CN107522811A - Anionic response type polyelectrolyte and preparation method and application - Google Patents
Anionic response type polyelectrolyte and preparation method and application Download PDFInfo
- Publication number
- CN107522811A CN107522811A CN201710767652.1A CN201710767652A CN107522811A CN 107522811 A CN107522811 A CN 107522811A CN 201710767652 A CN201710767652 A CN 201710767652A CN 107522811 A CN107522811 A CN 107522811A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- response type
- mixed
- type polyelectrolyte
- anionic
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to anionic response type polyelectrolyte and its preparation method and application, aqueous solution of sodium bisulfite is added in four-hole boiling flask, is heated to 65 80 DEG C；Allyl glycidyl ether and butyl acrylate are mixed with monomer mixture solution；Acrylamide and ALS are mixed with mixed aqueous solution；By acrylamide and ALS mixed aqueous solution, monomer mixture solution and ammonium persulfate aqueous solution, it is added drop-wise to respectively in reactor；Isothermal reaction, is cooled to room temperature, that is, prepares anionic response type polyelectrolyte.The present invention is on the basis of the early stage high molecular surfactant of type containing epoxy reaction, further explore and anionic monomer ALS is introduced in system, improve the solution dispersion and wettability of product, so as to quickly form hydrophobic layer in metal surface, by chemical reaction and physisorption, synergy improves carbon steel Q235 antiseptic property.
Description
Technical field
The present invention relates to a kind of anticorrosive metal response type polyelectrolyte, and in particular to a kind of anionic response type gathers
Electrolyte and preparation method and application.
Background technology
Metal erosion is considered as to be acted on by the deterioration or metal of the metal of electrochemical action by other corrosions of metal
And cause to consume.Iron, it is most widely used metal to be typically used as steel.In addition to its cost and intensity, corrosion resistance is to steel
For be an important challenge.In Process of Metallic Corrosion, the oxide of formation can not be firmly adhered to metal surface, lead
Spot corrosion is caused, causes structure to die down and is decomposed with metal.To equipment or the security of structure, the influence of reliability and efficiency is more than simple
Metal quality loss it is even more serious（Adewuyi A, Göpfert A, Wolff T. Succinyl amide gemini
surfactant from Adenopus breviflorus, seed oil: A potential corrosion
inhibitor of mild steel in acidic medium[J]. Industrial Crops & Products,
2014, 52(1):439-449.）.
Emulsion type epoxy coating is mainly used in industrial atmosphere anti-corrosion.With advances in technology, experienced additional emulsifying agent method,
Emulsification solidification method and self-emulsification three phases prepare aqueous epoxide resin paint.Wherein, self-emulsifying water borne epoxy resin applies
Material is to introduce polar group on epoxy molecule skeleton, because close and distant water-bound causes it to be dispersed in water shape automatically
Into latex, usually nanoscale, can be made high performance aqueous industrial coating（Millions of people, Zhang Yan, Yang Kai, wait water-based metals
The development and its application [J] modern coatings and application of anticorrosive paint, 2008,11 (11):51-53.）.With reference to anticorrosive paint
Development course, using the aqueous epoxy resins with self-emulsifying function study anti-corrosion of metal in acid solution environment with
Certain directive significance.Based on aqueous epoxy resins are prepared by radical polymerization, by further excellent on molecular structure
Change, introduce sulfonate ion, improve dissolving and the diffusion rate of system, improve antiseptic effect.Show with reference to pertinent literature, low
The preservative efficiency of anionic response type polyelectrolyte is substantially better than Gemini surface active agent under concentration（Qiu L G, Xie A
J, Shen Y H. Understanding the adsorption of cationic gemini surfactants on
steel surface in hydrochloric acid[J]. Materials Chemistry & Physics, 2004,
87(2–3):237-240.）.Show using testing result, anionic response type polyelectrolyte has in 1mol/L hydrochloric acid solutions
There are more excellent anti-corrosion effects.
The content of the invention
It is an object of the invention to provide a kind of anionic response type polyelectrolyte and preparation method and application,
Anionic response type polyelectrolyte has more excellent anti-corrosion of metal performance in 1mol/L hydrochloric acid solutions, equally in low concentration
Under have good inhibitory action to steel corrosion.
