of 12 weight portions.
Hollow-fibre membrane the most according to claim 1, it is characterised in that: described hollow fiber conduit gathers selected from nylon, terylene
The hollow pipe that ester or polyurethane fiber are made.
Hollow-fibre membrane the most according to claim 1, it is characterised in that described hollow pipe can be through nano-silica
SiClx, cerium oxide or alumina modified hollow fiber conduit.
8. the method preparing reinforced type polyvinylidene fluoride hollow fiber film as claimed in claim 1, it is characterised in that institute
State preparation method to comprise the steps:
Step one, the nano modification of hollow fiber conduit
(1) pretreatment: after hollow fiber conduit decocting in water, supersound washing in acetone solvent, subsequently baking oven is dried；
(2) being placed in flask by the hollow fiber conduit of 1-10 weight portion, the acetone by initiator dibenzoyl peroxide is molten subsequently
Liquid adds in flask, and the consumption of initiator is the 0.5-3% weight of hollow fiber conduit；Mix homogeneously, subsequently will be containing mixed liquor
Flask put in 50-70 DEG C of water-bath, logical nitrogen protection, cause 15min in advance；Butyl titanate by 1-10 weight portion is molten subsequently
In deionized water, adding in flask after stirring, react 20-80min under nitrogen is protected, reaction takes out hollow after terminating
Fiber pipe, be soaked in water 5min, dissolution unreacted monomer, prepares the hollow pipe through preliminary nano modification；
Step 2, prepare enhancement type hollow fiber film
(1) hollow pipe that step one prepares is passed sequentially through coating device and gel groove, be then around on wire drawing wheel；
(2) opening wire-feed motor and receive silk machine, the two rotating speed of regulation makes equipment run, and is added by casting solution in reactor, casting solution
Consist of: the Kynoar of 10-20 weight portion, the solvent of 50-80 weight portion and the porogen of 5-30 weight portion；Then to instead
Answer in still and pressurize, make casting solution lead to charge tube and carry to coating device；
(3) entering coagulation bath after above-mentioned hollow pipe coating feeding, the casting solution on hollow pipe outer surface is shaped through gel, shape
Film forming silk, collection membrane silk；
(4) film silk is sheared and is bound, and puts into immersion 24h in tank, is subsequently dried process, prepares enhancement type polyvinylidene fluoride hollow fine
Dimension film.
Method the most according to claim 1, it is characterised in that: the consumption of initiator is 1 weight % of hollow fiber conduit.
Method the most according to claim 8, it is characterised in that: in step one, the water-bath of (2nd) step is 60 DEG C.
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Cited By (3)
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| CN110743398A (en) * | 2019-11-26 | 2020-02-04 | 天津工业大学 | Preparation method of rare earth ion doped calcium alginate/carbon nanotube hydrogel antibacterial filter membrane |
| CN114085318A (en) * | 2021-10-21 | 2022-02-25 | 佛山市南海区苏科大环境研究院 | Amphiphilic double-sided structure nano-particle and super-hydrophilic hollow fiber membrane |
| CN115337791A (en) * | 2022-09-02 | 2022-11-15 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
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