CN103709401A - Nano-silver/poly(2-acrylamido-2-methylpropanesulfonic acid) doped polyaniline binary composite material and preparation method thereof - Google Patents
Nano-silver/poly(2-acrylamido-2-methylpropanesulfonic acid) doped polyaniline binary composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103709401A CN103709401A CN201410004717.3A CN201410004717A CN103709401A CN 103709401 A CN103709401 A CN 103709401A CN 201410004717 A CN201410004717 A CN 201410004717A CN 103709401 A CN103709401 A CN 103709401A
- Authority
- CN
- China
- Prior art keywords
- poly
- acrylamide
- methylpro panesulfonic
- panesulfonic acid
- preparation
- 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
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nano-silver/poly(2-acrylamido-2-methylpropanesulfonic acid) doped polyaniline binary composite material and a preparation method thereof. The binary composite material is formed by inlaying nano-silver particles in meshes of a mesh-shaped polymer made of poly(2-acrylamido-2-methylpropanesulfonic acid) doped polyaniline. The preparation method of the binary composite material comprises the following steps: dispersing aniline in poly(2-acrylamido-2-methylpropanesulfonic acid) emulsion containing nano-silver particles, and compounding the generated poly(2-acrylamido-2-methylpropanesulfonic acid) doped polyaniline and the nano-silver particles through in-situ polymerization so as to obtain the binary composite material. The preparation method is simple, low in cost and high in yield; and the prepared composite material has high electrical conductivity, very strong corrosion resistance and wide application potentiality.
Description
Technical field
The present invention relates to a kind of nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material and preparation method thereof; Belong to conductive polymers based field of compound material.
Background technology
Silver/polyaniline nano-composite material is a kind of important conductive polymers based composites.Due to polyaniline synthetic easy, there is the characteristics such as good environmental stability, unique doping and dedoping mechanism and the high conductivity of nanometer silver, high sensitivities, bactericidal properties, silver/polyaniline nano-composite material more and more receives publicity in the application in the fields such as photoelectric material, electrode materials, electrochemical capacitance material, bio-sensing, catalysis, sterilization, electromagnetic shielding.
Emulsion method is to prepare one of the most frequently used method of silver/polyaniline nano-composite material.Other parameters such as the kind by control surface promoting agent, consumption can be prepared the silver/polyaniline nano-composite material of different-shape, electroconductibility.Conventional tensio-active agent mainly contains polyvinyl alcohol, sodium lauryl sulphate, sodium alginate, Sodium dodecylbenzene sulfonate, bromination cetylamine etc.In the silver/polyaniline nano-composite material making at these tensio-active agents, nanometer silver dispersiveness is bad, easily reunites, and the chemical properties such as the silver/polyaniline nano-composite material electroconductibility making, erosion resistance improve limited, and application is limited to.
Summary of the invention
The object of the invention is to be to provide a kind of have high conductivity and highly corrosiveness-resistant nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material.
Another object of the present invention is to be to provide that technique is simple, low-cost, the method for high yield synthetic described nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material.
The invention provides nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, in the mesh that this binary matrix material is embedded in by nano silver particles the mesh polymkeric substance that poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline constructs, form; Described binary matrix material is dispersed in poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing nano silver particles by aniline, by in-situ polymerization by poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline generating and nano silver particles is compound obtains, wherein, the mol ratio of aniline and nano silver particles is 1～3.5:1; In described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion, the mass percent concentration of poly-(2-acrylamide-2-methylpro panesulfonic acid) is 5～30%; Described nano silver particles median size is 80～120nm.
Preferred nano silver particles median size is 90～110nm.
In described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion, the mass percent concentration of poly-(2-acrylamide-2-methylpro panesulfonic acid) is preferably 5～20%.
Described aniline: the mol ratio of nano silver particles is preferably 1.5～3:1.
Described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing nano silver particles is in poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing sodium hypophosphite, to add Silver Nitrate to carry out reduction reaction to obtain.
