CN111747673B - Modified concrete additive special for high-speed rail and preparation method thereof - Google Patents
Modified concrete additive special for high-speed rail and preparation method thereof Download PDFInfo
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- CN111747673B CN111747673B CN202010476595.3A CN202010476595A CN111747673B CN 111747673 B CN111747673 B CN 111747673B CN 202010476595 A CN202010476595 A CN 202010476595A CN 111747673 B CN111747673 B CN 111747673B
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
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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
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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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A modified concrete admixture special for high-speed rail and a preparation method thereof, comprising 60-84 parts of high-efficiency water reducing agent, 0.2-0.6 part of polypropylene fiber and 1-3.5 parts of water-absorbing resin; the high-efficiency water reducing agent is prepared by copolymerization reaction of acrylic acid, unsaturated polyoxyethylene ether and 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt which are used as comonomers under the condition of an initiator, a chain transfer agent and a reducing agent; the additive provided by the invention comprises 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt, and hydrophilic sulfonic acid groups are introduced by reacting alcoholic hydroxyl groups of the 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt with chlorosulfonic acid, so that a comonomer has a higher density of sulfonic groups with negative charges and positive ions (Ca) in cement2+) Electrostatic repulsion is generated between the cement particles, and water molecules among the cement particles and wrapped in the space net structure are released, so that the water reducing effect is improved.
Description
Technical Field
The invention belongs to the field of concrete admixtures, and particularly relates to a modified concrete admixture special for high-speed rails and a preparation method thereof.
Background
In the existing high-speed rail construction in China, concrete construction occupies a large proportion, and along with the rapid development of high-speed railway business and high-standard requirements on high-speed railways, the demand of high-performance concrete for the high-speed railways is more and more increased; concrete is a general term for engineering composite materials in which aggregate is cemented into a whole by a cementing material. The concrete is usually cement as cementing material and sand and stone as aggregate; mixing with water (containing additive or admixture) according to a certain proportion, and stirring to obtain the cement concrete, also called as common concrete;
because the concrete is subjected to capillary negative pressure in the hardening process of the cement, water absorbed by capillary pores and gel pores is lost, the relative humidity is reduced or CO in the air is mixed with the concrete2A reaction accompanied by volume shrinkage and finally causing plastic shrinkage, drying shrinkage, self-shrinkage, carbonization shrinkage, and the like of concrete, thereby causing a decrease in durability of concrete; therefore, the quality of the concrete has great influence on the quality of the structure, especially in the high-speed railway construction taking safety as the primary index,more importantly, high-performance concrete is produced at the same time; the high-performance concrete is prepared by adopting a modern concrete technology on the basis of greatly improving the performance of common concrete, and takes durability, high strength and low shrinkage as design indexes; among them, the admixture added to concrete is an important component for imparting high performance to the concrete, and among various concrete admixtures, a high efficiency water reducing agent which is representative of a hydraulic mixture having a fluidizing effect, an early strength agent which accelerates development of early strength of concrete, and the like, although they have good effects, each of these individual admixtures has advantages and disadvantages, and cannot intensively solve the problems of high compressive strength required for high performance concrete and control of shrinkage of concrete.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a modified concrete admixture special for high-speed rail, which comprises 60-84 parts of a high-efficiency water reducing agent, 0.2-0.6 part of polypropylene fiber and 1-3.5 parts of water-absorbing resin;
the high-efficiency water reducing agent is prepared by copolymerization reaction of acrylic acid, unsaturated polyoxyethylene ether and 3-allyloxy-2-hydrogen propyl sulfonate-1-propane sulfonic acid sodium salt serving as comonomers in the presence of an initiator, a chain transfer agent and a reducing agent; wherein the mass component ratio of acrylic acid, unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt, initiator, chain transfer agent and reducing agent is 1: (0.2-0.35): (0.12-0.2): (0.003-0.03): (0.006-0.01): (0.001-0.01); the specific reaction process is as follows:
preferably, the preparation method of the high efficiency water reducing agent comprises the following steps:
(1) preparation of 3-allyloxy-2-hydroxypropyl sulfonate-1-propanesulfonic acid sodium salt: 1) under the condition of ice-water bath, dripping chlorosulfonic acid into anhydrous pyridine according to a certain proportion to obtain an esterification reagent; 2) adding 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt into an esterification reagent, reacting for 1-3h at the temperature of 0-6 ℃, and performing rotary evaporation and concentration to remove pyridine to obtain the 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt; the specific reaction process is as follows:
(2) taking materials according to the mass ratio, and dissolving an initiator, a chain transfer agent and a reducing agent in water to serve as first drop of liquid; dissolving acrylic acid in water to prepare second dropping liquid with mass concentration of 55-65%;
(3) adding unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt and deionized water into a reaction kettle according to the mass ratio to prepare a mixed solution with the mass concentration of 3-6.8%, stirring and heating to 50-65 ℃, after the materials are dissolved, simultaneously adding a first dropping liquid and a second dropping liquid into the reaction kettle, and reacting for 3-5 hours at 80-100 ℃ after the dropping is finished;
(4) and after the reaction is finished, adjusting the pH value of the material to 7-9 to obtain the high-efficiency water reducing agent.
