CN101190401A - Hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof - Google Patents
Hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrophilic polyvinylidene fluoride hollow fiber microporous membrane and the preparation method thereof. The main composition and the mass content of the membrane are 70% to 90% of polyvinylidene fluoride, amphiphilic poly-(propylene oxide-oxirane), 5% to 29% of poly-(methacrylic acid- acrylic acid) or poly-(methacrylic acid methyl ester-vinyl alcohol) copolymer and 1% to 5% of nano-silicon dioxide. The membrane preparation method is that all the components are mixed and dissolved with aperture regulator, thickener and solvent to obtain the membrane preparation liquid; after that, the hollow fiber forming is carried out through a dry-wet spinning technique, and finally cleaning and drying are implemented. The obtained membrane has adjustable internal diameter and external diameter, 60% to 80% of porosity and the aperture ranging from 0.01micron to 0.2micron. As a water disposal separating membrane material with excellent performance, the invention has the advantages of being able to be fully humid, organic adsorption resistance and great water flux, etc.
Description
Technical field
The invention belongs to separation membrane material and membrane separation technique field, particularly be suitable for water treatment, based on hydrophilic Kynoar hollow-fibre membrane and their preparation method.
Background technology
Membrane separation technique, is widely used in fields such as medicine, chemical industry, the energy, food, environmental projects owing in use have advantages such as energy consumption is low, separating property good, non-secondary pollution at present as a kind of new separation technology.And select the separation membrane material of function admirable is the starting point and the core of membrane separation technique, also is the direction and the emphasis of membrane separation technique research and development.Separation membrane material mostly is polymer, mainly contain modified fibre, polyethylene, polypropylene, polyvinyl chloride, polyether sulfone, polysulfones, polyolefin, polyamide, Merlon, acrylic copolymer, fluoropolymer etc., the microporous barrier that is become by these polymer manufacture occupies leading position in film separation processes such as water treatment such as the micro-filtration of liquid, ultrafiltration, nanofiltration, counter-infiltration and gas purification, gas-liquid separation.As the polymer of membrane material, should have character such as heat-resisting, acid and alkali-resistance, anti-microbial attack, anti-solvent, and characteristics such as cost is moderate, the system film is convenient.In numerous potential polymeric film material, Kynoar (PVDF) is a kind of crystal polymer thing, C-F bond distance is short, the bond energy height, have good chemical stability and hear resistance, be to be used to one of preferred material for preparing diffusion barrier, in microporous membrane materials such as water treatment micro-filtration, ultrafiltration, occupy critical role.
Than other membrane material, the most outstanding characteristics of PVDF are that the surface can be low, has extremely strong hydrophobicity, these character make the PVDF microporous barrier in hydrophobic membrane processes such as membrane extraction and film distillation good advantage be arranged, but being used as membrane for water treatment be, the intrinsic strong-hydrophobicity of PVDF can cause two problems: the one, and be easy to generate absorption and pollute, when separating oil/aqueous systems (especially proteinaceous solution), membrane flux mainly separates index with two of rejection and will obviously descend, film shortening in service life; The 2nd, separation process needs bigger driving force, and test shows that average pore size is the PVDF micro-filtration membrane of 0.2 μ m, water flowing hardly under 0.1MPa pressure reduction.Therefore, the hydrophobicity of PVDF is the principal element of restriction PVDF microporous barrier in a lot of water treatment field large-scale application, by pvdf membrane being carried out hydrophilically modified realization PVDF microporous barrier high performance, realizing its water permeability, improve resistance tocrocking and realize that membrane structure and stable performance PVDF micro-filtration/milipore filter are used for the problem that extensive water treatment headman Cheng Bixu solves.
The method of PVDF diffusion barrier hydrophilic modifying mainly can be summed up as membrane surface modification and membrane body (or matrix) modification two big classes.
