CN108034025A - A kind of preparation method of high-dispersity polycarboxylic acid water reducing agents - Google Patents
A kind of preparation method of high-dispersity polycarboxylic acid water reducing agents Download PDFInfo
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- CN108034025A CN108034025A CN201711468666.XA CN201711468666A CN108034025A CN 108034025 A CN108034025 A CN 108034025A CN 201711468666 A CN201711468666 A CN 201711468666A CN 108034025 A CN108034025 A CN 108034025A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 35
- 229920000570 polyether Polymers 0.000 claims description 35
- 150000002148 esters Chemical class 0.000 claims description 31
- 239000002202 Polyethylene glycol Substances 0.000 claims description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 16
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
- -1 unsaturated phosphate ester Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 150000002118 epoxides Chemical class 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- 125000003368 amide group Chemical group 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- 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 4
- XNLJLJFJCYDTQM-UHFFFAOYSA-N 2-benzoylsulfanylpropanoic acid Chemical compound OC(=O)C(C)SC(=O)C1=CC=CC=C1 XNLJLJFJCYDTQM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- KDNYCTPSPZHJQF-UHFFFAOYSA-N 3-phenylbutan-2-ol Chemical compound CC(O)C(C)C1=CC=CC=C1 KDNYCTPSPZHJQF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 229920005646 polycarboxylate Polymers 0.000 abstract description 6
- 239000004568 cement Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 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
- 230000036632 reaction speed Effects 0.000 abstract description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 150000003573 thiols Chemical class 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of preparation method of high-dispersity polycarboxylic acid water reducing agents.The present invention has reaction speed fast, without heating, narrow molecular weight distribution, lower-cost advantage is easy to operate, is easy to industrialized production, has wide application prospects compared with conventional solution polymerization process.Wherein mainly use photoinitiator, improve reaction rate, polymerization speed is fast, and conversion rate of products is high, and the performance of prepared polycarboxylate water-reducer is stablized, molecular structure is comb-type structure, contain polar group in main chain, containing polyethylene oxide base segment in side chain forms space obstacle, is conducive to improve the dispersed and dispersed holding capacity of cement, low-dosage polymolecularity is embodied, the advantages that high-collapse-retentivity.
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of preparation side of high-dispersity polycarboxylic acid water reducing agents
Method.
Background technology
Direction with concrete to high performance and multifunction is developed, it is desirable to which concrete has high workability, high-strength
Degree, high-durability, and can meet in many applications in special circumstances.Super plasticizer with ultra-dispersed performance becomes high property
One of indispensable component in energy concrete.
In recent years, as country is to paying attention to further for energy-saving and emission-reduction and promoting rapidly for low-carbon economy theory, scientific and technical research
Person is also concerned with how to reduce its consumption to the energy while striving and improving cement water reducing agent performance.Particularly enterprise, just
The product of low energy consumption is being striven to find, not only can be cost-effective, but also the trouble that the examination ＆ approval that can reduce boiler are brought.
On the one hand, at present the process of production polycarboxylate water-reducer mostly using heating by the way of, such as heated using steam,
Heat-conducting oil heating etc., can all cause environmental pollution.
On the other hand, the production process of polycarboxylate water-reducer is all long at present, generally require 4-5 it is small when or so, production
Efficiency is slow, so needing anticipated stock, it is necessary to take certain stock, causes the wasting of resources, fixed assets investment is big.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of preparation side of high-dispersity polycarboxylic acid water reducing agents
Method.
