CN108822262A - 1200 molecular weight polyether polycarboxylate water-reducers of one kind and preparation method - Google Patents
1200 molecular weight polyether polycarboxylate water-reducers of one kind and preparation method Download PDFInfo
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- CN108822262A CN108822262A CN201810513171.2A CN201810513171A CN108822262A CN 108822262 A CN108822262 A CN 108822262A CN 201810513171 A CN201810513171 A CN 201810513171A CN 108822262 A CN108822262 A CN 108822262A
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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
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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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
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Abstract
The present invention provides a kind of 1200 molecular weight polyether polycarboxylate water-reducers and preparation methods.The parts by weight of component of the polycarboxylate water-reducer each component is：1200 molecular weight polyether polymeric monomers：310-330 parts, acrylic acid：4-14 parts, carboxylic acid ester monomer：2-9 parts, fluoro function monomer：2-5 parts, hydrogen peroxide：0.9-1.8 parts, flexible chain monomer：4-10 parts, reducing agent：0.32-0.5 parts, chain-transferring agent：0.3-0.7 parts, neutralizer：6-10 parts, surplus is water, and 1000 parts of gross mass, final product quality score is 40% after preparation, and sour ether ratio is within the scope of 2.7-3.3.The method carries out as follows：1, it feeds for the first time；2, add hydrogen peroxide；3, solution A, the addition of solution B；4, prepared by finished product.The present invention using 1200 molecular weight polyether monomer be used as raw material, acquisition in the environment can open suitable side chains length, compensate for the problem of short-side chain brings steric hindrance to weaken.
Description
Technical field：
The present invention relates to construction materials and polycarboxylate water-reducer technical field, are related specifically to a kind of 1200 molecular weight polyethers use
Polycarboxylate water-reducer and preparation method.
Background technique：
Polycarboxylate water-reducer has very superior performance in concrete application as third generation high-performance water reducing agent.
But due to the difference of sandstone material region type, common polycarboxylate water-reducer often be cannot be considered in terms of, especially in Machine-made Sand
The equal biggish raw material of powder containing quantities constantly expand under usage amount, it would be highly desirable to a kind of novel polycarboxylic acids diminishing that can be applicable in such situation
Agent is supplemented.
When common polycarboxylate water-reducer is in the case where fine powder material is more, unfolding for side chain is suppressed, and steric hindrance is made
Limited with playing, it is not high to show as water-reducing rate on concrete, and wrapped and slump retaining is poor, it is difficult to guarantee pumping and pour
Working performance.Solve problem above, it is necessary to carry out targeted design：Using the polyether monomer of 1200 molecular weight as raw material,
Acquisition in the environment being capable of open suitable side chains length；Lower sour ether ratio is designed, higher side chain density is obtained；It introduces
Main chain has the polymerized monomer of flexibility, and diminishing agent molecule is made to obtain preferable flexibility；The hydrophobic grouping of introducing, delays aquation
Process.
Patent CN103896506A discloses a kind of low molecular weight water-reducing agent and its preparation method and application, described in the invention
Polycarboxylate water-reducer includes the following steps：1) citric acid measured or its salt and catalyst are added in autoclave, and
Nitrogen displacement is carried out three times to reaction kettle；2) stirring is started, and reaction kettle is heated up, while a little epoxyalkane is added；3) to
Temperature increases after pressure decline, the epoxyalkane of metered amount is added, while in the case where maintaining reaction temperature, and reaction is enabled to hold
It is 30-50 minutes continuous, until pressure no longer declines；And reaction product is cooled down and is neutralized by (4), obtains the low molecular weight diminishing
Agent.
Patent CN103254420A discloses a kind of low molecular polyether water-reducing agent and its preparation method and application, the hair
In bright preparation method, first to alkyl oxyalkylene by p-hydroxybenzoate alkoxylate, then make products therefrom with it is suitable
Anhydride maleique carries out esterification to get the low molecular weight water-reducing agent of the invention is arrived.The low molecular weight water-reducing agent of the invention can
Be directly used as polycarboxylate water-reducer, can also with other type polycarboxylic acids water reducing agent compositionals, can also with other vinyl monomer copolymerizations at
High molecular weight polycarboxylate water-reducer.
