CN106431058B - A kind of high early strength poly-carboxylic type water-reducing agent and its preparation method and application - Google Patents
A kind of high early strength poly-carboxylic type water-reducing agent and its preparation method and application Download PDFInfo
- Publication number
- CN106431058B CN106431058B CN201610437876.1A CN201610437876A CN106431058B CN 106431058 B CN106431058 B CN 106431058B CN 201610437876 A CN201610437876 A CN 201610437876A CN 106431058 B CN106431058 B CN 106431058B
- Authority
- CN
- China
- Prior art keywords
- parts
- poly
- early strength
- reducing agent
- type water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of high early strength poly-carboxylic type water-reducing agents and its preparation method and application, which is made of the raw material below according to parts by weight：40-48 parts of polymethylacrylic acid, 12-20 parts of poly- silicon zinc sulfate, 8-16 parts of polyacrylamide, 3-10 parts of magnesium carbonate, 16-24 parts of polyethylene polyamine.Polymethylacrylic acid is mixed, heating stirring processing with the polyethylene polyamine solution of preparation, poly- silicon zinc sulfate is added and is handled with magnesium carbonate heating stirring, polyacrylamide heating stirring is then added, is down to room temperature to obtain the final product.The present invention has many advantages, such as that water-reducing rate is high, setting time is short, concrete 's air-containing is low, early strength is high, when for pre-cast concrete concrete, cement concrete early strength can be significantly improved, to demould ahead of time, improve production efficiency, pre-cast concrete concrete production energy consumption is reduced, Applicable temperature is relatively low, can be used under conditions of temperature is higher than -5 DEG C；Various group partition inter-capacitives are preferable, it can be ensured that the storage of water-reducing agent long period is uniform and stable.
Description
Technical field
The present invention relates to additive for building material technical field, specifically a kind of high early strength poly-carboxylic type water-reducing agent and its preparation
Methods and applications.
Background technology
Poly carboxylic acid series water reducer is compared with the water-reducing agents such as traditional naphthalene system, melamine series due to, water-reducing rate low with volume
High, the advantages that cement adaptability is good, it is increasingly becoming research and widely used water-reducing agent of new generation.With China's nuclear power, water conservancy,
The rise of the Large Infrastructure Projects such as bridge, tunnel, the especially planning implementation of state-owned railroads Line for Passenger Transportation net engineering, to polycarboxylic acids
The market demand sustainable growth of based water reducer.Poly carboxylic acid series water reducer common at present has certain deferred action, early strength
Develop slowly, concrete 1d compression strength is only capable of reach design strength 20~30%, especially low temperature or use large dosage
In the case of mineral admixture, early strength is lower, greatly limits its application range.
Invention content
The purpose of the present invention is to provide a kind of water-reducing rate height, setting time is short, concrete 's air-containing is low, early strength is high
High early strength poly-carboxylic type water-reducing agent and its preparation method and application, to solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides the following technical solutions：
A kind of high early strength poly-carboxylic type water-reducing agent, is made of the raw material below according to parts by weight：Polymethylacrylic acid 40-48
Part, 12-20 parts of poly- silicon zinc sulfate, 8-16 parts of polyacrylamide, 3-10 parts of magnesium carbonate, 16-24 parts of polyethylene polyamine.
As a further solution of the present invention：The high early strength poly-carboxylic type water-reducing agent, by below according to the raw material of parts by weight
Composition：42-46 parts of polymethylacrylic acid, 14-18 parts of poly- silicon zinc sulfate, 10-14 parts of polyacrylamide, 5-8 parts of magnesium carbonate, more second
18-22 parts of alkene polyamines.
As a further solution of the present invention：The high early strength poly-carboxylic type water-reducing agent, by below according to the raw material of parts by weight
Composition：44 parts of polymethylacrylic acid, 16 parts of poly- silicon zinc sulfate, 12 parts of polyacrylamide, 7 parts of magnesium carbonate, 20 parts of polyethylene polyamine.
