CN105417985A - Multi-branched polycarboxylate superplasticizer with tertiary amine groups and preparation method of polycarboxylate superplasticizer - Google Patents
Multi-branched polycarboxylate superplasticizer with tertiary amine groups and preparation method of polycarboxylate superplasticizer Download PDFInfo
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- CN105417985A CN105417985A CN201510940674.4A CN201510940674A CN105417985A CN 105417985 A CN105417985 A CN 105417985A CN 201510940674 A CN201510940674 A CN 201510940674A CN 105417985 A CN105417985 A CN 105417985A
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- 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
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- 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
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- 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
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- 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a multi-branched polycarboxylate superplasticizer with tertiary amine groups. The polycarboxylate superplasticizer is mainly formed through aqueous solution polymerization of four monomers including TPEG, acrylic acid, acrylate and 2-(dimethylamino)ethyl acrylate under the action of a polymerization initiator and has a comb type molecular structure, a main chain has negative ions, and branch chains have non-ionic polyoxypropylene hydrophilic structures and the tertiary amine groups. The product is added to concrete with higher cement content and can significantly improve the cement resistance and slump retaining performance of the concrete.
Description
Technical field
The present invention relates to a kind of mobility retention agent for materials such as grout, mortar and concrete, particularly relate to much higher side chain polycarboxylate water-reducer of a kind of anti-mud performance and preparation method thereof.
Background technology
Grout, sand-cement slurry and cement concrete material are the maximum a kind of material of construction of whole world consumption, widely use in a large number in all kinds of engineerings such as urban construction, Infrastructure, industrial civil building, hydro project, military engineering, transportation engineering.One of characteristic of cement concrete material is using ultimate compression strength as major design index.According to concrete strength rule, determine that the determinative of the ultimate compression strength of concrete base building material is water cement ratio, the water cement ratio of high-strength cement material require is less, and namely Water Usage Per Unit Volume is lower, and the strength of materials is higher.Can application property and serviceability in order to what keep newly mixing cement-based material, certain unnecessary water must be had could to meet the intensity of material and the requirement of application property.In order to reduce water cement ratio further, people have invented lignin sulfonate water reducer, naphthalene sulfonic salt formaldehyde condensation products, trimeric cyanamide sulfonation formaldehyde condensation products, acetone sulfonation formaldehyde condensation products and high-efficiency water-reducing agent of poly-carboxylic acid, this kind of material is joined the water cement ratio (w/C) that significantly can reduce cement-base composite material in concrete, this kind of have surface-active macromolecule dispersing agent, solve the basic demand of intensity and application property, meeting with concrete is the modern cement-based material Modern Construction needs of representative, modern concrete construction facilitates again widely using of concrete admixture, there is no concrete admixture or water reducer, modern concrete construction can not realize.
Polycarboxylic acids dehydragent is current state-of-the art efficient cement water reducing agent, and this water reducer is comb-type structure, different with the on-link mode (OLM) of side chain according to main chain, and polyester and polyethers and polyester polyethers can be divided into mix class.The feature of this kind of material is by artificial synthesis, and product controllability is comparatively strong, but this kind of water reducer in use still exists liquidity value added problem faster.
Summary of the invention
The present invention is mainly for the too fast problem of polycarboxylic acid concrete admixture slump-loss in use in prior art, and particularly application occasion the problems referred to above that silt content is high are especially outstanding, proposition is a kind of protects the much higher side chain polycarboxylate water-reducer of anti-mud performance that collapses.
Another object of the present invention is also to provide the above-mentioned preparation method with the multi-branched polycarboxylic water reducer of anti-mud function of slump protection.
