CN107759745A - The non-evaporating foster ultra early-strength polycarboxylate water-reducer and preparation method thereof of prefabricated components - Google Patents
The non-evaporating foster ultra early-strength polycarboxylate water-reducer and preparation method thereof of prefabricated components Download PDFInfo
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- CN107759745A CN107759745A CN201610705737.2A CN201610705737A CN107759745A CN 107759745 A CN107759745 A CN 107759745A CN 201610705737 A CN201610705737 A CN 201610705737A CN 107759745 A CN107759745 A CN 107759745A
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- preparation
- unsaturated
- acid
- carboxylic acid
- reducer
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Classifications
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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
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
Abstract
The invention discloses a kind of non-evaporating foster ultra early-strength polycarboxylate water-reducer and preparation method thereof of prefabricated components, by unsaturated APEO and water input reactor, being sufficiently stirred is completely dissolved solid；Unsaturated sulfonic acid salting liquid is added, stirs and adds oxidant, and solution A and B solution is added dropwise；Wait to be added dropwise, continue after reacting 1h, be warming up to 60 80 DEG C, condensing agent, amine monomers, carboxylic acid type monomer are added into reactor, after reacting 3 4h, is cooled to less than 30 DEG C, pH=6~7 are adjusted with alkali lye, add water to adjust to obtain the polycarboxylate water-reducer product of the present invention that mass concentration is 40%；The advantage of the invention is that：Technique is simple, reaction condition is easily-controllable, reaction rate is high, economic and environment-friendly, sintetics stable performance, can be applied to the various concrete constructions with early strong demand, the concrete construction of low temperature environment, the production technology particularly suitable for concrete prefabricated element.
Description
Technical field
The present invention relates to a kind of polycarboxylate water-reducer, specifically a kind of non-evaporating foster poly- carboxylic of ultra early-strength of prefabricated components
Sour water reducer and preparation method thereof, belong to concrete admixture field.
Background technology
It is more and more wider with the application of concrete prefabricated element, how early age strength of concrete is quickly improved, accelerate mould
Turnaround speed, accelerate production efficiency has turned into the trend of building industrialization development.Poly carboxylic acid series water reducer is to develop in recent years
A kind of new high performance water-reducing agent come, its molecular structure is in combed, and main chain is shorter, and side chain is longer, and multiple work are carried on main chain
Property group, and polarity is stronger, such as carboxylic group（-COOH）, sulfonic acid group（-SO3）.The super of polycarboxylate water-reducer is realized at present
Early strengthen typically has two kinds of approach：A kind of is polymer of the synthesis with certain early epistasis energy；One kind is early strong group by compounding
Divide to improve the early epistasis energy of polycarboxylate water-reducer.
Existing several ultra early-strength polycarboxylate water-reducers in the prior art, such as Application No. CN101205128A, the patent
It is 37 and 54 allyl polyglycol, acrylic acid, acrylamide, methylpropene sodium sulfonate in water to use ethylene oxide polymerization degree
Copolymerization obtains in solution.But allyl polyglycol polymerization activity is insufficient, synthesized polycarboxylic acids diminishing can be largely remained in
In agent, cause water reducer water-reducing rate low, and the allyl polyglycol remained can significantly extend the setting time of concrete, influence
The performance of product.In the same year, separately there is patent CN101289292A to disclose a kind of early strength polycarboxylic acid high performance dehydragent
Manufacture method, the early-strength water reducer are based on graft copolymerization carboxylic acid based polymer, and compound preferable accelerating component is matched somebody with somebody
System forms, and can be applied to the various concrete constructions with early strong demand.But this Compositional type high early strength poly-carboxylic water reducer is often
Existence and stability is poor while although Compositional type early strength water-reducing agent can improve the early strength of concrete, to a certain extent
Have a negative impact to concrete durability.The content of the invention
In order to solve the above problems, the present invention devise a kind of prefabricated components it is non-evaporating it is foster with ultra early-strength polycarboxylate water-reducer and its
Preparation method, there is early powerful functional group by polycarboxylic acids Molecular Design, and grafting, synthesize a kind of hyperbranched netted
The high molecular polymer of structure, there is obvious early epistasis energy, and concrete 28d intensity is had no adverse effect.
