CN107337766A - A kind of high-adaptability polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of high-adaptability polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN107337766A CN107337766A CN201611254169.5A CN201611254169A CN107337766A CN 107337766 A CN107337766 A CN 107337766A CN 201611254169 A CN201611254169 A CN 201611254169A CN 107337766 A CN107337766 A CN 107337766A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- 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
- 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
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
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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 invention discloses a kind of high-adaptability polycarboxylate water-reducer.High-adaptability polycarboxylate water-reducer of the present invention is 1 ~ 5 by mol ratio：1：0.1~0.3：0.05 ~ 0.2 carboxylic acid monomer A, high molecular weight polyether polymeric monomer B, functional polyalkylene cation polymeric monomer C and unsaturated phosphate ester monomer D carry out free radicals copolymerization reaction and are made.The high-adaptability polycarboxylate water-reducer of the present invention is applied to the high area of sandstone aggregate clay content, and has the advantages of low-dosage, high diminishing and high-thin arch dam；The preparation technology of the high-adaptability polycarboxylate water-reducer of the present invention is simple, and production process is green, cost is low.
Description
Technical field
The present invention relates to a kind of high-adaptability polycarboxylate water-reducer and preparation method thereof, belongs to concrete admixture technology neck
Domain.
Background technology
In recent years, as the development of concrete technology, the application of high performance water reducing agent of polyocarboxy acid are constantly popularized, with its volume
Low, many advantages, such as water-reducing rate is high, function of slump protection is excellent, contraction is low, energy-conserving and environment-protective, extensively should gradually it be obtained in numerous engineerings
With.But some problems are at the same time also exposed, particularly clay content wields influence to polycarboxylate water-reducer performance in sandstone
Significantly, so as to cause concrete fluidity poor, slump-loss is big, greatly constrains the popularization of polycarboxylate water-reducer with answering
With.And domestic construction is gradually decreased with sand and stone resources, some are used for construction material, sand on a large scale containing the higher sandstone of mud
Stone clay content excessive problem is urgently to be resolved hurrily.
It is general using punching when the clay content of sandstone aggregate is exceeded and influences working performance of concrete in practice of construction
The method for washing sandstone aggregate, but this method can destroy the grading of sandstone and can produce large amount of sewage pollution environment；And use super mix
Although the polycarboxylic acids of amount can improve the service behaviour of its concrete, the cost of folk prescription concrete can be substantially improved, can also be caused
The problems such as concrete disintegration is serious, setting time is long.
Because influence of the mud powder in sandstone aggregate to the dispersive property of polycarboxylate water-reducer is very notable, domestic and international expert
Scholar expands some row on research of the mud powder to polycarboxylate water-reducer performance impact, and the mechanism being widely recognized as at present is
Suction-operated of the layer structure of mud powder to polycarboxylate water-reducer.German professor J.Plank thinks clay and polycarboxylate water-reducer
Between physical action not only be present but also chemical action be present, wherein water reducer is adsorbed its surface by clay by physical action, then
Water reducer side chain or entirety are adsorbed onto by its interlayer by chemical action, so that subtracting with the polycarboxylic acids of cement granules effect
Aqua is largely reduced, and causes concrete performance to be remarkably decreased.Magarotto, which is taught from polycarboxylate water-reducer molecule structure, to be considered,
It was found that the polycarboxylate water-reducer that different type contains combed side-chain structure is all very sensitive to mud, this is due to the clay in mud powder
The combed side-chain structure of mineral matter interlayer structure and polycarboxylate water-reducer links comparison match, and polycarboxylate water-reducer is most of to change
The mode intercalation for learning absorption is adsorbed in the surface of clay mineral in clay mineral rather than in a manner of charge adsorption.State
The metal sun that interior professor Wang Lin then thinks the mud powder adsorptivity of itself and hydrophobic group oriented attachment collective effect and mud powder adsorbs from
The chelation of son and polycarboxylate water-reducer is the mechanism of mud powder absorption polycarboxylate water-reducer.
It can synthesize the polycarboxylate water-reducer with high-adaptability by designing polycarboxylic acid structure at present.Closing
Following technology path is usually taken during into such high-adaptability polycarboxylate water-reducer：Side chain dimensions are increased, introduces and can reduce
Functional group, polycarboxylic acids of the synthesis without PEO side chains, reduction polycarboxylic acids backbone charge density or the extension polyether lateral chain of adsorption by clay
Length etc..Professor Plank proposes that synthesis does not contain the polycarboxylate water-reducer of PEO side chains, does not use polymeric monomer and directly uses third
Olefin(e) acid and its hydroxy ester carry out copolymerization and are prepared for a kind of anti-stick soil type polycarboxylate water-reducer, have preferable using effect.It is domestic
Xiao Fei et al. on polycarboxylate water-reducer side chain by introducing anti-stick soil matrix group, so as to reduce EO on polycarboxylate water-reducer side chain
The hydrogen bond action of group and clay interlayer, the suppression adsorption by clay type polycarboxylate water-reducer of synthesis make mortar and concrete containing mud
With good service behaviour when measuring within the specific limits.A kind of anti-stick soil type is described in Chinese patent CN102923989A
Polycarboxylate water-reducer, polyethylene polyamine monomer has been used in the patent, mainly adsorbed using polyethylene polyamine chain in clay
Grain surface can play shielding peptizaiton, but only test to whether a type of soil, anti-mud performance have with universality
It is to be tested.Chinese patent CN102358763A is prepared for a kind of additive for suppressing side effect of clay, substantially belongs to a kind of small
Molecular regulation agent, but water-reducing rate is limited, is also required to be compounded with water reducer in.But preparation method solves aggregate and contains mud
Can not only cost be brought to greatly improve during amount problem, it also occur that the problems such as the compatibility of organic-inorganic component, storage stability.
