CN101721926B - Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof - Google Patents
Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof Download PDFInfo
- Publication number
- CN101721926B CN101721926B CN200910220544.8A CN200910220544A CN101721926B CN 101721926 B CN101721926 B CN 101721926B CN 200910220544 A CN200910220544 A CN 200910220544A CN 101721926 B CN101721926 B CN 101721926B
- Authority
- CN
- China
- Prior art keywords
- dip
- ketone
- sulfonation
- preparation
- aryl ether
- 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.)
- Active
Links
Abstract
The invention discloses a class novel sulfonated containing naphthyridine ketone structure copolymerization aryl ether sulfone composite nanometer filtering film and preparation method thereof.Sulfonation is composite material containing naphthyridine ketone structure copolymerization aryl ether sulfone, and with the mixture of the reagent such as alcohols, ethers, ketone for solvent, polyalcohol, polyhydric phenols or polyamine etc. are additive, preparation dip-coating solution.Adopt dip coating to be coated on ultrafiltration counterdie, at 30-150 DEG C, obtain NEW TYPE OF COMPOSITE NF membrane through heat treatment.Because sulfonation is containing the diazanaphthalene terphenyl structure containing full aromatic ring distortion non-co-planar in naphthyridine ketone structure copolymerization aryl ether sulfone strand, there is higher sparkling transition temperature, chemical stability is excellent, have extraordinary resistance to oxidation, resistance to elevated temperatures and excellent selective penetrated property, obtained composite nanometer filtering film has outstanding high temperature resistant, oxidation resistent susceptibility.Sulfonation contains the molecular structure of naphthyridine ketone structure copolymerization aryl ether sulfone containing, for example lower constitutional repeating unit:
wherein R
1, R
2, R
3all can be hydrogen atom, halogen atom, methyl or aryl; X can be
Description
Technical field
The invention belongs to technical field of membrane separation, relate to high-performance NF membrane and technology of preparing thereof, be related specifically to a kind of sulfonation containing naphthyridine ketone structure copolymerization aryl ether sulfone NF membrane and preparation method thereof.
Background technology
Nanofiltration is a kind of pressure-driven membrane separating process between counter-infiltration and ultrafiltration, the pore diameter range of NF membrane is at several ran, its to monovalention and molecular weight lower than 200 organic matter remove poor, and have higher removal efficiency to divalence or multivalent ion and the organic matter of molecular weight between 200 ~ 1000.Owing to having the features such as operating pressure is low, energy-conservation, NF membrane is widely used.Demineralized water process that NF membrane is mainly used in (1), as softened bitter, desalination.(2) the removing of harmful substance in drinking water.(3) water, wastewater treatment in.(4) food, beverage, pharmaceutical industry, as the concentrating and desalinating of whey, antibiotic purifying and concentrated etc.(5) the chemical engineering process aqueous solution concentrated, be separated, as concentrated, the phenolic wastewater treatment etc. of waste water from dyestuff.NF membrane mostly is composite membrane, and the preparation of composite membrane has can distinguish preferred composite bed and support layer material, realizes the optimized advantage of film properties.The preparation method of composite membrane mainly contains: weak solution dip coating, in-situ polymerization method, interfacial polymerization, Plasma Polymerization etc.The developing direction of composite membrane is exploitation resistance to oxidation, resistance to free chlorine, high desalination, high water flux, heat-resisting, pollution resistant composite film and extraordinary composite membrane.Composite nanometer filtering film is the polyamide-based composite membrane prepared through interfacial polymerization by polyamine and polynary acyl chlorides mostly, because the chlorine-resistant property of polyamide is not good enough, reducing agent must be added in former water except the free chlorine in anhydrating during use, to ensure that film properties deterioration does not occur, thus adding operating cost, the subsequent treatment also fed water brings certain difficulty.So the resistance to free chlorine performance improving film is one of vital task of current composite nanometer filtering film research.
Sulfonated polyether sulfone has acidproof, alkaline-resisting and chlorine-resistant property preferably, is the membrane material of a class function admirable.US Patent No. 4818387 discloses a kind of preparation method of sulfonated polyether sulfone composite membrane, the sulfonated polyether sulfone composite membrane adopting dip coating to prepare is soak surrounding in the aqueous solution of 100ppm at chlorinity, the performance of composite membrane is substantially constant, has extraordinary chlorine-resistant, oxidation resistent susceptibility.
