CN102086033B - Calcium-fluorine-phosphorus-oxygen composite hollow spheres and preparation method thereof - Google Patents
Calcium-fluorine-phosphorus-oxygen composite hollow spheres and preparation method thereof Download PDFInfo
- Publication number
- CN102086033B CN102086033B CN200910200060.7A CN200910200060A CN102086033B CN 102086033 B CN102086033 B CN 102086033B CN 200910200060 A CN200910200060 A CN 200910200060A CN 102086033 B CN102086033 B CN 102086033B
- Authority
- CN
- China
- Prior art keywords
- calcium
- phosphorus
- preparation
- composite hollow
- controlled
- 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
Images
Landscapes
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to calcium-fluorine-phosphorus-oxygen (Ca-F-P-O) composite hollow spheres and a preparation method thereof. The calcium-fluorine-phosphorus-oxygen (Ca-F-P-O) composite hollow spheres are characterized in that: the Ca-F-P-O composite hollow spheres comprise 40 to 65 mass percent of Ca, 4 to 15 mass percent of P, 20 to 35 mass percent of F and the balance of oxygen; and the hollow spheres have a dimension between 100 and 1,500 nanometers. The preparation method comprises the following steps of: taking a surfactant or a block polymer as a template and deionized water as a reaction medium, and preparing the Ca-F-P-O composite hollow spheres in a one-step reaction through a self-assembly process. The provided technical process is simple and reliable and is easily controlled, and the composite hollow spheres with controllable structures and shapes can be prepared, and can be significantly applied in biomedicine, catalysis and other aspects.
Description
Technical field
The present invention relates to a kind of calcium-fluoro-phosphorus-oxygen composite hollow ball and preparation method, adopt more precisely the template self-assembly process, prepare calcium-fluoro-phosphorus-oxygen composite hollow ball and method, belong to preparation technology and the Application Areas of nano material.
Background technology
Since 1973 extract hollow glass micro-ball from flyash, the physical and chemical performance that hollow ball is excellent with it and wide application prospect, caused numerous scientists and engineering technical personnel's research interest.The hollow micropartical of receiving has physicals and the surface propertys such as larger specific surface area, less density and unique light, electricity, magnetic.The shell that is rich in microvoid structure also has selective permeability, adsorptivity etc.Due to these special structure and performance, the hollow micropartical of receiving has important researching value and application prospect widely in fields such as biomedical (susceptibility reagent is as the controlled transportation of enzyme, protein etc. and delivery systme and artificial cell, medical diagnosis on disease etc.), crystal optics, catalysis (high-selectivity catalyst or support of the catalyst), microwave absorbing and emr fluids.
Research and develop at present the hollow ball material of Multiple components, comprised inorganic hollow ball material, organic hollow ball material and organic and inorganic composite hollow ball material etc.Inorganic micro-nano hollow ball Recent study is more, has prepared semi-conductor (as chalcogenide compound, titanium dioxide etc.) hollow ball, pottery (as carbide, nitride, oxide compound, silicate etc.) hollow ball, metal hollow ball, carbon hollow ball and metallic oxide hollow sphere etc.The calcium phosphate material is the primary structure of bone, there is good biological activity, can be connected with osseous tissue shape osteogenic, and can be absorbed by tissue in vivo, so the calcium phosphate hollow ball has very important potential application in fields such as drug release, catalysis.But calcium phosphate material is crystallization very easily, be difficult to obtain amorphous structure, therefore up to the present, trial in this respect is mainly with ending up in failure.Simultaneously, calcium phosphate material absorption rate in vivo is too fast, particularly in acidity, in stronger environment, easily decomposes, and this has just limited its application in the drug release field greatly.The research discovery, the calcium phosphate that fluorine replaces absorption rate in vivo slows down greatly, relatively stable in sour environment.Fluorine is the element of often encountering in life, closely related with our life.Just contain fluorine in the osseous tissue of human body.In addition, numerous food product is as all contained fluorine in tealeaves, egg yolk.Fluorine is also the important interpolation element of in toothpaste or tap water, is used for strong tooth.After the calcium phosphate that fluorine replaces absorbs in vivo, the hydroxyapatite in fluorine meeting and bone generates more stable fluorine substituted hydroxy phosphatic rock.Therefore, prepare the calcium phosphate hollow ball material that fluorine replaces, in drug release and catalytic field, there is potential application prospect.
