CN101921372B - Preparation method of cosolvent by compounding concrete admixture - Google Patents
Preparation method of cosolvent by compounding concrete admixture Download PDFInfo
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- CN101921372B CN101921372B CN2010102598948A CN201010259894A CN101921372B CN 101921372 B CN101921372 B CN 101921372B CN 2010102598948 A CN2010102598948 A CN 2010102598948A CN 201010259894 A CN201010259894 A CN 201010259894A CN 101921372 B CN101921372 B CN 101921372B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004567 concrete Substances 0.000 title claims abstract description 7
- 238000013329 compounding Methods 0.000 title claims abstract description 6
- 239000006184 cosolvent Substances 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- -1 polyoxyethylene Polymers 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 229920005646 polycarboxylate Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 229960003511 macrogol Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The invention discloses a preparation method of a cosolvent by compounding a concrete admixture, comprising the following steps of: (1) esterification reaction: mixing methyl-terminated polyethylene glycol containing 5-20 percent of cyclopropane in the mol ratio with methacrylic acid or acrylic acid with the mol ratio of 1:(2.5-10) and reacting at the temperature of 105-125DEG C for 3-6 hours; (2) polymerization reaction: adding water in the prepared carboxylate for diluting, adding an initiator the addition quantity of which is 2-13 percent of the mass of total reactants and reacting at the temperature of 70-90DEG C for 2.5-6 hours; (3) neutralization reaction: adding alkali in the substances and adjusting the pH value to be 5-7 to obtain a high polymer cosolvent; and (4) adding the neutralized water-soluble high polymer cosolvent in a polycarboxylic acid superplastic agent. After the cosolvent is added according a certain proportion, the solution is not demixed; and the preparation process is simpler and the reaction conditions are easy to control.
Description
Technical field
The present invention relates to a kind of preparation method of cement water reducing agent, particularly added the method for the not stratified efficient cement water reducing agent of the composite preparation of poly carboxylic acid parent of use different molecular structures of solubility promoter.
Background technology
At present, polycarboxylic acid polymer has obtained promoting and widespread use as efficient cement water reducing agent; Because the needs of function have had a mind to adjust the oxyethane in the side chain and the ratio of propylene oxide in the poly carboxylic acid molecular structure, perhaps since with a kind of molecular structure owing to the difference of the polymerization degree; Two kinds or two or more such water-soluble polymer solutions are after mixing is composite, when concentration reaches certain value; System can be divided into two immiscible phases by nature; Two all contain moisture mutually, constitute double-aqueous phase system, cause the unsettled defective of product.The present invention selects a kind of tensio-active agent according to the poly carboxylic acid of different HLB values, and the solution system is divided into immiscible biphase problem naturally.
Summary of the invention
The composite admixture of concrete provides compounding polycarboxylic acid with different molecular structures and does not produce stratified method in the object of the invention solution actual production.
The present invention is used for the preparation method of the solubility promoter of compounding concrete admixture, and the solution system is divided into immiscible biphase problem naturally, carries out according to the following step:
(1) esterification: will contain with the molar ratio computing is the terminal methyl polyoxyethylene glycol of 5%-20% Trimetylene; Wherein the molecular weight of terminal methyl polyoxyethylene glycol is 300-6000; With mol ratio is 1: methylacrylic acid or the vinylformic acid of 2.5-10 mix; Under nitrogen protection and catalyzer, reaction is 3-6 hour under 105-125 ℃ temperature; Wherein said catalyzer is sodium pyrosulfate, toluene sulfonic acide or the vitriol oil, perhaps the mixture of two of above-mentioned arbitrary proportion kinds or three kinds;
(2) polyreaction: with the carboxylate of above-mentioned preparation; Add the entry dilution, making its concentration is 30-50%, and adding total reactant is the initiator of 2-13% in mass; Reaction is 2.5-6 hour under 70-90 ℃ temperature; Initiated polymerization becomes water-soluble high-molecular substance, and wherein said initiator is Potassium Persulphate, ammonium persulphate, ydrogen peroxide 50 or Sodium Persulfate, perhaps the mixture of any two kinds or three kinds of above-mentioned substance or four kinds;
(3) neutralization reaction: in above-mentioned substance, add alkali, adjustment pH value promptly obtains the polymeric retention aid solvent at 5-7; Wherein said alkali is sodium hydroxide, Pottasium Hydroxide, calcium hydroxide or yellow soda ash, or their any two kinds and two or more mixtures;
(4) the water-soluble polymer solubility promoter after the above-mentioned neutralization of adding in polycarboxylate water-reducer, the ratio of adding is the 2-20% of solid mass ratio.