Preferably, the polypropylene fiber has a fiber diameter of 15 to 30 μm and a length of 10 to 20 mm.
Preferably, the water-absorbing resin is polyacrylic resin or acrylamide-acrylic acid copolymer.
Preferably, the initiator is at least one of ammonium persulfate or potassium persulfate.
Preferably, the chain transfer agent is at least one of dodecyl mercaptan or thioglycolic acid.
Preferably, the reducing agent is at least one of vitamin C or vitamin E.
A preparation method of a special modified concrete admixture for high-speed rail comprises the following steps:
(1) grinding the water-absorbing resin, and controlling the particle size of the water-absorbing resin to be 50-400 nm;
(2) and respectively weighing and mixing a high-efficiency water reducing agent, polypropylene fibers and water-absorbent resin according to the parts of the raw materials to obtain the special modified concrete admixture for the high-speed rail.
The invention has the following beneficial effects:
(1) the high-efficiency water reducing agent in the admixture comprises 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt, wherein the alcoholic hydroxyl of the 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt is reacted with chlorosulfonic acid to introduce hydrophilic sulfonic acid groups, so that a comonomer has sulfonic acid groups with higher density and negative charges, and the groups with the negative charges can be reacted with positive ions (Ca) in cement2+) The electrostatic interaction is generated between the two groups, and the electrostatic interaction can anchor the groups on the cement surface to form electric double layer distribution; thus, by the generated electrostatic repulsion, water molecules among cement particles and wrapped in the space net structure are released, so that the water reducing effect is improved, the water-cement ratio is reduced, the porosity is reduced, the pore diameter is refined, and the shrinkage of a hardened body is reduced;
(2) the high-efficiency water reducing agent is synthesized through free radical copolymerization, the process is simple and environment-friendly, the polypropylene fiber is introduced, the compressive strength of the concrete is improved, and the high-efficiency water reducing agent plays a vital role in controlling the shrinkage of the concrete; the water-absorbing resin is added, so that unreacted water in the concrete can be fully present in capillary pores within a long time, the generation of capillary pressure is avoided, and the shrinkage cracking of the concrete is reduced.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example 1
A modified concrete admixture special for high-speed rails comprises 80 parts of a high-efficiency water reducing agent, 0.4 part of polypropylene fibers and 2 parts of polyacrylic resin;
the high-efficiency water reducing agent is prepared by copolymerization reaction of acrylic acid, unsaturated polyoxyethylene ether and 3-allyloxy-2-hydrogen propyl sulfonate-1-propane sulfonic acid sodium salt serving as comonomers in the presence of an initiator, a chain transfer agent and a reducing agent; wherein the mass component ratio of acrylic acid, unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propane sulfonic acid sodium salt, potassium persulfate, dodecyl mercaptan and vitamin C is 1: 0.22: 0.18: 0.01: 0.009: 0.004.
a preparation method of a special modified concrete admixture for high-speed rail comprises the following steps:
(1) preparation of 3-allyloxy-2-hydrocapropyl sulfonate-1-propanesulfonic acid sodium salt: 1) under the condition of ice-water bath, dripping chlorosulfonic acid into anhydrous pyridine according to a certain proportion to obtain an esterification reagent; 2) adding 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt into an esterification reagent, reacting for 2h at 4 ℃, and removing pyridine by rotary evaporation and concentration to obtain the 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt;
(2) taking materials according to the mass ratio, and dissolving an initiator, a chain transfer agent and a reducing agent in water to serve as first drop of liquid; dissolving acrylic acid in water to prepare second dropping liquid with mass concentration of 55%;
(3) adding unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt and deionized water into a reaction kettle according to the mass ratio to prepare a mixed solution with the mass concentration of 4.5%, stirring and heating to 50 ℃, after the materials are dissolved, simultaneously dropwise adding a first dropwise added liquid and a second dropwise added liquid into the reaction kettle, and reacting for 4 hours at 85 ℃ after dropwise adding;
(4) after the reaction is finished, adjusting the pH value of the material to 7-9 to obtain the high-efficiency water reducing agent;
(5) grinding the water-absorbing resin, and controlling the particle size of the water-absorbing resin to be 50-400 nm;
(6) and respectively weighing and mixing the high-efficiency water reducing agent, the polypropylene fiber and the water-absorbent resin according to the parts of the raw materials to obtain the special modified concrete admixture for the high-speed rail.
