CN108192010A - A kind of poly carboxylic acid series water reducer of viscosity reduction type and preparation method thereof - Google Patents
A kind of poly carboxylic acid series water reducer of viscosity reduction type and preparation method thereof Download PDFInfo
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- CN108192010A CN108192010A CN201711472770.6A CN201711472770A CN108192010A CN 108192010 A CN108192010 A CN 108192010A CN 201711472770 A CN201711472770 A CN 201711472770A CN 108192010 A CN108192010 A CN 108192010A
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- carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The present invention provides a kind of poly carboxylic acid series water reducers of viscosity reduction type and preparation method thereof, belong to technical field of concrete additives.Technical solution for the water-reducing agent is copolymerized under the action of redox system and chain-transferring agent by unsaturated polyethylene glycol oxide gylcol ether polymeric monomer, unsaturated acid monomer and modified monomer containing ester group, wherein modified monomer containing ester group is salicylic acid and the carboxylate of maleic anhydride.The poly carboxylic acid series water reducer of viscosity reduction type that the present invention synthesizes is simple for process, at low cost, easily operated, has good dispersibility and dispersion retentivity, meets the needs of long-distance transportation；Viscosity reducing effect is apparent during applied in high performance concrete, can effectively reduce high-grade concrete viscosity, improves concrete slump retentivity, improves rheological property of concrete and working performance, is particularly suitable for preparing that high-strength, superelevation is strong, self-compacting concrete.In addition, there is extensive adaptability to different cement and aggregate.
Description
Technical field
The present invention relates to a kind of cement dispersants, and in particular to a kind of poly carboxylic acid series water reducer of viscosity reduction type and its preparation side
Method.Belong to technical field of concrete additives.
Background technology
Concrete is more and more used as one of four big building structural materials.In recent years, with China
It the characteristics of increasing of infrastructure, high-grade concrete is just with its intensity height, good integrity, small dead weight, steps into and builds city
, especially a large amount of use is in science of bridge building.In order to which concrete is made to reach high-strength or superelevation strong grade, it is necessary to using a large amount of
Cementitious material and relatively low water-cement ratio, this results in high-grade concrete there are the problem of viscosity is larger and flowing velocity is slow,
Cause difficulty of construction big, especially super high strength concrete high viscosity problem seems in China's pumping construction and is particularly acute, engineering thing
Therefore it takes place frequently.Poly carboxylic acid series water reducer has very high water-reducing rate, can effectively reduce concrete water amount, but cannot solve low
The big problem of concrete viscosity that water-cement ratio is brought.
Therefore, a kind of polycarboxylate water-reducer of novel viscosity reduction type is studied to be of great significance.Application No. is
201410453626.8 Chinese patent discloses a kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof, it be by 7%~
The derivatives monomer a, 80%~92% relative molecular mass M of 16% unsaturated acids or unsaturated acids are 600~5000 isoamyl
Enol polyoxyethylene ether monomer b and 6%~13% glycol ester monomer c is in the effect of redox system and chain-transferring agent
Under, it is copolymerized in 10 DEG C~60 DEG C aqueous solutions, and copolyreaction is obtained after adjusting PH to 6.8 with pH value adjustment agent
Object, wherein, the sum of weight of a, b, c monomer is 1.This water-reducing agent can effectively reduce low water binder ratio strong concrete
Slurry viscosity, and have without being used in combination just with high collapse protection type polycarboxylate water-reducer to the slump and stream of concrete
It is dynamic to spend the effect that keeps for a long time, but high there are still synthesis cost, and with cement and aggregate bad adaptability, viscosity reduction effect
The problems such as fruit is relatively undesirable.
Invention content
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of poly carboxylic acid series water reducer of viscosity reduction type
And preparation method thereof.
To achieve the above object, the present invention uses following technical proposals：Pass through the unsaturated polyoxyethylene allyl diglycol of application
Ethers polymeric monomer, unsaturated acid monomer and a kind of polycarboxylic-acid of novel viscosity reduction type of modified monomer copolymerization containing ester group
Water-reducing agent, it is intended to solve the conventional products viscosity height existing in mixing concrete and concrete state difference, isolation bleeding,
The problems such as taking off bottom.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of poly carboxylic acid series water reducer of viscosity reduction type, which is characterized in that big by unsaturated polyethylene glycol oxide gylcol ether
Monomer, unsaturated acid monomer and modified monomer containing ester group are copolymerized under the action of redox system and chain-transferring agent, are used
General formula (1) represents：
In formula, a, b, c correspond to modified monomer containing ester group, unsaturated acid monomer, unsaturated polyoxyethylene allyl diglycol respectively
The structural unit number of three kinds of raw materials of ethers polymeric monomer；N is averaged addition molal quantity for ethylene oxide, n=23-50；
R1 is hydrogen atom, methyl or acetate；R2, R3 are hydrogen atom or methyl.
