CN109252358A - A kind of preparation method of stretchable graphene oxide - Google Patents
A kind of preparation method of stretchable graphene oxide Download PDFInfo
- Publication number
- CN109252358A CN109252358A CN201810780361.0A CN201810780361A CN109252358A CN 109252358 A CN109252358 A CN 109252358A CN 201810780361 A CN201810780361 A CN 201810780361A CN 109252358 A CN109252358 A CN 109252358A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- stretchable
- preparation
- solution
- elastomer matrix
- 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.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of preparation method of stretchable graphene oxide, include the following steps: to be pre-stretched stretchable elastomer matrix;It will be immersed in positively charged polyelectrolyte solution by the stretchable elastomer matrix of pre-stretching, take out, wash after dipping;Then the stretchable elastomer matrix after washing is immersed in graphene oxide solution, is taken out after dipping, washed;It is repeated several times the process of the alternating impregnating in two kinds of solution, is realized in stretchable elastomer surface controllable growth graphene oxide;To the drying after the fiber that preceding program process is handled is replied, stretchable graphene oxide is finally obtained.Preparation method of the invention is simple, easily operated, at low cost, environmental protection;The thickness of graphene oxide can by control self assembly time and number accuracy controlling;Prepared graphene oxide has pleated structure, and pleated structure can be regulated and controled by pre-stretching.
Description
Technical field
The present invention relates to the preparation technical field of nano material more particularly to a kind of preparation sides of stretchable graphene oxide
Method.
Background technique
Graphene oxide is product of the graphite powder after chemical oxidation and removing, by sp2Carbon atom is constituted with honeycomb lattice
Two-dimentional monoatomic layer structure, bottom surface contains hydroxyl and epoxy group, and edge contains carboxyl, has unique physicochemical properties.
The special construction of graphene oxide determines that it with outstanding performance, such as high conductivity, high intensity, the high grade of transparency and is easy to repair
Decorations etc., so graphene oxide has many potential applications.
Stretchable electronic device has unique flexible, flexible and tensility, therefore is suitable for wearable device
The emerging fields such as part, stretchable displayer part, stretchable sensor and the medical device with biocompatibility.By graphite oxide
It is to prepare a kind of important way of stretchable electronic device that alkene, which is built into the pattern of fold and then generates tensility,.In addition, right
For graphene oxide, its microstructure, electron transport and mechanical performance etc. can all be influenced by fold.Compared to ideal
Complete planar structure, the generation of fold is capable of increasing specific surface area, adjusts light transmittance, changes surface wettability etc..Therefore, pleat
Wrinkle graphene suffers from fields such as stretchable electronic device, stress strain gauge, greasy dirt absorption, clean energy resourcies potentially answers
With.
The complex process of existing stretchable graphene oxide preparation method, graphene oxide at high cost and prepared
Thickness be unable to accuracy controlling.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of new stretchable graphene oxide, this method
Simple process and low cost, and prepared graphene oxide has orderly fold pattern, while its thickness can also be adjusted accurately
Control.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is to provide a kind of preparations of stretchable graphene oxide
Method, which comprises the steps of:
Step 1: stretchable elastomer matrix is pre-stretched;
Step 2: will be immersed in positively charged polyelectrolyte solution, soak by the stretchable elastomer matrix of pre-stretching
It takes out, washs after stain;Then the stretchable elastomer matrix after washing is immersed in graphene oxide solution, is taken after dipping
Out, it washs;It is repeated several times the process of the alternating impregnating in two kinds of solution, is realized in stretchable elastomer surface controllable growth oxygen
Graphite alkene;
Step 3: to the drying after the fiber that step 2 is handled is replied, finally obtaining stretchable graphene oxide.
Preferably, in the step 1, stretchable elastomer matrix is polyester ether elastic fiber, polyurethane fiber, diene
Class elastomer, composite elastic fiber, polyolefin elastic fiber or hard elastic fibre.