Object of the present invention can be achieved through the following technical solutions:
Have a racemosus chain polycarboxylate water-reducer for tertiary amine groups, it is characterized in that: this polycarboxylate water-reducer molecule is comb-type structure, and main chain has negatively charged ion, side chain has non-ionic polyoxyethylene or polyoxypropylene hydrophilic-structure and tertiary amine group; This polycarboxylate water-reducer under the effect of polymerization starter, carries out aqueous solution polymerization by following monomer reactant to form:
1) monomer A: be selected from one or more the mixture in vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and fumaric acid, monomer A accounts for the 3-10% of total reactant weight;
2) monomers B: its structural formula is as follows:
(CH
3)
2C=CHCH
2O[CH
2CH
2O]
m[CH
2CH(CH
3)-O]
n-OH
Wherein, m is 20-60, n is 0-10, and in monomers B, the content of polyoxyethylene glycol is 0.5-2%; Monomers B accounts for the 82-90% of total reactant weight;
3) monomer C: molecular formula is CH
2=C (R
1) COOR
2, wherein R
1for H or CH
3, R
2for CH
3-, CH
3cH
2-, other alkyl, HO-CH
2cH
2o-, HOCH
2cH (CH
3) O-or (CH
2cHO)-CH
2one in O-; Monomer C accounts for the 3-6% of total reactant weight; 4) monomer D: be selected from one or both the mixture in dimethylaminoethyl methacrylate or acrylate; Monomer D accounts for the 0.5-2% of total reactant weight;
5) deionized water of above-mentioned four kinds of monomer reactant gross weight 100-200% in addition again.
As preferred scheme, in described monomers B, m is 20-50, n is 5-10, and number-average molecular weight is 2000-3000.
More preferred scheme is: monomer A is acrylic or methacrylic acid; Monomers B is isopentenol polyoxyethylene ether or methacrylic polyoxyethylenated alcohol; Monomer C is the one in methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate, Hydroxyethyl acrylate.
What the present invention proposed a kind ofly prepares above-mentioned any one and has the preparation method of the multi-branched polycarboxylic water reducer of tertiary amine groups, and the method comprises the following steps successively:
1) monomers B is put in four mouthfuls of reaction flasks, blow three times with nitrogen, be heated to 10-100 DEG C with water-bath or oil bath;
2) in four mouthfuls of reaction flasks, drip the mixed aqueous solution of monomer A, C, D and chain-transfer agent respectively, drip the aqueous solution of initiators for polymerization in addition, control monomer and initiator solution add simultaneously, time for adding is 2-5 hour, after being added dropwise to complete, polyreaction 1-2 hour, polymeric reaction temperature 40-75 DEG C;
3) regulate the pH value of reactant aqueous solution to 6.0-6.5 with sodium hydroxide, described polycarboxylate water-reducer can be obtained.
In aforesaid method, described initiators for polymerization is selected from one or both the mixture in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, sodium formaldehyde sulphoxylate and xitix, and chain-transfer agent is Thiovanic acid or thiohydracrylic acid.
In aforesaid method, the preferred consumption of described initiators for polymerization is the 0.5-1.5% of reaction monomers gross weight.
In above-mentioned polymerization reaction system, the reactant soluble solids concentration of total reactant is 35-50%, preferably 40%.
The multi-branched polycarboxylic water reducer of tertiary amine groups that prepared by the present invention have not only itself has good anti-mud and protects the effect of collapsing, and, time used in combination with the polycarboxylate water-reducer of other classifications, more can significantly improve the function of slump protection of other products.
The multi-branched polycarboxylic water reducer with tertiary amine groups provided by the invention, compared with like product in the market, has the evident characteristic of the following aspects:
(1) main chain has negatively charged ion, nonionic, side chain has tertiary amine group, molecular structure is different from existing polycarboxylic acids dehydragent, to normal sands building stones, particularly high to silt content sand material has outstanding anti-mud and protects effect of collapsing, if be used alone, volume is that 0.10-0.22% (calculating with all gelling material) effect is better.
(2) in molecular structure, without slow setting component, concrete normal time of coagulation is not affected different seasons.
(3) more to silt content concrete especially has better function of slump protection.
Embodiment
For further illustrating embodiment of the present invention, now enumerate following examples, embodiment provides by way of illustration, but the scope of protection of present invention is never confined to following concrete embodiment.
embodiment 1
Monomer A 7g (vinylformic acid)
Monomers B 80g (isopentenol polyoxyethylene ether, EO is 50)
Monomer C4.0g (methyl acrylate)
Monomer D0.5g (dimethylaminoethyl methacrylate (being called for short DMAM))
80g monomers B is put in four-hole boiling flask, blows three times with nitrogen, be heated to 65 DEG C with oil bath.Drip monomer A respectively, the aqueous solution of the initiator of C, D and chain-transfer agent thiohydracrylic acid 0.33g and deionized water 68g, 0.8g ammonium persulphate and 68g deionized water.Two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulate the pH value of reactant aqueous solution to 6.0-6.5, cool to 30 DEG C with sodium hydroxide.Obtain the polycarboxylic acid aqueous solution that content is 40%.Be designated as water reducer PC-1.