The present invention also has following additional technical feature：
Preferably, the unsaturated polyethylene glycol oxide glycol ether polymeric monomer, is represented with general formula (2)：
R1 is hydrogen atom, methyl or acetate in formula；R2, R3 are hydrogen atom or methyl；N is being averaged for ethylene oxide
Addition molal quantity is 23-50.
Preferably, the unsaturated acid monomer is methacrylic acid.
Preferably, carboxylate of the modified monomer containing ester group for salicylic acid and maleic acid anhydride reactant.
Preferably, the preparation method of the modified monomer containing ester group includes the following steps：
1) solvent absolute ethyl alcohol is added in into reaction kettle, reactant salicylic acid, maleic anhydride, catalyst is to toluene sulphur
Acid carries out being to slowly warm up to 35-45 DEG C；
2) it maintains the temperature at 35-45 DEG C and reacts 3.0-4.0h；
3) after keeping the temperature, room temperature is cooled to get to modified monomer containing ester group.
Wherein, the molar ratio 1 of the salicylic acid and maleic anhydride:1, the catalyst p-methyl benzenesulfonic acid accounts for reactant
The 2%~3% of total weight.
Preferably, it the unsaturated polyethylene glycol oxide gylcol ether polymeric monomer, unsaturated acid monomer and is modified containing ester group
The molar ratio of monomer is 1：(3-5)：(0.1-0.3).
Preferably, the copolyreaction uses redox system, and wherein oxidant is persulfate or peroxide, is gone back
Former agent is iron ammonium sulfate.
Preferably, the dosage of the oxidant is the 0.2-2.5% of total monomer weight, oxidant ammonium persulfate and reducing agent
The weight ratio of iron ammonium sulfate is 1：(0.3-0.6).
The present invention also provides a kind of preparation method of the poly carboxylic acid series water reducer of above-mentioned viscosity reduction type, according to following steps into
Row：
1) it after unsaturated polyethylene glycol oxide glycol ether polymeric monomer is added in into water, is stirred continuously, adds in reduction thereto
Agent simultaneously stirs 10min；
2) A material and B is added to expect with metering pump in solution made from step 1), A material solutes are modified monomer containing ester group, first
The mass fraction of the mixture of base acrylic acid and mercaptopropionic acid is 80% aqueous solution, and B expects the oxidation for mass fraction 1.5-5%
Agent aqueous solution, A material 2.5-4.0h are dripped off, and B material 3.0-4.5h is added；
3) in step 2) A material add after, keep the temperature 1.0h, in NaOH and solution to pH=6-7 to get.
Poly carboxylic acid series water reducer molecular structure have designability, high performance potentiality are big, by select different structure and
The monomer of function, designs the molecular structure of specific polycarboxylate water-reducer, optimum organization control backbone polymerization degree, side chain lengths,
Functional group's type realizes the high performance of poly carboxylic acid series water reducer, prepares the polycarboxylate water-reducer with viscosity reduction, to solve
The problem of certainly concrete viscosity is big, flowing velocity is slow.The present invention is from design molecular structure, according to polycarboxylate water-reducer
Molecular structure and its mechanism of action utilize the maleic anhydride salicylic acid esters modified monomer from synthesis and methacrylic acid, insatiable hunger
Free radical polymerization is carried out with polyethylene glycol oxide glycol ether polymeric monomer etc., synthesizes a kind of polycarboxylic-acid diminishing of novel viscosity reduction type
Agent product, it is intended to which realizing reduces viscosity while concrete high-strength is spent, improve rheological property of concrete and working performance, with full
Sufficient engine request.
