CN101264428B - Method for modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer - Google Patents
Method for modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer Download PDFInfo
- Publication number
- CN101264428B CN101264428B CN2008100613880A CN200810061388A CN101264428B CN 101264428 B CN101264428 B CN 101264428B CN 2008100613880 A CN2008100613880 A CN 2008100613880A CN 200810061388 A CN200810061388 A CN 200810061388A CN 101264428 B CN101264428 B CN 101264428B
- Authority
- CN
- China
- Prior art keywords
- polyvinylidene fluoride
- membrane
- amphiphilic
- concentration
- ultrafiltration membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 57
- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 50
- 229920001577 copolymer Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000005266 casting Methods 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 32
- 229920001223 polyethylene glycol Polymers 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 21
- 238000012805 post-processing Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 238000001338 self-assembly Methods 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- 235000012489 doughnuts Nutrition 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 5
- 230000004907 flux Effects 0.000 abstract description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 18
- 238000002156 mixing Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- 238000005345 coagulation Methods 0.000 abstract description 2
- 230000015271 coagulation Effects 0.000 abstract description 2
- -1 polyoxyethylene methyl methacrylate Polymers 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QJNYIFMVIUOUSU-UHFFFAOYSA-N chloroethene;ethenyl acetate;furan-2,5-dione Chemical compound ClC=C.CC(=O)OC=C.O=C1OC(=O)C=C1 QJNYIFMVIUOUSU-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method of producing the hyperfiltration membrane of amphiphilic copolymer modified polyvinylidene fluoride, comprising the following steps: 1) mixing polyvinylidene fluoride, poly (methyl methacrylate - monomethyl ether polyoxyethylene methyl methacrylate), additives, non-solvent and solvent to form the casting film solution; 2) making the casting film solution into the polyvinylidene fluoride membrane by using the film forming machine and then soaking in the coagulation bath; 3) conducting the posttreatment of hydrophilicity; 4)obtaining the hydrophilic polyvinylidene fluoride ultrafiltration membrane after cleaning and drying. The method is characterized in that the brush shape, chain ball shape or dumbbell shape amphiphilic copolymer are mixed with the polyvinylidene fluoride to produce the polyvinylidene fluoride hyperfiltration membrane with hydrophilicity, anti-pollution, large flux and high retention rate by adopting the solution phase conversion method. The method has the advantages that the obtained membrane is provided with dozens to hundreds nanometer of particular densified hydrogel surface layers, the contact angle of the membrane surface canbe reduced below 60 degrees and can be lowered to 0 degree within tens of seconds, the water flux can reach 1000L /m<2>/ h (0.1Mpa) or above, the retention rate of BSA can reach 90% or more and the recovery rate of water cleaning flux can reach 90% or higher.
Description
Technical field
The invention belongs to the preparation of Kynoar (PVDF) diffusion barrier and modification technology field, particularly a kind of method of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer.
Background technology
Pvdf membrane is widely used at the film separation field, but at present in use greatest problem is exactly because the film that its hydrophobicity causes pollutes, and causes that flux descends, and separating property descends, and cleans or change the diaphragm expense thereby increase, and reduces film service life.Purpose of the present invention is exactly to solve the problem that poor, the easy pollution of current pvdf membrane hydrophily, flux and rejection can not improve simultaneously to membrane material modified.
Currently used three classes that mainly contain of hydrophilic modification means: the one, face coat, this method is simple, the most normal employing in industrial production, but coating instabilities such as film surface glycerine, easily run off and need wet method to preserve, the transportation difficulty; The 2nd, surface grafting, this method is obvious and steady in a long-term at the membrane surface modification effect, but undesirable to modified effect in the fenestra, and finished film in the grafting process multiple physicochemical change can take place, process is complicated, still fails to realize suitability for industrialized production so far; Blending and modifying, this procedure is simple, is most widely used, and the most important thing is to realize function modified purpose synchronously in film-forming process.