Sulfonation is be incorporated into by naphthyridine ketone structure on polyether sulfone molecular backbone containing naphthyridine ketone structure copolymerization aryl ether sulfone, the novel sulfonated polyether sulphone of a class obtained, owing to being introduced in main polymer chain by the diazanaphthalene terphenyl structure of full aromatic ring distortion non-co-planar, give novel polyether sulphone not only high temperature resistant but also soluble Good All-around Property.By sulfonation containing the film prepared by naphthyridine ketone structure copolymerization aryl ether sulfone, there is better selective, higher flux and better heat endurance.In diffusion barrier field, there is boundless application prospect.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of sulfonation containing naphthyridine ketone structure copolymerization aryl ether sulfone NF membrane and preparation method thereof.
Technical scheme of the present invention is as follows:
With sulfonation containing naphthyridine ketone structure copolymerization aryl ether sulfone for coating material, to form in the strand of this base polymer containing, for example lower construction unit:
Wherein R
1, R
2, R
3all can be hydrogen atom, halogen atom, methyl or aryl; X can be
When X is
time, sulfonation and copolymerization aryl ether sulfone can be called that sulfonation contains naphthyridine ketone structure hydroquinones type copolymerization aryl ether sulfone (SPPHES); When X is
or
time, sulfonation and copolymerization aryl ether sulfone can be called that sulfonation contains naphthyridine ketone structure '-biphenyl diphenol type copolyether sulfone (SPPBES); When X is
time, sulfonation and copolymerization aryl ether sulfone can be called that sulfonation contains naphthyridine ketone structure bisphenol S type copolyether sulfone; When X is
time, sulfonated polyether sulphone can be called that sulfonation contains naphthyridine ketone structure polyether sulfone (SPPES).
The preparation method of sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone, comprises the steps:
A) sulfonation of drying is joined in solvent containing naphthyridine ketone structure copolymerization aryl ether sulfone, additive, filter after dissolving completely and be mixed with dip-coating weak solution;
B) support counterdie be fixed on glass plate or on film machine, dip-coating weak solution be coated to the surface of film, discharge opeing, heat-treat, obtain sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone.
Invention institute adopts and supports counterdie is have the milipore filter or hollow fiber ultrafiltration membrane that non-woven fabrics supports, and the polymeric material forming support counterdie is contain naphthyridine ketone structure polyether sulphone, containing naphthyridine ketone structure PAEK, containing naphthyridine ketone structure poly (aryl ether sulfone ketone), containing any one or a few blend in naphthyridine ketone structure copolymerization aryl ether sulfone, bisphenol-a polysulfone, polyether sulfone, Kynoar, polyacrylonitrile etc.
Sulfonation of the present invention should be 0.5-3.0mmol/g containing the ion exchange capacity (IEC) of naphthyridine ketone structure copolymerization aryl ether sulfone, and preferred IEC is that the sulfonation of 1.0-2.5mmol/g is containing naphthyridine ketone structure copolymerization aryl ether sulfone.
In dip-coating weak solution of the present invention, sulfonation is 0.5-10% containing the percentage composition of naphthyridine ketone structure copolymerization aryl ether sulfone, is preferably 0.5-5%.
The solvent of dip-coating weak solution of the present invention can be any one or a few the mixture in methyl alcohol, ethanol, EGME, glycol dimethyl ether, ethylene glycol ethyl ether, butyl glycol ether, oxolane, dioxane, acetone, butanone, water etc.
Dip-coating weak solution of the present invention contains the organic additives such as polyalcohol, polyhydric phenols, polyamine or polyethylene glycol, and percentage composition, at 0-50%, is preferably 5-30%.
Dip-coating weak solution of the present invention can contain the inorganic additives such as lithium chloride, lithium nitrate or lithium perchlorate, and the percentage composition of inorganic additive is at 0-3%.
Time of immersion of the present invention is 0.5-10 minute, and heat treatment temperature is 30-150 DEG C, and heat treatment time is 5-100 minute.
Detailed description of the invention
Specific embodiments of the invention are described in detail below in conjunction with technical scheme.Embodiment lists preparation technology and the performance of NEW TYPE OF COMPOSITE NF membrane, and these examples are only used to that the present invention will be described, is not limit scope.
Embodiment 1
SPPBES after drying (sulfonation degree 0.9) 1g is dissolved in the mixed solvent of 41.5g EGME, ethanol and deionized water composition, adds 7.5g glycerine, be mixed with dip-coating weak solution.Inbred group breeding (PPESK) milipore filter is fixed on glass plate, the SPPBES dip-coating weak solution prepared is coated in ultrafiltration counterdie surface equably, after 5 minutes, and venting surplus liquid, at 90 DEG C, heat treatment 30 minutes, obtains SPPBES composite nanometer filtering film.Soak after 24 hours in water, under 1.2MPa, precompressed is after 0.5 hour, and 1.0MPa 1000mg/L aqueous sodium persulfate solution measures salt rejection rate and water flux, and the water flux of SPPBES composite nanometer filtering film is 44L/ (m
2h), salt rejection rate reaches 83%.
