CN106277899A - A kind of polycarboxylate water-reducer and preparation method thereof - Google Patents

A kind of polycarboxylate water-reducer and preparation method thereof Download PDF

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Publication number
CN106277899A
CN106277899A CN201610701031.9A CN201610701031A CN106277899A CN 106277899 A CN106277899 A CN 106277899A CN 201610701031 A CN201610701031 A CN 201610701031A CN 106277899 A CN106277899 A CN 106277899A
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reducer
preparation
polymeric monomer
polycarboxylate water
water
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CN201610701031.9A
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Inventor
裴继凯
刘冠杰
王自卫
任建国
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Shanxi Shan Great He Sheng Novel Material Limited-Liability Co
Shanxi University
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Shanxi Shan Great He Sheng Novel Material Limited-Liability Co
Shanxi University
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Priority to CN201610701031.9A priority Critical patent/CN106277899A/en
Publication of CN106277899A publication Critical patent/CN106277899A/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641Polyacrylates; Polymethacrylates
    • C04B24/2647Polyacrylates; Polymethacrylates containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

Abstract

The invention provides a kind of polycarboxylate water-reducer and preparation method thereof, belong to concrete admixture and prepare.Described polycarboxylate water-reducer is to be first that initiator prepares unsaturated polyether polymeric monomer by ethylene glycol monovinyl ether, then carries out being polymerized prepared with minor comonomer acrylic acid by unsaturated polyether polymeric monomer (EPEG).Hydrophilic group in the polycarboxylate water-reducer molecular structure that the present invention prepares is more, and water-reducing rate is high, and fluidity retentivity is remarkably reinforced, and anti-mud is remarkably reinforced, and therefore can meet higher construction requirement.

