CN109970922A - A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process - Google Patents
A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process Download PDFInfo
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- CN109970922A CN109970922A CN201910084249.8A CN201910084249A CN109970922A CN 109970922 A CN109970922 A CN 109970922A CN 201910084249 A CN201910084249 A CN 201910084249A CN 109970922 A CN109970922 A CN 109970922A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses a kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation processes, are formed by polyether macromonomer, anion active monomer, cation activity monomer, decrement monomer, chain-transferring agent, initiator through free radicals copolymerization reaction；Wherein, polyether macromonomer is isopentene group polyoxyethylene ether and/or methyl allyl polyoxyethylene ether；Anion active monomer is acrylic acid；Cation activity monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；Reduce the esterification reaction product that monomer is benzene alcohol or methylbenzene alcohol and acrylic acid；Chain-transferring agent is methylpropene sodium sulfonate；Initiator includes initiator system A and initiator system B, and initiator system A includes organic hydrogen peroxide and vitamin C, and initiator system B includes sodium hydrogensulfite and ferrous salt.The present invention adjusts backbone length by being grafted different function monomers to high-performance polycarboxylic acids water reducing agent, so that polycarboxylate water-reducer while with excellent water-reducing rate, also has early epistasis and decrement property.
Description
Technical field
The present invention relates to technical field of concrete additives, specifically a kind of shrinkage type Early-strength polycarboxylate superplasticizer is female
Liquid and preparation process.
Background technique
Polycarboxylate water-reducer is a kind of high performance concrete admixture, and main function is to reduce mixing water usage amount, is changed
Become rheological property and the workability etc. of concrete.High performance water reducing agent of polyocarboxy acid is by band sulfonic group, carboxyl, amino and to contain
The macromolecular compound for having the functional groups such as polyethylene oxide side chains to constitute usually in aqueous solution passes through free-radical polymerized principle
The high molecular surfactant with comb-type structure of synthesis.With the linear chain structures such as widely applied naphthalene system, aliphatic before
High efficiency water reducing agent is compared, and high performance water reducing agent of polyocarboxy acid has the superior performances such as higher water-reducing rate and slump retaining.Due to
There is more active group, the side chain connected on main chain is more, and Molecular Design is free on polycarboxylic acid water reducing agent strand
Degree is big.Therefore, polycarboxylate water-reducer is that recent domestic studies more active one of high-performance water reducing agent, while and mixing
The dominant direction of solidifying soil additive Future Development.
With the demand to high performance concrete, the coagulation of the Various Functions such as anti-mud agent, slump retaining agent, economization agent, early strength agent
Native additive starts to continuously emerge.Concrete cracking because caused by shrinking will lead to the intensity and the big discounting of durability of concrete
Button, so as to shorten the service life of concrete.The shrinkage cracking problem of concrete especially high performance concrete has caused
The great attention of engineering circles.Generally improve concrete shrinkage problem by adding swelling agent or economization agent at present.Swelling agent can
Dry for compensating concrete is shunk, and the volume of swelling agent typically constitutes from the 6% ~ 15% of binder total amount, and volume is big and necessary
Enough moisture-keeping maintainings are carried out to concrete.Economization agent is by reducing the surface tension of water in concrete pore, reducing moisture
The convergent force of evaporation process, to achieve the purpose that reduce distress in concrete.But economization agent there are problems that influencing concrete strength
And price is high, there is presently no promote the use of a large area.In addition, the early strength development of conventional concrete is slower, in order to
Improve the early strength of concrete, it will usually early strength agent be added, to promote the development of the early strong intensity of concrete.If can be to poly- carboxylic
The structure optimization of sour water-reducing agent changes the chemical structure of main chain, branch and carboxyl in polycarboxylate water-reducer molecule, develops simultaneously
Multi-functional polycarboxylate water-reducer with decrement property and early epistasis, will be of great significance to concrete structure performance is improved.
Summary of the invention
The object of the present invention is to provide a kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation processes.