Embodiment 2
SPPBES after drying (sulfonation degree 0.9) 1g is dissolved in the mixed solvent of 41.5g EGME, acetone and deionized water composition, adds 7.5g glycerine, be mixed with dip-coating weak solution.Inbred group breeding (PPESK) milipore filter is fixed on glass plate, the SPPBES dip-coating weak solution prepared is coated in ultrafiltration counterdie surface equably, after 5 minutes, and venting surplus liquid, at 90 DEG C, heat treatment 30 minutes, obtains SPPBES composite nanometer filtering film.Soak after 24 hours in water, under 1.2MPa, precompressed is after 0.5 hour, and 1.0MPa 1000mg/L aqueous sodium persulfate solution measures salt rejection rate and water flux, and the water flux of SPPBES composite nanometer filtering film is 61L/ (m
2h), salt rejection rate reaches 69%.
Embodiment 3
SPPHES after drying (sulfonation degree 0.69) 1g is dissolved in the mixed solvent of 27.2g EGME, 6.8g ethanol and 2.5g dimethylacetylamide composition, adds 12.5g glycerine, be mixed with dip-coating weak solution.Be fixed on glass plate by PPESK milipore filter, the SPPHES dip-coating weak solution prepared is coated in ultrafiltration counterdie surface equably, and after 5 minutes, venting surplus liquid, at 90 DEG C, heat treatment 30 minutes, obtains SPPHES composite nanometer filtering film.Soak after 24 hours in water, under 1.2MPa, precompressed is after 0.5 hour, and 1.0MPa 1000mg/L aqueous sodium persulfate solution measures salt rejection rate and water flux, and the water flux of SPPHES composite nanometer filtering film is 35L/ (m
2h), salt rejection rate reaches 93%.
Embodiment 4
SPPHES after drying (sulfonation degree 0.7) 1.5g is dissolved in the mixed solvent of 27g EGME, 6.5g ethanol and 2.5g dimethylacetylamide composition, adds 12.5g glycerine, be mixed with dip-coating weak solution.Be fixed on glass plate by PPESK milipore filter, the SPPHES dip-coating weak solution prepared is coated in ultrafiltration counterdie surface equably, and after 5 minutes, venting surplus liquid, respectively at heat treatment at 70 DEG C, 90 DEG C, 110 DEG C 30 minutes, obtains SPPHES composite nanometer filtering film.Soak after 24 hours in water, under 1.2MPa, precompressed is after 0.5 hour, and 1.0MPa 1000mg/L aqueous sodium persulfate solution measures salt rejection rate and water flux.At 70 DEG C, the salt rejection rate of heat treatment institute masking reaches 78%, and water flux is 89L/ (m
2h); At 90 DEG C, the salt rejection rate of heat treatment institute masking reaches 84%, and water flux is 69L/ (m
2h); At 110 DEG C, the salt rejection rate of heat treatment institute masking reaches 76%, and water flux is 49L/ (m
2h).
Embodiment 5
SPPHES after drying (sulfonation degree 0.85) 1g is dissolved in the mixed solvent of 27.2g EGME, 6.8g ethanol and 2.5g dimethylacetylamide composition, adds 12.5g glycerine, be mixed with dip-coating weak solution.Be fixed on glass plate by PPESK milipore filter, the SPPHES dip-coating weak solution prepared is coated in ultrafiltration counterdie surface equably, and after 5 minutes, venting surplus liquid, at 90 DEG C, heat treatment 30 minutes, obtains SPPHES composite nanometer filtering film.Soak after 24 hours in water, under 1.2MPa, precompressed is after 0.5 hour, and 1.0MPa 1000mg/L aqueous sodium persulfate solution measures salt rejection rate and water flux, and the water flux of SPPHES composite nanometer filtering film is 107L/ (m
2h), salt rejection rate reaches 94%.
