CN103275264A - Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof - Google Patents
Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103275264A CN103275264A CN2013101672209A CN201310167220A CN103275264A CN 103275264 A CN103275264 A CN 103275264A CN 2013101672209 A CN2013101672209 A CN 2013101672209A CN 201310167220 A CN201310167220 A CN 201310167220A CN 103275264 A CN103275264 A CN 103275264A
- Authority
- CN
- China
- Prior art keywords
- water
- viscosity
- acid
- reducing agent
- ceramic
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of preparation of water reducing agents, and discloses a water reducing agent capable of reducing viscosity of slurry as well as a preparation method and application of the water reducing agent. The method comprises the following steps of: adding acrylic acid and an unsaturated hydrophilic monomer into water; adding a reversible addition-fragmentation chain transfer (RAFT) reagent; heating, stirring and dissolving; adding an initiating agent to react for 3-5 hours at constant temperature; cooling to be 50-60 DEG C; regulating a pH value to obtain the water reducing agent capable of reducing the viscosity of the slurry. The water reducing agent prepared by the method is applied to ceramic slurries so that moisture content of the slurries is less than 30wt% and the viscosity of the ceramic slurries is reduced to be below 0.18Pa*s; and meanwhile, the slurry has high mobility. The water reducing agent prepared by the method is controlled in reaction process, simple in postprocessing process and can be used for promoting the development of ceramic industries in the high-quality, high-level and low-energy consumption direction.
Description
Technical field
The invention belongs to the water reducer preparing technical field, particularly a kind of water reducer that reduces slip viscosity and its preparation method and application.
Background technology
Ceramic industry is a high energy consumption industry, its energy loss all be sintering and drying process more than 80%, and the wet moulding technology has become the first-selected technology of producing ceramic, therefore, the key technical problem that the sector faces is exactly when reducing the ceramic size water ratio, keeps suitable flowability and the viscosity of slip system.Ceramic water reducing agent is a kind of of ceramic additive, also claims liquefactent, dispersion agent, thinner or dispergator, is widely used in technological processs such as ceramic industry defibrination, enamel frit makeing.
Ceramic water reducing agent is the dispersed of flowability, stability and the feed particles of improving ceramic slurry and interacts, and makes it under the situation of low water content, and viscosity is suitable, reduces energy consumption for drying, increases work efficiency, and improves product performance.Therefore, the ceramic water reducing agent that water-reducing property is good can promote that ceramic industry develops to the direction of less energy-consumption, high quality, high benefit.
China's ceramic industry generally uses inorganic salts such as water glass, yellow soda ash, tripoly phosphate sodium STPP, Sodium salts humic acids as ceramic water reducing agent at present.As Yang Shujin (Chinese pottery, 2008,44 (2): 23-25.) discover by yellow soda ash and water glass can be reduced the viscosity of black mud mud as composite water-reducing agent.But the mineral-type water reducer is subjected to the influence of factors such as its molecular structure, relative molecular mass, and it is limited to reduce the ceramic slurry system viscosity, and large usage quantity, has influenced the slip performance.Polymeric superplasticizer is because its hydrophilic group, hydrophobic group position and adjustable size can realize multiple functionalization structure, and is good than the mineral-type water reducer to particle surface covering and the covered effect of ceramic slurry, and its dispersion system is easier to stablize, the flowability better.Therefore, polymeric superplasticizer has become the very promising class water reducer of ceramic water reducing agent industry.
The more polymeric superplasticizer of research is the polycarboxylic acid polymeric superplasticizer at present, and polycarboxylic acid polymer ceramic water reducer mainly adopts radical polymerization to obtain, its molecular weight size and distribution and molecular structure etc. are uncontrollable, influence flowability and the viscosity of ceramic mud.Adopt active controlled reversible addition-fragmentation chain transfer free radical (RAFT) polymerization process to prepare compound with regular structure, molecular weight size and the controlled ceramic water reducing agent that distributes, can be under the situation that reduces the mud system water ratio, keep the ceramic slurry system viscosity suitable, make it have good flowability, have remarkable meaning for ceramic industry energy-saving and cost-reducing.
Summary of the invention
For the shortcoming and deficiency that overcome above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method who reduces the water reducer of slip viscosity.
Another purpose of the present invention is to provide the water reducer of the reduction slip viscosity that method for preparing obtains.
Still a further object of the present invention is to provide the application of above-mentioned water reducer in Production of Ceramics.
Purpose of the present invention realizes by following proposal:
A kind of preparation method who reduces the water reducer of slip viscosity specifically comprises following steps:
Vinylformic acid, unsaturated hydrophilic monomer are added to the water, add RAFT reagent again, the heated and stirred dissolving adds initiator, isothermal reaction 3～5h; Be cooled to 50～60 ℃, regulate pH, the water reducer of the slip viscosity that is reduced.