The method for preparing at present hollow ball is a lot, and relatively commonly used have template, emulsion method, spraying high-temperature decomposition, sonochemical method, hydro-thermal-solvent thermal reaction method, chemical induction rotation political reform, a solid phase method etc.Wherein with the most use is template, by the form of template, can be divided into hard template and soft template method etc. again.Soft template method prepares that hollow to receive atomic ultimate principle be to using micron-particle as template, be built into gradually certain thickness shell on its surface by means such as electrostatic adhesion, chemical reaction deposit or so-gels, then by thermal treatment or chemical process, remove template and obtain the corresponding hollow micropartical of receiving.Hard template method refer to take solids as prepared by template the hollow micropartical of receiving.Template commonly used has polystyrene particle, hollow glass micropearl and carbon ball etc., prepares rear pattern plate and removes by the method for calcining or dissolving.Hard template method exists need to remove that template particles, preparation cost are high, hollow receives the problems such as the micropartical productive rate is low.With hard template method, compare, soft template method template used has mobility, and sometimes also participates in forming shell, has certain advantage.Soft template commonly used has microbubble, drop, vesica, amphiphilic block copolymer, closed globular micelle etc.As everyone knows, tensio-active agent and block polymer can be in selective solvent self-assembly form the micella of different shape, comprise spherical, bar-shaped, vesica shape etc.At present, utilizing tensio-active agent and block polymer self-assembly to prepare hollow ball has had many bibliographical informations, has prepared the hollow ball particles such as silicon oxide, aluminum oxide, carbon, palladium, gan, titanium oxide, pure aluminium silicate, cupric oxide.But, about the report of calcium phosphate hollow ball seldom.The employing PMMA balls such as Wiliana are hard template, prepared calcium phosphate hollow ball [Wiliana Tjandra, Palaniswamy Ravi, Jia Yao and Kam C Tam, Synthesis ofhollow spherical calcium phosphate nanoparticles using polymeric nanotemplates, Nanotechnology 17 (2006) 5988-5994.].But, this technique more complicated, shape is also wayward.Ming-Yan Ma adopts calcium carbonate as hard template, same problem [Ming-Yan Ma also appears, Ying-Jie Zhu, Liang Li and Shao-Wen Cao, Nanostructured porous hollowellipsoidal capsules of hydroxyapatite and calcium silicate:preparation andapplication in drug delivery, J.Mater.Chem., 2008,18,2722-2727.].Up to the present, not yet find to adopt soft template to prepare the report of calcium phosphate hollow ball.
The present invention adopts tensio-active agent and block polymer as template first, and by self-assembly process, single step reaction is prepared calcium-fluoro-phosphorus-oxygen composite hollow ball.Below the present invention is elaborated.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing calcium-fluoro-phosphorus-oxygen composite hollow ball with soft template method.The present invention adopts tensio-active agent and block polymer as template first, and by self-assembly process, single step reaction is prepared calcium-fluoro-phosphorus-oxygen composite hollow ball.Specifically the present invention adopts deionized water as reaction medium, usings Phosphoric acid glycerol esters or its esters (Phosphoric acid glycerol esters disodium salt commonly used) as the phosphorus source, with HF, and NaF, KF, NH
4the fluorochemicals such as F, as the fluorine source, are usingd nitrocalcite, calcium halide, calcium acetate, calcium pantothenate, calcium carbonate, calcium hydroxide etc. as the calcium source.With P123, F127, Tween85, triton X100, the non-ionic type such as CTMB or ionogenic surfactant, as template, prepare the Ca-F-P-O hollow ball by self-assembly.