Description

A kind of polycarboxylate water-reducer and preparation method thereof
Technical field
The present invention relates to construction material, particularly to concrete admixture, particularly belong to one and utilize unsaturated polyether big Polycarboxylate water-reducer prepared by monomer and preparation method thereof.
Background technology
Water reducer is in modern concrete in addition to cement, sand, stone, water, admixture, a requisite component.Diminishing Agent is under conditions of ensureing that concrete mix workability is identical, reduces the additive of concrete water amount, uses water reducer Cement consumption, the workability improving concrete and durability can be reduced, be the core of ready-mixed concrete.It is generally believed that diminishing The development course of agent is divided into three phases: with the wood calcium first generation ordinary water-reducing agent stage as representative, with naphthalene water reducer as generation The second filial generation high efficiency water reducing agent stage of table and the current third generation high-performance water reducing agent stage with polycarboxylate water-reducer as representative.
The performance of polycarboxylate water-reducer and its molecular structure have close relationship.In water reducer molecule, it is by greatly The ethylene oxide side chains of monomer adsorbs with cement granules, it is provided that space steric effect realizes water-reducing effect.Therefore, poly-by changing The structure of carboxylic acid water reducer polymeric monomer, improves the performance of water reducer, is current study hotspot.
On domestic market, the main product of unsaturated polyether polymeric monomer is allyl polyethenoxy ether, methacrylic polyoxy Vinyl Ether and isopentene group polyoxyethylene ether, be commonly called as 3 carbon, 4 carbon and 5 carbon monomers, the most especially with 4 carbon and 5 carbon monomer applications For extensively.But the initiator production technology of existing product is complex so that polymeric monomer relatively costly, and the water reducer of synthesis The problem that generally there is anti-mud difference.Therefore, develop the unsaturated polyether polymeric monomer of a kind of simple in construction, excellent performance, thus The performance promoting polycarboxylate water-reducer just seems the most urgent.
Summary of the invention
It is desirable to provide a kind of polycarboxylate water-reducer and preparation method thereof.The preparation of this water reducer should use a kind of knot Structure is simple, the unsaturated polyether polymeric monomer of excellent performance, thus promotes the performance of polycarboxylate water-reducer.
A kind of polycarboxylate water-reducer that the present invention provides, it is characterised in that general structure is:
In formula: M is unsaturated polyether polymeric monomer, structural formula is:
A, b, n represent the degree of polymerization, a=60-140, b=20-35, n=50-100;
The preparation method of a kind of polycarboxylate water-reducer that the present invention provides, it is characterised in that step includes:
(1) preparation of polymeric monomer, in the autoclave closed, injects initiator ethylene glycol monovinyl ether and catalysis The mixed solution of agent Feldalat NM, stirring reacting by heating still are to 100-120 DEG C;Being continually fed into ethylene oxide gas, 6-8 is little in reaction Time, i.e. obtain unsaturated polyether polymeric monomer after cooling;
(2) preparation of water reducer, adds unsaturated polyether polymeric monomer and deionized water in the reactor, and heating is allowed to abundant Dissolve, make reaction end liquid;Acrylic acid, vitamin C, chain-transferring agent are sequentially added in deionized water dissolving, are configured to dropping Liquid;Control reaction end liquid temp 15~25 DEG C, in end liquid, add hydrogen peroxide, then dropping liquid is slowly dropped in reaction end liquid, Time for adding is 2~3h, stirs insulation reaction 1h at 15~25 DEG C;Then use sodium hydrate aqueous solution regulation pH value to 7 ~8, i.e. prepare the polycarboxylate water-reducer of solid content 35 40%.
The 1%-2% that consumption is ethylene glycol monovinyl ether quality of the catalyst sodium methoxide in described step (1);
Consumption is ethylene glycol monovinyl ether quality 25 50 times of ethylene oxide gas in described step (1);
Unsaturated polyether polymeric monomer molecular weight prepared by described step (1) is 2,300 4500;
Unsaturated polyether polymeric monomer and acrylic acid mol ratio in described step (2) are 1:2.8 4.5;
The 0.15%-0.3% that vitamin C consumption is polymeric monomer gross mass in described step (2);
The 0.8%-1.5% that hydrogen peroxide consumption is polymeric monomer gross mass in described step (2);
Chain-transferring agent in described step (2) is TGA, and consumption is the 0.5%-1% of polymeric monomer gross mass.
Compared with prior art, advantages of the present invention and beneficial effect:
The method comprises the steps of firstly, preparing polyether macromonomer, the initiator ethylene glycol monovinyl ether of use, it is different from existing 4 carbon With 5 carbon monomeric initiators, synthesis is simple, and convenient sources, cost is relatively low, and safe and nontoxic, pollution-free.Utilize this initiator system Standby unsaturated polyether polymeric monomer, technique is simple, process safety, and prepared polymeric monomer double bond retention rate is high, and polymerization activity is high.Pass through The kind of conversion polymeric monomer initiator, changes the charge environment of unsaturated double-bond in polymeric monomer so that the double bond of polymeric monomer is lived Property high, it is easy to carry out polyreaction.
Polycarboxylate water-reducer prepared by the present invention, the hydrophilic group in molecular structure is more so that water reducer molecule has Stronger hydrophilic, after cement mixing, can be adsorbed in cement particle surface by the effect of hydrogen bond, have relatively with cement granules Strong affinity, so that cement particle surface forms hydration shell, will not make the earth in sand material affect water-reducing effect, have The advantage that anti-mud is strong, in the case of sand material clay content height, effect is notable.
In a word, the hydrophilic group in polycarboxylate water-reducer molecular structure prepared by the present invention is more, and water-reducing rate is high, fluidity Retentivity is remarkably reinforced, and anti-mud is remarkably reinforced, and therefore can meet higher construction requirement.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Express for simplifying, represent unsaturated polyether polymeric monomer with EPEG below, be followed by numeral and represent the molecular weight of polymeric monomer.
Embodiment 1:
1) preparation of EPEG-2300 polymeric monomer
In beaker, add 20g ethylene glycol monovinyl ether and 0.2g Feldalat NM, stir.Anti-to the 1L high pressure closed Answer in still, inject ethylene glycol monovinyl ether and Feldalat NM mixed solution.Closed reactor, is warming up to 100 DEG C, starts to be passed through ring Oxidative ethane gas.Control temperature of reaction kettle and be not higher than 110 DEG C, sustained response 6h, add up to be passed through ethylene oxide gas about 520g, so Rear stopping is passed through ethylene oxide gas and reduces temperature of reaction kettle.Release product after cooling, be white waxy solid after cooling, i.e. For the EPEG polymeric monomer that mean molecule quantity is 2300.