The technical scheme is that：
A kind of non-evaporating foster ultra early-strength polycarboxylate water-reducer of prefabricated components, general structure are as follows：
；
In formula：R：-CH2CH2OH；A, b, c, n are the integer more than 0；
R'：
A kind of non-evaporating foster preparation method with ultra early-strength polycarboxylate water-reducer of above-mentioned prefabricated components, comprises the following steps：
（1）By in unsaturated APEO and water input reactor, its reclaimed water and the mass ratio of unsaturated APEO are
1 ︰ 1, being sufficiently stirred is completely dissolved solid；
（2）Unsaturated sulfonic acid salting liquid is added, stirs and adds oxidant, stirring reaction starts simultaneously that A is added dropwise is molten after 10 minutes
Liquid and B solution, 1~1.5h are added dropwise complete；
Wherein, the A liquid is the aqueous solution of unsaturated carboxylic acid, and the unsaturated carboxylic acid is acrylic acid or itaconic acid；
The B liquid is the aqueous solution of reducing agent and chain-transferring agent, wherein, the reducing agent is ascorbic acid,（It is total to account for all monomers
The 0.12%~0.2% of quality）.The chain-transferring agent is TGA or mercaptopropionic acid,（Account for all monomer gross mass 0.1%~
0.15%）；
（3）Wait to be added dropwise, continue after reacting 1h, be warming up to 60-80 DEG C, condensing agent, amine monomers, carboxylic are added into reactor
Acrylic monomer, react 3-4h after, be cooled to less than 30 DEG C, with alkali lye regulation pH=6~7, add water adjust to obtain mass concentration be
40%, obtain the non-evaporating foster ultra early-strength polycarboxylate water-reducer product of prefabricated components of the present invention.
Further, described unsaturated APEO, unsaturated sulfonic acid salt, unsaturated carboxylic acid, amine monomers, carboxylic acid
The mol ratio of class monomer is the ︰ 1~1.5 of 1 ︰, 0.2~0.3 ︰ 1.5~2：0.2~0.3.
Further, the unsaturated APEO is modified unsaturated allyl polyethenoxy ether, preferably methyl alkene
Propyl group APEO, molecular weight 2400.
Further, the unsaturated sulfonic acid salt is methylpropene sodium sulfonate or 2- acrylamide-2-methyl propane sulfonics.
Further, the unsaturated carboxylic acid is acrylic acid or itaconic acid.
Further, the condensing agent is N, N'- carbonyl dimidazoles.
Further, the oxidant is hydrogen peroxide, and the addition of the hydrogen peroxide accounts for all monomer gross mass
0.5%~1%.
Further, the amine monomers are ethylenediamine or diethylene triamine.
Further, the carboxylic acid type monomer is acrylic or methacrylic acid.
Further, the alkali lye is the sodium hydroxide solution of mass fraction 30%.
Further, all monomers are unsaturated APEO, unsaturated sulfonic acid salt, unsaturated carboxylic acid, amine
Monomer, the general name of carboxylic acid type monomer.
The advantage of the invention is that：
（1）The present invention uses H2O2- Vc is used as initiation system, normal temperature synthesis, is protected without nitrogen, technique is simple, reaction condition
It is easily-controllable, reaction rate is high, raw material is easy to get, and greatlys save energy consumption, environment friendliness；
（2）For the present invention using methyl alkenyl APEO as polymerized monomer, polymerization activity is high, can effectively improve polycarboxylic acids point
Peptizaiton of the son to cement granules；
（3）The present invention uses high molecular polymerization means, and main polymer chain skeleton is adjusted using polybasic carboxylic acids such as acrylic acid, itaconic acids
Structure, and hyperbranched condensation means are finally being utilized, change the distribution of polycarboxylic acids molecular skeleton both ends, finally give a kind of dispersiveness
It is good, hydrated cementitious can be promoted, properties of product are stable, to the polycarboxylate water-reducer of cement favorable dispersibility；
（4）Non-evaporating support of the prefabricated components of the present invention can be applied to have the various of early strong demand with ultra early-strength polycarboxylate water-reducer
Concrete construction, the concrete construction of low temperature environment, especially suitable for the production technology of concrete prefabricated element, while product
Can be stable, cement adaptability is good, and concrete 28d intensity is had no adverse effect.
With reference to specific embodiment, the invention will be further described.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Unless otherwise indicated, the percentage employed in the present invention is percetage by weight.
Embodiment 1
Methyl allyl polyoxyethylene ether 360g, water 320g are weighed, adds 1000ml round-bottomed flasks, as reaction bottom liquid.
Prepare dropping liquid A：19.44g acrylic acid, 40g water stir to be placed in and are added dropwise in bottle.
Prepare dropping liquid B：The anti-sepsis acid of 0.57g, 0.46g TGAs, 68g water stir to be placed in and are added dropwise in bottle.