Chinese patent CN102617811A describes a kind of preparation method of the anti-mud agent of amphoteric ethylene polymer concrete, then with first ester
The method polymerizeing after change, introduces cation group in the molecular structure, obtains a kind of anti-mud agent, but this method esterification and polymerization
Temperature is higher, is unfavorable for industrial applications, more due to introducing the vinyl monomer containing chlorion, inevitably results in reinforcing bar
Corrosion.
The content of the invention
A kind of preparation method of high-adaptability polycarboxylate water-reducer, the system are provided during the technical problems to be solved by the invention
Preparation Method has synthesized a kind of polycarboxylic acids macromolecular with large space steric effect and electron screening effect, realizes to clay mineral
The resistant function of matter, so as to reduce susceptibility of the polycarboxylate water-reducer to aggregate clay content, play the diminishing of polycarboxylate water-reducer
Effect, improve the workability and durability of concrete.
From the point of view of the structure of polycarboxylate water-reducer, its hydrophilic PEO side chain easily forms hydrogen bond structure with clay interlayer,
So that largely being reduced with the polycarboxylate water-reducer of cement granules effect, concrete performance is caused to be remarkably decreased.From this layer
Face consider, in the molecular structure of polycarboxylate water-reducer introduce the unsaturated monomer containing polycation macromolecular chain, the sun from
Sub- polymer chain structure can adsorb multiple clay particles, and in clay particle surface one layer of organic cationic polymer of formation
Diaphragm is adsorbed, absorption of the clay to water reducer active ingredient is effectively prevented, so as to increase substantially polycarboxylate water-reducer
Anti- mud performance and adaptability, while introduce phosphate adsorption group and can then be effectively improved hydrated cementitious entringite and formed initial stage
Crystal morphology, and then play water-reducing, slow-settling protect the effect of collapsing.So as to which suction of the clay to polycarboxylate water-reducer be greatly reduced
Attached effect, improve adaptability of the polycarboxylate water-reducer to sandstone aggregate.
The invention provides a kind of high-adaptability polycarboxylate water-reducer, is 1~5 by mol ratio：1：0.1~0.3：0.05~
0.2 carboxylic acid monomer A, high molecular weight polyether polymeric monomer B, functional polyalkylene cation polymeric monomer C and unsaturated phosphate ester monomer D enter
Row free radicals copolymerization reaction is made, wherein：
Shown in carboxylic acid monomer A structures such as formula (I)：
In formula, R1For H or COOM；R2For H, CH3Or CH2COOM；And work as R1For COOM when, R2It is asynchronously CH3Or
CH2COOM；M is hydrogen atom, alkali metal ion, alkaline-earth metal ion, ammonium ion or organic amine group；
Shown in high molecular weight polyether polymeric monomer B structure such as formula (II)：
In formula, R3For H or CH3；R4For the alkyl of H or 1~3 carbon atom；X1For CH2、CH2CH2、OCH2CH2Or
OCH2CH2CH2CH2；N is polyoxyethylated average addition molal quantity, for 25~150 integer；
Shown in functional polyalkylene cation polymeric monomer C-structure such as formula (III)：
In formula, m is the average addition molal quantity of NIPA, the integer for being 5~10；
Shown in unsaturated phosphate ester monomer D structures such as formula (IV)：
In formula, R5For H or CH3；R6For CH2CH2Or CH2CH2CH2。
The weight average molecular weight of high-adaptability polycarboxylate water-reducer of the present invention is 20000~60000；Molecular weight is too low,
Then the initial dispersion ability of water reducer reduces；Molecular weight is too high, then the initial dispersion ability of water reducer and later stage, which protect, collapses ability all
It can weaken.
High-adaptability polycarboxylate water-reducer of the present invention, the carboxylic acid monomer A are selected from acrylic acid, methacrylic acid, horse
Carry out any one in sour, itaconic acid or its sodium salt, sylvite, calcium salt, ammonium salt, organic amine salt；
The high molecular polyether polymeric monomer B is selected from allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, cyclobutenyl
Appointing in APEO, methyl butene base APEO, vinyl APEO, hydroxyl butyl vinyl APEO
Meaning is a kind of；
The functional polyalkylene cation polymeric monomer C is selected from maleimide end-sealed NIPA；
The unsaturated phosphate ester monomer D is selected from hydroxy ethyl phosphate, acrylic acid Hydroxypropyl phosphate ester, methyl-prop
Any one in olefin(e) acid hydroxyethyl phosphate, hydroxyethyl methacrylate propyl phosphate.
Present invention also offers the preparation method of above-mentioned high-adaptability polycarboxylate water-reducer, comprise the following steps：
(1) high molecular weight polyether polymeric monomer B and functional polyalkylene cationic monomer C are dissolved in aqueous solvent, stirring heating is molten
Solution is into the aqueous solution；
(2) mixed aqueous solution is mixed evenly into carboxylic acid monomer A, unsaturated phosphorus acid monomer D and water；
(3) in the presence of initiator, the mixed aqueous solution in step (2) is at the uniform velocity added dropwise in the solution in step (1),
Complete soln continues constant temperature insulation after being added dropwise, free radicals copolymerization reaction occurs for monomer in solution, after reaction terminates, in solution
It is 6~8 or so to add alkaline matter and be neutralized to pH value, produces the polycarboxylate water-reducer；
Monomer B and C in free radicals copolymerization reaction in step (3), because its molecular weight is higher, double bond content is relatively low, due to
Steric effect, cause double-bond polymerization difficult；In order to improve the conversion ratio of monomer B and C in the course of the polymerization process, monomer B and C charging
Mode is all fed intake using directly disposable before polymerization；
Initiator described in step (3) is free radical water soluble starter, including oxidation category initiator and redox are drawn
Send out agent；The oxidation category initiator is, individually from oxidation component as initiator, the redox initiator is from oxygen
Change the composition of component and reduction components as initiator；Wherein, when the initiator is oxidation category initiator, dosage is monomer
The 0.1%~2% of A+B+C+D gross masses, when the initiator is redox initiator, total dosage of wherein oxidation component accounts for
The mass ratio of both the 0.1%~2% of monomer A+B+C+D gross masses, oxidation component and reduction components is 0.4~4：1；
Oxidation component in the initiator disposable all feed intake can mix in step (1) with monomer B and monomer C
Close, or be configured to after the aqueous solution with the mixed aqueous solution in step (2) with water while at the uniform velocity instill in step (1) described solution；
And monomer A, monomer D, the reduction components in initiator, chain-transferring agent and water composition mixed aqueous solution, using even after stirring
The mode that speed is added dropwise is added in step (1) described solution；
Also include water miscible chain-transferring agent described in step (2) in mixed aqueous solution；The dosage of the chain-transferring agent is
The 0.05%~1% of monomer A+B+C+D gross masses, water miscible chain-transferring agent are equal to adjust the weight of prepared polycarboxylate water-reducer
Molecular weight；
In step (3), free radicals copolymerization reaction temperature is 35~85 DEG C, and reaction temperature is mainly divided with used initiator
It is relevant with half-life period to solve efficiency；Mixed aqueous solution time for adding was controlled at 2~5 hours；When initiator oxidation component solution is added dropwise
Between compared with monomer solution extend 0.5 hour；In order to improve the conversion ratio of monomer, it is necessary to drip follow-up continuation of insurance in initiator solution
Temperature, soaking time are 1~5h.
The preparation method of high-adaptability polycarboxylate water-reducer of the present invention, the oxidation category initiator include persulfate
Or water-soluble azo class compound；The redox initiator includes persulfate and bisulfites, sulphite, thio
Sulfate, pyrosulfite or the ferrous salt composition of any one, or peroxide and rongalite or L- it is anti-bad
The hematic acid composition of any one；The chain-transferring agent is mercaptan type chain transfer agent.
The preparation method of high-adaptability polycarboxylate water-reducer of the present invention, after step (3) copolyreaction terminates, further
Neutralized with alkaline matter, to strengthen the storage stability of product；Used alkaline matter includes monovalent metal and/or divalence gold
Hydroxide, oxide or the carbonate of category, ammonium hydroxide, organic amine；The dosage of alkaline matter is the pH of regulation reaction product
It is worth to 6~8.
The preparation method of high-adaptability polycarboxylate water-reducer of the present invention, the oxidation category initiator may be selected from persulfuric acid
Potassium, azo diisobutyl amidine hydrochloride, azodiisobutyronitrile；
The redox initiator may be selected from the composition, potassium peroxydisulfate and sulfurous acid of hydrogen peroxide and L-AA
The composition of the composition of hydrogen sodium, hydrogen peroxide and rongalite；
The chain-transferring agent may be selected from 2 mercaptopropionic acid, 3- mercaptopropionic acids, 2- mercaprols, 3- mercaprols, sulfydryl second
Acid, mercaptoethanol；
The alkaline matter may be selected from sodium hydroxide, triethanolamine, potassium hydroxide, triisopropanolamine.
The preparation method of high-adaptability polycarboxylate water-reducer of the present invention, carboxylic acid monomer A, high score described in step (3)
Mass concentration when sub- polyether macromonomer B, functional polyalkylene cation polymeric monomer C and unsaturated phosphorus acid monomer D polymerize is preferably 35
~50%.In free radicals copolymerization reaction, polymerization concentration also has significant impact to the performance of additive：Concentration is too low, water-reducing rate
Reduce, and production efficiency reduces；Concentration is too high, easily causes gel occurs in polymerization process, causes inventory disposal.
Present invention also offers application of the above-mentioned high-adaptability polycarboxylate water-reducer in concrete preparation, prepared height
Adaptability polycarboxylate water-reducer can be used directly, can also be selected to add a certain proportion of defoaming according to engineering practice
The functional form auxiliary agent such as agent, retarder, air entraining agent and thickener, is mixed by compounding mode, to adjust cement-based material
Air content, setting time and cohesiveness, improve the combination property of cement-based material.
The volume of the high-adaptability polycarboxylate water-reducer is the 0.1%~0.5% of total binder materials weight.Volume mistake
It is low, then it is unsatisfactory to the dispersion effect of cement；Volume is too high, then excreting water phenomenon easily occurs, also results in economically
Waste.Engineering staff can be preferred within this range according to actual conditions.
The high-adaptability polycarboxylate water-reducer of the present invention is applied to the high area of sandstone aggregate clay content, and has low-mix
The advantages of amount, high diminishing and high-thin arch dam；The preparation technology of the high-adaptability polycarboxylate water-reducer of the present invention is simple, and production process is green
Colour circle is protected, cost is low.