The modifier that is adopted in the blending and modifying is except polyvinylpyrrolidone (PVP), polyethylene glycol micromolecule additives (or pore-foaming agent) such as (PEG) commonly used, pvdf membrane is being obtained some new progresses aspect the hydrophiling antipollution blending and modifying in recent years, promptly improve the hydrophily of film, give its better antifouling property by the self assembly migration of amphipathic copolymer.Amphipathic copolymer is meant in the strand polymer that not only contains hydrophobic chain 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 the research that big molecular additives is used for the diffusion barrier hydrophilic modifying.Can directly pass through the amphipathic comb copolymer PVDF-g-POEM of ATRP (ATRP) preparation as PVDF, and prepare antipollution microporous barrier (US20070219322) as big molecular additives and PVDF blend; PVDF also can be by reversible addition-fracture chain transfer polymerization (RAFT) synthesizing amphipathic copolymer p VDF-g-PEGMA, as big molecular additives effectively the microcellular structure of controlling diaphragm (Macromolecules, 2003,36:9451-9457).The phenylethylene-maleic anhydride of amphiphilic macromolecular such as super high molecular weight (SMA) alternate copolymer or hyperbranched star-type polymer also can obviously improve hydrophily, antipollution modification (ANTEC, the 2006:1814-1818 of PES film and pvdf membrane; Colloids and Surfaces B:Biointerfaces, 2007,57:189-197; Langmuir, 2007,23:5779-5786).
By we can see in former study and the patent, the topological chain structure form of amphipathic copolymer directly influences the structural behaviour of blend film.Can design synthetic poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) P (MMA-POEM) of amphipathic copolymer respectively by radical polymerization and RAFT method with different chain structure forms.Wherein the hydrophobic section of amphipathic molecule is polymethyl methacrylate (PMMA), with PVDF good compatibility is arranged, and can not dissolve loss in film forming and use, and molecular weight of copolymer guarantees its comixing compatibility several ten thousand～tens0000. Hydrophilic section is a monomethyl ether polyethylene glycol oxide polymethacrylates (PPOEM), have good hydrophilicity 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 (seeing accompanying drawing one), 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, high rejection of film and water flux are provided, and the big finger-like pore structure of perhaps moving to fenestra inwall formation hydrone passage and film inside provides film high flux.The chain structure form of amphipathic copolymer is very crucial to the influence of the behavior that is separated of co-mixing system and surperficial self assembly 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 takes place on the easier film surface of moving to.Synthetic POEM and the PMMA price that is adopted 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 amphipathic copolymer with topological chain structure that the present invention is used is seen accompanying drawing one.
Except the molecule synthesis and the design of copolymer chain structure form, in blend inversion of phases process, the multilayered structure and the performance of the thermodynamics that can also be by co-mixing system and the cooperative effect control blend film of kinetic factor.Determine the epuilibrium thermodynamics factor by the thermodynamics phasor of measuring co-mixing system, form the influence to membrane structure such as (comprising polymer, copolymer, solvent, additive), concentration, temperature and the interaction between them as casting solution.Determine kinetics of diffusion factor such as coagulation bath composition, temperature by measuring the luminous flux kinetic curve, solvent/non-solvent, add in the coagulating bath and add the influence to membrane structure such as entry in solvent or the casting solution, film forming is carried out the hydrophiling post processing to film later, for example use hot-water soak, can further increase the extent of migration of amphipathic copolymer to the film surface.
We are (application number: 200710111147.8) reported once that PVC and amphipathic terpolymer are gathered (vinyl chloride-vinyl acetate-maleic anhydride) blend prepared alloy ultrafiltration membrane in the patent in early stage, find that water flux and rejection can increase simultaneously, water flux reaches 500L/m
2H, the BSA rejection is more than 90%.Solved the contradiction that current PVC milipore filter water flux and rejection can not improve simultaneously.We study its film forming dynamic process by luminous flax curve, find that amphipathic copolymer makes system be separated to the time-delay transformation that is separated by instantaneous, make its hydrophilic segment have time enough to move at the interface, and formed a dense thin hydrogel layer, and the inside of film is bigger finger-like pore, this special multilayered structure provides bigger water flux of film and higher rejection, and hydrogel layer has also given film hydrophilic preferably resistance tocrocking simultaneously.
The present invention mainly prepares modification synchronously by amphipathic copolymer p (MMA-POEM) and has big flux, high rejection, hydrophily and resistant to pollution PVDF milipore filter, and the gained pvdf membrane can be used for fields such as water purification, sewage disposal, middle water reuse, bio-medical.The technological means of being taked mainly comprises: the MOLECULE DESIGN of amphipathic copolymer and synthetic, blending and modifying and solution phase inversion.