Its preparation technology comprises:
1. at first tensio-active agent is joined in deionized water, concentration is controlled between 0.003M-0.3M, and temperature is controlled between room temperature-50 ℃, after magnetic agitation 12-24 hour, dissolves;
2. add Phosphoric acid glycerol esters or its esters as the phosphorus source in the water phase surfactant mixture of step 1 preparation, wherein the concentration in phosphorus source is controlled between 0.02M-2M.After magnetic agitation 1-3 hour, dissolve.Then add the fluorine source, the concentration of fluorion is controlled between 0.01M-2M, continues magnetic agitation and dissolves after 2-6 hour.Solution temperature is controlled between room temperature-50 ℃;
3. the calcium source is dissolved in deionized water, concentration is controlled between 0.1M-1M.After dissolving, prepared calcium solution is added drop-wise in the solution that step 2 obtains.Ca after dripping in solution: the P ratio is controlled between 1.0-1.67, and temperature is controlled between room temperature-50 ℃;
4. the solution that step 3 made continues to mix 12-24 hour, and temperature is controlled between room temperature-50 ℃;
5. solution step 4 made is ℃ standing 12-24 hour in room temperature-50.Filter, filter seasoning after washed with de-ionized water for powder, wash number is 3-5 time.
Raw material used in the present invention is industrial raw material commonly used, and application is a lot of in the field of study, has product to sell.Its preparation method is also well-known in this field.
The hollow ball preparation technology that the present invention proposes, can a step realize the preparation of hollow ball.Technological process is simple, is easy to control.Be applicable to the preparation of fluorine-containing calcium phosphate hollow ball.The size of prepared Ca-F-P-O hollow ball is between the 100-1500 nanometer.See Fig. 1.And the quality percentage composition of Ca is between 40-65wt%, and the quality percentage composition of P is between 4-15wt%, and the quality percentage composition of F is between 20-35wt%, and surplus is oxygen.
The accompanying drawing explanation
The pattern that Fig. 1 is the Ca-F-P-O hollow ball for preparing of the present invention.
Embodiment
Detailed description by the following examples, further illustrate substantive distinguishing features of the present invention and significant progressive, but the present invention absolutely not only is confined to described embodiment.
Embodiment 1
3 gram P123 are joined in 60 ml deionized water, and temperature is controlled at 35 ℃, and magnetic agitation was dissolved after 12 hours.Then add Phosphoric acid glycerol esters disodium salt 1.7 grams.Continue to stir after 1-3 hour and dissolve.Then add Sodium Fluoride 1 gram, continue to stir after 2-6 hour and dissolve.Four water-calcium nitrate 2 grams are dissolved in deionized water, and concentration is controlled between 0.1M-1M.After dissolving, solution slowly is added drop-wise in above-mentioned solution.Dropwise rear continuation mixing 12-24 hour.Then at the standing 12-24 hour of room temperature.Filter, washed with de-ionized water 3 times, will filter the powder seasoning.After dry, powder was 400 ℃ of calcinings 10 hours.Be prepared into the Ca-F-P-O composite hollow ball, wherein the quality percentage composition of Ca is 50wt%, and the quality percentage composition of P is 10wt%, and the quality percentage composition of F is 25wt%, and surplus is O.
Embodiment 2
6 gram F127 are joined in 60 ml deionized water, and temperature is controlled at 35 ℃, and magnetic agitation was dissolved after 12 hours.Add Phosphoric acid glycerol esters disodium salt 4.5 grams.Continue to stir after 1-3 hour and dissolve.Then add Sodium Fluoride 1.5 grams, continue to stir after 2-6 hour and dissolve.Four water-calcium nitrate 5 grams are dissolved in deionized water, and concentration is controlled between 0.1M-1M.After dissolving, solution is dripped and slowly is added in above-mentioned solution.Dropwise rear continuation mixing 12-24 hour.Then at the standing 12-24 hour of room temperature.Filter, washed with de-ionized water 3 times, will filter the powder seasoning.After dry, powder was 400 ℃ of calcinings 10 hours.Be prepared into the Ca-F-P-O composite hollow ball, wherein the quality percentage composition of Ca is 49wt%, and the quality percentage composition of P is 13wt%, and the quality percentage composition of F is 23wt%, and surplus is O.