Early-strength shrinkage type polycarboxylate superplasticizer mother liquor of the present invention, by polyether macromonomer, anion active monomer, sun from
Sub- activated monomer, decrement monomer, chain-transferring agent, initiator are formed through free radicals copolymerization reaction；Wherein:
Polyether macromonomer is isopentene group polyoxyethylene ether and/or methyl allyl polyoxyethylene ether；
Anion active monomer is acrylic acid, and quality is the 4% ~ 8% of polyether macromonomer；
Cation activity monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, and quality is the 8% ~ 15% of polyether macromonomer；
Reduce the esterification reaction product that monomer is benzene alcohol or methylbenzene alcohol and acrylic acid, quality be polyether macromonomer 3% ~
30%；
Chain-transferring agent is methylpropene sodium sulfonate, thioacetic acid, mercaptoethanol or mercaptopropionic acid, and quality is polyether macromonomer
1.2‰~2%；
Initiator includes initiator system A and initiator system B, the quality of initiator system A be polyether macromonomer 0.1% ~
1%；
Initiator system A includes organic hydrogen peroxide and vitamin C, and organic hydrogen peroxide and ascorbic mass ratio are 1:(1 ~ 2)；
Initiator system B includes sodium hydrogensulfite and ferrous salt, and sodium hydrogensulfite and ascorbic molar ratio are 1:(1.4 ~ 2),
The molar ratio of ferrous salt and organic hydrogen peroxide is 1:(0.75 ~ 1.5).
In the initiator system B, ferrous salt is preferably ferrous sulfide, and ferrous sulfide can also play help reducing agent simultaneously
Effect.
To avoid rate of polymerization caused by free radical is reduced in reaction process from reducing, it is additionally added and helps in free radicals copolymerization reaction
Reducing agent component, described to help reducing agent be preferably vulcanized sodium.
Further, the molar ratio of vulcanized sodium and iron ion in ferrous salt is (0.8 ~ 1.2): 1.
The preparation process of above-mentioned early-strength shrinkage type polycarboxylate superplasticizer mother liquor, comprising:
The first step, esterification synthesis decrement monomer, specifically:
It is simultaneously evenly dispersed that benzene alcohol or methylbenzene alcohol are added polymerization inhibitor, and acrylic acid and catalyst are added later, under 55 degree ~ 85 degree into
Row esterification, esterification products reduce monomer；Wherein, the molar ratio of acrylic acid and benzene alcohol or methylbenzene alcohol is (1 ~ 1.1): 1；
Polymerization inhibitor dosage is the 0.02% ~ 0.04% of acrylic acid quality；Catalyst be p-methyl benzenesulfonic acid or the concentrated sulfuric acid, dosage be benzene alcohol or
The 1% ~ 1.5% of the gross mass of methylbenzene alcohol and acrylic acid；
Second step, free-radical polymerized synthesis polycarboxylate water-reducer, specifically:
Polyether macromonomer is dissolved in deionized water, obtains solution a；
Anion active monomer, cation activity monomer and chain-transferring agent are dissolved in deionized water, obtain solution b；
Initiator solution is added dropwise into solution a；
Solution b and decrement monomer solution are added dropwise into solution a, is stirred under 50 degree ~ 70 degree and carries out polymerization reaction；
Third step adds sodium sulfocyanate and polyhydric alcohol amine to neutralize polymeric reaction product solution, obtains early-strength shrinkage type polycarboxylic acids
Water-reducing agent mother liquor.
Further, benzene alcohol is benzyl alcohol, benzyl carbinol, phenylpropanol or benzene butanol.
Further, methylbenzene alcohol is methylbenzyl alcohol, methyl benzyl carbinol, methyl phenylpropanol or methylbenzene butanol.
Further, polymerization inhibitor is hydroquinone, phenthazine, p-tert-Butylcatechol or MEHQ hydroquinone monomethyl ether, for hindering
The only auto polymerization of unsaturated carboxylic acid acrylic acid.
Preferably, the aqueous solution for helping reducing agent is added in polymerization process midway, it is described to help reducing agent for vulcanization
Sodium.
Preferably, defoaming agent is added in and in temperature-fall period, so that air content is met GB8076 and want
It asks, the mass ratio of defoaming agent and reaction mixture is 1:(1000 ~ 10000).
Compared to the prior art, the present invention have following features and the utility model has the advantages that
(1) present invention is by being grafted the monomer of different function to high-performance polycarboxylic acids water reducing agent, and is adjusted and led by technological parameter
Chain length, so that polycarboxylate water-reducer while with excellent water-reducing rate (water-reducing rate is up to 30% or more), also has early epistasis
With decrement property.