2) preparation of polycarboxylate water-reducer
Equipped with agitator, condensing tube 500ml reaction bulb in, by EPEG-2300 polymeric monomer 100g add 60g deionization In water, suitably heating is fully dissolved and is made reaction end liquid;Vitamin C 0.25g, acrylic acid 12.0g, TGA 0.50g are depended on In secondary addition 40.0g deionized water, mixing and stirring, it is configured to dropping liquid;Controlling reaction temperature is 20~25 DEG C, in reaction End liquid adds 1.5g H2O2, the most at the uniform velocity instilling dropping liquid, 3h dropping is complete;After continuing insulation reaction 1h, add 6g NaOH The solution being made into 70g water, stirs, and i.e. prepares polycarboxylate water-reducer.
Embodiment 2:
1) preparation of EPEG-2300 polymeric monomer
The preparation method of EPEG-2300 polymeric monomer is in the same manner as in Example 1.
2) preparation of polycarboxylate water-reducer
Equipped with agitator, condensing tube 500ml reaction bulb in, by EPEG-2300 polymeric monomer 100g add 60g deionization In water, suitably heating is fully dissolved and is made reaction end liquid;Vitamin C 0.15g, acrylic acid 8.7g, TGA 0.80g are depended on In secondary addition 40g deionized water, mixing and stirring, it is configured to dropping liquid;Controlling reaction temperature is 20~25 DEG C, at the reaction end Liquid adds 1.0g H2O2, the most at the uniform velocity instilling dropping liquid, 3h dropping is complete;Continue after insulation reaction 1h, add 5g NaOH with The solution that 60g water is made into, stirs, and i.e. prepares polycarboxylate water-reducer.
Embodiment 3:
1) preparation of EPEG-3500 polymeric monomer
In beaker, add 15g ethylene glycol monovinyl ether and 0.3g Feldalat NM, stir.Anti-to the 1L high pressure closed Answer in still, inject ethylene glycol monovinyl ether and Feldalat NM mixed solution.Closed reactor, is warming up to 100 DEG C, starts to be passed through ring Oxidative ethane gas.Control temperature of reaction kettle and be not higher than 110 DEG C, sustained response 8h, add up to be passed through ethylene oxide gas about 600g, so Rear stopping is passed through ethylene oxide gas and reduces temperature of reaction kettle.Release product after cooling, be white waxy solid after cooling, i.e. For the EPEG polymeric monomer that mean molecule quantity is 3500.
2) preparation of polycarboxylate water-reducer
Equipped with agitator, condensing tube 500ml reaction bulb in, by EPEG-3500 polymeric monomer 100g add 60g deionization In water, suitably heating is fully dissolved and is made reaction end liquid;Vitamin C 0.20g, acrylic acid 8.8g, TGA 0.75g are depended on In secondary addition 40g deionized water, mixing and stirring, it is configured to dropping liquid;Controlling reaction temperature is 20~25 DEG C, at the reaction end Liquid adds 1.2g H2O2, the most at the uniform velocity instilling dropping liquid, 3h dropping is complete;After continuing insulation reaction 1h, add 4.8g NaOH The solution being made into 58g water, stirs, and i.e. prepares polycarboxylate water-reducer.
Embodiment 4:
1) preparation of EPEG-3500 polymeric monomer
The preparation method of EPEG-3500 polymeric monomer is in the same manner as in Example 3.
2) preparation of polycarboxylate water-reducer
Equipped with agitator, condensing tube 500ml reaction bulb in, by EPEG-3500 polymeric monomer 100g add 60g deionization In water, suitably heating is fully dissolved and is made reaction end liquid;Vitamin C 0.20g, acrylic acid 9.2g, TGA 0.90g are depended on In secondary addition 40g deionized water, mixing and stirring, it is configured to dropping liquid;Controlling reaction temperature is 20~25 DEG C, at the reaction end Liquid adds 1.4g H2O2, the most at the uniform velocity instilling dropping liquid, 3h dropping is complete;After continuing insulation reaction 1h, add 5.4g NaOH The solution being made into 64g water, stirs, and i.e. prepares polycarboxylate water-reducer.
Embodiment 5:
1) preparation of EPEG-4500 polymeric monomer
In beaker, add 20g ethylene glycol monovinyl ether and 0.4g Feldalat NM, stir.Anti-to the 1L high pressure closed Answer in still, inject ethylene glycol monovinyl ether and Feldalat NM mixed solution.Closed reactor, is warming up to 100 DEG C, starts to be passed through ring Oxidative ethane gas.Control temperature of reaction kettle and be not higher than 110 DEG C, sustained response 4h, add up to be passed through ethylene oxide gas about 700g, so Rear stopping is passed through ethylene oxide gas.Because reactor volume is limited, therefore release about 300g reaction solution.Closed reactor again, Continue to be passed through ethylene oxide gas, sustained response 4h, the accumulative ethylene oxide gas about 200g that is passed through, then stop being passed through epoxy second Alkane gas also reduces temperature of reaction kettle.Releasing product after cooling, be white waxy solid after cooling, being mean molecule quantity is The EPEG polymeric monomer of 4500.
2) preparation of polycarboxylate water-reducer
Equipped with agitator, condensing tube 500ml reaction bulb in, by EPEG-4500 polymeric monomer 100g add 60g deionization In water, suitably heating is fully dissolved and is made reaction end liquid;Vitamin C 0.20g, acrylic acid 4.8g, TGA 0.80g are depended on In secondary addition 40g deionized water, mixing and stirring, it is configured to dropping liquid;Controlling reaction temperature is 20~25 DEG C, at the reaction end Liquid adds 1.2g H2O2, the most at the uniform velocity instilling dropping liquid, 3h dropping is complete;After continuing insulation reaction 1h, add 2.6g NaOH The solution being made into 54g water, stirs, and i.e. prepares polycarboxylate water-reducer.
The polycarboxylate water-reducer Performance comparision of above-described embodiment synthesis:
Carry out cement paste test with the polycarboxylate water-reducer prepared in above-described embodiment respectively and concrete slump tries Test and compare.
A. testing experiment is only starched according to GB/T 8077~2000 " Methods for testing uniformity of concrete admixture ", knot Fruit is as follows, is shown in Table 1:
Table 1 flowing degree of net paste of cement result of the test
B. concrete performance is carried out according to " Standard for test methods of properties of ordinary concrete mixture standard " GB/T50080 2002 Testing experiment, result is as follows, is shown in Table 2:
Table 2 concrete slump result of the test
By the data of Tables 1 and 2 it can be seen that the water reducer water-reducing rate obtained by the present invention is higher, cement is had good Good dispersibility and dispersion retentivity, can meet the work progress of longer time, have working performance of concrete relatively in using Big improvement, has preferable economy, has the biggest dissemination.
Additionally, embodiment of the present invention production process is reactant aqueous solution system, reactionless by-product, it is not necessary to carry out pure Change.Polymerization process is that room temperature is carried out, and does not the most produce penetrating odor in raw materials used and production process, discharges without " three wastes ", raw Production. art environmental protection.