Example 2
The special modified concrete admixture for the high-speed rail comprises 75 parts of a high-efficiency water reducing agent, 0.6 part of polypropylene fiber and 2.5 parts of polyacrylic resin;
the high-efficiency water reducing agent is prepared by copolymerization reaction of acrylic acid, unsaturated polyoxyethylene ether and 3-allyloxy-2-hydrogen propyl sulfonate-1-propane sulfonic acid sodium salt serving as comonomers in the presence of an initiator, a chain transfer agent and a reducing agent; wherein the mass component ratio of acrylic acid, unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt, ammonium persulfate, dodecyl mercaptan and vitamin C is 1: 0.35: 0.14: 0.02: 0.006: 0.005.
a preparation method of a special modified concrete admixture for high-speed rail comprises the following steps:
(1) preparation of 3-allyloxy-2-hydrocapropyl sulfonate-1-propanesulfonic acid sodium salt: 1) under the condition of ice-water bath, dripping chlorosulfonic acid into anhydrous pyridine according to a certain proportion to obtain an esterification reagent; 2) adding 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt into an esterification reagent, reacting for 3h at 0 ℃, and removing pyridine by rotary evaporation and concentration to obtain the 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt;
(2) taking materials according to the mass ratio, and dissolving an initiator, a chain transfer agent and a reducing agent in water to serve as first drop of liquid; dissolving acrylic acid in water to prepare a second dropping liquid with the mass concentration of 60%;
(3) adding unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt and deionized water into a reaction kettle according to the mass ratio to prepare a mixed solution with the mass concentration of 5.5%, stirring and heating to 65 ℃, after the materials are dissolved, simultaneously dropwise adding a first dropwise added liquid and a second dropwise added liquid into the reaction kettle, and reacting for 3 hours at 90 ℃ after dropwise adding is finished;
(4) after the reaction is finished, adjusting the pH value of the material to 7-9 to obtain the high-efficiency water reducing agent;
(5) grinding the water-absorbing resin, and controlling the particle size of the water-absorbing resin to be 50-400 nm;
(6) and respectively weighing and mixing a high-efficiency water reducing agent, polypropylene fibers and water-absorbent resin according to the parts of the raw materials to obtain the special modified concrete admixture for the high-speed rail.
Example 3
A modified concrete admixture special for high-speed rail comprises 66 parts of a high-efficiency water reducing agent, 0.3 part of polypropylene fiber and 3.5 parts of acrylamide-acrylic acid copolymer;
the high-efficiency water reducing agent is prepared by copolymerization reaction of acrylic acid, unsaturated polyoxyethylene ether and 3-allyloxy-2-hydrogen propyl sulfonate-1-propane sulfonic acid sodium salt serving as comonomers in the presence of an initiator, a chain transfer agent and a reducing agent; wherein the mass component ratio of acrylic acid, unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt, ammonium persulfate, thioglycolic acid and vitamin E is 1: 0.25: 0.17: 0.028: 0.006: 0.002.
a preparation method of a special modified concrete additive for high-speed rails comprises the following steps:
(1) preparation of 3-allyloxy-2-hydrocapropyl sulfonate-1-propanesulfonic acid sodium salt: 1) under the condition of ice-water bath, dripping chlorosulfonic acid into anhydrous pyridine according to a certain proportion to obtain an esterification reagent; 2) adding 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt into an esterification reagent, reacting for 3h at 4 ℃, and removing pyridine by rotary evaporation and concentration to obtain the 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt;
(2) taking materials according to the mass ratio, and dissolving an initiator, a chain transfer agent and a reducing agent in water to serve as first drop of liquid; dissolving acrylic acid in water to prepare a second dropping liquid with the mass concentration of 65%;
(3) adding unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt and deionized water into a reaction kettle according to the mass ratio to prepare a mixed solution with the mass concentration of 6.8%, stirring and heating to 55 ℃, after the materials are dissolved, simultaneously dropwise adding a first dropwise added liquid and a second dropwise added liquid into the reaction kettle, and reacting for 3 hours at 100 ℃ after dropwise addition is finished;
(4) after the reaction is finished, adjusting the pH value of the material to 7-9 to obtain the high-efficiency water reducing agent;
(5) grinding the water-absorbing resin, and controlling the particle size of the water-absorbing resin to be 50-400 nm;
(6) and respectively weighing and mixing a high-efficiency water reducing agent, polypropylene fibers and water-absorbent resin according to the parts of the raw materials to obtain the special modified concrete admixture for the high-speed rail.
The implementation effect is as follows:
the clear paste fluidity of the cement is tested according to GB/T8077-2000 concrete additive homogeneity test method by adopting reference cement, the water-cement ratio is 0.30, the admixture mixing amount is a bending solid mixing amount, a certain commercial polycarboxylic acid water reducing agent is adopted as the admixture of the comparative example, and the test result is shown in Table 1.