Preferably, in the step 1, the stretch ratio of pre-stretching is 200%~900%.
Preferably, in the step 2, positively charged polyelectrolyte solution is polyethylenimine solution, poly-vinyl alcohol solution
Or diallyl dimethyl ammoniumchloride solution.
Preferably, in the step 2, the concentration of positively charged polyelectrolyte solution is 0.05~3mg/mL, graphite oxide
The concentration of alkene solution is 0.05-3mg/mL.
Preferably, in the step 2, once the dip time in positively charged polyelectrolyte solution is 1-10min;One
The secondary dip time in graphene oxide solution is 1-10min.
Preferably, in the step 2, when washing, is washed with deionized.
Preferably, in the step 2, the number for repeating alternating impregnating process is 1~8 time.
Preferably, in the step 3, drying process is 40~60 DEG C of directly drying or natural dryings in an oven, dry
The dry time be 6~for 24 hours.
Preferably, in the step 3, preparation-obtained stretchable graphene oxide has orderly fold pattern.
Preferably, by control graphene oxide solution concentration and stretchable elastomer matrix dip time,
The thickness and the number of plies of dipping time accuracy controlling graphene oxide.
The present invention provides a kind of preparation methods of stretchable graphene oxide, first to stretchable elastomer matrix
It is pre-stretched, the then controllable growth oxidation on the stretchable fibrous matrix by pre-stretching by the method for LBL self-assembly
Graphene can produce graphene oxide fold using the stretching and release process of elastic substrates.Finally, elastic substrates can
Draftability imparts graphene oxide tensility.In the method that graphene oxide grows into elastic substrates surface, layer by layer certainly
Package technique has the advantages that preparation is simple, thickness is controllable, is not limited by substrate sizes and shape.The main drive of assembling
Including covalent bond absorption, coordinate bond absorption, electrostatic interaction and hydrogen bond action.
The present invention during LBL self-assembly, can dipping by controlling the concentration of graphene oxide, fiber when
Between, the thickness and the number of plies of dipping time accuracy controlling graphene oxide.Due to being returned after the tensility and pre-stretching of basis material
Multiple process makes graphene oxide have orderly fold pattern, and has stretchable characteristic.
Compared with prior art, the invention has the following beneficial effects:
1, preparation method of the invention is simple, easily operated, at low cost, environmental protection;
2, graphene oxide of the invention is prepared by the method for LBL self-assembly, therefore the thickness of graphene oxide can be with
By the time and the number accuracy controlling that control self assembly;
3, graphene oxide prepared by the present invention has pleated structure, and the tensility of flexible base material imparts oxidation
Graphene tensility;
4, the pleated structure of stretchable graphene oxide prepared by the present invention can be regulated and controled by pre-stretching.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of stretchable graphene oxide in embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of stretchable graphene oxide prepared by embodiment 1;(a) scanning electron microscope (SEM) photograph under low power;
(b) scanning electron microscope (SEM) photograph under high power.
Specific embodiment
Present invention will be further explained below with reference to specific examples.
Embodiment 1
In conjunction with Fig. 1, the preparation process of stretchable graphene oxide is as follows:
(1) 2.5g graphite and 2.5g sodium nitrate are weighed to be uniformly mixed in 1L flask, is slowly added to the sulfuric acid of 120mL, it will
Flask is transferred in ice-water bath, and keeps magnetic agitation, stirring rate 400r/min.Then Gao Meng is slowly added in 1h
Sour potassium continues to keep ice-water bath stirring 1h, then be transferred to flask in 35 DEG C of water-bath, constant temperature stirs 2h, by flask from 35
DEG C water-bath in take out after, be transferred in 98 DEG C of oil baths constant temperature and stir 0.5h, flask is taken out from oil bath, 230mL is added and goes
The hydrogen peroxide 350mL that mass fraction is 5% is added in ionized water after being cooled to room temperature, stirring stood 12h after 3 hours, filters.It will
The product obtained after suction filtration with mass fraction be 5% hydrogen chloride 1.2L be stirred in three times, wash, by gained dispersion liquid into
Row, which filters, separates yellow mercury oxide therein, and by obtained solid, 50 DEG C of dryings obtain graphite oxide for 24 hours in vacuum drying oven
(2) graphite oxide of step (1) is made into the dispersion liquid of 0.05mg/mL, ultrasonic disperse 6h obtains graphene oxide.