The essence of membrane surface modification is to introduce polar group or hydrophily macromolecular chain on the surface, mainly by methods (wherein chemical treatment, grafting belong to chemical modification method) such as chemical surface treatment, surface grafting, surface-coated.Though PVDF has good stable, still can so that taking place, chemical reaction introduce the performing hydrophilic modification on surface that groups such as the carbonyl of polarity, hydroxyl, carboxyl are realized polyvinylidene fluoride microporous film on the film surface under certain condition with strong acid or highly basic.But, the polar group that strong acid or highly basic are introduced on the pvdf membrane surface is little, not only initial hydrophilic effect is low, polar group also can be embedded into gradually below the film superficial layer by the rotation of Kynoar strand and cause hydrophily to be degenerated gradually, and process complexity, film-strength reduce, and also produces reluctant spent acid/salkali waste and pollute.It mainly is to generate the activated centre by technology such as irradiation, light-initiated, plasmas at material surface that grafting is handled, and the method by graft polymerization reaction obtains long hydrophily chain on the film surface again.And surface-coated is mainly to be by hydrogen bond, the mode of action such as crosslinked, introduces the ultra-thin hydrophilic cortex of one deck on the film surface.The advantage of surface grafting is that hydrophilic effect is good, hydrophily is lasting, and deficiency is that hydrophiling process complexity, film-strength decline and efficient are lower.In PVDF microporous barrier surface grafting hydrophilization methods, European patent (the patent No.: 0249513) reported that the using plasma technology contains unsaturated ethylene or acrylic monomer at pvdf membrane surface grafting acrylic acid, acrylamide etc., has obtained having better hydrophilic PVDF microporous barrier; United States Patent (USP) (the patent No.: in a kind of method for preparing hydrophilic PVDF ultrafiltration/micro-filtration membrane that 2006157404) discloses, adopted at film surface-coated or blend polymethyl vinyl ether (PVME) layer, and passed through further crosslinked its stability of raising hydrophilic layer of PVME; Chinese patent (the patent No.: 1704152) disclose the method that one-step method prepares hydrophilic PVDF microporous barrier, feature is when solvent evaporated method prepares microporous barrier film to be immersed in the hydrophily modified-high polymer solution such as containing polyvinyl alcohol, shitosan, obtains the PVDF microporous barrier on possess hydrophilic property top layer at last.
The membrane body method of modifying can be divided into chemical treatment modification and blending and modifying two big classes.The former generally carries out in two steps: at first be PVDF to be carried out " activation " handle, make the active site that produces easy oxidation on its strand or generate free radical, again according to the feature of active site, select for use the PVDF after suitable reagent and " activation " processing to react, thereby directly on its strand, introduce hydroxyl, carboxyl isopolarity group or grafting hydrophilic monomer.Such as, United States Patent (USP) (the patent No.: 2002147282) pass through ATRP, successfully on PVDF, introduce polyethylene glycol oxide methacrylate (POEM), the polymethylacrylic acid big molecules of hydrophily such as (PMAA), and then be prepared into PVDF microporous barrier with excellent hydrophilic with the PVDF of POEM or PMAA grafting.Blending and modifying then is according to the theory analysis of polyblend compatibility and experimental study, select suitable hydrophilic component and PVDF to carry out being prepared into the hydrophilic PVDF blend film by solution phase inversion process again after the liquid phase blend, this method has simple, the efficient advantages of higher of process; Characteristics such as the blend film that obtains keeps promptly that PVDF is high temperature resistant, favorable mechanical and chemical stability possess the hydrophily from hydrophilic component again.At present, the used hydrophilic component of research report mainly contains PMA, polyvinyl acetate, polymethyl methacrylate, gathers 1,4-butadiene hexanedioic acid etc.Such as, 4810384), the European patent (patent No.: 1464477 United States Patent (USP) (the patent No.:, 1682238) method of employing blend cellulose acetate, polyvinylpyrrolidone, hydroxy alkyl cellulose etc. prepares hydrophilic PVDF ultrafiltration/micro-filtration membrane, and the content of hydrophilizing agent is no more than 30%; United States Patent (USP) (the patent No.: 5151193) by the hydrophilic pvdf membrane of blend sulfonated polyether-ether-ketone (PEEKSO) preparation; United States Patent (USP) (the patent No.: compound the aluminium oxide of PVDF and calcining in 5914039,6024872), add polyvinyl alcohol (HPVA) again and obtained the high-throughout PVDF blend film of hydrophily.