Compared with prior art, the present invention has the advantages that：
1) due to selective oxidation ethylene be averaged addition molal quantity be 23-50 unsaturated polyethylene glycol oxide gylcol ether it is big
Monomer and unsaturated acid monomer, the introducing of-COOH is so that the water-reducing agent of synthesis has higher water-reducing rate, side chain polyoxyethylene
The introducing of alkene provides larger steric hindrance effect so that the water-reducing agent of synthesis has preferable dispersion retentivity；
2) lateral chain of ester group is introduced, can slowly be hydrolyzed in the alkaline environment of concrete, improve the dispersion retentivity of product；Together
When, lateral chain of ester group is short and molecular weight is small, and steric hindrance is small, and the water layer film thickness formed in concrete is also small, can release
More Free waters；Its hydroxy radical content is also few, and the hydrogen bond quantity for being capable of water in connection is also reduced, and can release again in this way
A certain amount of Free water；Side chain introduces phenyl ring, improves the amphipathic property of poly carboxylic acid series water reducer, releases polyoxyethylene
The free water that alkenyl chain is held onto can effectively reduce the viscosity of concrete；Using from synthesizing ester substance, drop is substantially reduced
The synthesis cost of viscous type poly carboxylic acid series water reducer.
3) main chain introduces methacrylic acid to reduce its HLB value, and HLB value can reduce it and combine water with water generation after reducing,
A certain amount of Free water can be released, shows high fluidity and low viscosity.
4) viscosity reduction type polycarboxylate water-reducer of the invention has the concrete of different cement and aggregate mixing extensive suitable
Ying Xing.
5) viscosity reduction type poly carboxylic acid series water reducer synthesis temperature of the invention is low, can exempt to heat, and saves energy consumption, economic and environment-friendly.
Specific embodiment
With reference to embodiment, the present invention will be further elaborated, it should explanation, the description below merely to
It explains the present invention, its content is not defined.
Embodiment 1：It is stated to simplify, HPEG23,50 and TPEG23,50 represent that ethylene oxide unit number is 23 and respectively
50 methallyl ethyl polyethylene-oxide ethylene glycol and isopentene group polyoxyethylene allyl diglycol；MAA represents methacrylic acid；
MAL represents maleic anhydride；SC represents salicylic acid；SA represents mercaptopropionic acid；The MA-SC of modified monomer containing ester group represents bigcatkin willow
The carboxylate of acid and maleic anhydride；(NH4)2S2O8Represent ammonium persulfate；FAS represents iron ammonium sulfate.
Synthesis example 1
Into four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device add in 23g absolute ethyl alcohols (0.5mol),
SC69g (0.5mol), 49g (0.5mol) maleic anhydride, catalyst p-methyl benzenesulfonic acid 3.0g, carry out being to slowly warm up to 40
DEG C, the reaction was continued at this temperature 3.0h.After reaction to get to 140g modified monomers containing ester group MA-SC.
Embodiment 1
100g deionized waters are added in four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device, are opened
Stirring adds in 107g HPEG23 (0.1mol), is stirred continuously thereto, and 0.25g FAS stirrings 15min is added in into flask
Afterwards, start to add A material and B material with metering pump.A material are 25.8g MAA (0.3mol), 2.36g MA-SC (0.01mol), 0.86g
SA and 7.26g deionized waters are made into the aqueous solution of mass fraction 80%；B material are 0.52g initiators (NH4)2S2O8Solution adds in
9.88g deionized waters are made into mass fraction 5% as aqueous solution.A material 2.5h is dripped off, and B material 3.0h is added.After A material add, at this
At a temperature of keep the temperature 1.0h, be neutralized to pH=6-7 with 30%NaOH, and add in quantitative water, acquisition mass fraction be 40% poly- carboxylic
Sour based water reducer product 1.
Embodiment 2
100g deionized waters are added in four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device, are opened
Stirring adds in 108.8g TPEG23 (0.1mol), is stirred continuously thereto, and 0.42g FAS stirrings 15min is added in into flask
Afterwards, start to add A material and B material with metering pump.A material are 21.5g MAA (0.25mol), 4.72g MA-SC (0.02mol), 1.0g
SA and 6.81g deionized waters are made into the aqueous solution of mass fraction 80%；B material are 0.85g initiators (NH4)2S2O8Solution adds in
16.15g deionized waters are made into mass fraction 1.5% as aqueous solution.A material 3.0h is dripped off, and B material 3.5h is added.After A material add,
1.0h is kept the temperature at this temperature, is neutralized to pH=6-7 with 30%NaOH, and add in quantitative water, and it is poly- for 40% to obtain mass fraction
Carboxylic acid water reducing agent product 2.