Patent CN106496445A discloses a kind of modified viscosity reduction type polycarboxylate water-reducer masterbatch of hydrophobic minor comonomer, in bottom material
In addition to 340-350 parts of polyether macromonomers, it is small to be added at one time 3.0-8.0 parts of hydrophobic minor comonomers, 1.0-3.0 parts of unsaturated sulfonic acid classes
Monomer, 7.0-12.0 part acrylic acid；After mixing evenly, 2.0-5.0 parts of hydrogen peroxide are added at one time, then start that initiator is added dropwise
Solution enters minor comonomer solution；Minor comonomer solution is made of 28.0-36.0 parts of acrylic acid and 25-40 parts of water；After being added dropwise, from
Dynamic heat preservation 1-2h, after being cooled to 30 degree, is added 6.0-10.0 parts of liquid alkaline.This modified mother liquor specific aim is suitable for low water-cement ratio or bone
The high cementitious material mixture of clast content in material can significantly reduce mixture viscosity, improve workability.
Summary of the invention：
The purpose of the present invention is to provide a kind of 1200 molecular weight polyether polycarboxylate water-reducers and preparation methods.
Design philosophy of the invention is the polyether monomer using 1200 molecular weight as raw material, and acquisition in the environment can
Open suitable side chains length.Side chain lengths are shorter, and steric hindrance effect can be weakened, and ask to make up short-side chain bring
Topic, backbone length need design comparison long, construct the molecular configuration of long main chain, short-side chain.In the case where side chain is shorter, design
Sour ether is relatively low, and side chain density is higher just to meet Molecular Geometries, obtains preferable steric hindrance effect.
In the longer situation of main chain, diminishing agent molecule faces the problem of flexibility deficiency, i.e. main chain rigidity is larger, can not wrap
Cement granules are wrapped, concrete difference wrapped is macroscopically shown as.For this situation, the polymerization that main chain has flexibility is introduced
Monomer makes diminishing agent molecule obtain preferable flexibility, obtains good package performance.On the other hand, introducing has hydrophobic function
The monomer and fluoro function monomer of energy, are grafted on diminishing agent molecule, and in adsorption process, hydrophobic grouping is poly- to moisture film layer surface
Collection, aligns on the liquid gas interface of bubble, reduces surface tension, makes to be easily formed many small gas in concrete mix
Bubble, bubble can generate ball and the effect of floating support, facilitate relatively sliding between cement granules, particles of aggregates in fresh concrete
It is dynamic, improve the workability of concrete mix.The hydrophobic grouping class monomer that the present invention also introduces, cooperates with work with hydrophilic group
With, it is in stable condition to be able to maintain moisture film, and it interferes water film to cement granules internal penetration, delays hydration process to a certain extent,
Make concrete that there are preferable state-retention capabilities.
To achieve the above object, the technical scheme is that:
A kind of 1200 molecular weight polyether polycarboxylate water-reducers, the parts by weight component of the polycarboxylate water-reducer each component are：
1200 molecular weight polyether polymeric monomers：310-330 parts, acrylic acid：4-14 parts,
Carboxylic acid ester monomer：2-9 parts, fluoro function monomer：2-5 parts,
Hydrogen peroxide：0.9-1.8 parts, flexible chain monomer：4-10 parts,
Reducing agent：0.32-0.5 parts, chain-transferring agent：0.3-0.7 parts,
Neutralizer：6-10 parts, surplus is water, and 1000 parts of gross mass, final product quality score is 40% after preparation, and sour ether ratio is in 2.7-
Within the scope of 3.3.
In the polycarboxylate water-reducer 1200 molecular weight polyether polymeric monomers by molecular weight 1200 allyl polyethenoxy
Ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, the one or more of vinyl butyl ether polyoxyethylene ether
Composition.