Technical scheme is as follows：
A kind of preparation method of high-dispersity polycarboxylic acid water reducing agents, includes the following steps：
(1) at 70-80 DEG C, polyether monomer and vinylamine are under metalloporphyrin/TBHP catalytic action, after reacting 3-5h,
Ending amino polyether monomer is obtained, the wherein mass ratio of polyether monomer, vinylamine and metalloporphyrin/TBHP is 100: 3-10: 0.1-
2；
(2) at 70-80 DEG C, polyethylene glycol and methacrylic acid that molecular weight is 2000-2300 in p-methyl benzenesulfonic acid and
Hydroquinone effect is lower to carry out esterification, reacts 6-8h, polyethylene glycol dimethacrylate monomer is made, wherein, poly- second
Glycol, methacrylic acid, the mass ratio of p-methyl benzenesulfonic acid and polymerization inhibitor are：100∶5-20∶1-5∶0.1-2.
(3) ending amino polyether monomer and water made from step (1) are added in reactor and dissolved, be then placed in ultraviolet light
Lower irradiation, is at the uniform velocity added dropwise the first solution in 1-2h and the second solution carries out polymerisation, after completion of dropwise addition, adds alkalescence and adjusts
Agent carries out being neutralized to pH=6-7, obtains a kind of polymer of crosslinking net, is high-dispersity polycarboxylic acid water reducing agents, wherein, first
Solution is photoinitiator and the aqueous solution of chain-transferring agent, and the second solution is unsaturated acids, unsaturated phosphate ester and step (2) are made
Esters monomer aqueous solution；The wavelength of above-mentioned ultraviolet light is 230-380mm, exposure intensity 20-110W/m2；Above-mentioned end amine
Base polyether monomer, unsaturated acids, the mass ratio of unsaturated phosphate ester and esters monomer are 100: 10-20: 3-5: 20-30, and light draws
Agent dosage is sent out as ending amino polyether monomer and the 1-5% of the gross mass of esters monomer, the dosage of chain-transferring agent is ending amino polyether
The 0.1-1% of the gross mass of monomer and esters monomer；
Above-mentioned polyether monomer is allyl polyethenoxy ether, methyl allyl polyoxyethylene ether or isopentene group polyoxyethylene
Ether, above-mentioned vinylamine are diethylenetriamine or triethylene tetramine, and above-mentioned unsaturated acids is acrylic acid, methacrylic acid, itaconic acid
Or maleic acid, above-mentioned unsaturated phosphate ester for vinyl phosphonic diethyl phthalate or 2- methyl -2- acrylic acid phosphinylidyne three (epoxide -
2,1- ethylidene) ester, the total amount of above-mentioned water make it that the mass concentration of obtained high-dispersity polycarboxylic acid water reducing agents is 45-55%.
In a preferred embodiment of the invention, the photoinitiator is 2- hydroxyls -4 '-(2- hydroxy ethoxy) -
2- methyl phenyl ketones, 1- hydroxy-cyclohexyl-phenyls ketone or 2- hydroxy-methyl phenyl-propane -1- ketone.
In a preferred embodiment of the invention, the chain-transferring agent is pungent two mercaptan of 3,6- dioxies -1,8-, 4- cyanogen
Base -4- (phenyl formyl sulfenyl) valeric acids or 2- (phenyl formyl sulfenyl) propionic acid.
In a preferred embodiment of the invention, the alkaline conditioner is sodium hydroxide, sodium metasilicate or ethanol
Amine.
The beneficial effects of the invention are as follows：The present invention is fast with reaction speed compared with conventional solution polymerization process, without
Heating, narrow molecular weight distribution, lower-cost advantage is easy to operate, is easy to industrialized production, has wide application prospects.Wherein
Photoinitiator is mainly used, improves reaction rate, polymerization speed is fast, and conversion rate of products is high, prepared polycarboxylate water-reducer
Performance stablize, molecular structure is comb-type structure, and polar group is contained in main chain, contains polyethylene oxide base segment shape in side chain
Into space obstacle, be conducive to improve the dispersed and dispersed holding capacity of cement, embody low-dosage polymolecularity, Gao Bao
The advantages that collapsing property.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
(1) end of polyether monomer is aminated：At 70-80 DEG C, allyl polyethenoxy ether is with diethylenetriamine in metal
Under porphyrin/TBHP catalytic action, after reacting 3-5h, end amido allyl polyethenoxy ether is obtained.Wherein allyl polyethenoxy
Ether: diethylenetriamine: the mass ratio of metalloporphyrin/TBHP is：100∶8∶1.
