CN110643004A - Preparation method of powdery polycarboxylate superplasticizer - Google Patents
Preparation method of powdery polycarboxylate superplasticizer Download PDFInfo
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- CN110643004A CN110643004A CN201810673270.7A CN201810673270A CN110643004A CN 110643004 A CN110643004 A CN 110643004A CN 201810673270 A CN201810673270 A CN 201810673270A CN 110643004 A CN110643004 A CN 110643004A
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a powdery polycarboxylate superplasticizer, which comprises the following steps: (1) preparing an esterified macromonomer; (2) preparing a molecular weight regulator; (3) carrying out bulk polymerization; (4) and (5) cooling the slices. The product of the invention is powdery, thereby saving the cost in the production, transportation and storage processes and reducing the product cost; the kneading machine is used for bulk polymerization, so that the problems of high reactant viscosity, difficult stirring and difficult heat dissipation in the bulk polymerization process of the polycarboxylate superplasticizer are solved.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a powdery polycarboxylic acid water reducing agent.
Background
The polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining property, strong molecular structure design, environmental protection and the like, and becomes the most important product in the current concrete admixture market. With the development of concrete technology, the application of the polycarboxylate superplasticizer also has some problems. On one hand, the variability of the environment, the diversity of concrete construction and the particularity of major engineering put forward the requirements of functional design on the concrete water reducing agent. On the other hand, the traditional polycarboxylic acid water reducing agent is synthesized by free radical polymerization in aqueous solution, and the solid content of the product is 10-50%, which causes great cost problem for long-distance transportation. In addition, in recent years, with the application of products such as grouting materials, dry mortar and powder coating materials in a large amount in building engineering, the demand for powder polycarboxylic acid water reducing agents has been increasing year by year, and polycarboxylic acid aqueous solutions are not available in these industries.
At present, the existing method for synthesizing a solid polycarboxylate superplasticizer generally comprises evaporating water from a polycarboxylate superplasticizer aqueous solution to obtain a solid polycarboxylate superplasticizer product. The technical proposal has the problems that the boiling point of water in a normal state is 100 ℃, and the energy consumed in the process of evaporating water is large. In addition, the polycarboxylate superplasticizer has a self-structure change under a high-temperature condition, and the performance of the polycarboxylate superplasticizer can be influenced after water is evaporated. For the above reasons, the popularization and application of the solid polycarboxylic acid water reducing agent are limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a powdery polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
a preparation method of a powdery polycarboxylate superplasticizer comprises the following steps:
(1) preparation of esterified macromonomer: adding tetrahydrofuran-propylene oxide copolymer glycol, unsaturated acid, polymerization inhibitor and catalyst into a first reaction kettle, heating to 100-120 ℃, carrying out heat preservation reaction for 3-5 hours, and removing generated water in the reaction process to obtain an esterified macromonomer; the unsaturated acid is methacrylic acid or acrylic acid; the polymerization inhibitor is hydroquinone or phenothiazine; the catalyst is concentrated sulfuric acid or sodium hydroxide;
(2) preparing a molecular weight regulator: adding sodium hypophosphite, isobutylene alcohol polyoxyethylene ether and water into a second reaction kettle, heating to 70-80 ℃, dripping hydrogen peroxide in 0.5h, keeping the temperature for 0.5-1 h after dripping is finished, then evaporating the materials to dryness, adding absolute ethyl alcohol for resuspension, stirring for 0.4-0.6 h at room temperature, and then filtering and vacuum drying to obtain a molecular weight regulator;
(3) bulk polymerization reaction: adding the esterified macromonomer prepared in the step (1) and the molecular weight regulator prepared in the step (2) into a reaction kettle of a kneader, stirring at the speed of 500-1000 rpm, heating to 75-80 ℃, dropwise adding the unsaturated monomer into the mixture for reaction when the material is in a liquid state, wherein the dropwise adding time is 1-3 h, adding the unsaturated monomer into an oxidation-reduction initiation system at 18-22 min intervals in three equal parts, and preserving heat for 0.5-2 h after the dropwise adding is finished to obtain a liquid polycarboxylic acid water reducer; the unsaturated monomer is at least one of acrylic acid, methacrylic acid, sodium cocoyl isethionate and 4-hydroxybutyl acrylate; the oxidant of the redox initiation system is azodicarbonamide, dibenzoyl peroxide, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate, and the reducing agent is cuprous naphthoate;
(4) cooling and slicing: and (4) allowing the liquid polycarboxylate superplasticizer obtained in the step (3) to flow into a slicing machine through a discharge pipe of a kneading machine for cooling and slicing to obtain the powdery polycarboxylate superplasticizer.
