CN110437388A - A kind of preparation method of high performance-price ratio polycarboxylate water-reducer - Google Patents
A kind of preparation method of high performance-price ratio polycarboxylate water-reducer Download PDFInfo
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- CN110437388A CN110437388A CN201910813140.3A CN201910813140A CN110437388A CN 110437388 A CN110437388 A CN 110437388A CN 201910813140 A CN201910813140 A CN 201910813140A CN 110437388 A CN110437388 A CN 110437388A
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- primitive
- high performance
- polycarboxylate water
- price ratio
- reducer
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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
- C04B24/16—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
- 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
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
- C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles 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
- 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
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—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
- 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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to cement concrete admixture technical fields, and in particular to a kind of preparation method of high performance-price ratio polycarboxylate water-reducer.The present invention synthesizes basic construct primitive under reducing agent effect using methyl allyl polyoxyethylene ether, acrylic acid, comonomer as polymerized monomer；Auxiliary is added into basic construct primitive and constructs primitive, obtains high performance-price ratio polycarboxylate water-reducer.The technology is guidance with molecular chemistry and supramolecular chemistry theory, and the basic construct primitive and auxiliary for establishing GPCA product Supramolecular Assembling construct primitive, and carry out the optimization of Supramolecular Assembling.Through test and application attestation, the related performance of high performance-price ratio polycarboxylate water-reducer assembled reaches the requirement of corresponding product primary standard, polymeric monomer dosage reduces by 10%~15% compared with similar products in product, primosome, which is tied to form, originally can reduce by 30%~40%, the ultimate cost of product reduces by 8%~15%, adaptability is improved, there is the stronger market competitiveness.
Description
Technical field
The invention belongs to cement concrete admixture technical fields, and in particular to a kind of high performance-price ratio polycarboxylate water-reducer
Preparation method.
Background technique
Concrete admixture has become one of the main component of cement concrete material, and wherein water-reducing agent is then most important group
Point.In concrete durability, workability, intensity and the big basic performance of economy four, additive is their indispensable weights
Want one of component.With the extensive application of cement concrete material, corresponding raw materials requirement amount increases, but currently, concrete
Raw material not only limited amount, material quality more outstanding is there is also problems, and especially sand material is insufficient and clay content
It is excessively high, seriously affect the intensity and durability of the workability and product in concrete preparation.Concrete performance is deteriorated most prominent
Be workability reduction, the basic skills solved at present: first is that increase additive dosage, second is that purifying sand material, these are arranged
Shi Douhui causes the raising of corresponding cost, and related enterprise is difficult to receive.But it is adjusted instantly using additive still simple easy
One of capable important method.Therefore the key that each enterprise faces is to solve the problems, such as that additive is at high cost.
Summary of the invention
The present invention is based on based on the status of additive market high expensive, establish to reduce preparation product cost, increasing
The thinking for adding adaptability proposes a kind of preparation method of high performance-price ratio polycarboxylate water-reducer.
The preparation of high performance-price ratio polycarboxylate water-reducer of the present invention is with theories such as molecular chemistry and supramolecular chemistries
For guidance, analysis and present Research, by repetition test and verifying, establish the supermolecule of product to manage the method mutually melted in fact
Assembly system is prepared for high performance-price ratio polycarboxylate water-reducer GPCA product.
Specifically, the present invention is being restored using methyl allyl polyoxyethylene ether, acrylic acid, comonomer as polymerized monomer
Agent effect is lower to synthesize basic construct primitive；Auxiliary is added into basic construct primitive and constructs primitive, obtains high performance-price ratio polycarboxylic acids
Water-reducing agent.
The basic construct primitive of high performance-price ratio polycarboxylate water-reducer GPCA is the polycarboxylate water-reducer of synthesis.Pass through reality
Reason is analyzed and test proves, what diminishing function was mainly determined by the steric factor of adsorbance and state of aggregation, wherein adsorbance master
It to be influenced by functional group in component, and the three-dimensional influence of state of aggregation is then related with the stereochemical structure of molecule.The present invention is using drop
The high methyl allyl polyoxyethylene ether polymeric monomer dosage of low price changes the kind and number of the comonomer in addition to acrylic acid
The technological approaches of amount, to develop combination comonomer system, the comonomer is sodium styrene sulfonate or itaconic acid
Or or mixtures thereof acrylonitrile or acrylamide.Selected comonomer is to have the effect of adjusting surface-active and adsorption capacity,
Polymerization system more originally can improve the dispersibility and function of slump protection of product.