Embodiment 3
150g deionized waters are added in four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device, are opened
Stirring adds in 225.8g HPEG50 (0.1mol), is stirred continuously thereto, and 0.51g FAS stirrings 15min is added in into flask
Afterwards, start to add A material and B material with metering pump.A material for 17.2g MAA (0.20mol), 3.54g MA-SC (0.015mol),
1.6g SA and 5.59g deionized waters are made into the aqueous solution of mass fraction 80%；B material are 1.02g initiators (NH4)2S2O8Solution
It adds in 19.4g deionized waters and is made into mass fraction 5% as aqueous solution.A material 3.0h is dripped off, and B material 3.5h is added.After A material add,
1h is kept the temperature at such a temperature, is neutralized to pH=6-7 with 30%NaOH, and add in quantitative water, and it is poly- for 40% to obtain mass fraction
Carboxylic acid water reducing agent product 3.
Embodiment 4
150g deionized waters are added in four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device, are opened
Stirring adds in 227.6g TPEG50 (0.1mol), is stirred continuously thereto, and 0.62g FAS stirrings 15min is added in into flask
Afterwards, start to add A material and B material with metering pump.A material are 25.8g MAA (0.3mol), 4.72g MA-SC (0.02mol), 1.6g
SA and 8.03g deionized waters are made into the aqueous solution of mass fraction 80%；B material are 1.23g initiators (NH4)2S2O8Solution adds in
23.4g deionized waters are made into mass fraction 5% as aqueous solution.A material 4.0h is dripped off, and B material 4.5h is added.After A material add, at this
At a temperature of keep the temperature 1.0h, be neutralized to pH=6-7 with 30%NaOH, and add in quantitative water, acquisition mass fraction be 40% poly- carboxylic
Sour based water reducer product 4.
Comparative example 1
100g deionized waters are added in four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device, are opened
Stirring adds in 108.8g TPEG23 (0.1mol), is stirred continuously thereto, and 0.54g FAS stirrings 15min is added in into flask
Afterwards, start to add A material and B material with metering pump.A material are 25.8g MAA (0.30mol), 0.6g SA and 6.60g deionized waters are matched
Into the aqueous solution of mass fraction 80%；B material are 1.0g initiators (NH4)2S2O8Solution adds in 19.0g deionized waters and is made into quality
Score 5% is aqueous solution.A material 3.0h is dripped off, and B material 3.5h is added.After A material add, 1.0 h are kept the temperature at such a temperature, with 30%
NaOH is neutralized to pH=6-7, and adds in quantitative water, and acquisition mass fraction is 40% poly carboxylic acid series water reducer contrast product 1.
Comparative example 2
150g deionized waters are added in four mouthfuls of glass flasks with thermometer, condenser pipe and agitating device, are opened
Stirring adds in 225.8g HPEG50 (0.1mol), is stirred continuously thereto, and 0.75g FAS stirrings 15min is added in into flask
Afterwards, start to add A material and B material with metering pump.A material are 17.2g MAA (0.20mol), 1.6g SA and 4.70g deionized waters are matched
Into the aqueous solution of mass fraction 80%；B material are 1.25g initiators (NH4)2S2O8Solution adds in 23.8g deionized waters and is made into matter
Amount score 5% is aqueous solution.A material 2.5h is dripped off, and B material 3.0h is added.After A material add, 1.0 h are kept the temperature at such a temperature, are used
30%NaOH is neutralized to pH=6-7, and adds in quantitative water, obtains mass fraction as the comparison production of 40% poly carboxylic acid series water reducer
Product 2.
Implementation result
Join board P.O42.5 cement in selection, using the test method of GB8076-2008, liquid poly carboxylic acid series water reducer is mixed
It measures as 0.30% (the solid meter of folding).Every cube of concrete mix cement：Sand：Stone：Water=490：684：1116：140, examination
It tests and the results are shown in Table 1.
Synthesizing polycarboxylic acid dehydragent performance comparison test in 1 embodiment of table and comparative example
From table 1 it follows that the novel poly carboxylic acid series water reducer synthesized in embodiment and the routine synthesized in comparative example
Poly carboxylic acid series water reducer product compare, there is big water-reducing rate and Gao Bao plasticity, flow time to be obviously shortened, using embodiment
The novel poly carboxylic acid series water reducer of synthesis prepare concrete viscosity is low, flow time is short, good fluidity, and without isolation bleeding
And bottom phenomenon is taken off, working performance and rheological property are excellent, suitable for preparing the concrete such as high-strength, the strong, self-compaction of superelevation.