Advantage of the present invention: the characteristics of the solubility promoter of method for preparing in the water reducer aqua after ethers and lipid are composite, add a certain proportion of solubility promoter; Solution is not stratified, and, this high molecular polymer solubility promoter and parent; In concrete uses, has same performance; The preparation process is fairly simple, and reaction conditions is easy to control.
Further set forth the present invention through instance below, but be not limited to the present invention.
Embodiment
Embodiment one:
It is 1500 terminal methyl Liquid Macrogol gram, vinylformic acid 65 grams that reaction flask adds the molecular weight contain 3% propylene oxide (mol ratio); Add 20 milliliters of benzene; Fed nitrogen 20 minutes; Under nitrogen protection, add composite catalyst (wherein composite catalyst is that p-methyl benzenesulfonic acid and sodium pyrosulfate mass ratio are 1: 1 mixture) 20g, 115-120 ℃ of reaction 6 hours.Add dilution water, be added dropwise in 90 ℃ the water 3 hours time simultaneously with the ammonium persulfate aqueous solution.Dropping finishes, and is warming up to 95 ℃ of reactions 1 hour, is cooled to 50 ℃, adds liquid caustic soda, and the adjustment pH value is 5-7.Obtain solid content and be 23% water-soluble polymer solubility promoter.
Double-aqueous phase system: lipid polycarboxylate water-reducer 20 grams, ethers poly carboxylic acid 20 grams, polynary carbohydrate 2 grams, water 58 grams.
The system solution that does not add solubility promoter after 24 hours, obvious layering occurs.
Add the solution of 3 gram solubility promoters, do not have the generation of demixing phenomenon.
Embodiment two:
Reaction flask adds and to contain 10% propylene oxide (mol ratio), molecular weight is 600 terminal methyl Liquid Macrogol gram, TEB 3K 200 grams; Fed nitrogen 20 minutes; Under nitrogen protection; Add composite catalyst (wherein composite catalyst is that p-methyl benzenesulfonic acid and sulfuric acid mass ratio are 1: 1 mixture) 20g, 110 ℃ of fractionator reactions 6 hours.Add dilution water and a certain proportion of ferrous sulfate, dripped ydrogen peroxide 50 5 hours down at 75-80 ℃.Dropwise, be warming up to 85 ℃ of reactions 1 hour, be cooled to 50 ℃, add liquid caustic soda, the adjustment pH value is 5-7.Obtain solid content and be 45% water-soluble polymer solubility promoter.
Double-aqueous phase system: lipid polycarboxylate water-reducer 40 grams, ethers poly carboxylic acid 40 grams, polynary carbohydrate 3 grams, water 17.
The system solution that does not add solubility promoter after 24 hours, obvious layering occurs.
Add the solution of 2 gram solubility promoters, do not have the generation of demixing phenomenon.
Embodiment three:
Reaction flask adds and to contain 4% propylene oxide (mol ratio), molecular weight is 800 terminal methyl Liquid Macrogol gram, methylacrylic acid 140 grams; Fed nitrogen 20 minutes; Under nitrogen protection; Add composite catalyst (wherein composite catalyst is that sodium pyrosulfate and sulfuric acid mass ratio are 1: 1 mixture) 20g, 120-125 ℃ of reaction 6 hours.Add dilution water and a certain proportion of Thiovanic acid, dripped sodium persulfate aqueous solution 3 hours down at 75-80 ℃.Sodium persulfate aqueous solution finishes, and is warming up to 85 ℃ of reactions 1 hour, is cooled to 50 ℃, adds liquid caustic soda, and the adjustment pH value is 5-7.Obtain solid content and be 40% water-soluble polymer solubility promoter.