In the prior art, it is VC that it is common, which to prepare reducing agent used, for basic construct primitive, though the raw material dosage is few, its
It is expensive, therefore the present invention is analyzed from principle, explores and seek cheap substitute, is applied through test, benefit
With the assembly containing reduction catalysts function, 40% or more cost can be reduced, reducing agent of the present invention is low molecule aldose
Or sulphite or iron sulfite or or mixtures thereof sodium phosphite or thiourea dioxide.The preferred grape of low molecule aldose
Sugar.
There are two effects for auxiliary construction unit of the present invention: first is that improving correlated performance, second is that reducing product cost.
Its performance improvement is according to intermolecular supermolecular mechanism power (Hyarogen-bonding, ionization power, master-visitor's active force and hydrophobic
The intermolecular power such as active force) and to concrete slurry function influence (diminishing function, water retaining function, slow-release function, early powerful,
Air-entraining function and defoaming function etc.).
From supermolecule concept, various performances are all the embodiments after intermolecular, intramolecular interaction, in products application
Simple target function substance is not present.Correlation function to be embodied, it is necessary to consider intermolecular interaction principle and shadow
The factor of sound.These factors mainly include material composition, kind, ratio, the temperature in the external world, pressure, mechanical force, electromagnetic force and luminous energy
Deng influence factor.
Any performance is all the embodiment of intermolecular interaction, had to when realizing performance component selection it is clear they it
Between interaction principle, so that it is determined that amount appropriate ratio, " medicine to " theory is much like with Chinese medicine for this, such as diminishing-water conservation, slow
Solidifying-early strong, bleed-defoaming, Acid-Base, their own targeting article kind is very much, it is important to how to be cooperated with its " medicine to "
Good, the function of the bigger various substances of performance under real world conditions achievees the purpose that improve product cost.
Auxiliary construct each function in primitive " targeting object " can there are many, this needs to consider its cost performance.It is of the present invention
Auxiliary construct primitive as water conservation primitive or slow setting primitive or early strong basis member or or mixtures thereof bleed primitive or defoaming primitive.More
Specifically, the water-retaining agent is cellulose ether or polyvinyl alcohol or or mixtures thereof water soluble starch or polyacrylamide；It is described
Retarder is or mixtures thereof sodium gluconate or molasses；The early strength agent be inorganic electrolyte or triethanolamine or high price sun from
Son (Ca2+, Mg2+, Fe3+, Al3+Or mixtures thereof)；The air entraining agent is rosin soap or polyethers or SPan-80；The defoaming agent
For organosilicon.
The present invention can refer to following various proportions in the application of different condition:
The weight ratio that the basic construct primitive and auxiliary construct primitive is 100:1~15.
The substance of the methyl allyl polyoxyethylene ether and acrylic acid the ratio between be 1:3~4.
The dosage of the comonomer is the 3~5% of polymerized monomer gross mass.
The dosage of the reducing agent is the 0.2~0.3% of polymerized monomer gross mass.
The dosage of the water conservation primitive is the 2~3% of polymerized monomer gross mass；The dosage of the slow setting primitive is that polymerization is single
The 1~2% of body gross mass；The dosage of the morning strong basis member is the 0.5~1.5% of polymerized monomer gross mass；The bleed primitive
Dosage be polymerized monomer gross mass 0.1~0.3%；It is described defoaming primitive dosage be polymerized monomer gross mass 0.01~
0.03%.
Its more specifically preparation step are as follows:
(1) synthesize basic construct primitive: reaction temperature is 20-30 DEG C, and polymerized monomer time for adding is 3-4h, is dripped
Finish, pH value is adjusted after insulation reaction 1h to 3.0~4.0, solid content 45%；
(2) it the Supramolecular Assembling of high performance-price ratio polycarboxylate water-reducer: feeds intake in the following order under constant stirring: basic structure
Build primitive-water conservation primitive-diminishing primitive-slow setting primitive-bleed primitive-defoaming primitive, feed intake finish continue stirring 1~
2h is up to polycarboxylate water-reducer.
