CN114516938A - Non-chlorine double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof - Google Patents
Non-chlorine double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN114516938A CN114516938A CN202210013410.4A CN202210013410A CN114516938A CN 114516938 A CN114516938 A CN 114516938A CN 202210013410 A CN202210013410 A CN 202210013410A CN 114516938 A CN114516938 A CN 114516938A
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent and a preparation method thereof, wherein the water reducing agent is prepared from HPEG, an initiator, carboxylic acid amphoteric monomers, acrylic acid, itaconic acid, a reducing agent, a chain transfer agent, water and liquid caustic soda, and the mass ratio of the HPEG to the initiator to the carboxylic acid amphoteric monomers to the acrylic acid to the itaconic acid to the reducing agent to the chain transfer agent is 100: 0.6-0.8: 0.25-1.5: 8.5-9: 4-7: 0.15-0.23: 0.3-0.5. The water reducer has low sensitivity to soil, the surface of soil particles is provided with negative charges, and the terminal group of a cation side chain in the molecule can be adsorbed on the surface of the soil particles, so that the sensitivity of the water reducer to the soil is reduced, and the water reducer can play a role in resisting the soil; compared with the polycarboxylate superplasticizer containing the quaternary ammonium salt cationic monomer, the polycarboxylate superplasticizer does not contain chloride ions, and can eliminate potential harm brought by corrosion of the chloride ions to reinforced concrete.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylate superplasticizer has the advantages of low mixing amount, high water reducing rate, strong slump retaining property, good cement particle dispersibility, environmental protection and the like, and is widely applied to concrete engineering. At present, most of polycarboxylic acid water reducing agent products on the market belong to anionic polycarboxylic acid water reducing agents, and in practical application, the polycarboxylic acid water reducing agents are often influenced by mixing factors such as cement, gravel aggregate and the like, and are expressed as obvious reduction of the flowing performance and the slump retaining performance, so that the problem of how to further improve the performance of the existing polycarboxylic acid products and simultaneously consider the adaptability and the stability of the products is the subject of research by relevant scholars in the field.
As will be appreciated by those skilled in the art, the mineral content of the cement is relatively complex, i.e., having a negative Zeta potential such as tricalcium silicate (C)3S) and dicalcium silicate (C)2S), also mineral components with a positive Zeta potential, such as tricalcium aluminate (C)3A) And tetracalcium aluminoferrite (C)4AF). Conventional anionic PCEs adsorb predominantly on C which exhibits a positive charge3A、C4AF, the cement can easily reach saturated adsorption. Meanwhile, the PCEs molecules are easily affected by calcium ions, form a coiled molecular conformation, affect the adsorption rate, and are not beneficial to the dispersion of cement particles. Cationic groups are added into an anionic polycarboxylic acid system to synthesize the amphoteric polycarboxylic acid water reducing agent SPCEs, theoretically, the extended conformation of the copolymer can be kept, and the introduced cationic groups are added to the main mineral C of the cement3S and C2S can improve the water reducing agent adsorption capacity of the water reducing agent in concrete, thereby reducing the admixture dosage and being beneficial to reducing the cost.
The main cationic monomers reported in the literature for synthesizing the amphoteric polycarboxylate superplasticizer are monomers containing chloride ions, such as methacryloyloxyethyl trimethyl ammonium chloride (DMC), acryloyloxyethyl trimethyl ammonium chloride (DAC), dimethyl diallyl ammonium chloride (DMDAAC), and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent.
The invention also aims to provide a preparation method of the non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent.
The technical scheme of the invention is as follows:
a non-chlorine double-comb type amphoteric polycarboxylate superplasticizer is prepared from HPEG, an initiator, carboxylic acid amphoteric monomers, acrylic acid, itaconic acid, a reducing agent, a chain transfer agent, water and liquid alkali, wherein,
HPEG, initiator, carboxylic acid amphoteric monomer, acrylic acid, itaconic acid, reducing agent and chain transfer agent with the mass ratio of 100: 0.6-0.8: 0.25-1.5: 8.5-9: 4-7: 0.15-0.23: 0.3-0.5;
the carboxylic acid amphoteric monomer is prepared by performing quaternization reaction on dimethylaminoethyl methacrylate, sodium chloroacetate, water, a polymerization inhibitor and liquid alkali at the temperature of 55-65 ℃,
the mol ratio of the dimethylaminoethyl methacrylate to the sodium chloroacetate is 1: 1-1.2,
the polymerization inhibitor consists of hydroquinone and phenothiazine in the mass ratio of 0.8-1.2 to 0.8-1.2.
In a preferred embodiment of the invention, the molar ratio of dimethylaminoethyl methacrylate to sodium chloroacetate is 1: 1.1.
In a preferred embodiment of the present invention, the polymerization inhibitor consists of hydroquinone and phenothiazine in a mass ratio of 1: 1.
In a preferred embodiment of the invention, the HPEG has the formula CH2＝CHCH2O(CH2CH2O)nH with a number average molecular weight of 2300-3。
In a preferred embodiment of the present invention, the initiator is ammonium persulfate and/or potassium persulfate.
In a preferred embodiment of the present invention, the reducing agent is at least one of sodium bisulfite, vitamin C, ferrous sulfate, and glucose.
In a preferred embodiment of the present invention, the chain transfer agent is at least one of thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and mercaptoethanol.
In a preferred embodiment of the invention, the solute of the liquid alkali is potassium hydroxide and/or sodium hydroxide.
In a preferred embodiment of the present invention, the reducing agent is vitamin C and the chain transfer agent is mercaptoethanol.
The preparation method of the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer has the following synthetic reaction formula:
wherein R is carboxylic acid amphoteric monomer.
The method specifically comprises the following steps:
(1) adding HPEG and part of deionized water into a reaction kettle, and heating the reaction kettle to 40-45 ℃ under continuous stirring;
(2) after the reaction kettle is stable, continuously stirring, and simultaneously adding an initiator into the material obtained in the step (1) at one time;
(3) keeping the temperature of the reaction kettle at 40-45 ℃, respectively dropwise adding a first mixed solution consisting of acrylic acid, itaconic acid, carboxylic acid amphoteric monomers and part of deionized water and a second mixed solution consisting of a reducing agent, a chain transfer agent and the rest of deionized water into the material obtained in the step (2), controlling the dropwise adding to be finished within 1-4h, and then keeping the temperature at 40-45 ℃ for reaction for 0.8-1.2 h;
(5) and (4) adding liquid caustic soda into the material obtained in the step (4) to obtain the non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent.
The beneficial effects of the invention are:
1. compared with the traditional anionic polycarboxylate superplasticizer, the invention introduces cations into the molecular structure, theoretically can keep the extended conformation of the copolymer, and the introduced cationic groups can increase the main mineral C of the cement through increasing3S and C2S can improve the water reducing agent adsorption capacity in the concrete; meanwhile, partial double carboxyl groups replace single carboxyl groups, and since itaconic acid contains one more carboxyl group than acrylic acid, the itaconic acid has stronger adsorption and dispersion effects than acrylic acid single carboxyl groups, and simultaneously, the steric hindrance of the polycarboxylic acid water reducing agent is correspondingly improvedThereby further improving the dispersion of cement particles.
2. The water reducer has low sensitivity to soil, the surface of soil particles is provided with negative charges, and the cation side chain end groups in the molecules can be adsorbed on the surface of the soil particles, so that the sensitivity of the water reducer to the soil is reduced, and the water reducer can play a role in resisting the soil.
3. Compared with the polycarboxylate superplasticizer containing the quaternary ammonium salt cationic monomer, the polycarboxylate superplasticizer does not contain chloride ions, and can eliminate potential harm brought by corrosion of the chloride ions to reinforced concrete.
4. The preparation method of the invention adopts normal pressure production, has low equipment requirement and convenient operation, and is beneficial to industrial production.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The reaction formula for the preparation of carboxylic acid-based amphoteric monomers in the following examples is as follows:
the method specifically comprises the following steps: 15.7g (0.1mol) of dimethylaminoethyl methacrylate, 100mL of water and 0.1g of polymerization inhibitor (composed of hydroquinone and phenothiazine in a mass ratio of 1: 1) are added into the reaction kettle. The temperature of the reaction kettle was raised to 60 + -3 deg.C with constant stirring. After the temperature is stable, slowly dropwise adding 12.8g (0.11mol) of sodium chloroacetate solution, controlling the dropwise adding to be finished within 1h, then adding liquid alkali, adjusting the pH to be 7-8, and reacting for 6 h. After the reaction is finished, heating to evaporate excessive water to obtain yellow sticky matter containing a small amount of white crystals, adding anhydrous methanol to dissolve a crude product, filtering out precipitated NaCl crystals and unreacted sodium chloroacetate, distilling to remove a methanol solution, washing by using an organic solvent, and drying to obtain the carboxylic acid amphoteric monomer.