embodiment 2
Monomer A 5g (methacrylic acid)
Monomers B 80g (methacrylic polyoxyethylenated alcohol, EO is 50)
Monomer C4g (ethyl propenoate)
Monomer D0.7g dimethylaminoethyl methacrylate (being called for short DMAM)
80g monomers B is put in four-hole boiling flask, blows three times with nitrogen, be heated to 65 DEG C with oil bath.Drip monomer A respectively, the aqueous solution of the initiator of C, D and chain-transfer agent Thiovanic acid 0.35g and deionized water 68g, 0.7g ammonium persulphate and 68g deionized water.Two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulate the pH value of reactant aqueous solution to 6.0-6.5, cool to 30 DEG C with sodium hydroxide.Obtain the polycarboxylic acid aqueous solution that content is 40%.Be designated as water reducer PC-2.
embodiment 3
Monomer A 7g (vinylformic acid)
Monomers B 80g (isopentenol polyoxyethylene ether, EO is 50)
Monomer C4g (Propylene glycol monoacrylate)
Monomer D0.5g (acrylate (being called for short DMA))
80g monomers B is put in four-hole boiling flask, blows three times with nitrogen, be heated to 65 DEG C with oil bath.Drip monomer A respectively, the aqueous solution of the initiator of C, D and chain-transfer agent thiohydracrylic acid 0.33g and deionized water 68g, 0.8g ammonium persulphate and 68g deionized water.Two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulate the pH value of reactant aqueous solution to 6.0-6.5, cool to 30 DEG C with sodium hydroxide.Obtain the polycarboxylic acid aqueous solution that content is 40%.Be designated as water reducer PC-3.
embodiment 4
Monomer A 8g (vinylformic acid)
Monomers B 80g (isopentenol polyoxyethylene ether, EO is 50)
Monomer C4g (Hydroxyethyl acrylate)
Monomer D0.5g (acrylate (being called for short DMA))
80g monomers B is put in four-hole boiling flask, blows three times with nitrogen, be heated to 65 DEG C with oil bath.Drip monomer A respectively, the aqueous solution of the initiator of C, D and chain-transfer agent thiohydracrylic acid 0.33g and deionized water 68g, 0.8g ammonium persulphate and 72g deionized water.Two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulate the pH value of reactant aqueous solution to 6.0-6.5, cool to 30 DEG C with sodium hydroxide.Obtain the polycarboxylic acid aqueous solution that content is 40%.Be designated as water reducer PC-4.
embodiment 5
Monomer A 9g (vinylformic acid)
Monomers B 80g (isopentenol polyoxyethylene ether, EO is 50)
Monomer C5.5g (Propylene glycol monoacrylate)
Monomer D0.5g (acrylate (being called for short DMA))
80g monomers B is put in four-hole boiling flask, blows three times with nitrogen, be heated to 65 DEG C with oil bath.Drip monomer A respectively, the aqueous solution of the initiator of C, D and chain-transfer agent thiohydracrylic acid 0.33g and deionized water 68g, 0.8g ammonium persulphate and 74g deionized water.Two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulate the pH value of reactant aqueous solution to 6.0-6.5, cool to 30 DEG C with sodium hydroxide.Obtain the polycarboxylic acid aqueous solution that content is 40%.Be designated as water reducer PC-5.
comparative example
Monomer A 9g (vinylformic acid)
Monomers B 80g (isopentenol polyoxyethylene ether, EO is 50)
80g monomers B is put in four-hole boiling flask, blows three times with nitrogen, be heated to 65 DEG C with oil bath.Drip monomer A and chain-transfer agent thiohydracrylic acid 0.33g and deionized water 68g water respectively, the aqueous solution of the initiator of 0.8g ammonium persulphate and 68g deionized water.Two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulate the pH value of reactant aqueous solution to 6.0-6.5, cool to 30 DEG C with sodium hydroxide.Obtain the polycarboxylic acid aqueous solution that content is 40%.Be designated as water reducer PC-0.