(2) preparation of esters monomer：At 70-80 DEG C, polyethylene glycol (molecular weight 2200) is being urged with methacrylic acid
Agent: p-methyl benzenesulfonic acid and polymerization inhibitor: hydroquinone effect is lower to carry out esterification, reacts 6-8h, the polyethylene glycol diformazan of system
Base acrylate monomer.The wherein quality of polyethylene glycol (molecular weight 2200), methacrylic acid, p-methyl benzenesulfonic acid and polymerization inhibitor
Than for：100∶15∶3∶0.7.
(3) the obtained end amido allyl polyethenoxy ether of step (1) and water are added in reactor and dissolved, reactor
It is placed under ultraviolet light and irradiates, the first solution is at the uniform velocity added dropwise in 1.5h and the second solution carries out polymerisation, after completion of dropwise addition, adds
Enter sodium hydroxide solution to carry out being neutralized to pH=6-7, obtain a kind of polymer of crosslinking net, be high dispersive polycarboxylic acids diminishing
Agent.Wherein the first solution is 2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones and pungent two mercaptan of 3,6- dioxy -1,8-
Aqueous solution, the second solution are the water of methacrylic acid, vinyl phosphonic diethyl phthalate and polyethylene glycol dimethacrylate monomer
Solution；The wavelength of above-mentioned ultraviolet light is 230-380mm, exposure intensity 20-110W/m2.Wherein：Hold amido pi-allyl polyoxy second
Alkene ether, methacrylic acid, the mass ratio of vinyl phosphonic diethyl phthalate and polyethylene glycol dimethacrylate monomer are 100: 10:
4∶30.2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones dosage is total matter of ending amino polyether monomer and esters monomer
The 2% of amount, the dosage of pungent two mercaptan of 3,6- dioxies -1,8- are the 0.7% of the gross mass of ending amino polyether monomer and esters monomer.
Wherein, the amount of water used in above steps make it that the mass concentration of the high-dispersity polycarboxylic acid water reducing agents is 50%.
Embodiment 2
(1) end of polyether monomer is aminated：At 70-80 DEG C, methyl allyl polyoxyethylene ether exists with triethylene tetramine
Under metalloporphyrin/TBHP catalytic action, after reacting 3-5h, end aminomethyl allyl polyethenoxy ether is obtained.Wherein methyl alkene
The mass ratio of propyl group polyoxyethylene ether, triethylene tetramine and metalloporphyrin/TBHP is：100∶5∶0.5.
(2) preparation of esters monomer：At 70-80 DEG C, polyethylene glycol (molecular weight 2200) is being urged with methacrylic acid
Agent：P-methyl benzenesulfonic acid and polymerization inhibitor：Hydroquinone effect is lower to carry out esterification, reacts 6-8h, the polyethylene glycol diformazan of system
Base acrylate monomer.Wherein polyethylene glycol (molecular weight 2200), methacrylic acid and the matter of p-methyl benzenesulfonic acid and polymerization inhibitor
Measuring ratio is：100∶20∶2∶1.