Used acrylic acid amount is that every 100mL water uses 15～30g vinylformic acid.
Described unsaturated monomer refers at least a in 2-acrylamide-2-methyl propane sulfonic acid and the methylene-succinic acid.
The Ionized negatively charged ion number of selected methylene-succinic acid is more, the wetting ability of 2-acrylamide-2-methyl propane sulfonic acid is strong, prepare water reducer and be used for Production of Ceramics, can with ceramic slurry in positively charged ion form more stable electrostatic stabilization layer, and form certain hydration layer, be conducive to the slip system and disperse.
The amount of used 2-acrylamide-2-methyl propane sulfonic acid is 5～15% of vinylformic acid quality.
The amount of used methylene-succinic acid is 5～10% of vinylformic acid quality.
Described heating refers to Heating temperature to 70～90 ℃.When temperature was hanged down, decomposition of initiator speed was slow, long reaction time, and reaction is not exclusively; The temperature of reaction height then can cause implode, makes molecular weight of product become big, and viscosity increases, even produces gel, reduces water-reducing effect.
Described RAFT reagent has two thioesters or trithio ester structure; comprise S; S '-two (α; α '-methyl-α ' '-acetic acid) trithiocarbonate, S-1-dodecyl-S '-(α; α '-dimethyl-α ' '-acetic acid) trithiocarbonate and 2-{[(ethyl sulfane base) the sulfo-acyl group]-at least a in the sulfane base butyric acid; be preferably S, S '-two (α, α '-methyl-α ' '-acetic acid) trithiocarbonate.
The amount of used RAFT reagent is 1～10% of vinylformic acid quality.
Described initiator refers at least a in ammonium persulphate and the azo two isocyano-valeric acids be preferably azo dicyano valeric acid.
The amount of used initiator is 0.5～1.5% of vinylformic acid quality.
It is 8～10 that described adjusting pH refers to utilize alkali lye to regulate the pH value.Under the alkaline condition, the negatively charged ion quantity of water reducer ionization increases, can with clay in positively charged ion form better electrostatic stabilization layer structure, be conducive to reduce the ceramic slurry system viscosity, and the pH value is greater than 10, or higher, can reduce the performance of ceramic again.
Described alkali lye refers to sodium hydroxide solution, potassium hydroxide solution or ammoniacal liquor, and the preferred mass mark is 20～50% sodium hydroxide solution.
Use argon shield in the described reaction process.
The water reducer of the reduction slip viscosity that aforesaid method obtains.
Above-mentioned water reducer is faint yellow liquid of vicidity, and product is non-volatile, has no irritating odor.
The application of described water reducer in Production of Ceramics.
Mechanism of the present invention is:
The water reducer molecular weight distribution of RAFT polymerization preparation is more even, join in the ceramic slurry system, behind the ceramic grain surface absorption carboxylate anion, the electrostatic stabilization layer that forms is more stable, make ceramic particle become more uniform charged particle, reduce the interaction between the charged particle that varies in size, make slip system stably dispersing, reduce the slip system viscosity.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) water reducer of the present invention's preparation is applied in the ceramic slurry, can make the slip water ratio below 30wt%, and the ceramic slurry system viscosity drops to below the 0.18Pa*s.
(2) water reducer of the present invention's preparation keeps it to have good mobility when reducing ceramic slurry system water ratio.
(3) it is controlled that the inventive method prepares the water reducer reaction process, and aftertreatment technology is simple, can promote ceramic industry to develop to the direction of high quality, high level and less energy-consumption.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
In there-necked flask, add 30g vinylformic acid, 1.5g methylene-succinic acid and 200mL deionized water, add 0.3g S again, S '-two (α, α '-methyl-α ' '-acetic acid) trithiocarbonate is warming up to 90 ℃, treat solution stirring dissolving after, the solution excluding air, under argon shield, 0.15g azo two isocyano-valeric acids are added in the solution isothermal reaction 3h; Cooling system to 50 ℃ is that 50% NaOH solution regulation system pH value is 10 with massfraction, obtains having the ceramic water reducing agent of water-reducing property.
Performance test:
The use of water reducer according to a conventional method, ceramic slurry viscosity characterizes by rotational viscosimeter test.The addition of water reducer is ceramic batch 0.3wt%, and when ratio of water to material was 3:7, the viscosity of ceramic slurry system was 0.18pa*s.