Above-mentioned hydrophilic PVDF microporous barrier and preparation method thereof has their own characteristics each, but still comes with some shortcomings part.Summary is got up, and these are not enough, and main performance has: membrane surface modification has often changed the aperture and the pore-size distribution on film surface to a certain extent; Physisorphtion only makes the hydrophily high polymer be adsorbed on film surface or inner by physisorption, and hydrophilizing agent very easily runs off when recycling, and causes hydrophily not keep for a long time; Chemical modification tends to influence the separation film strength to a certain extent, and treatment conditions are relatively harsh; Though the glycerol polymerization method can be fixed functional group with covalent bond, treatment process is more complicated often, and the hydrophilic radical of its grafting often moves in the film matrix under the effect of chain movement, causes degradation under the hydrophily; The loss easily of hydrophilic polyethene pyrrolidones, sulfonated polyether-ether-ketone or the cellulose that adopts in this property of body and the PVDF compatibility is poor, membrane structure lasting stability difference etc.
With reported in the past different, the present invention combines necessary factors such as the stability, film preparation efficient of the effect of hydrophilic modifying and persistence, membrane structure, on the basis of fully experiment, three kinds of hydrophilic PVDF hollow fiber microporous membranes of blending type that contain amphipathic copolymer are disclosed and based on the preparation method of solution inversion of phases principle.Prepared Kynoar hollow fiber microporous membrane has good hydrophilicity and high water flux, is high-performance micro-filtration or the milipore filter material that is suitable for the isolation and purification of systems such as water treatment, medicine separation.
Summary of the invention:
The purpose of this invention is to provide a kind of hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof.
1, a kind of hydrophilicity kynoar hollow fiber microporous membrane, membrane micropore aperture are that 0.01～0.2 micron, membrane porosity are 60～80%, film thickness is that 0.3～0.5 millimeter, film external diameter are 1～2 millimeter; The component of film and mass percent are: Kynoar, 70～90%; Amphipathic copolymer: poly-(methyl methacrylate-vinyl alcohol), poly-(methyl methacrylate-acrylic acid) or poly-(expoxy propane-oxirane), 5-29%; Silicon dioxide powder: 1～5%.
2, the method for forming by preparation preparation liquid, hollow-fibre membrane moulding, three steps of cleaning-drying successively for preparing the hydrophilicity kynoar hollow fiber microporous membrane, and the prescription or the technology in each step:
(1) preparation preparation liquid: with Kynoar, amphipathic copolymer, silicon dioxide powder, aperture adjustment agent, thickener and solvent, abundant stirring and dissolving under 20～60 ℃ obtains uniform preparation liquid after the standing and defoaming;
(2) hollow-fibre membrane moulding: the preparation liquid with 20～50 ℃ core liquid and 20～50 ℃ is emitted into the tubulose liquid film by spinning head, and this liquid film enters 20～40 ℃ by in the coagulating bath after through 5～30 centimetres air-gap, is frozen into solid-state hollow-fibre membrane through inversion of phases;
(3) cleaning-drying: solid-state hollow-fibre membrane dried in 10～30 ℃ of water loggings bubble cleans 40-60 hour, air obtain described Kynoar hollow fiber microporous membrane;
In hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof, the PVDF molecular weight of employing is 4 * 10
4～1 * 10
6, amphipathic copolymer is that molecular weight is 10
3～10
5, have poly-(methyl methacrylate-vinyl alcohol) of block or disordered structure, poly-(methyl methacrylate-acrylic acid) or poly-(expoxy propane-oxirane), the silicon dioxide powder particle diameter is 10～500 nanometers, solvent is N, N '-dimethyl formamide, N, N '-dimethylacetylamide or N-methyl pyrrolidone, thickener are 2 * 10
4～1 * 10
6Polyvinylpyrrolidone, aperture adjustment agent are lithium chloride or water;
In the preparation liquid of preparation, each component and quality percentage composition thereof are: Kynoar: 12～18%; Amphipathic copolymer, 2～8%; Silicon dioxide powder, 0.1～2%; Aperture adjustment agent: 1～5%; Thickener: 0.1～1%; Solvent: 70～84%;
In the hollow-fibre membrane forming step, each constituent mass of core liquid divides percentage to be: water: 40～100%, and a kind of solvent identical: 0～60% with the preparation liquid solvent; Each constituent mass of coagulating bath divides percentage to be: water: 30～100%; A kind of solvent identical: 0～70% with the preparation liquid solvent;