(3) the obtained end aminomethyl allyl polyethenoxy ether of step (1) and water are added in reactor and dissolved, instead
Answer device to be placed under ultraviolet light to irradiate, the first solution is at the uniform velocity added dropwise in 1.5h and the second solution carries out polymerisation, completion of dropwise addition
Afterwards, add sodium silicate solution to carry out being neutralized to pH=6-7, obtain a kind of polymer of crosslinking net, be high dispersive polycarboxylic acids
Water-reducing agent.Wherein the first solution is 1- hydroxy-cyclohexyl-phenyls ketone and 4- cyano group -4- (phenyl formyl sulfenyl) valeric acid
Aqueous solution, the second solution is acrylic acid, three (epoxide -2,1- ethylidene) ester of 2- methyl -2- acrylic acid phosphinylidyne and poly- second
The aqueous solution of diol dimethacrylate monomer；The wavelength of above-mentioned ultraviolet light is 230-380mm, exposure intensity 20-110W/
m2.Wherein：Hold aminomethyl allyl polyethenoxy ether, acrylic acid, three (epoxide -2,1- of 2- methyl -2- acrylic acid phosphinylidyne
Ethylidene) mass ratio of ester and polyethylene glycol dimethacrylate monomer is 100: 15: 5: 20.1- hydroxy-cyclohexyl-phenyls
Ketone dosage is ending amino polyether monomer and 3%, the 4- cyano group -4- (phenyl formyl sulfenyl) penta of the gross mass of esters monomer
The dosage of acid is the 0.5% of the gross mass of ending amino polyether monomer and esters monomer.
Wherein, the amount of water used in above steps make it that the mass concentration of the high-dispersity polycarboxylic acid water reducing agents is 50%.
Embodiment 3
(1) end of polyether monomer is aminated：At 70-80 DEG C, isopentene group polyoxyethylene ether monomer and diethylenetriamine
Under metalloporphyrin/TBHP catalytic action, after reacting 3-5h, end amido isopentene group polyoxyethylene ether monomer is obtained.It is wherein different
The mass ratio of pentenyl polyoxyethylene ether, diethylenetriamine and metalloporphyrin/TBHP is：100∶4∶1.2.
(2) preparation of esters monomer：At 70-80 DEG C, polyethylene glycol (molecular weight 2200) is being urged with methacrylic acid
Agent: p-methyl benzenesulfonic acid and polymerization inhibitor: hydroquinone effect is lower to carry out esterification, reacts 6-8h, the polyethylene glycol diformazan of system
Base acrylate monomer.Wherein polyethylene glycol (molecular weight 2200): methacrylic acid: the quality of p-methyl benzenesulfonic acid and polymerization inhibitor
Than for：100∶8∶2∶0.3.
(3) the obtained end amido isopentene group polyoxyethylene ether monomer of step (1) and water are added in reactor and dissolved,
Reactor, which is placed under ultraviolet light, to be irradiated, and the first solution is at the uniform velocity added dropwise in 1-2h and the second solution carries out polymerisation, knot is added dropwise
Shu Hou, adds monoethanolamine and carries out being neutralized to pH=6-7, obtain a kind of polymer of crosslinking net, is that high dispersive polycarboxylic acids subtracts
Aqua.Wherein the first solution is water-soluble for 2- hydroxy-methyls phenyl-propane -1- ketone and 2- (phenyl formyl sulfenyl) propionic acid
Liquid, the second solution are the aqueous solution of itaconic acid, vinyl phosphonic diethyl phthalate and vinyl phosphonic diethyl phthalate monomer；Above-mentioned ultraviolet light
Wavelength be 230-380mm, exposure intensity 20-110W/m2.Wherein：Hold amido isopentene group polyoxyethylene ether monomer, clothing health
The mass ratio of acid, vinyl phosphonic diethyl phthalate and polyethylene glycol dimethacrylate monomer is 100: 12: 3: 24.2- hydroxyls-
Aminomethyl phenyl propane -1- ketone dosage is ending amino polyether monomer and 1%, 2- (the phenyl formyls of the gross mass of esters monomer
Sulfenyl) dosage of propionic acid is the 0.3% of the gross mass of ending amino polyether monomer and esters monomer.
Wherein, the amount of water used in above steps make it that the mass concentration of the high-dispersity polycarboxylic acid water reducing agents is 50%.