After solid is completely dissolved, 6.95g methylpropene sodium sulfonates are added, 2.64g hydrogen peroxide, are started after 10 minutes same
When A liquid and B liquid is added dropwise, control A material 1h is dripped off, and B material 1.5h is dripped off, and is continued to be warming up to 60-80 DEG C after reacting 1h, is then added
0.2gN, N'- carbonyl dimidazoles, 10.8g ethylenediamines, 3.24g acrylic acid, insulation reaction 3h, 25 DEG C are cooled to, add 18.43g
30% alkali lye regulation pH=6~7, add water to adjust to obtain the polycarboxylic acids product of the present invention that mass concentration is 40%.
Embodiment 2
Methyl allyl polyoxyethylene ether 360g, water 320g are weighed, adds 1000ml round-bottomed flasks, as reaction bottom liquid.
Prepare dropping liquid A：17.21g acrylic acid, 4.03g itaconic acids, 43g water stir to be placed in and are added dropwise in bottle.
Prepare dropping liquid B：The anti-sepsis acid of 0.57g, 0.37g TGAs, 68g water stir to be placed in and are added dropwise in bottle.
After solid is completely dissolved, 6.95g methylpropene sodium sulfonates are added, 2.64g hydrogen peroxide, are started after 10 minutes same
When A liquid and B liquid is added dropwise, control A material 1h is dripped off, and B material 1.5h is dripped off, and is continued to be warming up to 60-80 DEG C after reacting 1h, is then added
0.2gN, N'- carbonyl dimidazoles, 13.5g ethylenediamines, 2.7g acrylic acid, insulation reaction 3h, 25 DEG C are cooled to, add 18.02g
30% alkali lye regulation pH=6~7, add water to adjust to obtain the polycarboxylic acids product of the present invention that mass concentration is 40%.
Embodiment 3
Methyl allyl polyoxyethylene ether 360g, water 320g are weighed, adds 1000ml round-bottomed flasks, as reaction bottom liquid.
Prepare dropping liquid A：15.89g acrylic acid, 6.41 itaconic acids, 44g water stir to be placed in and are added dropwise in bottle.
Prepare dropping liquid B：The anti-sepsis acid of 0.57g, 0.31g TGAs, 68g water stir to be placed in and are added dropwise in bottle.
After solid is completely dissolved, 6.95g methylpropene sodium sulfonates are added, 2.64g hydrogen peroxide, are started after 10 minutes same
When A liquid and B liquid is added dropwise, control A material 1h is dripped off, and B material 1.5h is dripped off, and is continued to be warming up to 60-80 DEG C after reacting 1h, is then added
0.18gN, N'- carbonyl dimidazoles, 10.8g ethylenediamines, 3.24g acrylic acid insulation reaction 3h, 25 DEG C are cooled to, add 21.40g
30% alkali lye regulation pH=6~7, add water to adjust to obtain the polycarboxylic acids product of the present invention that mass concentration is 40%.
Application Example
Concrete optimum is tested
With reference to GB8076-2008《Concrete admixture》、GB/T50081-2002《Normal concrete mechanical test method mark
It is accurate》It is required that carry out the slump of concrete optimum experimental check polycarboxylic acids product of the present invention, divergence, setting time, pressure resistance
The physical function parameters such as degree.When dependence test the results are shown in Table shown in 1, table 2 concrete match ratio.
The concrete mix of table 1（kg/m3）
| C | FA | K | S | G | W |
| 290 | 50 | 140 | 668 | 1102 | 160 |
Wherein：C is the prosperous P.O42.5R cement of sky China；FA is red two electric three-level flyash；K is Bao Xinsheng sources miberal powder；S is natural
River sand, modulus of fineness 2.8；G is 5-20mm continuous grading cobbles；W is running water.
The concrete physical parameter list of table 2
Wherein：Additive uses match ratio of the same race, is configured to the polycarboxylate water-reducer finished product of solid content 13%, admixture dosage is glue
The 2.0% of gel material dosage.25 DEG C of trial test environment temperature, ambient humidity 60%.
As can be seen from the test results：The non-evaporating foster use ultra early-strength polycarboxylate water-reducer of prefabricated components of the present invention can be notable
Shortening concrete coagulating time, concrete early strength rises soon, compared with common polycarboxylate water-reducer, concrete resistance to compression in 1 day
Intensity improves more than 90%, and compression strength is suitable with the concrete that common polycarboxylate water-reducer is prepared within 28 days.
Raw materials used in the present invention is to commonly use raw material in the production of this area, can be obtained from market, and for production
As a result will not have an impact；Various equipment employed in the present invention, it is the conventional equipment used in the production technology of this area,
And the operation of each equipment, parameter etc. are carried out according to routine operation, have no special feature.
