CN102716730A - Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material - Google Patents
Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material Download PDFInfo
- Publication number
- CN102716730A CN102716730A CN2012102377145A CN201210237714A CN102716730A CN 102716730 A CN102716730 A CN 102716730A CN 2012102377145 A CN2012102377145 A CN 2012102377145A CN 201210237714 A CN201210237714 A CN 201210237714A CN 102716730 A CN102716730 A CN 102716730A
- Authority
- CN
- China
- Prior art keywords
- graphene
- magnetic
- cyclodextrin
- preparation
- adsorption material
- 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.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method for a novel nano magnetic cyclodextrin/graphene biological adsorption material and particularly relates to modifying the surface of graphene with magnetic cyclodextrin through a surface modification technology. The novel method is characterized in that a nano magnetic particle is adopted as a carrier; coating modification is conduced on the nano magnetic particle to obtain the magnetic cyclodextrin with a core-shell structure; and then the functional graphene is modified with the magnetic cyclodextrin to prepare the novel magnetic nano biological adsorption material with super-strong adsorbability, easiness in separation and zero contamination. Through the adoption of the preparation method, the defect of high possibility of agglomeration of the graphene is overcome, the specific surface area of the adsorption material is greatly enlarged, the enveloping sites of cyclodextrin molecules are increased, and the range of adsorption objects is expanded. The adsorption material prepared by the invention has the advantages of strong controllability of a surface structure, reliable mechanical stability, strong recognition capability, high adsorptive capacity, easiness in desorption, reusability and the like; and simple and feasible ways and means are provided for treatment of environmental pollutants and recycling of waste.
Description
Technical field
The invention belongs to the preparation method of new bio sorbing material, particularly adopt a kind of method simply and easily to prepare the sorbing material of magnetic rings dextrin/Graphene as wastewater treatment.
Background technology
Cyclodextrin; Molecule shape is like a cylinder; A large amount of hydroxyls is contained in the outside, and inside is a hydrophobic cavity, can be combined into the Subjective and Objective inclusion compound with many inorganic, organic molecules; And can change by the physics of inclusion compound and chemical property, have protection, stablize the characteristic of guest molecule and selectivity oriented molecule; In addition, cyclodextrin have wide material sources, cheap, be prone to degraded, advantage such as pollution-free, therefore, it has important research and using value as sorbing material in fields such as environmental protection.But in practical application, cyclodextrin still is faced with some problems, like (1) unstable chemcial property, is prone to dissolving and runs off; (2) adsorption time is long, and is consuming time; (3) low to metal ion and organic pollutant adsorption amount; (4) the difficult separation; (5) bad mechanical property.How to resolve these problems and determined the application prospect of cyclodextrin in water treatment, it is carried out modification is a good solution.
Magnetic macromolecular microsphere is a kind of microballoon that polymer substance and inorganic magnetic material are combined.Because its particle diameter is little, specific area is big, combines with target substance easily; Because it has distinctive magnetic responsiveness, can carry out orientation through externally-applied magnetic field and separate simultaneously, not need centrifugally operated, help the simplification and the automation of separation process, be the research focus of current separation field.Introduce magnetic particle; Preparation magnetic rings dextrin, its good characteristic mainly contain that absorption property is strong, easily separated, non-secondary pollution, also can give its multiple functional groups through surface modification, copolymerization etc. simultaneously; And then can combine various advanced materials, make it have dual or multi-functional.
Graphene has very big specific area, and theoretical specific area reaches 2630m
2/ g.Graphene has obtained good application because of having very strong absorption property and favorable mechanical performance as sorbing material.In addition, the cooperative effect between Graphene and the nano material makes this composite that contains high surface area compare with single nano material to have very big superiority.With the Graphene is that the preparing carriers nano adsorption material also becomes the research focus.
With the Graphene is carrier material, and the grafting of magnetic rings dextrin to its surface, is prepared magnetic rings dextrin/Graphene composite nano materials.This composite has the favorable mechanical performance, has very big specific area, has increased the envelope site of bad dextrin molecule, obtains to have the biological adsorption agent that adsorbance is big, be easy to separate, reuse effective and non-secondary pollution.This composite can be used in the processing of separation and concentration and organic wastewater of heavy metal in the waste water.For the processing and the waste recovery utilization of environmental pollution provides simple ways and means.
Summary of the invention
The objective of the invention is to prepare magnetic rings dextrin/graphene nano biological adsorption agent.
