CN108993164A - A kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof - Google Patents

A kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof Download PDF

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Publication number
CN108993164A
CN108993164A CN201710422260.1A CN201710422260A CN108993164A CN 108993164 A CN108993164 A CN 108993164A CN 201710422260 A CN201710422260 A CN 201710422260A CN 108993164 A CN108993164 A CN 108993164A
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hollow fiber
kynoar
fiber membrane
membrane
pvdf microporous
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CN108993164B (en
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刘富
林海波
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • 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
    • 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes

Abstract

The present invention provides a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane, it includes the following steps: a) to mix Kynoar, the first organic solvent and pore-foaming agent, obtain Kynoar casting solution, b) spinning is carried out to the Kynoar casting solution, polyvinylidene fluoride hollow fiber primary membrane is made；And c) the polyvinylidene fluoride primary membrane is soaked in an etching solution, the pore-foaming agent in the polyvinylidene fluoride primary membrane is set to be etched and form multiple apertures, obtain Pvdf Microporous Hollow Fiber Membrane, wherein, Kynoar is crystallized to obtain the Kynoar of crystal type in Pvdf Microporous Hollow Fiber Membrane, and ratio shared by beta crystal is more than or equal to 30% in the Kynoar of crystal type.The present invention also provides a kind of Pvdf Microporous Hollow Fiber Membranes.

Description

A kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof
Technical field
The present invention relates to polymeric film material technical field more particularly to a kind of Pvdf Microporous Hollow Fiber Membrane and its systems Preparation Method.
Background technique
Kynoar (PVDF) is the fluoropolymer of semicrystalline, and host molecule segment group becomes line style- CH2CF2, fluorinated volume reaches 59%.- C-C- key in PVDF structure segment is surrounded by H atom and symmetrical F atom, is caused PVDF has excellent mechanical strength, heat-resistant stability, weatherability, resistance to oxidation, corrosion-resistant, chemicals-resistant, radiation hardness, highly crystalline Etc. performances.PVDF is the important membrane material of micro-filtration, ultra-filtration process, and the hollow-fibre membrane based on PVDF preparation is led in sewage treatment It is used widely in domain.
However, in sewage disposal process, when sewage is contacted with PVDF hollow-fibre membrane, it may appear that film surface pollution.It is dirty Particle, colloid, macromolecular solute in water etc. form the physics chemical actions such as absorption, deposition in film surface or fenestra, cause Membrane aperture gradually becomes smaller until blocking, causes the generation of UF membrane efficiency sharply to decline.
In recent years, for the antipollution of hollow-fibre membrane, mainly start in terms of several: first method is cleaning, i.e., Film surface is rinsed by solution such as acid, alkali, oxidants, and combines the techniques such as aeration, backwash, removes the dirt of hollow fiber membrane surface Contaminate object.But the first method easily makes membrane body be damaged, and declines to a great extent so as to cause the service life of hollow-fibre membrane.The Two kinds of methods are that addition is modified.For example Chinese patent application (application No. is 201010615945.6) is disclosed by being film-made Carbon nanotube is added in journey, with performances such as the anti-protein adsorption, the sterilizations that increase hollow-fibre membrane.Chinese patent application (application number 201010153211.0) to disclose by the way that polymethacrylates, propylene carbonate etc. are added in film-forming process, to increase Add the anti-organic contamination physical performance of hollow-fibre membrane.But this method easily leads to the mechanical performance decline of hollow-fibre membrane, fenestra knot It is big that structure adjusts difficulty.Chinese patent application (application No. is 201310519163.6) is unsaturated by generating carbon carbon in film surface Hydrophilic acrylic acid and alcohols monomer are grafted to PVDF ultrafiltration membrane surface to construct hydrophilic layer, hindered by key, hydroxyl and carboxyl etc. Every organic substance film surface absorption and deposition.But the method need to be chemically treated film surface to generate active site, Injury will cause to membrane body.Thus, finding novel pollution-resistant PVDF hollow-fibre membrane of one kind and preparation method thereof has ten Divide important science and application prospect.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of Pvdf Microporous Hollow Fiber Membrane and its preparation sides Method.The membrane body of the obtained Pvdf Microporous Hollow Fiber Membrane does not damage, and has preferable mechanical performance.
