CN105601843B - Ethers Early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
Ethers Early-strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN105601843B CN105601843B CN201610186337.5A CN201610186337A CN105601843B CN 105601843 B CN105601843 B CN 105601843B CN 201610186337 A CN201610186337 A CN 201610186337A CN 105601843 B CN105601843 B CN 105601843B
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- ethers
- polycarboxylate superplasticizer
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- strength polycarboxylate
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of ethers Early-strength polycarboxylate superplasticizers and preparation method thereof, belong to building concrete additive technical field.The preparation method of the ethers Early-strength polycarboxylate superplasticizer, it is first by methyl allyl alcohol polyoxyethylene ether and deionized water that molecular weight is 6,000 8000 mixed dissolution at normal temperatures, add in catalyst thereto again, then the solution B that the solution A being mixed by acrylic acid, Sulfonates unsaturated monomer, deionized water is added dropwise successively and is mixed by initiator, chain-transferring agent, deionized water carries out polymerizable aqueous reaction, it is stirred after being added dropwise, it is eventually adding lye to be neutralized, obtains ethers Early-strength polycarboxylate superplasticizer.The present invention in water-reducing agent molecular structure by introducing a large amount of rigid phenyl ring and sulfonate radical, significantly reduce the content of the carboxylic acid group with slow setting effect in polycarboxylic acids molecule, the early strong effect of polycarboxylate water-reducer molecule is greatly improved, and with certain water-reducing property, is had a extensive future.
Description
Technical field
The present invention relates to a kind of ethers Early-strength polycarboxylate superplasticizers and preparation method thereof, belong to building concrete additive
Technical field.
Background technology
It is particularly pre- in commerical ready-mixed concrete with the continuous development and progress of high performance water reducing agent of polyocarboxy acid synthetic technology
It is more urgent to the demand of new function water-reducing agent-Early-strength polycarboxylate superplasticizer in the actual production process of component processed, it
The working performance of concrete can be improved, significantly improve early strength, the production efficiency of concrete, while production energy can be reduced
Consumption.Early powerful polycarboxylate water-reducer can efficiently solve that early strength during winter construction is low, concrete is easily by freeze injury
The problems such as, while form cycling rate can be improved, it reduces and even removes steam curing expense from, accelerate construction progress, improve warp
Ji benefit.In recent years, large-scale high quality requirement engineering is more and more, also just there is higher requirement to concrete performance, and
Gathering for the early-strength for having high diminishing, high early epistasis energy also can be more and more extensive by the application of sour water-reducing agent.But it for a long time, uses
MOLECULE DESIGN mode is more rare to synthesize the research of Early-strength polycarboxylate superplasticizer, this significantly limits polycarboxylate water-reducer
Application in common prefabricated components concrete and high-strength pipe pile concrete.
CN103304181A discloses a kind of early-strength poly-carboxylic high-performance being made of by weight percentage following component
Water-reducing agent：The poly carboxylic acid series water reducer of 10-20%, the calcium chloride of 10-17%, the sodium nitrite of 10-20%, three second of 1-3%
Hydramine, surplus are water.Its mainly on the basis of common polycarboxylate water-reducer by simply compound be made, there is no from
Be improved on the molecular structure of basic polycarboxylate water-reducer, product there are adaptability it is poor and adjustment, synergy space not
The problem of big.
CN103450408A is disclosed with beta-unsaturated esters, diethanol monoisopropanolamine, 2- acrylamido-methyl propane sulfonic acid
It is raw material with methacrylic polyoxyethylene poly-oxygen propylene aether, under the action of catalyst, initiator, chain-transferring agent etc., one
The ethers Early-strength polycarboxylate superplasticizer that fixed condition is prepared through phthalein amination and polymerization process, preparation process is cumbersome, instead
Answer temperature high, more demanding to production equipment, processing safety is poor.
Therefore, by studying polycarboxylate water-reducer molecule relation be- tween structure and properties, synthesize with strong work(of more excellent morning
The polycarboxylate water-reducer of energy, will have great importance.
