CN108264638A - A kind of synthetic method of poly- naphthylamines load graphene - Google Patents
A kind of synthetic method of poly- naphthylamines load graphene Download PDFInfo
- Publication number
- CN108264638A CN108264638A CN201810287975.5A CN201810287975A CN108264638A CN 108264638 A CN108264638 A CN 108264638A CN 201810287975 A CN201810287975 A CN 201810287975A CN 108264638 A CN108264638 A CN 108264638A
- Authority
- CN
- China
- Prior art keywords
- naphthylamines
- poly
- load graphene
- synthetic method
- graphene
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Carbon And Carbon Compounds (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention belongs to material chemistry technical fields, are related to a kind of synthetic method of poly- naphthylamines load graphene.Using in-situ polymerization mode, by poly- naphthylamines, uniformly modification removes graphite oxide surface group to the present invention on graphene oxide, then by electron beam irradiation, realizes uniform modification of the poly- naphthylamines in graphene surface.The poly- naphthylamines load graphene of synthesis has good sensibility to benzene homologues gas.
Description
Technical field
The invention belongs to material chemistry technical fields, are related to a kind of synthetic method of poly- naphthylamines load graphene.
Background technology
The structure of poly- naphthylamines is：
It is a kind of conjugated polymer with condensed cyclic structure, in corrosion-inhibiting coating, electro-catalysis, electrochromism, electrochemical sensing
There is certain application prospect in the fields such as device, gas sensor.The conductivity of poly- naphthylamines is relatively low, can on graphene by the modification of poly- naphthylamines
Conductivity is greatly promoted, and the synergistic effect of the conjugated structure of the π of poly- naphthylamines-pi-conjugated strand and graphene can be promoted effectively
The sensitivity of sensor.But dispersibility of the grapheme material in various solvents is poor, it is difficult to realize the uniform of in-situ polymerization
Modification.
Invention content
In view of the shortcomings of the prior art, the purpose of the present invention is to provide a kind of preparation methods of poly- naphthylamines load graphene.
Include the following steps：
(1) naphthylamines monomer and graphite oxide are added in acidic aqueous solution, ultrasonic disperse obtains puce colloidal sol (colloidal sol
A it), then by oxidant is dissolved in acidic aqueous solution, and is slowly dropped in Sol A and obtains mixed sols.
(2) mixed sols that step (1) obtains is put into constant temperature in heat-preserving equipment to be stirred to react, obtains black precipitate；
(3) the poly- naphthylamines load graphene oxide of intermediate product is obtained after the black precipitate washing and drying for obtaining step (2)
Powder；
(4) obtained powder is subjected to electron beam irradiation, obtains the poly- naphthylamines load graphene powder of final product.
The addition of the graphite oxide is 0.2~1.5gL-1；The ultrasonic disperse time is 1~2h.Naphthylamines monomer is most
A concentration of 0.1~0.5molL in colloidal sol afterwards-1；Acidic aqueous solution pH is less than 2.
Oxidant includes a kind of or combination in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, ferric trichloride, oxidant
Molar ratio with naphthylamines monomer is 1: 1~3: 1.
Described to be persistently stirred to react the time as 12~24 hours, temperature is room temperature~60 DEG C.
The washing is alternately washed with deionized water and ethyl alcohol, is precipitated each time after washing using centrifuge or suction filtration is set
Standby to be filtered, filtration product is disperseed in deionized water or ethyl alcohol again, is repeatedly filtered until filtrate pH value is 7, last
It is secondary to be washed with ethyl alcohol with convenient and dry；The drying is dried in 50~80 DEG C of vacuum drying ovens, and vacuum drying condition is true
Reciprocal of duty cycle ＜ 133Pa.
The electron beam irradiation dosage is 30~160kGy.
The present invention is uniformly modified poly- naphthylamines on graphene oxide, then pass through electron beam irradiation using in-situ polymerization mode
Graphite oxide surface group is removed, realizes uniform modification of the poly- naphthylamines in graphene surface.In addition the trapezoidal conjugation knot of poly- naphthylamines
Structure ensures its preferable irradiation stability and thermal stability, is not depolymerizated in irradiation process.The poly- naphthylamines load graphite of synthesis
Alkene has good sensibility to benzene homologues gas.
Present disclosure and feature have revealed that as above, however the present invention that describes of front only briefly or pertains only to this
The specific part of invention, feature of the invention may have benzene homologues gas than the poly- naphthylamines of synthesis load graphene good
Sensibility.Content disclosed herein is related to more.Therefore, it is revealed interior should to be not limited to embodiment for protection scope of the present invention
Hold, and should be included in all the elements embodied in different piece combination and various replacements without departing substantially from the present invention and
Modification, and covered by claims of the present invention.
Description of the drawings
Fig. 1 is the TEM photos that poly- naphthylamines load graphene is synthesized using (embodiment 1) of the invention.
Specific embodiment
Embodiment 1
(1) 0.01mol naphthylamines monomer and 0.02g graphite oxides are added in 50mL acidic aqueous solutions, ultrasonic disperse 2h is obtained
It is dissolved in 50mL acidic aqueous solutions, and is slowly dropped to molten to puce colloidal sol (Sol A), then by 0.03mol ammonium persulfates
Mixed sols is obtained in glue A.
(2) mixed sols that step (1) obtains is put into constant temperature in 60 DEG C of heat-preserving equipments to be stirred to react 24 hours, is obtained black
Color precipitates；
(3) the black precipitate deionized water and ethyl alcohol obtained step (2) is alternately washed, each time after washing using centrifugation
Machine precipitates or pumping and filtering device is filtered, and filtration product is disperseed in deionized water or ethyl alcohol again, is repeatedly filtered until filtrate
PH value is that drying obtains the poly- naphthylamines load graphene oxide powder of intermediate product in 7,50 DEG C of vacuum drying ovens；
(4) obtained powder is subjected to 160kGy electron beam irradiations, obtains the poly- naphthylamines load graphene powder of final product,
TEM photos are as shown in Figure 1.On poly- naphthylamines uniform close load graphene film.
The dispersion of obtained powder is applied on six foot ceramic tube air-sensitive testing elements, is tested using WS-30A types gas sensor
To the response of the dimethylbenzene mixed gas of 30% toluene/70% under system testing various concentration.The dimethylbenzene of 1ppm30% toluene/70%
The sensitivity of mixed gas is 8.9.Meet gas sensing needs.
Embodiment 2,3
As a comparison：
Repeat above example 1, be added without graphite oxide, obtain it is poly- how amine powder, the dimethylbenzene of 1ppm30% toluene/70% mixes
The sensitivity for closing gas is 1.4.
Above example 1 is repeated, but without electron beam irradiation, obtains poly- naphthylamines load graphene oxide powder,
The sensitivity of the dimethylbenzene mixed gas of 1ppm30% toluene/70% is 1.41.9.
Contrast sample responds benzene homologues and is far below embodiment 1.
Embodiment 4
(1) 0.05mol naphthylamines monomer and 0.15g graphite oxides are added in 50mL acidic aqueous solutions, ultrasonic disperse 2h is obtained
It is dissolved in 50mL acidic aqueous solutions, and is slowly dropped to molten to puce colloidal sol (Sol A), then by 0.05mol potassium peroxydisulfates
Mixed sols is obtained in glue A.
(2) constant temperature is stirred to react 16 hours the mixed sols for obtaining step (1) at room temperature, obtains black precipitate；
(3) the black precipitate deionized water and ethyl alcohol obtained step (2) is alternately washed, each time after washing using centrifugation
Machine precipitates or pumping and filtering device is filtered, and filtration product is disperseed in deionized water or ethyl alcohol again, is repeatedly filtered until filtrate
PH value is that drying obtains the poly- naphthylamines load graphene oxide powder of intermediate product in 7,80 DEG C of vacuum drying ovens；
(4) obtained powder is subjected to 100kGy electron beam irradiations, obtains the poly- naphthylamines load graphene powder of final product.
The dispersion of obtained powder is applied on six foot ceramic tube air-sensitive testing elements, is tested using WS-30A types gas sensor
To the response of the dimethylbenzene mixed gas of 30% toluene/70% under system testing various concentration.The dimethylbenzene of 1ppm30% toluene/70%
The sensitivity of mixed gas is 11.5.
Embodiment 5
(1) 0.02mol naphthylamines monomer and 0.1g graphite oxides are added in 50mL acidic aqueous solutions, ultrasonic disperse 2h is obtained
Puce colloidal sol (Sol A), then 0.04mol sodium peroxydisulfates are dissolved in 50mL acidic aqueous solutions, and be slowly dropped to Sol A
In obtain mixed sols.
(2) constant temperature is stirred to react 12 hours the mixed sols for obtaining step (1) at room temperature, obtains black precipitate；
(3) the black precipitate deionized water and ethyl alcohol obtained step (2) is alternately washed, each time after washing using centrifugation
Machine precipitates or pumping and filtering device is filtered, and filtration product is disperseed in deionized water or ethyl alcohol again, is repeatedly filtered until filtrate
PH value is that drying obtains the poly- naphthylamines load graphene oxide powder of intermediate product in 7,50 DEG C of vacuum drying ovens；
(4) obtained powder is subjected to 30kGy electron beam irradiations, obtains the poly- naphthylamines load graphene powder of final product.
The sensitivity of the dimethylbenzene mixed gas of 1ppm30% toluene/70% is 5.7.
Embodiment 6
(1) 0.03mol naphthylamines monomer and 0.1g graphite oxides are added in 50mL acidic aqueous solutions, ultrasonic disperse 2h is obtained
Puce colloidal sol (Sol A), then 0.05mol ferric trichlorides are dissolved in 50mL acidic aqueous solutions, and be slowly dropped to Sol A
In obtain mixed sols.
(2) mixed sols that step (1) obtains is put into constant temperature in 50 DEG C of heat-preserving equipments to be stirred to react 18 hours, is obtained black
Color precipitates；
(3) the black precipitate deionized water and ethyl alcohol obtained step (2) is alternately washed, each time after washing using centrifugation
Machine precipitates or pumping and filtering device is filtered, and filtration product is disperseed in deionized water or ethyl alcohol again, is repeatedly filtered until filtrate
PH value is that drying obtains the poly- naphthylamines load graphene oxide powder of intermediate product in 7,60 DEG C of vacuum drying ovens；
(4) obtained powder is subjected to 80kGy electron beam irradiations, obtains the poly- naphthylamines load graphene powder of final product.
The sensitivity of the dimethylbenzene mixed gas of 1ppm30% toluene/70% is 7.1.
Claims (7)
1. a kind of synthetic method of poly- naphthylamines load graphene, which is characterized in that include the following steps：
(1) naphthylamines monomer and graphite oxide being added in acidic aqueous solution, ultrasonic disperse obtains puce colloidal sol (Sol A), then
Oxidant is dissolved in acidic aqueous solution, and is slowly dropped in Sol A and obtains mixed sols.
(2) mixed sols that step (1) obtains is put into constant temperature in heat-preserving equipment to be stirred to react, obtains black precipitate；
(3) the poly- naphthylamines load graphene oxide powder of intermediate product is obtained after the black precipitate washing and drying for obtaining step (2)；
(4) obtained powder is subjected to electron beam irradiation, obtains the poly- naphthylamines load graphene powder of final product.
2. a kind of synthetic method of poly- naphthylamines load graphene according to claim 1, it is characterised in that：The oxidation stone
The addition of ink is 0.2~1.5gL-1；The ultrasonic disperse time is 1~2h.Naphthylamines monomer in last colloidal sol a concentration of 0.1~
0.5molL-1；Acidic aqueous solution pH is less than 2.
3. a kind of synthetic method of poly- naphthylamines load graphene according to claim 1, it is characterised in that：Oxidant included
The molar ratio of a kind of or combination in ammonium sulfate, potassium peroxydisulfate, sodium peroxydisulfate, ferric trichloride, oxidant and naphthylamines monomer
It is 1: 1~3: 1.
4. a kind of synthetic method of poly- naphthylamines load graphene as described in claim 1, it is characterised in that：The constant temperature stirring is anti-
The reaction time answered is 12~24 hours, and temperature is room temperature~60 DEG C.
5. a kind of synthetic method of poly- naphthylamines load graphene as described in claim 1, it is characterised in that：The washing is to use
Deionized water and ethyl alcohol alternately wash, and are filtered each time after washing using centrifuge precipitation or pumping and filtering device, filtration product weight
Newly disperse in deionized water or ethyl alcohol, repeatedly filter until filtrate pH value be 7, washed for the last time with ethyl alcohol dry to facilitate
It is dry；The drying is dried in 50~80 DEG C of vacuum drying ovens, and vacuum drying condition is vacuum degree ＜ 133Pa.
6. a kind of synthetic method of poly- naphthylamines load graphene as described in claim 1, it is characterised in that：The electron beam spoke
It is 30~160kGy according to dosage.
It is 7. poly- made by a kind of synthetic method of poly- naphthylamines load graphene a kind of as described in claim 1~6 any one
Naphthylamines loads graphene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810287975.5A CN108264638B (en) | 2018-03-26 | 2018-03-26 | Synthesis method of polynaphthylamine-loaded graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810287975.5A CN108264638B (en) | 2018-03-26 | 2018-03-26 | Synthesis method of polynaphthylamine-loaded graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108264638A true CN108264638A (en) | 2018-07-10 |
| CN108264638B CN108264638B (en) | 2020-09-15 |
Family
ID=62777506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810287975.5A Active CN108264638B (en) | 2018-03-26 | 2018-03-26 | Synthesis method of polynaphthylamine-loaded graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108264638B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906065A (en) * | 2018-07-02 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of Nd doping LaFeO3The preparation method of nano particle |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772702A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Poly 1-naphthylamine nano hollow structure and its preparation method |
| CN103897183A (en) * | 2014-04-02 | 2014-07-02 | 电子科技大学 | Binary carbon material-conductive polymer composite nano gas-sensitive thin film and preparation method thereof |
| CN104448306A (en) * | 2014-12-09 | 2015-03-25 | 湖南科技大学 | Method for preparing poly(1,8-naphthylenediamine) graft graphene oxide and application of poly(1,8-naphthylenediamine) graft graphene oxide |
| CN104891476A (en) * | 2015-05-12 | 2015-09-09 | 上海大学 | Electron beam irradiation method for preparation of nitrogen-doped reducing graphene |
| CN104889417A (en) * | 2015-05-12 | 2015-09-09 | 上海大学 | Method for synthesizing nano-silver/reduction graphene composite material through electron beam irradiation |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN106280439A (en) * | 2016-08-16 | 2017-01-04 | 曹健 | The preparation of a kind of graphene-polyaniline composite material and method |
| US9718935B1 (en) * | 2016-04-20 | 2017-08-01 | Eastman Kodak Company | Method of preparing article with polyaniline pattern |
-
2018
- 2018-03-26 CN CN201810287975.5A patent/CN108264638B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772702A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Poly 1-naphthylamine nano hollow structure and its preparation method |
| CN103897183A (en) * | 2014-04-02 | 2014-07-02 | 电子科技大学 | Binary carbon material-conductive polymer composite nano gas-sensitive thin film and preparation method thereof |
| CN104448306A (en) * | 2014-12-09 | 2015-03-25 | 湖南科技大学 | Method for preparing poly(1,8-naphthylenediamine) graft graphene oxide and application of poly(1,8-naphthylenediamine) graft graphene oxide |
| CN104891476A (en) * | 2015-05-12 | 2015-09-09 | 上海大学 | Electron beam irradiation method for preparation of nitrogen-doped reducing graphene |
| CN104889417A (en) * | 2015-05-12 | 2015-09-09 | 上海大学 | Method for synthesizing nano-silver/reduction graphene composite material through electron beam irradiation |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| US9718935B1 (en) * | 2016-04-20 | 2017-08-01 | Eastman Kodak Company | Method of preparing article with polyaniline pattern |
| CN106280439A (en) * | 2016-08-16 | 2017-01-04 | 曹健 | The preparation of a kind of graphene-polyaniline composite material and method |
Non-Patent Citations (1)
| Title |
|---|
| 蔡晓生等: ""γ 辐照制备石墨烯/聚苯胺纳米复合材料及其超级电容器性能"", 《中国核科学技术进展报告（第三卷）——中国核学会2013年学术年会论文集第8册（辐射研究与应用分卷、同位素分卷、核农学分卷、辐射物理分卷）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906065A (en) * | 2018-07-02 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of Nd doping LaFeO3The preparation method of nano particle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108264638B (en) | 2020-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rabiee et al. | Ultra-sensitive electrochemical on-line determination of Clarithromycin based on Poly (L-Aspartic acid)/graphite oxide/pristine graphene/glassy carbon electrode | |
| CN108054021B (en) | Bicarbonate nickel-poly-dopamine-graphene composite material and preparation method and application | |
| Tan et al. | Formation of dual-responsive polystyrene/polyaniline microspheres with sea urchin-like and core-shell morphologies | |
| CN101910249A (en) | The preparation and the purposes of polyaniline that is used for the novelty of water treatment | |
| Liu et al. | A metal-catalyst free, flexible and free-standing chitosan/vacuum-stripped graphene/polypyrrole three dimensional electrode interface for high performance dopamine sensing | |
| CN104762077B (en) | The polymer oil-displacing agent of high temperature resistant salt resistance | |
| Luo et al. | Layer-by-layer self-assembled hybrid multilayer films based on poly (sodium 4-styrenesulfonate) stabilized graphene with polyaniline and their electrochemical sensing properties | |
| CN103435850A (en) | Preparation method for sea squirt nano-cellulose conductive paper | |
| CN108264638A (en) | A kind of synthetic method of poly- naphthylamines load graphene | |
| CN108212147A (en) | A kind of rare-earth-doped modification mangano-manganic oxide and its preparation method and application | |
| Hussein et al. | A highly efficient electrochemical sensor containing polyaniline/cerium oxide nanocomposites for hydrogen peroxide detection | |
| Kiani et al. | In-situ chemical synthesis of polypyrrole/silver nanocomposite for the use as a room temperature ammonia gas sensor | |
| Khan et al. | Sol–gel synthesis of poly (o-toluidine)@ Sn (II) silicate/CNT composites for ion selective membrane electrodes | |
| CN108864425A (en) | A kind of preparation method of poly- hydroxyanilines microballoon | |
| CN103772702B (en) | A kind of poly-naphthalidine nano hollow structure and preparation method thereof | |
| CN105237644A (en) | Cellulose with low polymerization degree and preparation method thereof | |
| CN103265699A (en) | Nanometer tin dioxide modified polyaniline nano-tube preparation method | |
| CN109298038B (en) | MnCo2O4Preparation method and application of polyaniline modified glassy carbon electrode | |
| CN104878406B (en) | A kind of electrochemical method for synthesizing of petal micrometer/nanometer structure polyaniline | |
| CN103787408A (en) | Preparation method of ammonium trifluorooxytitanate | |
| CN103936984B (en) | The method of polyaniline nano fiber is prepared in the regulation and control of a kind of using electric field | |
| Mavundla et al. | Synthesis and Characterization of Novel Nanophase Hexagonal Poly (2, 5‐dimethoxyaniline) | |
| Yu et al. | Synthesis of glycidyl ether of poly (bisphenol-A 1, 1′-ferrocene dicarboxylate) and its electrochemical behavior | |
| CN102898598B (en) | SO4<2->/ZrO2-Fe2O3-SiO2 doped mixed-crystal solid acid and preparation method thereof | |
| CN109239281A (en) | A kind of MnO2Load the synthetic method of poly- fluoroaniline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |