CN108034025B - Preparation method of high-dispersion polycarboxylate superplasticizer - Google Patents
Preparation method of high-dispersion polycarboxylate superplasticizer Download PDFInfo
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- CN108034025B CN108034025B CN201711468666.XA CN201711468666A CN108034025B CN 108034025 B CN108034025 B CN 108034025B CN 201711468666 A CN201711468666 A CN 201711468666A CN 108034025 B CN108034025 B CN 108034025B
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- 239000006185 dispersion Substances 0.000 title claims abstract description 22
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 31
- -1 polyoxyethylene chain Polymers 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 84
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 37
- 229920000570 polyether Polymers 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 30
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 30
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims description 27
- 150000002148 esters Chemical class 0.000 claims description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical group CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- ZYJWMQAABJXBHW-UHFFFAOYSA-N 1,8-bis(sulfanyl)octane-3,6-dione Chemical group SCCC(=O)CCC(=O)CCS ZYJWMQAABJXBHW-UHFFFAOYSA-N 0.000 claims description 7
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- HPSQKMAZWIIJBT-UHFFFAOYSA-N 2-(benzenecarbonothioylsulfanyl)propanoic acid Chemical compound OC(=O)C(C)SC(=S)C1=CC=CC=C1 HPSQKMAZWIIJBT-UHFFFAOYSA-N 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- YNKQCPNHMVAWHN-UHFFFAOYSA-N 4-(benzenecarbonothioylsulfanyl)-4-cyanopentanoic acid Chemical compound OC(=O)CCC(C)(C#N)SC(=S)C1=CC=CC=C1 YNKQCPNHMVAWHN-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000004568 cement Substances 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000004567 concrete Substances 0.000 description 7
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 108091029845 Aminoallyl nucleotide Proteins 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004575 stone Substances 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
-
- 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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- 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
Abstract
The invention discloses a preparation method of a high-dispersion polycarboxylate superplasticizer. Compared with the conventional solution polymerization method, the method has the advantages of high reaction speed, no need of heating, narrow molecular weight distribution, low cost, simple and convenient operation, easy industrial production and wide application prospect. The prepared polycarboxylic acid water reducer has stable performance, a comb-shaped molecular structure, a main chain containing polar groups and side chains containing polyoxyethylene chain segments to form space barrier, is beneficial to improving the dispersibility and the dispersibility retention capacity of cement, and embodies the advantages of low mixing amount, high dispersibility, high slump resistance and the like.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a high-dispersion polycarboxylic acid water reducer.
Background
With the development of high performance and multifunctionality of concrete, the concrete is required to have high workability, high strength and high durability and to be applicable to many special cases. Superplasticizers with ultra-dispersing properties have become one of the indispensable components in high-performance concrete.
In recent years, with the increasing importance of the country on energy conservation and emission reduction and the rapid popularization of the low-carbon economic concept, scientific and technological workers pay attention to how to reduce the energy consumption of the concrete water reducing agent while striving to improve the performance of the concrete water reducing agent. In particular, enterprises are striving to find products with low energy consumption, which not only can save cost, but also can reduce troubles brought by examination and approval of boilers.
On the one hand, most of the processes for producing the polycarboxylate superplasticizer currently adopt heating modes, such as steam heating and heat transfer oil heating, which can cause environmental pollution.
On the other hand, the production process of the existing polycarboxylic acid water reducing agent is long, generally needs about 4-5 hours, the production efficiency is low, and therefore the polycarboxylic acid water reducing agent needs to be stored in advance, needs to occupy certain stock, causes resource waste, and has large fixed asset investment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a high-dispersion polycarboxylic acid water reducing agent.
The technical scheme of the invention is as follows:
a preparation method of a high-dispersion polycarboxylate superplasticizer comprises the following steps:
(1) at 70-80 ℃, reacting a polyether monomer with vinylamine for 3-5h under the catalytic action of metalloporphyrin/TBHP to obtain an amine-terminated polyether monomer, wherein the mass ratio of the polyether monomer to the vinylamine to the metalloporphyrin/TBHP is 100: 3-10: 0.1-2;
(2) at 70-80 ℃, polyethylene glycol with molecular weight of 2000-2300 and methacrylic acid are subjected to esterification reaction under the action of p-toluenesulfonic acid and hydroquinone for 6-8h to prepare a polyethylene glycol dimethacrylate monomer, wherein the mass ratio of the polyethylene glycol, the methacrylic acid, the p-toluenesulfonic acid and the polymerization inhibitor is as follows: 100: 5-20: 1-5: 0.1-2.
(3) Adding the amine-terminated polyether monomer prepared in the step (1) and water into a reactor for dissolving, then placing the reactor under ultraviolet irradiation, and dropwise adding the first solution and the second solution at a constant speed within 1-2h for polymerizationAfter the dropwise addition, adding an alkaline regulator to neutralize until the pH value is 6-7, so as to obtain a crosslinked reticular polymer, namely the high-dispersion polycarboxylate superplasticizer, wherein the first solution is an aqueous solution of a photoinitiator and a chain transfer agent, and the second solution is an aqueous solution of an unsaturated acid, an unsaturated phosphate ester and the ester monomer prepared in the step (2); the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2(ii) a The mass ratio of the amine-terminated polyether monomer, the unsaturated acid, the unsaturated phosphate ester and the ester monomer is 100: 10-20: 3-5: 20-30, the dosage of the photoinitiator is 1-5% of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the chain transfer agent is 0.1-1% of the total mass of the amine-terminated polyether monomer and the ester monomer;
the polyether monomer is allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether or isopentenyl polyoxyethylene ether, the vinylamine is diethylenetriamine or triethylenetetramine, the unsaturated acid is acrylic acid, methacrylic acid, itaconic acid or maleic acid, the unsaturated phosphate is diethyl vinylphosphonate or 2-methyl-2-phosphinyl tris (oxy-2, 1-ethylene) acrylate, and the total amount of the water enables the mass concentration of the prepared high-dispersion polycarboxylic acid water reducer to be 45-55%.
In a preferred embodiment of the present invention, the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl methanone, or 2-hydroxy-methylphenyl propane-1-one.
In a preferred embodiment of the present invention, the chain transfer agent is 3, 6-dioxo-1, 8-octanedithiol, 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid or 2- (phenylthiocarbonylthio) propanoic acid.
In a preferred embodiment of the present invention, the alkaline modifier is sodium hydroxide, sodium silicate or ethanolamine.
The invention has the beneficial effects that: compared with the conventional solution polymerization method, the method has the advantages of high reaction speed, no need of heating, narrow molecular weight distribution, low cost, simple and convenient operation, easy industrial production and wide application prospect. The prepared polycarboxylic acid water reducer has stable performance, a comb-shaped molecular structure, a main chain containing polar groups and side chains containing polyoxyethylene chain segments to form space barrier, is beneficial to improving the dispersibility and the dispersibility retention capacity of cement, and embodies the advantages of low mixing amount, high dispersibility, high slump resistance and the like.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) Terminal amination of polyether monomer: and reacting the allyl polyoxyethylene ether with diethylenetriamine under the catalysis of metalloporphyrin/TBHP at 70-80 ℃ for 3-5h to obtain the terminal amino allyl polyoxyethylene ether. Wherein the mass ratio of allyl polyoxyethylene ether to diethylenetriamine to metalloporphyrin to TBHP is as follows: 100: 8: 1.
(2) Preparing an ester monomer: at 70-80 deg.C, polyethylene glycol (molecular weight is 2200) and methacrylic acid are esterified under the action of catalyst, p-toluenesulfonic acid, polymerization inhibitor and hydroquinone for 6-8h to prepare polyethylene glycol dimethacrylate monomer. Wherein the mass ratio of polyethylene glycol (molecular weight is 2200), methacrylic acid, p-toluenesulfonic acid and polymerization inhibitor is as follows: 100: 15: 3: 0.7.
(3) And (2) adding the terminal amino allyl polyoxyethylene ether prepared in the step (1) and water into a reactor for dissolving, placing the reactor under ultraviolet irradiation, dropwise adding the first solution and the second solution at a constant speed within 1.5h for polymerization, and after dropwise adding, adding a sodium hydroxide solution for neutralization until the pH value is 6-7 to obtain a crosslinked reticular polymer, namely the high-dispersion polycarboxylic acid water reducing agent. Wherein the first solution is an aqueous solution of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and 3, 6-dioxo-1, 8-octanedithiol, and the second solution is an aqueous solution of methacrylic acid, diethyl vinylphosphonate and a polyethylene glycol dimethacrylate monomer; the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2. Wherein: terminal amino allyl polyoxyethylene ether and methyl propylThe mass ratio of the olefine acid, the diethyl vinylphosphonate and the polyethylene glycol dimethacrylate monomer is 100: 10: 4: 30. The dosage of the 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is 2% of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the 3, 6-dioxo-1, 8-octanedithiol is 0.7% of the total mass of the amine-terminated polyether monomer and the ester monomer.
Wherein the amount of the water used in the steps enables the mass concentration of the high-dispersion polycarboxylic acid water reducing agent to be 50%.
Example 2
(1) Terminal amination of polyether monomer: under the catalysis of metalloporphyrin/TBHP at 70-80 ℃, reacting methyl allyl polyoxyethylene ether with triethylene tetramine for 3-5h to obtain the terminal amino methyl allyl polyoxyethylene ether. Wherein the mass ratio of the methyl allyl polyoxyethylene ether to the triethylene tetramine to the metalloporphyrin to the TBHP is as follows: 100: 5: 0.5.
(2) Preparing an ester monomer: polyethylene glycol (molecular weight 2200) with methacrylic acid at 70-80 ℃ in the presence of a catalyst: p-toluenesulfonic acid and inhibitor: and (3) carrying out esterification reaction under the action of hydroquinone for 6-8h to prepare the polyethylene glycol dimethacrylate monomer. Wherein the mass ratio of polyethylene glycol (molecular weight is 2200), methacrylic acid, p-toluenesulfonic acid and polymerization inhibitor is as follows: 100: 20: 2: 1.
(3) And (2) adding the terminal amino methyl allyl polyoxyethylene ether prepared in the step (1) and water into a reactor for dissolving, placing the reactor under ultraviolet irradiation, dropwise adding the first solution and the second solution at a constant speed within 1.5h for polymerization, and after dropwise adding, adding a sodium silicate solution for neutralization until the pH value is 6-7 to obtain a cross-linked reticular polymer, namely the high-dispersion polycarboxylic acid water reducing agent. Wherein the first solution is an aqueous solution of 1-hydroxy-cyclohexyl-phenyl ketone and 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid, and the second solution is an aqueous solution of acrylic acid, 2-methyl-2-propenoic acid phosphinyl tris (oxy-2, 1-ethylene) ester and polyethylene glycol dimethacrylate monomer; the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2. Wherein: terminal amino methyl allyl polyoxyethylene ether, acrylic acid, 2-methyl-2-propyleneThe mass ratio of the acid phosphinyl tris (oxy-2, 1-ethylene) ester to the polyethylene glycol dimethacrylate monomer is 100: 15: 5: 20. The dosage of the 1-hydroxy-cyclohexyl-phenyl ketone is 3 percent of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid is 0.5 percent of the total mass of the amine-terminated polyether monomer and the ester monomer.
Wherein the amount of the water used in the steps enables the mass concentration of the high-dispersion polycarboxylic acid water reducing agent to be 50%.
Example 3
(1) Terminal amination of polyether monomer: at 70-80 ℃, the isopentenyl polyoxyethylene ether monomer reacts with diethylenetriamine under the catalysis of metalloporphyrin/TBHP for 3-5h to obtain the terminal amino isopentenyl polyoxyethylene ether monomer. Wherein the mass ratio of the isopentenyl polyoxyethylene ether to the diethylenetriamine to the metalloporphyrin to the TBHP is as follows: 100: 4: 1.2.
(2) Preparing an ester monomer: at 70-80 deg.C, polyethylene glycol (molecular weight is 2200) and methacrylic acid are esterified under the action of catalyst, p-toluenesulfonic acid, polymerization inhibitor and hydroquinone for 6-8h to prepare polyethylene glycol dimethacrylate monomer. Wherein the mass ratio of polyethylene glycol (with the molecular weight of 2200) to methacrylic acid to p-toluenesulfonic acid to polymerization inhibitor is as follows: 100: 8: 2: 0.3.