The content of the invention
The object of the present invention is to provide a kind of ethers Early-strength polycarboxylate superplasticizers, solve production in the prior art
Product bad adaptability and adjustment, the problem of synergy space is little, have the characteristics that setting time is short, early strength is high；It is of the invention same
When its preparation method is provided.
The preparation method of ethers Early-strength polycarboxylate superplasticizer of the present invention, it is first 6000-8000 by molecular weight to be
Methyl allyl alcohol polyoxyethylene ether and deionized water mixed dissolution, then add in catalyst thereto at normal temperatures, then successively
Be added dropwise the solution A that is mixed by acrylic acid, Sulfonates unsaturated monomer, deionized water and by initiator, chain-transferring agent, go from
The solution B that sub- water is mixed into carries out polymerizable aqueous reaction, is stirred after being added dropwise, is eventually adding lye and is neutralized, obtained
To ethers Early-strength polycarboxylate superplasticizer.
Wherein, preferred technical solution is as follows：
It is counted using the gross mass of methyl allyl alcohol polyoxyethylene ether and deionized water as 100%, methallyl alcohol polyoxyethylene
Ether accounts for 45-65%.
The catalyst is one or both of ammonium persulfate, hydrogen peroxide, and dosage is methallyl alcohol polyoxy second
The 0.5-1wt% of alkene ether quality.
The dosage of acrylic acid is the 4-7wt% of methyl allyl alcohol polyoxyethylene ether quality in the solution A.
Sulfonates unsaturated monomer is one in sodium p styrene sulfonate, methylpropene sodium sulfonate in the solution A
Kind or two kinds, dosage be methyl allyl alcohol polyoxyethylene ether quality 3-5.5wt%.
Initiator is one or both of vitamin C, sodium hydrogensulfite in the solution B, and dosage is methyl alkene
The 2-4wt% of propyl alcohol polyoxyethylene ether quality.
The solution B Chain transfer agent is one or both of thioacetic acid, 3- mercaptopropionic acids, and dosage is methyl
The 3-6wt ‰ of allyl alcohol polyethenoxy ether quality.
Reaction temperature during described polymerisation is 5-30 DEG C, polymerize bottom liquid concentration 45-65%, reaction time 1.5-
3h。
The addition lye is neutralized to pH value as 5-7.
The solid content of the ethers Early-strength polycarboxylate superplasticizer is 20-60wt%.
Beneficial effects of the present invention are as follows：
(1) present invention is significantly reduced poly- by introducing a large amount of rigid phenyl ring and sulfonate radical in water-reducing agent molecular structure
The content of carboxylic acid group with slow setting effect in carboxylic acid molecules greatly improves the early strong effect of polycarboxylate water-reducer molecule,
And it with certain water-reducing property, has a extensive future；
(2) long-chain methyl allyl polyoxyethylene ether of the molecular weight for 6000-8000 is used, synthesizes the early strong of water-reducing agent
Effect is more preferable；
(3) preparation method is simple, and reaction temperature is low, and the requirement to production equipment is low, good operation safety.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation method of ethers Early-strength polycarboxylate superplasticizer is as follows：
Under normal temperature condition, in 1L glass flasks, 440g deionized waters are added in, open stirring, adding in 360g molecular weight is
6000 methyl allyl polyoxyethylene ether is treated fully to dissolve, and adds in the hydrogen peroxide that 1.8g concentration is 27.5wt%, then successively
The solution A that is mixed by 14.4g acrylic acid, 19.8g sodium p styrene sulfonates, 40g deionized waters is added dropwise and by 0.72g vitamins
C, the solution B that 1.08g thioacetic acid, 80g deionized waters are mixed into, time for adding 1.5h, addition concentration is after stirring 1h
The NaOH solution of 30wt% is neutralized to pH value as 5-7, and then moisturizing to solid content is 40wt%, obtains ethers early-strength polycarboxylic acids
Water-reducing agent.