Double-aqueous phase system: lipid polycarboxylate water-reducer 25 grams, ethers poly carboxylic acid 15 grams, polynary carbohydrate 3 grams, water 57.
The system solution that does not add solubility promoter after 24 hours, obvious layering occurs.
Add the solution of 8 gram solubility promoters, do not have the generation of demixing phenomenon.
Claims (1)
1. the preparation method who is used for the solubility promoter of compounding concrete admixture is characterized in that carrying out according to the following step:
(1) esterification: will contain with the molar ratio computing is the terminal methyl polyoxyethylene glycol of 5%-20% propylene oxide; Wherein the molecular weight of terminal methyl polyoxyethylene glycol is 300-6000; With mol ratio is 1: methylacrylic acid or the vinylformic acid of 2.5-10 mix; Under nitrogen protection and catalyzer, reaction is 3-6 hour under 105-125 ℃ temperature; Wherein said catalyzer is sodium pyrosulfate, toluene sulfonic acide or the vitriol oil, perhaps the mixture of two of above-mentioned arbitrary proportion kinds or three kinds;
(2) polyreaction: with the carboxylate of above-mentioned preparation; Add the entry dilution, making its concentration is 30-50%, and adding total reactant is the initiator of 2-13% in mass; Reaction is 2.5-6 hour under 70-90 ℃ temperature; Initiated polymerization becomes water-soluble high-molecular substance, and wherein said initiator is Potassium Persulphate, ammonium persulphate, ydrogen peroxide 50 or Sodium Persulfate, perhaps the mixture of any two kinds or three kinds of above-mentioned substance or four kinds;
(3) neutralization reaction: in above-mentioned substance, add alkali, adjustment pH value promptly obtains the polymeric retention aid solvent at 5-7; Wherein said alkali is sodium hydroxide, Pottasium Hydroxide, calcium hydroxide or yellow soda ash, or their any two kinds and two or more mixtures;
(4) the water-soluble polymer solubility promoter after the above-mentioned neutralization of adding in polycarboxylate water-reducer, the ratio of adding is the 2-20% of solid mass ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102598948A CN101921372B (en) | 2010-08-20 | 2010-08-20 | Preparation method of cosolvent by compounding concrete admixture |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102598948A CN101921372B (en) | 2010-08-20 | 2010-08-20 | Preparation method of cosolvent by compounding concrete admixture |
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| Publication Number | Publication Date |
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| CN101921372A CN101921372A (en) | 2010-12-22 |
| CN101921372B true CN101921372B (en) | 2012-07-04 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104609761B (en) * | 2015-02-13 | 2016-12-07 | 重庆欣材混凝土集团股份有限公司 | A kind of water reducing agent in series of polyocarboxy acid for concrete regulator and preparation method |
| CN107573783A (en) * | 2017-10-30 | 2018-01-12 | 惠州市华昱美实业有限公司 | A kind of metallic paint and its preparation technology |
| CN114522612A (en) * | 2022-03-22 | 2022-05-24 | 厦门宏发先科新型建材有限公司 | Preparation method and equipment of concrete water reducing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537126A (en) * | 2000-12-27 | 2004-10-13 | 株式会社日本触媒 | Polycarboxylic acid type copolymer, and preparation method and use thereof |
| CN1667009A (en) * | 2005-02-28 | 2005-09-14 | 江苏省建筑科学研究院有限公司 | A kind of carboxylic acid graft copolymer concrete slump retaining agent |
-
2010
- 2010-08-20 CN CN2010102598948A patent/CN101921372B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537126A (en) * | 2000-12-27 | 2004-10-13 | 株式会社日本触媒 | Polycarboxylic acid type copolymer, and preparation method and use thereof |
| CN1667009A (en) * | 2005-02-28 | 2005-09-14 | 江苏省建筑科学研究院有限公司 | A kind of carboxylic acid graft copolymer concrete slump retaining agent |
Non-Patent Citations (2)
| Title |
|---|
| 孙振平等.聚羧酸系减水剂大单体MPEGMA的制备.《建筑材料学报》.2009,第12卷(第1期),101-105. * |
| 李宁等.新型聚羧酸系高效减水剂的合成实验研究.《辽宁化工》.2009,第38卷(第3期),149-152. * |
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