In the present invention, polymeric monomer dosage reduces by 10%~15% compared with similar products, and reducing agent cost can reduce by 30%
~40%, the ultimate cost of product reduces by 8%~15%, and polycarboxylate water-reducer (GPCA) adaptability obtained using the present invention is high,
The supramolecular chemistry effect that auxiliary constructs primitive and basic construct primitive has been given full play to, the dispersion of product has been improved, protects function of collapsing
And adaptability, overall cost is low, has the stronger market competitiveness.
Specific embodiment
Embodiment 1
A kind of preparation method of high performance-price ratio polycarboxylate water-reducer, with methyl allyl polyoxyethylene ether, acrylic acid, clothing health
Acid is comonomer, and basic construct primitive is synthesized under the action of reducing agent glucose；Auxiliary is added into basic construct primitive
Primitive is constructed, high performance-price ratio polycarboxylate water-reducer is obtained.
It is water conservation primitive, slow setting primitive, early strong basis member, bleed primitive and defoaming primitive that the auxiliary, which constructs primitive,
Mixture.
The weight ratio that the basic construct primitive and auxiliary construct primitive is 100:1.
The substance of the methyl allyl polyoxyethylene ether and acrylic acid the ratio between be 1:3.
The dosage of the comonomer is the 3% of polymerized monomer gross mass.
The dosage of the reducing agent is the 0.2% of polymerized monomer gross mass.
The dosage of the water conservation primitive is the 2% of polymerized monomer gross mass；The dosage of the slow setting primitive is polymerized monomer
The 1% of gross mass；The dosage of the morning strong basis member is the 0.5% of polymerized monomer gross mass；The dosage of the bleed primitive is poly-
Close the 0.1% of monomer gross mass；The dosage of the defoaming primitive is the 0.01% of polymerized monomer gross mass.
The water-retaining agent is cellulose ether；
The retarder is sodium gluconate；
The early strength agent is triethanolamine；
The air entraining agent is rosin soap；
The defoaming agent is organosilicon.
The specific steps are that:
(1) synthesize basic construct primitive: reaction temperature is 30 DEG C, and polymerized monomer time for adding is 3.5h, is added dropwise, and is protected
For adjustment pH value to 3.0, solid content 45% obtains basic construct primitive after temperature reaction 1h；
(2) it the Supramolecular Assembling of high performance-price ratio polycarboxylate water-reducer: feeds intake in the following order under constant stirring: basic structure
Primitive-water conservation primitive-diminishing primitive-slow setting primitive-bleed primitive-defoaming primitive is built, feeds intake to finish and continues to stir 1.5h
To obtain the final product.
Embodiment 2
A kind of preparation method of high performance-price ratio polycarboxylate water-reducer, with methyl allyl polyoxyethylene ether, acrylic acid, propylene
Amide is comonomer, and basic construct primitive is synthesized under the action of reducing agent glucose；It is added into basic construct primitive auxiliary
It helps and constructs primitive, obtain high performance-price ratio polycarboxylate water-reducer.
It is water conservation primitive, slow setting primitive, early strong basis member, bleed primitive and defoaming primitive that the auxiliary, which constructs primitive,
Mixture.
The weight ratio that the basic construct primitive and auxiliary construct primitive is 100:7.
The substance of the methyl allyl polyoxyethylene ether and acrylic acid the ratio between be 1:3.5.
The dosage of the comonomer is the 4% of polymerized monomer gross mass.
The dosage of the reducing agent is the 0.25% of polymerized monomer gross mass.
The dosage of the water conservation primitive is the 2.5% of polymerized monomer gross mass；The dosage of the slow setting primitive is that polymerization is single
The 1.5% of body gross mass；The dosage of the morning strong basis member is the 1.0% of polymerized monomer gross mass；The dosage of the bleed primitive
It is the 0.2% of polymerized monomer gross mass；The dosage of the defoaming primitive is the 0.02% of polymerized monomer gross mass.