The present invention provides a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane comprising following steps:
A) Kynoar, the first organic solvent and pore-foaming agent are mixed, so that Kynoar is dissolved in described first has Solvent, obtains Kynoar casting solution, and first organic solvent includes N-Methyl pyrrolidone, N, N- dimethylacetamide At least one of amine, dimethyl sulfoxide, the temperature of dissolution are 40 DEG C~120 DEG C；
B) spinning is carried out to the Kynoar casting solution, polyvinylidene fluoride hollow fiber primary membrane is made；And
C) the polyvinylidene fluoride primary membrane is soaked in an etching solution, at the beginning of making the polyvinylidene fluoride Pore-foaming agent in filming is etched and forms multiple apertures, obtains Pvdf Microporous Hollow Fiber Membrane, wherein Kynoar exists It is crystallized to obtain the Kynoar of crystal type in Pvdf Microporous Hollow Fiber Membrane, β is brilliant in the Kynoar of crystal type Ratio shared by type is more than or equal to 30%.
The present invention also provides a kind of Pvdf Microporous Hollow Fiber Membrane that above-mentioned preparation method obtains, the Kynoar Hollow-fibre membrane includes multiple apertures, and the pore size of the aperture of the Pvdf Microporous Hollow Fiber Membrane is 1 nanometer~1 micro- Rice, the Kynoar containing crystal type in the Pvdf Microporous Hollow Fiber Membrane, beta crystal in the Kynoar of crystal type Shared ratio is more than or equal to 30%.
Compared to the prior art, this preparation method has the advantage that
Under 40 DEG C~120 DEG C of solution temperature, PVDF is dissolved in the first organic solvent, in film forming phase separation, PVDF will do it crystallization and obtain the Kynoar of beta crystal of the crystal form accounting more than or equal to 30%, i.e. alpha-crystal form structure in PVDF It can change to beta crystal.The PVDF of the beta crystal is based on two reasons: (1) temperature dissolved is higher (40 DEG C~120 DEG C)；(2) Dissolubility difference of the PVDF in the first organic solvent and etching solution is larger, first has due to the higher temperature and at this The difference of solvent and the solubility of etching solution can inhibit alpha-crystal form to grow, and PVDF is made to crystallize to form beta crystal.
Regulated and controled by the crystallization behavior to Kynoar, so that the PVDF crystalline in Kynoar casting solution The PVDF of beta crystal at crystal form accounting more than or equal to 30%.Since the PVDF of beta crystal has excellent piezoelectric property, Under electric field driven, which autonomous low amplitude vibrations or can be swung by a relatively large margin.And then it in use, reduces Or inhibits the absorption of particle, colloid, macromolecular solute etc. in the surface of Pvdf Microporous Hollow Fiber Membrane or fenestra and sink Product.In other words, the Pvdf Microporous Hollow Fiber Membrane has effective resistant to pollution performance in sewage disposal process.It can be with Understand, Pvdf Microporous Hollow Fiber Membrane can also be placed in electric field environment after operation stops, it is hollow by Kynoar The low amplitude vibrations of tunica fibrosa are swung by a relatively large margin, and are vibrated the polluter in film surface or fenestra and fallen off, to realize Self-cleaning to Pvdf Microporous Hollow Fiber Membrane.
The film of the Pvdf Microporous Hollow Fiber Membrane does not damage itself, and mechanical strength is good, corrosion resistance and thermostabilization Property it is excellent, can be used as seperation film and be applied to the fields such as water process, environmental protection, chemical industry, the energy, medicine, food, biology.
