CN103007787A - Novel method for amphiphilic copolymer modified PVDF (Polyvinylidene Fluoride) hollow fiber ultra-filtration membranes - Google Patents
Novel method for amphiphilic copolymer modified PVDF (Polyvinylidene Fluoride) hollow fiber ultra-filtration membranes Download PDFInfo
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Abstract
The invention relates to a novel method for amphiphilic copolymer modified PVDF (Polyvinylidene Fluoride) hollow fiber ultra-filtration membranes, and belongs to the technical field of preparation of PVDF membranes. The method comprises the following steps: (1) PVDF, amphiphilic copolymer, pore-foaming agent, nonsolvent and solvent are fully mixed, and are dissolved to obtain membrane casting liquid; (2) the membrane casting liquid is fed in a hollow fiber membrane spinning machine for extruding, is condensed and formed in a coagulating bath, and is wound and collected to obtain the PVDF hollow fiber membranes; (3) the PVDF hollow fiber membranes are dipped in hot water; and (4) finished products are obtained after cleaning and drying. The amphiphilic copolymer modified PVDF hollow fiber ultra-filtration membranes, prepared by the method, have the characteristics of permanent hydrophilcity, excellent pollution resistance, high throughput and high reject rate.
Description
Technical field
The present invention relates to a kind of new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film, belong to the preparing technical field of Kynoar (PVDF) film.
Background technology
At present, the UF/MF membrane technology that uses in the drinking water apparatus is just constantly expanded from two aspects of depth ﹠ wideth in the industry, and new membrane material constantly obtains development and application, and is penetrated into more industry, and the market in this field is just at expanding day.For existing UF/MF membrane material Main Problems, mainly there is following problem in the UF/MF film: (1) membrane material does not have permanent hydrophilic, and antifouling property is not good; (2) there are contradiction in flux and rejection, and the raising of flux often to reduce rejection as cost, improves rejection and then often reduces its flux; (3) intensity difference of membrane material breaks easily, especially the polymer film of phase inversion preparation; (4) usually need to add protection liquid film is carried out moisturizing, this is unfavorable for storage, transportation and the use of film, and easy breed bacteria, causes secondary pollution.Based on these problems, development high strength, large flux, resistant to pollution high-performance UF/MF film become one of the study hotspot in membrane technology field in recent years.
Summary of the invention
The purpose of this invention is to provide a kind of new method with amphipathic copolymer-modified PVDF doughnut hyperfiltration film of permanent hydrophilic, antifouling property excellence, high flux, high rejection.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film comprises the steps:
(1) with the PVDF(Kynoar), amphipathic copolymer, pore-foaming agent, non-solvent fully mix with solvent, dissolving obtains casting solution;
(2) casting solution is sent into the hollow-fibre membrane spinning-drawing machine and extruded, enter coagulation forming in the coagulating bath, obtain the PVDF hollow-fibre membrane after collecting through reeling;
(3) the PVDF hollow-fibre membrane is soaked in hot water, make the hydrophilic chain in the amphipathic copolymer further be enriched to the film surface;
(4) clean, obtain finished product after the drying, finished product is amphipathic copolymer-modified PVDF doughnut hyperfiltration film.
As the further setting of such scheme, the mass percent concentration of each component is respectively in the described casting solution: PVDF15-25%, amphipathic copolymer 5-12%, pore-foaming agent 3-15%, non-solvent 0.5-1%, solvent 50-75%.
The molecular weight of described PVDF is 1 * 10
5-1 * 10
6Amphipathic copolymer is poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylic acid acid esters), and molecular weight is 1 * 10
4-1 * 10
5Pore-foaming agent is any one in polyvinylpyrrolidone and the polyethylene glycol, and wherein the molecular weight of polyvinylpyrrolidone is 30000-40000, and the molecular weight of polyethylene glycol is 2 * 10
3-2 * 10
4Non-solvent is water; Solvent is any one in DMF, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO).
When described PVDF, amphipathic copolymer, pore-foaming agent, non-solvent fully mix with solvent, need under 95-97 ℃ temperature conditions, stir 10-15 hour.
Temperature when described casting solution is extruded in the hollow-fibre membrane spinning-drawing machine is 80-180 ℃.
The temperature of described coagulating bath is 20-70 ℃.
When described PVDF hollow-fibre membrane soaked in hot water, the temperature of hot water was 60-85 ℃, and soak time is 4-12 hour.
When described PVDF hollow-fibre membrane carried out drying, baking temperature was 30-60 ℃, and the time is 1-10 hour.
Based on " similar compatibility " principle, the present invention adopts the hydrophilic amphipathic copolymer (type comprises alternate copolymer, block copolymer, graft copolymer and random copolymer etc.) of end parent PVDF, an end as the blending and modifying agent, carry out solution blending with PVDF, by the get everything ready doughnut blend film of permanent hydrophilic of dry-jet wet-spinning silk legal system.Amphipathic copolymer additives in film forming procedure to the film surface enrichment and carry out self assembly, thereby realize the surface modification to the PVDF hollow-fibre membrane, significantly improved hydrophily and the contamination resistance of PVDF hollow-fibre membrane, and one step of modification and film preparation finishes.When the enrichment of amphipathic copolymer on the film surface surpasses certain degree, will form hydrogel layer on the film surface, thereby give the PVDF hollow-fibre membrane with the flux of milipore filter, the rejection of micro-filtration membrane.In addition, by the coupled action raising polymer separating layer of amphipathic copolymer and the interface binding intensity between the micropore stay pipe, develop a kind of compound MF film of high strength PVDF doughnut with strong interface binding power.
In a word, the present invention by amphipathic copolymer-modified dose to film surface enrichment, self assembly, obtain the permanent hydrophilic PVDF doughnut hyperfiltration film of antifouling property excellence, high flux, high rejection, efficiently solve poor, the easy pollution of pvdf membrane hydrophily in the existing filter plant, flux and rejection and the technical barrier such as can not improve simultaneously.On the basis of PVDF blend doughnut homogeneous membrane development, develop a kind of novel preparation method with PVDF doughnut composite micro porous film of strong interface binding power, Effective Raise the mechanical strength of PVDF hollow-fibre membrane.
Pvdf membrane is widely used at the film separation field, but present greatest problem in use is exactly because the film that its hydrophobicity causes pollutes, and causes that flux sharply descends, and holds back particle diameter and changes, clean or change diaphragm expense, the service life of having reduced film thereby increase.In order to improve its performance, need to carry out hydrophilic modification to membrane material, currently used three classes that mainly contain: the one, face coat, the method is simple, the most normal employing in industrial production, but the coatings such as film surface glycerine are unstable, easily run off and need wet method to preserve, the transportation difficulty; The 2nd, surface grafting, the method is for membrane surface modification successful and long-term stability, and is still undesirable to modified effect in the fenestra, and finished film in the grafting process multiple physicochemical change can occur, process is complicated, not yet can realize suitability for industrialized production so far; Blending and modifying, the method process is simple, is most widely used, and the most important thing is to realize synchronously in film-forming process the modification of film, need not loaded down with trivial details additional process.