Claims (10)
1. a kind of non-evaporating foster ultra early-strength polycarboxylate water-reducer of prefabricated components, general structure are as follows：
；
In formula：R：-CH2CH2OH；
A, b, c, n are the integer more than 0；
R'—。
A kind of 2. preparation method of poly carboxylic acid modified alcamines cement grinding aid as claimed in claim 1, it is characterised in that bag
Include following steps：
（1）By in unsaturated APEO and water input reactor, its reclaimed water and the mass ratio of unsaturated APEO are
1 ︰ 1, being sufficiently stirred is completely dissolved solid；
（2）Unsaturated sulfonic acid salting liquid is added, stirs and adds oxidant, stirring reaction starts simultaneously that A is added dropwise is molten after 10 minutes
Liquid and B solution, 1~1.5h are added dropwise complete；
Wherein, the A liquid is the aqueous solution of unsaturated carboxylic acid, and the unsaturated carboxylic acid is acrylic or methacrylic acid；
The B liquid is the aqueous solution of reducing agent and chain-transferring agent, wherein, the reducing agent is ascorbic acid,（Account for monomer gross mass
0.12%~0.2%）；
The chain-transferring agent is TGA or mercaptopropionic acid,（Account for the 0.1%~0.15% of monomer gross mass）；
（3）Wait to be added dropwise, continue after reacting 1h, be warming up to 60-80 DEG C, condensing agent, amine monomers, carboxylic are added into reactor
Acrylic monomer, after reacting 3-4h, less than 30 DEG C are cooled to, pH=6~7 are adjusted with alkali lye.
3. preparation method according to claim 2, it is characterised in that：Described unsaturated APEO, unsaturated sulphur
Hydrochlorate, unsaturated carboxylic acid, amine monomers, the mol ratio of carboxylic acid type monomer are the ︰ 1~1.5 of 1 ︰, 0.2~0.3 ︰ 1.5~2：0.2~
0.3。
4. the preparation method according to Claims 2 or 3, it is characterised in that：The unsaturated APEO is to be modified not
Saturation allyl polyethenoxy ether.
5. the preparation method according to Claims 2 or 3, it is characterised in that：The unsaturated sulfonic acid salt is metering system sulphur
Sour sodium or 2- acrylamide-2-methyl propane sulfonic.
6. the preparation method according to Claims 2 or 3, it is characterised in that：The unsaturated carboxylic acid is acrylic acid, itaconic acid
Or aconitic acid.
7. the preparation method according to Claims 2 or 3, it is characterised in that：The condensing agent is N, N'- carbonyl dimidazoles.
8. the preparation method according to Claims 2 or 3, it is characterised in that：The oxidant is hydrogen peroxide, the peroxide
The addition for changing hydrogen accounts for the 0.5%~1% of monomer gross mass.
9. the preparation method according to Claims 2 or 3, it is characterised in that：The amine monomers are ethylenediamine or diethyl two
Amine.
10. the preparation method according to Claims 2 or 3, it is characterised in that：The carboxylic acid type monomer is acrylic acid or methyl
Acrylic acid.
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| CN201610705737.2A CN107759745A (en) | 2016-08-22 | 2016-08-22 | The non-evaporating foster ultra early-strength polycarboxylate water-reducer and preparation method thereof of prefabricated components |
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| CN201610705737.2A CN107759745A (en) | 2016-08-22 | 2016-08-22 | The non-evaporating foster ultra early-strength polycarboxylate water-reducer and preparation method thereof of prefabricated components |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942222A (en) * | 2019-03-27 | 2019-06-28 | 山西佳维新材料股份有限公司 | A kind of preparation method of solid early strength polycarboxylic acid high performance dehydragent |
| CN114656600A (en) * | 2022-03-31 | 2022-06-24 | 华新水泥股份有限公司 | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer |
| CN116354653A (en) * | 2023-04-13 | 2023-06-30 | 山东中岩重科新材料科技有限公司 | Application of PC component concrete raising-free water reducing agent |
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| CN104861122A (en) * | 2015-04-22 | 2015-08-26 | 厦门路桥翔通建材科技有限公司 | Heat-source-free early strength polycarboxylate water reducer and preparation method thereof |
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- 2016-08-22 CN CN201610705737.2A patent/CN107759745A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104861122A (en) * | 2015-04-22 | 2015-08-26 | 厦门路桥翔通建材科技有限公司 | Heat-source-free early strength polycarboxylate water reducer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942222A (en) * | 2019-03-27 | 2019-06-28 | 山西佳维新材料股份有限公司 | A kind of preparation method of solid early strength polycarboxylic acid high performance dehydragent |
| CN114656600A (en) * | 2022-03-31 | 2022-06-24 | 华新水泥股份有限公司 | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer |
| CN116354653A (en) * | 2023-04-13 | 2023-06-30 | 山东中岩重科新材料科技有限公司 | Application of PC component concrete raising-free water reducing agent |
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