Detailed description of the invention
Fig. 1 is the infared spectrum for the Pvdf Microporous Hollow Fiber Membrane that the embodiment of the present invention 1 obtains.
Fig. 2 is surface scan Electronic Speculum (SEM) photo for the Pvdf Microporous Hollow Fiber Membrane that the embodiment of the present invention 1 obtains.
Fig. 3 is the section SEM photograph for the Pvdf Microporous Hollow Fiber Membrane that the embodiment of the present invention 1 obtains.
Fig. 4 is the surface SEM photograph for the Pvdf Microporous Hollow Fiber Membrane that the embodiment of the present invention 3 obtains.
Fig. 5 is the section SEM photograph for the Pvdf Microporous Hollow Fiber Membrane that the embodiment of the present invention 3 obtains.
Specific embodiment
Below in conjunction with the attached drawing in embodiment of the present invention, the technical solution in embodiment of the present invention is carried out clear Chu is fully described by, it is clear that described embodiment is only some embodiments of the invention, rather than whole realities Apply mode.Based on the embodiment in the present invention, those of ordinary skill in the art institute without creative efforts The every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation methods of Pvdf Microporous Hollow Fiber Membrane comprising following steps:
A) Kynoar, the first organic solvent and pore-foaming agent are mixed, so that Kynoar is dissolved in described first has Solvent, obtains Kynoar casting solution, and first organic solvent includes N-Methyl pyrrolidone, N, N- dimethylacetamide At least one of amine, dimethyl sulfoxide, the temperature of dissolution are 40 DEG C~120 DEG C；
B) spinning is carried out to the Kynoar casting solution, polyvinylidene fluoride hollow fiber primary membrane is made；And
C) the polyvinylidene fluoride primary membrane is soaked in an etching solution, at the beginning of making the polyvinylidene fluoride Pore-foaming agent in filming is etched and forms multiple apertures, obtains Pvdf Microporous Hollow Fiber Membrane, wherein Kynoar exists It is crystallized to obtain the Kynoar of crystal type in Pvdf Microporous Hollow Fiber Membrane, β is brilliant in the Kynoar of crystal type Ratio shared by type is more than or equal to 30%.
It is 4 hours~24 by the time of Kynoar, the first organic solvent and pore-foaming agent mixed dissolution in step a) Hour.Wherein, first organic solvent selects N-Methyl pyrrolidone, n,N-dimethylacetamide, dimethyl sulfoxide, with induction The crystallization behavior of Kynoar described in phase separation.It is appreciated that in order to preferably realize inducing action, it can be further The second organic solvent is added.Second organic solvent is hexamethyl-phosphoramide.Second organic solvent has with respect to first Solvent has higher solubility to PVDF, thus it is organic in first organic solvent i.e. second further to widen PVDF Poor solubility in solvent and etching solution, more conducively alpha-crystal form change to beta crystal.The additional amount of second organic solvent is not It limits, it is preferred that the volume ratio of first organic solvent and the second organic solvent is 30:70~80:20.
The mass fraction that the Kynoar accounts for the Kynoar casting solution is 12%~25%.It is poly- inclined in order to make Vinyl fluoride is preferably crystallized, and the mass fraction that the Kynoar accounts for the Kynoar casting solution is preferably 15% ~20%.
The effect of the pore-foaming agent is to make to form multiple apertures in the Pvdf Microporous Hollow Fiber Membrane.The pore-foaming agent Using water-soluble substances or inorganic carbonate, acted on and the removal of being etched property in order to subsequent with etching solution.Certainly, described The not complete removal of pore-foaming agent, in obtained Pvdf Microporous Hollow Fiber Membrane, there may be residuals.