(3) polyurethane fiber is pre-stretched, extensibility 200%.
(4) the above-mentioned polyurethane fiber by pre-stretching is immersed in the polyethylenimine solution of 0.05mg/mL, 1min
After take out, gained fiber is washed with deionized three times, the oxygen for the 0.05mg/mL for being then made into fiber impregnation in step (2)
It in graphite alkene dispersion liquid, is taken out after 1min, gained fiber is washed with deionized three times.Remember that alternating sorbent polyethyleneimine is molten
Liquid and graphene oxide dispersion are one layer, obtain one layer of the polyurethane fiber containing graphene oxide.
(5) fiber that step (3) is obtained slowly replied, obtain after natural drying it is stretchable containing graphite oxide
Alkene fiber.
Fig. 2 (a) and Fig. 2 (b) is respectively the low power of the stretchable graphene oxide of the present embodiment and the scanning electricity under high power
Mirror figure.It can be observed that prepared stretchable graphene oxide has the structure of fold from Fig. 2, polyurethane bottom fiber is straight
Diameter is about 140 μm.
Embodiment 2
(1) graphite oxide of step (1) in embodiment (1) is made into the dispersion liquid of 0.15mg/mL, ultrasonic disperse 6h is obtained
Graphene oxide.
(2) polyurethane fiber is pre-stretched, extensibility 500%.
(3) the above-mentioned polyurethane fiber by pre-stretching is immersed in the polyethylenimine solution of 0.15mg/mL, 5min
After take out, gained fiber is washed with deionized three times, then by fiber impregnation the 0.15mg/mL's being made by step (1)
It in graphene oxide dispersion, is taken out after 5min, gained fiber is washed with deionized three times.Remember alternating sorbent polyethyleneimine
Solution and graphene oxide dispersion are one layer.Repeat process for four times of alternating sorbent, obtain four layers containing graphene oxide
Polyurethane fiber.
(4) fiber obtained to step (3) is slowly replied, and obtains stretchable fiber containing graphene oxide.
Embodiment 3
(1) graphite oxide of step (1) in embodiment (1) is made into the dispersion liquid of 3mg/mL, ultrasonic disperse 6h obtains oxygen
Graphite alkene.
(2) polyurethane fiber is pre-stretched, extensibility 900%.
(3) the above-mentioned polyurethane fiber by pre-stretching is immersed in the polyethylenimine solution of 3mg/mL, after 10min
It takes out, gained fiber is washed with deionized three times, then by fiber impregnation in the 3mg/ being made by embodiment (1) step (1)
It in the graphene oxide dispersion of mL, is taken out after 10min, gained fiber is washed with deionized three times.Remember the poly- second of alternating sorbent
Alkene imide liquor and graphene oxide dispersion are one layer.Process eight times of alternating sorbent are repeated, eight layers of oxygen-containing fossil is obtained
The polyurethane fiber of black alkene.
(4) fiber obtained to step (3) is slowly replied, and obtains stretchable fiber containing graphene oxide.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention;Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention
It is interior.
Claims (10)
1. a kind of preparation method of stretchable graphene oxide, which comprises the steps of:
Step 1: stretchable elastomer matrix is pre-stretched;
Step 2: will be immersed in positively charged polyelectrolyte solution by the stretchable elastomer matrix of pre-stretching, after dipping
It takes out, washing;Then the stretchable elastomer matrix after washing is immersed in graphene oxide solution, is taken out after dipping,
Washing;It is repeated several times the process of the alternating impregnating in two kinds of solution, realizes and is aoxidized in stretchable elastomer surface controllable growth
Graphene;
Step 3: to the drying after the fiber that step 2 is handled is replied, finally obtaining stretchable graphene oxide.
2. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 1,
Stretchable elastomer matrix is polyester ether elastic fiber, polyurethane fiber, elastodiene fibre, composite elastic fiber, gathers
Olefin elastic fibers or hard elastic fibre.
3. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 1,
The stretch ratio of pre-stretching is 200%~900%.
4. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 2,
Positively charged polyelectrolyte solution is that polyethylenimine solution, poly-vinyl alcohol solution or diallyl dimethyl ammoniumchloride are molten
Liquid.
5. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 2,
The concentration of positively charged polyelectrolyte solution is 0.05~3mg/mL, and the concentration of graphene oxide solution is 0.05-3mg/mL.
6. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 2,
Once the dip time in positively charged polyelectrolyte solution is 1-10min;The once dipping in graphene oxide solution
Time is 1-10min, and the number for repeating alternating impregnating process is 1~8 time.
7. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 2,
It is washed with deionized when washing.
8. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 3,
Drying process is 40~60 DEG C of directly drying or natural dryings in an oven, drying time for 6~for 24 hours.
9. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: in the step 3,
Preparation-obtained stretchable graphene oxide has orderly fold pattern.
10. a kind of preparation method of stretchable graphene oxide as described in claim 1, it is characterised in that: by controlling oxygen
The dip time of the concentration of graphite alkene solution and stretchable elastomer matrix, dipping time accuracy controlling graphene oxide
Thickness and the number of plies.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810780361.0A CN109252358A (en) | 2018-07-16 | 2018-07-16 | A kind of preparation method of stretchable graphene oxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810780361.0A CN109252358A (en) | 2018-07-16 | 2018-07-16 | A kind of preparation method of stretchable graphene oxide |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109252358A true CN109252358A (en) | 2019-01-22 |
Family
ID=65049182
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810780361.0A Pending CN109252358A (en) | 2018-07-16 | 2018-07-16 | A kind of preparation method of stretchable graphene oxide |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109252358A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109900198A (en) * | 2019-02-25 | 2019-06-18 | 武汉工程大学 | A kind of preparation method of the transparent strain sensing devices of ultra-thin high resiliency |
CN109916292A (en) * | 2019-02-25 | 2019-06-21 | 武汉工程大学 | A kind of preparation method of multi-layer capacity formula flexible intelligent wearable sensors part |
CN109971021A (en) * | 2019-04-03 | 2019-07-05 | 东华大学 | A kind of fold graphene oxide/latex fexible film and its preparation and application |
CN113322546A (en) * | 2021-05-08 | 2021-08-31 | 浙江大学 | Method for preparing high-elongation graphene fibers |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103149246A (en) * | 2012-09-27 | 2013-06-12 | 中国石油大学(华东) | Graphene film humidity sensor |
CN106119841A (en) * | 2016-06-23 | 2016-11-16 | 江苏大学 | A kind of preparation method of graphene oxide/polyelectrolyte self-assembled film layer by layer |
CN106987017A (en) * | 2017-04-25 | 2017-07-28 | 中国人民解放军国防科学技术大学 | A kind of construction method of graphenic surface fold |