The water-retaining agent is polyvinyl alcohol；
The retarder is molasses；
The early strength agent is triethanolamine；
The air entraining agent is SPan-80；
The defoaming agent is organosilicon.
The specific steps are that:
(1) synthesize basic construct primitive: reaction temperature is 20 DEG C, and polymerized monomer time for adding is 3h, is added dropwise, and is kept the temperature
For adjustment pH value to 4.0, solid content 45% obtains basic construct primitive after reacting 1h；
(2) it the Supramolecular Assembling of high performance-price ratio polycarboxylate water-reducer: feeds intake in the following order under constant stirring: basic structure
Primitive-water conservation primitive-diminishing primitive-slow setting primitive-bleed primitive-defoaming primitive is built, feeds intake to finish and continues to stir 1h i.e.
.
Embodiment 3
A kind of preparation method of high performance-price ratio polycarboxylate water-reducer, with methyl allyl polyoxyethylene ether, acrylic acid, benzene second
Alkene sodium sulfonate is comonomer, synthesizes basic construct primitive under the effect of reducing agent glucose；It is added into basic construct primitive
Auxiliary constructs primitive, obtains high performance-price ratio polycarboxylate water-reducer.
It is water conservation primitive, slow setting primitive, early strong basis member, bleed primitive and defoaming primitive that the auxiliary, which constructs primitive,
Mixture.
The weight ratio that the basic construct primitive and auxiliary construct primitive is 100:15.
The substance of the methyl allyl polyoxyethylene ether and acrylic acid the ratio between be 1:4.
The dosage of the comonomer is the 5% of polymerized monomer gross mass.
The dosage of the reducing agent is the 0.3% of polymerized monomer gross mass.
The dosage of the water conservation primitive is the 3% of polymerized monomer gross mass；The dosage of the slow setting primitive is polymerized monomer
The 2% of gross mass；The dosage of the morning strong basis member is the 1.5% of polymerized monomer gross mass；The dosage of the bleed primitive is poly-
Close the 0.3% of monomer gross mass；The dosage of the defoaming primitive is the 0.03% of polymerized monomer gross mass.
The water-retaining agent is polyacrylamide；
The retarder is sodium gluconate；
The early strength agent is triethanolamine；
The air entraining agent is rosin soap；
The defoaming agent is organosilicon.
The specific steps are that:
(1) synthesize basic construct primitive: reaction temperature is 25 DEG C, and polymerized monomer time for adding is 4h, is added dropwise, and is kept the temperature
For adjustment pH value to 3.5, solid content 45% obtains basic construct primitive after reacting 1h；
(2) it the Supramolecular Assembling of high performance-price ratio polycarboxylate water-reducer: feeds intake in the following order under constant stirring: basic structure
Primitive-water conservation primitive-diminishing primitive-slow setting primitive-bleed primitive-defoaming primitive is built, feeds intake to finish and continues to stir 2h i.e.
.
The assembling of 1 embodiment 1-3 of table matches
The cement paste performance (42.5 cement) of 2 embodiment 1-3GPEG of table and ether product
3 embodiment 1-3GPCA of table and control sample concrete performance
Note: comparative sample 1 is certain domestic well-known renowned company's ether product；Comparative sample 2 is that certain external renowned company's ethers produces
Product.
Three products and the measurement of the performance, price of two market similar products by embodiment with compare as it can be seen that this hair
In the range of bright product (GPCA) changes in basis and auxiliary primitive condition, performance is above commercially available control sample, but price
(yuan/ton) reduces by 200~400 yuan/ton.Therefore high performance-price ratio polycarboxylate water-reducer of the invention is under current sand material quality
Drop, admixture dosage increase, and economic benefit reduces, and have significantly slow Jie's effect, therefore have the preferable market competitiveness.
Claims (10)
1. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer, which is characterized in that with methyl allyl polyoxyethylene ether, third
Olefin(e) acid, comonomer are polymerized monomer, synthesize basic construct primitive under reducing agent effect；It is added into basic construct primitive auxiliary
It helps and constructs primitive, obtain high performance-price ratio polycarboxylate water-reducer.
2. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that described
Comonomer is sodium styrene sulfonate or itaconic acid or or mixtures thereof acrylonitrile or acrylamide.
3. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that described
Reducing agent is low molecule aldose or sulphite or iron sulfite or or mixtures thereof sodium phosphite or thiourea dioxide.
4. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that described
Auxiliary constructs primitive as water conservation primitive or slow setting primitive or early strong basis member or or mixtures thereof bleed primitive or defoaming primitive.
5. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that the base
Plinth constructs primitive and auxiliary constructs the weight ratio of primitive as 100:1~15.
6. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that the first
The substance of base allyl polyethenoxy ether and acrylic acid the ratio between be 1:3~4.
7. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that described total
The dosage of polycondensation monomer is the 3~5% of polymerized monomer gross mass.
8. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that described to go back
The dosage of former agent is the 0.2~0.3% of polymerized monomer gross mass.
9. a kind of preparation method of high performance-price ratio polycarboxylate water-reducer according to claim 1, which is characterized in that the guarantor
The dosage of water base member is the 2~3% of polymerized monomer gross mass；The dosage of the slow setting primitive be polymerized monomer gross mass 1~
2%；The dosage of the morning strong basis member is the 0.5~1.5% of polymerized monomer gross mass；The dosage of the bleed primitive is that polymerization is single
The 0.1~0.3% of body gross mass；The dosage of the defoaming primitive is the 0.01~0.03% of polymerized monomer gross mass.
10. a kind of -9 described in any item preparation methods of high performance-price ratio polycarboxylate water-reducer, feature exist according to claim 1
In, the specific steps are that:
(1) synthesize basic construct primitive: reaction temperature is 20-30 DEG C, and polymerized monomer time for adding is 3-4h, is added dropwise, and is protected
For adjustment pH value to 3.0~4.0, solid content 45% obtains basic construct primitive after temperature reaction 1h；
(2) it the Supramolecular Assembling of high performance-price ratio polycarboxylate water-reducer: feeds intake in the following order under constant stirring: basic construct base
Member-water conservation primitive-diminishing primitive-slow setting primitive-bleed primitive-defoaming primitive feeds intake to finish and continues 1~2h of stirring i.e.
Obtain high performance-price ratio polycarboxylate water-reducer.
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Citations (3)
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|---|---|---|---|---|
| CN104861121A (en) * | 2014-02-25 | 2015-08-26 | 北京麦凯特科技有限公司 | Reactive powder concrete dedicated polycarboxylic acid water reducing agent and preparation method thereof |
| CN105130269A (en) * | 2015-08-21 | 2015-12-09 | 大连建科北方化学有限公司 | High-water-reduction high-early-strength type polycarboxylic acid water reducing agent and pyrogen-free preparation method thereof |
| CN109517114A (en) * | 2017-09-18 | 2019-03-26 | 太原工业学院 | A kind of morning strong collapse protective poly-carboxylic acid type water-reducing agent and preparation method thereof |
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2019
- 2019-08-30 CN CN201910813140.3A patent/CN110437388A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104861121A (en) * | 2014-02-25 | 2015-08-26 | 北京麦凯特科技有限公司 | Reactive powder concrete dedicated polycarboxylic acid water reducing agent and preparation method thereof |
| CN105130269A (en) * | 2015-08-21 | 2015-12-09 | 大连建科北方化学有限公司 | High-water-reduction high-early-strength type polycarboxylic acid water reducing agent and pyrogen-free preparation method thereof |
| CN109517114A (en) * | 2017-09-18 | 2019-03-26 | 太原工业学院 | A kind of morning strong collapse protective poly-carboxylic acid type water-reducing agent and preparation method thereof |
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| Title |
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| 中国建筑学会建材分会混凝土外加剂应用技术专业委员会编: "《聚羧酸系高性能减水剂制备、性能与应用技术新进展》", 31 May 2013, 北京理工大学出版社 * |
| 阮承祥主编: "《混凝土外加剂及其工程应用》", 31 December 2008, 江西科学技术出版社 * |
| 陈德展主编: "《开启化学之门》", 31 October 2013, 山东科学技术出版社 * |
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