Embodiment 4
(1) end of polyether monomer is aminated：At 70-80 DEG C, methyl allyl polyoxyethylene ether monomer and divinyl three
Amine is under metalloporphyrin/TBHP catalytic action, after reacting 3-5h, obtains end aminomethyl allyl polyethenoxy ether monomer.Its
The mass ratio of middle methyl allyl polyoxyethylene ether monomer, diethylenetriamine and metalloporphyrin/TBHP is：100∶8∶2.
(2) preparation of esters monomer：At 70-80 DEG C, polyethylene glycol (molecular weight 2200) is being urged with methacrylic acid
Agent: p-methyl benzenesulfonic acid and polymerization inhibitor: hydroquinone effect is lower to carry out esterification, reacts 6-8h, the polyethylene glycol diformazan of system
Base acrylate monomer.The wherein quality of polyethylene glycol (molecular weight 2200), methacrylic acid, p-methyl benzenesulfonic acid and polymerization inhibitor
Than for：100∶5∶2∶0.1.
(3) the obtained end aminomethyl allyl polyethenoxy ether monomer of step (1) and water are added to molten in reactor
Solution, reactor, which is placed under ultraviolet light, to be irradiated, and the first solution is at the uniform velocity added dropwise in 1-2h and the second solution carries out polymerisation, is added dropwise
After, add sodium hydroxide solution and carry out being neutralized to pH=6-7, obtain a kind of polymer of crosslinking net, be high dispersive
Polycarboxylate water-reducer.Wherein the first solution is 2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones and 3,6- dioxy -1,8-
Pungent two thiol solution, the second solution for maleic acid, three (epoxide -2,1- ethylidene) ester of 2- methyl -2- acrylic acid phosphinylidyne and
The aqueous solution of polyethylene glycol dimethacrylate monomer；The wavelength of above-mentioned ultraviolet light is 230-380mm, exposure intensity 20-
110W/m2.Wherein：Hold aminomethyl allyl polyethenoxy ether, maleic acid, three (oxygen of 2- methyl -2- acrylic acid phosphinylidyne
Base -2,1- ethylidene) mass ratio of ester and polyethylene glycol dimethacrylate monomer is 100: 10: 5: 25.2- hydroxyls -4 ' -
(2- hydroxy ethoxies) -2- methyl phenyl ketones dosage is the 1% of the gross mass of ending amino polyether monomer and esters monomer, 3,6- bis-
The dosage of pungent two mercaptan of oxygen -1,8- is the 0.3% of the gross mass of ending amino polyether monomer and esters monomer.
Wherein, the amount of water used in above steps make it that the mass concentration of the high-dispersity polycarboxylic acid water reducing agents is 50%.
Comparative example 1
(1) 200 parts of methyl allyl polyoxyethylene ether and 200 parts of water are added in reaction kettle, open mixer,
And temperature is risen to 60 DEG C；
(2) be added dropwise 2.5 parts of hydrogen peroxide solutions respectively, 1 part of ascorbic acid and 1.5 parts of 2- thioacetic acid mixed solution with
And 20 parts of acrylic acid solution, 3h are dripped off, when curing 1 is small, finally, 25 parts of sodium hydroxide solution is added, makes its neutralization, you can
Obtain polycarboxylate water-reducer.
Embodiment 1-4 and comparative example 1 are synthesized to obtained sample, using standard cement, according to GB 8076-2008《Coagulation
Native additive》, survey its concrete water-reducing ratio, the slump, Slump Time losing of Large and workability etc..Concrete mix is：
Cement 360kg/m3, sand 780kg/m3, stone 1050kg/m3, the slump controls as shown in table 1 in 210 ± 10mm, acquired results.