The preparation method of the high early strength poly-carboxylic type water-reducing agent, comprises the steps of：
1) polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the matter of polyethylene polyamine and ethanol solution
Amount is than being 1: 8-10；Polyethylene polyamine solution is made；
2) polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 55-60 DEG C, and at such a temperature at stirring
30-40min is managed, then is warming up to 70-75 DEG C in the time of 10min, poly- silicon zinc sulfate and magnesium carbonate is then added, then in 70-
15-20min is stirred at 75 DEG C, then is warming up to 80-85 DEG C in the time of 10min, polyacrylamide is then added, and in 80-
40-50min is stirred at 85 DEG C, is then down to 55-60 DEG C, and heating stirring 20-30min, is down to room temperature up to high early strength poly-carboxylic
Type water-reducing agent.
Application of the high early strength poly-carboxylic type water-reducing agent in cement concrete admixture.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention has water-reducing rate under the collective effect of each raw material, and using water-reducing agent made from above-mentioned preparation method
It high, the advantages that setting time is short, concrete 's air-containing is low, early strength is high, when being used for pre-cast concrete concrete, can significantly carry
High cement concrete early strength improves production efficiency to demould ahead of time, reduces pre-cast concrete concrete production energy consumption.This
Various accelerating component synergies are excellent in invention water-reducing agent, and Applicable temperature is relatively low, can make under conditions of temperature is higher than -5 DEG C
With；Various group partition inter-capacitives are preferable, it can be ensured that the storage of water-reducing agent long period is uniform and stable.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of high early strength poly-carboxylic type water-reducing agent is made of the raw material below according to parts by weight：Poly- first
40 parts of base acrylic acid, 12 parts of poly- silicon zinc sulfate, 8 parts of polyacrylamide, 3 parts of magnesium carbonate, 16 parts of polyethylene polyamine.
Polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the quality of polyethylene polyamine and ethanol solution
Than being 1: 8；Polyethylene polyamine solution is made.Polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 55 DEG C, and
Stir process 30min at this temperature, then 70 DEG C are warming up in the time of 10min, poly- silicon zinc sulfate and magnesium carbonate is then added,
15min is stirred at 70 DEG C again, then is warming up to 80 DEG C in the time of 10min, polyacrylamide is then added, and at 80 DEG C
40min is stirred, 55 DEG C, and heating stirring 20min is then down to, is down to room temperature up to high early strength poly-carboxylic type water-reducing agent.
Embodiment 2
In the embodiment of the present invention, a kind of high early strength poly-carboxylic type water-reducing agent is made of the raw material below according to parts by weight：Poly- first
48 parts of base acrylic acid, 20 parts of poly- silicon zinc sulfate, 16 parts of polyacrylamide, 10 parts of magnesium carbonate, 24 parts of polyethylene polyamine.
Polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the quality of polyethylene polyamine and ethanol solution
Than being 1: 10；Polyethylene polyamine solution is made.Polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 60 DEG C, and
Stir process 40min at such a temperature, then 75 DEG C are warming up in the time of 10min, poly- silicon zinc sulfate and carbonic acid is then added
Magnesium, then 20min is stirred at 75 DEG C, then 85 DEG C are warming up in the time of 10min, polyacrylamide is then added, and 85
50min is stirred at DEG C, is then down to 60 DEG C, and heating stirring 30min, is down to room temperature up to high early strength poly-carboxylic type water-reducing agent.
Embodiment 3
In the embodiment of the present invention, a kind of high early strength poly-carboxylic type water-reducing agent is made of the raw material below according to parts by weight：Poly- first
42 parts of base acrylic acid, 14 parts of poly- silicon zinc sulfate, 10 parts of polyacrylamide, 5 parts of magnesium carbonate, 18 parts of polyethylene polyamine.
Polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the quality of polyethylene polyamine and ethanol solution
Than being 1: 9；Polyethylene polyamine solution is made.Polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 58 DEG C, and
Stir process 35min at this temperature, then 72 DEG C are warming up in the time of 10min, poly- silicon zinc sulfate and magnesium carbonate is then added,
18min is stirred at 72 DEG C again, then is warming up to 82 DEG C in the time of 10min, polyacrylamide is then added, and at 82 DEG C
45min is stirred, 58 DEG C, and heating stirring 25min is then down to, is down to room temperature up to high early strength poly-carboxylic type water-reducing agent.
Embodiment 4
In the embodiment of the present invention, a kind of high early strength poly-carboxylic type water-reducing agent is made of the raw material below according to parts by weight：Poly- first
42-46 parts of base acrylic acid, 14-18 parts of poly- silicon zinc sulfate, 10-14 parts of polyacrylamide, 5-8 parts of magnesium carbonate, polyethylene polyamine 18-
22 parts.
Polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the quality of polyethylene polyamine and ethanol solution
Than being 1: 9；Polyethylene polyamine solution is made.Polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 58 DEG C, and
Stir process 35min at this temperature, then 72 DEG C are warming up in the time of 10min, poly- silicon zinc sulfate and magnesium carbonate is then added,
18min is stirred at 72 DEG C again, then is warming up to 82 DEG C in the time of 10min, polyacrylamide is then added, and at 82 DEG C
45min is stirred, 58 DEG C, and heating stirring 25min is then down to, is down to room temperature up to high early strength poly-carboxylic type water-reducing agent.
Embodiment 5
In the embodiment of the present invention, a kind of high early strength poly-carboxylic type water-reducing agent is made of the raw material below according to parts by weight：Poly- first
44 parts of base acrylic acid, 16 parts of poly- silicon zinc sulfate, 12 parts of polyacrylamide, 7 parts of magnesium carbonate, 20 parts of polyethylene polyamine.
Polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the quality of polyethylene polyamine and ethanol solution
Than being 1: 9；Polyethylene polyamine solution is made.Polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 58 DEG C, and
Stir process 35min at this temperature, then 72 DEG C are warming up in the time of 10min, poly- silicon zinc sulfate and magnesium carbonate is then added,
18min is stirred at 72 DEG C again, then is warming up to 82 DEG C in the time of 10min, polyacrylamide is then added, and at 82 DEG C
45min is stirred, 58 DEG C, and heating stirring 25min is then down to, is down to room temperature up to high early strength poly-carboxylic type water-reducing agent.
Comparative example 1
In addition to without containing poly- silicon zinc sulfate, formula and preparation process are consistent with embodiment 5.
Documents 2
Only contain polymethylacrylic acid and poly- silicon zinc sulfate, formula and preparation process are consistent with embodiment 5.
The water-reducing agent that embodiment 1-5 and comparative example 1-2 are obtained carries out properties comparison
1, flowing degree of net paste of cement and its retention property
Flowing degree of net paste of cement and fluidity gradual loss are according to GB/8077-2000《Concrete admixture homogeneity is tested
Method》It carries out.Using Yadong P.0.42.5R cement, W/C=0.29.Test result is as shown in table 1.
1 flowing degree of net paste of cement of table and its retention property
As it can be seen from table 1 the mobility using the high early strength poly-carboxylic type water-reducing agent of the method for the present invention preparation and flowing
Degree keeps effect to have a distinct increment under the collective effect of each component.
2, high early strength poly-carboxylic type water-reducing agent technical indicator
High early strength poly-carboxylic type water-reducing agent prepared by embodiment 1-5 and the water-reducing agent that comparative example 1-2 is obtained are mixed by 2%
Amount incorporation is detected in batch concrete according to concerned countries standard respectively.
Water-reducing rate, bleeding rate ratio, air content, setting time difference are according to GB8076-2008《Concrete admixture》It is surveyed
Fixed and calculating.Concrete sample make, maintenance and detection etc. are according to GB/T50080-2002《Normal concrete mix physical performance tries
Test method standard》,GB/T50081-2002《Standard for test methods of mechanical properties of ordinary concrete》It carries out.Test result such as table 2
It is shown.
2 water-reducing agent performance test results of table
As can be seen from Table 2, the high early strength poly-carboxylic type water-reducing agent described in the embodiment of the present invention meets GB8076-2008
《Concrete admixture》About the requirement of the index of correlation of early-strength high-performance water-reducing agent in standard.It is compared with comparative example 1-2,
The present invention is advantageous on the key indexes such as water-reducing rate, compressive strength rate, shrinkage ratio under the collective effect of each component,
High early strength poly-carboxylic type water-reducing agent using effect of the present invention is excellent, and cost advantage is apparent, is worth a wide range of and promotes.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (4)
1. a kind of preparation method of high early strength poly-carboxylic type water-reducing agent, which is characterized in that the high early strength poly-carboxylic type water-reducing agent, by
It is formed below according to the raw material of parts by weight：40-48 parts of polymethylacrylic acid, 12-20 parts of poly- silicon zinc sulfate, polyacrylamide 8-16
Part, 3-10 parts of magnesium carbonate, 16-24 parts of polyethylene polyamine；
It comprises the steps of：
1) polyethylene polyamine is mixed with the ethanol solution that volumetric concentration is 75%, the mass ratio of polyethylene polyamine and ethanol solution
It is 1: 8-10；Polyethylene polyamine solution is made；
2) polymethylacrylic acid is mixed with polyethylene polyamine solution, is heated to 55-60 DEG C, and stir process at such a temperature
30-40min, then 70-75 DEG C is warming up in the time of 10min, poly- silicon zinc sulfate and magnesium carbonate is then added, then in 70-75
15-20min is stirred at DEG C, then is warming up to 80-85 DEG C in the time of 10min, polyacrylamide is then added, and in 80-85
40-50min is stirred at DEG C, is then down to 55-60 DEG C, and heating stirring 20-30min, is down to room temperature up to high early strength poly-carboxylic type
Water-reducing agent.
2. the preparation method of high early strength poly-carboxylic type water-reducing agent according to claim 1, which is characterized in that by below according to weight
Measure the raw material composition of part：42-46 parts of polymethylacrylic acid, 14-18 parts of poly- silicon zinc sulfate, 10-14 parts of polyacrylamide, magnesium carbonate
5-8 parts, 18-22 parts of polyethylene polyamine.
3. the preparation method of high early strength poly-carboxylic type water-reducing agent according to claim 2, which is characterized in that by below according to weight
Measure the raw material composition of part：44 parts of polymethylacrylic acid, 16 parts of poly- silicon zinc sulfate, 12 parts of polyacrylamide, 7 parts of magnesium carbonate, more second
20 parts of alkene polyamines.
4. high early strength poly-carboxylic type water-reducing agent is in cement concrete admixture as made from claim 1-3 any the methods
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610437876.1A CN106431058B (en) | 2016-06-08 | 2016-06-08 | A kind of high early strength poly-carboxylic type water-reducing agent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610437876.1A CN106431058B (en) | 2016-06-08 | 2016-06-08 | A kind of high early strength poly-carboxylic type water-reducing agent and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106431058A CN106431058A (en) | 2017-02-22 |
| CN106431058B true CN106431058B (en) | 2018-11-13 |
Family
ID=58183721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610437876.1A Expired - Fee Related CN106431058B (en) | 2016-06-08 | 2016-06-08 | A kind of high early strength poly-carboxylic type water-reducing agent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106431058B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117105569B (en) * | 2023-09-22 | 2024-10-11 | 湖南湘鑫科贸发展有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891414A (en) * | 2010-07-07 | 2010-11-24 | 广东省长大公路工程有限公司 | Polycarboxylic acid type special additive for lightweight aggregate concrete |
| JP4895693B2 (en) * | 2006-06-06 | 2012-03-14 | 住友大阪セメント株式会社 | Method for producing concrete and concrete |