Flowing degree of net paste of cement, admixture dosage is 1.4g, 87g water, 300g Wan An 42.5 ordinary Portland cement.Concrete experiments adopts same cement, and volume is 0.22% (cement weight), and the degree of mobilization experiment of sand-cement slurry is reference national standard: GB/T2419-2005 Test method for fluidity of cement mortar
The flowing degree of net paste of cement rheological parameters' change with time list (unit: millimeter) of sample
| Product designation | Initial paste flowing degree | Paste flowing degree after one hour |
| PC-0 | 210 | 188 |
| PC-1 | 220 | 230 |
| PC-2 | 222 | 225 |
| PC-3 | 240 | 251 |
| PC-4 | 215 | 226 |
| PC-5 | 223 | 232 |
The sand-cement slurry degree of mobilization rheological parameters' change with time list (unit: millimeter) of sample
| Product designation | Initial Mortar'S Flowability | Mortar'S Flowability after one hour |
| PC-0 | 198 | 189 |
| PC-1 | 201 | 210 |
| PC-2 | 204 | 216 |
| PC-3 | 211 | 231 |
| PC-4 | 207 | 218 |
| PC-5 | 203 | 217 |
Claims (9)
1. have a racemosus chain polycarboxylate water-reducer for tertiary amine groups, it is characterized in that: the molecule of this polycarboxylate water-reducer is comb-type structure, and main chain has negatively charged ion, side chain has non-ionic polyoxyethylene or polyoxypropylene hydrophilic-structure and tertiary amine group; This polycarboxylate water-reducer under the effect of polymerization starter, carries out aqueous solution polymerization by following monomer reactant to form: 1) monomer A: be selected from one or more the mixture in vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid and fumaric acid, monomer A accounts for the 3-10% of total reactant weight;
2) monomers B: its structural formula is as follows:
(CH
3)
2C=CHCH
2O[CH
2CH
2O]
m[CH
2CH(CH
3)-O]
n-OH
Wherein, m is 20-60, n is 0-10, and in monomers B, the content of polyoxyethylene glycol is 0.5-2%; Monomers B accounts for the 82-90% of total reactant weight;
3) monomer C: molecular formula is CH
2=C (R
1) COOR
2, R
1for H or CH
3; R
2for CH
3-, CH
3cH
2-, other alkyl, HO-CH
2cH
2o-, HOCH
2cH (CH
3) O-or (CH
2cHO)-CH
2one in O-; Monomer C accounts for the 3-6% of total reactant weight;
4) monomer D: be selected from one or both the mixture in dimethylaminoethyl methacrylate or acrylate; Monomer D accounts for the 0.5-2% of total reactant weight;
5) deionized water of above-mentioned four kinds of monomer reactant gross weight 100-200% in addition again.
2. have the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 1, it is characterized in that: in the molecular formula of described monomers B, m is 20-50, n is 5-10, and the number-average molecular weight of monomers B is 2000-3000.
3. there is the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 2, it is characterized in that: monomer A is acrylic or methacrylic acid; Monomers B is isopentenol polyoxyethylene ether or methacrylic polyoxyethylenated alcohol; Monomer C is the one in methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate, Hydroxyethyl acrylate.
4. as described in claims 1 to 3, any one has a preparation method for the multi-branched polycarboxylic water reducer of tertiary amine groups, it is characterized in that: carry out according to the following steps successively:
1) monomers B is put in four mouthfuls of reaction flasks, blow three times with nitrogen, be heated to 10-100 DEG C with water-bath or oil bath;
2) in above-mentioned four mouthfuls of reaction flasks, drip the mixed aqueous solution of monomer A, C, D and chain-transfer agent respectively, drip the aqueous solution of initiators for polymerization in addition, control monomer and initiator solution add simultaneously, time for adding is 2-5 hour, after being added dropwise to complete, polyreaction 1-2 hour, polymeric reaction temperature 40-75 DEG C;
3) regulate the pH value of reactant aqueous solution to 6.0-6.5 with sodium hydroxide, described polycarboxylate water-reducer can be obtained;
In above-mentioned steps, described initiators for polymerization is selected from one or both the mixture in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, sodium formaldehyde sulphoxylate and xitix, and chain-transfer agent is Thiovanic acid or thiohydracrylic acid.
5. there is the preparation method of the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 4, it is characterized in that: the consumption of described initiators for polymerization is the 0.5-1.5% of reaction monomers gross weight.
6. have the preparation method of the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 5, it is characterized in that: in reaction system, the concentration of soluble solids is 35-50%.
7. have the preparation method of the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 6, it is characterized in that: in reaction system, the concentration of soluble solids is 40%.