Carboxylic acid ester monomer is by methyl methacrylate, butyl methacrylate, acrylic acid in the polycarboxylate water-reducer
Ethyl ester, glycidyl methacrylate, dimethylaminoethyl methacrylate, alkyl phenyl polyethylene oxides ether butenoate,
Triphenyl ethyl phenoxy ethers methacrylate, isooctyl methacrylate, lauryl methacrylate, poly dimethyl
Siloxanes monomethacrylates, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, ten trifluoro of methacrylic acid
One or more of compositions of monooctyl ester.
Fluoro function monomer is by acrylic acid trifluoro ethyl ester, methacrylic acid 2,2,2- trifluoro in the polycarboxylate water-reducer
One or more of compositions of ethyl ester, 2- (trifluoromethyl) methyl acrylate.
Reducing agent is by sodium dithionite, sodium formaldehyde sulphoxylate, ascorbic acid, Asia in the polycarboxylate water-reducer
Sodium bisulfate, sodium pyrosulfite, sodium hypophosphite, Dextrose Monohydrate, the one or more of of maltodextrin form.
Flexible chain monomer is by bis- (4- amino-benzene oxygen) ethane of 1,2-, bis- (the 4- ammonia of 1,3- in the polycarboxylate water-reducer
Phenoxyl) propane and bis- (4- amino-benzene oxygen) butane of Isosorbide-5-Nitrae-, cyclobutane tetracarboxylic dianhydride, 4,4 one diaminodiphenyl ethers,
One or more of compositions of two amido detergent alkylates, two amido octadecyl benzene.
The polycarboxylate water-reducer Chain transfer agent by thioacetic acid, mercaptopropionic acid, mercaptoethanol, mercaprol one
Kind or several compositions.
In the polycarboxylate water-reducer neutralizer by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate,
Sodium methoxide, sodium ethoxide, ethanol amine, diethanol amine, triethanolamine, the one or more of of triisopropanolamine form.
It is 27.5% industrial grade hydrogen peroxide that hydrogen peroxide, which is mass percent, in the polycarboxylate water-reducer.
A kind of preparation method of 1200 molecular weight polyether polycarboxylate water-reducer, the method carry out as follows：
1, it feeds for the first time：By 310-330 parts of 1200 molecular weight polyether polymeric monomers, 4-14 parts of acrylic acid, 2-9 parts of carboxylic acid
Ester monomer and 180-220 parts of water are added in reaction kettle, and agitating and heating waits for its dissolution；
2, add hydrogen peroxide：Temperature of reaction kettle is controlled at 40-45 DEG C, after the temperature in reaction kettle is stablized, is added at one time 0.9-
1.8 parts of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A are added dropwise into reaction kettle after five minutes, solution B is added
Afterwards, start that solution A is added dropwise in 10 minutes, solution A time for adding is 2-4 hours, and solution B time for adding is 2.5-4.5 hours；It is molten
Liquid B is uniformly mixed by 0.32-0.5 parts of reducing agents, 0.3-0.7 parts of chain-transferring agents and 80-100 parts of water, and solution A is by 40-54
Part acrylic acid, 2-5 parts of fluoro function monomers, 4-10 parts of flexible chain monomers and 50-70 parts of water are uniformly mixed；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 1-3 hours, when reaction solution temperature is lower than 30 DEG C,
6-10 parts of neutralizers are slowly added to, moisturizing subtracts to the 1200 molecular weight polyether polycarboxylic acids that 1000 parts are 40% to get mass fraction
Aqua.
