CN106178974B - 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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- CN106178974B CN106178974B CN201610708136.7A CN201610708136A CN106178974B CN 106178974 B CN106178974 B CN 106178974B CN 201610708136 A CN201610708136 A CN 201610708136A CN 106178974 B CN106178974 B CN 106178974B
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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
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
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- 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
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Abstract
The present invention relates to a kind of high-throughput, resistant to pollution reinforced type polyvinylidene fluoride hollow fiber films and preparation method thereof, the hollow-fibre membrane has hollow tube and separating layer, the hollow tube be by nano-titanium dioxide modified hollow fiber conduit, the separating layer include the Kynoar of 10 20 parts by weight, 50 80 parts by weight solvent and 5 30 parts by weight pore-foaming agent；Separating layer is located at the surface of hollow tube；In preparation, after doughnut pipe surface coats upper feed liquid, into during coagulating bath, the butyl titanate of surface graft modification starts to hydrolyze, it hydrolyzes obtained hydrophilic nano titanium dioxide granule to migrate to film surface, enhances the adhesive force between film layer and hollow tube.In transition process, help to penetrate through membrane pore structure, improve membrane flux, while making fenestra evenly, porosity improves, and hydrophily and anti-fouling performance improve, and this method of modifying is easy to operate, and production cost is relatively low, suitable for promoting the use of on a large scale.
Description
【Technical field】
The invention belongs to membrane material manufacturing field, be related to it is a kind of it is high-throughput, resistant to pollution enhancement type polyvinylidene fluoride is hollow
Tunica fibrosa and preparation method thereof.
【Background technology】
More and more considerations uses high-precision membrane separation technique, membrane separation technique to have normal in water technology application
The lower operation of temperature, without phase-state change, it is energy-efficient, do not generate the features such as pollution in process of production, in drink water purifying, Industry Waste
Water process, food, water for beverages purification, degerming, bioactive substance recycling, refined etc. are used widely.But it is practical
Film strength and resistance tocrocking are most important indexs during use, in particular, hollow-fibre membrane is since film wire is thinner, intensity
It is poor, due to the disturbance of aeration in MBR wastewater treatments, often there is the phenomenon that fracture of wire, causes deteriorating water quality；Simultaneously because film
The hydrophobic property of material itself causes the pollution of fenestra and film surface during use, permeability rate is made to decline, membrane lifetime is caused to subtract
Small, operating cost increases, and in order to expand the application of film, control fouling membrane has become the Main way of research.
For the issue of improvement of film wire intensity, this side is surrounded using Thermal inactive, fusion drawn and liner enhancing etc.
Face is unfolded, and film strength can be substantially improved in the above technology.In recent years, patent CN102219969A " Kynoar-polyether sulfone
Blend hollow fiber membrane and Thermal inactive preparation method " etc. is to improve film wire intensity using thermotropic phase method；Fusion drawn skill
Art is difficult to be widely used in sewage disposal since membrane material type is limited；United States Patent (USP) US5472607 discloses one kind
Liner PVDF hollow-fibre membranes, but such film hydrophily is poor, it is easy to pollute, and the adhesive force between film layer and liner is poor.
In the main organic/inorganic nano particle doping of film hydrophilically modified aspect, the modification of organic polymer bulk graft and hydrophily
Substance blending etc., wherein nano-TiO2Due to good chemical stability, chemical resistance, uvioresistant ability and huge
Specific surface area be widely used in the modification of membrane material.But due to the surface energy of nano material height, it is easy to happen reunion, is formed
Offspring is difficult to infiltrate the shortcomings of poor with dispersion stabilization in organic phase, can not show satisfactory effect.China
Application for a patent for invention CN102091540A " sulfonated polyether sulfones/TiO2Nano combined ultrafiltration membrane preparation method " passes through 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, however it still has deficiency in terms of hydrophily and permeability；Further for Pvdf Microporous Hollow Fiber Membrane, as existing skill
The Chinese invention patent application CN201310309928.0 of art is disclosed Kynoar, composite thinning agent and amphipathic polymerization
Object engrafted nanometer oxide particle, which is blended, prepares casting solution, and hydrophilia polyvinylidene fluoride hollow fiber membrane is so made；
CN201210552806.2 discloses a kind of Kynoar/Pd nano particle hydridization hollow-fibre membrane, wherein being also to prepare to gather
Object gel/Pd nano particle hybrid dispersion liquid is closed, i.e. the prior art is prepared corresponding hollow in this kind of Kynoar of modification
It is to mix Kynoar with nano particle when tunica fibrosa, solution, which causes to mix uneven, nano particle, to be unevenly distributed
The problem of, and then the hydrophily and permeability of the hollow-fibre membrane finally influenced.