Claims (8)

1. a polycarboxylate water-reducer, it is characterised in that structural formula is:
In formula: M is unsaturated polyether polymeric monomer (EPEG), and structural formula is:
A, b, n represent the degree of polymerization, a=60-140, b=20-35, n=50 100.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 1, it is characterised in that step includes:
(1) preparation of polymeric monomer, in the autoclave closed, injects initiator ethylene glycol monovinyl ether and catalyst first The mixed solution of sodium alkoxide, stirring reacting by heating still are to 100-120 DEG C;It is continually fed into ethylene oxide gas, reacts 6-8 hour, Unsaturated polyether polymeric monomer is i.e. obtained after cooling;
(2) preparation of water reducer, adds unsaturated polyether polymeric monomer and deionized water in the reactor, and heating is allowed to the most molten Solve, make reaction end liquid;Acrylic acid, vitamin C, chain-transferring agent are sequentially added in deionized water dissolving, are configured to dropping liquid; Control reaction end liquid temp 15~25 DEG C, in end liquid, add hydrogen peroxide, then dropping liquid is slowly dropped in reaction end liquid, dropping Time is 2~3h, stirs insulation reaction 1h at 15~25 DEG C;Then use sodium hydrate aqueous solution regulation pH value is to 7~8, I.e. prepare the polycarboxylate water-reducer of solid content 35 40%.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 2, it is characterised in that: first in described step (1) The consumption of sodium alkoxide is the 1%-2% of ethylene glycol monovinyl ether quality.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 2, it is characterised in that described step (1) medium ring The consumption of oxidative ethane gas is 25 50 times of ethylene glycol monovinyl ether quality.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 2, it is characterised in that in described step (2) Unsaturated polyether polymeric monomer and acrylic acid mol ratio are 1:2.8 4.5.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 2, it is characterised in that in described step (2) Vitamin C consumption is the 0.15%-0.3% of polymeric monomer gross mass.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 2, it is characterised in that in described step (2) Hydrogen peroxide consumption is the 0.8%-1.5% of polymeric monomer gross mass.
The preparation method of a kind of polycarboxylate water-reducer the most as claimed in claim 2, it is characterised in that in described step (2) Chain-transferring agent is TGA, and consumption is the 0.5%-1% of polymeric monomer gross mass.
CN201610701031.9A 2016-08-22 2016-08-22 A kind of polycarboxylate water-reducer and preparation method thereof Pending CN106277899A (en)