Embodiment 6
SPPHES after drying (sulfonation degree 0.65) 1.5g is dissolved in the mixed solvent of 27g EGME, 6.5g ethanol and 2.5g dimethylacetylamide composition, adds 12.5g glycerine, be mixed with dip-coating weak solution.Be fixed on glass plate by PPESK milipore filter, the SPPHES dip-coating weak solution prepared is coated in ultrafiltration counterdie surface equably, and after 5 minutes, venting surplus liquid, at 90 DEG C, heat treatment 20 minutes, obtains SPPHES composite nanometer filtering film.Soak after 24 hours in water, under 1.2MPa, precompressed is after 0.5 hour, and 1.0MPa 1000mg/L aqueous sodium persulfate solution measures salt rejection rate and water flux, and the water flux of SPPHES composite nanometer filtering film is 43L/ (m
2h), salt rejection rate reaches 87%.
After the made SPPHES composite membrane of embodiment 6 processes 2 hours in boiling water, the water flux of composite membrane is 47L/ (m
2h), it is 88% that salt rejection rate reaches, and water flux adds nearly 10% than before process, and salt rejection rate change is little, illustrates that composite membrane has extraordinary heat resistance; Prepared composite nanometer filtering film soaks 20 days in the HCl aqueous solution of 0.1mol/L, the water flux of composite membrane and substantially constant to the salt rejection rate of sodium sulphate; Composite membrane soaks 10 days in the 0.1mol/LNaOH aqueous solution, the water flux of film and substantially constant to the salt rejection rate of sodium sulphate; Composite membrane soaks 20 days in 100mg/LNaClO solution, the water flux of film and substantially constant to the salt rejection rate of sodium sulphate; Illustrate that SPPES composite membrane has extraordinary acid and alkali-resistance and chlorine-resistant property.
Claims (7)
1. sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone, is characterized in that the polymer forming composite material is containing, for example lower construction unit:
Wherein R
1, R
2, R
3be all hydrogen atom, halogen atom, methyl or aryl; X is
2. the preparation method of sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone according to claim 1, comprises the steps:
A) sulfonation of drying is dissolved in solvent and additive containing naphthyridine ketone structure copolymerization aryl ether sulfone, is mixed with dip-coating weak solution;
B) dip-coating weak solution be coated on support counterdie, discharge opeing, heat-treats, and obtains sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone;
Supporting counterdie is have the miillpore filter or doughnut miillpore filter that non-woven fabrics supports, and forms that to support the polymeric material of counterdie be containing naphthyridine ketone structure polyether sulphone, containing naphthyridine ketone structure PAEK, containing naphthyridine ketone structure poly (aryl ether sulfone ketone), containing any one or a few blend in naphthyridine ketone structure copolymerization aryl ether sulfone, bisphenol-a polysulfone, polyether sulfone, Kynoar, polyacrylonitrile;
Sulfonation is 0.5-3.0mmol/g containing the ion exchange capacity of naphthyridine ketone structure copolymerization aryl ether sulfone; In dip-coating weak solution, sulfonation is 0.5-10% containing the percentage composition of naphthyridine ketone structure copolymerization aryl ether sulfone;
Dip-coating weak solution contains polyalcohol, polyhydric phenols or polyamine organic additive, and percentage composition is at 0-50%;
Time of immersion is 0.5-10 minute, and heat treatment temperature is 30-150 DEG C, and heat treatment time is 5-100 minute.
3. preparation method according to claim 2, is characterized in that: sulfonation is 1.0-2.5mmol/g containing the ion exchange capacity of naphthyridine ketone structure copolymerization aryl ether sulfone.
4. preparation method according to claim 2, is characterized in that: the solvent of dip-coating weak solution is any one or a few the mixture in methyl alcohol, ethanol, EGME, glycol dimethyl ether, ethylene glycol ethyl ether, butyl glycol ether, oxolane, dioxane, acetone, butanone, water.
5. preparation method according to claim 2, is characterized in that: in dip-coating weak solution, sulfonation is 0.5-5% containing the percentage composition of naphthyridine ketone structure copolymerization aryl ether sulfone.
6. preparation method according to claim 2, is characterized in that: dip-coating weak solution contains the inorganic additives such as lithium chloride, lithium nitrate or lithium perchlorate, and percentage composition is at 0-3%.