Summary of the invention
The method that the purpose of this invention is to provide a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer.The method of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer comprises the steps:
1) with Kynoar, poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate), additive, non-solvent and solvent blend, stirred 20～50 hours down at 50～90 ℃, filtration, vacuum defoamation obtain casting solution, and each component of casting solution and concentration thereof are as follows:
The molecular weight of Kynoar is 1 * 10
5～1.0 * 10
6, concentration is 10～20wt%; As preferably, molecular weight is 2.1 * 10
5, concentration is 12～20wt%;
The molecular weight of poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) is 1 * 10
4～1 * 10
5, concentration is 1～10wt%; As preferably, molecular weight is 2 * 10
4～1 * 10
5, concentration is 3～10wt%;
Additive is: polyvinylpyrrolidone, molecular weight are 30,000,0.5～6wt%; As preferably, concentration is 1～5wt%;
Polyethylene glycol, molecular weight are 2 * 10
2～2 * 10
4, 5～20wt%; As preferably, molecular weight is 6 * 10
2～6 * 10
3, concentration is 5～15wt%
Solvent is: N, and N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO), concentration is 60～90wt%;
Non-solvent is: H
2O, concentration is 0.1～2wt%; As preferred concentration is 0.5～2wt%;
2) with 30～80 ℃ casting solution through film-forming machine, immerse in 30～90 ℃ of coagulating baths, obtain polyvinylidene fluoride film, air themperature is that 10～40 ℃, relative humidity are 30～90%;
3) with the polyvinylidene fluoride film that obtains, in 40～90 ℃ of hot water, soaked 1～24 hour, carry out the hydrophiling post processing;
4) polyvinylidene fluoride film of hydrophiling post processing is taken out earlier with 30～50 ℃ of washed with de-ionized water 1～24 hour,, obtain the hydrophilicity kynoar milipore filter room temperature～60 ℃ drying 2～48 hours.The structural form of described poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) is respectively random brush shape, the spherical and three block dumbbell shapeds of two block chains.Random brush copolymer is by free-radical polymerized synthetic, and two block chains are spherical and three block dumbbell shaped copolymers are synthetic by reversible addition-fragmentation chain transfer free radical polymerization.Amphipathic copolymer is preferably random brush shape and two block chains are spherical.The hydrophobic segment of poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) is a polymethyl methacrylate, and hydrophilic segment is a monomethyl ether polyethylene glycol oxide polymethyl methacrylate.Poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) can spontaneously move to the polyvinylidene fluoride film surface self assembly effect takes place, and forms the fine and close hydrogel top layer of tens nanometers～hundreds of nanometer.The hydrophilicity kynoar milipore filter is dull and stereotyped homogeneous membrane, flat composite membrane, doughnut homogeneous membrane or hollow fiber composite membrane.
Coagulating bath is H
2The mixed solution of O and organic solvent, wherein the concentration of organic solvent is 0.1～50wt%.The hot water temperature of hydrophiling post processing is preferably 50～90 ℃, and the time of hydrophiling post processing is preferably 1～20 hour.Baking temperature is preferably room temperature～50 ℃, is preferably 2～24 hours drying time.The beneficial effect that the present invention compared with prior art has:
1) film preparation and modification are carried out synchronously, and process is simple;
2) employing has the amphipathic copolymer p (MMA-POEM) and PVDF blend film forming of topological chain structure (brush shape, spherical, the dumbbell shaped of chain), and amphipathic molecule forms ultra-thin hydrogel layer, the film good hydrophilic property at film and fenestra surface self assembly;
3) film forming procedure can be operated at normal temperatures, has saved energy consumption, greatly reduces production cost;
4) from the multilayered structure form of the cooperative effect controlling diaphragm of the kinetics of diffusion of the epuilibrium thermodynamics of casting solution and film forming, the gained membrane structure is controlled stablizes, has repeatability;
5) gained PVDF milipore filter has big flux and high rejection simultaneously, and hydrophily and resistance tocrocking are strong.
Description of drawings
Fig. 1 be amphipathic copolymer p (MMA-POEM) by the formed molecular chain structure form of aquation schematic diagram; Among the figure: (a) brush shape (b) chain spherical (c) dumbbell shaped;
Fig. 2 (a) is the upper surface SEM photo of PVDF flat plate ultrafiltration membrane among the embodiment 10;
Fig. 2 (b) is the lower surface SEM photo of PVDF flat plate ultrafiltration membrane among the embodiment 10;
Fig. 2 (c) is the section SEM photo of PVDF flat plate ultrafiltration membrane among the embodiment 10.
