CN108250370B - Polycarboxylic acids and their use in cement - Google Patents

Polycarboxylic acids and their use in cement Download PDF

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CN108250370B
CN108250370B CN201711417783.3A CN201711417783A CN108250370B CN 108250370 B CN108250370 B CN 108250370B CN 201711417783 A CN201711417783 A CN 201711417783A CN 108250370 B CN108250370 B CN 108250370B
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monomer
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cement
water
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CN108250370A (en
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孔祥明
田红伟
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Tsinghua University
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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
    • 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
    • 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
    • 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
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • 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
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The invention relates to a polycarboxylic acid and application thereof in cement. The polycarboxylic acid provided by the invention has a comb-shaped structure and is formed by randomly copolymerizing a first monomer A, an unsaturated carboxylic acid monomer B and a functional monomer C, wherein the first monomer is selected from at least one of an unsaturated polyether monomer and an unsaturated polyester monomer, and the molar ratio of the monomers is A: b: c is 1: (8-50): (0-5). The polycarboxylic acid provided by the invention can be used as a dispersing agent, can be greatly prolonged and can effectively control the retention of cement slump and fluidity without bleeding under the condition of not doping a retarder, and the engineering requirements are met.

Description

Polycarboxylic acids and their use in cement
Technical Field
The present invention relates to a polycarboxylic acid and its use in cement.
Background
Concrete is one of the materials widely used worldwide, of which cement is an important component as a cementitious material. The cement can be divided into the following properties: 1) general cement, the cement that general civil engineering and building engineering usually adopted mainly refers to: six types of cement specified in GB 175-2007, namely portland cement, ordinary portland cement, portland slag cement, pozzolanic portland cement, portland fly ash cement and composite portland cement; 2) special cement, which refers to cement with special purposes, such as G-grade oil well cement and road portland cement; 3) the characteristic cement: refers to cement with a certain outstanding performance. Such as: rapid hardening portland cement, low-heat slag portland cement, expanded sulphoaluminate cement, phosphoaluminate cement, and phosphate cement. Although the variety of cement is various, portland cement, which is generally called portland cement, is mainly used in China and the world.
As a new energy-saving and environment-friendly variety, sulphoaluminate cement is gradually paid more and more attention. Because of the excellent characteristics of early strength, quick hardening, high strength, high anti-permeability, high freezing resistance, corrosion resistance, low shrinkage and no shrinkage, the mortar has more and more applications in cement mortar or concrete which needs special performance, such as repairing and leaking stoppage, grouting and grouting, marine concrete and the like. Meanwhile, the production of the sulphoaluminate cement adopts alumina, gypsum and limestone with lower grade as raw materials, and the sulphoaluminate cement is prepared by firing clinker which is mainly composed of anhydrous calcium sulphoaluminate and dicalcium silicate and is finely ground by adding a proper amount of sulfate. The production process has the advantages of low energy consumption, low emission and the like. Has great application and popularization space.
However, it is known that many properties of cement mortar or concrete, such as strength and durability, depend on the water cement ratio, i.e., the ratio of the amount of water used for mixing to the amount of cement. The lower the water-cement ratio, the higher the strength and generally the better the durability. However, the reduction of the water-cement ratio simultaneously lowers workability, fluidity, etc. of mortar or concrete. Therefore, water reducing agents, as a dispersant with dispersed cement particles, have become an indispensable component in modern mix ratios of concrete or mortar. The addition of a small amount of water reducing agent can greatly improve the fluidity of mortar or concrete and reduce the water consumption. Particularly, the polycarboxylic acid water reducing agent has become a main variety of the current cement concrete water reducing agent due to the performances of high water reducing rate (25-40%), diversification of molecular structure, easy regulation and control and the like.