Embodiment
The present invention is specifically described below in conjunction with specific embodiment, to be best understood from the content of the invention,
But the content of embodiment is not intended to limit the protection domain of the invention.
The weight average molecular weight and polymerisation conversion of polycarboxylate water-reducer described in embodiment are to use high productivity computing instrument
(GPC) it is measured.Wherein splitter is using two gel chromatographic columnses series connection of Shodex SB806+803,40 DEG C of column temperature, flowing
It is mutually 0.1M NaNO3The aqueous solution, flow velocity 1.0ml/min, sample size are the 20 μ l0.5% aqueous solution；Detector：Shodex
RI-71 type differential refraction detectors；Standard curve making uses polyethylene glycol GPC reference material (Sigma-Aldrich, molecular weight
1010000,478000,263000,118000,44700,18600,6690,1960,628,232).
The raw material used in synthetic example and comparative example are listed in table 1, as follows：
Compound numbers in the synthetic example of table 1 and comparative example
| Code name | Compound name | Source |
| A-1 | Acrylic acid | It is commercially available |
| A-2 | Methacrylic acid | It is commercially available |
| A-3 | Maleic acid | It is commercially available |
| A-4 | Itaconic acid | It is commercially available |
| A-5 | PAA | It is commercially available |
| B-1 | Allyl polyethenoxy ether (n=25) | It is commercially available |
| B-2 | Methyl allyl polyoxyethylene ether (n=50) | It is commercially available |
| B-3 | Cyclobutenyl APEO (n=75) | It is commercially available |
| B-4 | Methyl butene base APEO (n=100) | It is commercially available |
| B-5 | Vinyl APEO (n=150) | It is commercially available |
| B-6 | Hydroxyl butyl vinyl APEO (n=100) | It is commercially available |
| C-1 | Maleimide end-sealed NIPA (m=5) | It is commercially available |
| C-2 | Maleimide end-sealed NIPA (m=10) | It is commercially available |
| C-3 | Maleimide end-sealed NIPA (m=15) | It is commercially available |
| D-1 | Hydroxy ethyl phosphate | It is commercially available |
| D-2 | Acrylic acid Hydroxypropyl phosphate ester | It is commercially available |
| D-3 | Hydroxy ethyl phosphate | It is commercially available |
| D-4 | Hydroxyethyl methacrylate propyl phosphate | It is commercially available |
Embodiment 1
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 200.0g distilled water,
275.0g monomer B-1 and 20.1g monomer C-1, stir rising temperature for dissolving.85 DEG C are warming up to, it is then that 18.0g monomers A-1,2.6g is mono-
Body D-1,1.1g 3- mercaptopropionic acids and 100.0g water are mixed and uniform monomer solution are made, and it is at the uniform velocity added dropwise into circle
In the flask of bottom, time for adding 3h.At the uniform velocity it is added dropwise simultaneously molten by 110.0g distilled water and initiator that 5.4g potassium peroxydisulfates are prepared
Liquid, time for adding 3.5h.Complete soln continues constant temperature insulation 3h after being added dropwise, be then cooled to 40 DEG C or so, add hydrogen
Sodium oxide molybdena is neutralized to pH=7.0 or so, obtains the high-adaptability polycarboxylate water-reducer that solid content is 43.5%.
Embodiment 2
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
275.0g monomer B-1 and 102.7g monomer C-2, stir rising temperature for dissolving.80 DEG C are warming up to, then by 21.5g monomers A-2,11.3g
Monomer D-2,3.5g TGA and 80.0g water, which mix, is made uniform monomer solution, and it is at the uniform velocity added dropwise into round bottom
In flask, time for adding 2.5h.At the uniform velocity it is added dropwise and is matched somebody with somebody by 120.0g distilled water and 6.15g azo diisobutyl amidine hydrochlorides simultaneously
The initiator solution put, time for adding 3h.Complete soln continues constant temperature insulation 3h after being added dropwise, be then cooled to 40 DEG C
Left and right, add triethanolamine and be neutralized to pH=7.0 or so, obtain the high-adaptability polycarboxylate water-reducer that solid content is 49.2%.
Embodiment 3
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
275.0g monomer B-1,48.3g monomer C-3 and 3.4g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.35 DEG C are warming up to, so
29.0g monomer A-3,11.3g monomer D-3,1.76g mercaptoethanol, 0.92g L-AAs and 250.0g water are mixed afterwards and stirred
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h by mixing into uniform monomer solution.Monomer solution is added dropwise
Continue constant temperature insulation 3h afterwards, be then cooled to 30 DEG C or so, add potassium hydroxide and be neutralized to pH=7.5 or so, obtain solid content
For 43.3% high-adaptability polycarboxylate water-reducer.
Embodiment 4
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
275.0g monomer B-1 and 60.3g monomer C-1, stir rising temperature for dissolving.50 DEG C are warming up to, it is then that 32.5g monomers A-4,3.0g is mono-
Body D-4,2.38g 2 mercaptopropionic acid, 0.97g sodium hydrogensulfites and 150.0g water mix and uniform monomer solution are made,
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h.At the uniform velocity it is added dropwise by 140.0g distilled water and 3.54g persulfuric acid simultaneously
The initiator solution of potassium configuration, time for adding 2.5h.Complete soln continues constant temperature insulation 4h after being added dropwise, then cool
To 40 DEG C or so, add sodium hydroxide and be neutralized to pH=7.5 or so, obtain the high-adaptability polycarboxylic acids that solid content is 41.5% and subtract
Aqua.