The technical solution adopted in the present invention is：
The preparation method of anionic response type polyelectrolyte, it is characterised in that：
Comprise the following steps：
Aqueous solution of sodium bisulfite is added in four-hole boiling flask, then heating water bath is to 65-80 DEG C；
Allyl glycidyl ether and butyl acrylate are mixed with monomer mixture solution；
Acrylamide and ALS are mixed with mixed aqueous solution；
By acrylamide and ALS mixed aqueous solution, monomer mixture solution and ammonium persulfate aqueous solution, difference is simultaneously
It is added drop-wise in reactor, time for adding 0.5-1.5h；
3-5h is reacted under constant temperature, is cooled to room temperature, that is, prepares anionic response type polyelectrolyte；
Sodium hydrogensulfite, allyl glycidyl ether, butyl acrylate, acrylamide, allyl in aqueous solution of sodium bisulfite
The mass ratio of ammonium persulfate is in base sodium sulfonate and ammonium persulfate aqueous solution（0.7-0.9）:（12-16）:（2-4）:（2-4）:
（6-10）:（3.0-3.6）.
Aqueous solution of sodium bisulfite be according to 0.7g-0.9g sodium hydrogensulfite be dissolved in 26g-28g distilled water prepare and
Into.
ALS and acrylamide mixed aqueous solution be according to 6g-10g ALS and 2g-4g third
What the distilled water that acrylamide is dissolved in 18-23g was formulated.
Allyl glycidyl ether and Butyl Acrylate Monomer solution be according to 12g-16g allyl glycidyl ether and
What 2g-4g butyl acrylate mixed preparing formed.
Ammonium persulfate aqueous solution is that the distilled water that 30g-35g is dissolved according to 3g-3.5g ammonium persulfate is formulated.
Anionic response type polyelectrolyte made from preparation method as mentioned.
Application of the anionic response type polyelectrolyte in terms of carbon steel Q235 anti-corrosions as mentioned.
The present invention has advantages below：
On the basis of the early stage high molecular surfactant of type containing epoxy reaction, further exploration introduces the present invention in system
Anionic monomer ALS, the solution dispersion and wettability of product are improved, so as to quickly in metal
Surface forms hydrophobic layer, and by chemical reaction and physisorption, synergy improves carbon steel Q235 antiseptic property.Experiment
As a result show, in 1mol/L hydrochloric acid solutions, anionic response type Polyelectrolyte Concentration is equal in 0.25mg/L-2.5mg/L
Better than the anti-corrosion of metal performance of the high molecular surfactant of type containing epoxy reaction.Show in the environment of strong acid, anionic
Response type polyelectrolyte can preferably reduce carbon steel Q235 corrosion rate, have stronger corrosion resistance.
Embodiment
With reference to embodiment, the present invention will be described in detail.
The preparation method of anionic response type polyelectrolyte of the present invention, in patent, " type containing epoxy reaction is high
Molecular surface active agent and its preparation method and application（Application number： 201611144228.3）" on the basis of, introduce new gather
Monomer ALS is closed, accounts for the 10-30wt% of total monomer amount, to improve the solution dispersion of response type polyelectrolyte, so as to
Further improve steel anti-corrosive performance of the response type polyelectrolyte in sour environment.Specifically include following steps：
Aqueous solution of sodium bisulfite is added in four-hole boiling flask, then heating water bath is to 65-80 DEG C；
Allyl glycidyl ether and butyl acrylate are mixed with monomer mixture solution；
Acrylamide and ALS are mixed with mixed aqueous solution；
By acrylamide and ALS mixed aqueous solution, monomer mixture solution and ammonium persulfate aqueous solution, it is added dropwise respectively
Into reactor, time for adding 0.5-1.5h；
3-5h is reacted under constant temperature, is cooled to room temperature, that is, prepares anionic response type polyelectrolyte；
Sodium hydrogensulfite, allyl glycidyl ether, butyl acrylate, acrylamide, allyl in aqueous solution of sodium bisulfite
The mass ratio of ammonium persulfate is in base sodium sulfonate and ammonium persulfate aqueous solution（0.7-0.9）:（12-16）:（2-4）:（2-4）:
（6-10）:（3.0-3.6）.