However, most of the polycarboxylic acid water reducing agents currently available on the market are designed for portland cement. Unlike portland cement, the sulphoaluminate cement composition consists mainly of anhydrous calcium sulphoaluminate, gypsum and other silicate phases. Has the characteristics of high hydration speed, high coagulation time and the like. Meanwhile, the surface properties of cement particles and hydration product phases are different, so that the traditional polycarboxylic acid water reducing agent cannot be successfully applied to a sulphoaluminate cement system. The main problems are that the concrete has the defects of insufficient dispersion performance, small initial flow or slump, large mixing amount, poor flow retention or slump retention and the like. Therefore, the invention discloses a polycarboxylate superplasticizer specially applied to a sulphoaluminate system. The modified asphalt is doped into sulphoaluminate cement mortar or concrete, and has the excellent performances of small doping amount, good dispersibility, good slump retention and the like.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention provides a polycarboxylic acid and the use of the polycarboxylic acid in cement, particularly sulphoaluminate cement, particularly as a dispersant. Under the condition of not doping a retarder, the polycarboxylic acid provided by the invention can be used as a dispersing agent, can be greatly prolonged, can effectively control the slump and fluidity of cement, does not bleed, and meets engineering requirements.
In a first aspect, the present invention provides a polycarboxylic acid having a comb-shaped structure, and formed by randomly copolymerizing a first monomer a, an unsaturated carboxylic acid monomer B, and a functional monomer C, wherein the first monomer is at least one selected from an unsaturated polyether monomer and an unsaturated polyester monomer, and the molar ratio of the raw materials is a: b: c is 1: (8-50): (0-5), preferably, A: b: c is 1: (9-30): (0-5), more preferably, A: b: c is 1: (9-30): (0.01-5), more preferably, A: b: c is 1: (9-30): (0.5 to 4).
According to some embodiments of the present invention, the unsaturated polyester monomer has the structure of formula (1),
Figure BDA0001522363100000021
wherein:
a represents an alkylene group having 2 to 4 carbon atoms;
b represents an alkylene group having 2 to 4 carbon atoms and being different from A;
R1and R2Each independently represents H or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group;
R3represents H or an alkyl group having 1 to 4 carbon atoms;
x represents an alkylene group having 0 to 5 carbon atoms;
m represents an integer of 0 to 200, preferably 20 to 140;
n represents an integer of 0 to 200, preferably 20 to 140;
m+n>10。
according to some embodiments of the present invention, the unsaturated polyether monomer has the structure of formula (2),
Figure BDA0001522363100000031
wherein:
e represents an alkylene group having 2 to 4 carbon atoms;
f represents an alkylene group having 2 to 4 carbon atoms and being different from E;
R4and R5Each independently represents H or an alkyl group having 1 to 5 carbon atoms, preferably a methyl group;
R6represents H or an alkyl group having 1 to 4 carbon atoms;
y represents an alkylene group having 0 to 5 carbon atoms;
p represents an integer of 0 to 200, preferably 20 to 140;
q represents an integer of 0 to 200, preferably 20 to 140;
p+q>10。
preferably, the molecular weight of the unsaturated polyether monomer is 2000-8000, preferably 2000-5000. According to one embodiment, the unsaturated polyether monomer is HPEG-4000.
Preferably, the molecular weight of the unsaturated polyester monomer is 2000-8000, preferably 2000-5000.
According to some embodiments of the invention, the unsaturated carboxylic acid monomer is selected from at least one of Acrylic Acid (AA), methacrylic acid, itaconic acid, fumaric acid, and maleic acid (anhydride).
According to some embodiments of the invention, the functional monomer is at least one of sodium allylsulfonate (A L S), N, N-Dimethylacetoacetamide (DMAA), 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), sodium p-styrenesulfonate (SSS), N, N, N-trimethyl-3- (2-methallylamido) -1-chloropropylamine chloride (MAPTAC, CAS number: 51410-72-1), 3-methacryloxypropyltrimethoxysilane (KH570), and styrene (St).
In a second aspect the invention provides the use of the polycarboxylic acid as a dispersant in mortars or concretes having sulphoaluminate cement as the main cementitious material.
According to some embodiments of the invention, the dispersant does not comprise any other auxiliary agent.
According to some embodiments of the invention, the dispersant is not used simultaneously with the retarder.
According to some embodiments of the present invention, the dispersant is added to the sulphoaluminate cement in an amount of 0.1 to 2.0 wt%, preferably 0.5 to 1.5 wt%.
The invention has the following beneficial technical effects: the polycarboxylic acid provided by the invention is used as a sulphoaluminate cement dispersant, has improved water-reducing dispersion effect, can greatly prolong and effectively control the retention of slump and fluidity under the condition of not doping a retarder, does not bleed water, and meets engineering requirements.
Drawings
FIG. 1 shows the initial dispersion effect at different loadings for SAC1 cement systems at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (HPEG) of 10 and 12.
FIG. 2 shows the initial dispersion effect at various loadings for SAC1 cement systems at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (HPEG) of less than 8 or greater than 50.
FIG. 3 shows the fluidity retention at different loadings (0.002 for 0.2 wt%, 0.005 for 0.5 wt%, 0.01 for 1 wt%, and 0.015 for 1.5 wt%) for molar ratios of unsaturated carboxylic acid (AA) to macromonomer (HPEG) of 10 and 12 for SAC1 cement systems.
FIG. 4 shows the retention of flow at different loadings for SAC1 cement systems at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (HPEG) of less than 8 or greater than 50.
FIG. 5 illustrates the flow retention of a copolymeric functional monomer dispersant on a SAC1 system when the unsaturated carboxylic acid is AA and the macromonomer is HPEG at 0.5 wt%.
FIG. 6 illustrates the flow retention of a copolymeric functional monomer dispersant on a SAC1 system when the unsaturated carboxylic acid is AA and the macromonomer is HPEG at 1.5 wt%.
FIG. 7 illustrates the flow retention of different dispersants for a SAC2 system when the unsaturated carboxylic acid is AA and the macromonomer is HPEG at 1.5 wt% loading.
FIG. 8 illustrates the flow retention of different dispersants to a SAC2 system when the unsaturated carboxylic acid is AA and the macromonomer is HPEG at 2.0 wt% loading.
FIG. 9 illustrates the initial dispersing effect at a loading of 1.5% wt for SAC1 cement systems at molar ratios of unsaturated carboxylic acid (MA) to macromonomer (HPEG) of 10 and 12.
FIG. 10 illustrates the retention of flow at different loadings of unsaturated carboxylic acid (MA) and macromonomer (HPEG) at molar ratios of 10 and 12 for a SAC1 cement system.
FIG. 11 illustrates the initial dispersion effect at different loadings for SAC1 cement systems at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (TPEG) of 10 and 12.
FIG. 12 illustrates the retention of flow at 1.5% wt loading for SAC1 cement systems at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (TPEG) of 10 and 12.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The invention adopts an aqueous solution free radical copolymerization method to synthesize polycarboxylic acid.
The starting materials used in the examples and comparative examples were commercially available and analytically pure, unless otherwise specified.
The unsaturated polyether monomer HPEG is available from Oakk chemical Co., Ltd, Liaoning and has a molecular weight of 4000.
The unsaturated polyester monomer TPEG is available from Oakk chemical Co., Ltd, Liaoning and has a molecular weight of 4000.
The PCE is a common polycarboxylic acid water reducer in the market.
Example 1
Synthesizing PCE 4000-10: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA and 24g of water were mixed uniformly to prepare dropwise A, and 0.204g of 3-MPA, 0.125gVc and 25g of water were mixed uniformly to prepare dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 29.8%.
Example 2
Synthesizing PCE 4000-12: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. Dropwise A was prepared by mixing 10.8gAA and 24g of water, and dropwise B was prepared by mixing 0.241g of 3-MPA, 0.147gVc and 25g of water. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured and found to be 28.9%.
Example 3
And synthesizing the PCE 4000-16: weighing 150g of water and 80g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.77g of H with the mass concentration of 30%2O2Added into a three-neck flask. 23.04gAA and 50g of water were mixed uniformly to prepare dropwise A, and 0.505g of 3-MPA, 0.308gVc and 30g of water were mixed uniformly to prepare dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured and found to be 28.4%.
Example 4
Synthesizing PCE 4000-22: weighing 150g of water and 80g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 1.04g of H with the mass concentration of 30%2O2Added into a three-neck flask. Will be 31.68gAA and 70g of water are mixed uniformly to prepare a dropwise addition A, and 0.684g of 3-MPA, 0.417gVc and 35g of water are mixed uniformly to prepare a dropwise addition B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured and found to be 28.6%.
Example 5
Synthesizing PCE 4000-25: weighing 150g of water and 80g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 1.18g of H with the mass concentration of 30%2O2Added into a three-neck flask. Dropwise A was prepared by mixing 36.00gAA and 75g of water, and dropwise B was prepared by mixing 0.773g of 3-MPA, 0.471gVc and 40g of water. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 29.1%.
Example 6
Synthesizing PCE 4000-30: weighing 150g of water and 80g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 1.41g of H with the mass concentration of 30%2O2Added into a three-neck flask. 43.20gAA and 90g of water are mixed uniformly to prepare a dropwise addition A, and 0.921g of 3-MPA, 0.562gVc and 40g of water are mixed uniformly to prepare a dropwise addition B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured and found to be 28.6%.
Example 7
Synthesizing PCE 4000-50: weighing 82.00g of water and 50.00g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at 150rpm, heating to 65 ℃, and weighing 1.45g of H with the mass concentration of 30%2O2Added into a three-neck flask. Uniformly mixing 45.00gAA and 95.00g of waterDropwise A was prepared, and dropwise B was prepared by uniformly mixing 1.35g of 3-MPA, 0.58gVc and 45.00g of water. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 29.9%.
Example 8
Synthetic PCE4000-10 (TPEG): weighing 82g of water and 50g of TPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA and 24g of water were mixed uniformly to prepare dropwise A, and 0.204g of 3-MPA, 0.125gVc and 25g of water were mixed uniformly to prepare dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.0%.
Example 9
Synthetic PCE4000-12 (TPEG): weighing 82g of water and 50g of TPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. Dropwise A was prepared by mixing 10.8gAA and 24g of water, and dropwise B was prepared by mixing 0.241g of 3-MPA, 0.147gVc and 25g of water. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.1%.
Example 10
Synthesizing PCE 4000-10-DM-2: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA, 2.48g DMAA and 33g water are mixed evenly to prepare the mixture which is drippedA, 0.241g3-MPA, 0.147gVc and 25g water are mixed uniformly to prepare dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.0%.
Example 11
Synthesizing PCE 4000-10-MA-2: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA, 5.55g of MAPTAC and 40g of water are mixed uniformly to prepare a dropwise A, and 0.241g of 3-MPA, 0.147gVc and 25g of water are mixed uniformly to prepare a dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured and found to be 28.1%.
Example 12
Synthesizing PCE 4000-10-AM-2: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA, 5.18g AMPS and 40g water were mixed uniformly to make dropwise A, and 0.241g3-MPA, 0.147gVc and 25g water were mixed uniformly to make dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.0%.
Example 13
Synthesizing PCE 4000-10-VPA-2: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA, 2.7g VPA and 33g water are mixed evenly to prepare the mixtureDropwise adding A, and uniformly mixing 0.241g of 3-MPA, 0.147gVc and 25g of water to prepare dropwise adding B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 29.8%.
Example 14
Synthesizing PCE 4000-10-St-0.5: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.33g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA and 30g of water were mixed uniformly to prepare dropwise A, 0.21g of 3-MPA, 0.130gVc and 25g of water were mixed uniformly to prepare dropwise B, and 0.65gSt was used as dropwise C. Dropwise adding the A, the B and the C into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the A is 3 hours, the dropwise adding time of the B is 3.5 hours, and the dropwise adding time of the C is 3 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 26.7%.
Example 15
Synthesizing PCE 4000-10-Si-0.5: weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.33g of H with the mass concentration of 30%2O2Added into a three-neck flask. 9gAA, 1.55gKH570 and 30g of water are mixed uniformly to prepare a dropwise A, and 0.21g of 3-MPA, 0.130g of Vc and 25g of water are mixed uniformly to prepare a dropwise B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured and found to be 28.8%.
Example 16
Synthetic PCE4000-10 (MA): weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.31g of H with the mass concentration of 30%2O2Is added toIn a neck flask. Dropwise A was prepared by mixing 12.25gMA and 30g of water, and dropwise B was prepared by mixing 0.29g of 3-MPA, 0.12gVc and 25g of water. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.1%.