Embodiment 2
In there-necked flask, add 30g vinylformic acid, 3g2-acrylamide-2-methyl propane sulfonic acid and 200mL deionized water, add 0.5g S-1-dodecyl-S '-(α again, α '-dimethyl-α ' '-acetic acid) trithiocarbonate, be warming up to 90 ℃, after treating the solution stirring dissolving, the solution excluding air is under argon shield, the 0.15g ammonium persulphate is added in the solution isothermal reaction 3h; Cooling system to 50 ℃ is that 40% potassium hydroxide solution regulation system pH value is 10 with massfraction, obtains having the ceramic water reducing agent of water-reducing property.
Performance test:
The use of water reducer according to a conventional method, ceramic slurry viscosity characterizes by rotational viscosimeter test.The addition of water reducer is ceramic batch 0.3wt%, and when ratio of water to material was 3:7, the viscosity of ceramic slurry system was 0.175pa*s.
Embodiment 3
In there-necked flask, add 60g vinylformic acid, 3g2-acrylamide-2-methyl propane sulfonic acid, 6g methylene-succinic acid vinylformic acid and 200mL deionized water, add 6g2-{[(ethyl sulfane base again) the sulfo-acyl group]-sulfane base butyric acid, be warming up to 70 ℃, after treating the solution stirring dissolving, the solution excluding air, under argon shield, 0.9g azo two isocyano-valeric acids are added in the solution isothermal reaction 4h; Cooling system to 60 ℃ is 8 with ammoniacal liquor regulation system pH value, obtains having the ceramic water reducing agent of water-reducing property.
Performance test:
The use of water reducer according to a conventional method, ceramic slurry viscosity characterizes by rotational viscosimeter test.The addition of water reducer is ceramic batch 0.3wt%, and when ratio of water to material was 3:7, the viscosity of ceramic slurry system was 0.168pa*s.
Embodiment 4
In there-necked flask, add 60g vinylformic acid, 9g2-acrylamide-2-methyl propane sulfonic acid, 3g methylene-succinic acid and 200mL deionized water, add 3g S again, S '-two (α, α '-methyl-α ' '-acetic acid) trithiocarbonate is warming up to 75 ℃, treat solution stirring dissolving after, the solution excluding air, under argon shield, 0.6g azo two isocyano-valeric acids are added in the solution isothermal reaction 5h; Cooling system to 55 ℃ is that 30% NaOH solution regulation system pH value is 8 with massfraction, obtains having the ceramic water reducing agent of water-reducing property.
Performance test:
The use of water reducer according to a conventional method, ceramic slurry viscosity characterizes by rotational viscosimeter test.The addition of water reducer is ceramic batch 0.3wt%, and when ratio of water to material was 3:7, the viscosity of ceramic slurry system was 0.165pa*s.
Embodiment 5
In there-necked flask, add 45g vinylformic acid, 4.5g2-acrylamide-2-methyl propane sulfonic acid, 3.6g methylene-succinic acid and 200mL deionized water, add 3g S again, S '-two (α, α '-methyl-α ' '-acetic acid) trithiocarbonate is warming up to 75 ℃, treat solution stirring dissolving after, the solution excluding air, under argon shield, 0.6g azo two isocyano-valeric acids are added in the solution isothermal reaction 3h; Cooling system to 60 ℃ is that 30% NaOH solution regulation system pH value is 8 with massfraction, obtains having the ceramic water reducing agent of water-reducing property.
Performance test:
The use of water reducer according to a conventional method, ceramic slurry viscosity characterizes by rotational viscosimeter test.The addition of water reducer is ceramic batch 0.3wt%, and when ratio of water to material was 3:7, the viscosity of ceramic slurry system was 0.171pa*s.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a preparation method who reduces the water reducer of slip viscosity is characterized in that specifically comprising following steps: vinylformic acid, unsaturated hydrophilic monomer are added to the water, add RAFT reagent again, heated and stirred dissolving, adding initiator, isothermal reaction 3～5h; Be cooled to 50～60 ℃, regulate pH, the water reducer of the slip viscosity that is reduced.
2. method according to claim 1 is characterized in that: used acrylic acid amount is that every 100mL water uses 15～30g vinylformic acid.
3. method according to claim 1 is characterized in that: described unsaturated monomer refers at least a in 2-acrylamide-2-methyl propane sulfonic acid and the methylene-succinic acid; The amount of used 2-acrylamide-2-methyl propane sulfonic acid is 5～15% of vinylformic acid quality; The amount of used methylene-succinic acid is 5～10% of vinylformic acid quality.