The backbone length of polycarboxylate water-reducer has an impact to early strong effect, so, the present invention is by adjusting metering system sulphur
The dosage of sour sodium adjusts the backbone length of polycarboxylate water-reducer, to obtain optimal early strong effect.The present invention further through
Grafted cation monomer on the main chain of conventional anion polycarboxylate water-reducer, and find, introducing suitable cationic monomer can promote
The early hydration of water inlet mud, significantly improves early strength.The present invention is grafted decrement monomer on the main chain of polycarboxylate water-reducer, is
Main chain provides hydrophobic grouping, low-moisture surface tension is dropped, to reduce the cracking of concrete.
(2) redox system initiator of present invention selection composite highly effective is, it can be achieved that quickly cause copolymerization.It is specific next
It says, the present invention uses two groups of redox initiation system ammonium persulfate/sodium hydrogensulfites and organic hydrogen peroxide/ferrous salt, over cure
Sour ammonium/sodium hydrogensulfite and the equal room temperature initiator of organic hydrogen peroxide/ferrous salt, selected two groups of initiation systems are used cooperatively,
It is remarkably improved Raolical polymerizable rate, and can guarantee the water-reducing property and stability of obtained product.
(3) it is added in preferred embodiment of the invention and helps reducing agent, help reducing agent can be the organic hydrogen peroxide/Asia of initiation system
The ferric ion that molysite generates is reduced into ferrous ion, brings back to life the reducing agent of failure, uses less amount of ferrous iron in this way
Salt can make polymerization reaction continue to carry out, save raw material.The present invention passes through methylacryoyloxyethyl three in comonomer
Ammonio methacrylate introduces cation group, can further strengthen the dispersibility of cement slurry and the salt resistance of water-reducing agent, alkali resistance.
Specific embodiment
In order to illustrate the embodiments of the present invention more clearly and/or technical solution in the prior art, this hair is described below
Bright specific embodiment.It should be evident that only the embodiment of the present invention is described below, for ordinary skill people
For member, without creative efforts, other embodiments can also be obtained.
Embodiment
Embodiment
In the present embodiment, the preparation process of polycarboxylate superplasticizer mother liquor is as follows:
The first step, esterification synthesis decrement monomer, specifically:
It is simultaneously evenly dispersed that benzene alcohol or methylbenzene alcohol are added polymerization inhibitor, and acrylic acid and catalyst are added later, under 55 degree ~ 85 degree into
Row esterification is reacted 3 hours ~ 4 hours, and gained esterification products reduce monomer；Wherein, acrylic acid and benzene alcohol or methylbenzene alcohol
Molar ratio be (1 ~ 1.1): 1；Polymerization inhibitor dosage is the 0.02% ~ 0.04% of acrylic acid quality；Catalyst be p-methyl benzenesulfonic acid or
The concentrated sulfuric acid, dosage are the 1% ~ 1.5% of the gross mass of benzene alcohol or methylbenzene alcohol and acrylic acid.
In the present embodiment, benzene alcohol uses benzyl alcohol, benzyl carbinol, phenylpropanol or benzene butanol；Methylbenzene alcohol uses methylbenzene first
Alcohol, methyl benzyl carbinol, methyl phenylpropanol or methylbenzene butanol；Polymerization inhibitor uses hydroquinone, phenthazine, to tert-butyl o benzene two
Phenol or MEHQ hydroquinone monomethyl ether, for preventing the auto polymerization of unsaturated carboxylic acid acrylic acid.
Second step, free-radical polymerized synthesis polycarboxylate water-reducer, specifically:
Polyether macromonomer is dissolved in deionized water, obtains solution a；
Anion active monomer, cation activity monomer and chain-transferring agent are dissolved in deionized water, obtain solution b；
Initiator solution is added into solution a；
Solution b and decrement monomer solution are added dropwise into solution a, time for adding is 1.5 hours ~ 2.5 hours, in 50 while dropwise addition
~ 70 degree of degree lower stirrings, carry out polymerization reaction；After being added dropwise to complete, continues to keep 50 degree ~ 70 degree of temperature condition, stir and continue
Reaction 1.5 hours ~ 2.5 hours.