Embodiment 3
2 gram Tween 85 are joined in 60 ml deionized water, and temperature is controlled at 35 ℃, and magnetic agitation was dissolved after 12 hours.Add Phosphoric acid glycerol esters disodium salt 10 grams.Continue to stir after 1-3 hour and dissolve.Then add Sodium Fluoride 5 grams, continue to stir after 2-6 hour and dissolve.Four water-calcium nitrate 13 grams are dissolved in deionized water, and concentration is controlled between 0.1M-1M.After dissolving, solution slowly is added drop-wise in above-mentioned solution.Dropwise rear continuation mixing 12-24 hour.Then at the standing 12-24 hour of room temperature.Filter, washed with de-ionized water 3 times, will filter the powder seasoning.After dry, powder was 400 ℃ of calcinings 10 hours.Be prepared into the Ca-F-P-O composite hollow ball, wherein the quality percentage composition of Ca is 44wt%, and the quality percentage composition of P is 10wt%, and the quality percentage composition of F is 22wt%, and surplus is O.
Embodiment 4
2 gram triton X-100 are joined in 60 ml deionized water, and temperature is controlled at 45 ℃, magnetic agitation 12 hours.Then add Phosphoric acid glycerol esters disodium salt 10 grams.Continue to stir after 1-3 hour and dissolve.Then add hydrogen fluoride 2 grams, continue to stir 2-6 hour.Four water-calcium nitrate 12 grams are dissolved in deionized water, and concentration is controlled between 0.1M-1M.After dissolving, solution slowly is added drop-wise in above-mentioned solution.Dropwise rear continuation mixing 12-24 hour.Then at the standing 12-24 hour of room temperature.Filter, washed with de-ionized water 3 times, will filter the powder seasoning.After dry, powder was 400 ℃ of calcinings 10 hours.Be prepared into the Ca-F-P-O composite hollow ball, wherein the quality percentage composition of Ca is 55wt%, and the quality percentage composition of P is 9wt%, and the quality percentage composition of F is 20wt%, and surplus is O.
Embodiment 5
4 gram P123 are joined in 60 ml deionized water, and temperature is controlled at 50 ℃, and magnetic agitation was dissolved after 24 hours.Then add Phosphoric acid glycerol esters disodium salt 4.5 grams.Continue to stir after 1-3 hour and dissolve.Then add ammonium fluoride 2 grams, continue to stir after 2-6 hour and dissolve.Four water-calcium nitrate 6 grams are dissolved in deionized water, and concentration is controlled between 0.1M-1M.After dissolving, solution slowly is added drop-wise in above-mentioned solution.Dropwise rear continuation mixing 12-24 hour.Then at the standing 12-24 hour of room temperature.Filter, washed with de-ionized water 3 times, will filter the powder seasoning.After dry, powder was 400 ℃ of calcinings 10 hours.Be prepared into the Ca-F-P-O composite hollow ball, wherein the quality percentage composition of Ca is 45wt%, and the quality percentage composition of P is 8wt%, and the quality percentage composition of F is 24wt%, and surplus is O.
Embodiment 6
4 gram P123 are joined in 60 ml deionized water, and temperature is controlled at room temperature, and magnetic agitation was dissolved after 12 hours.Then add Phosphoric acid glycerol esters disodium salt 8 grams.Continue to stir after 1-3 hour and dissolve.Then add hydrogen fluoride 2 grams, continue to stir 2-6 hour.Four water-calcium nitrate 12 grams are dissolved in deionized water, and concentration is controlled between 0.1M-1M.After dissolving, solution slowly is added drop-wise in above-mentioned solution.Dropwise rear continuation mixing 12-24 hour.Then at the standing 12-24 hour of room temperature.Filter, washed with de-ionized water 5 times, will filter the powder seasoning.After dry, powder was 400 ℃ of calcinings 10 hours.Be prepared into the Ca-F-P-O composite hollow ball, wherein the quality percentage composition of Ca is 52wt%, and the quality percentage composition of P is 9wt%, and the quality percentage composition of F is 30wt%, and surplus is O.
Claims (7)
1. the preparation method of calcium-fluoro-phosphorus-oxygen composite hollow ball, the quality percentage composition of described Ca-F-P-O composite hollow ball Ca is 40-65%, and the quality percentage composition of P is 4-15wt%, and the quality percentage composition of F is 20-35%, surplus is oxygen, is characterised in that the processing step of preparation is:
(a) at first tensio-active agent is joined in deionized water, concentration is controlled between 0.003M-0.3M, and temperature is controlled between room temperature-50 ℃, and magnetic agitation makes it to dissolve;
(b) add the phosphorus source in the solution obtained at step a, wherein the concentration in phosphorus source is controlled between 0.02M-2M, and magnetic agitation makes it to dissolve; Then add the fluorine source, concentration is controlled between 0.01M-2M, continues magnetic agitation and dissolves after 2-6 hour, and solution temperature is controlled between room temperature-50 ℃;
(c) the calcium source is dissolved in deionized water, concentration is controlled between 0.1M-1M, after dissolving, calcium source solution slowly is added drop-wise in the solution that step b obtains, drip the Ca in solution afterwards: the P ratio is controlled between 1.0-1.67, and temperature is controlled between room temperature-50 ℃;
(d) solution that step c obtained continues to mix 12-24 hour, and temperature is controlled between room temperature-50 ℃, then standing in the temperature range of room temperature-50 ℃, resulting filter powder is cleaned after filtering after seasoning;
Described tensio-active agent is cats product cetyl trimethylammonium bromide, block polymer, Tween85, triton * 100 or their mixture;
Described phosphorus source is the Phosphoric acid glycerol esters disodium salt;
Described fluorine source is Sodium Fluoride, hydrogen fluoride, ammonium fluoride or Potassium monofluoride;
Described calcium source is nitrocalcite, calcium halide, calcium acetate, calcium pantothenate, calcium carbonate, calcium hydroxide or their mixture.
2. by the preparation method of calcium claimed in claim 1-fluoro-phosphorus-oxygen composite hollow ball, it is characterized in that described block polymer is P123 or F127.
3. by the preparation method of calcium claimed in claim 1-fluoro-phosphorus-oxygen composite hollow ball, it is characterized in that the step a magnetic agitation time is 12-24 hour.
4. by the preparation method of calcium claimed in claim 1-fluoro-phosphorus-oxygen composite hollow ball, it is characterized in that in step b adding the magnetic agitation time behind the phosphorus source is within 1-3 hour, to make it to dissolve; Behind interpolation fluorine source, the magnetic agitation time is within 2-6 hour, to make it to dissolve.
5. by the preparation method of calcium claimed in claim 3-fluoro-phosphorus-oxygen composite hollow ball, it is characterized in that the steps d time of repose is 12-24 hour.
6. by the preparation method of calcium claimed in claim 1-fluoro-phosphorus-oxygen composite hollow ball, it is characterized in that steps d is standing, filter rear filter powder is to use washed with de-ionized water.
7. by the preparation method of calcium claimed in claim 1-fluoro-phosphorus-oxygen composite hollow ball, it is characterized in that the washed with de-ionized water number of times is 3-5 time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910200060.7A CN102086033B (en) | 2009-12-07 | 2009-12-07 | Calcium-fluorine-phosphorus-oxygen composite hollow spheres and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910200060.7A CN102086033B (en) | 2009-12-07 | 2009-12-07 | Calcium-fluorine-phosphorus-oxygen composite hollow spheres and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102086033A CN102086033A (en) | 2011-06-08 |
| CN102086033B true CN102086033B (en) | 2014-01-01 |
Family
ID=44098062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910200060.7A Expired - Fee Related CN102086033B (en) | 2009-12-07 | 2009-12-07 | Calcium-fluorine-phosphorus-oxygen composite hollow spheres and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102086033B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6210715B1 (en) * | 1997-04-01 | 2001-04-03 | Cap Biotechnology, Inc. | Calcium phosphate microcarriers and microspheres |
-
2009
- 2009-12-07 CN CN200910200060.7A patent/CN102086033B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6210715B1 (en) * | 1997-04-01 | 2001-04-03 | Cap Biotechnology, Inc. | Calcium phosphate microcarriers and microspheres |
Non-Patent Citations (3)
| Title |
|---|
| Jingxian Zhang et al..Synthesis of mesoporous calcium phosphate using hybrid templates.《Microporous and Mesoporous Materials》.2007,第111卷411-416. * |
| Ultrasonic Controlled Morphology Transformation of Hollow Calcium Phosphate Nanospheres: A Smart and Biocompatible Drug Release System;Yurong Cai et al.;《Chemistry of Materials》;20070601;第19卷(第13期);第3081-3083页 * |
| Yurong Cai et al..Ultrasonic Controlled Morphology Transformation of Hollow Calcium Phosphate Nanospheres: A Smart and Biocompatible Drug Release System.《Chemistry of Materials》.2007,第19卷(第13期),第3081-3083页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102086033A (en) | 2011-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103420364B (en) | A kind of preparation method of grapheme/hydroxyapatcomposite composite material | |
| Zhang et al. | A mild and efficient biomimetic synthesis of rodlike hydroxyapatite particles with a high aspect ratio using polyvinylpyrrolidone as capping agent | |
| US11027259B2 (en) | Preparation method for hollow molybdate composite microspheres and method for catalyzing ammonia borane hydrolysis to produce hydrogen | |
| Zeng | Synthetic architecture of interior space for inorganic nanostructures | |
| CN110330004B (en) | Method for regulating morphology of hydroxyapatite micro-nano material by using phosphorus source | |
| CN103785859B (en) | Method for manufacturing nanometer mesoporous material | |
| Yang et al. | Hydrothermal synthesis of hierarchical hydroxyapatite: preparation, growth mechanism and drug release property | |
| CN104058380B (en) | Preparation method of ellipsoidal ion-doped hydroxyapatite microspheres with porous surfaces | |
| CN107376795A (en) | A kind of preparation method of polyvinyl alcohol/hydroxyapatite composite microspheres | |
| Tao et al. | Evolution of amorphous calcium phosphate to hydroxyapatite probed by gold nanoparticles | |
| CN106115642B (en) | A kind of large scale hydroxyapatite porous microsphere material and preparation method thereof | |
| CN101880034A (en) | Preparation method and application of porous hydroxyapatite | |
| CN102515244B (en) | Hollow cuprous oxide nanometre material and preparation method for same | |
| CN113460986B (en) | Method for preparing hydroxyapatite microsphere with core-shell structure by one-step method and application thereof | |
| CN103058159B (en) | Hollow hierarchical hydroxyapatite microspheres and preparation method and application thereof | |
| CN105883742A (en) | Preparation method of nano beta-tricalcium phosphate | |
| CN109734056A (en) | Metal oxide/preparation method of fold rGO composite nano materials and the preparation method of fold nano-metal-oxide | |
| CN105061810B (en) | A kind of antibacterial electronic cigarette appearance material and its preparation method and application | |
| CN101269832A (en) | Process for producing nano-cerium dioxide with high-specific surface area and high hole capacity | |
| Cheng et al. | Control of pore size of the bubble-template porous carbonated hydroxyapatite microsphere by adjustable pressure | |
| JP2005097052A (en) | Hydroxyapatite with large surface area and its manufacturing method | |
| KR101318348B1 (en) | Method for Preparing Hydroxyapatite from Vaterite Containing Catecholamine | |
| CN102086033B (en) | Calcium-fluorine-phosphorus-oxygen composite hollow spheres and preparation method thereof | |
| CN101550593A (en) | Method for preparing upcoversion nanocrystalline on rare-earth adulterating fluoride | |
| CN107661510B (en) | Methoxy BODIPY-nucleic acid-ferroferric oxide compound and preparation method thereof |
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: 20140101 Termination date: 20171207 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |