CN104861127B - A kind of preparation method and applications of anti-chamotte mould polycarboxylate water-reducer - Google Patents
A kind of preparation method and applications of anti-chamotte mould polycarboxylate water-reducer Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of anti-chamotte mould polycarboxylate water-reducer, the production efficiency for improving anti-chamotte mould polycarboxylate water-reducer, save energy, strengthen the anti-anti- mud performance of chamotte mould polycarboxylate water-reducer agent and through when protect plasticity energy.A kind of preparation method of anti-chamotte mould polycarboxylate water-reducer of the present invention includes：Under 5~35 DEG C of normal temperature conditions; isobutene alcohol APEO, maleic anhydride beta cyclodextrin are mixed soluble in water; add acrylic acid and to styrylformic acid ester mixed liquor; add hydrogen peroxide; mercaptopropionic acid and ascorbic acid mixed liquor, acrylic acid are added under nitrogen protection and to styrylformic acid ester mixed liquor, sodium dithionite; it is 67 to add sodium hydrate aqueous solution regulation pH, that is, obtain anti-chamotte mould polycarboxylate water-reducer, and anti-chamotte mould polycarboxylate water-reducer of the invention is cup-like structure.
Description
Technical field
The present invention relates to construction material cement water reducing agent field, more particularly to a kind of system of anti-chamotte mould polycarboxylate water-reducer
Preparation Method and its application.
Background technology
Anti- chamotte mould polycarboxylate water-reducer be in the eighties in last century propose a class by the unsaturated monomer containing carboxyl with
The water reducer of new generation that other monomers are polymerized, has that volume is low, water-reducing rate is high, function is adjustable due to it, an environmental protection etc.
Advantage, oneself is widely used in middle low grade ready-mixed concrete industry, but anti-chamotte mould polycarboxylate water-reducer in low grade coagulation
Clay mineral component in native application process to aggregate is particularly sensitive.With the explosive growth of concrete construction amount in recent years,
Quality sand and stone aggregate resources fall sharply, and aggregate clay content is improved constantly, and with the increase of clay content, mixes anti-chamotte mould polycarboxylic acids diminishing
Agent concrete initial fluidity, slump-retaining can constantly reduce.Although can be eased by improving water reducer volume,
But the problems such as being easily caused concrete coagulating time overlength and compressive strength rate and reduce, and greatly increase cost.
One kind is disclosed in patent CN 101798197A and suppresses the clay content slow release polycarboxylate water reducing agent that gathers materials, it leads
To be formed by anti-chamotte mould polycarboxylate water-reducer, retarder and natural zeolite powder compounding.Because clay mineral can be preferentially adsorbed on
Natural zeolite powder particle surface, so anti-chamotte mould polycarboxylate water-reducer molecule is liberated, it is easier to be adsorbed in cement granules table
Face, so as to alleviate the clay problem excessive to polycarboxylic acids Molecular Adsorption.But excessive gathering can be also adsorbed due to zeolite loose structure
Carboxylic acid molecules, therefore ready-mixed concrete will reach identical fluidity, can still increase volume.
A kind of anti-mud agent of amphoteric ethylene polymer is disclosed in patent CN 102617811A, in traditional polycarboxylic acids point
Vinyl-based cationic monomer is introduced in minor structure.The anti-mud agent mainly uses the absorption to soil and quaternary amine positive and negative charge
Effect, absorption of the shielding clay to water reducer.But, used as a class sacrifice agent, not only production cost is high for the product, but also need
It is combined other water reducers to be used in conjunction with, its cost performance is not so good as small molecule quaternary ammonium salt compound.
Anti- chamotte mould polycarboxylate water-reducer of a kind of anti-chamotte mould and preparation method thereof is disclosed in patent CN103897116A, is adopted
It is monomer with vinyl APEO, SSS, acrylic acid and acrylamides, in Redox Initiator
It is polymerized under system.The invention is polymeric monomer with activity vinyl APEO higher, and reaction conversion ratio is higher, is produced
Product water-reducing rate is big.But its molecule is in pectinate texture, side chain is easily accessible clay frame structure, causes water reducer volume excessive.
But prior art prepares anti-chamotte mould polycarboxylate water-reducer, has different degrees of requirement, generated time for temperature
It is long, need heating, expend the energy, the prepared anti-anti- mud of chamotte mould polycarboxylate water-reducer and through when to protect plasticity poor.