8. there is the preparation method of the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 4, it is characterized in that: body of itemizing below is reactant:
Monomer A is vinylformic acid, 7g,
Monomers B is isopentenol polyoxyethylene ether, and EO is 50,80g,
Monomer C is Propylene glycol monoacrylate, 4g,
Monomer D is acrylate, 0.5g;
Carry out in the steps below successively: 80g monomers B is put in four-hole boiling flask, three times are blown with nitrogen, 65 DEG C are heated to oil bath, drip monomer A respectively, C, D and chain-transfer agent thiohydracrylic acid 0.33g and deionized water 68g, the aqueous solution of the initiator of 0.8g ammonium persulphate and 68g deionized water, two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulates the pH value of reactant aqueous solution to 6.0-6.5 with sodium hydroxide, cool to 30 DEG C, obtain the polycarboxylic acid aqueous solution that content is 40%.
9. there is the preparation method of the multi-branched polycarboxylic water reducer of tertiary amine groups according to claim 4, it is characterized in that: body of itemizing below is reactant:
Monomer A is methacrylic acid, 5g,
Monomers B is methacrylic polyoxyethylenated alcohol, and EO is 50,80g,
Monomer C is ethyl propenoate, 4g,
Monomer D is dimethylaminoethyl methacrylate, 0.7g;
Carry out in the steps below successively: 80g monomers B is put in four-hole boiling flask, three times are blown with nitrogen, 65 DEG C are heated to oil bath, drip monomer A respectively, C, D and chain-transfer agent Thiovanic acid 0.35g and deionized water 68g, the aqueous solution of the initiator of 0.7g ammonium persulphate and 68g deionized water, two liquid drip simultaneously, time for adding 3 hours, soaking time 2 hours, regulates the pH value of reactant aqueous solution to 6.0-6.5 with sodium hydroxide, cool to 30 DEG C, obtain the polycarboxylic acid aqueous solution that content is 40%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317342A (en) * | 2016-08-17 | 2017-01-11 | 广州市建筑科学研究院有限公司 | Slow-release early-strengthening polycarboxylate superplasticizer and preparation method thereof |
| CN110642994A (en) * | 2019-09-27 | 2020-01-03 | 贵州石博士科技有限公司 | Preparation method of stone powder adaptive polycarboxylate superplasticizer |
| CN111303352A (en) * | 2020-03-04 | 2020-06-19 | 山西佳维新材料股份有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN114057955A (en) * | 2020-08-04 | 2022-02-18 | 江苏苏博特新材料股份有限公司 | Slow-release defoaming polymer cement dispersant and preparation method thereof |
| CN114634602A (en) * | 2022-05-19 | 2022-06-17 | 济南城建集团有限公司 | Hyperbranched solid polycarboxylic acid water reducing agent and preparation method thereof |
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| CN102617065A (en) * | 2012-03-06 | 2012-08-01 | 上海市建筑科学研究院(集团)有限公司 | Multi-branch polycarboxylic acid water reducing agent with slump-retaining performance and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617065A (en) * | 2012-03-06 | 2012-08-01 | 上海市建筑科学研究院(集团)有限公司 | Multi-branch polycarboxylic acid water reducing agent with slump-retaining performance and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317342A (en) * | 2016-08-17 | 2017-01-11 | 广州市建筑科学研究院有限公司 | Slow-release early-strengthening polycarboxylate superplasticizer and preparation method thereof |
| CN106317342B (en) * | 2016-08-17 | 2018-10-23 | 广州市建筑科学研究院有限公司 | A kind of sustained release Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN110642994A (en) * | 2019-09-27 | 2020-01-03 | 贵州石博士科技有限公司 | Preparation method of stone powder adaptive polycarboxylate superplasticizer |
| CN111303352A (en) * | 2020-03-04 | 2020-06-19 | 山西佳维新材料股份有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN114057955A (en) * | 2020-08-04 | 2022-02-18 | 江苏苏博特新材料股份有限公司 | Slow-release defoaming polymer cement dispersant and preparation method thereof |
| CN114057955B (en) * | 2020-08-04 | 2024-05-03 | 江苏苏博特新材料股份有限公司 | Slow-release defoaming polymer cement dispersing agent and preparation method thereof |
| CN114634602A (en) * | 2022-05-19 | 2022-06-17 | 济南城建集团有限公司 | Hyperbranched solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN114634602B (en) * | 2022-05-19 | 2022-07-29 | 济南城建集团有限公司 | Preparation method of hyperbranched solid polycarboxylate superplasticizer |
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