The modifier that adopts in the blending and modifying is except micromolecule additives (or pore-foaming agent) such as polyvinylpyrrolidone (PVP) commonly used, polyethylene glycol (PEG), pvdf membrane is being obtained some new progresses aspect the hydrophiling antipollution blending and modifying in recent years, namely improve the hydrophily of film by the self assembly migration of amphipathic copolymer, give its better antifouling property.Amphipathic copolymer refers in the strand polymer that not only contains lipophile (hydrophobicity) segment but also contain hydrophilic segment.The amphiphilic character of this quasi-molecule makes it can carry out the self assembly of molecular level, is with a wide range of applications, and particularly can be used as large molecular additives for separating of film hydrophilically modified research.Our company from MOLECULE DESIGN, has synthesized PMMA base and the amphipathic copolymer of SMA base with different chain structure forms in view of above-mentioned Research Thinking by radical polymerization and RAFT method.Wherein the hydrophobic section of PMMA base amphipathic molecule is PMMA, with PVDF good compatibility is arranged, can be in film forming and use procedure loss by dissolution, and molecular weight of copolymer guarantees its comixing compatibility several ten thousand～tens0000; Hydrophilic section is P(PEGMA), have good hydrophily and biocompatibility.Hydrophilic strand run in the casting solution water or in the inversion of phases process, the motive force that reduces interfacial free energy can with hydrone generation aquation, improve the migration rate of amphipathic copolymer, form the comparatively fine and close hydrogel top layer of thin (tens～hundreds of nanometer) on the film surface, the high rejection of film and water flux are provided, and the large finger-like pore structure of perhaps moving to fenestra inwall formation hydrone passage and film inside provides film high flux.And at supercritical CO
2Pass through the amphipathic copolymer SMA of free-radical polymerized synthetic straight chain type, the molecular weight (M with strict alternating structure and superelevation in the medium
W10
6G/mol), can mutually tangle with the PVDF strand, thereby have good hydrophilic modifying effect, and be difficult for running off.The topological structure form of amphipathic copolymer chain is very crucial on the impact of the phase separation of co-mixing system and surface self-organization behavior.Synthesize random brush copolymer P (MMA-r-POEM) by free-radical polymerized, but the strand of random copolymer tangles in co-mixing system easily, be difficult for moving to the surface of film; Can obtain the controlled amphipathic block of structure (the spherical and ABA dumbbell shaped of AB chain) copolymer p (MMA-b-POEM) by RAFT, the steric effect of hydrophilic segment in inversion of phases solution of the spherical copolymer of two block chains is less, and the self assembly behavior occurs on the easier film surface of moving to.Synthetic POEM and the PMMA price that adopts of copolymer all is lower than PVDF, the synthetic route simple possible, therefore with design pvdf membrane is carried out modification by the molecule synthesis of amphipathic copolymer, can obtain good modified effect, have the prospect of industrial applications.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view one in time, during 0s;
Fig. 2 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view two in time, during 150s;
Fig. 3 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view in time, during 250s;
Fig. 4 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view in time, during 350s;
Fig. 5 is that the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 150 times SEM photo;
Fig. 6 is that the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 500 times SEM photo;
Fig. 7 is the SEM photo of outer surface after the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 100000 times;
Fig. 8 is the SEM photo of inner surface after the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 100000 times.
The specific embodiment
The new method of the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of embodiment 1 the present invention comprises the steps:
(1) PVDF, amphipathic copolymer, pore-foaming agent, non-solvent are fully mixed with solvent, dissolving obtains casting solution;
(2) casting solution is sent into the hollow-fibre membrane spinning-drawing machine and extruded, enter coagulation forming in the coagulating bath, obtain the PVDF hollow-fibre membrane after collecting through reeling;
(3) the PVDF hollow-fibre membrane is soaked in hot water;
(4) clean, obtain finished product after the drying.
Wherein, the mass percent concentration of each component is respectively in the casting solution: PVDF15%, amphipathic copolymer 5%, pore-foaming agent 4%, non-solvent 1%, solvent 75%.
The molecular weight of PVDF is 3 * 10
5-1 * 10
6Amphipathic copolymer is poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylic acid acid esters), and molecular weight is 2 * 10
4-1 * 10
5Pore-foaming agent is polyvinylpyrrolidone, and the molecular weight of polyvinylpyrrolidone is 30000; Non-solvent is water; Solvent is DMF.
When PVDF, amphipathic copolymer, pore-foaming agent, non-solvent fully mix with solvent, need under 95 ℃ temperature conditions, stir 15 hours.
Temperature when casting solution is extruded in the hollow-fibre membrane spinning-drawing machine is 80 ℃.
The temperature of coagulating bath is 20 ℃.
When the PVDF hollow-fibre membrane soaked in hot water, the temperature of hot water was 60 ℃, and soak time is 12 hours.
When the PVDF hollow-fibre membrane carried out drying, baking temperature was 30 ℃, and the time is 10 hours.
The new method of the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of embodiment 2 the present invention comprises the steps:
(1) PVDF, amphipathic copolymer, pore-foaming agent, non-solvent are fully mixed with solvent, dissolving obtains casting solution;
(2) casting solution is sent into the hollow-fibre membrane spinning-drawing machine and extruded, enter coagulation forming in the coagulating bath, obtain the PVDF hollow-fibre membrane after collecting through reeling;
(3) the PVDF hollow-fibre membrane is soaked in hot water;
(4) clean, obtain finished product after the drying.