The method of the present invention abandons the existing technology that nano particle is directly blended with Kynoar casting solution, but will
Hydrolyzable is that the organic polymer of nano particle is grafted on hollow pipe surface, it is made to utilize dimethyl methyl during surface coating
The problem of organic base effect of amide is hydrolyzed, easily reunites so as to avoid nano particle.Enhance between film layer and hollow tube
Adhesive force, and then hydrophily, permeability and the excellent hollow-fibre membrane of contamination resistance is made.
【Invention content】
It is an object of the invention to overcome Pvdf Microporous Hollow Fiber Membrane hydrophily and infiltration obtained by the prior art
Property insufficient disadvantage, while in order to improve its contamination resistance, one is provided especially for the hollow-fibre membrane of sewage disposal
The preparation method of kind reinforced type polyvinylidene fluoride hollow fiber film and the Pvdf Microporous Hollow Fiber Membrane.
A kind of reinforced type polyvinylidene fluoride hollow fiber film, the hollow-fibre membrane is divided into hollow tube and separating layer, described
Hollow tube is by nano-titanium dioxide modified hollow fiber conduit；The separating layer includes the poly- inclined fluorine of 10-20 parts by weight
The pore-foaming agent of ethylene, the solvent of 50-80 parts by weight and 5-30 parts by weight；The separating layer is located at the surface of hollow tube.
The solvent is N, N dimethyl acetamide, dimethylformamide and N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), phosphorus
At least one of triethylenetetraminehexaacetic acid ester is a variety of；Preferably N, N dimethyl acetamide；
The pore-foaming agent is polyvinylpyrrolidone, polyethylene glycol, diethylene glycol (DEG), ethylene glycol；Preferably polyethylene glycol and poly-
Vinylpyrrolidone is with weight ratio for 5:6 mixture；
Preferably, the separating layer include the Kynoar of 18 parts by weight, 60 parts by weight N, N dimethyl acetamide,
The polyvinylpyrrolidone of the polyethylene glycol of 10 parts by weight, 12 parts by weight.
The hollow tube can also be fine by nano silicon dioxide, cerium oxide or alumina modified macromolecule terylene
Tie up hollow tube.
Further, the present invention relates to a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film, feature exists
In the preparation method includes the following steps：
Step 1: the nano modification of hollow fiber conduit
(1) it pre-processes：After hollow fiber conduit boiling, the supersound washing in acetone solvent is dried in subsequent baking oven；
(2) hollow fiber conduit of 1-10 parts by weight is placed in flask, then by the third of initiator dibenzoyl peroxide
Ketone solution adds in flask, and the dosage of initiator is the 0.5-3 weight % of hollow tube；It is uniformly mixed, is then put into mixture
In 50-70 DEG C of water-bath, leads to nitrogen protection, cause 15min in advance；The butyl titanate of 1-10 parts by weight is then dissolved in deionized water
In, it is added in flask after stirring evenly, 20-80min is reacted under nitrogen protection, takes out hollow tube after reaction, uses water logging
5min is steeped, unreacted monomer is dissolved out, the hollow tube through preliminary nano modification is made；
Step 2: preparing enhancement type hollow fiber film
(1) hollow tube made from step 1 is passed sequentially through into coating device and gel slot, be then wound on wire drawing wheel；
(2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and feed liquid is added in reaction kettle, feed liquid
Group becomes：The pore-foaming agent of the Kynoar of 10-20 parts by weight, the solvent and 5-30 parts by weight of 50-80 parts by weight；Then to anti-
It answers in kettle and pressurizes, so that feed liquid is passed through expects pipe and conveyed to coating device；
(3) above-mentioned hollow tube is coated and enters coagulation bath after feeding, the length of 2-10 meters or so, on hollow tube outer surface
Feed liquid gel sizing, formed film wire, collect film wire；
(4) film wire shearing is bound, and is put into sink and is impregnated for 24 hours, displaces solvent and additive (such as unreacted initiation
Agent, butyl titanate, pore-foaming agent etc.)；It is subsequently dried processing, reinforced type polyvinylidene fluoride hollow fiber film is made.