7. preparation method according to claim 2, is characterized in that: dip-coating weak solution contains polyalcohol, polyhydric phenols or polyamine organic additive, and percentage composition is at 5-30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910220544.8A CN101721926B (en) | 2009-12-01 | 2009-12-01 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910220544.8A CN101721926B (en) | 2009-12-01 | 2009-12-01 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101721926A CN101721926A (en) | 2010-06-09 |
| CN101721926B true CN101721926B (en) | 2015-12-16 |
Family
ID=42443837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910220544.8A Active CN101721926B (en) | 2009-12-01 | 2009-12-01 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101721926B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512995B (en) * | 2011-12-09 | 2014-05-21 | 浙江工业大学 | Sulfonated polysulfone blended nanometer calcium carbonate composite polysulfone membrane and preparation method thereof |
| CN102698617B (en) * | 2012-06-08 | 2014-10-08 | 厦门大学 | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof |
| CN103788374A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Sulfonated polyarylether sulfone and preparation method thereof, and reverse osmosis membrane and making method thereof |
| CN103785308B (en) * | 2012-10-29 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
| CN103191656B (en) * | 2013-03-29 | 2015-01-28 | 中国科学技术大学 | Preparation method of polymer micro-filtration membrane |
| CN104248914B (en) * | 2013-06-28 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of reverse osmosis membrane and preparation method thereof |
| CN113522040A (en) * | 2021-07-30 | 2021-10-22 | 天津大学 | Method for preparing high-performance carbon dioxide separation composite membrane containing twisted structure through interfacial polymerization |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818387A (en) * | 1984-06-15 | 1989-04-04 | Nitto Electric Industrial Co., Ltd. | Sulfonated polysulfone composite semipermeable membranes and process for producing the same |
-
2009
- 2009-12-01 CN CN200910220544.8A patent/CN101721926B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818387A (en) * | 1984-06-15 | 1989-04-04 | Nitto Electric Industrial Co., Ltd. | Sulfonated polysulfone composite semipermeable membranes and process for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 杂萘联苯共聚芳醚砜的磺化;张守海等;《2009年全国高分子学术论文报告会》;20090822;第553页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101721926A (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101721926B (en) | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof | |
| JP6211059B2 (en) | Ultrafiltration membranes made from sulfonated polyphenylene sulfone | |
| JP6882267B2 (en) | Method for Producing Membrane Using Lactamide Solvent | |
| KR20170080627A (en) | Copolymers for making membranes | |
| US20130277318A1 (en) | Ultrafiltration membranes fabricated from sulfonated polyphenylenesulfones | |
| KR20150036007A (en) | Composite membranes comprising a sulfonated polyphenylenesulfone and their use in forward osmosis processes | |
| CN106669468A (en) | Metal doped g-C3N4 based visible light catalysis flat plate type ultra-filtration membrane and preparation method | |
| CN110756061B (en) | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof | |
| CA2008502A1 (en) | Membranes | |
| KR101240736B1 (en) | Polymer compositions, water-treatment membranes and water-treatment modules comprising the same | |
| WO2019016082A1 (en) | Sulfonated polyarylethersulfones and membranes thereof | |
| WO2017220363A1 (en) | Process for removing arsenic compounds from aqueous systems | |
| JP6312148B2 (en) | High performance positively charged composite membranes and their use in nanofiltration processes | |
| CN1597074A (en) | Polyaryl ether sulphone compound separation membrane and its preparation method | |
| CN101721927A (en) | Ultrafiltration membrane copoly(phthalazinone aryl ether sulfone) and preparation method thereof | |
| KR20120083695A (en) | Polyacrylonitrile copolymer, method for manufacturing membrane including the same, membrane including the same and water treatment module using the same | |
| CN111282455B (en) | External pressure type hollow fiber industrial nanofiltration membrane and preparation method thereof | |
| JP2023126212A (en) | Membrane manufacturing with cosolvent in polymer dope solution | |
| KR101514688B1 (en) | A novel preparation method of hydrophilic membrane having excellent water permeability, size exclusion selectivity, and anti-fouling using the blend solution of PVDF and partially sulfonated polyarylene-based polymers | |
| CN110841489A (en) | Novel composite nanofiltration membrane and preparation method and application thereof | |
| US10307717B2 (en) | Porous membranes and associated separation modules and methods | |
| CN112892250B (en) | Chlorine-resistant amino acid modified polyether sulfone reverse osmosis membrane and preparation method thereof | |
| CN112337318B (en) | Polyphenylene sulfide/porous carbon nanofiber composite membrane and preparation method thereof | |
| EP3571242B1 (en) | New membranes | |
| CN117018878A (en) | Preparation method of high-penetrability alloy hollow fiber ultrafiltration membrane with twisted structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Jian Xigao Inventor after: Zhang Shouhai Inventor after: Wang Jinyan Inventor after: Liu Cheng Inventor before: Jian Xigao Inventor before: Zhang Shouhai Inventor before: Yang Daling Inventor before: Wang Jinyan Inventor before: Liu Cheng |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: JIAN XIGAO ZHANG SHOUHAI YANG DALING WANG JINYAN LIU CHENG TO: JIAN XIGAO ZHANG SHOUHAI WANG JINYAN LIU CHENG |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |