CN106117459A - A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis - Google Patents
A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis Download PDFInfo
- Publication number
- CN106117459A CN106117459A CN201610585861.XA CN201610585861A CN106117459A CN 106117459 A CN106117459 A CN 106117459A CN 201610585861 A CN201610585861 A CN 201610585861A CN 106117459 A CN106117459 A CN 106117459A
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- Prior art keywords
- reducer
- room temperature
- water
- preparation
- polycarboxylate water
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 41
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 4
- 239000011718 vitamin C Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- ZJCOXZXHUMVTTE-UHFFFAOYSA-N 2-(prop-2-enoylamino)tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCC(CS(O)(=O)=O)NC(=O)C=C ZJCOXZXHUMVTTE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- MYOWBHNETUSQPA-UHFFFAOYSA-N tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCS(O)(=O)=O MYOWBHNETUSQPA-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 241000143437 Aciculosporium take Species 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- WWTCFWQBOOLMOL-UHFFFAOYSA-N 14-(prop-2-enoylamino)tetradecane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCCCCCCNC(=O)C=C WWTCFWQBOOLMOL-UHFFFAOYSA-N 0.000 abstract 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 abstract 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to additive for building material technical field, especially relate to polycarboxylate water-reducer of a kind of room temperature synthesis and preparation method thereof, by unsaturated polyether methyl allyl polyoxyethylene ether, hydrogen peroxide and 2 acrylamido myristyl sulfonic acid join and are made into end liquid in deionized water, then drip by acrylic acid, methacrylic acid and chain-transferring agent Thioglycolic acid composition solution A and vitamin C aqueous solution, stir, at room temperature carry out free radicals copolymerization reaction, after reaction terminates, the pH value of reaction system liquid caustic soda is regulated to 67, obtain polycarboxylate water-reducer, gained water reducer of the present invention can keep permanent dispersibility, and a chain length, water reducer stably dispersing performance is good, preparation technology is simple, can synthesize under room temperature, energy consumption is little, there is good economic benefit.
Description
Technical field
The present invention relates to additive for building material technical field, especially relate to the polycarboxylate water-reducer of a kind of room temperature synthesis
And preparation method thereof.
Background technology
Along with the development of building trade, in engineer applied, the requirement to water reducer steps up.Poly carboxylic acid series water reducer is
Novel, the environmental protection water reducer generally acknowledged both at home and abroad, have that volume is low, it is strong to protect plasticity, at the bottom of slump-loss, cement adaptability wide
Etc. advantage, develop such water reducer and there is good research and application prospect.
At present, the common method preparing polycarboxylate water-reducer is: 1. the direct copolymerization of polymerisable monomer: the letter of the method technique
Single, but first synthesize polymeric monomer, middle isolated and purified process is loaded down with trivial details, and industry cost for purification is higher, is not suitable for factorial praluction；2.
Polymerization Post functionalization method: the method mainly utilizes the polycarboxylic acid polymer of known molecular amount, at higher temperature under catalyst action
Under be grafted by esterification, at present this type of method adjust molecular weight difficulty, esterification yield is relatively low, and higher reaction temperature makes it possible to
Consumption is big, and the feature of environmental protection is not good enough.
Chinese patent (CN103172798A) discloses a kind of utilization unsaturated polyoxyethylene ether, 2-acrylamide-2-first
Base propane sulfonic acid, acrylic acid and acrylamide pass through free-radical polymerized high-performance polycarboxylic acids water reducing agent in aqueous, but
It is high to there is reaction temperature in the method, the problems such as the response time is long, and molecular weight is wayward.
Summary of the invention
For the shortcoming existing for above-mentioned prior art, it is an object of the invention to provide that a kind of molecular weight is controlled, diminishing
The preparation method of the polycarboxylate water-reducer of a kind of room temperature synthesis that rate height, little loss of slump and response time are short.
The technical scheme is that
The present invention, by using redox system, causes radical polymerization, makes reaction at room temperature to carry out, pass through
Adjustment vitamin C, with proportion relation suitable between thioglycolic acid, makes polyreaction the most still have high conversion, prevents former
The waste expected the generation being effectively controlled high temperature secondary reaction.This water reducer introduces 2-acrylamido myristyl sulfonic acid,
According to space steric effect, in water reducer, side chain is the longest, and water reducer stably dispersing performance is the best, and the present invention uses 2-acrylamide
Base myristyl sulfonic acid replaces traditional 2-acrylamide-2-methyl propane sulfonic, and side chain is longer, the water reducer water-reducing rate of synthesis
Height, function of slump protection is good, applied widely, is suitable for industrialization large-scale production.
Advantages of the present invention and beneficial effect:
The most at room temperature can synthesize, energy consumption is little, economic and environment-friendly, reduces production cost
2. present invention introduces monomer 2-acrylamido myristyl sulfonic acid, be substantially reduced reaction activity, improve altogether
Poly-ratio, the simultaneously slow releasing function of amido link, make the dispersibility that water reducer holding is permanent, and a chain length, water reducer stably dispersing
Performance is good.
3. the preparation method technique of the present invention is simple, and reaction condition is gentle, is advantageously implemented industrialized production.
Detailed description of the invention
Below by embodiment, the present invention will be further elaborated, and the description below is only for explaining the present invention, not
Its content is defined.
Embodiment 1
The polycarboxylate water-reducer of a kind of room temperature synthesis, is made up of the raw material of following weight portion:
Solution B: VC 1.4
Deionized water 130
The preparation method of the polycarboxylate water-reducer of a kind of room temperature synthesis: under room temperature, drips solution A, during dropping in end liquid
Between be 3 hours, in end liquid, drip solution B simultaneously, time for adding is 3.5 hours；After being added dropwise to complete, insulation continues reaction 30 points
Clock, being subsequently adding liquid caustic soda that mass concentration is 32% regulation pH value is 6-7, continues stirring reaction 20 minutes, both described poly-carboxylic
Acid water reducer.
Embodiment 2
The polycarboxylate water-reducer of a kind of room temperature synthesis, is made up of the raw material of following weight portion:
Solution B: VC 1.7
Deionized water 150
The preparation method of the polycarboxylate water-reducer of a kind of room temperature synthesis: under room temperature, drips solution A, during dropping in end liquid
Between be 3 hours, in end liquid, drip solution B simultaneously, time for adding is 3.5 hours；After being added dropwise to complete, insulation continues reaction 30 points
Clock, being subsequently adding liquid caustic soda that mass concentration is 32% regulation pH value is 6-7, continues stirring reaction 20 minutes, both described poly-carboxylic
Acid water reducer.
Embodiment 3
The polycarboxylate water-reducer of a kind of room temperature synthesis, is made up of the raw material of following weight portion:
Solution B: VC 2.1
Deionized water 170
The preparation method of the polycarboxylate water-reducer of a kind of room temperature synthesis: under room temperature, drips solution A, during dropping in end liquid
Between be 3 hours, in end liquid, drip solution B simultaneously, time for adding is 3.5 hours；After being added dropwise to complete, insulation continues reaction 30 points
Clock, being subsequently adding liquid caustic soda that mass concentration is 32% regulation pH value is 6-7, continues stirring reaction 20 minutes, both described poly-carboxylic
Acid water reducer.
Embodiment 4
The polycarboxylate water-reducer of a kind of room temperature synthesis, is made up of the raw material of following weight portion:
Solution B: VC 2.4
Deionized water 190
The preparation method of the polycarboxylate water-reducer of a kind of room temperature synthesis: under room temperature, drips solution A, during dropping in end liquid
Between be 3 hours, in end liquid, drip solution B simultaneously, time for adding is 3.5 hours；After being added dropwise to complete, insulation continues reaction 30 points
Clock, being subsequently adding liquid caustic soda that mass concentration is 32% regulation pH value is 6-7, continues stirring reaction 20 minutes, both described poly-carboxylic
Acid water reducer.
Comparative example 1
The polycarboxylate water-reducer of a kind of room temperature synthesis, is made up of the raw material of following weight portion:
Solution B: VC 2.1
Deionized water 170
The preparation method of the polycarboxylate water-reducer of a kind of room temperature synthesis: under room temperature, drips solution A, during dropping in end liquid
Between be 3 hours, in end liquid, drip solution B simultaneously, time for adding is 3.5 hours；After being added dropwise to complete, insulation continues reaction 30 points
Clock, being subsequently adding liquid caustic soda that mass concentration is 32% regulation pH value is 6-7, continues stirring reaction 20 minutes, both described poly-carboxylic
Acid water reducer.
Application Example
Use reference cement, test cement according to " Methods for testing uniformity of concrete admixture " (GB/T8077-2000)
Paste flowing degree, water reducer volume is the solid volume of folding, and test data is shown in Table 1.
Table 1
As can be seen from the table, the High-efficiency polycarboxylic acid water reducer that prepared by the present invention has that fluidity is big, the high spy of water-reducing rate
Point.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not limited by embodiment
System, the change made, modifies, combines, substitutes, simplifies and all should be under other any spirit without departing from the present invention and principle
Equivalence substitute mode, within being included in protection scope of the present invention.
Claims (3)
1. the preparation method of the polycarboxylate water-reducer of a room temperature synthesis, it is characterised in that comprise the following steps:
A. take the methyl allyl polyoxyethylene ether of weight portion, 30% hydrogen peroxide, 2-acrylamido myristyl sulfonic acid add
Enter in deionized water, be made into end liquid；
B. take the acrylic acid of weight portion, methacrylic acid, thioglycolic acid mixing, stir, wiring solution-forming A；
C. take the vitamin C of weight portion to join in deionized water and mix, stir, wiring solution-forming B；
D. under room temperature, dripping the solution A in step b in end liquid, time for adding is 3 hours, drips step c in end liquid simultaneously
In solution B, time for adding is 3.5 hours；
E., after being added dropwise to complete, carry out free radicals copolymerization reaction, insulation reaction 30 minutes, be subsequently adding the liquid that mass concentration is 32%
Alkali regulation pH value be 6-7, then stirring 20 minutes, both described polycarboxylate water-reducer.
The preparation method of polycarboxylate water-reducer the most according to claim 1, it is characterised in that: the parts by weight of raw materials used
Number is: methyl allyl polyoxyethylene ether 340-380,30% hydrogen peroxide 2.5-4.5,2-acrylamido myristyl sulfonic acid
5-10, acrylic acid (AA) 35-40, methacrylic acid (MAA) 5-10, Thioglycolic acid 1.5-2.2, vitamin C 1.4-2.4；
Described methyl allyl polyoxyethylene ether, 2-acrylamido myristyl sulfonic acid, acrylic acid, methacrylic acid are anti-
Answer monomer, with deionized water as solvent, carry out free radicals copolymerization reaction.
3. according to the preparation method of the polycarboxylate water-reducer described in any one of claim 1-2, it is characterised in that: described methyl
The molecular weight of allyl polyethenoxy ether is 2000-2400.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610585861.XA CN106117459A (en) | 2016-07-22 | 2016-07-22 | A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610585861.XA CN106117459A (en) | 2016-07-22 | 2016-07-22 | A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106117459A true CN106117459A (en) | 2016-11-16 |
Family
ID=57290370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610585861.XA Pending CN106117459A (en) | 2016-07-22 | 2016-07-22 | A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117459A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602762A (en) * | 2017-09-29 | 2018-01-19 | 济南大学 | For one kind with N, N methylene-bisacrylamides are micro- cross-linked polycarboxylic's high efficiency water reducing agent of cross-linking monomer and preparation method thereof |
| CN109627394A (en) * | 2018-11-30 | 2019-04-16 | 陕西科技大学 | A kind of polycarboxylate concrete dehydragent and preparation method thereof being adapted to Machine-made Sand |
| CN117069415A (en) * | 2023-10-16 | 2023-11-17 | 四川蜀道建筑科技有限公司 | Anti-urinary polycarboxylate superplasticizer, concrete and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004087602A1 (en) * | 2003-04-03 | 2004-10-14 | Construction Research & Technology Gmbh | Cement additive |
| CN104371075A (en) * | 2014-11-22 | 2015-02-25 | 萧县鑫固混凝土外加剂有限公司 | Method for preparing polycarboxylate superplasticizer synthesized at room temperature |
-
2016
- 2016-07-22 CN CN201610585861.XA patent/CN106117459A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004087602A1 (en) * | 2003-04-03 | 2004-10-14 | Construction Research & Technology Gmbh | Cement additive |
| CN104371075A (en) * | 2014-11-22 | 2015-02-25 | 萧县鑫固混凝土外加剂有限公司 | Method for preparing polycarboxylate superplasticizer synthesized at room temperature |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602762A (en) * | 2017-09-29 | 2018-01-19 | 济南大学 | For one kind with N, N methylene-bisacrylamides are micro- cross-linked polycarboxylic's high efficiency water reducing agent of cross-linking monomer and preparation method thereof |
| CN109627394A (en) * | 2018-11-30 | 2019-04-16 | 陕西科技大学 | A kind of polycarboxylate concrete dehydragent and preparation method thereof being adapted to Machine-made Sand |
| CN117069415A (en) * | 2023-10-16 | 2023-11-17 | 四川蜀道建筑科技有限公司 | Anti-urinary polycarboxylate superplasticizer, concrete and preparation method thereof |
| CN117069415B (en) * | 2023-10-16 | 2024-01-26 | 四川蜀道建筑科技有限公司 | Anti-urinary polycarboxylate superplasticizer, concrete and preparation method thereof |
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