Compared with prior art, the positive effect of the present invention is:
1, for the present invention using the polyether monomer of 1200 molecular weight as raw material, acquisition in the environment being capable of open appropriate side
Chain length；
2, the present invention is makes up the problem of short-side chain brings steric hindrance to weaken, the long main chain of design comparison, constructs long main chain, short
The molecular configuration of side chain, in the case where side chain is shorter, side chain density is higher just to meet Molecular Geometries, obtain preferable
Steric hindrance effect, therefore the sour ether ratio in the present invention is within the scope of 2.7-3.3；
3, in the longer situation of main chain, diminishing agent molecule faces the problem of flexibility deficiency, i.e. main chain rigidity is larger, can not wrap up
Firmly cement granules macroscopically show as concrete difference wrapped.For above situation, present invention introduces main chains to have flexibility
Polymerized monomer makes diminishing agent molecule obtain preferable flexibility, obtains good package performance；
4, the present invention is grafted on diminishing agent molecule using the carboxylic acid ester monomer and fluoro function monomer with hydrophobic function,
In adsorption process, hydrophobic grouping aligns on the liquid gas interface of bubble to water film surface aggregation, reduces surface tension,
Make to be easily formed many micro-bubbles in concrete mix, bubble can generate ball and the effect of floating support, help newly to mix coagulation
Opposite sliding in soil between cement granules, particles of aggregates, improves the workability of concrete mix；
5, present invention introduces hydrophobic grouping class monomer, act synergistically with hydrophilic group, it is in stable condition to be able to maintain moisture film, interferes
Water film delays hydration process to cement granules internal penetration to a certain extent, makes concrete that there is preferable state to keep energy
Power.
Specific embodiment
Clear, complete description further is carried out to technical solution of the present invention below with reference to embodiment.
Embodiment 1：
1, it feeds for the first time：It is 1 by 310 parts of Losec chemistry TPEG1200 monomers, 6 parts of acrylic acid, 9 parts of mass ratioes:1 triphenyl
Ethyl phenoxy ethers methacrylate and the composition of dimethyl silicone polymer monomethacrylates, 180 parts of water are added to
In reaction kettle, agitating and heating waits for its dissolution；
2, add hydrogen peroxide：Reactor temperature is measured, the temperature in reaction kettle is controlled at 40 DEG C, after temperature is stablized, disposably adds
Enter 0.9 part of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A is added dropwise after five minutes, after initiator is added, 10 minutes
Inside start that solution A is added dropwise, solution A time for adding is 2 hours, and solution B time for adding is 2.5 hours；Solution B is by 0.32 part of sulfurous
Sour hydrogen sodium, 0.55 part of mercaprol and 80 parts of water are uniformly mixed, and solution A is 1 by 54 parts of acrylic acid, 5 parts of mass ratioes:1
Composition, the 7 parts of mass ratioes 1 of 2,2,2- trifluoro ethyl ester of acrylic acid trifluoro ethyl ester and methacrylic acid:Bis- (the 4- amino of 11,3-
Phenoxy group) composition, the 70 parts of water of propane and bis- (4- amino-benzene oxygen) butane of Isosorbide-5-Nitrae-are uniformly mixed；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 1 hour, when reaction solution temperature is lower than 30 DEG C, delay
Slowly be added 8 parts of potassium hydroxide, moisturizing to 1000 parts to get mass fraction be 40% 1200 molecular weight polyether polycarboxylic acids diminishings
Agent.
Embodiment 2
1, it feeds for the first time：By 315 parts of Losec chemistry MPEG1200 monomers, 7 parts of acrylic acid, 7 parts of triphenyl ethyl phenoxy ethers
Methacrylate and 185 parts of water are added in reaction kettle, and agitating and heating waits for its dissolution；
2, add hydrogen peroxide：Reactor temperature is measured, the temperature in reaction kettle is controlled at 41 DEG C, after temperature is stablized, disposably adds
Enter 1 part of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A is added dropwise after five minutes, after initiator is added, 10 minutes
Inside start that solution A is added dropwise, solution A time for adding is 2.5 hours, and solution B time for adding is 3 hours；Solution B is by 0.35 part of one water
Glucose, 0.5 part of thioacetic acid and 85 parts of water are uniformly mixed, solution A by 50 parts of acrylic acid, 4 parts of acrylic acid trifluoro ethyl esters,
6 parts of mass ratioes are 1:Bis- (4- amino-benzene oxygen) ethane and 4 of 11,2-, the composition of 4 one diaminodiphenyl ethers, 65 parts of water are equal
It is even to mix；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 1.5 hours, when reaction solution temperature is lower than 30 DEG C,
10 parts of sodium bicarbonates are slowly added to, moisturizing subtracts to the 1200 molecular weight polyether polycarboxylic acids that 1000 parts are 40% to get mass fraction
Aqua.