| Sample | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Water-reducing rate/% | 30 | 40 | 41 | 40 | 42 |
| Slump T0 | 200 | 205 | 210 | 205 | 210 |
| Through when slump T1h | 150 | 205 | 200 | 200 | 210 |
| Workability | Generally | It is good | It is good | Preferably | Preferably |
| 28d compressive strength rates/%, are not less than | 135 | 160 | 165 | 155 | 165 |
Those of ordinary skill in the art understand, when technical scheme changes in following ranges, remain able to
To same as the previously described embodiments or similar technique effect, protection scope of the present invention is still fallen within：
A kind of preparation method of high-dispersity polycarboxylic acid water reducing agents, includes the following steps：
(1) at 70-80 DEG C, polyether monomer and vinylamine are under metalloporphyrin/TBHP catalytic action, after reacting 3-5h,
Ending amino polyether monomer is obtained, the wherein mass ratio of polyether monomer, vinylamine and metalloporphyrin/TBHP is 100: 3-10: 0.1-
2；
(2) at 70-80 DEG C, polyethylene glycol and methacrylic acid that molecular weight is 2000-2300 in p-methyl benzenesulfonic acid and
Hydroquinone effect is lower to carry out esterification, reacts 6-8h, polyethylene glycol dimethacrylate monomer is made, wherein, poly- second
Glycol, methacrylic acid, the mass ratio of p-methyl benzenesulfonic acid and polymerization inhibitor are：100∶5-20∶1-5∶0.1-2.
(3) ending amino polyether monomer and water made from step (1) are added in reactor and dissolved, be then placed in ultraviolet light
Lower irradiation, is at the uniform velocity added dropwise the first solution in 1-2h and the second solution carries out polymerisation, after completion of dropwise addition, adds alkalescence and adjusts
Agent carries out being neutralized to pH=6-7, obtains a kind of polymer of crosslinking net, is high-dispersity polycarboxylic acid water reducing agents, wherein, first
Solution is photoinitiator and the aqueous solution of chain-transferring agent, and the second solution is unsaturated acids, unsaturated phosphate ester and step (2) are made
Esters monomer aqueous solution；The wavelength of above-mentioned ultraviolet light is 230-380mm, exposure intensity 20-110W/m2；Above-mentioned end amine
Base polyether monomer, unsaturated acids, the mass ratio of unsaturated phosphate ester and esters monomer are 100: 10-20: 3-5: 20-30, and light draws
Agent dosage is sent out as ending amino polyether monomer and the 1-5% of the gross mass of esters monomer, the dosage of chain-transferring agent is ending amino polyether
The 0.1-1% of the gross mass of monomer and esters monomer；
Above-mentioned polyether monomer is allyl polyethenoxy ether, methyl allyl polyoxyethylene ether or isopentene group polyoxyethylene
Ether, above-mentioned vinylamine are diethylenetriamine or triethylene tetramine, and above-mentioned unsaturated acids is acrylic acid, methacrylic acid, itaconic acid
Or maleic acid, above-mentioned unsaturated phosphate ester for vinyl phosphonic diethyl phthalate or 2- methyl -2- acrylic acid phosphinylidyne three (epoxide -
2,1- ethylidene) ester, the total amount of above-mentioned water make it that the mass concentration of obtained high-dispersity polycarboxylic acid water reducing agents is 45-55%.