In a preferred embodiment of the present invention, in the step (1), the weight ratio of the tetrahydrofuran-propylene oxide copolymerized glycol, the unsaturated acid, the polymerization inhibitor and the catalyst is 100: 5 to 15: 1 to 5: 1 to 3.
In a preferred embodiment of the present invention, in the step (2), the weight ratio of the sodium hypophosphite, the isobutylene alcohol polyoxyethylene ether, the water, the hydrogen peroxide and the water ethanol is 100: 50-70: 100: 1-2: 200-400.
In a preferred embodiment of the present invention, in the step (3), the weight ratio of the esterified macromonomer prepared in the step (1), the molecular weight regulator prepared in the step (2), and the unsaturated monomer is 100: 0.5 to 1: 10 to 20.
In a preferred embodiment of the present invention, the redox initiation system is used in an amount of 1.0 to 5.0 wt% based on the mass of the esterified macromonomer.
In a preferred embodiment of the present invention, the molecular weight of the polyoxyethylene methacrylate is 500 to 1000.
In a preferred embodiment of the present invention, the molecular weight of the tetrahydrofuran-propylene oxide copolyol is 2000 to 4000.
The invention has the beneficial effects that:
1. the product of the invention is in powder shape, thereby saving the cost in the production, transportation and storage processes and reducing the product cost
2. The kneading machine is used for bulk polymerization, so that the problems of high reactant viscosity, difficult stirring and difficult heat dissipation in the bulk polymerization process of the polycarboxylate superplasticizer are solved;
3. the molecular weight regulator used in the invention is single-substituted hypophosphorous acid, which can overcome the defect of wide molecular weight distribution of bulk polymerization products;
4. the product contains a tetrahydrofuran-propylene oxide copolymerized glycol structure, is applied to concrete, and has excellent water reducing, slump retaining and early strength performances.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) Preparation of esterified macromonomer: adding 100g of tetrahydrofuran-propylene oxide copolyol with molecular weight of 2000, 5g of acrylic acid, 1g of hydroquinone and 1g of concentrated sulfuric acid into a reaction kettle, heating to 100 ℃, keeping the temperature for reaction for 5 hours, and removing generated water in the reaction process.
(2) Preparing a molecular weight regulator: adding 100g of sodium hypophosphite, 50g of isobutenol polyoxyethylene ether with the molecular weight of 500 and 100g of water into a reaction kettle, heating to 75 ℃, dropwise adding 1g of hydrogen peroxide within 0.5h, preserving heat for 0.5h after dropwise adding, then evaporating the reaction liquid to dryness, adding 230g of absolute ethyl alcohol, stirring the suspension at room temperature for 0.4h, then filtering, and drying the filter cake in vacuum to obtain the molecular weight regulator.
(3) Bulk polymerization reaction: adding 100g of the esterified macromonomer prepared in the step (1) and 0.6g of the molecular weight regulator prepared in the step (2) into a reaction kettle of a kneader, starting a stirring shaft, regulating the stirring speed to 500rpm, heating to 70 ℃, dripping 15g of methacrylic acid into the reaction kettle for reaction when reactants in the kettle are in a liquid state, wherein the dripping time is 1.5h, simultaneously adding 2g of azodicarbonamide and 1g of cuprous naphthanate in trisection at 18min intervals, preserving heat for 0.5h after the dripping is finished, and finally obtaining a product with the solid content of 100%.
(4) Cooling and slicing: and (4) allowing the liquid polycarboxylate superplasticizer obtained in the step (3) to flow into a slicing machine through a discharge pipe of a kneading machine for cooling and slicing.