Aqueous solution of sodium bisulfite be according to 0.7g-0.9g sodium hydrogensulfite be dissolved in 26g-28g distilled water prepare and
Into.
ALS and acrylamide mixed aqueous solution be according to 6g-10g ALS and 2g-4g third
What the distilled water that acrylamide is dissolved in 18-23g was formulated.
Allyl glycidyl ether and Butyl Acrylate Monomer solution be according to 12g-16g allyl glycidyl ether and
What 2g-4g butyl acrylate mixed preparing formed.
Ammonium persulfate aqueous solution is that the distilled water that 30g-35g is dissolved according to 3g-3.5g ammonium persulfate is formulated.
Embodiment 1：The distilled water of 0.8g sodium hydrogensulfite and 27g is added in four-hole boiling flask, heating water bath to 70
DEG C, with 15g allyl glycidyl ethers and 2g butyl acrylate mixed preparing monomer solutions；By 3g acrylamide and 7g alkene
The distilled water that the mixing of propyl sulfonic acid sodium is dissolved in 22g prepares monomer mixed aqueous solution；3.4g ammonium persulfate is dissolved in 31g distillation
The ammonium persulfate aqueous solution that water is prepared.Monomer mixture solution, monomer mixed aqueous solution and persulfuric acid is added dropwise respectively into reactor
Aqueous ammonium, time for adding control is 0.9h, reacts 5h under constant temperature, is finally cooled to room temperature, that is, obtains anionic
Response type polyelectrolyte.
Embodiment 2：The distilled water of 0.7g sodium hydrogensulfite and 28g is added in four-hole boiling flask, heating water bath to 65
DEG C, with 12g allyl glycidyl ethers and 4g butyl acrylate mixed preparing monomer solutions；By 4g acrylamide and 8g alkene
The distilled water that the mixing of propyl sulfonic acid sodium is dissolved in 19g prepares monomer mixed aqueous solution；3.2g ammonium persulfate is dissolved in 30g distillation
The ammonium persulfate aqueous solution that water is prepared.Monomer mixture solution, monomer mixed aqueous solution and persulfuric acid is added dropwise respectively into reactor
Aqueous ammonium, time for adding control is 1.2h, reacts 4.5h under constant temperature, is finally cooled to room temperature, that is, obtains anion
Type response type polyelectrolyte.
Embodiment 3：The distilled water of 0.7g sodium hydrogensulfite and 27g is added in four-hole boiling flask, heating water bath to 75
DEG C, with 15g allyl glycidyl ethers and 3.5g butyl acrylate mixed preparing monomer solutions；By 3.2g acrylamide with
The distilled water that 7.5g ALS mixing is dissolved in 20g prepares monomer mixed aqueous solution；3.1g ammonium persulfate is dissolved in
The ammonium persulfate aqueous solution that 33g distilled water is prepared.Monomer mixture solution, monomer mixed aqueous solution is added dropwise respectively into reactor
And ammonium persulfate aqueous solution, time for adding control is 1.4h, reacts 3h under constant temperature, is finally cooled to room temperature, that is, obtains
Anionic response type polyelectrolyte.
Embodiment 4：The distilled water of 0.8g sodium hydrogensulfite and 28g is added in four-hole boiling flask, heating water bath to 65
DEG C, with 14g allyl glycidyl ethers and 2.5g butyl acrylate mixed preparing monomer solutions；By 3g acrylamide and 8g
The distilled water that ALS mixing is dissolved in 22g prepares monomer mixed aqueous solution；3g ammonium persulfate is dissolved in 31g distillation
The ammonium persulfate aqueous solution that water is prepared.Monomer mixture solution, monomer mixed aqueous solution and persulfuric acid is added dropwise respectively into reactor
Aqueous ammonium, time for adding control is 0.9h, reacts 3.5h under constant temperature, is finally cooled to room temperature, that is, obtains anion
Type response type polyelectrolyte.