The pore-foaming agent also has the function of the viscosity of certain adjusting Kynoar casting solution, in favor of spinning Process forms hollow-fibre membrane.The pore-foaming agent can be water-soluble substances or inorganic carbonate.The water-soluble substances are specific Including polyethylene glycol, polyvinylpyrrolidone, water-soluble inorganic nanoparticle (such as sodium chloride, lithium chloride etc.), polyoxyethylene, At least one of polyox-yethylene-polyoxypropylene block copolymer, diglycol, triethylene-glycol.The inorganic carbon Hydrochlorate specifically includes at least one of calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, barium carbonate.
The mass percent that the pore-foaming agent accounts for the Kynoar casting solution is 1%~15%.In order to obtain uniformly The aperture of distribution, the mass percent that the pore-foaming agent accounts for the Kynoar casting solution is 3%~12%.
Before step b), it may also include the step of a pair of of Kynoar casting solution carries out deaeration.Gather inclined fluorine to described Ethylene casting solution deaeration processing can be by vacuumizing and standing realization.
In step b) obtained Kynoar can be squeezed out by way of twin-screw, single screw rod or plunger type Screw Extrusion Doughnut primary membrane.
It is described poly- when the polyvinylidene fluoride primary membrane to be soaked in the etching solution in step c) The pore-foaming agent and the etching solution of the nascent film surface of vinylidene fiber act on, and in the polyvinylidene fluoride primary membrane Surface formed aperture, the etching solution is slowly arrived via the aperture on the surface of the polyvinylidene fluoride primary membrane at this time Up to inside the polyvinylidene fluoride primary membrane, and further acted on the pore-foaming agent inside polyvinylidene fluoride primary membrane And it is further formed multiple apertures.
When the pore-foaming agent is inorganic carbonate, the etching solution selects acid solution, using inorganic carbonate with Reaction between the acid solution and be dissolved inorganic carbonate and " chemically etching " is fallen, form aperture.When the cause When hole agent is water-soluble substances, the etching solution is water or acid solution, is dissolvable in water water using water-soluble substances And " physical etching " is fallen, and aperture is formed.
The etching solution is acid solution or water.The acid solution is sulfuric acid, in hydrochloric acid, phosphoric acid, nitric acid, acetic acid At least one.Mole solubility of the acid solution is unlimited, preferably 1.5mol/L~4.0mol/L.
It is 1 hour~72 hours that the polyvinylidene fluoride primary membrane, which immerses the soaking time in the etching solution, Preferably 1 hour~24 hours.The soaking process can carry out at room temperature.
Further, in the polyvinylidene fluoride primary membrane after etching solution immersion, it can also carry out water extraction and wash The step of, to remove the impurity such as the remaining etching solution in the Pvdf Microporous Hollow Fiber Membrane.
The present invention also provides a kind of Pvdf Microporous Hollow Fiber Membranes obtained using above-mentioned preparation method.It is described to gather inclined fluorine Ethylene hollow-fibre membrane includes multiple apertures.The aperture of the aperture is 1 nanometer~1 micron.Between the multiple aperture mutually Connection.
Containing the Kynoar of crystal type in the Pvdf Microporous Hollow Fiber Membrane, in the Kynoar of crystal type Ratio shared by beta crystal is more than or equal to 30%.In order to which the Pvdf Microporous Hollow Fiber Membrane has better self-cleaning performance, Ratio shared by beta crystal is more than or equal to 50% in the Kynoar of crystal type.
The methods of relatively existing chemical modification causes the damage of film big, and the Kynoar that this method is prepared is hollow The membrane damage of tunica fibrosa is smaller, and mechanical strength is good, corrosion resistance and good heat stability, can be used as seperation film and is applied to The fields such as water process, environmental protection, chemical industry, the energy, medicine, food, biology.
The preparation method simple process of the Pvdf Microporous Hollow Fiber Membrane, high-efficient, suitable industrialized production.