Embodiment 3
1, it feeds for the first time：By 320 parts of goodization chemistry APEG1200 monomers, 12 parts of acrylic acid, 6 parts of dimethyl silicone polymer list first
Base acrylate and 190 parts of water are added in reaction kettle, and agitating and heating waits for its dissolution；
2, add hydrogen peroxide：Reactor temperature is measured, the temperature in reaction kettle is controlled at 42 DEG C, after temperature is stablized, disposably adds
Enter 1.3 parts of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A is added dropwise after five minutes, after initiator is added, 10 minutes
Inside start that solution A is added dropwise, solution A time for adding is 2.3 hours, and solution B time for adding is 2.8 hours；Solution B is by 0.4 part time
Sodium phosphite, 0.4 part of mercaptopropionic acid and 90 parts of water are uniformly mixed, solution A by 44 parts of acrylic acid, 3 parts of methacrylic acids 2,
2,2- trifluoro ethyl esters, 5 parts of cyclobutane tetracarboxylic dianhydrides and 60 parts of water are uniformly mixed；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 2 hours, when reaction solution temperature is lower than 30 DEG C, delay
Slow 9 parts of mass ratioes of addition are 1:1 sodium methoxide and the composition of ethanol amine, moisturizing are 40% to get mass fraction to 1000 parts
1200 molecular weight polyether polycarboxylate water-reducers.
Embodiment 4
1, it feeds for the first time：By 324 parts of Losec chemistry TPEG1200 monomers, 10 parts of acrylic acid, 2.5 parts of alkyl phenyl polyethylene oxides
Ether butenoate and 195 parts of water are added in reaction kettle, and agitating and heating waits for its dissolution；
2, add hydrogen peroxide：Reactor temperature is measured, the temperature in reaction kettle is controlled at 43 DEG C, after temperature is stablized, disposably adds
Enter 1.5 parts of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A is added dropwise after five minutes, after initiator is added, 10 minutes
Inside start that solution A is added dropwise, solution A time for adding is 3.3 hours, and solution B time for adding is 3.8 hours；Solution B is anti-by 0.45 part
Bad hematic acid, 0.3 part of mass ratio are 1:2 thioacetic acid and composition, the 95 parts of water of mercaptopropionic acid are uniformly mixed, solution A
It is uniformly mixed by 46 parts of acrylic acid, 3.5 parts of 2- (trifluoromethyl) methyl acrylates, 4.5 part of two amido octadecyl benzene and 65 parts of water
It closes；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 1.8 hours, when reaction solution temperature is lower than 30 DEG C,
8.5 parts of sodium ethoxides are slowly added to, moisturizing subtracts to the 1200 molecular weight polyether polycarboxylic acids that 1000 parts are 40% to get mass fraction
Aqua.
Embodiment 5
1, it feeds for the first time：By 321 parts of goodization chemistry APEG1200 monomers, 4 parts of acrylic acid, 3.5 parts of ten trifluoros of methacrylic acid
Monooctyl ester and 210 parts of water are added in reaction kettle, and agitating and heating waits for its dissolution；
2, add hydrogen peroxide：Reactor temperature is measured, the temperature in reaction kettle is controlled at 44 DEG C, after temperature is stablized, disposably adds
Enter 1.65 parts of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A is added dropwise after five minutes, after initiator is added, 10 minutes
Inside start that solution A is added dropwise, solution A time for adding is 4 hours, and solution B time for adding is 4.5 hours；Solution B is by 0.48 part of formaldehyde
It closes sodium bisulphite, 0.7 part of mercaptoethanol and 100 parts of water to be uniformly mixed, solution A is by 48 parts of acrylic acid, 2 parts of mass ratioes 1:
The composition of 1 acrylic acid trifluoro ethyl ester and 2- (trifluoromethyl) methyl acrylate, 10 part of two amido detergent alkylate and 50 parts
Water is uniformly mixed；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 2.5 hours, when reaction solution temperature is lower than 30 DEG C,
Be slowly added to 10 parts of triisopropanolamines, moisturizing to 1000 parts be 40% to get mass fraction 1200 molecular weight polyether polycarboxylic acids
Water-reducing agent.