The specific embodiment
The method of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer comprises the steps:
1) with Kynoar, poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate), additive, non-solvent and solvent blend, stirred 20～50 hours down at 50～90 ℃, filtration, vacuum defoamation obtain casting solution, and each component of casting solution and concentration thereof are as follows:
The molecular weight of Kynoar is 1 * 10
5～1.0 * 10
6, concentration is 10～20wt%; As molecular weight is 2.1 * 10
5, concentration is 12～20wt%;
The molecular weight of poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) is 1 * 10
4～1 * 10
5, concentration is 1～10wt%; As preferably, molecular weight is 2 * 10
4～1 * 10
5, concentration is 3～10wt%;
Additive is: polyvinylpyrrolidone, molecular weight are 30,000,0.5～6wt%; As preferably, concentration is 1～5wt%;
Polyethylene glycol, molecular weight are 2 * 10
2～2 * 10
4, 5～20wt%; As preferably, molecular weight is 6 * 10
2～6 * 10
3, concentration is 5～15wt%
Solvent is: N, and N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO), concentration is 60～90wt%;
Non-solvent is: H
2O, concentration is 0.1～2wt%; As preferred concentration is 0.5～2wt%;
The synthetic method of described poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) P (MMA-POEM) is as follows: monomer, initator and other reactive materials under proper condition by radical polymerization, are obtained poly-(methyl methacrylate-r-monomethyl ether polyethylene glycol oxide methyl methacrylate) P (MMA-r-POEM) of random brush copolymer; With catalyst, chain-transferring agent, initator, monomer obtains poly-(methyl methacrylate-b-monomethyl ether polyethylene glycol oxide methyl methacrylate) P (MMA-b-POEM) of the spherical block copolymer of chain by reversible addition-fragmentation chain transfer free radical polymerization (RAFT) method under proper condition, and poly-(the monomethyl ether polyethylene glycol oxide methyl methacrylate-b-methyl methacrylate-b-monomethyl ether polyethylene glycol oxide methyl methacrylate) P (POEM-b-MMA-b-POEM) of dumbbell shaped block copolymer.
2) with 30～80 ℃ casting solution through film-forming machine, immerse in 30～90 ℃ of coagulating baths, obtain polyvinylidene fluoride film, air themperature is that 10～40 ℃, relative humidity are 30～90%; Film-forming machine obtains hollow-fibre membrane when adopting the doughnut spinning-drawing machine, wherein interior coagulating bath is H
2O, temperature is 20～50 ℃, outer coagulating bath is mixed solution H
2(0～30wt%), temperature is 20～50 ℃ to O/DMAC, and dried segment distance is 5～30cm; Film-forming machine obtains flat sheet membrane when adopting purl machine, and wherein scraper gap is 50～300 μ m, and the sky time of exposing to the sun is 5～30s;
3) with the polyvinylidene fluoride film that obtains, in 40～90 ℃ of hot water, soaked 1～24 hour, carry out the hydrophiling post processing;
4) polyvinylidene fluoride film of hydrophiling post processing is taken out earlier with 30～50 ℃ of washed with de-ionized water 1～24 hour,, obtain the hydrophilicity kynoar milipore filter room temperature～60 ℃ drying 2～48 hours.
The structural form of described poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) is respectively random brush shape, the spherical and three block dumbbell shapeds of two block chains.The hydrophobic segment of poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) is a polymethyl methacrylate, and hydrophilic segment is a monomethyl ether polyethylene glycol oxide polymethyl methacrylate.Poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methyl methacrylate) can spontaneously move to the polyvinylidene fluoride film surface self assembly effect takes place, and forms the fine and close hydrogel top layer of tens nanometers～hundreds of nanometer.The hydrophilicity kynoar milipore filter is dull and stereotyped homogeneous membrane, flat composite membrane, doughnut homogeneous membrane or hollow fiber composite membrane.
Coagulating bath is H
2The mixed solution of O and organic solvent, wherein the concentration of organic solvent is 0.1～50wt%.The hot water temperature of hydrophiling post processing is preferably 50～90 ℃, and the time of hydrophiling post processing is preferably 1～20 hour.Baking temperature is preferably room temperature～50 ℃, is preferably 2～24 hours drying time.Performance measurement: water flux adopts the homemade dead-end filtration device in laboratory to measure, wet film after promptly cleaning is earlier at 0.15MPa precompressed 30min, measure its water flux at 0.1MPa then, and to measure pH be that (molecular weight is 6 for 7.4 BSA, 7000) rejection of solution continues to measure the flux recovery rate after water cleans.(Dataphysics, measure by contact angle measurement Germany) by OCA20 for dried dry film surface contact angle.(FEI Finland) observes by field emission scanning electron microscope SIRION-100 for the surface of dry film and fracture morphology.
Following examples are done more detailed description to the present invention, but described embodiment is not construed as limiting the invention.