The hollow tube is the hollow tube made of nylon, dacron polyester or the polyurethane fiber.
Preferably, the dosage of initiator is 1 weight % of hollow tube；The dosage of initiator dibenzoyl peroxide is should
Control, but concentration of the dibenzoyl peroxide in acetone soln is reacted without influence.
Preferably, the water-bath of (2) step is 60 DEG C in step 1.
About the principle of the present invention：The first step is to the organic polymer that the modification of hollow tube is by hydrolyzable for nano material
Tetrabutyl titanate ester is grafted on the hollow tube of PET materials, in case uniformly hydrolysis dispersion in later stage film forming procedure.Meanwhile it is right
Nano-titanium dioxide is just will produce after the preliminary nano modification of step 1, butyl titanate hydrolysis itself, therefore in the present invention
The first step is that hydrolyzable is grafted on PET materials at the organic polymer of nano-size titania using the method for graft polymerization
Hollow pipe surface, in later stage film forming procedure using the weak organic bases of dimethylacetylamide effect be hydrolyzed into nano-titanium dioxide
Particle, it is evenly dispersed in film；Wherein existing literature (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, beneficial effects of the present invention are：The nano modification hollow tube of the present invention, the present invention can water
Solution is that the organic polymer of nano particle is grafted on hollow pipe surface, it is made to utilize dimethylformamide during surface coating
Organic base effect be hydrolyzed, and in the phase process that forms a film in coagulating bath, hydrophilic titanium dioxide nanoparticle is to film
Outer surface migrates, and can improve the hydrophily of film surface, simultaneously because the addition of inorganic material makes film strength increase.It enhances
Adhesive force between film layer and hollow tube.In transition process, helps to penetrate through membrane pore structure, improve membrane flux, while making film
Evenly, porosity improves in hole, and hydrophily and anti-fouling performance improve, and this method of modifying is easy to operate, and production cost is relatively low,
Suitable for promoting the use of on a large scale.Directly Kynoar is mixed with nano particle in compared with prior art, it is logical in the pure water of film
In amount, doughnut film-strength etc. be improved, it is final so that the hydrophily and permeability of doughnut are improved.
【Description of the drawings】
Fig. 1：The mechanism of modification figure of the nano modification liner enhancing hollow-fibre membrane of the present invention.
【Specific implementation mode】
With reference to the accompanying drawings and examples, the specific implementation mode of invention is described in further detail.Following embodiment
For illustrating the present invention, but it is not limited to the scope of the present invention.
Embodiment 1：
By hollow fiber conduit boiling 1h, taking-up is dried, and is placed into and is used supersound washing 30min in acetone solvent, in removal
The oil stain on blank pipe surface and other impurity, are finally putting into 80 DEG C of baking oven and dry, and obtain pretreated hollow fiber conduit.
The pretreated hollow fiber conduits of 5g are placed in the three-necked flask of 500ml, and 0.05g initiators (BPO) are dissolved in
It in 50ml acetone, is then added in three-necked flask, is uniformly mixed, puts it into 70 degree of water-baths, lead to nitrogen protection, it is pre- to cause
15min.5g butyl titanates are dissolved in 20ml deionized waters, are rapidly added in three-necked flask after stirring evenly, are continued in nitrogen
40min is reacted under gas shielded, takes out hollow tube after reaction, and be soaked in water 5min, dissolution unreacted monomer etc., naturally dry
It is spare.