(3) And (2) adding the terminal amino isopentenyl polyoxyethylene ether monomer prepared in the step (1) and water into a reactor for dissolving, placing the reactor under ultraviolet irradiation, dropwise adding the first solution and the second solution at a constant speed within 1-2h for polymerization reaction, and after dropwise adding, adding ethanolamine for neutralization until the pH is 6-7 to obtain a crosslinked reticular polymer, namely the high-dispersion polycarboxylic acid water reducer. Wherein the first solution is an aqueous solution of 2-hydroxy-methylphenylpropane-1-one and 2- (phenylthiocarbonylthio) propionic acid, and the second solution is an aqueous solution of itaconic acid, diethyl vinylphosphonate and diethyl vinylphosphonate monomers; the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2. Wherein: terminal amino isopentenyl polyoxyethylene ether monomer, itaconic acid, diethyl vinylphosphonate and polyethylene glycol dimethacrylateThe mass ratio of the monomers is 100: 12: 3: 24. The dosage of the 2-hydroxy-methyl phenyl propane-1-ketone is 1 percent of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the 2- (phenyl thiocarbonylthio) propionic acid is 0.3 percent of the total mass of the amine-terminated polyether monomer and the ester monomer.
Wherein the amount of the water used in the steps enables the mass concentration of the high-dispersion polycarboxylic acid water reducing agent to be 50%.
Example 4
(1) Terminal amination of polyether monomer: under the catalysis of metalloporphyrin/TBHP at 70-80 ℃, reacting the methyl allyl polyoxyethylene ether monomer with diethylenetriamine for 3-5h to obtain the terminal amino methyl allyl polyoxyethylene ether monomer. Wherein the mass ratio of the methyl allyl polyoxyethylene ether monomer to the diethylenetriamine to the metalloporphyrin/TBHP is as follows: 100: 8: 2.
(2) Preparing an ester monomer: at 70-80 deg.C, polyethylene glycol (molecular weight is 2200) and methacrylic acid are esterified under the action of catalyst, p-toluenesulfonic acid, polymerization inhibitor and hydroquinone for 6-8h to prepare polyethylene glycol dimethacrylate monomer. Wherein the mass ratio of polyethylene glycol (molecular weight is 2200), methacrylic acid, p-toluenesulfonic acid and polymerization inhibitor is as follows: 100: 5: 2: 0.1.
(3) And (2) adding the terminal amino methyl allyl polyoxyethylene ether monomer prepared in the step (1) and water into a reactor for dissolving, placing the reactor under ultraviolet irradiation, dropwise adding the first solution and the second solution at a constant speed within 1-2h for polymerization reaction, and after dropwise adding, adding a sodium hydroxide solution for neutralization until the pH value is 6-7 to obtain a crosslinked reticular polymer, namely the high-dispersion polycarboxylic acid water reducer. Wherein the first solution is a solution of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and 3, 6-dioxo-1, 8-octanedithiol, and the second solution is an aqueous solution of maleic acid, 2-methyl-2-phosphinyl tris (oxy-2, 1-ethylene) acrylate and polyethylene glycol dimethacrylate monomer; the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2. Wherein: terminal amino methyl allyl polyoxyethylene ether, maleic acid, 2-methyl-2-acrylic phosphinyl tris (oxy-2, 1-ethylene) ester and polyethyleneThe mass ratio of the diol dimethacrylate monomer is 100: 10: 5: 25. The dosage of the 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is 1 percent of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the 3, 6-dioxo-1, 8-octanedithiol is 0.3 percent of the total mass of the amine-terminated polyether monomer and the ester monomer.
Wherein the amount of the water used in the steps enables the mass concentration of the high-dispersion polycarboxylic acid water reducing agent to be 50%.