Embodiment 5：The distilled water of 0.7g sodium hydrogensulfite and 26g is added in four-hole boiling flask, heating water bath to 70
DEG C, with 15g allyl glycidyl ethers and 3g butyl acrylate mixed preparing monomer solutions；By 2.7g acrylamide and 7.6g
ALS mixing be dissolved in 23g distilled water prepare monomer mixed aqueous solution；2.9g ammonium persulfate is dissolved in 34g's
The ammonium persulfate aqueous solution that distilled water is prepared.Monomer mixture solution, monomer mixed aqueous solution and mistake is added dropwise respectively into reactor
Ammonium sulfate solution, time for adding control is 1h, reacts 5h under constant temperature, is finally cooled to room temperature, that is, obtains anion
Type response type polyelectrolyte.
Anionic response type polyelectrolyte prepared by the present invention can have excellent anticorrosive in strong acidic environment
Performance.When anionic response type polyelectrolyte dosage is 2.5mg/L, its anticorrosive efficiency reaches 87.5%；When dosage is
During 0.5mg/L, its anticorrosive efficiency is 1.588 times of the high molecular surfactant of type containing epoxy reaction, shows anionic
Response type polyelectrolyte has more excellent under strong acid environment relative to the high molecular surfactant of type containing epoxy reaction
Corrosion resistance of metals.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is that claim of the invention is covered.
Claims (7)
1. the preparation method of anionic response type polyelectrolyte, it is characterised in that：
Comprise the following steps：
Aqueous solution of sodium bisulfite is added in four-hole boiling flask, then heating water bath is to 65-80 DEG C；
Allyl glycidyl ether and butyl acrylate are mixed with monomer mixture solution；
Acrylamide and ALS are mixed with mixed aqueous solution；
By acrylamide and ALS mixed aqueous solution, monomer mixture solution and ammonium persulfate aqueous solution, difference is simultaneously
It is added drop-wise in reactor, time for adding 0.5-1.5h；
3-5h is reacted under constant temperature, is cooled to room temperature, that is, prepares anionic response type polyelectrolyte；
Sodium hydrogensulfite, allyl glycidyl ether, butyl acrylate, acrylamide, allyl in aqueous solution of sodium bisulfite
The mass ratio of ammonium persulfate is in base sodium sulfonate and ammonium persulfate aqueous solution（0.7-0.9）:（12-16）:（2-4）:（2-4）:
（6-10）:（3.0-3.6）.
2. the preparation method of anionic response type polyelectrolyte according to claim 1, it is characterised in that：
Aqueous solution of sodium bisulfite is that the distilled water that 26g-28g is dissolved according to 0.7g-0.9g sodium hydrogensulfite is formulated.
3. the preparation method of anionic response type polyelectrolyte according to claim 1, it is characterised in that：
ALS and acrylamide mixed aqueous solution are the acryloyls of the ALS and 2g-4g according to 6g-10g
What the distilled water that amine is dissolved in 18-23g was formulated.
4. the preparation method of anionic response type polyelectrolyte according to claim 1, it is characterised in that：
Allyl glycidyl ether and Butyl Acrylate Monomer solution are the allyl glycidyl ether and 2g- according to 12g-16g
What 4g butyl acrylate mixed preparing formed.
5. the preparation method of anionic response type polyelectrolyte according to claim 1, it is characterised in that：
Ammonium persulfate aqueous solution is that the distilled water that 30g-35g is dissolved according to 3g-3.5g ammonium persulfate is formulated.
6. anionic response type polyelectrolyte made from preparation method as claimed in claim 1.
7. application of the anionic response type polyelectrolyte as claimed in claim 6 in terms of carbon steel Q235 anti-corrosions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710767652.1A CN107522811A (en) | 2017-08-31 | 2017-08-31 | Anionic response type polyelectrolyte and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710767652.1A CN107522811A (en) | 2017-08-31 | 2017-08-31 | Anionic response type polyelectrolyte and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107522811A true CN107522811A (en) | 2017-12-29 |
Family
ID=60682899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710767652.1A Pending CN107522811A (en) | 2017-08-31 | 2017-08-31 | Anionic response type polyelectrolyte and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107522811A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154030A (en) * | 2020-02-07 | 2020-05-15 | 四川大学 | Preparation and application of polyoxyalkylene-containing epoxy acrylate polymer active fatliquor |
| CN113840945A (en) * | 2019-04-16 | 2021-12-24 | 埃科莱布美国股份有限公司 | Multi-charge cationic compounds derived from polyamines and use of compositions thereof for corrosion inhibition in aqueous systems |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282296A (en) * | 2008-11-14 | 2011-12-14 | 恩索恩公司 | Method for the post-treatment of metal layers |
| CN106749896A (en) * | 2016-12-13 | 2017-05-31 | 陕西科技大学 | High molecular surfactant of type containing epoxy reaction and its preparation method and application |
-
2017
- 2017-08-31 CN CN201710767652.1A patent/CN107522811A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282296A (en) * | 2008-11-14 | 2011-12-14 | 恩索恩公司 | Method for the post-treatment of metal layers |
| CN106749896A (en) * | 2016-12-13 | 2017-05-31 | 陕西科技大学 | High molecular surfactant of type containing epoxy reaction and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113840945A (en) * | 2019-04-16 | 2021-12-24 | 埃科莱布美国股份有限公司 | Multi-charge cationic compounds derived from polyamines and use of compositions thereof for corrosion inhibition in aqueous systems |
| CN113840945B (en) * | 2019-04-16 | 2023-09-26 | 埃科莱布美国股份有限公司 | Use of multi-charged cationic compounds derived from polyamines and compositions thereof for corrosion inhibition in aqueous systems |
| CN111154030A (en) * | 2020-02-07 | 2020-05-15 | 四川大学 | Preparation and application of polyoxyalkylene-containing epoxy acrylate polymer active fatliquor |
| CN111154030B (en) * | 2020-02-07 | 2021-04-27 | 四川大学 | Preparation and application of polyoxyalkylene-containing epoxy acrylate polymer active fatliquor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788343B (en) | A kind of Diamond Search aqueous epoxy curing agent | |
| CN106589213B (en) | A kind of aqueous metallic paint self-crosslinking acrylic lotion and preparation method thereof | |
| CN105175615B (en) | A kind of aqueous environment protection filmogen applied to steel fastener surface and preparation method and application | |
| CN110229573A (en) | A kind of aqueous rusty anti-corrosive primer and preparation method thereof | |
| CN109486264A (en) | A kind of corrosion-resistant optical cable epoxide resin coating material | |
| CN105802432B (en) | A kind of antiseptic and rustproof paint of water-base epoxy and preparation method thereof | |
| CN107286797B (en) | Self-emulsified aqueous epoxy phosphate anti-corrosion lotion and preparation method thereof | |
| CN107522811A (en) | Anionic response type polyelectrolyte and preparation method and application | |
| CN105177559A (en) | Salt-spray-resistant aluminum profile rare earth silane processing liquid and preparation method thereof | |
| CN109880484A (en) | A kind of water-base epoxy thickness slurry anti-decaying paint and its preparation method and application | |
| CN103965706A (en) | Polymer composite emulsion for metal surface treatment and preparation method thereof | |
| CN104987802A (en) | Rustproof metal surface treatment agent and preparation method thereof | |
| CN106432588A (en) | Preparation method of acrylic emulsion for damping paints | |
| CN104004448A (en) | Single-component cathodic electrophoretic coating for automotive primer | |
| CN105086720A (en) | Anticorrosive metal surface treating agent and preparation method thereof | |
| CN104988482A (en) | Polyacid metal surface treating agent and preparation method thereof | |
| CN102993842A (en) | Styrene-acrylic emulsion aqueous rust coating and preparation method thereof | |
| CN107057421B (en) | A kind of rebar surface nanosizing composite coating and the preparation method and application thereof | |
| CN104988478A (en) | Metal surface treatment agent for gelatinous film and preparation method of metal surface treatment agent | |
| CN106749896B (en) | High molecular surfactant of type containing epoxy reaction and its preparation method and application | |
| CN105038481A (en) | Lubricating metal surface treatment agent and preparation method therefor | |
| CN109929068A (en) | A kind of in-situ modified water-based acrylic resin of polyaniline and preparation method thereof | |
| CN109135465A (en) | A kind of fume pipeline corrosion resistant coating | |
| CN103450800A (en) | Modified silanized metal surface pretreatment agent containing polyoxyethylene sorbitan monooleate and preparation method thereof | |
| CN105177555A (en) | High-inhibition-rate aluminum profile rare earth silane processing liquid and preparation method thereof |
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: 20171229 |
|
| RJ01 | Rejection of invention patent application after publication |