Embodiment 5
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
220.0g monomer B-2,13.7g monomer C-2 and 1.72g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.65 DEG C are warming up to,
Then by 36.0g monomer A-1,1.2g monomer D-4,1.06g3- mercaprol, 0.23g rongalites and 260.0g water
Uniform monomer solution is made in mixing, it is at the uniform velocity added dropwise in round-bottomed flask, time for adding 3h.Monomer solution drips
Add and continue constant temperature insulation 2h after finishing, be then cooled to 40 DEG C or so, add triisopropanolamine and be neutralized to pH=7.0 or so, obtain
To the high-adaptability polycarboxylate water-reducer that solid content is 35.8%.
Embodiment 6
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
330.0g monomer B-3 and 58.0g monomer C-3, stir rising temperature for dissolving.75 DEG C are warming up to, it is then that 36.0g monomers A-1,4.5g is mono-
Body D-3,1.15g 2 mercaptopropionic acid and 100.0g water, which mix, is made uniform monomer solution, and it is at the uniform velocity added dropwise into circle
In the flask of bottom, time for adding 2h.At the uniform velocity it is added dropwise simultaneously molten by 150.0g distilled water and initiator that 4.32g potassium peroxydisulfates are prepared
Liquid, time for adding 2.5h.Complete soln continues constant temperature insulation 3h after being added dropwise, be then cooled to 40 DEG C or so, add hydrogen
Sodium oxide molybdena is neutralized to pH=7.0 or so, obtains the high-adaptability polycarboxylate water-reducer that solid content is 47.3%.
Embodiment 7
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
440.0g monomer B-4 and 8.1g monomer C-1, stir rising temperature for dissolving.85 DEG C are warming up to, it is then that 36.0g monomers A-1,4.5g is mono-
Body D-2,1.03g TGA and 100.0g water, which mix, is made uniform monomer solution, and it is at the uniform velocity added dropwise into round bottom
In flask, time for adding 2h.The initiator by 150.0g distilled water and the configuration of 3.07g azodiisobutyronitriles is at the uniform velocity added dropwise simultaneously
The aqueous solution, time for adding 2.5h.Complete soln continues constant temperature insulation 3h after being added dropwise, be then cooled to 40 DEG C or so, add
Enter triethanolamine and be neutralized to pH=7.0 or so, obtain the high-adaptability polycarboxylate water-reducer that solid content is 48.3%.
Embodiment 8
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
330.0g monomer B-5,20.5g monomer C-2 and 1.13g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.45 DEG C are warming up to,
Then 18.0g monomer A-1,0.5g monomer D-1,0.86g mercaptoethanol, 0.35g L-AAs and 280.0g water are mixed and stirred
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 3h by mixing into uniform monomer solution.Monomer solution is added dropwise
Continue constant temperature insulation 1.5h afterwards, be then cooled to 30 DEG C or so, add potassium hydroxide and be neutralized to pH=7.5 or so, admittedly contained
Measure the high-adaptability polycarboxylate water-reducer for 42.5%.
Embodiment 9
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
220.0g monomer B-6 and 19.3g monomer C-3, stir rising temperature for dissolving.55 DEG C are warming up to, it is then that 7.2g monomers A-1,1.1g is mono-
Body D-1,0.38g 2 mercaptopropionic acid, 0.78g sodium hydrogensulfites and 120.0g water mix and uniform monomer solution are made,
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h.At the uniform velocity it is added dropwise by 120.0g distilled water and 2.83g persulfuric acid simultaneously
The initiator solution of potassium configuration, time for adding 2.5h.Complete soln continues constant temperature insulation 2h after being added dropwise, then cool
To 40 DEG C or so, add sodium hydroxide and be neutralized to pH=7.5 or so, obtain the high-adaptability polycarboxylic acids that solid content is 35.6% and subtract
Aqua.
Embodiment 10
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
275.0g monomer B-1,85.6g monomer C-2 and 1.37g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.55 DEG C are warming up to,
Then by 70.5g monomer A-5,7.9g monomers D-1,0.95g 3- mercaprols, 0.21g rongalites and 300.0g water
Uniform monomer solution is made in mixing, it is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h.Monomer solution drips
Add and continue constant temperature insulation 2h after finishing, be then cooled to 40 DEG C or so, add triisopropanolamine and be neutralized to pH=7.0 or so, obtain
To the high-adaptability polycarboxylate water-reducer that solid content is 46.2%.
Embodiment 11
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
220.0g monomer B-2,24.1g monomer C-1 and 1.02g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.40 DEG C are warming up to,
Then 34.4g monomer A-2,2.1g monomer D-1,0.97g mercaptoethanol, 0.24g L-AAs and 200.0g water are mixed and stirred
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h by mixing into uniform monomer solution.Monomer solution is added dropwise
Continue constant temperature insulation 2h afterwards, be then cooled to 30 DEG C or so, add potassium hydroxide and be neutralized to pH=7.5 or so, obtain solid content
For 40.2% high-adaptability polycarboxylate water-reducer.
Embodiment 12
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
220.0g monomer B-6,14.5g monomer C-3 and 0.91g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.45 DEG C are warming up to,
Then 19.5g monomer A-4,0.8g monomer D-2,0.69g mercaptoethanol, 0.32g L-AAs and 225.0g water are mixed and stirred
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h by mixing into uniform monomer solution.Monomer solution is added dropwise
Continue constant temperature insulation 1.5h afterwards, be then cooled to 30 DEG C or so, add sodium hydroxide and be neutralized to pH=7.5 or so, admittedly contained
Measure the high-adaptability polycarboxylate water-reducer for 36.5%.
