CN110105504A - A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application - Google Patents
A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application Download PDFInfo
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- CN110105504A CN110105504A CN201910444070.9A CN201910444070A CN110105504A CN 110105504 A CN110105504 A CN 110105504A CN 201910444070 A CN201910444070 A CN 201910444070A CN 110105504 A CN110105504 A CN 110105504A
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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
- 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
- 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
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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
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/30—Inorganic 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
- 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-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation method and application, the water-reducing agent is by including that following molar part raw material is prepared: 10-30 parts of small molecule unsaturated carboxylic acids, the ester of 3-8 parts of small molecule unsaturated carboxylic acids, 1-5 parts of small molecule unsaturated carboxylic acids salt, 2-6 parts of polyethyleneglycol diacrylates, 1-5 parts of unsaturated polyether class polymeric monomers, 8-20 parts of acrylamide monomers, initiator and chain-transferring agent；Wherein the acrylamide monomers be acrylamide (AM), 2- acrylamide-2-methyl propane sulfonic (AMPS), 2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS) three kinds of monomer compositions group.The high-thin arch dam slow-setting polycarboxylic acid water reducing agent of excellent combination property has been finally obtained according to the workability and slump retaining design water-reducing agent molecular structure of construction demand, in construction, low-dosage can obtain higher water-reducing rate, it can guarantee to construct, and slump retaining is excellent, the slump is not lost substantially in 3 hours, has wide applicability in concrete construction.
Description
Technical field
The invention belongs to concrete admixture fields, and in particular to a kind of polycarboxylate water-reducer agent and its preparation and application.
Background technique:
With the rapid development of our country's economy with the raising of building level, high-speed railway, highway bridge, traffic tunnel, city
City's rail traffic, building it is rapidly growing, concrete structures towards enlargement, complicate, high stratification, execution conditions
Diversified direction is developed, therefore also to the intensity of concrete, workability and durability, more stringent requirements are proposed, Er Qieji
It all requires to use pump concrete, this also just keeps concrete preferably flowing during the long distance delivery of pumping
The retentivity of property and the slump, otherwise will lead to the slump-loss of fresh concrete and can not construct, this is for construction
Unit will cause great economic loss.In order to keep the good working performance of concrete, meets different requirement of engineering, need
The water-reducing agent of different function is added in fresh concrete.In the water-reducing agent of various series, polycarboxylate high performance water-reducing agent
It is the cracking high-performance water reducing agent of latest developments.Since the chemical molecular structure-rich of poly carboxylic acid series water reducer is changeable, such as monomer
Type, position of functional group, molecular weight, molecular weight distribution etc. change, and all may cause structure and performance is very different.
Carboxylic acid group's monomer is mainly formed with it can be divided into modified polyether class, poly- (methyl) acrylates esters and maleic acid copolymerized species.
But the now widely used polycarboxylate water-reducer of these types often occurs newly mixing mixed in use due to the defect of its own
The too fast problem of solidifying soil slump-loss.Especially in hot weather, the influence of the factors such as long-distance sand transport, concrete slump
It loses even more serious, it is difficult to guarantee the quality of concrete construction.
The method for solving concrete slump loss at present mainly has 1) compounding retarder, it is desirable to be able to play collaboration and make
With, but the addition of retarder can be such that concrete coagulating time extends, and also have certain influence on concrete strength；2) it is mixed after using
Method, i.e. concrete are mixed later through adding water-reducing agent after a period of time；3) secondary or water-reducing agent is repeatedly added, it can be certain
The workability of degree improvement concrete；4) it is used in combination using slump retaining agent and water-reducing agent.In first method, additional retarder
The slump-loss control of concrete is remained difficult to reach practical application request, second and the third method mix water-reducing agent
Amount proposes very high requirement, and incorporation cannot reach requirement less, super the problem of mixing and will lead to concrete strength decline.4th
In kind of method, will not setting time to concrete and intensity adversely affect, therefore be to study more method at present.
CN105174795A discloses a kind of concrete slump retaining agent, and which are added Methyl celluloses usually to overcome water-reducing agent slump-loss
Disadvantage, but preparation method is complicated, especially when introducing cellulosic structure, in order to protect active group thereon, also needs
To use this method for being unsuitable for industrialized production of nitrogen protection.CN103214206A discloses a kind of sustained-release polycarboxylic and subtracts
Aqua is component A: polyoxyethylene ether/polyethenoxy ether, component B:(methyl) acrylic acid/itaconic acid and component C:(methyl)
Three kinds of components of sodium allylsulfonate are copolymerized, and preparation process comparative degree is simple, but the slump retaining of gained water-reducing agent is still difficult to
Meet practice of construction demand.Therefore, there is an urgent need to develop a kind of collapse protective poly-carboxylic acid high efficiency water reducing agents, to improve polycarboxylic acids diminishing
The performance of agent product widens the kind of concrete admixture to meet the requirement of different engineerings.CN104692700A discloses one
Kind polycarboxylic acid slump retaining agent, is isopentene group polyoxyethylene ether, acrylic acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate and 2- third
The copolymerization of acrylamide -2- methyl propane sulfonic acid is made, but its hydrophilic monomer ratio being added for slump retaining is very big, in order to reach
High water-reducing rate is bound to that very high volume is added, may intensity to coagulation degree or even construction quality have an adverse effect.
Many documents are that partial amides or other unsaturated carboxylate type monomers replacement a part is added in the prior art
Acrylic acid, by ester group, hydrolysis such as CN106397684A, CN109535342A, CN102898061A of amide groups,
The method recorded in CN107739424A, CN109053967A, but ester group, amide groups or ether in common polycarboxylic acid slump retaining agent
The hydrolysis of key receives environment and is affected, it is difficult to achieve the effect that stable sustained-release, for example lead in the strong slow releasing function sometime put
It causes concrete isolation, bleeding occur, and influences the construction of concrete；Or can only release in the early stage with slump retaining, the later period, guarantor was collapsed
Property is difficult to be guaranteed.Therefore, need to develop a kind of slump retaining (slump-loss is little in 3 hours) for having long-term slow setting concurrently and
High water reducing rate (30% or more) water-reducing agent under low-dosage is worth building engineering construction with actual application study.
Summary of the invention
Slump retaining (the slump-loss < in 3 hours that long-term slow setting is had concurrently the purpose of the present invention is to provide a kind of
10%), and under low-dosage there is the polycarboxylate water-reducer of high water reducing rate.Technical thought of the invention is to introduce different function
Energy monomer synthesizes the polycarboxylic acids macromolecular of specific structure, and the ratio for adjusting each function monomer subtracts polyocarboxy acid type obtained
Aqua has both the advantages of long-time slump retaining and high water reducing rate, can satisfy the rigors of current concrete construction, to overcome
The disadvantage of common polycarboxylate water-reducer later period slump retaining difference in the prior art.
Above-mentioned purpose of the invention is addressed by the following technical programs:
A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent is by including that following molar part raw material is prepared:
Ester, the 1-5 parts of small molecule unsaturation carboxylics of 10-30 parts of small molecule unsaturated carboxylic acids, 3-8 parts of small molecule unsaturated carboxylic acids
Acid salt, 2-6 parts of polyethyleneglycol diacrylates, 1-5 parts of unsaturated polyether class polymeric monomers, 8-20 parts of acrylamide monomers,
Initiator and chain-transferring agent；Wherein the acrylamide monomers include 2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS).
In optimal technical scheme of the present invention, the high-thin arch dam slow-setting polycarboxylic acid water reducing agent is by including following molar part
Raw material is prepared: 10-20 parts of small molecule unsaturated carboxylic acids, the ester of 4-6 parts of small molecule unsaturated carboxylic acids, 2-3 parts of small molecules are not
The salt of saturated carboxylic acid, 2-4 parts of polyethyleneglycol diacrylates, 1-3 parts of unsaturated polyether class polymeric monomers, 10-15 parts of acrylamides
Class monomer, initiator and chain-transferring agent；Wherein the acrylamide monomers are acrylamide (AM), 2- acrylamide -2- first
The group of base propane sulfonic acid (AMPS), 2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS) three kinds of monomer compositions.