Take polyvinylidene fluoride resin：Dimethylacetamide solvent：Polyethylene glycol additive：Polyvinylpyrrolidone additive
By weight 18:60:10:12 mixed ingredients, are stirred evenly using machine mixer, are then taken off by the way of negative pressure
Bubble, manufactured casting solution is positioned in batch can after deaeration, 70 degree of heat preservations；It is 10 with mass ratio:90 dimethylacetylamide：Water is mixed
Bonding solvent is that coagulating bath is recycled, and then prepares nano modification lining-reinforced hollow-fibre membrane in following manner：
1) the nona modified fiber hollow tube pulled in fiber roller is passed sequentially through into coating device and gel slot, then wound
In on wire drawing wheel；
2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and the speed of the two is 15 ms/min, will
Casting solution is added in reaction kettle, then pressurizes into reaction kettle, so that casting solution is passed through expects pipe and is conveyed to coating device；
3) modified fibre hollow tube enters coagulation bath under the traction of receive silk machine after coating device coats feeding, in
Immersion precipitation inversion of phases occurs for the feed liquid on blank pipe outer surface and gel is shaped, and loses flowability, and forms film wire, passes through wire drawing wheel
It collects.
4) a certain number of film wire shearings will be collected to bind, be put into sink and impregnate for 24 hours, thoroughly to displace solvent and add
Add agent.
5) processing is dried in film, obtains the lining-reinforced hollow membrane.
Following performance measurement is carried out to above-mentioned film：
1) being averaged for obtained hollow-fibre membrane of solution-air and the double method of testing pore-size distribution analysis-e/or determinings of liquid liquid is used
Aperture is 0.3 micron, and internal diameter is 1.0 millimeters, and outer diameter is 2.0 millimeters.
2) the doughnut film-strength measured using universal tensile machine is 150N.
3) use the 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) it is 38 degree to use the hollow-fibre membrane contact angle size that dynamic contact angle analyzer measures.
Embodiment 2
In addition to the addition of initiator is 0.1g, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 155N；Pure water flux is 2550L/m2.h；Contact angle size is 42.5
Degree.
Embodiment 3
In addition to the addition of initiator is 0.03g, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 160N；Pure water flux is 2410L/m2.h；Contact angle size is 45 degree.
Embodiment 4
Except the bath temperature in step 1 is 70 DEG C, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 158N；Pure water flux is 2550L/m2.h；Contact angle size is 46 degree.
Embodiment 5
In addition to pore-foaming agent replaces polyvinylpyrrolidone and polyethylene glycol using the polyvinylpyrrolidone of same weight ratio,
Remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 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
It is 15:55:14:Outside 10, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 170N；Pure water flux is 2150L/m2.h；Contact angle size is 56 degree.
It can be seen that with weight ratio being 5 when pore-foaming agent is polyethylene glycol and polyvinylpyrrolidone:6 mixture detaches
The each group that layer is included is divided into the dosage of preferable amount ratio and initiator for (2) in the 1 weight % and step 1 of hollow tube
The water-bath of step be 60 DEG C be the application technical solution in highly preferred scheme, obtained hollow-fibre membrane is in intensity, pure
Best performance in terms of water flux and contact angle.
Comparative example 1
Except the dosage of initiator is 0.01g, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 170N；Pure water flux is 2230L/m2.h；Contact angle size is 58 degree.
Comparative example 2
Except the dosage of initiator is 0.3g, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 165N；Pure water flux is 2350L/m2.h；Contact angle size is 60 degree.
Comparative example 3
Except the bath temperature in step 1 is 45 DEG C, remaining is the same as embodiment 1；
Test result is that doughnut film-strength is 169N；Pure water flux is 2250L/m2.h；Contact angle size is 50 degree.