Embodiment 1 preparation process is as follows:
1) with Kynoar, poly-(methyl methacrylate-r-monomethyl ether polyethylene glycol oxide methyl methacrylate), additive, non-solvent and solvent blend, stirred 36 hours down at 70 ℃, filtration, vacuum defoamation obtain casting solution, and each component of casting solution and concentration thereof are as follows:
The molecular weight of Kynoar is 2.1 * 10
5, concentration is 10wt%;
The molecular weight of poly-(methyl methacrylate-r-monomethyl ether polyethylene glycol oxide methyl methacrylate) is 2.8 * 10
4, concentration is 2wt%;
Additive is: polyvinylpyrrolidone, molecular weight are 30,000, and concentration is 0.5wt%;
Polyethylene glycol, molecular weight are 6 * 10
2, concentration is 5wt%;
Solvent is: N, and the N-dimethylacetylamide, concentration is 81.7wt%;
Non-solvent is: H
2O, concentration is 0.8wt%; Each set of dispense ratio is:
PVDF/P(MMA-r-POEM)/PEG/PVP/H
2O/DMAc＝10/2/5/0.5/0.8/81.7；
2) with 30 ℃ casting solution process doughnut spinning-drawing machine, obtain polyvinylidene fluoride film, wherein interior coagulating bath is H
2O, temperature is 40 ℃; Outer coagulating bath is H
2O, temperature is 40 ℃; Dried segment distance is 10cm.
Air themperature is that 30 ℃, relative humidity are 75%;
3) with the polyvinylidene fluoride film that obtains, in 70 ℃ of hot water, soaked 6 hours, carry out the hydrophiling post processing;
4) polyvinylidene fluoride film of hydrophiling post processing is taken out earlier with 30 ℃ of washed with de-ionized water 2 hours,, obtain the hydrophilicity kynoar milipore filter 30 ℃ of air dryings 24 hours.
Performance measurement: water flux adopts the homemade dead-end filtration device in laboratory to measure, wet film after promptly cleaning is earlier at 0.15MPa precompressed 30min, measure its water flux at 0.1MPa then, and measure the rejection that pH is 7.4 BSA solution, clean the back through water and continue mensuration flux recovery rate.Dried dry film surface contact angle is measured by the OCA20 contact angle measurement.The surface of dry film and fracture morphology are observed by field emission scanning electron microscope SIRION-100.The water flux of prepared pvdf membrane, rejection, contact angle see attached list 1.The SEM form of film is seen accompanying drawing 2.
Embodiment 2 preparation processes are with embodiment 1.
Embodiment 3 preparation processes are with embodiment 1.
Embodiment 4 preparation processes are with embodiment 1.
Embodiment 5 preparation processes are with embodiment 1.
Embodiment 6 preparation processes are with embodiment 1.
Embodiment 7 preparation processes are with embodiment 1.
Embodiment 8 preparation processes are with embodiment 1
Embodiment 9 preparation processes are with embodiment 1.
Embodiment 10 preparation processes are with embodiment 1, and wherein filming technology is a flat sheet membrane, and scraper gap is 250 μ m, and the sky time of exposing to the sun is 10s.
Implement 11 preparation processes with embodiment 1, wherein filming technology is a flat sheet membrane, and scraper gap is 250 μ m, and the sky time of exposing to the sun is 10s.
Implement 12 preparation processes with embodiment 1, wherein filming technology is a flat sheet membrane, and scraper gap is 250 μ m, and the sky time of exposing to the sun is 10s.