Example 2
(1) Preparation of esterified macromonomer: adding 100g of tetrahydrofuran-propylene oxide copolyol with the molecular weight of 3000, 10g of methacrylic acid, 3g of hydroquinone and 2g of concentrated sulfuric acid into a reaction kettle, heating to 110 ℃, keeping the temperature for reaction for 4 hours, and removing generated water in the reaction process.
(2) Preparing a molecular weight regulator: adding 100g of sodium hypophosphite, 60g of isobutenol polyoxyethylene ether with the molecular weight of 800 and 100g of water into a reaction kettle, heating to 80 ℃, dripping 1.5g of hydrogen peroxide in 0.5h, preserving heat for 0.5h after dripping is finished, then evaporating the reaction liquid to dryness, adding 300g of absolute ethyl alcohol, stirring the suspension at room temperature for 0.5h, then filtering, and drying the filter cake in vacuum to obtain the molecular weight regulator.
(3) Bulk polymerization reaction: adding 100g of the esterified macromonomer prepared in the step (1) and 0.8g of the molecular weight regulator prepared in the step (2) into a reaction kettle of a kneader, starting a stirring shaft, regulating the stirring speed to 800rpm, heating to 78 ℃, dropwise adding 10g of mixed solution of acrylic acid and 7g of sodium cocoyl isethionate into the reaction kettle for reaction when reactants in the kettle are in a liquid state, wherein the dropwise adding time is 2 hours, adding 3g of diisopropyl peroxydicarbonate and 1g of cuprous naphthanate in trisection at the same time, the adding time interval is 20 minutes, preserving heat for 1 hour after the dropwise adding is finished, and finally obtaining a product with the solid content of 100%.
(4) Cooling and slicing: and (4) allowing the liquid polycarboxylate superplasticizer obtained in the step (3) to flow into a slicing machine through a discharge pipe of a kneading machine for cooling and slicing.
Example 3
(1) Preparation of esterified macromonomer: 100g of tetrahydrofuran-propylene oxide copolyol with the molecular weight of 4000, 15g of methacrylic acid, 5g of phenothiazine and 3g of sodium hydroxide are added into a reaction kettle, the temperature is increased to 120 ℃, the reaction is carried out for 3 hours under the condition of heat preservation, and the generated water is removed in the reaction process.
(2) Preparing a molecular weight regulator: adding 100g of sodium hypophosphite, 70g of isobutenol polyoxyethylene ether with the molecular weight of 1000 and 100g of water into a reaction kettle, heating to 70 ℃, dropwise adding 2g of hydrogen peroxide within 0.5h, preserving heat for 0.5h after dropwise adding, then evaporating the reaction liquid to dryness, adding 400g of absolute ethyl alcohol, stirring the suspension at room temperature for 0.6h, then filtering, and drying the filter cake in vacuum to obtain the molecular weight regulator.
(3) Bulk polymerization reaction: adding 100g of the esterified macromonomer prepared in the step (1) and 1g of the molecular weight regulator prepared in the step (2) into a reaction kettle of a kneader, starting a stirring shaft, regulating the stirring speed to 1000rpm, heating to 80 ℃, dropwise adding a mixed solution of 5g of acrylic acid and 12g of 4-hydroxybutyl acrylate into the reaction kettle for reaction when reactants in the kettle are in a liquid state for 3 hours, adding 2g of dibenzoyl peroxide and 1.5g of cuprous naphthoate in trisection at the same time, wherein the adding time interval is 22 minutes, and preserving heat for 1 hour after the dropwise addition is finished to finally obtain a product with the solid content of 100%.
(4) Cooling and slicing: and (4) allowing the liquid polycarboxylate superplasticizer obtained in the step (3) to flow into a slicing machine through a discharge pipe of a kneading machine for cooling and slicing.
The powder polycarboxylic acid water reducing agent obtained in the examples 1 to 3 and the Point-MS polycarboxylic acid mother liquor are tested for slump and other performances by using standard cement according to GB 8076 plus 2008 concrete admixture. The concrete mixing proportion is as follows: cement 360kg/m3770kg/m of sand31038kg/m of stone3The results obtained are shown in Table 1.