TABLE 1 Cement paste fluidity test
Further performance parameters for examples 1-3 and comparative examples are given in table 2.
TABLE 2 Performance parameters of modified concrete admixtures for high-speed rails
Concrete for testing: P.O 52.5.5 cement, broken stone, standard sand, water and an additive are adopted, the raw materials are weighed according to the proportioning composition given in the table 3, and a tipping bucket type concrete mixer is used for mixing the raw materials together; the additive of the comparative example adopts a certain commercial polycarboxylic acid water reducing agent;
TABLE 3 concrete basic mix proportion (kg/m3)
Forming the concrete for testing into a concrete test piece with the thickness of 100 multiplied by 515mm, curing the concrete test piece under the conditions that the temperature is 20 +/-2 ℃ and the humidity is more than 90 percent, and measuring the working performance of the concrete and the compression resistance and shrinkage performance indexes of the concrete test piece;
TABLE 4 concrete and concrete test piece Performance test
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The special modified concrete admixture for the high-speed rail is characterized by comprising 60-84 parts of a high-efficiency water reducing agent, 0.2-0.6 part of polypropylene fiber and 1-3.5 parts of water-absorbing resin;
the high-efficiency water reducing agent is prepared by copolymerization reaction of acrylic acid, unsaturated polyoxyethylene ether and 3-allyloxy-2-hydrogen propyl sulfonate-1-propane sulfonic acid sodium salt serving as comonomers in the presence of an initiator, a chain transfer agent and a reducing agent; wherein the mass component ratio of acrylic acid, unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt, initiator, chain transfer agent and reducing agent is 1: (0.2-0.35): (0.12-0.2): (0.003-0.03): (0.006-0.01): (0.001-0.01);
the preparation method of the high-efficiency water reducing agent comprises the following steps:
(1) preparation of 3-allyloxy-2-hydrocapropyl sulfonate-1-propanesulfonic acid sodium salt: 1) under the condition of ice-water bath, dripping chlorosulfonic acid into anhydrous pyridine according to a certain proportion to obtain an esterification reagent; 2) adding 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt into an esterification reagent, reacting for 1-3h at 0-6 ℃, and removing pyridine by rotary evaporation and concentration to obtain the 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt;
(2) taking materials according to the mass ratio, and dissolving an initiator, a chain transfer agent and a reducing agent in water to serve as first drop of liquid; dissolving acrylic acid in water to prepare second dropping liquid with mass concentration of 55-65%;
(3) adding unsaturated polyoxyethylene ether, 3-allyloxy-2-hydrogen propyl sulfonate-1-propanesulfonic acid sodium salt and deionized water into a reaction kettle according to the mass ratio to prepare a mixed solution with the mass concentration of 3-6.8%, stirring and heating to 50-65 ℃, after the materials are dissolved, simultaneously adding a first dropping liquid and a second dropping liquid into the reaction kettle, and reacting for 3-5 hours at 80-100 ℃ after the dropping is finished;
(4) and after the reaction is finished, adjusting the pH value of the material to 7-9 to obtain the high-efficiency water reducing agent.
2. The special modified concrete admixture for high-speed rail according to claim 1, wherein the polypropylene fiber has a fiber diameter of 15-30 μm and a length of 10-20 mm.
3. The special modified concrete admixture for high-speed rail according to claim 1, wherein the water-absorbent resin is polyacrylic resin or acrylamide-acrylic acid copolymer.
4. The special modified concrete admixture for high-speed rails according to claim 1, wherein the initiator is at least one of ammonium persulfate or potassium persulfate.
5. The special modified concrete admixture for high-speed rail according to claim 1, wherein the chain transfer agent is at least one of dodecyl mercaptan or thioglycolic acid.
6. The special modified concrete admixture for high-speed rail according to claim 1, wherein the reducing agent is at least one of vitamin C or vitamin E.
7. The preparation method of the special modified concrete admixture for high-speed rail according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
(1) grinding the water-absorbing resin, and controlling the particle size of the water-absorbing resin to be 50-400 nm;
(2) and respectively weighing and mixing a high-efficiency water reducing agent, polypropylene fibers and water-absorbent resin according to the parts of the raw materials to obtain the special modified concrete admixture for the high-speed rail.
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| CN102358768B (en) * | 2011-07-22 | 2014-01-22 | 广州市建筑科学研究院有限公司 | Modified ether polycarboxylic acid water reducing agent and preparation method thereof |
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Application publication date: 20201009 Assignee: JIANGSU LANQUAN NEW MATERIAL CO.,LTD. Assignor: JIANGSU BAIRUIJI NEW MATERIAL Co.,Ltd. Contract record no.: X2022980010521 Denomination of invention: A special modified concrete admixture for high-speed railway and its preparation method Granted publication date: 20220617 License type: Common License Record date: 20220715 |
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