Subordinate list one: the structure of PVDF milipore filter and performance parameter
| Sample number | Contact angle (°) | The dynamic change time (S) | Water flux (L/m 2h) | Rejection BSA (%) | Flux recovery rate (%) |
| Embodiment 1 | 60.2 | 60.0 | 1450.9 | 97.3 | 92.9 |
| Embodiment 2 | 56.0 | 40.0 | 1830.6 | 95.5 | 93.7 |
| Embodiment 3 | 58.4 | 45.0 | 1568.8 | 94.8 | 96.5 |
| Embodiment 4 | 59.5 | 38.0 | 1620.1 | 96.8 | 94.3 |
| Embodiment 5 | 45.5 | 30.0 | 1855.1 | 97.2 | 96.3 |
| Sample number | Contact angle (°) | The dynamic change time (S) | Water flux (L/m 2h) | Rejection BSA (%) | Flux recovery rate (%) |
| Embodiment 6 | 55.9 | 33.0 | 1232.3 | 95.0 | 97.2 |
| Embodiment 7 | 63.2 | 55.2 | 1023.4 | 90.7 | 92.6 |
| Embodiment 8 | 52.5 | 40.6 | 1365.7 | 93.8 | 94.1 |
| Embodiment 9 | 57.6 | 50.1 | 1198.4 | 95.6 | 93.2 |
| Embodiment 10 | 45.0 | 20.0 | 2036.6 | 90.0 | 96.2 |
| Embodiment 11 | 40.2 | 15.0 | 2589.2 | 96.0 | 95.3 |
| Embodiment 12 | 50.4 | 32.0 | 1828.6 | 93.5 | 94.2 |
Claims (9)
1. the method for a modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer is characterized in that comprising the steps:
1) with Kynoar, poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylate), additive, non-solvent and solvent blend, stirred 20～50 hours down at 50～90 ℃, filtration, vacuum defoamation obtain casting solution, and each component of casting solution and concentration thereof are as follows:
The molecular weight of Kynoar is 1 * 10
5～1.0 * 10
6, concentration is 10～20wt%;
The molecular weight of poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylate) is 1 * 10
4～1 * 10
5, concentration is 1～10wt%;
Additive is: polyvinylpyrrolidone, molecular weight are 30,000, and concentration is 0.5～6wt%;
Polyethylene glycol, molecular weight are 2 * 10
2～2 * 10
4, concentration is 5～20wt%;
Solvent is: N, and N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO), concentration is 60～90wt%;
Non-solvent is: H
2O, concentration is 0.1～2wt%;
Each component percentage composition sum of casting solution is 100wt%;
2) with 30～80 ℃ casting solution through film-forming machine, immerse in 30～90 ℃ of coagulating baths, obtain polyvinylidene fluoride film, air themperature is that 10～40 ℃, relative humidity are 30～90%;
3) with the polyvinylidene fluoride film that obtains, in 40～90 ℃ of hot water, soaked 1～24 hour, carry out the hydrophiling post processing;
4) polyvinylidene fluoride film of hydrophiling post processing is taken out earlier with 30～50 ℃ of washed with de-ionized water 1～24 hour,, obtain the hydrophilicity kynoar milipore filter room temperature～60 ℃ drying 2～48 hours.
2. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1, it is characterized in that, the structural form of described poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylate) is respectively random brush shape, the spherical and three block dumbbell shapeds of two block chains.
3. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 2, it is characterized in that described random brush copolymer by free-radical polymerized synthetic, two block chains are spherical and three block dumbbell shaped copolymers are synthetic by reversible addition-fragmentation chain transfer free radical polymerization.
4. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1, it is characterized in that, the hydrophobic segment of described poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylate) is a polymethyl methacrylate, and hydrophilic segment is a monomethyl ether polyethylene glycol oxide polymethacrylates.
5. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1 is characterized in that, described coagulating bath is H
2The mixed solution of O and organic solvent, wherein the concentration of organic solvent is 0.1～50wt%.
6. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1 is characterized in that, the hot water temperature of described hydrophiling post processing is 50～90 ℃, and the time of hydrophiling post processing is 1～20 hour.
7. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1 is characterized in that, described baking temperature is room temperature～50 ℃, and be 2～24 hours drying time.
8. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1, it is characterized in that, described poly-(methyl methacrylate-monomethyl ether polyethylene glycol oxide methacrylate) can spontaneously move to the polyvinylidene fluoride film surface self assembly effect takes place, and forms the fine and close hydrogel top layer of tens nanometers～hundreds of nanometer.