Table 1 comparison of the properties of the examples
The test result shows that the powder polycarboxylate superplasticizer has high water reducing rate, so that the concrete added with the superplasticizer has good slump retaining performance, and the early strength of the concrete is improved.
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
a preparation method of a powdery polycarboxylate superplasticizer comprises the following steps:
(1) preparation of esterified macromonomer: adding tetrahydrofuran-propylene oxide copolymer glycol, unsaturated acid, polymerization inhibitor and catalyst into a first reaction kettle, heating to 100-120 ℃, carrying out heat preservation reaction for 3-5 hours, and removing generated water in the reaction process to obtain an esterified macromonomer; the unsaturated acid is methacrylic acid or acrylic acid; the polymerization inhibitor is hydroquinone or phenothiazine; the catalyst is concentrated sulfuric acid or sodium hydroxide;
(2) preparing a molecular weight regulator: adding sodium hypophosphite, isobutylene alcohol polyoxyethylene ether and water into a second reaction kettle, heating to 70-80 ℃, dripping hydrogen peroxide in 0.5h, keeping the temperature for 0.5-1 h after dripping is finished, then evaporating the materials to dryness, adding absolute ethyl alcohol for resuspension, stirring for 0.4-0.6 h at room temperature, and then filtering and vacuum drying to obtain a molecular weight regulator;
(3) bulk polymerization reaction: adding the esterified macromonomer prepared in the step (1) and the molecular weight regulator prepared in the step (2) into a reaction kettle of a kneader, stirring at the speed of 500-1000 rpm, heating to 75-80 ℃, dropwise adding the unsaturated monomer into the mixture for reaction when the material is in a liquid state, wherein the dropwise adding time is 1-3 h, adding the unsaturated monomer into an oxidation-reduction initiation system at 18-22 min intervals in three equal parts, and preserving heat for 0.5-2 h after the dropwise adding is finished to obtain a liquid polycarboxylic acid water reducer; the unsaturated monomer is at least one of acrylic acid, methacrylic acid, sodium cocoyl isethionate and 4-hydroxybutyl acrylate; the oxidant of the redox initiation system is azodicarbonamide, dibenzoyl peroxide, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate, and the reducing agent is cuprous naphthoate;
(4) cooling and slicing: and (4) allowing the liquid polycarboxylate superplasticizer obtained in the step (3) to flow into a slicing machine through a discharge pipe of a kneading machine for cooling and slicing to obtain the powdery polycarboxylate superplasticizer.
In the step (1), the weight ratio of the tetrahydrofuran-propylene oxide copolymerized glycol to the unsaturated acid to the polymerization inhibitor to the catalyst is 100: 5-15: 1-5: 1-3. In the step (2), the weight ratio of the sodium hypophosphite, the isobutenol polyoxyethylene ether, the water, the hydrogen peroxide and the water ethanol is 100: 50-70: 100: 1-2: 200-400. In the step (3), the weight ratio of the esterified macromonomer prepared in the step (1), the molecular weight regulator prepared in the step (2) and the unsaturated monomer is 100: 0.5-1: 10-20. The dosage of the redox initiation system is 1.0-5.0 wt% of the mass of the esterified macromonomer. The molecular weight of the isobutenol polyoxyethylene ether is 500-1000. The molecular weight of the tetrahydrofuran-propylene oxide copolymerized glycol is 2000-4000.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. A preparation method of a powdery polycarboxylate superplasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of esterified macromonomer: adding tetrahydrofuran-propylene oxide copolymer glycol, unsaturated acid, polymerization inhibitor and catalyst into a first reaction kettle, heating to 100-120 ℃, carrying out heat preservation reaction for 3-5 hours, and removing generated water in the reaction process to obtain an esterified macromonomer; the unsaturated acid is methacrylic acid or acrylic acid; the polymerization inhibitor is hydroquinone or phenothiazine; the catalyst is concentrated sulfuric acid or sodium hydroxide;
(2) preparing a molecular weight regulator: adding sodium hypophosphite, isobutylene alcohol polyoxyethylene ether and water into a second reaction kettle, heating to 70-80 ℃, dripping hydrogen peroxide in 0.5h, keeping the temperature for 0.5-1 h after dripping is finished, then evaporating the materials to dryness, adding absolute ethyl alcohol for resuspension, stirring for 0.4-0.6 h at room temperature, and then filtering and vacuum drying to obtain a molecular weight regulator;
(3) bulk polymerization reaction: adding the esterified macromonomer prepared in the step (1) and the molecular weight regulator prepared in the step (2) into a reaction kettle of a kneader, stirring at the speed of 500-1000 rpm, heating to 75-80 ℃, dropwise adding the unsaturated monomer into the mixture for reaction when the material is in a liquid state, wherein the dropwise adding time is 1-3 h, adding the unsaturated monomer into an oxidation-reduction initiation system at 18-22 min intervals in three equal parts, and preserving heat for 0.5-2 h after the dropwise adding is finished to obtain a liquid polycarboxylic acid water reducer; the unsaturated monomer is at least one of acrylic acid, methacrylic acid, sodium cocoyl isethionate and 4-hydroxybutyl acrylate; the oxidant of the redox initiation system is azodicarbonamide, dibenzoyl peroxide, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate, and the reducing agent is cuprous naphthoate;
(4) cooling and slicing: and (4) allowing the liquid polycarboxylate superplasticizer obtained in the step (3) to flow into a slicing machine through a discharge pipe of a kneading machine for cooling and slicing to obtain the powdery polycarboxylate superplasticizer.
2. The method of claim 1, wherein: in the step (1), the weight ratio of the tetrahydrofuran-propylene oxide copolymerized glycol to the unsaturated acid to the polymerization inhibitor to the catalyst is 100: 5-15: 1-5: 1-3.
3. The method of claim 1, wherein: in the step (2), the weight ratio of the sodium hypophosphite, the isobutenol polyoxyethylene ether, the water, the hydrogen peroxide and the water ethanol is 100: 50-70: 100: 1-2: 200-400.
4. The method of claim 1, wherein: in the step (3), the weight ratio of the esterified macromonomer prepared in the step (1), the molecular weight regulator prepared in the step (2) and the unsaturated monomer is 100: 0.5-1: 10-20.
5. The method of claim 1, wherein: the dosage of the redox initiation system is 1.0-5.0 wt% of the mass of the esterified macromonomer.
6. The method of claim 1, wherein: the molecular weight of the isobutenol polyoxyethylene ether is 500-1000.
7. The method of claim 1, wherein: the molecular weight of the tetrahydrofuran-propylene oxide copolymerized glycol is 2000-4000.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1655272A1 (en) * | 2004-11-04 | 2006-05-10 | Mapei S.p.A. | Superplasticizers for extending the workability of mortars |
| CN103025810A (en) * | 2010-07-21 | 2013-04-03 | Sika技术股份公司 | Regulator molecule |
| CN103012694A (en) * | 2012-09-13 | 2013-04-03 | 北京工业大学 | Preparation method of polyester type pure solid polycarboxylic acid high-performance water reducing agent |
| CN104829177A (en) * | 2015-04-21 | 2015-08-12 | 北京中科嘉固建筑材料科技有限公司 | High strength crack resistant concrete and preparation method, composition and application thereof |
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- 2018-06-26 CN CN201810673270.7A patent/CN110643004B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1655272A1 (en) * | 2004-11-04 | 2006-05-10 | Mapei S.p.A. | Superplasticizers for extending the workability of mortars |
| CN103025810A (en) * | 2010-07-21 | 2013-04-03 | Sika技术股份公司 | Regulator molecule |
| CN103012694A (en) * | 2012-09-13 | 2013-04-03 | 北京工业大学 | Preparation method of polyester type pure solid polycarboxylic acid high-performance water reducing agent |
| CN104829177A (en) * | 2015-04-21 | 2015-08-12 | 北京中科嘉固建筑材料科技有限公司 | High strength crack resistant concrete and preparation method, composition and application thereof |
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