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CN107793538A (en) * 2017-10-24 2018-03-13 济南大学 A kind of preparation method and application of polycarboxylate water-reducer
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CN113980203A (en) * 2021-11-22 2022-01-28 山东交通学院 Polycarboxylate superplasticizer with controllable structure based on EPEG polyether macromonomer and preparation method thereof
CN114195421A (en) * 2020-09-17 2022-03-18 江苏尼高科技有限公司 Preparation method of polycarboxylic acid admixture for machine-made sand concrete
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CN107793538A (en) * 2017-10-24 2018-03-13 济南大学 A kind of preparation method and application of polycarboxylate water-reducer
CN108102085A (en) * 2017-12-22 2018-06-01 上海东大化学有限公司 Polyether monomer, polycarboxylate water-reducer and its methods for making and using same from it
CN109608593A (en) * 2018-12-04 2019-04-12 山西佳维新材料股份有限公司 A kind of preparation method of polyethers synthesis water reducing type polycarboxylate water-reducer
CN109627401A (en) * 2018-12-04 2019-04-16 山西佳维新材料股份有限公司 A kind of preparation method of polyethers synthesis collapse protective poly-carboxylic acid water reducing agent
CN109679086A (en) * 2018-12-24 2019-04-26 联泓(江苏)新材料研究院有限公司 A kind of polyether macromonomer and preparation method thereof and polycarboxylate water-reducer prepared therefrom
CN109651568A (en) * 2019-01-08 2019-04-19 山西佳维新材料股份有限公司 A kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer
CN109705282A (en) * 2019-01-08 2019-05-03 山西佳维新材料股份有限公司 A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer
CN109880022A (en) * 2019-02-28 2019-06-14 河南城建学院 A kind of high-adaptability polycarboxylate water-reducer and its synthetic method
CN111333829A (en) * 2020-04-26 2020-06-26 辽宁奥克化学股份有限公司 Unsaturated polyether monomer, polycarboxylate superplasticizer and preparation method thereof
WO2021217762A1 (en) * 2020-04-26 2021-11-04 辽宁奥克化学股份有限公司 Unsaturated polyether monomer, and polycarboxylate superplasticizer and preparation method therefor
CN114195421A (en) * 2020-09-17 2022-03-18 江苏尼高科技有限公司 Preparation method of polycarboxylic acid admixture for machine-made sand concrete
CN114195421B (en) * 2020-09-17 2023-08-29 江苏尼高科技有限公司 Preparation method of polycarboxylic acid additive for machine-made sand concrete
CN113980203A (en) * 2021-11-22 2022-01-28 山东交通学院 Polycarboxylate superplasticizer with controllable structure based on EPEG polyether macromonomer and preparation method thereof
CN114524908A (en) * 2021-12-17 2022-05-24 广东科隆智谷新材料股份有限公司 Polycarboxylate superplasticizer based on continuous bulk polymerization and preparation method thereof
CN114524908B (en) * 2021-12-17 2023-11-10 广东科隆智谷新材料股份有限公司 Polycarboxylate superplasticizer based on continuous bulk polymerization and preparation method thereof
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Application publication date: 20170104