Embodiment 2
The preparation method of ethers Early-strength polycarboxylate superplasticizer is as follows：
Under normal temperature condition, in 1L glass flasks, 193.8g deionized waters are added in, open stirring, add in 360g molecular weight
It for 7000 methyl allyl polyoxyethylene ether, treats fully to dissolve, adds in 3.6g ammonium persulfates, be then added dropwise successively by 25.2g
Solution A that acrylic acid, 10.8g methylpropene sodium sulfonates, 40g deionized waters are mixed into and by 1.44g sodium hydrogensulfites, 2.16g
The solution B that mercaptopropionic acid, 80g deionized waters are mixed into, time for adding 2h add in the NaOH that concentration is 30wt% after stirring 1h
Solution is neutralized to pH value as 5-7, and then moisturizing to solid content is 40wt%, obtains ethers Early-strength polycarboxylate superplasticizer.
Embodiment 3
The preparation method of ethers Early-strength polycarboxylate superplasticizer is as follows：
Under normal temperature condition, in 1L glass flasks, 300g deionized waters are added in, open stirring, adding in 360g molecular weight is
8000 methyl allyl polyoxyethylene ether is treated fully to dissolve, and it is the hydrogen peroxide of 27.5wt% and 1.5g over cures to add in 1g concentration
Sour ammonium, be then added dropwise successively the solution A that is mixed by 21.6g acrylic acid, 9g sodium p styrene sulfonates, 40g deionized waters and by
The solution B that 1.08g vitamin Cs, 0.8g thioacetic acid, 1g mercaptopropionic acids, 80g deionized waters are mixed into, time for adding 2.5h,
It is 5-7 to add in the NaOH solution that concentration is 30wt% to be neutralized to pH value after stirring 0.5h, and then moisturizing to solid content is 40wt%,
Obtain ethers Early-strength polycarboxylate superplasticizer.
Embodiment 4
The preparation method of ethers Early-strength polycarboxylate superplasticizer is as follows：
Under normal temperature condition, in 1L glass flasks, 400g deionized waters are added in, open stirring, adding in 360g molecular weight is
6000 methyl allyl polyoxyethylene ether is treated fully to dissolve, add in 3g ammonium persulfates, be then added dropwise successively by 18g acrylic acid,
Solution A that 8g sodium p styrene sulfonates, 8.2g methylpropene sodium sulfonates, 40g deionized waters are mixed into and by 0.6g vitamin Cs,
The solution B that 1g thioacetic acid, 0.6g sodium hydrogensulfites, 0.5 mercaptopropionic acid, 80g deionized waters are mixed into, time for adding 3h,
It is 5-7 to add in the NaOH solution that concentration is 30wt% to be neutralized to pH value after stirring 0.5h, and then moisturizing to solid content is 40wt%,
Obtain ethers Early-strength polycarboxylate superplasticizer.
Using standard cement, the product that embodiment 1-4 is obtained and common polycarboxylate water-reducer are compared, according to
GB8076-2008《Concrete admixture》, measure its slump and each age strength of concrete.Wherein, concrete mix is:
Cement 360kg/m3, sand 803kg/m3, stone 982kg/m3, in 180 ± l0mm, testing result is shown in Table 1 for slump control.
1 properties of product Testing index of table
As can be seen from Table 1, using the prepared early strength of concrete of product of the present invention than common polycarboxylate water-reducer
High, early-strength type water-reducing agent can significantly improve early strength of concrete, be mixed especially suitable for prefabricated component and pile pile
Coagulate the production of soil.
Claims (8)
1. a kind of preparation method of ethers Early-strength polycarboxylate superplasticizer, it is characterised in that：It is first 6000-8000's by molecular weight
Methyl allyl alcohol polyoxyethylene ether and deionized water mixed dissolution, then add in catalyst thereto at normal temperatures, then drip successively
Add the solution A that is mixed by acrylic acid, Sulfonates unsaturated monomer, deionized water and by initiator, chain-transferring agent, deionization
The solution B that water is mixed into carries out polymerizable aqueous reaction, is stirred after being added dropwise, is eventually adding lye and is neutralized, obtained
Ethers Early-strength polycarboxylate superplasticizer；
The dosage of acrylic acid is the 4-7wt% of methyl allyl alcohol polyoxyethylene ether quality in solution A；
In solution A Sulfonates unsaturated monomer be sodium p styrene sulfonate, one or both of methylpropene sodium sulfonate,
Dosage is the 3-5.5wt% of methyl allyl alcohol polyoxyethylene ether quality.