The photoinitiator is 2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, 1- hydroxy-cyciohexyls-benzene
Base ketone or 2- hydroxy-methyl phenyl-propane -1- ketone.The chain-transferring agent for pungent two mercaptan of 3,6- dioxies -1,8-, 4- cyano group -
4- (phenyl formyl sulfenyl) valeric acids or 2- (phenyl formyl sulfenyl) propionic acid.The alkaline conditioner is hydroxide
Sodium, sodium metasilicate or monoethanolamine.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (4)
- A kind of 1. preparation method of high-dispersity polycarboxylic acid water reducing agents, it is characterised in that：Include the following steps：(1) at 70-80 DEG C, polyether monomer under metalloporphyrin/TBHP catalytic action, after reacting 3-5h, is obtained with vinylamine The mass ratio of ending amino polyether monomer, wherein polyether monomer, vinylamine and metalloporphyrin/TBHP is 100: 3-10: 0.1-2；(2) at 70-80 DEG C, the polyethylene glycol that molecular weight is 2000-2300 is with methacrylic acid in p-methyl benzenesulfonic acid and to benzene Diphenol effect is lower to carry out esterification, reacts 6-8h, polyethylene glycol dimethacrylate monomer is made, wherein, polyethylene glycol, The mass ratio of methacrylic acid, p-methyl benzenesulfonic acid and polymerization inhibitor is：100∶5-20∶1-5∶0.1-2.(3) ending amino polyether monomer and water made from step (1) are added in reactor and dissolved, be then placed under ultraviolet light and shine Penetrate, the first solution and the second solution be at the uniform velocity added dropwise in 1-2h and carries out polymerisation, after completion of dropwise addition, add alkaline conditioner into Row is neutralized to pH=6-7, obtains a kind of polymer of crosslinking net, is high-dispersity polycarboxylic acid water reducing agents, wherein, the first solution For photoinitiator and the aqueous solution of chain-transferring agent, the second solution is unsaturated acids, unsaturated phosphate ester and ester made from step (2) The aqueous solution of class monomer；The wavelength of above-mentioned ultraviolet light is 230-380mm, exposure intensity 20-110W/m2；Above-mentioned end amido gathers Ether monomer, unsaturated acids, the mass ratio of unsaturated phosphate ester and esters monomer are 100: 10-20: 3-5: 20-30, photoinitiator Dosage is ending amino polyether monomer and the 1-5% of the gross mass of esters monomer, and the dosage of chain-transferring agent is ending amino polyether monomer With the 0.1-1% of the gross mass of esters monomer；Above-mentioned polyether monomer is allyl polyethenoxy ether, methyl allyl polyoxyethylene ether or isopentene group polyoxyethylene ether, Above-mentioned vinylamine is diethylenetriamine or triethylene tetramine, and above-mentioned unsaturated acids is acrylic acid, methacrylic acid, itaconic acid or horse Next sour, above-mentioned unsaturated phosphate ester is three (epoxide -2,1- of vinyl phosphonic diethyl phthalate or 2- methyl -2- acrylic acid phosphinylidyne Ethylidene) ester, the total amount of above-mentioned water make it that the mass concentration of obtained high-dispersity polycarboxylic acid water reducing agents is 45-55%.
- 2. preparation method as claimed in claim 1, it is characterised in that：The photoinitiator is 2- hydroxyls -4 '-(2- hydroxyl second Epoxide) -2- methyl phenyl ketones, 1- hydroxyls-cyclohexyl-phenyl ketone or 2- hydroxy-methyl phenyl-propane -1- ketone.
- 3. preparation method as claimed in claim 1, it is characterised in that：The chain-transferring agent is pungent two sulphur of 3,6- dioxies -1,8- Alcohol, 4- cyano group -4- (phenyl formyl sulfenyl) valeric acids or 2- (phenyl formyl sulfenyl) propionic acid.
- 4. preparation method as claimed in claim 1, it is characterised in that：The alkaline conditioner is sodium hydroxide, sodium metasilicate Or monoethanolamine.
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| CN109553729A (en) * | 2018-11-28 | 2019-04-02 | 中国建材检验认证集团厦门宏业有限公司 | A kind of anti-chamotte mould water-reducing agent of both sexes and preparation method thereof |
| CN112707673A (en) * | 2020-09-15 | 2021-04-27 | 科之杰新材料集团有限公司 | Super-shrinkage type polycarboxylate superplasticizer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553729A (en) * | 2018-11-28 | 2019-04-02 | 中国建材检验认证集团厦门宏业有限公司 | A kind of anti-chamotte mould water-reducing agent of both sexes and preparation method thereof |
| CN112707673A (en) * | 2020-09-15 | 2021-04-27 | 科之杰新材料集团有限公司 | Super-shrinkage type polycarboxylate superplasticizer and preparation method thereof |
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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 |