9. the method for a kind of modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer according to claim 1, it is characterized in that described hydrophilicity kynoar milipore filter is dull and stereotyped homogeneous membrane, flat composite membrane, doughnut homogeneous membrane or hollow fiber composite membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100613880A CN101264428B (en) | 2008-04-25 | 2008-04-25 | Method for modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100613880A CN101264428B (en) | 2008-04-25 | 2008-04-25 | Method for modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101264428A CN101264428A (en) | 2008-09-17 |
| CN101264428B true CN101264428B (en) | 2010-10-13 |
Family
ID=39987252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100613880A Expired - Fee Related CN101264428B (en) | 2008-04-25 | 2008-04-25 | Method for modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101264428B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543731B (en) * | 2009-03-23 | 2013-07-31 | 杭州洁弗膜技术有限公司 | Method for preparing fiber braided tube embedded enhanced type polymer hollow fiber microporous membrane |
| CN101837251B (en) * | 2010-04-07 | 2012-05-23 | 南京工业大学 | Hydrophilic modification method of polyvinylidene fluoride porous membrane surface by amphiphilic molecules |
| CN102166484A (en) * | 2011-05-15 | 2011-08-31 | 王剑鸣 | Hydrophilic polyvinylidene fluoride hollow fiber composite membrane and preparation method |
| CN102502489A (en) * | 2011-11-21 | 2012-06-20 | 天津工业大学 | Preparation method for hollow hydrogen storage porous capsule |
| CN103127840A (en) * | 2011-11-28 | 2013-06-05 | 中化蓝天集团有限公司 | Polyvinylidene fluoride (PVDF) resin membrane preparing formula for water treatment membrane |
| CN102553463B (en) * | 2011-12-09 | 2013-10-16 | 苏州中色德源环保科技有限公司 | Method for preparing braided tube/polymer composite hollow fibrous membrane by thermal induction method |
| CN102512971B (en) * | 2011-12-09 | 2013-10-16 | 苏州中色德源环保科技有限公司 | Method for preparing composite flat ultrafiltration membrane |
| CN103007787A (en) * | 2012-12-19 | 2013-04-03 | 绍兴锐意环保科技有限公司 | Novel method for amphiphilic copolymer modified PVDF (Polyvinylidene Fluoride) hollow fiber ultra-filtration membranes |
| CN103055711B (en) * | 2012-12-28 | 2015-02-25 | 东华大学 | Method for preparing amphiphilic block copolymer modified polyvinylidene fluoride hollow fiber membrane |
| CN103357277B (en) * | 2013-07-24 | 2015-12-09 | 浙江师范大学 | A kind of have milipore filter of heavy metal ion adsorbed function and preparation method thereof |
| CN104190265A (en) * | 2014-08-31 | 2014-12-10 | 浙江大学 | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof |
| CN106478975B (en) * | 2016-10-21 | 2019-10-25 | 苏州科技大学 | The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of difunctional block polymer |
| CN108993169B (en) * | 2017-06-07 | 2020-10-16 | 中国科学院宁波材料技术与工程研究所 | Polyvinylidene fluoride microporous membrane and preparation method thereof |
| CN107486039A (en) * | 2017-08-02 | 2017-12-19 | 同济大学 | It is a kind of suitable for modification NF membrane of industrial effluent reusing and its preparation method and application |
| CN109382002B (en) * | 2017-08-02 | 2021-06-04 | 浙江工业大学 | Intelligent switch membrane based on nanogel and preparation method thereof |
| CN107626216B (en) * | 2017-10-25 | 2021-03-02 | 乳源东阳光氟树脂有限公司 | Polyvinylidene fluoride self-assembled porous membrane |
| CN108246114A (en) * | 2018-02-28 | 2018-07-06 | 江苏沛尔膜业股份有限公司 | A kind of two-component hydrophilic PVDF ultrafiltration membrane and preparation method thereof |
| SG11202011789PA (en) * | 2018-06-08 | 2020-12-30 | Arkema Inc | Fluoropolymer latex coatings for membranes |
| CN109847595A (en) * | 2018-12-21 | 2019-06-07 | 三达膜科技（厦门）有限公司 | A kind of preparation method of the big compound polyvinylidene fluoride hollow fiber ultrafiltration membrane of flux inner support |
| CN109663510B (en) * | 2019-01-25 | 2021-07-23 | 苏州科技大学 | Zwitterionic random copolymer P (MMA)x-r-CBMAy) Modified PVDF antifouling film and preparation method thereof |
| CN112973467B (en) * | 2019-12-02 | 2022-12-13 | 欧美新材料(浙江)有限公司 | Preparation method of composite nanofiltration membrane and composite nanofiltration membrane |
| CN111013406A (en) * | 2019-12-30 | 2020-04-17 | 恩泰环保科技（常州）有限公司 | Hydrophilization modified polyolefin separation membrane and preparation method thereof |
| CN112090288A (en) * | 2020-08-05 | 2020-12-18 | 杭州晟聚环保科技有限公司 | Preparation method of amphiphilic sulfone polymer and blend membrane |
| CN112717714A (en) * | 2021-01-12 | 2021-04-30 | 浙江易膜新材料科技有限公司 | Preparation method of SMA and PVDF blended hollow fiber membrane |
| CN113083031B (en) * | 2021-04-27 | 2022-12-23 | 贵州省材料产业技术研究院 | Electrically neutral polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN114405287B (en) * | 2022-01-24 | 2022-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Superstrong oil stain resistance oil-water separation membrane and preparation method and application thereof |