The present invention is based on the principle of chemical modification, and magnetic rings dextrin and Graphene surface are glued together through crosslinked, and it specifically may further comprise the steps:
A. the preparation of functionalization graphene
Graphite powder adds in the nitration mixture, and mixing adds potassium permanganate; Under the condition of reflux, react a period of time, under condition of ice bath, add hydrogen peroxide solution then until no longer reacting; Carry out centrifugally then, washing, after the drying, obtain surface-functionalized Graphene.Its concrete parameter is: red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio are 1: 3～1: 6, and the mixing mixing time is 20～50min, and strong oxidizer is a potassium permanganate, and addition is 4.0～7.0g, and soak time is 12～18h, and activation temperature is 85～100 ℃.
B. the preparation of magnetic rings dextrin/Graphene sorbing material
Cyclodextrin, magnetic particle and crosslinking agent are joined mixing reaction in the ammonia spirit, add functionalization graphene solution then, mixing, reacting by heating utilizes externally-applied magnetic field to separate then, after washing, the drying, obtains magnetic rings dextrin/graphene composite material.Its concrete parameter: the magnetic nano-particle particle diameter is 5～30nm, and magnetic particle and cyclodextrin mass ratio are 1: 3～1: 5, and the ammoniacal liquor mass concentration is 10～20%; Crosslinking agent is the glutaraldehyde or the epoxychloropropane of mass concentration 25%, and addition 5～10mL, crosslinking time are 1～2h; The Graphene solution concentration is 0.2～0.5mg/mL; Mixing time is 0.5～1.5h, and the reacting by heating temperature is 50～70 ℃, and the reaction time is 1～3h.
Magnetic rings dextrin/Graphene sorbing material that the present invention is prepared, it has following advantage:
(1) Graphene is well disperseed, prevent local the reunion, strengthen the mechanical performance of sorbing material;
(2) have high specific area, thereby improved adsorption rate and adsorbance, stability is strong;
(3) non-secondary pollution is the friendly type sorbing material of a kind of environmental protection;
(4) solved the difficult actual application problem of separating of sorbing material.
Description of drawings
Fig. 1 magnetic rings dextrin/Graphene sorbing material synthesis mechanism sketch map.
The specific embodiment
Instance 1: the preparation of magnetic rings dextrin/Graphene sorbing material
A. the preparation of functionalization graphene
Take by weighing the 1.0g graphite powder and add (red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio: 1: 6) in the 150mL nitration mixture (, adding the acid of nitric acid after vulcanization under stirring earlier), behind the stirring reaction 20min, add 5.0g potassium permanganate again, 85 ℃ of oil baths, reflux, reaction 13h at ice-water bath.Under the condition of ice bath, slowly add the dropping hydrogen peroxide solution until no longer reacting, centrifugal, use watery hydrochloric acid and washing with alcohol respectively successively, the dry functionalization graphene that gets.
B. the preparation of magnetic rings dextrin/Graphene sorbing material
Cyclodextrin, 0.5g magnetic particle, the 5mL glutaraldehyde of 1.5g are added in the ammoniacal liquor of 30mL 10% stirring reaction 1h under the normal temperature.The Graphene solution of getting 10mL 0.2mg/mL is added in the mixed liquor, electronic stirring 1h under 50 ℃.Taking-up is left standstill the back and is separated with magnet, washs to neutrality with ethanol, secondary water washing respectively, and vacuum drying gets magnetic rings dextrin/Graphene.
Instance 2: the preparation of magnetic rings dextrin/Graphene sorbing material
A. the preparation of functionalization graphene
Take by weighing the 1.0g graphite powder and add (red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio: 1: 5) in the 150mL nitration mixture (, adding the acid of nitric acid after vulcanization under stirring earlier), behind the stirring reaction 30min, add 6.0g potassium permanganate again, 90 ℃ of oil baths, reflux, reaction 15h at ice-water bath.Under the condition of ice bath, slowly add the dropping hydrogen peroxide solution until no longer reacting, centrifugal, use watery hydrochloric acid and washing with alcohol respectively successively, the dry functionalization graphene that gets.
B. the preparation of magnetic rings dextrin/Graphene sorbing material
Cyclodextrin, 0.5g magnetic particle, the 6mL glutaraldehyde of 2.0g are added in the ammoniacal liquor of 30mL 15% stirring reaction 1.5h under the normal temperature.The Graphene solution of getting 10mL 0.3mg/mL is added in the mixed liquor, electronic stirring 2h under 60 ℃.Taking-up is left standstill the back and is separated with magnet, washs to neutrality with ethanol, secondary water washing respectively, and vacuum drying gets magnetic rings dextrin/Graphene.
Instance 3: the preparation of magnetic rings dextrin/Graphene sorbing material
A. the preparation of functionalization graphene
Take by weighing the 1.0g graphite powder and add (red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio: 1: 3) in the 150mL nitration mixture (, adding the acid of nitric acid after vulcanization under stirring earlier), behind the stirring reaction 50min, add 7.0g potassium permanganate again, 100 ℃ of oil baths, reflux, reaction 16h at ice-water bath.Under the condition of ice bath, slowly add the dropping hydrogen peroxide solution until no longer reacting, centrifugal, use watery hydrochloric acid and washing with alcohol respectively successively, the dry functionalization graphene that gets.
B. the preparation of magnetic rings dextrin/Graphene sorbing material
Cyclodextrin, 0.5g magnetic particle, the 10mL glutaraldehyde of 2.5g are added in the ammoniacal liquor of 30mL 20% stirring reaction 2h under the normal temperature.The Graphene solution of getting 10mL 0.5mg/mL is added in the mixed liquor, electronic stirring 3h under 70 ℃.Taking-up is left standstill the back and is separated with magnet, washs to neutrality with ethanol, secondary water washing respectively, and vacuum drying gets magnetic rings dextrin/Graphene.
Claims (4)
1. the preparation of the biological sorbing material of nano-magnetic cyclodextrin/Graphene is characterized in that method comprises following A, two steps of B successively:
A. the preparation of functionalization graphene
Graphite powder makes functionalization graphene through peroxidating and surface activation process in the presence of nitration mixture and strong oxidizer, its surface has multiple functional groups such as hydroxyl and carboxyl.
B. the preparation of magnetic rings dextrin/graphene composite material
Cyclodextrin, magnetic particle and crosslinking agent are joined solubilizing reaction in the ammonia spirit; Add functionalization graphene solution then, hybrid reaction is under certain condition utilized under the condition of externally-applied magnetic field and is separated; After washing, the drying, obtain magnetic rings dextrin/graphene composite material.
2. the method for claim 1; It is characterized in that in the preparation process of functionalization graphene that red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio are 1: 3～1: 6 in the nitration mixture, the mixing mixing time is 20～50min; Strong oxidizer is a potassium permanganate; Addition is 4.0～7.0g, soak time 12～16h, and activation temperature is 85～100 ℃.
3. the method for claim 1; It is characterized in that in the preparation process of magnetic rings dextrin/graphene composite material that the magnetic nano-particle particle diameter is 5～30nm, magnetic particle and cyclodextrin mass ratio are 1: 3～1: 5; The ammoniacal liquor mass concentration is 10～20%; Crosslinking agent is the glutaraldehyde or the epoxychloropropane of mass concentration 25%, and addition is 5～10mL, and cross-linking reaction time is 1～2h.
4. the method for claim 1; It is characterized in that in the preparation process of magnetic rings dextrin/graphene composite material; The Graphene solution concentration is 0.2～0.5mg/mL; Mixing mixing time in the reactant mixture is 0.5～1.5h, and the temperature of reacting is 50～70 ℃, and the reaction time is 1～3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210237714.5A CN102716730B (en) | 2012-07-11 | 2012-07-11 | Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210237714.5A CN102716730B (en) | 2012-07-11 | 2012-07-11 | Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102716730A true CN102716730A (en) | 2012-10-10 |
| CN102716730B CN102716730B (en) | 2014-04-02 |
Family
ID=46942675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210237714.5A Expired - Fee Related CN102716730B (en) | 2012-07-11 | 2012-07-11 | Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102716730B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977247A (en) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | Preparation method of magnetic functionalized graphene oxide based molecularly imprinted hybrid material |
| CN103102421A (en) * | 2013-01-30 | 2013-05-15 | 哈尔滨工业大学 | Preparation method of core-shell structure magnetic nano-molecular imprinting polymer for separating starch polysaccharides |
| CN103357388A (en) * | 2013-08-05 | 2013-10-23 | 新乡医学院 | Preparation method for cyclodextrin- graphene microsphere used for water purification |