| CN102923989A (en) * | 2012-11-16 | 2013-02-13 | 北京建筑工程学院 | Clay-resistant polycarboxylate water reducer and preparation method thereof |
| CN104016615A (en) * | 2014-06-13 | 2014-09-03 | 石家庄市长安育才建材有限公司 | Slow release type efficient polycarboxylic acid water reducer and preparation method thereof |
| CN104163636A (en) * | 2014-07-31 | 2014-11-26 | 青岛华承天机械制造有限公司 | High-efficiency ceramic water reducing agent |
-
2016
- 2016-06-08 CN CN201610437876.1A patent/CN106431058B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4895693B2 (en) * | 2006-06-06 | 2012-03-14 | 住友大阪セメント株式会社 | Method for producing concrete and concrete |
| CN101891414A (en) * | 2010-07-07 | 2010-11-24 | 广东省长大公路工程有限公司 | Polycarboxylic acid type special additive for lightweight aggregate concrete |
| CN102923989A (en) * | 2012-11-16 | 2013-02-13 | 北京建筑工程学院 | Clay-resistant polycarboxylate water reducer and preparation method thereof |
| CN104016615A (en) * | 2014-06-13 | 2014-09-03 | 石家庄市长安育才建材有限公司 | Slow release type efficient polycarboxylic acid water reducer and preparation method thereof |
| CN104163636A (en) * | 2014-07-31 | 2014-11-26 | 青岛华承天机械制造有限公司 | High-efficiency ceramic water reducing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106431058A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103951304B (en) | A kind of concrete intensifier and its preparation method and application | |
| CN104310839B (en) | Concrete intensifier and preparation method | |
| CN103965416B (en) | Component high-early strength type polycarboxylic acids dehydragent and preparation method thereof | |
| CN107640921B (en) | Preparation method of high-adaptability alkali-free accelerator auxiliary material | |
| CN104478284A (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| CN102936110A (en) | Lignosulfonate-polycarboxylic acid copolymerized composite high-performance water reducer and preparation method thereof | |
| CN103693881A (en) | Polycarboxylic acid water reducer, application and preparation method of polycarboxylic acid water reducer | |
| CN105801765A (en) | Preparation method of anti-segregation type polycarboxylic acid water reducer of concrete | |
| CN103613307B (en) | Slump type polycarboxylate superplasticizer and preparation method thereof | |
| CN110746553A (en) | Low-shrinkage viscosity-reduction type polycarboxylate superplasticizer and preparation method and application thereof | |
| CN106746891B (en) | A kind of wet mixing mortar additive and preparation method thereof | |
| CN104030599A (en) | Antifreezing polycarboxylic acid composite pumping water reducing agent and application thereof | |
| CN106431058B (en) | A kind of high early strength poly-carboxylic type water-reducing agent and its preparation method and application | |
| CN107935443A (en) | A kind of modified concrete water-reducing agent and preparation method thereof | |
| CN102807653A (en) | Co-polycarboxylic acid high efficiency water reducer capable of compounding with naphthalene formaldehyde water reducer and method for preparing same | |
| CN102659338B (en) | Polycarboxylic water reducer applicable to manufactured sand and preparation method of polycarboxylic water reducer | |
| CN107935431A (en) | A kind of Concrete synergist and preparation method thereof | |
| CN104478285B (en) | A kind of it is applied to the activation reinforcing agent of cement concrete, purposes and preparation method thereof | |
| CN105017489A (en) | prenylpolyethoxy ether water reducer and preparation method thereof | |
| CN109320707B (en) | Hyperbranched highway concrete retarder and preparation method and application thereof | |
| CN105948559A (en) | Negative temperature concrete antifreezer | |
| CN108219079B (en) | Polycarboxylic acid water reducing agent, and preparation method and use method thereof | |
| CN103588417A (en) | Modifier of sodium lignosulfonate concrete water reducing agent | |
| CN104016616A (en) | Novel high-strength and energy-saving polycarboxylate superplasticizer and preparation method thereof | |
| CN106698999A (en) | Concrete liquid expanding agent 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181113 Termination date: 20200608 |