In acrylamide monomer, the molar ratio of AM, AMPS, AMSS is 3-10: 1-3: 1-2, preferably 5-8: 1.5-3:
1-2。
Further, the small molecule unsaturated carboxylic acid is selected from at least one of acrylic acid, methacrylic acid；Described small point
The ester of sub- unsaturated carboxylic acid is at least one of the methyl esters of acrylic acid and/or methacrylic acid, ethyl ester, propyl ester and butyl ester；It is described
The salt of small molecule unsaturated carboxylic acid is the sodium salt of acrylic acid and/or methacrylic acid and at least one of sylvite；The unsaturation
Polyethers polymeric monomer is allyl polyethenoxy ether (APEG), isoamyl dilute alcohol polyoxyethylene ether (TPEG) and methallyl alcohol polyoxy
At least one of vinethene (HPEG), number average molecular weight 500-4000, preferably 1500-3000.
Further, the number-average molecular weight of polyethylene glycol (PEG) is 200-1000 in the polyethyleneglycol diacrylate,
It is preferred that 400-600.
The initiator of copolyreaction and even transfer agent are not particularly limited in the present invention, are this fields conventionally used for polymerization
Initiator and even transfer agent.The example of initiator includes oxidation dibenzoyl (BPO), azodiisobutyronitrile (AIBN), mistake
Ammonium sulfate, potassium peroxydisulfate；The example of chain-transferring agent includes mercaptopropionic acid, thioacetic acid, mercaptoethanol and isopropanol.Initiator
Dosage and the dosage of chain-transferring agent depending on required water-reducing agent macromolecular weight, according in the present invention to diminishing agent molecule
The requirement of amount and dispersibility, the dosage of added initiator are the 0.2-2%, preferably 0.6- of the amount of comonomer total material
1%；The added 0.4-3%, preferably 0.8-1.2% for connecting the amount that transfer agent dosage is comonomer total material.Initiator amount
Less, diminishing agent molecule dispersion retentivity is poor, this is because free-radical contents are low, the conversion ratio of monomer is also decreased.But
Initiator amount cannot be excessive, and otherwise free radical quantity is excessive, and backbone chain length shortens, and polymer molecular weight reduces, and molecule
Amount dispersibility is also deteriorated therewith, and the slump retaining space steric effect of water-reducing agent can not effectively embody.Therefore it needs to select properly to draw
Send out agent dosage.Chain-transferring agent dosage is few, also not can guarantee the dispersion retentivity of diminishing agent molecule, but chain-transferring agent dosage is excessive,
The degree of polymerization of polymer reduces, and molecular weight is lower, and dispersion holding performance can reduce again.Therefore, suitable initiator and chain tra nsfer
Agent dosage has an important influence the dispersion retentivity of the molecular weight of diminishing agent molecule, molecular weight distribution and molecule.
Optionally, a certain amount of polymerization inhibitor, polymerization inhibitor can also be added in the copolyreaction for preparing water-reducing agent in the present invention
Selected from hydroquinone.
Inventor is it has been unexpectedly found that middle in polycarboxylate water-reducer preparation process be added a certain amount of 2- acrylamide
Base -2- Phenyl-ethanesulfonic acid (AMSS) is used as function monomer, while polyethylene glycol dipropyl of a certain amount of band there are two double bond is added
Olefin(e) acid ester makes water-reducing agent macromolecular generate certain branched structure, although not bright for the initial slump for mixing concrete
It is aobvious to improve, but (slump-loss < 10% in 3 hours) is greatly improved to concrete slump gradual loss.Therefore, originally
Invention additionally provides a kind of 2- acrylamido -2- Phenyl-ethanesulfonic acid and polyethyleneglycol diacrylate in polycarboxylate water-reducer
Purposes, participated in as functional monomer in the polymerization reaction of polycarboxylate water-reducer preparation, water-reducing agent obtained is as mixed
Solidifying soil additive under low-dosage (0.3% or less) has excellent slump retaining, and the concrete mixed slump in 3 hours is damaged
It loses less than 10%.2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS) is used as function monomer, and dosage is water-reducing agent polymerized monomer
The 2-7.5% of the amount of total substance, preferably 3-5%；The molecular weight of (PEG) of polyethylene glycol in polyethyleneglycol diacrylate
For 200-1000, preferably 400-600, dosage is the 3-12%, preferably 5-8% of the amount of the total substance of water-reducing agent polymerized monomer
The present invention also provides a kind of preparation methods of high-thin arch dam slow-setting polycarboxylic acid water reducing agent, including following step
It is rapid:
According to the proportion by small molecule unsaturated carboxylic acid, the ester of small molecule unsaturated carboxylic acid, small molecule unsaturated carboxylic acid salt,
Polyethyleneglycol diacrylate, unsaturated polyether class polymeric monomer, acrylamide monomers, initiator, chain-transferring agent and water are added
Into reaction vessel, temperature reaction cools down after reaction, is neutralized with lye, obtains product high-thin arch dam retardation setting type polycarboxylic acids and subtracts
Aqua.
Wherein, the dosage of water is not particularly limited, and reaction system can be made uniformly to mix, and keeps certain reaction rate i.e.
Can, the dosage of general water is 1-2 times of total mass of raw material.Reaction temperature is 40-80 DEG C, reaction time 3-6 hour.
Optionally, reaction close at the end of, polymerization inhibitor can also be added, polymerization inhibitor is selected from hydroquinone.
The preparation method of high-thin arch dam slow-setting polycarboxylic acid water reducing agent of the present invention, raw material are easy to get, and step is simple, are made and produce
The big number-average molecular weight of product water-reducing agent is 20,000 or so, and molecular weight distribution is relatively narrow (less than 2).
Third object of the present invention is the high-thin arch dam slow-setting polycarboxylic acid water reducing agent in cement/concrete engineering construction
In application.
High-thin arch dam slow-setting polycarboxylic acid water reducing agent provided by the invention has as the additive in cement, concrete construction
The workability for improving to effect cement, can reach higher water-reducing rate under low-dosage, while being also able to maintain excellent guarantor and collapsing
Property.Confirm water-reducing agent high-thin arch dam slow-setting polycarboxylic acid water reducing agent excellent combination property provided by the invention, and easily manufactured, at
This is cheap, is a kind of environmentally protective novel water-reducing agent, has good market popularization value.In addition, obtained in the present invention
High collapse protection type polycarboxylate water-reducer with slowly releasing effect can also be used in combination with high water reduction type polycarboxylate water-reducer.And it is not
It can be only used in normal concrete, can also apply in high performance concrete, with other air entraining agents, retarder, defoaming agent
Equal composition of concrete admixture use, and reach more preferably properties of product.
The present invention achieve compared with the existing technology it is following the utility model has the advantages that
One, by selecting specific functional monomer, design has synthesized the molecular structure of water-reducing agent, by matching to each monomer
The control of ratio obtains a kind of with slow setting, the water-reducing agent of high-collapse-retentivity.Water-reducing agent provided by the invention can be right under low-dosage
Cement/concrete construction workability improves significantly, and gradual loss is less than 10% in 3 hours for the slump, effectively
Ground meets concrete conveyance in modern architecture industry and requires over long distances, for a long time, has wider adaptability.
Two, inventor is it has been unexpectedly found that be added a certain amount of polyethyleneglycol diacrylate and 2- acrylamido-
2- Phenyl-ethanesulfonic acid (AMSS) is used as functional monomer, improves significantly to water-reducing agent slump retaining gradual loss tool.
Three, in addition to being related to for water-reducing agent molecular structure, initiator in suitable water-reducing agent polymerization reaction is also filtered out
With the dosage of chain-transferring agent, polycarboxylate water-reducer molecule amount distribution obtained is moderate, as concrete admixture, has prolonged
Disperse retentivity.
Specific embodiment
Combined with specific embodiments below to high-thin arch dam slow-setting polycarboxylic acid water reducing agent and preparation method thereof of the invention make into
One step illustrates, but the present invention is not limited to following embodiments.The method is conventional method unless otherwise instructed.The former material
Material can obtain unless otherwise instructed from public commercial source.
Embodiment 1
A certain amount of acrylic acid, methyl acrylate, sodium acrylate, poly- second is added in the 500mL flask equipped with blender
Omega-diol diacrylate, methyl allyl alcohol polyoxyethylene ether (HPEG, number-average molecular weight 2400), acrylamide (AM), 2- propylene
Amide -2- methyl propane sulfonic acid (AMPS), 2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS) and deionized water, are heated to 50 DEG C,
Stirring dissolves raw material all, is warming up to 70 DEG C, and initiator sodium peroxydisulfate and chain-transferring agent thioacetic acid, time for adding 3 is added dropwise
Hour, 1 hour is kept the temperature, is cooled to room temperature, is neutralized with NaOH solution after reaction, product polycarboxylate water-reducer is made.
Wherein each raw material dosage is 0.5mol acrylic acid, 0.2mol methyl acrylate, 0.1mol sodium acrylate, 0.1mol gather
Ethylene glycol (PEG400) diacrylate, 0.05mol methyl allyl alcohol polyoxyethylene ether (HPEG), 0.3mol acrylamide
(AM), 0.1mol 2- acrylamide-2-methyl propane sulfonic (AMPS), 0.05mol 2- acrylamido -2- Phenyl-ethanesulfonic acid
(AMSS), 0.01mol sodium peroxydisulfate and 0.013mol thioacetic acid.
Embodiment 2
Unsaturated polyether class polymeric monomer is changed to allyl polyethenoxy ether (APEG, number-average molecular weight 1800), other are the same as real
Apply example 1.
Embodiment 3
Unsaturated polyether class polymeric monomer is changed to isoamyl dilute alcohol polyoxyethylene ether (TPEG, number-average molecular weight 2500), other are same
Embodiment 1.
Embodiment 4
The dosage of acrylamide monomers is changed to 0.3molAM, 0.15molAMPS, 0.05mol AMSS, other are the same as implementation
Example 1.
Embodiment 5
The dosage of acrylamide monomers is changed to 0.3molAM, 0.05molAMPS, 0.1mol AMSS, other same embodiments
1。
Embodiment 6
The dosage of acrylamide monomers is changed to 0.4molAM, 0.05molAMPS, 0.05mol AMSS, other are the same as implementation
Example 1.
Embodiment 7
The dosage of acrylamide monomers is changed to 0.3molAM, 0.1molAMPS, 0.1mol AMSS, other same embodiments
1。
Embodiment 8
The dosage of acrylamide monomers is changed to 0.5molAM, 0.1molAMPS, 0.05mol AMSS, other same embodiments
1。
Embodiment 9
The dosage of acrylamide monomers is changed to 0.3molAM, 0.2molAMPS, 0.2mol AMSS, other same embodiments
1。
Embodiment 10
The dosage of acrylamide monomers is changed to 0.3molAM, 0.1molAMPS, 0.02mol AMSS, other same embodiments
1。
Embodiment 11
The dosage of acrylamide monomers is changed to 0.3molAM, 0.1molAMPS, 0.15mol AMSS, other same embodiments
1。
Embodiment 12
Initiator amount is changed to 0.005mol sodium peroxydisulfate, and chain-transferring agent dosage is changed to 0.008mol thioacetic acid, other
With embodiment 1.
Embodiment 13
Initiator amount is changed to 0.015mol sodium peroxydisulfate, and chain-transferring agent dosage is changed to 0.02mol thioacetic acid, other are same
Embodiment 1.
Embodiment 14
Polyethylene glycol number-average molecular weight is 600 in polyethyleneglycol diacrylate, other are the same as embodiment 1.
Comparative example 1
The dosage of acrylamide monomers is changed to 0.3molAMPS, 0.15mol AMSS, other are the same as embodiment 1.
Comparative example 2
The dosage of acrylamide monomers is changed to 0.45molAM, other are the same as embodiment 1.
Comparative example 3
The dosage of acrylamide monomers is changed to 0.35molAM, 0.1molAMPS, other are the same as embodiment 1.
Comparative example 4
The dosage of acrylamide monomers is changed to 0.35molAM, 0.1molAMSS, other are the same as embodiment 1.
Comparative example 5
It is added without polyethyleneglycol diacrylate, other are the same as embodiment 1.