Comparative example 1
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, add 200.0g distilled water and
275.0g monomer B-1, stir rising temperature for dissolving.Be warming up to 85 DEG C, then by 18.0g monomer A-1,1.1g3- mercaptopropionic acids and
100.0g water mixes and uniform monomer solution is made, and it is at the uniform velocity added dropwise in round-bottomed flask, time for adding 3h.Together
When the initiator solution prepared by 110.0g distilled water and 5.4g potassium peroxydisulfates, time for adding 3.5h is at the uniform velocity added dropwise.It is all molten
Liquid continues constant temperature insulation 3h after being added dropwise, be then cooled to 40 DEG C or so, adds sodium hydroxide and is neutralized to pH=7.0 or so,
Obtain the polycarboxylate water-reducer that solid content is 41.5%.
Comparative example 2
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
220.0g monomer B-6 and 0.91g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.It is warming up to 45 DEG C, it is then that 19.5g is mono-
Body A-4,0.69g mercaptoethanol, 0.32g L-AAs and 215.0g water mix and uniform monomer solution are made, will
It is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h.Monomer solution continues constant temperature insulation 1.5h after being added dropwise, then drop
Temperature adds sodium hydroxide and is neutralized to pH=7.5 or so to 30 DEG C or so, obtains the polycarboxylate water-reducer that solid content is 35.5%.
Comparative example 3
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 200.0g distilled water,
275.0g monomer B-1 and 20.1g monomer C-1, stir rising temperature for dissolving.85 DEG C are warming up to, then by 18.0g monomers A-1,1.1g
3- mercaptopropionic acids and 100.0g water, which mix, is made uniform monomer solution, and it is at the uniform velocity added dropwise in round-bottomed flask, dripped
It is 3h between added-time.The initiator solution prepared by 110.0g distilled water and 5.4g potassium peroxydisulfates, time for adding are at the uniform velocity added dropwise simultaneously
For 3.5h.Complete soln continues constant temperature insulation 3h after being added dropwise, be then cooled to 40 DEG C or so, adds sodium hydroxide and is neutralized to
PH=7.0 or so, obtain the polycarboxylate water-reducer that solid content is 43.3%.
Comparative example 4
In the 1L glass round bottom flask equipped with thermometer, agitator and dropping funel, addition 220.0g distilled water,
220.0g monomer B-6,14.5g monomer C-3 and 0.91g concentration are 30% hydrogen peroxide, stir rising temperature for dissolving.45 DEG C are warming up to,
Then 19.5g monomer A-4,0.69g mercaptoethanol, 0.32g L-AAs and 225.0g water are mixed and are made uniformly
Monomer solution, it is at the uniform velocity added dropwise in round-bottomed flask, time for adding 2h.Monomer solution continues constant temperature after being added dropwise to be protected
Warm 1.5h, 30 DEG C or so are then cooled to, add sodium hydroxide and be neutralized to pH=7.5 or so, it is 36.4% to obtain solid content
Polycarboxylate water-reducer.
Above-mentioned relevant synthetic example and the synthesis condition of comparative example and the molecular mass regimes of product are listed in table 2.
The 2-in-1 synthesis condition and molecular weight of product situation into embodiment and comparative example of table
Application Example 1
The clay adaptability of the high-adaptability polycarboxylate water-reducer prepared for the evaluation present invention, with reference to GB/T8077-2012
Standard carries out the test of flowing degree of net paste of cement to synthetic example and comparative example, and the net slurry after testing 30 minutes and 1 hour
Fluidity.Test cement uses the cement of south of the River little Ye fields P. II 52.5, weighs cement 300g, amount of water 87g.In actual test
The cement of respective quality is substituted using a small amount of montmorillonite, montmorillonite is 250 mesh powder samples of Tangshan production.Test result such as table 3.
The cement paste comparing result of table 3
From the point of view of result of the test：Not plus during montmorillonite, comparative example and comparative example, it can be seen that in polycarboxylic acid structure
After middle introducing polycation macromolecular chain and bound phosphate groups, diminishing and function of slump protection can be obviously improved.After adding montmorillonite, from
As can be seen that with the increase of montmorillonite content, synthetic example only needs to improve a little for embodiment 1, embodiment 8 and embodiment 12
Volume is constant with regard to that can keep paste flowing degree；And from comparative example 1 as can be seen that as the increase of montmorillonite content is, it is necessary to significantly
Degree, which improves volume, could improve fluidity reluctantly, and lose comparatively fast, illustrate polycation substantially without fluidity after 60 minutes
The introducing of macromolecular chain and bound phosphate groups has a clear superiority to its anti-mud performance；And from comparative example 4 as can be seen that with illiteracy
The increase of native content is taken off, its anti-mud performance can be significantly improved after introducing polycation macromolecular chain；From whole implementation example and right
From the point of view of ratio, it is also seen that raising of the introducing of bound phosphate groups to its diminishing function of slump protection and anti-mud performance serves collaboration
Effect.