The preparation method of Pvdf Microporous Hollow Fiber Membrane of the invention is illustrated combined with specific embodiments below:
Embodiment 1
15g Kynoar, 40g dimethyl sulfoxide and 40g hexamethyl-phosphoramide are added to the container by step (1), and 80 DEG C Stirring and dissolving 5 hours；5g polyethylene glycol is added, 80 DEG C are stirred 1 hour；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 20 minutes obtained, then 80 DEG C of standing and defoamings 12 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system；
Step (3) solidifies hollow-fibre membrane primary membrane by 25 DEG C of deionized water, then by the hollow fibre after solidification Dimension film, which is immersed in 25 DEG C of deionized water, keeps 24 hours, sufficiently removal dimethyl sulfoxide, hexamethyl-phosphoramide and poly- second two Alcohol obtains Pvdf Microporous Hollow Fiber Membrane after dry.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.In electric field environment, by three days, this gathered inclined fluorine Ethylene hollow-fibre membrane is to the adsorption rate of bovine serum albumin(BSA) less than 0.5%.
Infrared absorption spectrum test also is carried out to the Pvdf Microporous Hollow Fiber Membrane.The result is shown in Figure 1.Have Fig. 1 as it can be seen that In 470cm-1、511cm-1、840cm-1These three positions correspond to the beta crystal absorption peak of PVDF.This obtained Kynoar There are beta crystal PVDF in hollow-fibre membrane.
Pattern test also is carried out to the Pvdf Microporous Hollow Fiber Membrane.As a result see Fig. 2 and Fig. 3.It can by Fig. 2 to Fig. 3 See, Pvdf Microporous Hollow Fiber Membrane surface and section have beta crystal structure.
Embodiment 2
Step (1) by 16g Kynoar, 40g hexamethyl-phosphoramide and 40g N-Methyl pyrrolidone, be added container In, 60 DEG C stirring and dissolving 12 hours；4g diglycol is added, is stirred 3 hours；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 25 minutes obtained, then 60 DEG C of standing and defoamings 24 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system and by substrate of woven tube；
Step (3) solidifies hollow-fibre membrane primary membrane by 30 DEG C of deionized water, then by the hollow fibre after solidification Dimension film, which is immersed in 30 DEG C of deionized water, is kept for 18 hours, sufficiently remove hexamethyl-phosphoramide, N-Methyl pyrrolidone and Diglycol obtains Pvdf Microporous Hollow Fiber Membrane after dry.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.Beta crystal institute in Pvdf Microporous Hollow Fiber Membrane The crystal form ratio accounted for is 53%.
Embodiment 3
Step (1) is by 18g Kynoar, 6g polyoxyethylene, 50gN, N- dimethyl acetamide and 26g hexamethyl phosphoric acid Amide is added to the container, 70 DEG C stirring and dissolving 8 hours；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 30 minutes obtained, then 70 DEG C of standing and defoamings 18 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system；
Step (3) solidifies hollow-fibre membrane primary membrane by 30 DEG C of deionized waters, then by the doughnut after solidification Film, which is immersed in 25 DEG C of deionized water, keeps 20 hours, sufficiently removal polyoxyethylene, n,N-dimethylacetamide and hexamethyl Phosphoamide obtains Pvdf Microporous Hollow Fiber Membrane after dry.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.Beta crystal institute in Pvdf Microporous Hollow Fiber Membrane The crystal form ratio accounted for is 60%.
Pattern test also is carried out to the Pvdf Microporous Hollow Fiber Membrane.As a result see Fig. 3.
As seen from Figure 3, there are apparent beta crystal structures in the section of Pvdf Microporous Hollow Fiber Membrane.