Comparative example 4
The grafting of Kynoar, composite thinning agent and amphipathic nature polyalcohol is received using disclosed in CN201310309928.0
Rice oxide particle, which is blended, prepares casting solution, and hydrophilia polyvinylidene fluoride hollow fiber membrane is made according to corresponding method；
Test result is that doughnut film-strength is 140N；Pure water flux is 1850L/m2.h；Contact angle size is 68 degree.
Comparative example 5
Pvdf Microporous Hollow Fiber Membrane is prepared using method disclosed in CN201210552806.2.
Test result is that doughnut film-strength is 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 member, without departing from the technical principles of the invention, several improvements and modifications, these improvements and modifications can also be made
Also it should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of reinforced type polyvinylidene fluoride hollow fiber film, which is characterized in that the hollow-fibre membrane is divided into hollow tube and divides
Absciss layer, the hollow tube are by nano-titanium dioxide modified hollow fiber conduit；The separating layer includes 10-20 parts by weight
Kynoar, 50-80 parts by weight solvent and 5-30 parts by weight pore-foaming agent；The separating layer is located at the table of hollow tube
Face；
The preparation method of the hollow tube is that the hollow fiber conduit of 1-10 parts by weight is placed in flask, by initiator peroxidating two
The acetone soln of benzoyl adds in flask, and the dosage of initiator is the 0.5-3% weight of hollow fiber conduit；It is uniformly mixed, with
The flask containing mixed liquor is put into 50-70 DEG C of water-bath afterwards, leads to nitrogen protection, causes 15min in advance；Then by 1-10 parts by weight
Butyl titanate be dissolved in deionized water, added in flask after stirring evenly, 20-80min reacted under nitrogen protection, react
After take out hollow fiber conduit, be soaked in water 5min, dissolves out unreacted monomer, is made by nano-titanium dioxide modified
Blank pipe；
The building method of the separating layer is that the hollow tube is passed sequentially through coating device and gel slot, is then wound in receipts silk
On wheel；Wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and casting solution is added in reaction kettle, casting solution group
Become：The pore-foaming agent of the Kynoar of 10-20 parts by weight, the solvent and 5-30 parts by weight of 50-80 parts by weight；Then to reaction
It pressurizes in kettle, so that casting solution is passed through expects pipe and conveyed to coating device；Enter coagulation bath after the hollow tube is coated feeding, it is hollow
Casting solution on tube outer surface is shaped by gel, forms film wire, collects film wire；Film wire is sheared and is bound, is put into sink and soaks
Bubble for 24 hours, is subsequently dried processing, obtains the reinforced type polyvinylidene fluoride hollow fiber film that separating layer is located at hollow pipe surface.
2. hollow-fibre membrane according to claim 1, which is characterized in that the solvent is N, N dimethyl acetamide, diformazan
At least one of base formamide and N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), triethyl phosphate or multi-solvents.
3. hollow-fibre membrane according to claim 1, which is characterized in that the pore-foaming agent is polyvinylpyrrolidone, gathers
Ethylene glycol, diethylene glycol (DEG) and/or ethylene glycol.
4. hollow-fibre membrane according to claim 3, which is characterized in that the pore-foaming agent is polyethylene glycol and polyethylene pyrrole
Pyrrolidone is with weight ratio for 5:6 mixture.
5. hollow-fibre membrane according to claim 1, which is characterized in that the separating layer includes the poly- inclined fluorine of 18 parts by weight
The N of ethylene, 60 parts by weight, N dimethyl acetamide, the polyethylene glycol of 10 parts by weight, 12 parts by weight polyvinylpyrrolidone.
6. hollow-fibre membrane according to claim 1, it is characterised in that：It is poly- that the hollow fiber conduit is selected from nylon, terylene
Hollow tube made of ester or polyurethane fiber.