Application Example 2
Adaptability for the further evaluation polycarboxylate water-reducer of the invention prepared to different regions Machine-made Sand, with reference to GB/T
8077-2012 standards carry out the test of Mortar'S Flowability to synthetic example and comparative example, and after testing 1 hour and 2 hours
Mortar'S Flowability.Test cement uses the cement of south of the River little Ye fields P. II 52.5；Flyash is Nanning second-level ash；Fine aggregate selects respectively
Take the Machine-made Sand (its clay content with when content of stone powder different) in Guizhou, Sichuan and Zhejiang, wherein Guizhou Machine-made Sand content of stone powder
15%th, MB values 0.50, modulus of fineness 2.8, Sichuan Machine-made Sand content of stone powder 11%, MB values 0.75, modulus of fineness 3.0, Zhejiang machine
Sandstone powder content 12% processed, MB values 1.35, modulus of fineness 2.9.Choose embodiment 1, embodiment 8, embodiment 12, the and of comparative example 1
The sample of comparative example 4 carries out adaptability contrast experiment.Mortar mix ratio is：Cement 280, flyash 70, Machine-made Sand 750, water
155.Test result such as table 4.
The mortar comparing result of table 4
From the point of view of result of the test, the high-adaptability polycarboxylate water-reducer pair of embodiment 1, embodiment 8 and the synthesis of embodiment 12
The Machine-made Sand of different regions has a good adaptability, and comparative example 1 needs to increase substantially volume could improve flowing reluctantly
Degree, and lose comparatively fast, substantially without fluidity after 2h, the polycarboxylate water-reducer that comparative example 4 synthesizes contains polycation and divided greatly
Subchain, improve a little volume equally has good adaptability to the Machine-made Sand of different regions, illustrates the introducing of bound phosphate groups
The diminishing function of slump protection of polycarboxylate water-reducer and anti-mud performance can be increased substantially.From the point of view of whole implementation example and comparative example, this
The high-adaptability polycarboxylate water-reducer of invention synthesis has good dispersive property and adaptability to the Machine-made Sand of different regions.
Application Example 3
High diminishing high-thin arch dam and anti-mud performance for the further evaluation high-adaptability polycarboxylate water-reducer of the invention prepared,
With reference to GB/T8076-2008《Concrete admixture》Specified in method test concrete the slump and divergence.Cement is
The cement of south of the River little Ye fields P. II 52.5；Miberal powder is Shoudu Iron and Steel Co S95 level miberal powders；Flyash is Nanning second-level ash；Sand is river sand, clay content
For 3%, the middle sand of modulus of fineness 2.6；Stone, the stone of particle diameter 5~25.Choose embodiment 1, embodiment 8, embodiment 12, right
The sample of ratio 1 and comparative example 4 carries out adaptability contrast experiment.The match ratio of concrete is：Cement 267, miberal powder 53, fine coal
Ash 60, sand 767, stone 1060, water 163.Test result such as table 5.
The concrete performance correction data of table 5
From the point of view of concrete test result：When carrying out concrete using the sandstone material that clay content is 3%, the Gao Shi of synthesis
Answering property polycarboxylate water-reducer (embodiment 1,8,12) only needs relatively low volume with regard to that can show obvious anti-mud performance and good
Diminishing function of slump protection；And the polycarboxylate water-reducer (comparative example 1) not containing polycation macromolecular chain will increase substantially volume
Can just there are initial extension degree and the slump, and the loss of its concrete is more serious, does not have divergence after 60 minutes, collapses
Degree also only has 95mm, and illustrate polycation macromolecular chain structure can increase substantially diminishing function of slump protection and anti-mud performance；
The polycarboxylate water-reducer that comparative example 4 synthesizes contains polycation macromolecular chain but does not contain bound phosphate groups, improves a little volume
Good diminishing function of slump protection can be equally showed, polycarboxylic acids diminishing can also be increased substantially by illustrating the introducing of bound phosphate groups
The diminishing function of slump protection of agent and anti-mud performance, synergy is played together with polycation polymeric monomer structure.
Claims (10)
- A kind of 1. high-adaptability polycarboxylate water-reducer, it is characterised in that：It is 1 ~ 5 by mol ratio：1：0.1~0.3：0.05 ~ 0.2 Carboxylic acid monomer A, high molecular weight polyether polymeric monomer B, functional polyalkylene cation polymeric monomer C and unsaturated phosphate ester monomer D are carried out certainly It is made by base copolyreaction, wherein：Carboxylic acid monomer A structures such as formula（Ⅰ）It is shown：C:Users dell Desktop 1.GIF(Ⅰ)；In formula, R1For H or COOM；R2For H, CH3Or CH2COOM；And work as R1For COOM when, R2It is asynchronously CH3Or CH2COOM；M For hydrogen atom, alkali metal ion, alkaline-earth metal ion, ammonium ion or organic amine group；High molecular weight polyether polymeric monomer B structure such as formula（Ⅱ）It is shown：C:Users dell Desktop 1.GIF(Ⅱ)；In formula, R3For H or CH3；R4For the alkyl of H or 1 ~ 3 carbon atom；X1For CH2、CH2CH2、OCH2CH2Or OCH2CH2CH2CH2；N is polyoxyethylated average addition molal quantity, for 25 ~ 150 integer；Functional polyalkylene cation polymeric monomer C-structure such as formula（Ⅲ）It is shown：C:\Users\dell\Desktop\ͼƬ2.jpg（Ⅲ）；In formula, m is poly-（NIPA）Average addition molal quantity, be 5 ~ 10 integer；Unsaturated phosphate ester monomer D structures such as formula（Ⅳ）It is shown：C:\Users\dell\Desktop\ͼƬ3.jpg（Ⅳ）；In formula, R5For H or CH3；R6For CH2CH2Or CH2CH2CH2。
- A kind of 2. high-adaptability polycarboxylate water-reducer according to claim 1, it is characterised in that the poly- carboxylic of high-adaptability The weight average molecular weight of sour water reducer is 20000 ~ 60000.
- A kind of 3. high-adaptability polycarboxylate water-reducer according to claim 2, it is characterised in that the carboxylic acid monomer A choosings From any one in acrylic acid, methacrylic acid, maleic acid, itaconic acid or its sodium salt, sylvite, calcium salt, ammonium salt, organic amine salt Kind；The high molecular polyether polymeric monomer B is selected from allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, cyclobutenyl polyoxy It is any one in vinethene, methyl butene base APEO, vinyl APEO, hydroxyl butyl vinyl APEO Kind；The functional polyalkylene cation polymeric monomer C is selected from maleimide end-sealed gather（NIPA）；The unsaturated phosphate ester monomer D is selected from hydroxy ethyl phosphate, acrylic acid Hydroxypropyl phosphate ester, methacrylic acid Any one in hydroxyethyl phosphate, hydroxyethyl methacrylate propyl phosphate.
- A kind of 4. preparation method of high-adaptability polycarboxylate water-reducer described in any one of claims 1 to 3, it is characterised in that Comprise the following steps：（1）High molecular weight polyether polymeric monomer B and functional polyalkylene cationic monomer C are dissolved in aqueous solvent, stirring rising temperature for dissolving into The aqueous solution；（2）Mixed aqueous solution is mixed evenly into carboxylic acid monomer A, unsaturated phosphorus acid monomer D and water；（3）In the presence of initiator, by step（2）In mixed aqueous solution be at the uniform velocity added dropwise to step（1）In solution in, all Solution continues constant temperature insulation after being added dropwise, free radicals copolymerization reaction occurs for monomer in solution, after reaction terminates, is added in solution It is 6 ~ 8 or so that alkaline matter, which is neutralized to pH value, produces the polycarboxylate water-reducer；Step（3）Described in initiator be free radical water soluble starter, including oxidation category initiator and redox initiator； The oxidation category initiator is, individually from oxidation component as initiator, the redox initiator is from oxidation component Composition with reduction components is as initiator；When the initiator is oxidation category initiator, dosage is the 0.1% ~ 2% of monomer A+B+C+D gross masses；The initiator is During redox initiator, total dosage of wherein oxidation component accounts for the 0.1% ~ 2% of monomer A+B+C+D gross masses, oxidation component and The mass ratio of both reduction components is 0.4 ~ 4：1；Step（2）Described in also include water miscible chain-transferring agent in mixed aqueous solution, the dosage of the chain-transferring agent is monomer A The 0.05% ~ 1% of+B+C+D gross masses；Oxidation component in the initiator can be in step（1）In disposable all feed intake mixed with monomer B and monomer C, or It is configured to water after the aqueous solution and step（2）In mixed aqueous solution simultaneously at the uniform velocity instill step（1）In the solution；And monomer A, the reduction components in monomer D, initiator, chain-transferring agent and water composition mixed aqueous solution, use after stirring and are at the uniform velocity added dropwise Mode add step（1）In the solution.
- A kind of 5. preparation method of high-adaptability polycarboxylate water-reducer according to claim 4, it is characterised in that step （3）Middle free radicals copolymerization reaction temperature is 35 ~ 85 DEG C, and mixed aqueous solution time for adding was controlled at 2 ~ 5 hours；Initiator oxidation group Solution time for adding is divided to extend 0.5 hour compared with mixed aqueous solution；Follow-up continuation of insurance temperature is dripped in initiator solution, soaking time is 1~5h。
- A kind of 6. preparation method of high-adaptability polycarboxylate water-reducer according to claim 5, it is characterised in that the oxygen Changing class initiator includes persulfate or water-soluble azo class compound；The redox initiator includes persulfate and Asia Disulfate, sulphite, thiosulfate, pyrosulfite or the ferrous salt composition of any one, or peroxide with Rongalite or the L-AA composition of any one；The chain-transferring agent is mercaptan type chain transfer agent.
- A kind of 7. preparation method of high-adaptability polycarboxylate water-reducer according to claim 6, it is characterised in that step （3）Described in alkaline matter include hydroxide, oxide or the carbonate of monovalent metal and/or divalent metal, ammonium hydroxide, Organic amine.
- A kind of 8. preparation method of high-adaptability polycarboxylate water-reducer according to claim 7, it is characterised in that the oxygen Change class initiator and may be selected from potassium peroxydisulfate, azo diisobutyl amidine hydrochloride, azodiisobutyronitrile；The redox initiator may be selected from the composition, potassium peroxydisulfate and sodium hydrogensulfite of hydrogen peroxide and L-AA Composition, the composition of hydrogen peroxide and rongalite；The chain-transferring agent may be selected from 2 mercaptopropionic acid, 3- mercaptopropionic acids, 2- mercaprols, 3- mercaprols, TGA, mercapto Base ethanol；The alkaline matter may be selected from sodium hydroxide, triethanolamine, potassium hydroxide, triisopropanolamine.
- A kind of 9. preparation method of high-adaptability polycarboxylate water-reducer according to claim 8, it is characterised in that step （3）Described in carboxylic acid monomer A, high molecular polyether polymeric monomer B, functional polyalkylene cation polymeric monomer C and unsaturated phosphorus acid monomer D gather Mass concentration during conjunction is 35 ~ 50%.
- A kind of 10. application process of high-adaptability polycarboxylate water-reducer described in any one of claims 1 to 3, it is characterised in that The volume of the high-adaptability polycarboxylate water-reducer is the 0.1% ~ 0.5% of total binder materials weight.
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