Application Example
1. gel chromatography is analyzed
Gel aqueous phase chromatography is U.S. Waters gel permeation chromatograph using instrument, and test gained is Abietyl modified poly-
The molecular weight of carboxylic acid water reducer and its distribution.When polycarboxylate water-reducer with 1.0L/min flow velocity pass through chromatographic column, it is different size of
Molecule is separated by pillar at different rates, and chromatogram column temperature control is at 40 DEG C, elutriant 0.1mol/LNa2SO4
Aqueous solution, with the polyethylene glycol calibration standard curve of different molecular weight monodispersity.
2. paste flowing degree is tested
To investigate high-thin arch dam slow-setting polycarboxylic acid water reducing agent produced by the present invention to flowing degree of net paste of cement and water-reducing rate,
Test relevant criterion referring to specified in GB/T 8077-2012 " concrete admixture homogeneity test method " executes.Test is surveyed
Each embodiment has been determined under identical volume to the paste flowing degree of reference cement.
Test is that concrete admixture examines dedicated fiducial cement with cement in embodiment, is by the silicon of the following index of quality
The P.I type portland cement of 42.5 strength grades made of acid salt cement clinker and dihydrate gypsum intergrinding.Reference cement removes
Meet outside 42.5 strength grade technical requirements, also compound tricalcium aluminate content 6-8%, tricalcium silicate content 50-55%, free oxygen
Change calcium content and is no more than 1.2%, alkali (Na2O+0.658K2O) content is no more than 1.0%, and cement specific surface area is 320 ± 20m2/
kg.Operating condition is that the ratio of mud is 0.30, and polycarboxylate water-reducer volume is 0.16% (folding is solid).
3. concrete test
Concrete slump and gradual loss are carried out referring to GB8076-2008 " concrete admixture ".Using conch
PO42.5 cement, concrete mix are cement: flyash: sand: stone: water=320: 125: 750: 1110: 180.Diminishing
Agent volume is 0.12% (folding is solid) of cementitious material.
Characterize data, performance test results such as the following table 1 to high-thin arch dam slow-setting polycarboxylic acid water reducing agent produced by the present invention
It is shown:
Table 1
Continued 1
In concrete construction, in addition to good, the little loss of slump to the quiet slurry fluidity of cement, the good requirement of workability is gone back
Require certain heat-resisting quantity.In temperature higher summer, guarantee that concrete has fluidity retentivity appropriate and coagulates
Tie the time.Therefore, also the slump retaining under currently preferred polycarboxylate water-reducer at high temperature (45 DEG C) is tested, is tied
Fruit is shown in Table 2:
Table 2
* the judgment criteria of workability is different with the slump of concrete mix, is divided into 4 grades, is that T4 (collapses respectively
Degree >=160mm), T3 (slump 100-160mm), T2 (slump 10-100mm), T1 (slump < 10mm).
It can be seen that high-thin arch dam slow-setting polycarboxylic acid water reducing agent provided by the invention by the data of Tables 1 and 2 and have both guarantor
The summation performance of collapsing property and high water reducing rate, and the polycarboxylate water-reducer mix after concrete slump gradual loss very
It is small, 3 hours basic frees of losses (loss is less than 10% within the slump 3 hours).Polycarboxylate water-reducer of the invention is under low-dosage, water
The quiet slurry fluidity of mud can not reduced not only as time went on, or even also can increase, this and general polycarboxylate water-reducer water
The quiet slurry fluidity of mud can be compared as the time gradually decreases, and have big advantage.Avoid concrete initial flow degree tune
It is excessive, it causes the initial bleeding isolation of concrete and final strength is caused to decline.And polycarboxylate water-reducer provided by the invention is mixed
Concrete after conjunction is also able to maintain good workability under the high temperature conditions, at 45 DEG C after 3h workability can also in T3 rank,
It ensure that construction in the construction in summer or temperature higher area, extends the application range of water-reducing agent.Diminishing of the present invention
The excellent comprehensive performance of agent is to use specific function monomer, and to the proportion of monomer by the MOLECULE DESIGN to water-reducing agent
It is screened, has achieved the purpose that hydrolysis substance and anion slow release.
Claims (10)
1. a kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent is by including that following molar part raw material is prepared:
10-30 parts of small molecule unsaturated carboxylic acids, the ester of 3-8 parts of small molecule unsaturated carboxylic acids, 1-5 parts of small molecule unsaturated carboxylic acids
Salt, 2-6 part polyethyleneglycol diacrylate, 8-20 parts of acrylamide monomers, cause 1-5 parts of unsaturated polyether class polymeric monomers
Agent and chain-transferring agent；Wherein the acrylamide monomers include 2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS).
2. water-reducing agent as described in claim 1, which is characterized in that the water-reducing agent is by including prepared by following molar part raw material
It obtains: ester, the 2-3 parts of small molecule unsaturated carboxylic acids of 10-20 parts of small molecule unsaturated carboxylic acids, 4-6 parts of small molecule unsaturated carboxylic acids
Salt, 2-4 parts of polyethyleneglycol diacrylates, 1-3 parts of unsaturated polyether class polymeric monomers, 10-15 parts of acrylamide monomers, draw
Send out agent and chain-transferring agent；Wherein the acrylamide monomers are acrylamide (AM), 2- acrylamide-2-methyl propane sulfonic
(AMPS), the group of 2- acrylamido -2- Phenyl-ethanesulfonic acid (AMSS) three kinds of monomer compositions.
3. water-reducing agent as claimed in claim 2, which is characterized in that wherein the molar ratio of AM, AMPS, AMSS are 3-10: 1-3
: 1-2, preferably 5-8: 1.5-3: 1-2.
4. water-reducing agent as described in any one of claims 1-3, which is characterized in that polyethylene glycol in polyethyleneglycol diacrylate
Number-average molecular weight be 200-1000, preferably 400-600.
5. water-reducing agent as described in any one of claims 1-3, which is characterized in that the small molecule unsaturated carboxylic acid is selected from propylene
At least one of acid, methacrylic acid；The ester of the unsaturated carboxylic acid be the methyl esters of acrylic acid and/or methacrylic acid, ethyl ester,
At least one of propyl ester and butyl ester；The salt of the unsaturated carboxylic acid is the sodium salt and sylvite of acrylic acid and/or methacrylic acid
It is at least one；The unsaturated polyether class polymeric monomer is allyl polyethenoxy ether (APEG), isoamyl dilute alcohol polyoxyethylene ether
(TPEG) and at least one of methyl allyl alcohol polyoxyethylene ether (HPEG), number-average molecular weight 500-4000, preferably 1500-
3000。
6. water-reducing agent as described in any one of claims 1-3, which is characterized in that initiator be selected from oxidation dibenzoyl (BPO),
At least one of azodiisobutyronitrile (AIBN), ammonium persulfate, potassium peroxydisulfate；Chain-transferring agent is selected from mercaptopropionic acid, sulfydryl second
At least one of acid, mercaptoethanol and isopropanol.
7. water-reducing agent as claimed in claim 6, which is characterized in that the dosage of the initiator is the amount of comonomer total material
0.2-2%, preferably 0.6-1%；The chain-transferring agent dosage is the 0.4-3% of the amount of comonomer total material, preferably
0.8-1.2%.
8. use of the combination of polyethyleneglycol diacrylate and 2- acrylamido -2- Phenyl-ethanesulfonic acid in polycarboxylate water-reducer
On the way, which is characterized in that prepared in the polymerization reaction of polycarboxylate water-reducer as functional monomer participation.
9. the preparation method of any one of the claim 1-7 high-thin arch dam slow-setting polycarboxylic acid water reducing agent, comprising the following steps:
According to the proportion by small molecule unsaturated carboxylic acid, the ester of small molecule unsaturated carboxylic acid, the salt of small molecule unsaturated carboxylic acid, poly- second
Omega-diol diacrylate, unsaturated polyether class polymeric monomer, acrylamide monomers, initiator, chain-transferring agent and water are added to instead
It answers in container, temperature reaction cools down after reaction, is neutralized with lye, obtains product high-thin arch dam slow-setting polycarboxylic acid water reducing agent.
10. any one of the claim 1-7 high-thin arch dam slow-setting polycarboxylic acid water reducing agent is in cement/concrete engineering construction
Using.
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