Comparative example 1
(1) Adding 200 parts of methyl allyl polyoxyethylene ether and 200 parts of water into a reaction kettle, opening a stirrer, and raising the temperature to 60 ℃;
(2) respectively dripping 2.5 parts of hydrogen peroxide solution, 1 part of ascorbic acid, 1.5 parts of 2-mercaptoacetic acid mixed solution and 20 parts of acrylic acid solution, finishing dripping for 3 hours, curing for 1 hour, and finally adding 25 parts of sodium hydroxide solution to neutralize, thus obtaining the polycarboxylic acid water reducing agent.
The water-reducing rate, slump loss with time, workability and the like of the concrete were measured using the samples synthesized in examples 1 to 4 and comparative example 1, according to GB 8076-2008 "concrete admixture". The concrete mixing proportion is as follows: cement 360kg/m3780kg/m of sand3Stone 1050kg/m3The slump was controlled to 210. + -.10 mm, and the results are shown in Table 1.
| Sample (I) | Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 |
| Water reduction rate/%) | 30 | 40 | 41 | 40 | 42 |
| Slump T0 | 200 | 205 | 210 | 205 | 210 |
| Slump with time T1h | 150 | 205 | 200 | 200 | 210 |
| Workability | In general | Good taste | Good taste | Is preferably used | Is preferably used |
| 28d compression strength ratio of not less than% | 135 | 160 | 165 | 155 | 165 |
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
a preparation method of a high-dispersion polycarboxylate superplasticizer comprises the following steps:
(1) at 70-80 ℃, reacting a polyether monomer with vinylamine for 3-5h under the catalytic action of metalloporphyrin/TBHP to obtain an amine-terminated polyether monomer, wherein the mass ratio of the polyether monomer to the vinylamine to the metalloporphyrin/TBHP is 100: 3-10: 0.1-2;
(2) at 70-80 ℃, polyethylene glycol with molecular weight of 2000-2300 and methacrylic acid are subjected to esterification reaction under the action of p-toluenesulfonic acid and hydroquinone for 6-8h to prepare a polyethylene glycol dimethacrylate monomer, wherein the mass ratio of the polyethylene glycol, the methacrylic acid, the p-toluenesulfonic acid and the polymerization inhibitor is as follows: 100: 5-20: 1-5: 0.1-2.
(3) Adding the amine-terminated polyether monomer prepared in the step (1) and water into a reactor for dissolving, then placing the reactor under ultraviolet light for irradiation, dropwise adding a first solution and a second solution at a constant speed within 1-2h for polymerization reaction, and after dropwise adding, adding an alkaline regulator for neutralization until the pH value is 6-7 to obtain a crosslinked reticular polymer, namely the high-dispersion polycarboxylic acid water reducing agent, wherein the first solution is an aqueous solution of a photoinitiator and a chain transfer agent, and the second solution is an aqueous solution of an unsaturated acid, an unsaturated phosphate ester and the ester monomer prepared in the step (2); the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2(ii) a The mass ratio of the amine-terminated polyether monomer, the unsaturated acid, the unsaturated phosphate ester and the ester monomer is 100: 10-20: 3-5: 20-30, the dosage of the photoinitiator is 1-5% of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the chain transfer agent is 0.1-1% of the total mass of the amine-terminated polyether monomer and the ester monomer;
the polyether monomer is allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether or isopentenyl polyoxyethylene ether, the vinylamine is diethylenetriamine or triethylenetetramine, the unsaturated acid is acrylic acid, methacrylic acid, itaconic acid or maleic acid, the unsaturated phosphate is diethyl vinylphosphonate or 2-methyl-2-phosphinyl tris (oxy-2, 1-ethylene) acrylate, and the total amount of the water enables the mass concentration of the prepared high-dispersion polycarboxylic acid water reducer to be 45-55%.
The photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 1-hydroxy-cyclohexyl-phenyl ketone or 2-hydroxy-methyl phenyl propane-1-ketone. The chain transfer agent is 3, 6-dioxo-1, 8-octanedithiol, 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid or 2- (phenylthiocarbonylthio) propanoic acid. The alkaline regulator is sodium hydroxide, sodium silicate or ethanolamine.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (4)
1. A preparation method of a high-dispersion polycarboxylate superplasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) at 70-80 ℃, reacting a polyether monomer with diethylenetriamine or triethylene tetramine for 3-5h under the catalytic action of metalloporphyrin/TBHP to obtain an amine-terminated polyether monomer, wherein the mass ratio of the polyether monomer to the diethylenetriamine or the triethylene tetramine to the metalloporphyrin/TBHP is 100: 3-10: 0.1 to 2;
(2) at 70-80 ℃, polyethylene glycol with molecular weight of 2000-2300 and methacrylic acid are subjected to esterification reaction under the action of p-toluenesulfonic acid and hydroquinone for 6-8h to prepare a polyethylene glycol dimethacrylate monomer, wherein the mass ratio of the polyethylene glycol, the methacrylic acid, the p-toluenesulfonic acid and the polymerization inhibitor is as follows: 100: 5-20: 1-5: 0.1 to 2;
(3) adding the amine-terminated polyether monomer prepared in the step (1) and water into a reactor for dissolving, then placing the reactor under ultraviolet irradiation, and dropwise adding the amine-terminated polyether monomer and water at a constant speed within 1-2hCarrying out polymerization reaction on the first solution and the second solution, and after dropwise adding is finished, adding an alkaline regulator to neutralize until the pH is =6-7, so as to obtain a crosslinked reticular polymer, namely the high-dispersion polycarboxylic acid water reducing agent, wherein the first solution is an aqueous solution of a photoinitiator and a chain transfer agent, and the second solution is an aqueous solution of an unsaturated acid, an unsaturated phosphate ester and the ester monomer prepared in the step (2); the wavelength of the ultraviolet light is 230-380mm, and the irradiation intensity is 20-110W/m2(ii) a The mass ratio of the amine-terminated polyether monomer to the unsaturated acid to the unsaturated phosphate ester monomer is 100: 10-20: 3-5: 20-30 percent of photoinitiator, wherein the dosage of the photoinitiator is 1-5 percent of the total mass of the amine-terminated polyether monomer and the ester monomer, and the dosage of the chain transfer agent is 0.1-1 percent of the total mass of the amine-terminated polyether monomer and the ester monomer;
the polyether monomer is allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether or isopentenyl polyoxyethylene ether, the unsaturated acid is acrylic acid, methacrylic acid, itaconic acid or maleic acid, the unsaturated phosphate is diethyl vinylphosphonate or 2-methyl-2-acrylic phosphinyl tris (oxy-2, 1-ethylene) ester, and the total amount of the water enables the mass concentration of the prepared high-dispersion polycarboxylic acid water reducer to be 45-55%.
2. The method of claim 1, wherein: the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 1-hydroxy-cyclohexyl-phenyl ketone or 2-hydroxy-methyl phenyl propane-1-ketone.
3. The method of claim 1, wherein: the chain transfer agent is 3, 6-dioxo-1, 8-octanedithiol, 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid or 2- (phenylthiocarbonylthio) propanoic acid.
4. The method of claim 1, wherein: the alkaline regulator is sodium hydroxide, sodium silicate or ethanolamine.
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| CN102181062A (en) * | 2011-04-10 | 2011-09-14 | 北京工业大学 | Preparation method for synthesizing high-performance polycarboxylic acid water reducing agent by undergoing one-step amidation reaction |
| CN107337767A (en) * | 2016-12-30 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the water reducer of phosphorous acid groups |
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| JP3336456B2 (en) * | 1998-12-25 | 2002-10-21 | 日本シーカ株式会社 | Cement dispersant and concrete composition containing the dispersant |
| CN102181062A (en) * | 2011-04-10 | 2011-09-14 | 北京工业大学 | Preparation method for synthesizing high-performance polycarboxylic acid water reducing agent by undergoing one-step amidation reaction |
| CN107337767A (en) * | 2016-12-30 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of the water reducer of phosphorous acid groups |
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Application publication date: 20180515 Assignee: Kezhijie new material group (Hainan) Co.,Ltd. Assignor: KZJ NEW MATERIALS GROUP Co.,Ltd. Contract record no.: X2022980006964 Denomination of invention: A preparation method of highly dispersed polycarboxylic acid water reducer Granted publication date: 20200306 License type: Common License Record date: 20220606 |