Embodiment 4
Step (1) is by 14g Kynoar, 2g polyoxyethylene, 2g polyethylene glycol, 20g dimethyl sulfoxide, 22g N, N- diformazan Yl acetamide and 40g hexamethyl-phosphoramide are added to the container, 50 DEG C stirring and dissolving 12 hours；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 30 minutes obtained, then 50 DEG C of standing and defoamings 24 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system；
Step (3) solidifies hollow-fibre membrane primary membrane by 30 DEG C of deionized water, then by the hollow fibre after solidification Dimension film, which is immersed in 30 DEG C of deionized water, keeps 20 hours, sufficiently removal polyoxyethylene, polyethylene glycol dimethyl sulfoxide, N, N- bis- Methylacetamide and hexamethyl-phosphoramide obtain Pvdf Microporous Hollow Fiber Membrane after dry.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.β is brilliant in the Pvdf Microporous Hollow Fiber Membrane Crystal form ratio shared by type is 63%.
The Pvdf Microporous Hollow Fiber Membrane reaches 100% to the bovine serum albumin(BSA) rejection of 1g/L, in electric field loop In border, after operation 3 days, to the adsorption rate of bovine serum albumin(BSA) less than 1%.
Embodiment 5
Step (1) contracts 20g Kynoar, 1g polyox-yethylene-polyoxypropylene block copolymer, 1g sodium chloride, 2g mono- Diethylene glycol, 46g n,N-dimethylacetamide and 30g hexamethyl-phosphoramide are added to the container, and 65 DEG C of stirring and dissolvings 10 are small When；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 40 minutes obtained, then 65 DEG C of standing and defoamings 18 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system；
Step (3) solidifies hollow-fibre membrane primary membrane by 30 DEG C of deionized water, then by the hollow fibre after solidification Dimension film, which is immersed in 30 DEG C of deionized water, keeps 20 hours, sufficiently removal polyox-yethylene-polyoxypropylene block copolymer, a contracting Diethylene glycol and n,N-dimethylacetamide obtain Pvdf Microporous Hollow Fiber Membrane after dry.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.β is brilliant in the Pvdf Microporous Hollow Fiber Membrane Crystal form ratio shared by type is 39%.
The Pvdf Microporous Hollow Fiber Membrane is in electric field environment, after operation 3 days, to the adsorption rate of bovine serum albumin(BSA) Less than 3%.
Embodiment 6
Step (1) is by 18g Kynoar, 2g magnesium carbonate, 3g polyoxyethylene, 33gN- methyl pyrrolidone and 44g pregnancy Base phosphoamide is added to the container, 100 DEG C stirring and dissolving 4 hours；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 25 minutes obtained, then 100 DEG C of standing and defoamings 12 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system；
Step (3) solidifies hollow-fibre membrane primary membrane by 25 DEG C of deionized water, then by the hollow fibre after solidification Keep 10 hours in the aqueous citric acid solution of the dimension film 2mol/L that is immersed in 30 DEG C, 10 hours in being immersed in room temperature water, sufficiently Magnesium carbonate, polyoxyethylene, N-Methyl pyrrolidone and hexamethyl-phosphoramide are removed, obtains the hollow fibre of Kynoar after dry Tie up film.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.β is brilliant in the Pvdf Microporous Hollow Fiber Membrane Crystal form ratio shared by type is 45%.
The Pvdf Microporous Hollow Fiber Membrane is in electric field environment, after operation 3 days, to the adsorption rate of bovine serum albumin(BSA) Less than 2%.
Embodiment 7
Step (1) is sub- by 15g Kynoar, 3g diglycol, 1g polyoxyethylene, 5g polyethylene glycol, 36g diformazan Sulfone and 40g hexamethyl-phosphoramide are added to the container, 90 DEG C stirring and dissolving 6 hours；
Step (2) will sufficiently dissolve the vacuum defoamation of Kynoar casting solution 25 minutes obtained, then 90 DEG C of standing and defoamings 16 hours, doughnut primary membrane was prepared through hollow-fibre membrane spinning system；
Step (3) solidifies hollow-fibre membrane primary membrane by 30 DEG C of deionized water, then by the hollow fibre after solidification Dimension film, which is immersed in 30 DEG C of deionized water, is kept for 24 hours, sufficiently remove diglycol, polyoxyethylene, polyethylene glycol, Dimethyl sulfoxide and hexamethyl-phosphoramide obtain Pvdf Microporous Hollow Fiber Membrane after dry.