In the preparation liquid preparation steps, component and quality percentage composition thereof are in the described preparation liquid: Kynoar: molecular weight is 4 * 10
4～1 * 10
6, 12～18%; Amphipathic copolymer: molecular weight is 10
3～10
5Poly-(methyl methacrylate-vinyl alcohol), poly-(methyl methacrylate-acrylic acid) or poly-(expoxy propane-expoxy propane), 2～8%; Silica: particle diameter is the silicon dioxide powder of 10～500 nanometers, 0.1～2%; Aperture adjustment agent: lithium chloride or water, 1～5%; Thickener: molecular weight is 2 * 10
4～1 * 10
6Polyvinylpyrrolidone, 0.1～1%; Solvent: N, N '-dimethyl formamide, N, N '-dimethylacetylamide or N-methyl pyrrolidone: 70～84%;
In the forming step of hollow-fibre membrane, described each constituent mass of core liquid divides percentage to be: water: 40～100%; Solvent: N, N '-dimethyl formamide, N, identical with the preparation liquid solvent a kind of in N '-dimethylacetylamide or the N-methyl pyrrolidone: 0～60%; Each constituent mass of described coagulating bath divides percentage to be: water: 30～100%; Solvent: N, N '-dimethyl formamide, N, identical with the preparation liquid solvent a kind of in N '-dimethylacetylamide or the N-methyl pyrrolidone: 0～70%;
In hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof, in (methyl methacrylate-vinyl alcohol) copolymer of employing, the molar percentage of hydrophilic monomer vinyl alcohol groups is 50～80%; The molar percentage of hydrophobic monomer methyl methacrylate group is 20～50%; In poly-(methyl methacrylate-acrylic acid) copolymer, the molar percentage of hydrophilic monomer acrylic acid groups is 40～60%; The molar percentage of hydrophobic monomer methyl methacrylate group is 40～60%; In (expoxy propane-oxirane) copolymer, the molar percentage of hydrophilic monomer ethylene oxide group is 30～80%; The molar percentage of hydrophobic monomer propylene oxide group is 20～70%.
Advantage of the present invention:
(1) amphipathic copolymer is for containing the block copolymer of hydrophobic segment and hydrophilic segment simultaneously, according to the similar compatibility principle, the existence of hydrophobic segment will make amphipathic copolymer and PVDF have good compatibility, and the structure of film and the stability of intensity and persistence are good.
(2) given film-forming method, hydrophilic segment is enriched in the surface of film in the film forming procedure, is blended into the hydrophily that a small amount of amphipathic copolymer can significantly improve film in PVDF.
(3) existence of hydrophobic segment in the amphipathic copolymer makes between amphipathic copolymer and the PVDF adhesion strong, is difficult for running off at film use amphipathic copolymer, and the film hydrophily is lasting.
(4) hydrophilic component on blend film surface forms hydrated sheath by hydrogen bond, can effectively hinder hydrophobic organic compound matter (as the material of formation film pollutions such as protein) in the absorption of film surface, improves the resistance tocrocking of film in the water treatment applications process.
(5) preparation method of hydrophilic PVDF microporous barrier different from the past, the amphipathic copolymer method of employing provided by the present invention blend in preparation liquid, the preparation and the hydrophiling process that can realize the PVDF hollow fiber microporous membrane are integrated, and preparation and modification efficiency height are realized large-scale application easily.
(6) by nanometer SiO
2Improve the mechanical strength of doughnut, guaranteed film endurance impact in use.
(7) hydrophilic PVDF doughnut membrane preparation method provided by the present invention, conditions such as the composition of length of hydrophilic chain by the control copolymer and content, coagulating bath, temperature, spinning speed, structure and performances such as the wall thickness of controlling diaphragm, pore size, porosity, hydrophily easily.
Description of drawings
Fig. 1 is the forming process schematic diagram of hollow-fibre membrane;
Fig. 2 is a test PVDF hollow fiber microporous membrane sample flux modular construction schematic diagram;
Fig. 3 (a) is a PVDF hollow fiber microporous membrane electron scanning micrograph (section) among the embodiment 9-A;
Fig. 3 (b) is a PVDF hollow fiber microporous membrane electron scanning micrograph (inner surface) among the embodiment 9-A;
Fig. 3 (c) is a PVDF hollow fiber microporous membrane electron scanning micrograph (outer surface) among the embodiment 9-A.