Example 17
Synthetic PCE4000-12 (MA): weighing 82g of water and 50g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at the rotating speed of 150rpm, heating to 65 ℃, and weighing 0.37g of H with the mass concentration of 30%2O2Added into a three-neck flask. 14.70g of 14.70gMA and 35g of water were mixed homogeneously to give drop A, and 0.34g of 3-MPA, 0.15gVc and 30g of water were mixed homogeneously to give drop B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.1%.
Comparative example 1
Synthesizing PCE 4000-5: weighing 82.00g of water and 50.00g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at 150rpm, heating to 65 ℃, and weighing 0.17g of H with the mass concentration of 30%2O2Added into a three-neck flask. 4.50g of 4.50gAA and 20.00g of water were mixed homogeneously to give drop A, and 0.16g of 3-MPA, 0.07gVc and 25.00g of water were mixed homogeneously to give drop B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 29.9%.
Comparative example 2
Synthesizing PCE 4000-60: weighing 82.00g of water and 50.00g of HPEG, dissolving and mixing uniformly, pouring into a three-neck flask in a constant-temperature water bath, uniformly stirring by a stirring paddle at 150rpm, heating to 65 ℃, and weighing 1.73g of H with the mass concentration of 30%2O2Added into a three-neck flask. Will 5400gAA and 110.00g water were mixed well to make drop A, and 1.62g3-MPA, 0.69gVc and 50.00g water were mixed well to make drop B. Dropwise adding the dropwise A and the dropwise adding the dropwise B into a three-neck flask at a constant speed by a peristaltic pump, wherein the dropwise adding time of the dropwise adding A is 3 hours, and the dropwise adding time of the dropwise adding B is 3.5 hours. After the dropwise addition, the temperature was maintained for 1 hour. After the reaction, the actual solid content was measured, and the measurement result was 30.0%.
TABLE 1
Figure BDA0001522363100000101
Figure BDA0001522363100000111
Performance testing
Two kinds of sulphoaluminate cements, designated by the codes SAC1 and SAC2, were experimentally tested by measuring the initial fluidity and the retention of the neat paste of comparative examples 1-2 and examples 1-17 under the condition of 0.35 water-cement ratio with reference to GBT "test method for homogeneity of concrete admixture", wherein the compositions of SAC1 and SAC2 are shown in the following table. The results are shown in FIGS. 1-12.
Table 2 two sulphoaluminate cements chemical composition (wt.%)
Figure BDA0001522363100000112
FIG. 1 illustrates that for SAC1 cement systems, the initial dispersion effect at different loadings is better than that of the water reducing agent commonly used on the market at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (HPEG) of 10 and 12.
FIG. 2 illustrates that for SAC1 cement systems, the initial dispersion is poor at different loadings when the molar ratio of unsaturated carboxylic acid (AA) to macromonomer (HPEG) is less than 8 or greater than 50.
FIG. 3 shows that for SAC1 cement systems, the unsaturated carboxylic acid (AA) and macromonomer (HPEG) molar ratios were 10 and 12, and the flow retention was superior to that of the commercially available water reducer at different loadings (0.2%, 0.5%, 1.0% and 1.5%).
FIG. 4 illustrates that for a SAC1 cement system, the retention of flow at different loadings is poor when the molar ratio of unsaturated carboxylic acid (AA) to macromonomer (HPEG) is less than 8 or greater than 50.
FIG. 5 shows that the fluidity retention of the copolymerized functional monomer dispersant on the SAC1 system is better than that of the water reducing agent commonly used on the market when the unsaturated carboxylic acid is AA and the macromonomer is HPEG under the content of 0.5 percent.
FIG. 6 shows that the fluidity retention of the copolymerized functional monomer dispersant on the SAC1 system is better than that of the common water reducing agent in the market when the unsaturated carboxylic acid is AA and the macromonomer is HPEG under the doping amount of 1.5 percent.
FIG. 7 shows that the fluidity retention of different dispersants to the SAC2 system is better than that of the common water reducing agent in the market when the unsaturated carboxylic acid is AA and the macromonomer is HPEG at the doping amount of 1.5%.