In the present embodiment, polyether macromonomer is isopentene group polyoxyethylene ether and/or methyl allyl polyoxyethylene ether；Yin
Ion activity monomer is acrylic acid, and quality is the 4% ~ 8% of polyether macromonomer；Cation activity monomer is methacryloxypropyl second
Base trimethyl ammonium chloride, quality are the 8% ~ 15% of polyether macromonomer；Reducing monomer is benzene alcohol or methylbenzene alcohol and acrylic acid
Esterification reaction product, quality are the 3% ~ 30% of polyether macromonomer；Chain-transferring agent is methylpropene sodium sulfonate, and quality is polyethers
1.2 ‰ ~ the 2% of polymeric monomer；Initiator includes initiator system A and initiator system B, and the quality of initiator system A is that polyethers is big
The 0.1% ~ 1% of monomer；Initiator system A includes organic hydrogen peroxide and vitamin C, organic hydrogen peroxide and ascorbic mass ratio
For 1:(1 ~ 2)；Initiator system B includes sodium hydrogensulfite and ferrous sulfide, and sodium hydrogensulfite and ascorbic molar ratio are 1:
The molar ratio of (1.4 ~ 2), ferrous sulfide and organic hydrogen peroxide is 1:(0.75 ~ 1.5).Sulphur is added in free radicals copolymerization reaction midway
Change sodium, the molar ratio of iron ion is (0.8 ~ 1.2) in vulcanized sodium and ferrous salt: 1.
Third step adds sodium sulfocyanate and polyhydric alcohol amine to neutralize polymeric reaction product solution, it is poly- to obtain early-strength shrinkage type
Carboxylic acid water reducer mother liquor.Preferably, defoaming agent is added, meets air content in reaction mixture in and in temperature-fall period
The mass ratio of GB8076 requirement, defoaming agent and reaction mixture is 1:(1000 ~ 10000).
Referring to GB8076-2008 " concrete admixture " early-strength high-performance water-reducing agent related request, reference cement is selected,
Solid volume 0.2% is rolled over, the concrete performance for testing the present embodiment product the results are shown in Table 1.
The concrete performance of 1 the present embodiment product of table
Polycarboxylate superplasticizer mother liquor water-reducing rate of the present invention is high, all has good adaptability to the cement of various different manufacturers, special
Not Shi Yongyu various high-strength, super high strength concretes, can be widely used for the concrete works such as skyscraper, highway, mine, municipal administration.
Using the high efficiency water reducing agent, concrete slump can be made to improve 20cm or more；And 3 days concrete crushing strength highests are close to
50%, i.e. the early strength of concrete is significantly increased.
Water-reducing agent and sky referring to prepared by national standard JC/T603-2004 " cement mortar dry shrinkage test method " measurement embodiment
The Dry-shrinkage Ratio of Cement Mortar of white sample, water-reducing agent volume are that 0.2%(folding is solid), it keeps the fluidity of mortar in 130 ~ 140mm, is surveyed
The 28d shrinkage ratio of the opposite blank sample obtained is 75% ~ 80%, i.e. the shrinking percentage with respect to blank sample 28d reduces 20% or more.
It is provided for the embodiments of the invention technical solution above to be described in detail, specific case used herein
The principle and embodiment of the embodiment of the present invention are expounded, the explanation of above embodiments is only applicable to help to understand this
The principle of inventive embodiments；At the same time, for those skilled in the art, according to an embodiment of the present invention, in specific embodiment party
There will be changes in formula and application range, in conclusion the contents of this specification are not to be construed as limiting the invention.
Claims (10)
1. a kind of early-strength shrinkage type polycarboxylate superplasticizer mother liquor, it is characterized in that:
By polyether macromonomer, anion active monomer, cation activity monomer, decrement monomer, chain-transferring agent, initiator through freedom
Base copolyreaction forms；Wherein:
Polyether macromonomer is isopentene group polyoxyethylene ether and/or methyl allyl polyoxyethylene ether；
Anion active monomer is acrylic acid, and quality is the 4% ~ 8% of polyether macromonomer；
Cation activity monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, and quality is the 8% ~ 15% of polyether macromonomer；
Reduce the esterification reaction product that monomer is benzene alcohol or methylbenzene alcohol and acrylic acid, quality be polyether macromonomer 3% ~
30%；
Chain-transferring agent is methylpropene sodium sulfonate, thioacetic acid, mercaptoethanol or mercaptopropionic acid, and quality is polyether macromonomer
1.2‰~2%；
Initiator includes initiator system A and initiator system B, the quality of initiator system A be polyether macromonomer 0.1% ~
1%；
Initiator system A includes organic hydrogen peroxide and vitamin C, and organic hydrogen peroxide and ascorbic mass ratio are 1:(1 ~ 2)；
Initiator system B includes sodium hydrogensulfite and ferrous salt, and sodium hydrogensulfite and ascorbic molar ratio are 1:(1.4 ~ 2),
The molar ratio of ferrous salt and organic hydrogen peroxide is 1:(0.75 ~ 1.5).
2. early-strength shrinkage type polycarboxylate superplasticizer mother liquor as described in claim 1, it is characterized in that:
In the initiator system B, ferrous salt is ferrous sulfide.
3. early-strength shrinkage type polycarboxylate superplasticizer mother liquor as described in claim 1, it is characterized in that:
It is additionally added in free radicals copolymerization reaction and helps reducing agent component, it is described to help reducing agent for vulcanized sodium.
4. early-strength shrinkage type polycarboxylate superplasticizer mother liquor as claimed in claim 3, it is characterized in that:
The molar ratio of iron ion is (0.8 ~ 1.2) in the vulcanized sodium and ferrous salt: 1.
5. the preparation process of early-strength shrinkage type polycarboxylate superplasticizer mother liquor described in claim 1, characterized in that include:
The first step, esterification synthesis decrement monomer, specifically:
It is simultaneously evenly dispersed that benzene alcohol or methylbenzene alcohol are added polymerization inhibitor, and acrylic acid and catalyst are added later, under 55 degree ~ 85 degree into
Row esterification, esterification products reduce monomer；Wherein, the molar ratio of acrylic acid and benzene alcohol or methylbenzene alcohol is (1 ~ 1.1): 1；
Polymerization inhibitor dosage is the 0.02% ~ 0.04% of acrylic acid quality；Catalyst be p-methyl benzenesulfonic acid or the concentrated sulfuric acid, dosage be benzene alcohol or
The 1% ~ 1.5% of the gross mass of methylbenzene alcohol and acrylic acid；
Second step, free-radical polymerized synthesis polycarboxylate water-reducer, specifically:
Polyether macromonomer is dissolved in deionized water, obtains solution a；
Anion active monomer, cation activity monomer and chain-transferring agent are dissolved in deionized water, obtain solution b；
Initiator solution is added dropwise into solution a；
Solution b and decrement monomer solution are added dropwise into solution a, is stirred under 50 degree ~ 70 degree and carries out polymerization reaction；
Third step adds sodium sulfocyanate and polyhydric alcohol amine to neutralize polymeric reaction product solution, obtains early-strength shrinkage type polycarboxylic acids
Water-reducing agent mother liquor.
6. preparation process described in claim 5, it is characterized in that:
The benzene alcohol is benzyl alcohol, benzyl carbinol, phenylpropanol or benzene butanol.
7. preparation process described in claim 5, it is characterized in that:
The methylbenzene alcohol is methylbenzyl alcohol, methyl benzyl carbinol, methyl phenylpropanol or methylbenzene butanol.
8. preparation process described in claim 5, it is characterized in that:
The polymerization inhibitor is hydroquinone, phenthazine, p-tert-Butylcatechol or MEHQ hydroquinone monomethyl ether, for preventing unsaturated carboxylic
The auto polymerization of acid acrylic acid.
9. preparation process described in claim 5, it is characterized in that:
The aqueous solution for helping reducing agent is added in polymerization process midway, described to help reducing agent for vulcanized sodium.
10. preparation process described in claim 5, it is characterized in that:
It neutralizes in temperature-fall period, is added defoaming agent into polymeric reaction product solution, the mass ratio of defoaming agent and reaction mixture is
1:(1000 ~ 10000).
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| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
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| CN112708042B (en) * | 2019-11-25 | 2021-11-19 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
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| CN112608420B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
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| CN112708041A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN112708041B (en) * | 2019-11-25 | 2021-12-24 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN111019065A (en) * | 2019-12-26 | 2020-04-17 | 南京瑞固聚合物有限公司 | High-molecular-weight polycarboxylic acid water reducing agent and preparation method thereof |
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| CN112707673A (en) * | 2020-09-15 | 2021-04-27 | 科之杰新材料集团有限公司 | Super-shrinkage type polycarboxylate superplasticizer and preparation method thereof |
| CN112645631A (en) * | 2020-12-28 | 2021-04-13 | 江苏开放大学（江苏城市职业学院） | Antifreezing concrete composite water reducing agent and preparation method thereof |
| CN114181355A (en) * | 2021-11-25 | 2022-03-15 | 陕西科之杰新材料有限公司 | Ester-ether mixed viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
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