7. a kind of method preparing reinforced type polyvinylidene fluoride hollow fiber film as described in claim 1, which is characterized in that institute
Preparation method is stated to include the following steps：
Step 1: the nano modification of hollow fiber conduit
(1) it pre-processes：After hollow fiber conduit boiling, the supersound washing in acetone solvent is dried in subsequent baking oven；
(2) hollow fiber conduit of 1-10 parts by weight is placed in flask, it is then that the acetone of initiator dibenzoyl peroxide is molten
Liquid adds in flask, and the dosage of initiator is the 0.5-3% weight of hollow fiber conduit；It is uniformly mixed, will then contain mixed liquor
Flask be put into 50-70 DEG C of water-bath, lead to nitrogen protection, cause 15min in advance；It is then that the butyl titanate of 1-10 parts by weight is molten
It in deionized water, is added in flask after stirring evenly, 20-80min is reacted under nitrogen protection, taken out after reaction hollow
Fibre pipe, be soaked in water 5min, dissolves out unreacted monomer, and the hollow tube through preliminary nano modification is made；
Step 2: preparing enhancement type hollow fiber film
(1) hollow tube made from step 1 is passed sequentially through into coating device and gel slot, be then wound on wire drawing wheel；
(2) wire-feed motor and receive silk machine are opened, adjusting the two rotating speed makes equipment run, and casting solution is added in reaction kettle, casting solution
Group becomes：The pore-foaming agent of the Kynoar of 10-20 parts by weight, the solvent and 5-30 parts by weight of 50-80 parts by weight；Then to anti-
It answers in kettle and pressurizes, so that casting solution is passed through expects pipe and conveyed to coating device；
(3) enter coagulation bath after above-mentioned hollow tube being coated feeding, the casting solution on hollow tube outer surface is shaped by gel, shape
At film wire, film wire is collected；
(4) film wire shearing is bound, and is put into sink and is impregnated for 24 hours, is subsequently dried processing, and the hollow fibre of enhancement type polyvinylidene fluoride is made
Tie up film.
8. according to the method described in claim 7, it is characterized in that：The dosage of initiator is 1 weight % of hollow fiber conduit.
9. according to the method described in claim 7, it is characterized in that：The water-bath of (2) step is 60 DEG C in step 1.
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| CN114085318B (en) * | 2021-10-21 | 2023-08-01 | 佛山市南海区苏科大环境研究院 | Amphiphilic double-sided neural structure nano-particle and super-hydrophilic hollow fiber membrane |
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| CN102151498B (en) * | 2011-03-16 | 2013-01-02 | 何善媛 | Nanometer cross-linking PVDF/PU blending hollow fiber ultrafiltration membrane and preparation method |
| CN102166485A (en) * | 2011-05-27 | 2011-08-31 | 上海应用技术学院 | Modified polyvinylidene fluoride (PVDF) hollow fibrous membrane and preparation method thereof |
| CN102430352A (en) * | 2011-09-07 | 2012-05-02 | 三达膜科技（厦门）有限公司 | Polyvinylidene fluoride organic-inorganic hybrid membrane and preparation method thereof |
| CN103127840A (en) * | 2011-11-28 | 2013-06-05 | 中化蓝天集团有限公司 | Polyvinylidene fluoride (PVDF) resin membrane preparing formula for water treatment membrane |
| CN103240008A (en) * | 2012-02-08 | 2013-08-14 | 沃盛环保科技（上海）有限公司 | Whisker reinforced polyvinylidene fluoride hollow fiber film and preparation technology thereof |
| CN102921318B (en) * | 2012-11-21 | 2015-01-07 | 海南立昇净水科技实业有限公司 | External-pressure type charged hollow fiber nano-filtration membrane and preparation method therefor |
| CN103657453A (en) * | 2013-12-17 | 2014-03-26 | 常熟丽源膜科技有限公司 | Hollow fiber ultrafiltration membrane |
| CN104524996A (en) * | 2014-12-30 | 2015-04-22 | 山东华夏神舟新材料有限公司 | Polyvinylidene fluoride hollow fibrous membranes with pressure response characteristic and preparation method thereof |
| CN105749766B (en) * | 2016-03-02 | 2018-02-09 | 同济大学 | A kind of Kynoar/TiO2The preparation method of Nano sol composite hyperfiltration membrane |
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2016
- 2016-08-23 CN CN201610708136.7A patent/CN106178974B/en active Active
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