FIG. 8 shows that the fluidity retention of different dispersants to the SAC2 system is better than that of the common water reducing agent in the market when the unsaturated carboxylic acid is AA and the macromonomer is HPEG at the content of 2.0%.
FIG. 9 shows that for SAC1 cement systems, the initial dispersion effect was better than the commercial water reducer at 1.5% loadings at molar ratios of unsaturated carboxylic acid (MA) to macromonomer (HPEG) of 10 and 12.
FIG. 10 illustrates that for SAC1 cement systems, the flow retention was superior to that of the conventional water reducing agent on the market at different loadings at molar ratios of unsaturated carboxylic acid (MA) to macromonomer (HPEG) of 10 and 12.
FIG. 11 illustrates that for SAC1 cement systems, the initial dispersion effect at different loadings is better than that of the water reducing agent commonly used on the market at molar ratios of unsaturated carboxylic acid (AA) to macromonomer (TPEG) of 10 and 12.
FIG. 12 illustrates that for SAC1 cement systems, the unsaturated carboxylic acid (AA) and macromonomer (TPEG) molar ratios were 10 and 12, and the flow retention was superior to that of the conventional water reducing agent on the market at 1.5% incorporation.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.

Claims (8)

1. The use of polycarboxylic acid as a dispersant in mortar or concrete with sulphoaluminate cement as a main cementing material, wherein the polycarboxylic acid has a comb-shaped molecular structure and is formed by randomly copolymerizing a first monomer A, an unsaturated carboxylic acid monomer B and a functional monomer C, the first monomer is at least one of an unsaturated polyether monomer and an unsaturated polyester monomer, and the molar ratio of the monomers is A: b: c is 1: (22-25): (0 to 5) of a surfactant,
the unsaturated polyester monomer has a structure shown in a formula (1),
Figure FDA0002494413660000011
wherein:
a represents an alkylene group having 2 to 4 carbon atoms;
b represents an alkylene group having 2 to 4 carbon atoms and being different from A;
R1and R2Each independently represents H or an alkyl group having 1 to 5 carbon atoms;
R3represents H or an alkyl group having 1 to 4 carbon atoms;
x represents an alkylene group having 0 to 5 carbon atoms;
m represents an integer of 0 to 200;
n represents an integer of 0 to 200;
m+n>10；
the unsaturated polyether monomer has a structure shown in a formula (2),
Figure FDA0002494413660000012
wherein:
e represents an alkylene group having 2 to 4 carbon atoms;
f represents an alkylene group having 2 to 4 carbon atoms and being different from E;
R4and R5Each independently represents H or an alkyl group having 1 to 5 carbon atoms;
R6represents H or an alkyl group having 1 to 4 carbon atoms;
y represents an alkylene group having 0 to 5 carbon atoms;
p represents an integer of 0 to 200;
q represents an integer of 0 to 200;
p+q>10；
the functional monomer C is at least one of sodium allylsulfonate, N, N-dimethylacetoacetamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium p-styrenesulfonate, N, N, N-trimethyl-3- (2-methallylamido) -1-propylamine chloride, 3-methacryloxypropyltrimethoxysilane and styrene.
2. Use according to claim 1, characterized in that, in formula (1), R1And R2Is methyl; m represents an integer of 20 to 140, and n represents an integer of 20 to 140.
3. Use according to claim 1, characterized in that, in formula (2), R4And R5Is methyl; p represents an integer of 20 to 140, and q represents an integer of 20 to 140.
4. Use according to any one of claims 1 to 3, characterized in that the unsaturated carboxylic acid monomer is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid.
5. Use according to claim 1, characterized in that the dispersant does not comprise any other auxiliary agent.
6. Use according to claim 1 or 5, characterized in that the dispersant is not used simultaneously with the retarder.
7. Use according to claim 1, wherein the dispersant is incorporated in the sulphoaluminate cement in an amount of from 0.1 to 2.0 wt%.
8. Use according to claim 7, wherein the dispersant is incorporated in the sulphoaluminate cement in an amount of from 0.5 to 1.5 wt%.
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