The structural formula of HPEG in the following examples is CH2＝CHCH2O(CH2CH2O)nH with a number average molecular weight of 2300-3。
Example 1
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA, 5g of itaconic acid, 0.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc and 0.5g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-1.
Example 2
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 4g of itaconic acid, 0.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc and 0.5g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-2.
Example 3
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution composed of 9gAA, 6g of itaconic acid, 0.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution composed of 0.2gVc and 0.5g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-3.
Example 4
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 7g of itaconic acid, 0.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc and 0.5g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-4.
Example 5
100g of HPEG and an appropriate amount of deionized water were added to the kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 6g of itaconic acid, 0.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-5.
Example 6
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 6g of itaconic acid, 0.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc and 0.3g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-6.
Example 7
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution composed of 9gAA, 6g of itaconic acid, 0.25g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution composed of 0.2gVc and 0.4g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-7.
Example 8
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 6g of itaconic acid, 0.75g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-8.
Example 9
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The reactor temperature was raised to 40 + -3 deg.C with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 6g of itaconic acid, 1g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-9.
Example 10
100g of HPEG and an appropriate amount of deionized water were added to the reaction kettle. The temperature of the reactor was raised to 40. + -. 3 ℃ with constant stirring. After the reaction kettle is stabilized at 40 +/-3 ℃, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40 +/-3 ℃, a first mixed solution consisting of 9gAA g of itaconic acid, 6g of itaconic acid, 1.5g of carboxylic acid amphoteric monomer and deionized water and a second mixed solution consisting of 0.2gVc g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After dripping, the mixture is kept at 40 +/-3 ℃ for 1 h. And finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, and adjusting the final pH to 5.5-6 to obtain the non-chlorine double-comb type amphoteric polycarboxylate superplasticizer SPC-10.
Comparative example 1
100g of HPEG and deionized water were added to the kettle. The temperature of the reaction kettle was raised to 40-45 ℃ with constant stirring. After the reaction kettle is stabilized at the set temperature, 0.7g of ammonium persulfate is added at one time under continuous stirring. Then, the reaction kettle is kept at the temperature of 40-45 ℃, a first mixed solution consisting of 12gAA and deionized water and a second mixed solution consisting of 0.2gVc and 0.5g of mercaptoethanol are respectively dripped, and the dripping is finished within 3 hours. After the dripping is finished, the temperature is kept for 1h at 40-45 ℃. Finally, adding liquid caustic soda (30 wt% of potassium hydroxide or sodium hydroxide) into the reaction kettle, adjusting the final pH to 5.5-6 to obtain a polycarboxylate superplasticizer sample, and recording the sample as a comparative sample.
Fluidity test of cement paste
For the non-chlorine double-comb type amphoteric polycarboxylate water reducer prepared in the above examples 1 to 10 and the anionic polycarboxylate water reducer obtained in the comparative example, the neat paste fluidity of cement was tested according to GB/T8077-2000 "concrete admixture homogeneity test method", the water-cement ratio (W/C) was 0.29, the folded solid content of the water reducer was 0.2%, 1% of montmorillonite was additionally added, the initial and flow degrees after 60min and 120min were measured, and the test results are shown in table 1 below:
TABLE 1 Cement paste fluidity Retention test results
As can be seen from the data in Table 1, when the water-cement ratio is 0.29, the folding and fixing content of the water reducing agent is 0.2%, and the mud content is 1%, compared with the anionic polycarboxylate water reducing agent in the comparative example, the synthesized non-chlorine double-comb type amphoteric polycarboxylate water reducing agent has the advantages that the initial fluidity of cement paste is well improved, the slow release performance is good, and the fluidity loss in 60min and 120min is excellent.
Concrete test
Proper amounts of retarder, defoamer, air entraining agent, water and the like are added into the polycarboxylate superplasticizer SPC-5, SPC-6, SPC-7, SPC-8, SPC-9 and the comparison sample to prepare concrete admixtures P-1, P-2, P-3, P-4, P-5 and comparison. Then, the concrete in the table 2 is matched and trial-prepared, the mud content of the selected machine-made sand is 4, 5%, and the trial-prepared result is shown in the table 3.
TABLE 2 concrete mix proportions
TABLE 3 concrete test results for various embodiments
Comparative 1 is the 1.2% incorporation of the cured product of comparative example 1, and comparative 2 is the 1.35% incorporation of the cured product of comparative example 1.