| CN103464122A (en) * | 2013-09-23 | 2013-12-25 | 青岛大学 | Preparation method of graphene/chitosan adsorbent resin |
| CN104785215A (en) * | 2015-04-03 | 2015-07-22 | 山东大学 | Magnetic cyclodextrin-carbon nanofiber composite material and preparation method thereof |
| CN105267976A (en) * | 2015-10-14 | 2016-01-27 | 重庆华邦制药有限公司 | Graphene-oxide cyclodextrin compound and preparation method thereof |
| CN105668854A (en) * | 2016-03-03 | 2016-06-15 | 程礼华 | Graphene water purification multistage filter element device and technique thereof |
| CN105797692A (en) * | 2016-04-28 | 2016-07-27 | 河海大学 | Magnetic-beta-cyclodextrin-graphene oxide composition, preparation method and application thereof |
| CN105820377A (en) * | 2016-06-03 | 2016-08-03 | 江苏华昌织物有限公司 | Preparation method for load cyclodextrin magnetic graphene |
| CN106000337A (en) * | 2016-06-07 | 2016-10-12 | 新疆大学 | Preparation method for magnetic catalytic adsorption material |
| CN106186159A (en) * | 2016-08-03 | 2016-12-07 | 四川理工学院 | A kind of adsorbing material removing water Methylene Blue and the minimizing technology to water Methylene Blue thereof |
| CN108766779A (en) * | 2018-04-25 | 2018-11-06 | 深圳万佳互动科技有限公司 | Cobalt nickel-based super capacitor, its powder and raw powder's production technology |
| CN117504942A (en) * | 2023-11-23 | 2024-02-06 | 南京工业大学 | Cu (copper) alloy 2 O-based catalyst, preparation method thereof and application thereof in degradation of organic pollutants in water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579316A (en) * | 2008-05-14 | 2009-11-18 | 陕西北美基因股份有限公司 | Preparation method of superparamagnetic cyclodextrin composite particles |
| WO2011011061A2 (en) * | 2009-07-21 | 2011-01-27 | The Board Of Trustees Of The Leland Stanford Junior University | Method of regulating angiogenesis and lymphangiogenesis, and a pharmaceutical composition for effecting anti-angiogenic and anti-lymphangiogenic cancer therapy |
| CN102183557A (en) * | 2011-01-22 | 2011-09-14 | 青岛大学 | Preparation method of cyclodextrin functionalized graphene |
-
2012
- 2012-07-11 CN CN201210237714.5A patent/CN102716730B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579316A (en) * | 2008-05-14 | 2009-11-18 | 陕西北美基因股份有限公司 | Preparation method of superparamagnetic cyclodextrin composite particles |
| WO2011011061A2 (en) * | 2009-07-21 | 2011-01-27 | The Board Of Trustees Of The Leland Stanford Junior University | Method of regulating angiogenesis and lymphangiogenesis, and a pharmaceutical composition for effecting anti-angiogenic and anti-lymphangiogenic cancer therapy |
| CN102183557A (en) * | 2011-01-22 | 2011-09-14 | 青岛大学 | Preparation method of cyclodextrin functionalized graphene |
Non-Patent Citations (2)
| Title |
|---|
| 《西北工业大学学报》 20110831 季文等 磁性beta-环糊精聚合物/TiO2的制备及光催化性能 , * |
| 季文等: "磁性β-环糊精聚合物/TiO2的制备及光催化性能", 《西北工业大学学报》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977247B (en) * | 2012-12-12 | 2014-07-16 | 天津工业大学 | Preparation method of magnetic functionalized graphene oxide based molecularly imprinted hybrid material |
| CN102977247A (en) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | Preparation method of magnetic functionalized graphene oxide based molecularly imprinted hybrid material |
| CN103102421A (en) * | 2013-01-30 | 2013-05-15 | 哈尔滨工业大学 | Preparation method of core-shell structure magnetic nano-molecular imprinting polymer for separating starch polysaccharides |
| CN103357388A (en) * | 2013-08-05 | 2013-10-23 | 新乡医学院 | Preparation method for cyclodextrin- graphene microsphere used for water purification |
| CN103464122A (en) * | 2013-09-23 | 2013-12-25 | 青岛大学 | Preparation method of graphene/chitosan adsorbent resin |
| CN104785215B (en) * | 2015-04-03 | 2017-11-24 | 山东大学 | A kind of magnetic cyclodextrin carbon nano-fiber composite material and preparation method thereof |
| CN104785215A (en) * | 2015-04-03 | 2015-07-22 | 山东大学 | Magnetic cyclodextrin-carbon nanofiber composite material and preparation method thereof |
| CN105267976B (en) * | 2015-10-14 | 2018-09-11 | 重庆华邦制药有限公司 | The compound and preparation method thereof of graphene oxide and cyclodextrin |
| CN105267976A (en) * | 2015-10-14 | 2016-01-27 | 重庆华邦制药有限公司 | Graphene-oxide cyclodextrin compound and preparation method thereof |
| CN105668854A (en) * | 2016-03-03 | 2016-06-15 | 程礼华 | Graphene water purification multistage filter element device and technique thereof |
| CN105668854B (en) * | 2016-03-03 | 2018-05-29 | 程礼华 | Graphene water body purification multi-stage filter core device and its technique |