-
2018
- 2018-07-16 CN CN201810780361.0A patent/CN109252358A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103149246A (en) * | 2012-09-27 | 2013-06-12 | 中国石油大学(华东) | Graphene film humidity sensor |
CN106119841A (en) * | 2016-06-23 | 2016-11-16 | 江苏大学 | A kind of preparation method of graphene oxide/polyelectrolyte self-assembled film layer by layer |
CN106987017A (en) * | 2017-04-25 | 2017-07-28 | 中国人民解放军国防科学技术大学 | A kind of construction method of graphenic surface fold |
Non-Patent Citations (1)
Title |
---|
胡希丽等: "聚乙烯醇氧化石墨烯导电棉织物的制备", 《棉纺织技术》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109900198A (en) * | 2019-02-25 | 2019-06-18 | 武汉工程大学 | A kind of preparation method of the transparent strain sensing devices of ultra-thin high resiliency |
CN109916292A (en) * | 2019-02-25 | 2019-06-21 | 武汉工程大学 | A kind of preparation method of multi-layer capacity formula flexible intelligent wearable sensors part |
CN109971021A (en) * | 2019-04-03 | 2019-07-05 | 东华大学 | A kind of fold graphene oxide/latex fexible film and its preparation and application |
CN113322546A (en) * | 2021-05-08 | 2021-08-31 | 浙江大学 | Method for preparing high-elongation graphene fibers |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109252358A (en) | A kind of preparation method of stretchable graphene oxide | |
Cheng et al. | A novel strategy for fabricating robust superhydrophobic fabrics by environmentally-friendly enzyme etching | |
Cao et al. | Robust fluorine-free superhydrophobic PDMS–ormosil@ fabrics for highly effective self-cleaning and efficient oil–water separation | |
Jin et al. | A durable, superhydrophobic, superoleophobic and corrosion-resistant coating with rose-like ZnO nanoflowers on a bamboo surface | |
CN105544221B (en) | A kind of superhydrophobic fabric and its construction method | |
Liang et al. | Stable superhydrophobic and superoleophilic soft porous materials for oil/water separation | |
Ragesh et al. | A review on ‘self-cleaning and multifunctional materials’ | |
CN105088415B (en) | A kind of wet spinning graphene oxide solution and preparation method thereof and a kind of graphene fiber and preparation method thereof | |
CN110644240B (en) | Preparation method of multifunctional durable and self-repairing super-hydrophobic fabric surface | |
CN105702483B (en) | A kind of paper substrate composite polypyrrole film and preparation method thereof | |
CN107469410A (en) | A kind of durability super-hydrophobic coat for water-oil separating and preparation method thereof | |
Mai et al. | One-step fabrication of flexible, durable and fluorine-free superhydrophobic cotton fabrics for efficient oil/water separation | |
Xue et al. | Biomimetic superhydrophobic surfaces by combining mussel-inspired adhesion with lotus-inspired coating | |
CN104532664B (en) | Universal preparation method for self-cleaning superhydrophobic paper | |
CN104251753B (en) | Elastic stress sensor based on oxidized grapheme electrospinning PU (polyurethane) film | |
Xu et al. | Superhydrophobic cotton fabrics prepared by one-step water-based sol–gel coating | |
Yin et al. | Water-repellent functional coatings through hybrid SiO2/HTEOS/CPTS sol on the surfaces of cellulose fibers | |
CN109183396A (en) | A method of graphene is promoted in dacron area load amount | |
CN108505323A (en) | A kind of method that super-hydrophobic oleophobic flame retardant coating arranges base material | |
Zhu et al. | Assembly of graphene nanosheets and SiO2 nanoparticles towards transparent, antireflective, conductive, and superhydrophilic multifunctional hybrid films | |
CN105898981A (en) | Stretchable electrode based on conductive fabric and preparation method thereof | |
CN105327526A (en) | Metal fiber felt used for separating emulsifying oil and modification method and application thereof | |
CN105544187B (en) | A kind of superhydrophobic fabric and preparation method thereof | |
CN107008161B (en) | A kind of modified composite membrane of Prussian blue/carboxy methylcellulose gel and preparation method and purposes | |
Afroz et al. | Self-cleaning textiles: Structure, fabrication and applications |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190122 |
|
RJ01 | Rejection of invention patent application after publication |