The above embodiments of the present invention are the description of the invention and cannot limit the present invention, with the claims in the present invention
Any change and combination in the comparable meaning and scope of book, are all considered as in the range of claims.
Claims (10)
1. a kind of poly carboxylic acid series water reducer of viscosity reduction type, which is characterized in that by the unsaturated big list of polyethylene glycol oxide gylcol ether
Body, unsaturated acid monomer and modified monomer containing ester group are copolymerized under the action of redox system and chain-transferring agent, with logical
Formula (1) represents：
In formula, a, b, c correspond to modified monomer containing ester group, unsaturated acid monomer, unsaturated polyethylene glycol oxide glycol ether respectively
The structural unit number of three kinds of raw materials of class polymeric monomer；N is averaged addition molal quantity for ethylene oxide, n=23-50；
R1 is methyl；R2, R3 are hydrogen atom or methyl.
2. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 1, which is characterized in that the unsaturation polyoxyethylene
Allyl diglycol ethers polymeric monomer is represented with general formula (2)：
R1 is hydrogen atom, methyl or acetate in formula；R2, R3 are hydrogen atom or methyl；N is that the average addition of ethylene oxide rubs
That number is 23-50.
3. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 1, which is characterized in that the unsaturated acid monomer is
Methacrylic acid.
4. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 1, which is characterized in that the modified monomer containing ester group
For salicylic acid and the carboxylate of maleic acid anhydride reactant.
5. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 4, which is characterized in that the modified monomer containing ester group
Preparation method include the following steps：
1) solvent absolute ethyl alcohol is added in into reaction kettle, reactant salicylic acid, maleic anhydride, catalyst p-methyl benzenesulfonic acid,
It carries out being to slowly warm up to 35-45 DEG C；
2) it maintains the temperature at 35-45 DEG C and reacts 3.0-4.0h；
3) after keeping the temperature, room temperature is cooled to get to modified monomer containing ester group.
Wherein, the molar ratio of the salicylic acid and maleic anhydride is 1:1, it is total that the catalyst p-methyl benzenesulfonic acid accounts for reactant
The 2%~3% of weight.
6. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 1, which is characterized in that the unsaturation polyoxyethylene
The molar ratio for changing glycol ether polymeric monomer, unsaturated acid monomer and the modified monomer containing ester group is 1：(3-5)：(0.1-0.3).
7. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 1, which is characterized in that the copolymerization is gone back using oxidation
Former initiation system, wherein oxidant are persulfate or peroxide, and reducing agent is iron ammonium sulfate.
8. the poly carboxylic acid series water reducer of viscosity reduction type according to claim 1, which is characterized in that the dosage of the oxidant is
The weight ratio of the 0.2-2.5% of total monomer weight, oxidant and reducing agent iron ammonium sulfate is 1：(0.3-0.6).
9. viscosity reduction type poly carboxylic acid series water reducer according to claim 1, which is characterized in that the chain-transferring agent is sulfhydrylation
Object is closed, dosage is the 0.2-1.0% of total monomer weight.
10. according to the preparation method of the poly carboxylic acid series water reducer of claim 1-9 any one of them viscosity reduction types, feature exists
In following the steps below：
1) it after unsaturated polyethylene glycol oxide gylcol ether polymeric monomer is added in into water, is stirred continuously, adds in reducing agent thereto
And stir 15min；
2) A material and B is added to expect with metering pump in solution made from step 1), A material solutes are modified monomer containing ester group, mercaptopropionic acid
The aqueous solution that mass fraction with the mixture of methacrylic acid is 80%, aqueous oxidizing agent solution of the B material for mass fraction 1.5-5%
Liquid, A material 2.5-4.0h are dripped off, and B material 3.0-4.5h is added；
3) in step 2) A material add after, at such a temperature keep the temperature 1.0h after, in NaOH and solution to pH=6-7 to get.
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| CN110041468A (en) * | 2019-04-26 | 2019-07-23 | 四川同舟化工科技有限公司 | Viscosity reduction type polycarboxylate water-reducer |
| CN110790529A (en) * | 2019-12-11 | 2020-02-14 | 广东科隆智谷新材料股份有限公司 | High-strength concrete viscosity-reducing water reducer and preparation method thereof |
| CN112390921A (en) * | 2020-11-05 | 2021-02-23 | 云南建投高分子材料有限公司 | Synthetic viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
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