Embodiment 6
1, it feeds for the first time：By 330 parts of Losec chemistry MPEG1200 monomers, 14 parts of acrylic acid, 2 parts of mass ratioes 1:1 methyl-prop
The composition of olefin(e) acid hexafluoro butyl ester and dodecafluoroheptyl methacrylate, 220 parts of water are added in reaction kettle, and agitating and heating waits for it
Dissolution；
2, add hydrogen peroxide：Reactor temperature is measured, the temperature in reaction kettle is controlled at 45 DEG C, after temperature is stablized, disposably adds
Enter 1.8 parts of hydrogen peroxide；
3, solution A, the addition of solution B：To, successively start that solution B, solution A is added dropwise after five minutes, after initiator is added, 10 minutes
Inside start that solution A is added dropwise, solution A time for adding is 3.5 hours, and solution B time for adding is 4 hours；Solution B is by 0.5 part of quality
Than being 2:1 sodium formaldehyde sulphoxylate and composition, 0.5 part of thioacetic acid and the 88 parts of water of ascorbic acid uniformly mix and
At solution A is by 40 parts of acrylic acid, 2.5 parts of mass ratioes 1:12,2,2- trifluoro ethyl ester of methacrylic acid and 2- (trifluoromethyl) third
The composition of e pioic acid methyl ester, 4 parts of mass ratioes 1:The composition of 1 cyclobutane tetracarboxylic dianhydride and two amido octadecyl benzene, 55
Part water is uniformly mixed；
4, prepared by finished product：It after completion of dropwise addition, keeps temperature constant, cures 3 hours, when reaction solution temperature is lower than 30 DEG C, delay
Slowly be added 6 parts of diethanol amine, moisturizing to 1000 parts to get mass fraction be 40% 1200 molecular weight polyether polycarboxylic acids diminishings
Agent.
Example detection result：
1200 molecular weight polyether polycarboxylate water-reducers and common diminishing prepared by test above-described embodiment 1,2,3,4,5,6 respectively
Cement paste initial fluidity and 1h mobility of the agent under comparable sodium, and in the more concrete of fine powder material content just
The beginning slump/divergence and through when the slump/divergence.Testing cement used is new 42.5 ordinary portland cement of China, with reference to GB/
8076-2008《Concrete admixture》Testing standard.
Different Water-reducing Admixtures To Cements net slurry flow effects（New 42.5 ordinary portland cement of China）
| Water-reducing agent type | Initial fluidity mm | 1h mobility mm |
| Ordinary water-reducing agent | 230 | 215 |
| Embodiment 1 | 230 | 225 |
| Embodiment 2 | 230 | 220 |
| Embodiment 3 | 235 | 210 |
| Embodiment 4 | 240 | 220 |
| Embodiment 5 | 230 | 215 |
| Embodiment 6 | 235 | 215 |
Different water-reducing agents influence normal concrete mobility（New 42.5 ordinary portland cement of China）
| Water-reducing agent type | Initial slump/divergence mm | Through when the slump/divergence mm |
| Ordinary water-reducing agent | 190/500 | 170/430 |
| Embodiment 1 | 200/480 | 165/435 |
| Embodiment 2 | 180/495 | 175/420 |
| Embodiment 3 | 190/480 | 180/440 |
| Embodiment 4 | 185/500 | 165/425 |
| Embodiment 5 | 200/510 | 165/430 |
| Embodiment 6 | 190/495 | 170/435 |
The different water-reducing agents concrete flowability more on fine powder material content influences（New 42.5 ordinary portland cement of China）
| Water-reducing agent type | Initial slump/divergence mm | Through when the slump/divergence mm |
| Ordinary water-reducing agent | 170/460 | 120/360 |
| Embodiment 1 | 200/530 | 165/480 |
| Embodiment 2 | 210/500 | 170/485 |
| Embodiment 3 | 220/510 | 160/475 |
| Embodiment 4 | 230/520 | 155/470 |
| Embodiment 5 | 210/495 | 170/490 |
| Embodiment 6 | 210/510 | 155/495 |
According to above-mentioned cement paste initial fluidity, the data comparison of 1h mobility, embodiment 1,2,3,4,5,6 and common diminishing