| CN115920658B (en) * | 2023-01-15 | 2023-10-20 | 安徽科博瑞环境科技有限公司 | Low-surface-energy anti-pollution hollow fiber membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015773A (en) * | 2006-12-29 | 2007-08-15 | 浙江大学 | Porous polyvinylidene blending porous membrane and process for producing same |
| US20070219322A1 (en) * | 2000-09-11 | 2007-09-20 | Massachusetts Institute Of Technology | Graft copolymers, methods for grafting hydrophilic chains onto hydrophobic polymers, and articles thereof (BROWN-TLO) |
-
2008
- 2008-04-25 CN CN2008100613880A patent/CN101264428B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070219322A1 (en) * | 2000-09-11 | 2007-09-20 | Massachusetts Institute Of Technology | Graft copolymers, methods for grafting hydrophilic chains onto hydrophobic polymers, and articles thereof (BROWN-TLO) |
| CN101015773A (en) * | 2006-12-29 | 2007-08-15 | 浙江大学 | Porous polyvinylidene blending porous membrane and process for producing same |
Non-Patent Citations (1)
| Title |
|---|
| J.F. Hester et al..Design and performance of foul-resistant poly(vinylidene fluoride) membranes prepared in a single-step by surface segregation.《Journal of Membrane Science》.2002,第202卷119-135. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101264428A (en) | 2008-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101264428B (en) | Method for modifying polyvinylidene fluoride ultrafiltration membrane by amphiphilic co-polymer | |
| CN101293183B (en) | Method for preparing hydrophilic polyvinyl chloride alloy ultrafiltration membrane | |
| Liu et al. | Preparation of hydrophilic and antifouling polysulfone ultrafiltration membrane derived from phenolphthalin by copolymerization method | |
| Huang et al. | Improved antifouling performance of ultrafiltration membrane via preparing novel zwitterionic polyimide | |
| Shi et al. | Zwitterionic polyethersulfone ultrafiltration membrane with superior antifouling property | |
| Wu et al. | Blended PVC/PVC-g-PEGMA ultrafiltration membranes with enhanced performance and antifouling properties | |
| CN100411722C (en) | Porous polyvinylidene blending porous membrane and process for producing same | |
| Fan et al. | Fabrication of polyvinyl chloride ultrafiltration membranes with stable antifouling property by exploring the pore formation and surface modification capabilities of polyvinyl formal | |
| Hernández-Guerrero et al. | Honeycomb structured polymer films via breath figures | |
| Mu et al. | Remarkable improvement of the performance of poly (vinylidene fluoride) microfiltration membranes by the additive of cellulose acetate | |
| Zhao et al. | Hydrophilic and anti-fouling PVDF blend ultrafiltration membranes using polyacryloylmorpholine-based triblock copolymers as amphiphilic modifiers | |
| CN103007787A (en) | Novel method for amphiphilic copolymer modified PVDF (Polyvinylidene Fluoride) hollow fiber ultra-filtration membranes | |
| CN100562356C (en) | Hydrophilic polyvinyl chloride alloy doughnut filter membrane and preparation method thereof | |
| CN102886213B (en) | Separate film, its manufacture method and include its water treatment facilities | |
| Rong et al. | Preparation and characterization of novel zwitterionic poly (arylene ether sulfone) ultrafiltration membrane with good thermostability and excellent antifouling properties | |
| CN1730141A (en) | Process for preparing co-mixed polyethersulfone platform complex film | |
| Xu et al. | Antifouling membranes with bi-continuous porous structures and high fluxes prepared by vapor-induced phase separation | |
| Hong et al. | Tuning the surface hydrophobicity of honeycomb porous films fabricated by star-shaped POSS-fluorinated acrylates polymer via breath-figure-templated self-assembly | |
| CN104437124A (en) | Self-cleaning polyvinylidene fluoride microporous film and preparation method thereof | |
| CN101195084B (en) | Hydrophilic polyvinyl chloride alloy ultrafiltration membrane and production method thereof | |
| CN112370978A (en) | Polysulfone ultrafiltration membrane and preparation method thereof | |
| Fan et al. | pH and thermal-dependent ultrafiltration membranes prepared from poly (methacrylic acid) grafted onto polyethersulfone synthesized by simultaneous irradiation in homogenous phase | |
| CN103122067B (en) | Polysiloxane imide segmented copolymer, asymmetric membrane and preparation methods | |
| Chen et al. | Enhanced performances of chlorinated polyvinyl chloride (CPVC) ultrafiltration membranes by styrene-maleic anhydride copolymer | |
| Su et al. | Preparation of pH-responsive membranes with amphiphilic copolymers by surface segregation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101013 Termination date: 20150425 |
|
| EXPY | Termination of patent right or utility model |