2. the preparation method of ethers Early-strength polycarboxylate superplasticizer according to claim 1, it is characterised in that：With methyl alkene
The gross mass of propyl alcohol polyoxyethylene ether and deionized water is 100% meter, and methyl allyl alcohol polyoxyethylene ether accounts for 45-65%.
3. the preparation method of ethers Early-strength polycarboxylate superplasticizer according to claim 1, it is characterised in that：Catalyst is
One or both of ammonium persulfate, hydrogen peroxide, dosage are the 0.5-1wt% of methyl allyl alcohol polyoxyethylene ether quality.
4. the preparation method of ethers Early-strength polycarboxylate superplasticizer according to claim 1, it is characterised in that：In solution B
Initiator is one or both of vitamin C, sodium hydrogensulfite, and dosage is the 2- of methyl allyl alcohol polyoxyethylene ether quality
4wt%。
5. the preparation method of ethers Early-strength polycarboxylate superplasticizer according to claim 1, it is characterised in that：In solution B
Chain-transferring agent is one or both of thioacetic acid, 3- mercaptopropionic acids, and dosage is methyl allyl alcohol polyoxyethylene ether quality
3-6wt ‰.
6. the preparation method of ethers Early-strength polycarboxylate superplasticizer according to claim 1, it is characterised in that：Polymerisation
When reaction temperature for 5-30 DEG C, reaction time 1.5-3h；It is eventually adding lye and is neutralized to pH value as 5-7.
7. a kind of ethers Early-strength polycarboxylate superplasticizer, it is characterised in that：Using any preparation methods of claim 1-6
It is prepared.
8. ethers Early-strength polycarboxylate superplasticizer according to claim 7, it is characterised in that：Ethers early-strength polycarboxylic acids subtracts
The solid content of aqua is 20-60wt%.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106632892B (en) * | 2016-12-28 | 2019-11-26 | 江苏奥克化学有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN106866895A (en) * | 2017-03-27 | 2017-06-20 | 南宁新泰瑞科建材有限公司 | A kind of high-performance poly carboxylic acid series water reducer and preparation method thereof |
| CN107446090A (en) * | 2017-09-07 | 2017-12-08 | 江苏百瑞吉新材料有限公司 | A kind of synthetic method of Early-strength polycarboxylate superplasticizer |
| CN108101404A (en) * | 2017-12-28 | 2018-06-01 | 科之杰新材料集团有限公司 | A kind of preparation method of sustained-release polycarboxylic water reducer |
| CN111592622B (en) * | 2019-02-21 | 2022-06-10 | 天水师范学院 | Method and device for preparing early-strength polycarboxylate superplasticizer |
| CN110128601A (en) * | 2019-05-22 | 2019-08-16 | 上饶市天佳新型材料有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN111410451A (en) * | 2020-03-30 | 2020-07-14 | 深圳港创建材股份有限公司 | Raw material formula of graphene polycarboxylate superplasticizer and preparation and use methods of water reducer |
| CN114702628B (en) * | 2022-03-25 | 2023-12-26 | 湖南中岩建材科技有限公司 | Water reducer modifier and preparation method and application thereof |
| CN115849760B (en) * | 2022-12-28 | 2023-12-01 | 科之杰新材料集团有限公司 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
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| CN102718426A (en) * | 2012-06-21 | 2012-10-10 | 马清浩 | Modified carboxylic acid water-reducing agent and preparation method thereof |
| CN103965416A (en) * | 2014-04-18 | 2014-08-06 | 北京建筑大学 | Early-strength polycarboxylate water reducing agent for component and preparation method for early-strength polycarboxylate water reducing agent |
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