The specific embodiment
Micropore size disclosed in this invention is that 0.01～0.2 micron, membrane porosity are 60～80%, film thickness is that 0.3～0.5 millimeter, film external diameter are 1～2 millimeter, contain a kind of hydrophilicity kynoar hollow fiber microporous membrane of amphipathic copolymer and silica nanometer powder blend components, is that phase inversion open by the present invention, that be made up of three steps prepares:
(1) preparation preparation liquid: with Kynoar, amphipathic copolymer, silicon dioxide powder, aperture adjustment agent, thickener and solvent, abundant stirring and dissolving becomes uniform preparation liquid under 20～60 ℃, obtains being used to prepare the preparation liquid of hollow-fibre membrane after the degassing;
(2) hollow-fibre membrane moulding: 20～50 ℃ preparation liquid is emitted into the tubulose liquid film via spinning head with 20～50 ℃ core liquid, this liquid film enters 20～40 ℃ after through 5～30 centimetres air-gap and is solidified into hollow-fibre membrane by coagulating bath, and film-forming is that the mass exchange between component and core liquid (in fact also being interior coagulating bath) in the liquid film, the outer coagulating bath (being usually said coagulating bath) is gone into shown in the accompanying drawing 1.
(3) cleaning-drying: solid-state hollow-fibre membrane dried in 10～30 ℃ of water loggings bubble cleans 40-60 hour, air obtain described Kynoar hollow fiber microporous membrane.
Kynoar of the present invention (PVDF) molecular weight is 4 * 10
4～1 * 10
6, 12～18%.
Amphipathic copolymer of the present invention: molecular weight is 10
3～10
5Poly-(methyl methacrylate-acrylic acid) (PMMA-AA), poly-(expoxy propane-oxirane) (PPO-EO) or poly-(methyl methacrylate-vinyl alcohol) (PMMA-VAc), 2-8%.The molar percentage of hydrophilic monomer acrylic acid groups (AA) is 40～60% among the PMMA-AA; The molar percentage of hydrophobic monomer methyl methacrylate group (MMA) is 40～60%; The molar percentage of hydrophilic monomer ethylene oxide group (EO) is 30～80% among the PPO-EO; The molar percentage of hydrophobic monomer propylene oxide group (PO) is 20～70%; The molar percentage of hydrophilic monomer vinyl alcohol groups (VAc) is 50～80% among the PMMA-VAc; The molar percentage of hydrophobic monomer methyl methacrylate group (MMA) is 20～50%.
Silica (SiO of the present invention
2) particle diameter of powder is in 10～500 nanometers.
Among the present invention, the middle PVDF of hydrophilicity kynoar hollow fiber microporous membrane, amphipathic copolymer, SiO
2The ratio that depends on these components in the preparation liquid Deng component ratio.In hollow-fibre membrane moulding and cleaning process, the solvent in the preparation liquid, thickener and aperture adjustment agent major part all are dissolved in coagulating bath or the rinse water, have only PVDF, amphipathic copolymer and SiO basically
2Three kinds of components are retained in the hollow fiber microporous membrane that obtains at last, and are basic identical in the ratio of these three kinds of components and the preparation liquid in the film.
Aperture adjustment agent of the present invention is lithium chloride (LiCl) or water.
Thickener of the present invention is that molecular weight is 2 * 10
4～1 * 10
6Between polyvinylpyrrolidone (PVP).
Solvent of the present invention: N, N '-dimethyl formamide (DMF), N, N '-dimethylacetylamide (DMAC) or N-methyl pyrrolidone (NMP).
In the preparation liquid of preparation, each component and quality percentage composition thereof are: PVDF, 12～18%; The aperture adjustment agent, 1～5%; Thickener, 0.1～1%; Solvent, 70～84%.
In the hollow-fibre membrane forming step, adopt consisting of of core liquid: water, 40～100%; A kind of solvent identical with preparation liquid, 0～60%.
In the hollow-fibre membrane forming step, adopt each constituent mass of coagulating bath to divide percentage to be: 30～100%; A kind of solvent identical with preparation liquid, 0～70%.
Pore size, porosity and cutoff performance that molecular weight by changing amphipathic copolymer and content, hydrophilic unit chain length and content can be controlled Kynoar doughnut filter membrane.Main method is: improve the hydrophily of film by the content that improves hydrophilic radical in the amphipathic copolymer, by nanometer SiO
2Improve film strength; Content, the content that improves solvent in core liquid or the coagulating bath by improving aperture conditioning agent in the preparation liquid, improve the temperature of core liquid or coagulating bath or reduce the size that air gap improves membrane micropore; Thickness by spray silk speed controlling diaphragm.
PVDF hollow fiber microporous membrane pattern and structural characterization: will obtain the PVDF hollow-fibre membrane, with SEM (JSM-5510LV, Japan) observe film microstructure and film thickness, (DEMO9500 presses the tribute instrument with mercury injection method, Micromecritics Instrument Corp, U.S.) measure the average pore size and the porosity of film.
The hydrophily of PVDF hollow fiber microporous membrane and hydrophilic stability sign:, drip the contact angle of method contact angle instrument (OCA20, Dataphysics, Germany) mensuration water with seat and (be labeled as C on the film surface with freshly prepd pvdf membrane dry 10h under 65 ℃
0), according to C
0Size represent the hydrophily of film: C
0More little, the hydrophily of film is good more.The PVDF hollow-fibre membrane is immersed in the deionized water 50 ℃ of concussions 2 days, 10 days, 30 days, and be labeled as C respectively
2, C
10, C
30, film is taken out dry 10h under back 60 ℃, respectively by measuring the contact angle of water on the film surface, represent the stability of amphipathic copolymer in pvdf membrane according to the variation of contact angle: contact angle is not if increase, and then amphipathic copolymer is stable in the film again.
The mensuration of PVDF hollow fiber microporous membrane water flux: choose the long PVDF hollow-fibre membrane of 30 20cm and be packaged into as shown in Figure 2 membrane module.Precompressed 30min under 0.15MPa measures the water flux of every 20min by film then under 0.1MPa, each sample is surveyed and averaged for 5 times.
The embodiment of the following stated PVDF doughnut filter membrane and preparation method thereof, the implementation step of all embodiment is all identical with aforementioned implementation step.It should be noted that described embodiment is not construed as limiting the invention, all distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Kynoar/poly-(expoxy propane-oxirane) (PPO-EO) preparation of hollow fiber microporous membrane
Preparation process is as follows:
(1) preparation of preparation liquid:
Get the 90g Kynoar, 10g expoxy propane-ethylene oxide copolymer (PPO-EO) is dissolved in 500gN, after N '-dimethyl formamide (DMF) adds thermal agitation for 50 ℃ and was mixed with transparent blend solution in 10 hours, add 2.5g nano silicon, 10gLiCl, 2.5g polyvinylpyrrolidone PVPK30 and continue to stir and obtained uniform preparation liquid in 20 hours.
(2) preparation of hollow-fibre membrane:
With vacuum defoamation under 20 ℃ of conditions of preparation liquid of gained 2 hours.Preparation liquid is emitted into the tubulose liquid film through spinning head, and this liquid film is solidified into hollow-fibre membrane through entering behind the air-gap in the coagulating bath;
(3) cleaning and dry:
Solid-state hollow-fibre membrane dried in soaking and washing 40 hours, the air in 30 ℃ water obtain the Kynoar hollow fiber microporous membrane.
The structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 1.
Table one
Embodiment 2.
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 2.
Table two
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 3.
Table three
Embodiment 4.
Kynoar/poly-(methyl methacrylate-acrylic acid) (PMMA-AA) preparation of hollow fiber microporous membrane
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 4.
Table four
Embodiment 5.
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 5.
Table five
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 6.
Table six
Embodiment 7.
Kynoar/poly-(methyl methacrylate-vinyl alcohol) (PMMA-VAc) preparation of hollow fiber microporous membrane
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 7.
Table seven
Embodiment 8.
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 8.
Table eight
Embodiment 9.
Implementation step such as embodiment 1, the structure of every implementation condition and gained PVDF hollow fiber microporous membrane and performance are as shown in Table 9.
Table nine
Claims (8)
1. hydrophilicity kynoar hollow fiber microporous membrane is characterized in that the membrane micropore aperture is that 0.01～0.2 micron, membrane porosity are 60～80%, film thickness is that 0.3～0.5 millimeter, film external diameter are 1～2 millimeter; The main component of film is Kynoar, amphipathic copolymer, silica, and wherein the specification of each composition and mass percent are:
Kynoar: molecular weight is 4 * 10
4～1 * 10
6, 70～90%;
Amphipathic copolymer: molecular weight is 10
3～10
5Poly-(methyl methacrylate-vinyl alcohol), poly-(methyl methacrylate-acrylic acid) or poly-(expoxy propane-oxirane), 5-29%;
Silica: particle diameter is 10～500 nano-silica powders: 1～5%.
2. the Kynoar doughnut filter membrane of claim 1, wherein said poly-(methyl methacrylate-vinyl alcohol) for having the copolymer of block or disordered structure, wherein the molar percentage of hydrophilic monomer vinyl alcohol groups is 50～80%; The molar percentage of hydrophobic monomer methyl methacrylate group is 20～50%.
3. the hydrophilicity kynoar hollow fiber microporous membrane of claim 1, wherein said poly-(methyl methacrylate-acrylic acid) for having the copolymer of block or disordered structure, wherein the molar percentage of hydrophilic monomer acrylic acid groups is 40～60%; The molar percentage of hydrophobic monomer methyl methacrylate group is 40～60%.
4. the hydrophilicity kynoar hollow fiber microporous membrane of claim 1, wherein said poly-(expoxy propane-oxirane) copolymer is the copolymer with block or disordered structure, wherein the molar percentage of hydrophilic monomer ethylene oxide group is 30～80%; The molar percentage of hydrophobic monomer propylene oxide group is 20～70%.
5. the preparation method of the hydrophilicity kynoar hollow fiber microporous membrane of claim 1, it comprises the steps:
(1) preparation liquid preparation:, become uniform preparation liquid 20～60 ℃ of following stirring and dissolving with Kynoar, amphipathic copolymer, silica, aperture adjustment agent, thickener and solvent;
(2) hollow-fibre membrane moulding: the preparation liquid with 20～50 ℃ of core liquid and 20～50 ℃ is emitted into the tubulose liquid film through spinning head, and this liquid film enters after through 5～30 centimetres air-gap in 20～40 ℃ the coagulating bath and is solidified into hollow-fibre membrane;
(3) cleaning-drying: solid-state hollow-fibre membrane dried in 10～30 ℃ of water loggings bubble cleans 40-60 hour, air obtain described poly-hydrophilic PVDF hollow fiber microporous membrane.
In the preparation liquid preparation steps, component and quality percentage composition thereof are in the described preparation liquid: Kynoar: molecular weight is 4 * 10
4～1 * 10
6, 12～18%; Amphipathic copolymer: molecular weight is 10
3～10
5Poly-(methyl methacrylate-vinyl alcohol), poly-(methyl methacrylate-acrylic acid) or poly-(expoxy propane-expoxy propane), 2～8%; Silica: particle diameter is the silicon dioxide powder of 10～500 nanometers, 0.1～2%; Aperture adjustment agent: lithium chloride or water, 1～5%; Thickener: molecular weight is 2 * 10
4～1 * 10
6Polyvinylpyrrolidone, 0.1～1%; Solvent: N, N '-dimethyl formamide, N, N '-dimethylacetylamide or N-methyl pyrrolidone: 70～84%;
In the forming step of hollow-fibre membrane, described each constituent mass of core liquid divides percentage to be: water: 40～100%; Solvent: N, N '-dimethyl formamide, N, identical with the preparation liquid solvent a kind of in N '-dimethylacetylamide or the N-methyl pyrrolidone: 0～60%; Each constituent mass of described coagulating bath divides percentage to be: water: 30～100%; Solvent: N, N '-dimethyl formamide, N, identical with the preparation liquid solvent a kind of in N '-dimethylacetylamide or the N-methyl pyrrolidone: 0～70%.
6. the Kynoar doughnut filter membrane preparation method of claim 5, wherein said poly-(methyl methacrylate-vinyl alcohol) for having the copolymer of block or disordered structure, wherein the molar percentage of hydrophilic monomer vinyl alcohol groups is 50～80%; The molar percentage of hydrophobic monomer methyl methacrylate group is 20～50%.
7. the hydrophilicity kynoar hollow fiber microporous membrane preparation method of claim 5, wherein said poly-(methyl methacrylate-acrylic acid) for having the copolymer of block or disordered structure, wherein the molar percentage of hydrophilic monomer acrylic acid groups is 40～60%; The molar percentage of hydrophobic monomer methyl methacrylate group is 40～60%.
8. the hydrophilicity kynoar hollow fiber microporous membrane preparation method of claim 5, wherein said poly-(expoxy propane-oxirane) copolymer is the copolymer with block or disordered structure, and wherein the molar percentage of hydrophilic monomer ethylene oxide group is 30～80%; The molar percentage of hydrophobic monomer propylene oxide group is 20～70%.
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