The cement paste initial fluidity and 1h mobility of agent are not much different substantially, when being applied to normal concrete, embodiment 1,2,3,
4,5,6 initial slumps/divergence and through when the slump/divergence also with ordinary water-reducing agent base without too big difference.From coagulation
The mobility that native mobility data comparison can be seen that the more concrete of fine powder material content of embodiment 1,2,3,4,5,6 is far good
Mobility when adding ordinary water-reducing agent.In conclusion the 1200 molecular weight polyether polycarboxylate water-reducer is in fine powder material content
Also high water reducing rate can be shown in more concrete, wrapped and slump retaining is preferable.
All features disclosed in this specification or disclosed all formulas, volume and step, in addition to mutually exclusive spy
Other than sign and/or formula, volume, it can combine in any way.This specification（Including claim, abstract）Disclosed in
Any feature can be replaced by other alternative features that are equivalent or have similar purpose unless specifically stated.It is i.e. unless special
It does not describe, each feature is an example in a series of equivalent or similar characteristics.
Described above is only the non-limiting embodiment of invention, a large amount of embodiment can also be derived, for this field
Those of ordinary skill for, not departing from the invention design and under the premise of do not make creative work, can also do
The embodiment of several modifications and improvements out, these are all within the scope of protection of the present invention.
Claims (10)
1. a kind of 1200 molecular weight polyether polycarboxylate water-reducers, it is characterised in that：The polycarboxylate water-reducer each component
Parts by weight component is：
1200 molecular weight polyether polymeric monomers：310-330 parts, acrylic acid：4-14 parts,
Carboxylic acid ester monomer：2-9 parts, fluoro function monomer：2-5 parts,
Hydrogen peroxide：0.9-1.8 parts, flexible chain monomer：4-10 parts,
Reducing agent：0.32-0.5 parts, chain-transferring agent：0.3-0.7 parts,
Neutralizer：6-10 parts, surplus is water, and 1000 parts of gross mass, final product quality score is 40% after preparation, and sour ether ratio is in 2.7-
Within the scope of 3.3.
2. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
Allyl polyethenoxy ether, methacrylic polyoxyethylene of the 1200 molecular weight polyether polymeric monomers by molecular weight 1200 in water-reducing agent
One or more of compositions of ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether.
3. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
Carboxylic acid ester monomer is sweet by methyl methacrylate, butyl methacrylate, ethyl acrylate, Glycidyl methacrylate in water-reducing agent
Grease, dimethylaminoethyl methacrylate, alkyl phenyl polyethylene oxides ether butenoate, triphenyl ethyl phenoxy ethers methyl
Acrylate, isooctyl methacrylate, lauryl methacrylate, dimethyl silicone polymer monomethacrylates,
Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, the one or more of of ten trifluoro monooctyl ester of methacrylic acid form.
4. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
Fluoro function monomer is by acrylic acid trifluoro ethyl ester, methacrylic acid 2,2,2- trifluoro ethyl ester, 2- (trifluoromethyl) third in water-reducing agent
One or more of compositions of e pioic acid methyl ester.
5. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
In water-reducing agent reducing agent by sodium dithionite, sodium formaldehyde sulphoxylate, ascorbic acid, sodium hydrogensulfite, sodium pyrosulfite,
Sodium hypophosphite, Dextrose Monohydrate, the one or more of of maltodextrin form.
6. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
Flexible chain monomer is by bis- (4- amino-benzene oxygen) ethane of 1,2-, bis- (4- amino-benzene oxygen) propane of 1,3- and Isosorbide-5-Nitrae-in water-reducing agent
Bis- (4- amino-benzene oxygen) butane, cyclobutane tetracarboxylic dianhydride, 4,4 one diaminodiphenyl ethers, two amido detergent alkylates, two
One or more of compositions of amido octadecyl benzene.
7. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
Water-reducing agent Chain transfer agent is made of the one or more of thioacetic acid, mercaptopropionic acid, mercaptoethanol, mercaprol.
8. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
Neutralizer is by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethyl alcohol in water-reducing agent
Amine, diethanol amine, triethanolamine, the one or more of of triisopropanolamine form.
9. 1200 molecular weight polyether polycarboxylate water-reducer according to claim 1, it is characterised in that：The polycarboxylic acids
It is 27.5% industrial grade hydrogen peroxide that hydrogen peroxide, which is mass percent, in water-reducing agent.
10. a kind of preparation method of 1200 molecular weight polyether polycarboxylate water-reducer as described in claim 1, feature exist
In：The method carries out as follows：
（1）, for the first time feed：By 310-330 parts of 1200 molecular weight polyether polymeric monomers, 4-14 parts of acrylic acid, 2-9 parts of carboxylic
Acid ester monomer and 180-220 parts of water are added in reaction kettle, and agitating and heating waits for its dissolution；
（2）Plus hydrogen peroxide：Temperature of reaction kettle is controlled at 40-45 DEG C, after the temperature in reaction kettle is stablized, is added at one time
0.9-1.8 parts of hydrogen peroxide；
（3）, solution A, the addition of solution B：To, successively start that solution B, solution A are added dropwise into reaction kettle after five minutes, solution B adds
After entering, start that solution A is added dropwise in 10 minutes, solution A time for adding is 2-4 hours, and solution B time for adding is 2.5-4.5 hours；
Solution B is uniformly mixed by 0.32-0.5 parts of reducing agents, 0.3-0.7 parts of chain-transferring agents and 80-100 parts of water, and solution A is by 40-
54 parts of acrylic acid, 2-5 parts of fluoro function monomers, 4-10 parts of flexible chain monomers and 50-70 parts of water are uniformly mixed；
（4）, finished product preparation：It after completion of dropwise addition, keeps temperature constant, cures 1-3 hours, be lower than 30 DEG C to reaction solution temperature
When, be slowly added to 6-10 parts of neutralizers, moisturizing to 1000 parts be 40% to get mass fraction the poly- carboxylic of 1200 molecular weight polyethers
Sour water-reducing agent.
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| CN112694573A (en) * | 2020-12-31 | 2021-04-23 | 浙江衢州鼎盛建材有限公司 | Cement slump loss resistant water reducer with early strength function |
| CN112851373A (en) * | 2021-02-01 | 2021-05-28 | 湖北工业大学 | High-dispersity ceramic water reducing agent and preparation method thereof |
| CN112898716A (en) * | 2021-02-02 | 2021-06-04 | 湖北工业大学 | Preparation method of low-viscosity flexible composite material dispersing agent and low-viscosity flexible composite material dispersing agent |
| CN114478942A (en) * | 2022-01-26 | 2022-05-13 | 四川同舟化工科技有限公司 | Polycarboxylate superplasticizer capable of effectively resisting influence of flocculating agent and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112694573A (en) * | 2020-12-31 | 2021-04-23 | 浙江衢州鼎盛建材有限公司 | Cement slump loss resistant water reducer with early strength function |
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| CN112898716A (en) * | 2021-02-02 | 2021-06-04 | 湖北工业大学 | Preparation method of low-viscosity flexible composite material dispersing agent and low-viscosity flexible composite material dispersing agent |
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| CN114478942B (en) * | 2022-01-26 | 2023-08-08 | 四川同舟化工科技有限公司 | Polycarboxylate superplasticizer capable of effectively resisting influence of flocculant and preparation method thereof |
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