| CN105797692A (en) * | 2016-04-28 | 2016-07-27 | 河海大学 | Magnetic-beta-cyclodextrin-graphene oxide composition, preparation method and application thereof |
| CN105820377A (en) * | 2016-06-03 | 2016-08-03 | 江苏华昌织物有限公司 | Preparation method for load cyclodextrin magnetic graphene |
| CN106000337A (en) * | 2016-06-07 | 2016-10-12 | 新疆大学 | Preparation method for magnetic catalytic adsorption material |
| CN106000337B (en) * | 2016-06-07 | 2018-06-22 | 新疆大学 | A kind of preparation method of magnetism catalytic adsorption material |
| CN106186159A (en) * | 2016-08-03 | 2016-12-07 | 四川理工学院 | A kind of adsorbing material removing water Methylene Blue and the minimizing technology to water Methylene Blue thereof |
| CN108766779A (en) * | 2018-04-25 | 2018-11-06 | 深圳万佳互动科技有限公司 | Cobalt nickel-based super capacitor, its powder and raw powder's production technology |
| CN108766779B (en) * | 2018-04-25 | 2020-10-09 | 上海朗银压力容器有限公司 | Cobalt-nickel-based supercapacitor, powder thereof and preparation method of powder |
| CN117504942A (en) * | 2023-11-23 | 2024-02-06 | 南京工业大学 | Cu (copper) alloy 2 O-based catalyst, preparation method thereof and application thereof in degradation of organic pollutants in water |
| CN117504942B (en) * | 2023-11-23 | 2024-04-12 | 南京工业大学 | Cu (copper) alloy 2 O-based catalyst, preparation method thereof and application thereof in degradation of organic pollutants in water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102716730B (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102716730B (en) | Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material | |
| CN104998623B (en) | A kind of composite magnetic nano particle adsorbent and its preparation method and application | |
| CN102716722A (en) | Preparation method of graphene-based novel nano magnetic biological adsorbent | |
| CN106076271B (en) | A kind of nano-magnetic polylysine/（Graphene oxide-carbon nanotube）The preparation method and application of biological adsorption material | |
| CN103432994B (en) | Preparation method of magnetic graphene based oil absorption foam material | |
| CN104084126B (en) | The preparation method of biomass-based iron aluminium complex spherical charcoal | |
| CN103394332A (en) | Preparation method of nanometer magnetic chitosan/graphene biological adsorption material | |
| CN104923161A (en) | Preparation method of magnetic graphene oxide and application thereof | |
| CN105457602A (en) | Novel nano composite material with micro-pore structure as well as preparation and application thereof | |
| CN106732470A (en) | A kind of preparation of 2 mercaptopyrimidine modified magnetic CNT porous adsorbent | |
| CN102977247A (en) | Preparation method of magnetic functionalized graphene oxide based molecularly imprinted hybrid material | |
| CN106365239A (en) | Preparation method and application of magnetic graphene oxide/chitosan adsorbent | |
| CN107511132A (en) | A kind of magnetic ferroferric oxide nano-particles and its Plasma modification method and application | |
| CN104001474A (en) | Carbon-coated ferroferric oxide core-shell nano particle and preparation method thereof | |
| CN108246269B (en) | Lithium ion adsorbent and preparation method and application thereof | |
| CN105251448A (en) | Preparation method of magnetic graphene composite material | |
| CN102688752A (en) | Preparation method and application of Beta-cyclodextrin grafted carbon nano tube adsorbing material | |
| CN104785215A (en) | Magnetic cyclodextrin-carbon nanofiber composite material and preparation method thereof | |
| CN110404510A (en) | A kind of metal-organic framework materials and its preparation method and application of petal-shaped core-shell structure | |
| Chai et al. | In-suit ion-imprinted bio-sorbent with superior adsorption performance for gallium (III) capture | |
| US11638910B1 (en) | Lanthanum-iron-loaded carbon nanotube film for environmental restoration, preparation and application thereof | |
| CN104353435A (en) | Nitrogen heterocyclic ring compound modified magnetic polystyrene microsphere, preparation method and application thereof | |
| CN102600814A (en) | Preparation method of novel magnetic nano biosorption material | |
| CN109174049B (en) | Preparation method and application of imprinted porous lithium/rubidium ion adsorption material | |
| Zhang et al. | Phosphorylated-CNC/MWCNT thin films-toward efficient adsorption of rare earth La (III) |
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: 20140402 Termination date: 20140711 |
|
| EXPY | Termination of patent right or utility model |