Wherein, the mass percent concentration of each component is respectively in the casting solution: PVDF25%, amphipathic copolymer 9.5%, pore-foaming agent 15%, non-solvent 0.5%, solvent 50%.
The molecular weight of PVDF is 1 * 10
5-5 * 10
5Amphipathic copolymer is poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylic acid acid esters), and molecular weight is 1 * 10
4-3 * 10
4Pore-foaming agent is polyethylene glycol, and the molecular weight of polyethylene glycol is 2 * 10
3-6 * 10
3Non-solvent is water; Solvent is 1-METHYLPYRROLIDONE.
When PVDF, amphipathic copolymer, pore-foaming agent, non-solvent fully mix with solvent, need under 97 ℃ temperature conditions, stir 10 hours.
Temperature when casting solution is extruded in the hollow-fibre membrane spinning-drawing machine is 180 ℃.
The temperature of coagulating bath is 70 ℃.
When the PVDF hollow-fibre membrane soaked in hot water, the temperature of hot water was 85 ℃, and soak time is 4 hours.
When the PVDF hollow-fibre membrane carried out drying, baking temperature was 60 ℃, and the time is 1 hour.
The new method of the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of embodiment 3 the present invention comprises the steps:
(1) PVDF, amphipathic copolymer, pore-foaming agent, non-solvent are fully mixed with solvent, dissolving obtains casting solution;
(2) casting solution is sent into the hollow-fibre membrane spinning-drawing machine and extruded, enter coagulation forming in the coagulating bath, obtain the PVDF hollow-fibre membrane after collecting through reeling;
(3) the PVDF hollow-fibre membrane is soaked in hot water;
(4) clean, obtain finished product after the drying.
Wherein, the mass percent concentration of each component is respectively in the casting solution: PVDF20%, amphipathic copolymer 1 2%, pore-foaming agent 7%, non-solvent 1%, solvent 60%.
The molecular weight of PVDF is 2 * 10
5-4 * 10
5Amphipathic copolymer is poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylic acid acid esters), and molecular weight is 6 * 10
4-1 * 10
5Pore-foaming agent is polyvinylpyrrolidone, and the molecular weight of polyvinylpyrrolidone is 40000; Non-solvent is water; Solvent is dimethyl sulfoxide (DMSO).
When PVDF, amphipathic copolymer, pore-foaming agent, non-solvent fully mix with solvent, need under 96 ℃ temperature conditions, stir 12 hours.
Temperature when casting solution is extruded in the hollow-fibre membrane spinning-drawing machine is 120 ℃.
The temperature of coagulating bath is 50 ℃.
When the PVDF hollow-fibre membrane soaked in hot water, the temperature of hot water was 70 ℃, and soak time is 8 hours.
When the PVDF hollow-fibre membrane carried out drying, baking temperature was 45 ℃, and the time is 6 hours.
The hydrogel top layer that has tens to tens unique nanometer thickness by the prepared amphipathic copolymer-modified PVDF doughnut hyperfiltration film of new method of the present invention.The film surface contact angle reaches 70
oBelow, in several minutes, drop to 0.Homogeneous UF film external pressure water flux reaches 300 L/m
2More than the h0.1MPa, interior setting-out flux reaches 400 L/m
2More than the h0.1MPa, to glucan T100(mean molecule quantity 100,000 Da) reach more than 90%; The external pressure water flux of the compound MF film of high strength reaches 800 L/m
2More than the h0.1MPa, interior setting-out flux reaches 1000 L/m
2More than the h0.1MPa, film is after water cleans, and the flux recovery rate reaches more than 90%.
Fig. 1 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view one in time, during 0s; Fig. 2 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view two in time, during 150s; Fig. 3 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view in time, during 250s; Fig. 4 is that water droplet is at the amphipathic copolymer-modified PVDF doughnut hyperfiltration film surface of the present invention decay view in time, during 350s.Water droplet shown in Fig. 1 to Fig. 4 is that same water drips.Among Fig. 1, the water contact angle of film is 78.2 ± 1.4
o(10 times measure mean values), the contact angle of this and pure pvdf membrane (is about 120
o) compared significant decline.Can find out that from these data the interpolation of amphipathic copolymer and surface enrichment have significantly reduced the water contact angle of PVDF hollow-fibre membrane, and contact angle decay in time is faster, show that amphipathic copolymer-modified pvdf membrane has better hydrophily.
Fig. 5 is that the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 150 times SEM photo.Fig. 6 is that the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 500 times SEM photo.Fig. 7 is the SEM photo of outer surface after the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 100000 times.Fig. 8 is the SEM photo of inner surface after the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention amplifies 100000 times.As can be seen from the figure, film has two finger-like pore structures of almost symmetry, and the inner surface of film can be observed the existence of micropore.Even and under * 100,000 times multiplication factor, also be difficult to observe the existence of micropore at film outer surface, the film inner surface is more coarse than outer surface.This structure of PVDF hollow-fibre membrane makes the suitable role who takes on parting surface of its outer surface, so the film that the present invention develops is suitable to the external pressure liquid separating film.
Following table is the amphipathic copolymer-modified PVDF doughnut hyperfiltration film of the present invention and the domestic and international major vendor PVDF hollow-fibre membrane performance parameter table of comparisons:
The present invention with micropore braided fiber hollow tube as supporter, adopting amphipathic copolymer is the blending and modifying agent, prepare high strength PVDF hollow fiber composite membrane by the solution phase conversion method, and adopt amphipathic copolymer weak solution pre-coated stay pipe, by the coupled action raising polymer separating layer of amphipathic copolymer and the interface binding intensity between the micropore stay pipe.This technology has solved the easily difficult problem of fracture of phase inversion membrane intensity difference, film silk effectively.
Above-described embodiment only is used for explaining inventive concept of the present invention, but not to the restriction of rights protection of the present invention, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should fall into protection scope of the present invention.
Claims (8)
1. the new method of an amphipathic copolymer-modified PVDF doughnut hyperfiltration film is characterized in that comprising the steps:
(1) PVDF, amphipathic copolymer, pore-foaming agent, non-solvent are fully mixed with solvent, dissolving obtains casting solution;
(2) casting solution is sent into the hollow-fibre membrane spinning-drawing machine and extruded, enter coagulation forming in the coagulating bath, obtain the PVDF hollow-fibre membrane after collecting through reeling;
(3) the PVDF hollow-fibre membrane is soaked in hot water;
(4) clean, obtain finished product after the drying.
2. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 1, it is characterized in that: the mass percent concentration of each component is respectively in the described casting solution: PVDF15-25%, amphipathic copolymer 5-12%, pore-foaming agent 3-15%, non-solvent 0.5-1%, solvent 50-75%.
3. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 2, it is characterized in that: the molecular weight of described PVDF is 1 * 10
5-1 * 10
6Amphipathic copolymer is poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylic acid acid esters), and molecular weight is 1 * 10
4-1 * 10
5Pore-foaming agent is any one in polyvinylpyrrolidone and the polyethylene glycol, and wherein the molecular weight of polyvinylpyrrolidone is 30000-40000, and the molecular weight of polyethylene glycol is 2 * 10
3-2 * 10
4Non-solvent is water; Solvent is any one in DMF, 1-METHYLPYRROLIDONE, the dimethyl sulfoxide (DMSO).
4. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 1, it is characterized in that: when described PVDF, amphipathic copolymer, pore-foaming agent, non-solvent fully mix with solvent, need under 95-97 ℃ temperature conditions, stir 10-15 hour.
5. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 1, it is characterized in that: the temperature when described casting solution is extruded in the hollow-fibre membrane spinning-drawing machine is 80-180 ℃.
6. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 1, it is characterized in that: the temperature of described coagulating bath is 20-70 ℃.
7. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 1, it is characterized in that: when described PVDF hollow-fibre membrane soaked in hot water, the temperature of hot water was 60-85 ℃, and soak time is 4-12 hour.
8. the new method of amphipathic copolymer-modified PVDF doughnut hyperfiltration film as claimed in claim 1, it is characterized in that: when described PVDF hollow-fibre membrane carried out drying, baking temperature was 30-60 ℃, and the time is 1-10 hour.
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