As can be seen from the test results in Table 3, the nonchlorine amphoteric polycarboxylate superplasticizer provided by the invention shows good dispersing performance and slump retaining performance in concrete tests, particularly under the condition of high mud content. Meanwhile, the workability of the concrete is improved to a certain extent, and the mechanical property is not affected; the invention has the advantages of appropriate reaction conditions, simple process, high efficiency, low cost, suitability for large-scale industrial production methods, excellent water reducing agent performance, good dispersion performance and mud and slump resistance.
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 (10)
1. A non-chlorine double-comb type amphoteric polycarboxylate superplasticizer is characterized in that: is prepared from HPEG, an initiator, carboxylic acid amphoteric monomer, acrylic acid, itaconic acid, a reducing agent, a chain transfer agent, water and liquid alkali,
HPEG, initiator, carboxylic acid amphoteric monomer, acrylic acid, itaconic acid, reducing agent and chain transfer agent with the mass ratio of 100: 0.6-0.8: 0.25-1.5: 8.5-9: 4-7: 0.15-0.23: 0.3-0.5;
the carboxylic acid amphoteric monomer is prepared by performing quaternization reaction on dimethylaminoethyl methacrylate, sodium chloroacetate, water, a polymerization inhibitor and liquid alkali at the temperature of 55-65 ℃,
the mol ratio of the dimethylaminoethyl methacrylate to the sodium chloroacetate is 1: 1-1.2,
the polymerization inhibitor consists of hydroquinone and phenothiazine in the mass ratio of 0.8-1.2 to 0.8-1.2.
2. The non-chlorine double-comb type amphoteric polycarboxylate superplasticizer according to claim 1, wherein: the molar ratio of the dimethylaminoethyl methacrylate to the sodium chloroacetate is 1: 1.1.
3. The non-chlorine double-comb type amphoteric polycarboxylate superplasticizer according to claim 1, wherein: the polymerization inhibitor consists of hydroquinone and phenothiazine in a mass ratio of 1: 1.
4. The non-chlorine double comb type amphoteric polycarboxylic acid water reducing agent according to any one of claims 1 to 3, characterized in that: the structural formula of the HPEG is CH2＝CHCH2O(CH2CH2O)nH with the number average molecular weight of 2300-2500g/cm3。
5. The non-chlorine double comb type amphoteric polycarboxylic acid water reducing agent according to any one of claims 1 to 3, characterized in that: the initiator is ammonium persulfate and/or potassium persulfate.
6. The non-chlorine double comb type amphoteric polycarboxylic acid water reducing agent according to any one of claims 1 to 3, characterized in that: the reducing agent is at least one of sodium bisulfite, vitamin C, ferrous sulfate and glucose.
7. The non-chlorine double comb type amphoteric polycarboxylic acid water reducing agent of any one of claims 1 to 3, characterized in that: the chain transfer agent is at least one of thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid and mercaptoethanol.
8. The non-chlorine double comb type amphoteric polycarboxylic acid water reducing agent according to any one of claims 1 to 3, characterized in that: the solute of the liquid alkali is potassium hydroxide and/or sodium hydroxide.
9. The non-chlorine double comb type amphoteric polycarboxylic acid water reducing agent according to any one of claims 1 to 3, characterized in that: the reducing agent is vitamin C, and the chain transfer agent is mercaptoethanol.
10. The method for preparing the non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
(1) adding HPEG and part of deionized water into a reaction kettle, and heating the reaction kettle to 40-45 ℃ under continuous stirring;
(2) after the reaction kettle is stable, continuously stirring, and simultaneously adding an initiator into the material obtained in the step (1) at one time;
(3) keeping the temperature of the reaction kettle at 40-45 ℃, respectively dropwise adding a first mixed solution consisting of acrylic acid, itaconic acid, carboxylic acid amphoteric monomers and part of deionized water and a second mixed solution consisting of a reducing agent, a chain transfer agent and the rest of deionized water into the material obtained in the step (2), controlling the dropwise adding to be finished within 1-4h, and then keeping the temperature at 40-45 ℃ for reaction for 0.8-1.2 h;
(5) and (4) adding liquid caustic soda into the material obtained in the step (4) to obtain the non-chlorine double-comb type amphoteric polycarboxylic acid water reducing agent.
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| CN115109198A (en) * | 2022-05-24 | 2022-09-27 | 厦门路桥翔通建材科技有限公司 | High-workability double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof |
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| CN115109198A (en) * | 2022-05-24 | 2022-09-27 | 厦门路桥翔通建材科技有限公司 | High-workability double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof |
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