The Pvdf Microporous Hollow Fiber Membrane is tested for the property.β is brilliant in the Pvdf Microporous Hollow Fiber Membrane Crystal form ratio shared by type is 55%.
The Pvdf Microporous Hollow Fiber Membrane is in electric field environment, after operation 3 days, to the adsorption rate of bovine serum albumin(BSA) Less than 1.5%.100% is reached to silicon dioxide microparticle rejection, flux 1000L/m2h。
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (10)

1. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane comprising following steps:
A) Kynoar, the first organic solvent and pore-foaming agent are mixed, so that Kynoar is dissolved in described first organic molten Agent, obtains Kynoar casting solution, first organic solvent include N-Methyl pyrrolidone, n,N-dimethylacetamide, At least one of dimethyl sulfoxide, the temperature of dissolution are 40 DEG C~120 DEG C；
B) spinning is carried out to the Kynoar casting solution, polyvinylidene fluoride hollow fiber primary membrane is made；And
C) the polyvinylidene fluoride primary membrane is soaked in an etching solution, makes the polyvinylidene fluoride primary membrane In pore-foaming agent be etched and form multiple apertures, obtain Pvdf Microporous Hollow Fiber Membrane, wherein Kynoar is poly- inclined It is crystallized to obtain the Kynoar of crystal type in vinyl fluoride hollow-fibre membrane, beta crystal institute in the Kynoar of crystal type The ratio accounted for is more than or equal to 30%.
2. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane as described in claim 1, which is characterized in that in step a) The mass fraction that the Kynoar accounts for the Kynoar casting solution is 12%~25%.
3. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane as described in claim 1, which is characterized in that in step a) The second organic solvent is further added into the Kynoar casting solution, second organic solvent is hexamethyl phosphoric acid acyl Amine.
4. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane as described in claim 1, which is characterized in that in step a) The pore-foaming agent includes that polyethylene glycol, polyvinylpyrrolidone, water-soluble inorganic nanoparticle, polyoxyethylene, polyoxyethylene-are poly- At least one of oxypropylene block copolymer, diglycol, triethylene-glycol, inorganic carbonate.
5. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane as described in claim 1, which is characterized in that in step a) The mass percent that the pore-foaming agent accounts for the Kynoar casting solution is 1%~15%.
6. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane as described in claim 1, which is characterized in that in step a) The time of the dissolution is 4 hours~24 hours.
7. a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane as described in claim 1, which is characterized in that in step c) The etching solution is water or acid solution, and the acid solution is sulfuric acid, in hydrochloric acid, phosphoric acid, nitric acid, acetic acid, citric acid At least one.
8. a kind of using the Pvdf Microporous Hollow Fiber Membrane obtained such as any one of claim 1 to 7 preparation method, feature exists In the Pvdf Microporous Hollow Fiber Membrane includes multiple apertures, the aperture of the aperture of the Pvdf Microporous Hollow Fiber Membrane Size is 1 nanometer~1 micron, the Kynoar containing crystal type in the Pvdf Microporous Hollow Fiber Membrane, crystal type Ratio shared by beta crystal is more than or equal to 30% in Kynoar.
9. a kind of Pvdf Microporous Hollow Fiber Membrane as claimed in claim 8, which is characterized in that the Kynoar of crystal type Ratio shared by middle beta crystal is more than or equal to 50%.
10. a kind of Pvdf Microporous Hollow Fiber Membrane as claimed in claim 8, which is characterized in that in the Kynoar The classification of empty fiber membrane is doughnut homogeneous membrane, hollow fiber composite membrane or hollow-fibre membrane asymmetric membrane.
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