The content of the invention
A kind of preparation method and applications of anti-chamotte mould polycarboxylate water-reducer are the embodiment of the invention provides, anti-chamotte mould is prepared
Polycarboxylate water-reducer takes short, efficiency high, is not required to heating, save energy, and prepared anti-chamotte mould polycarboxylate water-reducer agent resists
Mud performance and through when protect modeling superior performance.
The preparation method of the anti-chamotte mould polycarboxylate water-reducer of the present invention, introduces amount of activated slightly higher before polymerisation starting
Acrylic acid -4- vinyl benzoic acid ester mix monomers, can improve the relatively low maleic anhydride-beta-schardinger dextrin monomer conversion of activity,
And then shorten anti-chamotte mould polycarboxylate water-reducer generated time, improve production efficiency；Meanwhile, urged present invention introduces ternary redox
Change system, can under normal temperature condition the efficiently relatively low maleic anhydride-beta-schardinger dextrin of catalysis activity, isobutene alcohol polyoxyethylene
Ether and acrylic acid polymerisation, without heating, low-carbon (LC), efficient, environmental protection are adapted to industrial-scale production to production process.
Further, the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould that prepared by the present invention introduces cup in polycarboxylic acids molecular structure
Shape and rigid structure unit, can increase polycarboxylic acids molecule space steric hindrance, weaken the interspersed effect of itself and clay mineral, ensure compared with
While high water reducing rate, the anti-mud function of anti-chamotte mould polycarboxylate water-reducer is effectively improved.
In view of this, the present invention provides a kind of preparation method and applications of anti-chamotte mould polycarboxylate water-reducer, it may include：
(1) under 5~35 DEG C of normal temperature conditions, isobutene alcohol APEO, maleic anhydride-beta-schardinger dextrin are mixed and is dissolved in
In water, monomer solution is obtained；
(2) acrylic acid and 4- vinyl benzoic acid esters are mixed to get acrylic acid and 4- vinyl benzoic acid ester mixed liquors；
(3) to the addition part acrylic acid and 4- vinyl benzoic acid ester mixed liquors in the monomer solution；
(4) hydrogen peroxide is added；
(5) mercaptopropionic acid and ascorbic acid mixed liquor, residual acrylic acid and 4- vinyl benzene first are added under nitrogen protection
Acid esters mixed liquor, sodium dithionite；
(6) it is 6-7 to add sodium hydrate aqueous solution regulation pH, obtains anti-chamotte mould polycarboxylate water-reducer.
Preferably, the butenol APEO, acrylic acid, 4- vinyl benzoic acids ester, maleic anhydride-β-ring paste
Essence, mercaptopropionic acid, ascorbic acid, sodium dithionite, hydrogen peroxide quality proportioning are 100-130：15-25：1-5：5-15：
0.1-10.0：0.3-1.2：0.1-1.0：0.5-5.0.
Preferably, in mass, step (2) part acrylic acid and 4- vinyl benzoic acid esters mixed liquor are described third
(5-15) % of olefin(e) acid and 4- vinyl benzoic acid ester mixed liquors.
Preferably, step (5) addition in 2.0-3.5 hours is finished.
Preferably, the sodium dithionite starts addition after reaction carries out 0.5-1.5 hours.
Preferably, the acrylic acid and 4- vinyl benzoic acid esters mixed liquor are the aqueous solution, and mass concentration is (80-
95) %.
Preferably, in mass, the concentration of the monomer solution is (50-70) %, and the hydrogen peroxide is (27-
50) the % aqueous solution, the mercaptopropionic acid and ascorbic acid mixed liquor are (1-15) % aqueous solution, and the sodium dithionite is used
(20-40) % aqueous solution.
The present invention also provides a kind of anti-chamotte mould polycarboxylate water-reducer, and the anti-chamotte mould polycarboxylate water-reducer uses foregoing anti-mud
The preparation method of type polycarboxylate water-reducer is obtained.
Preferably, the anti-chamotte mould polycarboxylate water-reducer is cup-like structure.
The present invention also provides application of the anti-chamotte mould polycarboxylate water-reducer in concrete.
The problem larger to sandstone clay content sensitiveness it is an object of the invention to be directed to anti-chamotte mould polycarboxylate water-reducer, often
Synthesize an anti-chamotte mould polycarboxylate water-reducer of the anti-chamotte mould of class cup-like structure with three-element catalytic system under the conditions of temperature.By increasing space
Steric hindrance weakens interspersed suction-operated of the molecule to clay mineral, when solution clay content is higher, anti-chamotte mould polycarboxylate water-reducer volume
Greatly, the too fast phenomenon of concrete gradual loss.
It is the present invention relates to process characteristic：1. improved with phenylethylene rigid radical by introducing cyclodextrin cup-like structure
Polycarboxylic acids molecule branch chain size, weakens and the interspersed effect of clay interlayer, the raising anti-mud performance of product；2. by amount of activated monomer with
Inert monomer premix merges introducing three-element catalytic system, and polycarboxylic acids is realized by reducing activation energy, raising initial reaction speed
The normal temperature of production technology, high efficiency.The invention is related to product not only with water-reducing rate higher, is also protected with preferably anti-mud
Collapse effect, the ready-mixed concrete production status that sandstone aggregate is nervous, clay content is too high can be effectively improved.
Specific embodiment
A kind of preparation method and applications of anti-chamotte mould polycarboxylate water-reducer are the embodiment of the invention provides, anti-chamotte mould is prepared
Polycarboxylate water-reducer takes short, efficiency high, is not required to heating, save energy, and prepared anti-chamotte mould polycarboxylate water-reducer agent resists
Mud performance and through when protect modeling superior performance.
The present invention provides a kind of preparation method of anti-chamotte mould polycarboxylate water-reducer, including：
Material prepare, butenol APEO, acrylic acid, 4- vinyl benzoic acids ester, maleic anhydride-beta-schardinger dextrin,
Mercaptopropionic acid, ascorbic acid, sodium dithionite, hydrogen peroxide quality proportioning are 100-130：15-25：1-5：5-15：0.1-
10.0：0.3-1.2：0.1-1.0：0.5-5.0；
Under 5~35 DEG C of normal temperature conditions, isobutene alcohol APEO, maleic anhydride-beta-schardinger dextrin are mixed and is dissolved in water
In, monomer solution is obtained, mass concentration is (50-70) %；
Acrylic acid and 4- vinyl benzoic acids ester are mixed, the aqueous solution that mass concentration is (80-95) % is configured to, obtained
Acrylic acid and 4- vinyl benzoic acid ester mixed liquors；
To acrylic acid and 4- vinyl benzoic acid ester mixed liquors described in addition (5-15) % in the monomer solution；
Add (27-50) % aqueous hydrogen peroxide solutions；
It is the mercaptopropionic acid and ascorbic acid mixed aqueous solution, residue of (1-15) % to add mass concentration under nitrogen protection
The acrylic acid and 4- vinyl benzoic acid esters mixed liquor, mass concentration are the sodium dithionite of (20-40) %, in 2.0-
Addition is finished in 3.5 hours, and wherein sodium dithionite starts addition after reaction carries out 0.5-1.5 hours；
It is 6-7 to add sodium hydrate aqueous solution regulation pH, obtains anti-chamotte mould polycarboxylate water-reducer.
Anti- chamotte mould polycarboxylate water-reducer prepared by the present invention is cup-like structure, is mainly used in concrete field.
The preparation method of the anti-chamotte mould polycarboxylate water-reducer of the present invention, introduces amount of activated slightly higher before polymerisation starting
Acrylic acid -4- vinyl benzoic acid ester mix monomers, can improve the relatively low maleic anhydride-beta-schardinger dextrin monomer conversion of activity,
And then shorten anti-chamotte mould polycarboxylate water-reducer generated time, improve production efficiency；Meanwhile, urged present invention introduces ternary redox
Change system, can under normal temperature condition the efficiently relatively low maleic anhydride-beta-schardinger dextrin of catalysis activity, isobutene alcohol polyoxyethylene
Ether and acrylic acid polymerisation, without heating, low-carbon (LC), efficient, environmental protection are adapted to industrial-scale production to production process.
Further, the anti-chamotte mould polycarboxylate water-reducer that prepared by the present invention introduces cup-shaped and firm in polycarboxylic acids molecular structure
Property construction unit, polycarboxylic acids molecule space steric hindrance can be increased, weaken the interspersed effect of itself and clay mineral, ensureing diminishing higher
While rate, the anti-mud function of anti-chamotte mould polycarboxylate water-reducer is effectively improved.
Anti- chamotte mould polycarboxylate water-reducer prepared by the present invention takes short, efficiency high, is not required to heating, save energy, prepared
The anti-mud performance of anti-chamotte mould polycarboxylate water-reducer agent that goes out and through when protect modeling superior performance.
In order that those skilled in the art more fully understands technical scheme, below by specific embodiment pair
The present invention is described in further detail.
Embodiment 1
18.0g acrylic acid is mixed with 4.0g 4- vinyl benzoic acid esters, and adds deionized water, be configured to 80% dense
The solution A of degree.
0.7g ascorbic acid is mixed with 1.0g mercaptopropionic acids, and adds deionized water, be configured to the solution B of 5% concentration.
3.0g sodium dithionites are mixed with 7.0g deionized waters, the solution C of 30% concentration is configured to.
At 20 DEG C of normal temperature, by isobutene alcohol APEO that 120.0g molecular weight is 2400 and 7.0g maleic anhydrides-β-
Cyclodextrin is added in reactor, is added 98.0g deionized waters and is configured to monomer mass concentration for 56% large monomer solution, so
3.0g solution As, the uniform rear addition hydrogenperoxide steam generators of 3.0g 27.5% to be mixed are added afterwards.Said mixture is stirred 10 minutes
Start that solution B, remaining solution A and solution C is added dropwise under nitrogen protection afterwards, dropwise addition was controlled at 2.0,2.5,1.5 hours respectively
Interior completion, wherein solution C are added dropwise after reaction starts 0.5 hour.Completion of dropping without insulation, after temperature is down to room temperature naturally
It is 6-7 to adjust pH with 30% sodium hydrate aqueous solution, obtains final product the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould.
Embodiment 2
21.0g acrylic acid is mixed with 2.5g 4- vinyl benzoic acid esters, and adds deionized water, be configured to 85% dense
The solution A of degree.
0.5g ascorbic acid is mixed with 0.5g mercaptopropionic acids, and adds deionized water, be configured to the solution of 2.5% concentration
B。
1.5g sodium dithionites are mixed with deionized water, the solution C of 35% concentration is configured to.
At 5 DEG C of normal temperature, by isobutene alcohol APEO and 5.5g maleic anhydrides-β-ring that 130.0g molecular weight is 2400
Dextrin is added in reactor, is added 60.0g deionized waters and is configured to monomer mass concentration for 69% large monomer solution, then
Add 2.0g solution As, the uniform rear addition hydrogenperoxide steam generators of 1.5g 27.5% to be mixed.After said mixture is stirred 10 minutes
Start that solution B, remaining solution A and solution C is added dropwise under nitrogen protection, dropwise addition was controlled in 2.0,2.0,1.0 hours respectively
Complete, wherein solution C started to be added dropwise in 0.5 hour after reaction.Completion of dropping is used without insulation after temperature is down to room temperature naturally
30% sodium hydrate aqueous solution adjustment pH is 6-7, obtains final product the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould.
Embodiment 3
15.0g acrylic acid is mixed with 4.0 4- vinyl benzoic acid esters, and adds deionized water, be configured to 90% concentration
Solution A.
1.0g ascorbic acid is mixed with 0.6g mercaptopropionic acids, and adds deionized water, be configured to the solution of 15% concentration
B。
2.0g sodium dithionites are mixed with deionized water, the solution C of 20% concentration is configured to.
At 35 DEG C of normal temperature, by isobutene alcohol APEO that 100.0g molecular weight is 2400 and 15.0g maleic anhydrides-β-
Cyclodextrin is added in reactor, is added 30.0g deionized waters and is configured to monomer mass concentration for 79% large monomer solution, so
1.0g solution As, the uniform rear addition hydrogenperoxide steam generators of 5.0g 27.5% to be mixed are added afterwards.Said mixture is stirred 10 minutes
Start that solution B, remaining solution A and solution C is added dropwise under nitrogen protection afterwards, dropwise addition was controlled at 2.0,2.5,1.5 hours respectively
Interior completion, wherein solution C started to be added dropwise in 1.5 hours after reaction.Completion of dropping without insulation, after temperature is down to room temperature naturally
It is 6-7 to adjust pH with 30% sodium hydrate aqueous solution, obtains final product the anti-chamotte mould polycarboxylate water-reducer of anti-chamotte mould.
Embodiment 4
The present invention weakens polycarboxylic acids molecule (PCE) by introducing maleic anhydride-beta-schardinger dextrin class large space steric hindrance monomer
Interlayer with clay composition interts effect, so as to obtain anti-mud performance, the more preferable product of function of slump protection.
According to the preparation method of anti-chamotte mould polycarboxylate water-reducer of the invention, in the case of other conditions identical, make respectively
Standby two kinds of anti-chamotte mould polycarboxylate water-reducers, A groups mix maleic anhydride-beta-schardinger dextrin for non-, and B groups mix 6% maleic anhydride-β-ring paste
Essence, contrasts its suction-operated with clay, as a result as shown below：
The anti-chamotte mould polycarboxylate water-reducer of 1 two kinds of table compares with montmorillonite effect
From the result of table 1, under conditions of not argillaceous, two kinds of PCE show preferable initial dispersion with warp
When protect plasticity energy, fully meet product construction requirement.With clay substitute 2% cement after, common PCE concrete flowabilities diminish and
Gradual loss is serious, 1 hour slump-loss up to 50mm.The opposite PCE for mixing 6% maleic anhydride-beta-schardinger dextrin monomer is initial
Fluidity still reaches 180mm, without obvious gradual loss, maintains preferable service behaviour.When clay replacement amount is more than 4%
When, common PCE mixings concrete slump only has 80mm, without any mobility after 1 hour, but under the conditions of, mixes maleic acid
The PCE of acid anhydride-beta-schardinger dextrin monomer then show good initial dispersion effect and through when protect modeling ability, 1 hour slump-loss
No more than 20mm.These results suggest that the introducing of maleic anhydride-beta-schardinger dextrin monomer can increase polycarboxylic acids molecule space steric hindrance,
Weaken itself and the interspersed effect of clay mineral, while high water reducing rate is ensured, effectively increase anti-chamotte mould polycarboxylate water-reducer
Anti- mud function, it was demonstrated that its big cup-shaped space structure effectively limits suction-operated of the polycarboxylic acids molecule to clay.
Embodiment 5
Such as embodiment 1, solution A is added in two steps, labeled as feed postition 2；Other conditions are identical, change adding for solution A
Add mode, is changed to continuously be slowly added dropwise solution A, labeled as feed postition 1；Other conditions are identical, change the addition side of solution A
Formula, is changed to a property time and adds solution A, labeled as feed postition 3.Anti- chamotte mould polycarboxylic acids prepared by three kinds of adding methods of solution A
Water reducer performance test data is as shown in table 2.
The B of table 2 expects concrete performance test result under different dropwise addition modes
From the result of table 2, the concrete initial slump of feed postition 2 is significantly greater than feed postition 1, while feed postition
The slump almost free of losses after 2 concrete 1 hour, and the concrete slump of feed postition 1 then have lost 10mm, feed postition 3
Although initial dispersion effect is excellent, slump-loss is exceedingly fast, less than 10 minutes entirely without mobility.Reason is：Isobutene alcohol
The polymerization activity of APEO is relatively low, and when minor comonomer is using continuous dropwise addition, initial reaction stage activated monomer concentration is relatively low,
Can not effectively be polymerized between isobutene alcohol polyoxyethylene ether monomer, react in initial 1 hour without the generation of obvious diminishing molecular structure.Phase
When anti-minor comonomer is using disposable being added completely into, initial reaction stage activated monomer concentration is higher, quick each other to form macromolecule
Polyacrylic polymer, TPEG conversion ratios are relatively low, and product initial stage dispersion effect is preferable, but gradual loss is fast.The result verification
Active minor comonomer feed postition is to the water-reducing property of product and protects plasticity and can have a material impact.
Early stage of the present invention adds (5-15) % acrylic acid and 4- vinyl benzoic acid ester mixed liquors, and the later stage is under nitrogen protection
Remainder, obtained anti-chamotte mould polycarboxylate water-reducer water-reducing property and guarantor's plasticity is added to significantly improve.
In addition, the generated time than commonsense method 4-6 hours, the preparation method of anti-chamotte mould polycarboxylate water-reducer of the invention
It is time-consuming 3 hours, preparation time is greatlyd save, efficiency high is conducive to industrialized production.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (10)
1. a kind of preparation method of anti-chamotte mould polycarboxylate water-reducer, it is characterised in that including：
(1) under 5~35 DEG C of normal temperature conditions, isobutene alcohol APEO, maleic anhydride-beta-schardinger dextrin are mixed and is dissolved in water
In, obtain monomer solution；
(2) acrylic acid and 4- vinyl benzoic acid esters are mixed to get acrylic acid and 4- vinyl benzoic acid ester mixed liquors；
(3) to the addition part acrylic acid and 4- vinyl benzoic acid ester mixed liquors in the monomer solution；
(4) hydrogen peroxide is added；
(5) mercaptopropionic acid and ascorbic acid mixed liquor, residual acrylic acid and 4- vinyl benzoic acid esters are added under nitrogen protection
Mixed liquor, sodium dithionite；
(6) it is 6-7 to add sodium hydrate aqueous solution regulation pH, obtains anti-chamotte mould polycarboxylate water-reducer.
2. the preparation method of the anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that the isobutene
Alcohol APEO, acrylic acid, 4- vinyl benzoic acids ester, maleic anhydride-beta-schardinger dextrin, mercaptopropionic acid, ascorbic acid, company two
Sodium sulfite, hydrogen peroxide quality proportioning are 100-130：15-25：1-5：5-15：0.1-10.0：0.3-1.2：0.1-1.0：
0.5-5.0。
3. the preparation method of the anti-chamotte mould polycarboxylate water-reducer according to claim 2, it is characterised in that in mass,
Step (3) part acrylic acid and 4- vinyl benzoic acid esters mixed liquor are that the acrylic acid and 4- vinyl benzoic acids ester are mixed
Close (5-15) % of liquid.
4. the preparation method of the anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that step (5) exists
Addition is finished in 2.0-3.5 hours.
5. the preparation method of the anti-chamotte mould polycarboxylate water-reducer according to claim 4, it is characterised in that the company two is sub-
Sodium sulphate starts addition after reaction carries out 0.5-1.5 hours.
6. the preparation method of the anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that the acrylic acid
It is the aqueous solution with 4- vinyl benzoic acid esters mixed liquor, mass concentration is (80-95) %.
7. the preparation method of the anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that in mass,
The concentration of the monomer solution be (50-70) %, the hydrogen peroxide be (27-50) % aqueous solution, the mercaptopropionic acid and
Ascorbic acid mixed liquor is (1-15) % aqueous solution, and the sodium dithionite uses (20-40) % aqueous solution.
8. a kind of anti-chamotte mould polycarboxylate water-reducer, it is characterised in that the anti-chamotte mould polycarboxylate water-reducer uses claim 1-7
The preparation method of the anti-chamotte mould polycarboxylate water-reducer described in any one is obtained.
9. the anti-chamotte mould polycarboxylate water-reducer according to claim 8, it is characterised in that the anti-chamotte mould polycarboxylic acids diminishing
Agent is cup-like structure.
10. application of the anti-chamotte mould polycarboxylate water-reducer described in claim 8 in concrete.
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| CN106749901A (en) * | 2015-11-20 | 2017-05-31 | 衡阳市银利实业有限公司 | A kind of method for preparing anti-chamotte mould cement water reducing agent |
| CN105778012A (en) * | 2016-03-21 | 2016-07-20 | 中国科学院兰州化学物理研究所 | Method for preparing anti-mud polycarboxylic acid water reducing agents |
| CN106397686A (en) * | 2016-09-29 | 2017-02-15 | 湖北工业大学 | Modified polycarboxylate superplasticizer master batch and preparation method thereof |
| CN107501479A (en) * | 2017-08-16 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
| CN108948294B (en) * | 2018-07-04 | 2021-04-16 | 武汉源锦建材科技有限公司 | Anti-mud slow-release slump retaining agent containing cyclodextrin side groups and preparation method thereof |
| CN109534715B (en) * | 2018-12-14 | 2021-05-28 | 南京福盛新材料有限公司 | Anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN111592272A (en) * | 2019-09-11 | 2020-08-28 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Polycarboxylate superplasticizer for machine-made sand concrete prestressed component and preparation method thereof |
| CN113321776B (en) * | 2021-06-21 | 2023-08-25 | 山西宝路加交通科技有限公司 | Mud-resistant polycarboxylate water reducer |
| CN114133467B (en) * | 2021-12-16 | 2023-04-18 | 科之杰新材料集团浙江有限公司 | Unsaturated esterified monomer and ester low-bleeding polycarboxylate superplasticizer and preparation method thereof |
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