The present invention also provides the preparation method of nano silver particles/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, the method is that silver nitrate solution is added drop-wise in poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing sodium hypophosphite, at 35～45 ℃, issue raw reduction reaction, make the emulsion containing nano silver particles; To gained, containing in the emulsion of nano silver particles, add after aniline, ultrasonic dispersion, then under agitation condition, drip the ammonium persulfate initiator that concentration is 1.5～2.5g/mL, polyreaction at 0～5 ℃; After polyreaction completes, breakdown of emulsion, washing, after being dried, obtains; Wherein, aniline: the mol ratio of Silver Nitrate is 1～3.5:1; The mol ratio of sodium hypophosphite and Silver Nitrate is 1～1.5:2.
Described aniline: the mol ratio of Silver Nitrate is preferably 1.5～3:1.
Described silver nitrate solution concentration is 0.1～0.3g/mL, and drop rate is 15～20/min.
In described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion, the mass percent concentration of poly-(2-acrylamide-2-methylpro panesulfonic acid) is 5～30%; Be preferably 5～20%.
The drop rate of described ammonium persulfate initiator is 15～20/min.
The described reduction reaction time is 60～120min.
Described polymerization reaction time is 10～14h.
Poly-(2-acrylamide-2-methylpro panesulfonic acid) of the present invention preparation method (PAAMPS): 2-acrylamide-2-methyl propane sulfonic is dissolved in to obtain massfraction after suitable quantity of water be 1～30% the aqueous solution, to this aqueous solution, adding concentration is the ammonium persulfate initiator of 2-acrylamide-2-methyl propane sulfonic monomer 0.05～0.15wt%, and temperature is risen to 45～70 ℃, isothermal reaction 2～4h, makes PAAMPS.
The preparation method of nanometer silver of the present invention/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, comprises the following steps:
1) preparation of nano silver particles emulsion: will gather (2-acrylamide-2-methylpro panesulfonic acid) and be added to the water preparation to obtain massfraction be poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion of 5～30%, in described emulsion, add sodium hypophosphite solution, make the mass concentration of sodium phosphate in described emulsion reach 0.003～0.009g/mL, after stirring, described emulsion is warming up to 35～45 ℃, to dripping concentration in described emulsion, be simultaneously that the silver nitrate solution of 0.1～0.3g/mL carries out reduction reaction, after reduction reaction completes, obtain containing nano silver particles emulsion, the mol ratio of described sodium hypophosphite and Silver Nitrate is 1～1.5:2,
2) preparation of nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material: add aniline containing in the PAAMPS emulsion of nano silver particles at step 1) gained, ultrasonic dispersion 5～15min, again under agitation condition, control temperature at 0～5 ℃, the speed of 15～20/min of take drips the aqueous solution of the ammonium persulphate that concentration is 1.5～2.5g/mL, initiated polymerization, and react 10～14h, after having reacted, add excessive propanone breakdown of emulsion, product is first by ethanol, after distilled water repetitive scrubbing, at 60～70 ℃, be 10～14h time of drying, make nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, wherein, aniline: the reaction mol ratio of Silver Nitrate is 1～3.5:1, the mol ratio of aniline and ammonium persulphate is 1:1.
Beneficial effect of the present invention: the present invention (PAAMPS) has prepared nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material of high conductivity and erosion resistance in emulsion at poly-(2-acrylamide-2-methylpro panesulfonic acid) first by simple process.The PAAMPS that the present invention adopts not only plays good emulsification, dissemination to nano silver particles in the emulsion polymerization process of aniline, the nano silver particles obtaining is regular spheroidal particle, the even about 100nm of size distribution left and right, be difficult for reuniting, simultaneously itself also can doped polyaniline, further improve conductivity and the corrosion resistance nature of matrix material, experimental results demonstrate: conductivity of composite material can reach 3.23S/cm, corrosion electric current density can reach 0.24mA/cm
2, there is good application prospect; Meanwhile, preparation method's technique of the present invention is simple, easy and simple to handle, and cost is low, productive rate is high, can suitability for industrialized production.
Accompanying drawing explanation
Poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline (PANI) that [Fig. 1] is comparative example 1 and embodiment 1 prepare the infrared spectrogram of nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material (Ag/PANI) matrix material.
The size distribution normal curve figure of the nano silver particles that [Fig. 2] makes for embodiment 1.
[Fig. 3] is the particle diameter column distribution plan of the Nano silver grain of embodiment 1 preparation.
The scanning electron microscope diagram of the nanometer silver that [Fig. 4] makes for embodiment 1.
The scanning electron microscope diagram of the Ag/PANI matrix material that [Fig. 5] makes for embodiment 1: a is 20,000 *, b is 50,000 *.
Embodiment
Below in conjunction with specific embodiment, be intended to further illustrate the present invention, and unrestricted the scope of protection of the invention.Embodiment 1
Get 5.0g PAAMPS and join that in 95.0g distilled water, to be configured to massfraction be 5% PAAMPS emulsion, 0.44g sodium hypophosphite is dissolved in 10mL distilled water and joins in the emulsion of PAAMPS of 100mL massfraction 5%, subsequently after electric stirring 15 minutes, reaction system is warming up to 40 ℃, the silver nitrate solution 10mL that dropping contains 1.42g, rate of addition is controlled at 15～20 droplets/minute, 70 minutes reaction times; Obtain nanometer silver emulsion; The emulsion that takes a morsel acetone breakdown of emulsion, washing, dry, the nanometer silver obtaining is detected, as shown in Figures 2 and 3, scanning electron microscope diagram is as shown in Figure 4 for the size distribution figure of nano silver particles.
In the nanometer silver emulsion making, add 2.50g aniline, after ultrasonic dispersion 10 minutes, under electric stirring condition, to reaction system, drip the aqueous solution initiation aniline polymerization that 30mL contains 5.71g ammonium persulphate, 15～20 droplets/minute of rate of addition, temperature of reaction is controlled at 0～5 ℃, and the reaction times is 12 hours; Reaction product is used to excessive propanone breakdown of emulsion, successively use after distilled water, ethanol, distilled water wash 3 times 60～70 ℃ dry 12 hours, obtain binary matrix material; Infrared spectrogram is as Fig. 1, and scanning electron microscope diagram is as Fig. 5.
Four probe method is tested the specific conductivity of binary matrix material, and test result shows that the specific conductivity of matrix material is 2.92S/cm, the test to binary matrix material corrosion resistance nature: corrosion electric current density can reach 0.24mA/cm
2.
Get 15.0g PAAMPS and join that in 85.0g distilled water, to be configured to massfraction be 15% PAAMPS emulsion, 0.88g sodium hypophosphite is dissolved in 10mL distilled water and joins in the emulsion of PAAMPS of 100mL massfraction 15%, subsequently after electric stirring 15 minutes, reaction system is warming up to 40 ℃, the silver nitrate solution 10mL that dropping contains 2.84g, rate of addition is controlled at 15～20 droplets/minute, 70 minutes reaction times; Obtain nanometer silver emulsion;
In the nano silver microemulsion liquid making, add 2.50g aniline, after ultrasonic dispersion 10 minutes, under electric stirring condition, to reaction system, drip the aqueous solution initiation aniline polymerization that 30mL contains 5.71g ammonium persulphate, 15～20 droplets/minute of rate of addition, temperature of reaction is controlled at 0～5 ℃, and the reaction times is 12 hours; Reaction product is used to excessive propanone breakdown of emulsion, successively use after distilled water, ethanol, distilled water wash 3 times 60～70 ℃ dry 12 hours, obtain binary matrix material.
Four probe method is tested the specific conductivity of matrix material, and test result shows that the specific conductivity of matrix material is 3.23S/cm, the multiple test to binary matrix material corrosion resistance nature: corrosion electric current density is 0.18mA/cm
2.
Comparative example 1
The preparation of PAAMPS doped polyaniline material
5.8g PAAMPS (0.028mol) is dissolved in to 375mL deionized water, and then by 2.6g aniline and PAAMPS emulsion mix and blend 1 hour, 5.8g ammonium persulphate is dissolved in to 25mL deionized water, the PAAMPS emulsion of aniline and ammonium persulfate solution are all used nitrogen to carry out purifying treatment, ammonium persulfate solution is dropwise joined in the PAAMPS emulsion of aniline, at 5 ℃, react 24 hours, subsequently, acetone is added to the polyaniline that is settled out PAAMPS doping in reacted emulsion, with acetone, wash away unreacted monomer and oligomer, polyaniline room temperature in vacuum drying oven of the PAAMPS doping obtaining is overnight dry, four probe method is carried out specific conductivity test to the PAAMPS doped polyaniline making, test result shows that the electric conductivity of PAAMPS doped polyaniline material is 0.4S/cm.
Comparative example 2
The preparation method of binary matrix material is identical with embodiment 1, just changes emulsifying agent into Sodium dodecylbenzene sulfonate.
Four probe method is tested the specific conductivity of binary matrix material, and test result shows that the specific conductivity of matrix material is 2.62S/cm, the test to binary matrix material corrosion resistance nature: corrosion electric current density is 1.49mA/cm
2.
Claims (10)
1. nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, it is characterized in that, in the mesh that is embedded in the mesh polymkeric substance that poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline constructs by nano silver particles, form; Described binary matrix material is dispersed in poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing nano silver particles by aniline, by in-situ polymerization by poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline generating and nano silver particles is compound obtains, wherein, the mol ratio of aniline and nano silver particles is 1～3.5:1; In described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion, the mass percent concentration of poly-(2-acrylamide-2-methylpro panesulfonic acid) is 5～30%; Described nano silver particles median size is 80～120nm.
2. nanometer silver as claimed in claim 1/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, is characterized in that described aniline: the mol ratio of nano silver particles is 1.5～3:1.
3. nanometer silver as claimed in claim 1 or 2/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, it is characterized in that, described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing nano silver particles is in poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing sodium hypophosphite, to add Silver Nitrate to carry out reduction reaction to obtain.
4. the preparation method of nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary matrix material, it is characterized in that, silver nitrate solution is added drop-wise in poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion containing sodium hypophosphite, at 35～45 ℃, issue raw reduction reaction, make the emulsion containing nano silver particles; To gained, containing in the emulsion of nano silver particles, add after aniline, ultrasonic dispersion, then under agitation condition, drip the ammonium persulfate initiator that concentration is 1.5～2.5g/mL, polyreaction at 0～5 ℃; After polyreaction completes, breakdown of emulsion, washing, after being dried, obtains; Wherein, aniline: the mol ratio of Silver Nitrate is 1～3.5:1; The mol ratio of sodium hypophosphite and Silver Nitrate is 1～1.5:2.
5. preparation method as claimed in claim 4, is characterized in that, described aniline: the mol ratio of Silver Nitrate is 1.5～3:1.
6. preparation method as claimed in claim 4, is characterized in that, described silver nitrate solution concentration is 0.1～0.3g/mL, and drop rate is 15～20/min.
7. preparation method as claimed in claim 4, is characterized in that, in described poly-(2-acrylamide-2-methylpro panesulfonic acid) emulsion, the mass percent concentration of poly-(2-acrylamide-2-methylpro panesulfonic acid) is 5～30%.
8. preparation method as claimed in claim 4, is characterized in that, the drop rate of described ammonium persulfate initiator is 15～20/min.
9. the preparation method as described in claim 4～8 any one, is characterized in that, the described reduction reaction time is 60～120min.
10. the preparation method as described in claim 4～8 any one, is characterized in that, described polymerization reaction time is 10～14h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410004717.3A CN103709401B (en) | 2014-01-06 | 2014-01-06 | Nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410004717.3A CN103709401B (en) | 2014-01-06 | 2014-01-06 | Nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103709401A true CN103709401A (en) | 2014-04-09 |
| CN103709401B CN103709401B (en) | 2016-01-20 |
Family
ID=50402778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410004717.3A Expired - Fee Related CN103709401B (en) | 2014-01-06 | 2014-01-06 | Nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103709401B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353477A (en) * | 2008-09-10 | 2009-01-28 | 中南大学 | Preparation of polyaniline / argentum nano composite material |
| CN101492537A (en) * | 2008-07-28 | 2009-07-29 | 南京理工大学 | Poly-organic acid or macromolecule organic acid doping polyaniline material and electrochemical preparation method |
| CN102604087A (en) * | 2012-03-08 | 2012-07-25 | 长春工业大学 | Preparation method of water-soluble conductive polyaniline |
-
2014
- 2014-01-06 CN CN201410004717.3A patent/CN103709401B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492537A (en) * | 2008-07-28 | 2009-07-29 | 南京理工大学 | Poly-organic acid or macromolecule organic acid doping polyaniline material and electrochemical preparation method |
| CN101353477A (en) * | 2008-09-10 | 2009-01-28 | 中南大学 | Preparation of polyaniline / argentum nano composite material |
| CN102604087A (en) * | 2012-03-08 | 2012-07-25 | 长春工业大学 | Preparation method of water-soluble conductive polyaniline |
Non-Patent Citations (2)
| Title |
|---|
| VLADIMIR LYUTOV.VESSELA TSAKOVA: ""Silver particles-modified polysulfonic acid-doped polyaniline"", 《J SOLID STATE ELECTROCHEM》 * |
| 李芝华等: ""核壳型银/聚苯胺纳米复合材料的导电性能"", 《高分子材料科学与工程》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103709401B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Intermolecular interaction and the extended wormlike chain conformation of chitin in NaOH/urea aqueous solution | |
| Han et al. | Dual functional biocomposites based on polydopamine modified cellulose nanocrystal for Fe3+-pollutant detecting and autoblocking | |
| Chen et al. | High sensitivity ammonia sensor using a hierarchical polyaniline/poly (ethylene-co-glycidyl methacrylate) nanofibrous composite membrane | |
| CN103613760B (en) | The preparation method of polyaniline/ferroferoxide oxide electromagnetic composite material | |
| CN104098770B (en) | A kind of synthetic method of helical structure polyaniline nano fiber | |
| CN102604085B (en) | Preparation method of polyaniline/carbon nano tube/nano-copper composite material | |
| Wang et al. | Enhancing the electrospinnability of low molecular weight polymers using small effective cross-linkers | |
| CN103224704B (en) | Preparation method for polyaniline/polypyrrole binary composite nanotube | |
| Zhao et al. | Effect of additives on the properties of polyaniline nanofibers prepared by high gravity chemical oxidative polymerization | |
| CN102942832B (en) | Preparation method of block macromolecule-nanometer metallic-film composite conductive material | |
| CN104558323A (en) | High-water-solubility nanometer hexagonal boron nitride and preparation method of polymer composite hydrogel of high-water-solubility nanometer hexagonal boron nitride | |
| WO2017214741A1 (en) | Process for preparing chitosan/polyvinyl alcohol composite electrically-conductive nanofibre | |
| Mondal et al. | High lignin containing hydrogels with excellent conducting, self-healing, antibacterial, dye adsorbing, sensing, moist-induced power generating and supercapacitance properties | |
| Milakin et al. | Biocompatible and antibacterial gelatin-based polypyrrole cryogels | |
| CN105420832A (en) | High sensitivity temperature sensitive conductive composite fiber and preparation method thereof | |
| CN102251396A (en) | Method for preparing conductive non-woven fabric by using in-situ polymerization method | |
| CN105367700A (en) | Strong-basicity ternary composite metal-graphene-ion exchange resin material and preparing method thereof | |
| CN104448303B (en) | A kind of ethylene-vinyl acetate copolymer/polyaniline composite conducting material and preparation method thereof | |
| Lu et al. | Synthesis of submicron PEDOT particles of high electrical conductivity via continuous aerosol vapor polymerization | |
| CN102875978A (en) | Preparation method of gold nanoparticle/poly(3,4-dioxyethyl)thiophene (PEDOT) composite material | |
| CN102558553A (en) | Preparation method of one-dimensional conductive polyanion/attapulgite nano composite material | |
| CN104064783B (en) | A kind of preparation method of anode of microbial fuel cell magnetic conductive nano fibrous membrane | |
| CN103951778B (en) | Super dense styrene-acrylic emulsion prepares the method for Graphene/styrene-t butyl ester composite conducting material | |
| CN103011132B (en) | Preparation method of monodisperse carbon nano bowl | |
| CN103709401B (en) | Nanometer silver/poly-(2-acrylamide-2-methylpro panesulfonic acid) doped polyaniline binary composite 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: 20160120 Termination date: 20220106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |