CN108097071A - A kind of preparation method of improved polyvinylidene fluoride NF membrane - Google Patents
A kind of preparation method of improved polyvinylidene fluoride NF membrane Download PDFInfo
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- CN108097071A CN108097071A CN201711176072.1A CN201711176072A CN108097071A CN 108097071 A CN108097071 A CN 108097071A CN 201711176072 A CN201711176072 A CN 201711176072A CN 108097071 A CN108097071 A CN 108097071A
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- 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
- B01D67/0016—Coagulation
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
Abstract
A kind of preparation method of improved polyvinylidene fluoride NF membrane, belongs to technical field of membrane.First, Kynoar ultrafiltration membranes are prepared using phase inversion, i.e.,：Kynoar, solvent, additive, pore-foaming agent and compound with amino, carboxyl, sulfonic group or hydroxy functional group are mixed, it is heated to 50 90 DEG C and stirs evenly, standing and defoaming under vacuum environment, obtain casting solution, then using scraper knifing and immerse coagulating bath film forming or through spinneret flow out to coagulating bath form a film, obtain Kynoar ultrafiltration membranes；Polyvinylidene fluoride NF membrane is prepared using interfacial polymerization, i.e.,：Aqueous phase monomers aqueous solution and oil phase monomer organic solution are taken up in order of priority coated on Kynoar ultrafiltration membranes surface, then by being thermally treated resulting in polyvinylidene fluoride NF membrane respectively using the method for calibrated shot.Preparing NF membrane has stability, more cost-effective, and can be to avoid environmental pollution.
Description
Technical field
The present invention relates to technical field of membrane separation, more particularly to a kind of preparation side of improved polyvinylidene fluoride NF membrane
Method.
Background technology
Membrane separation technique substance separation with concentration field have extensive use, can operate at normal temperatures, have it is energy saving,
The advantage of environmental protection.Nanofiltration-membrane technique is one kind of membrane separation technique, is one between ultrafiltration membrane technique and reverse osmosis technology
Kind pressure-driven membrane technology.NF membrane has nano level membrane aperture, and in most cases with charge on film, so nanofiltration
Film can operationally retain the organic matter of divalent or multivalent ion and larger molecular weight, and monovalention is allowed to pass through.Cause
This, the special performance based on NF membrane is widely used in wastewater treatment, food industry, chemical and medicine industry industry and Drinking Water Industry
Deng.
Commercialization NF membrane series is main including NF, NTR, UTC, MPT, SU etc. at present, and commercialization NF membrane is mostly compound
Film.Composite membrane generally comprises basement membrane and function separating layer, and its preparation method is usually first to coat polynary aqueous amine phase in membrane surface
Then solution is coated with the organic phase solution of polynary acyl chlorides, by the interface polymerization reaction of aqueous phase solution and organic phase solution and
Function separating layer is formed in membrane surface.
Kynoar (PVDF) has good chemical stability and thermal stability, is preferable filmogen, with it
His membrane material, which is compared, to have a clear superiority, and has extensive use in water treatment field.However its hydrophobicity is strong, when using it as basement membrane
When preparing sodium filter membrane, one side aqueous phase solution is difficult to be uniformly distributed that the function separating layer to be formed is caused to have defect on its surface；
On the other hand the function separating layer and the combination power of basement membrane prepared by interfacial polymerization is poor, easily come off from membrane surface and
Prepared composite membrane is made to lose nanofiltration effect.Therefore, at present using polyvinylidene fluoride (PVDF) ultrafiltration membrane as the commercialization NF membrane of basement membrane
It is also rarely found.Although research before me solves the above problem, but it cannot be guaranteed that aqueous phase monomers are molten during long-time service
The stability of the concentration of liquid and oil phase monomer solution and not economic and environment-friendly enough.
The content of the invention
In view of the deficiencies of the prior art, it is a primary object of the present invention to solve the prior art the defects of, the present invention provide
On the one hand a kind of preparation method of polyvinylidene fluoride NF membrane, this method improve function separating layer and Kynoar ultrafiltration
Combination power between basement membrane so that the NF membrane of preparation has good separating property and can remain stable for a long time, on the other hand
It is greatly saved with amino, carboxyl, sulfonic group or the small molecule of hydroxy functional group or the dosage of polymer, preferably ensure that
Aqueous phase monomers solution, the stability of oil phase monomer solution long-time service, and more economical environmental protection.
The present invention provides a kind of preparation methods of improved polyvinylidene fluoride NF membrane, which is characterized in that including such as
Lower step：
(1) Kynoar ultrafiltration membranes are prepared using phase inversion, i.e.,：By Kynoar, solvent, additive, cause
Hole agent and compound (such as small molecule or polymer) mixing with amino, carboxyl, sulfonic group or hydroxy functional group, heating
It to 50-90 DEG C and stirs evenly, standing and defoaming under vacuum environment obtains casting solution, then using scraper knifing and immerses solidification
Bath film forming flows out to coagulating bath film forming through spinneret, obtains Kynoar ultrafiltration membranes；
(2) polyvinylidene fluoride NF membrane is prepared using interfacial polymerization, i.e.,：Using the method for calibrated shot respectively by water
Phase monomer solution and oil phase monomer organic solution are taken up in order of priority coated on Kynoar ultrafiltration membranes surface, then through overheat
Processing obtains polyvinylidene fluoride NF membrane.
Preferably, the solvent, additive, pore-foaming agent for phase inversion prepare the common solvent of ultrafiltration membrane, additive and
Pore-foaming agent, wherein solvent are generally n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N- methylpyrroles
One or more in alkanone, acetone, tetrahydrofuran etc., additive and pore-foaming agent be generally lithium chloride, polyvinylpyrrolidone,
One or more in polyethylene glycol, glycerine etc..
Preferably, the compound with amino, carboxyl, sulfonic group or hydroxy functional group can be piperazine, polyethylene
Alcohol, polyglutamic acid, melamine, sulfonated polyether sulfone, sulfonated polysulfone, o-phenylenediamine, dimethyl-m-phenylenediamine, Isosorbide-5-Nitrae-hexamethylene two
One or more in amine, N, N- dimethyleyelohexanes diamines, triethanolamine, polyethyleneimine etc., it is described with amino, carboxyl
Or the compound of hydroxy functional group is added to directly as additive in casting solution, adds in total amount as casting solution gross mass
0.01 ‰ -2%.
Further preferably, Kynoar, additive, the mass percent concentration of pore-foaming agent divide in step (1) casting solution
It Wei 8%~20%, 0.01%~5%, 0.01%~5%.
Preferably, the aqueous phase monomers are piperazine, m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, equal benzene triamine, N, N- bis-
One kind in methylresorcinol diamines, Isosorbide-5-Nitrae-cyclohexanediamine, N, N- dimethyleyelohexanes diamines, triethanolamine, polyethyleneimine etc. or
A variety of, the mass percent concentration scope of the aqueous phase monomers solution is 0.05%~5%.
Preferably, the solute of the oil phase monomer organic solution for pyromellitic trimethylsilyl chloride, 1,3,5- hexamethylene, three formyl chloride,
One or more in three acyl chlorides of biphenyl, 5- oxygen formyl-isophthaloyl chlorine, paraphthaloyl chloride, o-phthaloyl chloride etc., solvent are
One or more in n-hexane, normal heptane etc., the mass percent concentration of the oil phase monomer organic solution for 0.05%~
2%.
Preferably, additive or catalyst can be also added in the aqueous phase monomers solution, the additive added in or catalysis
Agent is generally one kind or more in dodecyl sodium sulfate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, triethylamine etc.
Kind, the mass percent concentration scope for adding in additive or catalyst is 0~0.5%.
Preferably, the Kynoar ultrafiltration membranes can be plate membrane or tunica fibrosa, when the Kynoar surpasses
When filter basement membrane is plate membrane, using scraper knifing and coagulating bath film forming is immersed；When the Kynoar ultrafiltration membranes are fiber
During film, casting solution flows out to coagulating bath through spinneret and forms a film.
Preferably, by the way that the small molecule or polymer that carry amino, carboxyl, sulfonic group or hydroxy functional group are directly mixed
In casting solution, the combination power that is on the one hand greatly improved between function separating layer and Kynoar ultrafiltration membranes ensures made
On the one hand the stability of standby NF membrane can save small molecule or poly- of this kind with amino, carboxyl, sulfonic group or hydroxy functional group
Close the dosage of object, more cost-effective and more conducively industrialization.
Preferably, the Kynoar ultrafiltration membranes can have other supporting layers or without other supporting layers, institute
It can be non-woven fabrics, woven tube or tow to state support layer material, and the structure of support layer material can be polyester, nylon, poly- third
Alkene, polyhexamethylene adipamide, polyethylene terephthalate, it is poly- between paraphenylene terephthalamide's m-phenylene diamine (MPD), poly- paraphenylene terephthalamide, right
One or more in phenylenediamine, polyvinyl chloride, polyacrylonitrile, polyamide, polyurethanes, polyvinyl formal.
Aqueous phase monomers solution and oil phase monomer solution are surpassed coated on Kynoar respectively using the method for calibrated shot
Membrane surface is filtered, then by being thermally treated resulting in polyvinylidene fluoride NF membrane.The present invention is carried by being added in casting solution
Amino, carboxyl, the small molecule or polymer of sulfonic group or hydroxy functional group, on the one hand introduce amino, carboxyl, sulfonic acid on basement membrane
Base or hydroxy functional group improve the combination power between function separating layer and Kynoar ultrafiltration membranes, avoid in function point
Occurs defect on absciss layer；On the one hand small molecule or polymerization with amino, carboxyl, sulfonic group or hydroxy functional group are greatly reduced
The dosage of object, so as to save cost.Aqueous phase monomers solution and oil phase monomer solution are applied respectively using the method for calibrated shot
Kynoar ultrafiltration membranes surface is overlying on, on the one hand ensure that aqueous phase monomers solution and oil phase monomer in the long-term use
The stability of the concentration of solution, on the one hand avoids waste and environmental pollution.The method of the present invention technological process is simple, it can be achieved that even
Continuous metaplasia production, nanofiltration functional layer uniform, controllable, defect are few, have broader application prospect in fields such as water process.
The present invention has the following advantages and beneficial effect：The present invention provides a kind of improved polyvinylidene fluoride NF membrane
Preparation method, on the one hand this method can ensure the stability of prepared nanofiltration film properties, on the one hand more cost-effective, and can
To avoid environmental pollution.
Specific embodiment
Below with reference to specific embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
The present invention provides a kind of preparation methods of improved polyvinylidene fluoride NF membrane, which is characterized in that including such as
Lower step：
(1) Kynoar ultrafiltration membranes are prepared using phase inversion, i.e.,：By Kynoar, solvent, additive, cause
Hole agent and small molecule or mixed with polymers with amino, carboxyl, sulfonic group or hydroxy functional group, are heated to 50-90 DEG C simultaneously
Stir evenly, standing and defoaming under vacuum environment obtains casting solution, then using scraper knifing and immerse coagulating bath film forming or will casting
Film liquid flows out to coagulating bath film forming through spinneret, obtains Kynoar ultrafiltration membranes；
(2) polyvinylidene fluoride NF membrane is prepared using interfacial polymerization, i.e.,：Using the method for calibrated shot respectively by water
Phase monomer solution and oil phase monomer solution are coated on Kynoar ultrafiltration membranes surface, then by being thermally treated resulting in poly- inclined fluorine
Vinyl NF membrane.
As the preferred embodiment of above-described embodiment, to prepare ultrafiltration membrane normal for phase inversion for the solvent, additive, pore-foaming agent
Solvent, additive and pore-foaming agent, wherein solvent are generally n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan
One or more in base sulfoxide, N-Methyl pyrrolidone, acetone, tetrahydrofuran, additive and pore-foaming agent be generally lithium chloride,
One or more in polyvinylpyrrolidone, polyethylene glycol, glycerine.
As the preferred embodiment of above-described embodiment, the small molecule with amino, carboxyl, sulfonic group or hydroxy functional group
Or polymer can be piperazine, polyvinyl alcohol, polyglutamic acid, melamine, sulfonated polyether sulfone, one kind in sulfonated polysulfone or more
Kind, it is described to be added to amino, the small molecule of carboxyl or hydroxy functional group or polymer directly as additive in casting solution,
Add in 0.01 ‰ -2% that total amount is casting solution gross mass.
As the preferred embodiment of above-described embodiment, the aqueous phase monomers for piperazine, m-phenylene diamine (MPD), o-phenylenediamine, to benzene two
Amine, equal benzene triamine, N, N- dimethyl-m-phenylenediamines, Isosorbide-5-Nitrae-cyclohexanediamine, N, N- dimethyleyelohexanes diamines, triethanolamine, poly- second
One or more in alkene imines, the concentration range of the aqueous phase monomers solution is 0.05%~5%.
As the preferred embodiment of above-described embodiment, the solute of the oil phase monomer solution is pyromellitic trimethylsilyl chloride, 1,3,5-
One kind in three formyl chloride of hexamethylene, three acyl chlorides of biphenyl, 5- oxygen formyl-isophthaloyl chlorine, paraphthaloyl chloride, o-phthaloyl chloride
Or it is a variety of, solvent is n-hexane, the one or more in normal heptane, and the concentration of the oil phase monomer solution is 0.05%~2%.
As the preferred embodiment of above-described embodiment, the Kynoar ultrafiltration membranes can be plate membrane or tunica fibrosa,
When the Kynoar ultrafiltration membranes are plate membrane, using scraper knifing and coagulating bath film forming is immersed；Gather inclined fluorine when described
When ethylene ultrafiltration membranes are tunica fibrosa, casting solution flows out to coagulating bath through spinneret and forms a film.
As the preferred embodiment of above-described embodiment, by small point that will carry amino, carboxyl, sulfonic group or hydroxy functional group
Son or polymer are directly mixed in casting solution, are on the one hand greatly improved between function separating layer and Kynoar ultrafiltration membranes
Combination power, ensure that the stability of prepared NF membrane, on the one hand can save this kind with amino, carboxyl, sulfonic group or hydroxyl
The small molecule of base functional group or the dosage of polymer, more cost-effective and more conducively industrialization.
As the preferred embodiment of above-described embodiment, the Kynoar ultrafiltration membranes can have other supporting layers or not
With other supporting layers, the support layer material can be non-woven fabrics, woven tube or tow, and the structure of support layer material can be
For polyester, nylon, polypropylene, polyhexamethylene adipamide, polyethylene terephthalate, it is poly- between paraphenylene terephthalamide's isophthalic two
Amine, poly- paraphenylene terephthalamide, p-phenylenediamine, polyvinyl chloride, polyacrylonitrile, polyamide, polyurethanes, polyvinyl formal
In one or more.
As the preferred embodiment of above-described embodiment, using the method for calibrated shot respectively by aqueous phase monomers solution and oil phase list
Liquid solution be coated on Kynoar ultrafiltration membranes surface, on the one hand ensure that in the long-term use aqueous phase monomers solution and
The stability of the concentration of oil phase monomer solution, on the one hand avoids waste and environmental pollution.
The test of following embodiment film properties is room temperature condition.
Embodiment 1
Weigh Kynoar 660g, lithium chloride 50g, polyvinylpyrrolidone 130g, n,N-dimethylacetamide
3160g, piperazine 1g are heated to 85 DEG C and stir evenly after mixing, standing and defoaming under vacuum environment, and casting solution is made.Then will
Casting solution is flowed out to through spinneret in pure water coagulating bath, and Kynoar ultrafiltration membranes are made；By prepared Kynoar
The tubule that ultrafiltration membranes carry threeway different length by two respectively with certain speed, while existed respectively using two peristaltic pumps
The n-hexane for the pyromellitic trimethylsilyl chloride that the piperazine aqueous solution and concentration that calibrated shot concentration is 0.2% in two tubules are 0.1%
Solution, adjustment Kynoar basement membrane pass through speed and the length of two tubules so that aqueous phase monomers solution and oil phase monomer are molten
The time that liquid is successively coated to Kynoar ultrafiltration membranes is respectively 10min and 1min, then again fills film by being heat-treated
It puts to obtain polyvinylidene fluoride NF membrane.The NF membrane is to 1g/L MgSO4Rejection for 88%, the retention to 1g/L NaCl
Rate is 28%, possesses preferable separating effect to monovalent ion and divalent ion, and it retains separation property after continuous operation 100h
It can not decline, possess preferable stability.
Embodiment 2
Kynoar 330g, lithium chloride 30g, polyvinylpyrrolidone 64g, n,N-dimethylacetamide 1580g are weighed,
Polyglutamic acid 0.5g is heated to 80 DEG C and stirs evenly after mixing, standing and defoaming under vacuum environment, and casting solution is made.Then will
Casting solution is flowed out to through spinneret in pure water coagulating bath, and Kynoar ultrafiltration membranes are made；By prepared Kynoar
The tubule that ultrafiltration membranes carry threeway different length by two respectively with certain speed, while existed respectively using two peristaltic pumps
The n-hexane for the pyromellitic trimethylsilyl chloride that the piperazine aqueous solution and concentration that calibrated shot concentration is 0.5% in two tubules are 0.1%
Solution, adjustment Kynoar basement membrane pass through speed and the length of two tubules so that aqueous phase monomers solution and oil phase monomer are molten
The time that liquid is successively coated to Kynoar ultrafiltration membranes is respectively 10min and 1min, then again fills film by being heat-treated
It puts to obtain polyvinylidene fluoride NF membrane.The NF membrane is to 1g/L MgSO4Rejection for 83%, 1g/L NaCl are cut
It is 24% to stay rate, possesses preferable separating effect, and its retention separation after continuous operation 120h to monovalent ion and divalent ion
Performance does not decline, and possesses preferable stability.
Embodiment 3
Kynoar 330g, lithium chloride 30g, polyvinylpyrrolidone 64g, n,N-dimethylacetamide 1580g are weighed,
Melamine 0.5g is heated to 80 DEG C and stirs evenly after mixing, standing and defoaming under vacuum environment, and casting solution is made.Then adopt
It with 200 μm of scraper knifing on non-woven fabrics, and forms a film in pure water coagulating bath, obtains the Kynoar with non-woven fabrics support
Ultrafiltration membranes.Then the equal benzene three for being respectively 0.2% by piperazine aqueous solution and concentration that concentration is 1% by quantitative coating unit
Formyl chloride hexane solution is successively coated on Kynoar ultrafiltration membranes, and the time is respectively 10min and 1min, and is put
Polyvinylidene fluoride NF membrane is made in the 3min in 60 DEG C of baking ovens.The NF membrane is to 1g/L MgSO4Rejection for 90%,
Rejection to 1g/L NaCl is 33%, possesses preferable separating effect, and continuous operation to monovalent ion and divalent ion
It retains separating property and does not decline after 85h, possesses preferable stability.
Claims (8)
1. a kind of preparation method of improved polyvinylidene fluoride NF membrane, which is characterized in that include the following steps：
(1) Kynoar ultrafiltration membranes are prepared using phase inversion, i.e.,：By Kynoar, solvent, additive, pore-foaming agent
And the compound mixing with amino, carboxyl, sulfonic group or hydroxy functional group, it is heated to 50-90 DEG C and stirs evenly, vacuum
Standing and defoaming under environment obtains casting solution, then using scraper knifing and immerses coagulating bath film forming or flows out to through spinneret solidifying
Gu bath film forming, obtains Kynoar ultrafiltration membranes；
(2) polyvinylidene fluoride NF membrane is prepared using interfacial polymerization, i.e.,：It is respectively that water is mutually single using the method for calibrated shot
Body aqueous solution and oil phase monomer organic solution are taken up in order of priority coated on Kynoar ultrafiltration membranes surface, then through Overheating Treatment
Obtain polyvinylidene fluoride NF membrane.
A kind of 2. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that step
Suddenly (1) solvent for n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, acetone,
One or more in tetrahydrofuran, additive and pore-foaming agent are lithium chloride, in polyvinylpyrrolidone, polyethylene glycol, glycerine
One or more；Kynoar, additive, the mass percent concentration of pore-foaming agent are respectively 8% in step (1) casting solution
~20%, 0.01%~5%, 0.01%~5%.
A kind of 3. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that institute
State the compound with amino, carboxyl, sulfonic group or hydroxy functional group for piperazine, polyvinyl alcohol, polyglutamic acid, melamine,
Sulfonated polyether sulfone, sulfonated polysulfone o-phenylenediamine, dimethyl-m-phenylenediamine, Isosorbide-5-Nitrae-cyclohexanediamine, N, N- dimethyleyelohexanes diamines, three
One or more in ethanolamine, polyethyleneimine add in total amount as the 0.01 ‰ -2% of casting solution gross mass.
A kind of 4. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that water
Phase monomer is piperazine, m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, equal benzene triamine, N, N- dimethyl-m-phenylenediamines, Isosorbide-5-Nitrae-hexamethylene
Diamines, N, the one or more in N- dimethyleyelohexanes diamines, triethanolamine, polyethyleneimine, the aqueous phase monomers solution
Mass percent concentration scope is 0.05%~5%.
A kind of 5. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that institute
The solute of oil phase monomer organic solution is stated as pyromellitic trimethylsilyl chloride, three formyl chloride of 1,3,5- hexamethylenes, three acyl chlorides of biphenyl, 5- oxygen first
One or more in acyl-isophthaloyl chlorine, paraphthaloyl chloride, o-phthaloyl chloride, solvent are one in n-hexane, normal heptane
Kind is a variety of, and the mass percent concentration of the oil phase monomer organic solution is 0.05%~2%.
A kind of 6. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that institute
State and additive or catalyst be additionally added in aqueous phase monomers solution, the additive or catalyst added in for dodecyl sodium sulfate,
One or more in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, triethylamine add in the matter of additive or catalyst
It is 0~0.5% to measure percent concentration scope.
A kind of 7. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that institute
It is plate membrane or tunica fibrosa to state Kynoar ultrafiltration membranes, when the Kynoar ultrafiltration membranes are plate membrane, is used
Scraper knifing simultaneously immerses coagulating bath film forming；When the Kynoar ultrafiltration membranes are tunica fibrosa, casting solution is through spinneret stream
Go out to coagulating bath and form a film.
A kind of 8. preparation method of improved polyvinylidene fluoride NF membrane described in accordance with the claim 1, which is characterized in that institute
Kynoar ultrafiltration membranes are stated with other supporting layers or without other supporting layers, the support layer material can be nonwoven
Cloth, woven tube or tow, the structure of support layer material is polyester, nylon, polypropylene, polyhexamethylene adipamide, poly- terephthaldehyde
Sour glycol ester, it is poly- between paraphenylene terephthalamide's m-phenylene diamine (MPD), poly- paraphenylene terephthalamide, p-phenylenediamine, polyvinyl chloride, polyacrylonitrile, poly-
One or more in amide, polyurethanes, polyvinyl formal.
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