4. method according to claim 1, it is characterized in that: described RAFT reagent has two thioesters or trithio ester structure, comprise S, S '-two (α, α '-methyl-α ' '-acetic acid) trithiocarbonate, S-1-dodecyl-S '-(α, α '-dimethyl-α ' '-acetic acid) trithiocarbonate and 2-{[(ethyl sulfane base) the sulfo-acyl group]-at least a in the sulfane base butyric acid; Described initiator refers at least a in ammonium persulphate and the azo two isocyano-valeric acids.
5. method according to claim 1, it is characterized in that: the amount of used RAFT reagent is 1～10% of vinylformic acid quality; The amount of used initiator is 0.5～1.5% of vinylformic acid quality.
6. method according to claim 1, it is characterized in that: described heating refers to be heated to 70～90 ℃; It is 8～10 that described adjusting pH refers to utilize alkali lye to regulate the pH value.
7. method according to claim 6, it is characterized in that: described alkali lye refers to sodium hydroxide solution, potassium hydroxide solution or ammoniacal liquor.
8. the water reducer of the reduction slip viscosity for preparing according to each described method of claim 1～7.
9. the application of described water reducer in Production of Ceramics according to Claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101672209A CN103275264A (en) | 2013-05-08 | 2013-05-08 | Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101672209A CN103275264A (en) | 2013-05-08 | 2013-05-08 | Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103275264A true CN103275264A (en) | 2013-09-04 |
Family
ID=49057901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101672209A Pending CN103275264A (en) | 2013-05-08 | 2013-05-08 | Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103275264A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848634A (en) * | 2014-02-26 | 2014-06-11 | 佛山市功能高分子材料与精细化学品专业中心 | High molecular ceramic water reducing agent and preparation method thereof |
| CN103864981A (en) * | 2014-02-26 | 2014-06-18 | 佛山市功能高分子材料与精细化学品专业中心 | Macromolecular ceramic additive as well as preparation method and application thereof |
| CN104261720A (en) * | 2014-09-22 | 2015-01-07 | 厦门天润锦龙建材有限公司 | Ether polycarboxylate superplasticizer and preparation method thereof |
| CN106750055A (en) * | 2016-11-25 | 2017-05-31 | 合众（佛山）化工有限公司 | A kind of block polymer dispersant of RAFT technologies synthesis |
| CN107722161A (en) * | 2017-09-26 | 2018-02-23 | 广东省石油与精细化工研究院 | A kind of clay grinding macromolecule diluent and preparation method thereof |
| CN109397476A (en) * | 2018-10-22 | 2019-03-01 | 广东翔华科技股份有限公司 | A kind of water-saving toilet pan high-pressure slip casting process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950336A (en) * | 2004-07-28 | 2007-04-18 | 可泰克斯有限合伙公司 | Polymers produced by using sulphur compounds in the form of transfer agents for controlled radical polymerisation of acrylic acid and the use thereof |
| CN101838433A (en) * | 2010-05-13 | 2010-09-22 | 中科院广州化学有限公司 | Method for preparing polycarboxylic compound ceramic water reducing agent |
| CN101921359A (en) * | 2010-09-29 | 2010-12-22 | 湖南省原子能农业应用研究所 | Polyacrylic acid or copolymer thereof and preparation method of polyacrylate or copolymer salt thereof |
| CN102675504A (en) * | 2012-05-09 | 2012-09-19 | 中科院广州化学有限公司 | Efficient water reducing agent for low-thixotropy ceramic slurry and preparation method thereof |
| CN102775546A (en) * | 2011-05-10 | 2012-11-14 | 永港伟方（北京）科技股份有限公司 | Branched polyacrylic acid dispersant, and preparation method and application thereof |
-
2013
- 2013-05-08 CN CN2013101672209A patent/CN103275264A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1950336A (en) * | 2004-07-28 | 2007-04-18 | 可泰克斯有限合伙公司 | Polymers produced by using sulphur compounds in the form of transfer agents for controlled radical polymerisation of acrylic acid and the use thereof |
| CN101838433A (en) * | 2010-05-13 | 2010-09-22 | 中科院广州化学有限公司 | Method for preparing polycarboxylic compound ceramic water reducing agent |
| CN101921359A (en) * | 2010-09-29 | 2010-12-22 | 湖南省原子能农业应用研究所 | Polyacrylic acid or copolymer thereof and preparation method of polyacrylate or copolymer salt thereof |
| CN102775546A (en) * | 2011-05-10 | 2012-11-14 | 永港伟方（北京）科技股份有限公司 | Branched polyacrylic acid dispersant, and preparation method and application thereof |
| CN102675504A (en) * | 2012-05-09 | 2012-09-19 | 中科院广州化学有限公司 | Efficient water reducing agent for low-thixotropy ceramic slurry and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 柳宜强等: "超分散剂的合成及其对墙地砖浆料流变性、坯体强度的研究", 《中国陶瓷》, vol. 45, no. 3, 15 March 2009 (2009-03-15), pages 10 - 12 * |
| 黄清泉等: "AA-AMPS共聚物陶瓷分散剂的制备及分散性能", 《精细化工》, vol. 30, no. 3, 15 March 2013 (2013-03-15), pages 339 - 343 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848634A (en) * | 2014-02-26 | 2014-06-11 | 佛山市功能高分子材料与精细化学品专业中心 | High molecular ceramic water reducing agent and preparation method thereof |
| CN103864981A (en) * | 2014-02-26 | 2014-06-18 | 佛山市功能高分子材料与精细化学品专业中心 | Macromolecular ceramic additive as well as preparation method and application thereof |
| CN103864981B (en) * | 2014-02-26 | 2016-01-13 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of polymer ceramic additive and its preparation method and application |
| CN103848634B (en) * | 2014-02-26 | 2016-11-09 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of polymer ceramic water reducer and preparation method thereof |
| CN104261720A (en) * | 2014-09-22 | 2015-01-07 | 厦门天润锦龙建材有限公司 | Ether polycarboxylate superplasticizer and preparation method thereof |
| CN106750055A (en) * | 2016-11-25 | 2017-05-31 | 合众（佛山）化工有限公司 | A kind of block polymer dispersant of RAFT technologies synthesis |
| CN107722161A (en) * | 2017-09-26 | 2018-02-23 | 广东省石油与精细化工研究院 | A kind of clay grinding macromolecule diluent and preparation method thereof |
| CN107722161B (en) * | 2017-09-26 | 2020-10-27 | 广东省石油与精细化工研究院 | Polymer diluent for clay grinding and preparation method thereof |
| CN109397476A (en) * | 2018-10-22 | 2019-03-01 | 广东翔华科技股份有限公司 | A kind of water-saving toilet pan high-pressure slip casting process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103275264A (en) | Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof | |
| CN102603996B (en) | Ether type polycarboxylic acid slump retaining agent and preparation method thereof | |
| CN103468028B (en) | A kind of Efficient calcium slurry dispersant and preparation method thereof | |
| CN107488276B (en) | Preparation method of nano calcium carbonate for high-thixotropy PVC paste | |
| CN103435051B (en) | Production technology of high-dispersity white carbon black for green tire | |
| CN101475200A (en) | Preparation of subsphaeroidal barium sulfate by sulfuric acid process and use in copper foil substrate | |
| CN113003981B (en) | Superfine composite mineral admixture grinding aid and preparation method thereof | |
| CN106830043A (en) | A kind of method of surface modified nano calcium carbonate | |
| CN103755883A (en) | Polycarboxylic acid type high efficiency ceramic water reducing agent, preparation method and application thereof | |
| CN103833941A (en) | Comb type polycarboxylic acid efficient ceramic water reducer and preparation method and application thereof | |
| CN103274703B (en) | Water-saving water reducing agent as well as preparation method and application thereof | |
| CN103881003B (en) | A kind of polycarboxylic acid series ceramic water reducing agent and its preparation method and application | |
| CN105754034B (en) | N hydroxymethyl acrylamide modified polycarboxylic acid ceramic water reducing agent and its normal temperature preparation method and application | |
| CN102716694A (en) | Cellulose graft copolymer ceramic slurry dispersing agent and preparation method thereof | |
| CN112811456A (en) | Nano calcium carbonate with high specific surface area and preparation method thereof | |
| CN113353962A (en) | Method for preparing active nano calcium carbonate at normal temperature and high concentration | |
| CN105836782A (en) | Calcite type calcium carbonate and preparation method thereof | |
| CN112500018B (en) | Degradable efficient gypsum retarder and preparation method and application thereof | |
| CN104892856B (en) | A kind of preparation method of polycarboxylate water-reducer | |
| CN115745460B (en) | Cement raw material energy-saving auxiliary agent and preparation method and application thereof | |
| CN107417160A (en) | The synthetic method of silane-modified ammonium polyacrylate water reducer under a kind of microwave action | |
| CN104445221A (en) | New microwave-assisted method for preparing white carbon black from rice hull ash | |
| CN104163432B (en) | Vermiculitum after acidifying | |
| CN116023672A (en) | Composite filler of tricalcium phosphate special for polymerization and preparation method thereof | |
| CN103848634B (en) | A kind of polymer ceramic water reducer 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130904 |
|
| WD01 | Invention patent application deemed withdrawn after publication |