CN110734244B - Anti-mud polycarboxylate superplasticizer and preparation method thereof - Google Patents
Anti-mud polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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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
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
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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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Abstract
The invention discloses an anti-mud polycarboxylic acid water reducer and a preparation method thereof, wherein the anti-mud polycarboxylic acid water reducer comprises a terminal group modified polycarboxylic acid water reducer and a polyamine polyether modified water reducer; the end group modified polycarboxylate superplasticizer is prepared by reacting the following raw materials: bottom materials, A liquid, B liquid, neutralizing liquid and water; the raw materials of the polyamine polyether modified water reducing agent comprise the following components in parts by weight: 240 parts of polyethylene glycol monomethyl ether 220-15 parts, 12-15 parts of thionyl chloride, 30-33 parts of polyethylene polyamine, 75-85 parts of phosphorous acid, 75-80 parts of formaldehyde and 22-25 parts of neutralizing solution. The mud-resistant polycarboxylate superplasticizer provided by the invention has excellent dispersing effect and good mud slump loss resistant effect, and can reduce the using amount of the polycarboxylate superplasticizer by 10-20% for concrete with high mud content of sand and stone; and simultaneously, the workability of the concrete can be improved and the compressive strength of the concrete can be improved.
Description
Technical Field
The invention relates to the technical field of concrete admixture synthesis, in particular to a mud-resistant polycarboxylic acid water reducing agent and a preparation method thereof.
Background
Sandstone is used as a basic material with the largest consumption in the engineering construction process, and is often used as a concrete raw material to be widely applied to the fields of house construction and capital construction. Along with the increase of construction strength in recent years, the demand for gravels is continuously increased, but because the country gradually controls the exploitation of the gravels and protects the ecological environment, high-quality gravels aggregate resources are sharply reduced, the mud content of the aggregates is continuously increased, and a plurality of stirring stations directly use the machine-made sand to replace river sand and river sand. Because the common polycarboxylic acid water reducing agent is sensitive to the mud content of the aggregate, a series of problems of poor cement adaptability, poor concrete fluidity, quick slump loss and the like occur, and the performance and the using effect of the polycarboxylic acid water reducing agent are greatly reduced.
At present, the problem of high mud content of raw materials is solved by adding substances which enable mud to be preferentially adsorbed, such as a mud inhibitor, a surfactant and the like, but the use cost is high, and the problem that the high mud content affects the compressive strength of concrete cannot be solved, so that further research on the mud-resistant polycarboxylic acid water reducing agent is needed.
Patent CN108047396A discloses a polycation anti-mud type polycarboxylate water reducer, which is prepared by introducing polycation monomers into a polycarboxylate molecular structure, hydrolyzing and releasing under an alkaline condition to change the physicochemical property of clay minerals and reduce the consumption of the mineral surface and a crystal layer on the water reducer, thereby playing a role in resisting mud. However, the product has complicated synthesis steps, complicated production equipment, introduction of chloride ions into the product and low water reducing rate.
Patent CN103467670B discloses an anti-mud polycarboxylic acid water reducing agent, which can avoid the adsorption of mud content on the water reducing agent and solve the problem of low concrete strength by introducing quaternary ammonium salt groups and aminotrimethylene phosphoric acid into the molecular structure of polycarboxylic acid. However, the method is not suitable for industrialization, and the water reducing capacity of the product is poor.
Patent CN103803846B discloses an anti-mud polycarboxylic acid water reducing agent, which is high in water reducing rate and good in adaptability by introducing silane monomers into a polycarboxylic acid molecular structure, but the method needs to use a large amount of expensive silane monomers as raw materials, is high in cost and is low in market application.
The mud-resistant polycarboxylic acid water reducing agents are synthesized by different methods, and have certain dispersing performance and effective mud resistance, but the slump loss of concrete is high due to the fact that the slump loss of the concrete is general and the concrete with high slump loss time requirement. Therefore, research and development of the mud-resistant polycarboxylate superplasticizer which has excellent water reducing performance and a certain slump retaining function has high application value.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a mud-resistant polycarboxylic acid water reducing agent and a preparation method thereof, aiming at concrete with high sand and stone mud content, so as to solve the technical problems that the water reducing agent in the prior art has general mud resistance and slump loss resistance, and concrete with high slump loss requirement and high slump loss speed.
To achieve the above technical object, the present invention provides a first solution: an anti-mud polycarboxylate superplasticizer comprises a polycarboxylate superplasticizer with modified terminal groups and a polyamine polyether modified superplasticizer; wherein,
the end group modified polycarboxylic acid water reducing agent is prepared by the following raw materials: bottom materials, A liquid, B liquid, neutralizing liquid and water;
the raw materials of the polyamine polyether modified water reducing agent comprise the following components in parts by weight: 240 parts of polyethylene glycol monomethyl ether 220-15 parts, 12-15 parts of thionyl chloride, 30-33 parts of polyethylene polyamine, 75-85 parts of phosphorous acid, 75-80 parts of formaldehyde and 22-25 parts of neutralizing solution.
The present invention provides a second solution: a preparation method of a mud-resistant polycarboxylate superplasticizer comprises the following steps: preparing a modified polyether monomer, preparing a terminal group modified polycarboxylic acid water reducing agent, preparing a polyamine polyether modified water reducing agent and preparing an anti-mud polycarboxylic acid water reducing agent; wherein,
the preparation of the modified polyether monomer comprises the following steps: mixing a polyether macromonomer and an anhydride small monomer, adding a catalyst, and reacting to obtain the modified polyether monomer;
the preparation of the end group modified polycarboxylate superplasticizer comprises the following steps: mixing and stirring the modified polyether monomer, unsaturated polyoxyethylene ether, unsaturated amide and water until the modified polyether monomer, the unsaturated polyoxyethylene ether, the unsaturated amide and the water are dissolved, and adding an initiator to obtain a base material; dropwise adding the solution A and the solution B into the base material, reacting after the dropwise adding is finished, and adding a neutralizing solution to obtain the end group modified polycarboxylic acid water reducer;
the preparation method of the polyamine polyether modified water reducing agent comprises the following steps: adding thionyl chloride into polyethylene glycol monomethyl ether, adding ethylene polyamine after the reaction is finished, and continuing the reaction to obtain polyamine polyether; continuously adding phosphorous acid and formaldehyde to carry out Mannich reaction, and adding a neutralization solution after the reaction is finished to obtain a polyamine polyether modified water reducing agent containing a phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylate superplasticizer and the polyamine polyether modified polycarboxylate superplasticizer according to a certain proportion to obtain the anti-mud polycarboxylate superplasticizer.
The preparation method of the anti-mud polycarboxylate superplasticizer is used for preparing the anti-mud polycarboxylate superplasticizer.
Compared with the prior art, the invention has the beneficial effects that:
the mud-resistant polycarboxylate superplasticizer provided by the invention has excellent dispersing effect and good mud slump loss resistant effect, and can reduce the using amount of the polycarboxylate superplasticizer by 10-20% for concrete with high mud content of sand and stone;
the mud-resistant polycarboxylate superplasticizer provided by the invention can improve the workability of concrete and improve the compressive strength of the concrete.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
For the first solution, the invention provides an anti-mud polycarboxylic acid water reducer, which comprises a terminal group modified polycarboxylic acid water reducer and a polyamine polyether modified water reducer; wherein,
the end group modified polycarboxylic acid water reducing agent is prepared by the following raw materials: bottom materials, A liquid, B liquid, neutralizing liquid and water;
the polyamine polyether modified water reducing agent is prepared by reacting the following raw materials in parts by weight: 240 parts of polyethylene glycol monomethyl ether (MPEG) 220-15 parts of thionyl chloride, 30-33 parts of polyethylene polyamine, 75-85 parts of phosphorous acid, 75-80 parts of formaldehyde, 22-25 parts of neutralizing solution and water. Wherein the mass fraction of formaldehyde is 37%.
The mud-resistant polycarboxylate superplasticizer provided by the invention is prepared by preparing a polycarboxylate superplasticizer with modified terminal groups and a polyamine polyether modified superplasticizer respectively, and then compounding the prepared polycarboxylate superplasticizer with modified terminal groups and the polyamine polyether modified superplasticizer in proportion.
The polycarboxylic acid water reducing agent modified by the end group weakens the intercalation adsorption effect in soil, so that the anti-soil effect is generated, and the tail end of the polycarboxylic acid water reducing agent modified by the end group is an ester group, so that the ester group can be hydrolyzed to slowly release carboxyl in the cement alkaline environment, so that a certain slump retaining effect is achieved; phosphate radicals are introduced into the molecular structure of the polyamine polyether modified water reducer, and the special steric hindrance of the synthesized single-chain structure modified water reducer can effectively weaken the adsorption between water reducer molecules and clay layers, and has a certain mud resistance effect; the two water reducing agents with the anti-mud effect are compounded according to a certain proportion, and on the premise of ensuring the water reducing effect, the anti-mud effect of the water reducing agent is further improved due to the intermolecular synergistic effect.
In the invention, the bottom material is prepared by the following raw materials in parts by weight: 10-15 parts of modified polyether monomer, 360 parts of unsaturated polyoxyethylene ether 320-containing organic silicon, 4-8 parts of unsaturated amide, 240 parts of water 210-containing organic silicon and 0.4-0.6 part of initiator.
In the invention, the solution A is prepared by the following raw materials in parts by weight: 27-39 parts of unsaturated carboxylic acid, 5-8 parts of unsaturated carboxylic ester and 30-35 parts of water.
In the invention, the liquid B is prepared by the following raw materials in parts by weight: 0.3-0.5 part of reducing agent, 1.6-2.0 parts of chain transfer agent and 30-35 parts of water.
In the invention, the neutralization solution is one or two of sodium hydroxide or potassium hydroxide aqueous solution. Preferably, the mass fraction is 32% sodium hydroxide solution.
In the invention, the modified polyether monomer is prepared by the following raw materials in parts by weight: 300 portions of polyether macromonomer, 10 portions to 15 portions of anhydride small monomer, 0.25 portion to 0.35 portion of catalyst and water; wherein the molar ratio of the polyether macromonomer to the anhydride small monomer is 1: (1-1.5). The modified monomer is synthesized by the esterification reaction of the active hydroxyl at the tail end of the polyether monomer chain segment and the dicarboxyl functional group compound, so that the size of the polyether chain segment is increased, and the mud resistance effect is improved; meanwhile, the tail end of the modified monomer is an ester group, and the ester group is hydrolyzed in the alkaline environment of cement to slowly release carboxyl, so that a certain slump retaining effect is achieved.
In the present invention, the unsaturated polyoxyethylene ether is 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG), and the number average molecular weight of the 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG) is 3000.
In the present invention, the unsaturated amide is acrylamide.
In the invention, the initiator is one or more of hydrogen peroxide, sodium persulfate and potassium persulfate.
In the present invention, the unsaturated carboxylic acid is acrylic acid.
In the present invention, the unsaturated carboxylic acid ester is one or both of hydroxyethyl acrylate and ethyl acrylate.
In the invention, the reducing agent is one or more of sodium sulfite, sodium bisulfite and vitamin C.
In the invention, the chain transfer agent is one or more of thioglycolic acid, mercaptopropionic acid or mercaptoethanol.
In the invention, the polyether macromonomer is one or more of methallyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether and ethylene glycol monovinyl polyethylene glycol ether, and the number average molecular weight of the polyether macromonomer is 2400-4000.
In the present invention, the acid anhydride small monomer is one or more of maleic anhydride, phthalic anhydride, and succinic anhydride.
In the invention, the catalyst is one or more of azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride and azobiscyanovaleric acid.
In the present invention, the number average molecular weight of the above-mentioned polyethylene glycol monomethyl ether (MPEG) is 1000-2000.
In the invention, the polyethylene polyamine is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine.
In the present invention, the weight ratio of the terminal group-modified polycarboxylic acid water-reducing agent to the polyamine polyether-modified water-reducing agent is (1-3: 1), preferably 2.3: 1. Within the proportion range, the obtained mud-resistant polycarboxylic acid water reducing agent has the best performance.
For the second solution of the invention, the invention provides a preparation method of the anti-mud polycarboxylic acid water reducing agent, which comprises the following steps:
preparing a modified polyether monomer: placing a polyether macromonomer and an anhydride small monomer in a dry three-neck flask, adding a catalyst, introducing nitrogen, continuously stirring, heating to 50-70 ℃, continuously reacting for 3-4 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: sequentially adding the modified polyether monomer, unsaturated polyoxyethylene ether, unsaturated amide and water into a three-neck flask, continuously stirring until the modified polyether monomer, the unsaturated polyoxyethylene ether, the unsaturated amide and the water are completely dissolved, and adding an initiator to obtain a bottom material; dissolving unsaturated carboxylic acid and unsaturated carboxylic ester in water to obtain solution A; dissolving a reducing agent and a chain transfer agent in water to obtain a solution B, and dropwise adding the solution A and the solution B when the temperature of the base material in the flask rises to 25 ℃; wherein the liquid A is dripped out after 3h, the liquid B is dripped out after 3.5h, the temperature is kept for 1h at 36-38 ℃ after the dripping is finished, the neutralization solution is added to adjust the pH value to 7, and water is added to dilute the product to 40 percent of solid content, so as to obtain the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into a lye tank, cooling after reacting for 1.5h, adding polyethylene polyamine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; continuously adding phosphorous acid into the three-neck flask, stirring uniformly, heating to 100 ℃, slowly adding formaldehyde, carrying out Mannich reaction, keeping the reaction for 2-3h, adding the neutralization solution into the three-neck flask, and supplementing water until the mass concentration is 40% to obtain the polyamine polyether modified water reducing agent containing the phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylate superplasticizer and the polyamine polyether modified polycarboxylate superplasticizer according to a certain proportion to obtain the mud-resistant polycarboxylate superplasticizer.
The preparation method of the mud-resistant polycarboxylate superplasticizer is used for preparing the mud-resistant polycarboxylate superplasticizer in the first solution.
In the invention, the preparation sequence of the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer is not limited in sequence.
Example 1
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: putting 330g of methallyl alcohol polyoxyethylene ether and 12.5g of succinic anhydride into a dry three-neck flask, adding 0.30g of azodiisobutyl amidine hydrochloride, introducing nitrogen and continuously stirring, heating to 60 ℃, continuously reacting for 3.5 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: adding 340g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG), 12.5g of the modified polyether monomer and 6g of acrylamide into a three-neck flask in sequence, adding 225g of water, continuously stirring until the mixture is dissolved, and adding 0.5g of sodium persulfate to obtain a base material; dissolving 33g of acrylic acid and 6g of hydroxyethyl acrylate in 33g of water, and marking as solution A; dissolving 0.4g of vitamin C and 1.8g of mercaptopropionic acid in 35g of water, and marking as a solution B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 20g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 230g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 13.5g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into a lye tank, reacting for 1.5h, cooling, adding 31.5g of tetraethylenepentamine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; continuously adding 80g of phosphorous acid into a three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 77.5g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 23.5g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40%, thereby obtaining the polyamine polyether modified water reducer containing the phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the proportion of 1:1 to obtain the anti-mud polycarboxylic acid water reducer.
Example 2
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: placing 300g of isopentenol polyoxyethylene ether and 10g of maleic anhydride into a dry three-neck flask, adding 0.25g of azobisisobutyrimidazoline hydrochloride, introducing nitrogen and continuously stirring, heating to 50 ℃, continuously reacting for 3 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: adding 320g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG), 10g of the modified polyether monomer and 4g of acrylamide into a three-neck flask in sequence, adding 210g of water, continuously stirring until the modified polyether monomer and the acrylamide are completely dissolved, and adding 0.4g of hydrogen peroxide to obtain a base material; 27g of acrylic acid and 5g of hydroxyethyl acrylate are dissolved in 33g of water and are marked as solution A; dissolving 0.3g of vitamin C and 1.6g of mercaptopropionic acid in 35g of water, and marking as a solution B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 15g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 220g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 12g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into a lye tank, cooling after reacting for 1.5h, adding 30g of triethylene tetramine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; continuously adding 75g of phosphorous acid into a three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 75g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 22g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40% to obtain the polyamine polyether modified water reducer containing the phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the proportion of 1.5:1 to obtain the anti-mud polycarboxylic acid water reducer.
Example 3
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: placing 360g of ethoxy vinyl polyglycol ether and 15g of phthalic anhydride in a dry three-neck flask, adding 0.35g of azodicyano valeric acid, introducing nitrogen and continuously stirring, heating to 70 ℃, continuously reacting for 4 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: sequentially adding 360g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG), 15g of the modified polyether monomer and 8g of acrylamide into a three-neck flask, adding 240g of water, continuously stirring until the components are completely dissolved, and adding 0.6g of potassium persulfate to obtain a bottom material; dissolving 39g of acrylic acid and 8g of hydroxyethyl acrylate in 33g of water, and marking as solution A; dissolving 0.5g of vitamin C and 2.0g of mercaptopropionic acid in 35g of water, and marking as a solution B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 25g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 240g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 15g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into a lye tank, cooling after reacting for 1.5h, adding 33g of pentaethylenehexamine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine; continuously adding 85g of phosphorous acid into a three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 80g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 25g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40%, thereby obtaining the polyamine polyether modified water reducer containing the phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the ratio of 2.3:1 to obtain the anti-mud polycarboxylic acid water reducer.
Example 4
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: placing 320g of hydroxybutyl vinyl polyglycol ether and 12g of phthalic anhydride in a dry three-neck flask, adding 0.30g of azodiisobutyl amidine hydrochloride, introducing nitrogen and continuously stirring, heating to 65 ℃, continuously reacting for 3 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: sequentially adding 330g of 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG), 12g of the modified polyether monomer and 6g of acrylamide into a three-neck flask, adding 220g of water, continuously stirring until the modified polyether monomer is completely dissolved, and adding 0.55g of hydrogen peroxide to obtain a base material; dissolving 30g of acrylic acid and 5g of hydroxyethyl acrylate in 33g of water, and marking as solution A; dissolving 0.45 part of vitamin C and 1.6 parts of mercaptopropionic acid in 35g of water, and marking as a solution B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 18g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 230g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 13g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into a lye tank, cooling after reacting for 1.5h, adding 31g of hexaethyleneheptamine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; continuously adding 78g of phosphorous acid into a three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 76g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 23g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40% to obtain the polyamine polyether modified water reducer containing the phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the ratio of 2.3:1 to obtain the anti-mud polycarboxylic acid water reducer.
Example 5
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: putting 340g of isopentenol polyoxyethylene ether and 14g of succinic anhydride into a dry three-neck flask, adding 0.34g of azobisisobutyrimidazoline hydrochloride, introducing nitrogen and continuously stirring, heating to 55 ℃, continuously reacting for 4 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: adding 350g of 4-hydroxybutyl vinyl polyoxyethylene ether VPEG, 13g of the modified polyether monomer and 6g of acrylamide into a three-neck flask in sequence, adding 230g of water, continuously stirring until the components are completely dissolved, and adding 0.55g of sodium persulfate to obtain a bottom material; dissolving 36g of acrylic acid and 7g of hydroxyethyl acrylate in 33g of water, and marking as solution A; dissolving 0.45g of vitamin C and 1.9g of mercaptopropionic acid in 35g of water, and marking as liquid B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 24g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 235g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 14g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into an alkali liquor tank, reacting for 1.5h, cooling, adding 32g of diethylenetriamine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; and continuously adding 82g of phosphorous acid into the three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 78g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 24g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40% to obtain the polyamine polyether modified water reducer containing the phosphoric acid structure.
Preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylate superplasticizer and the polyamine polyether modified polycarboxylate superplasticizer according to the proportion of 1.5:1 to obtain the anti-mud polycarboxylate superplasticizer.
Example 6
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: placing 350g of hydroxybutyl vinyl polyglycol ether and 15g of phthalic anhydride in a dry three-neck flask, adding 0.32g of azodicyano valeric acid, introducing nitrogen and continuously stirring, heating to 65 ℃, continuously reacting for 3 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: adding 350g of 4-hydroxybutyl vinyl polyoxyethylene ether VPEG, 13g of the modified polyether monomer and 7g of acrylamide into a three-neck flask in sequence, adding 235g of water, continuously stirring until the components are completely dissolved, and adding 0.48g of potassium persulfate to obtain a bottom material; 35g of acrylic acid and 6g of hydroxyethyl acrylate are dissolved in 33g of water and are marked as solution A; dissolving 0.36g of vitamin C and 1.7g of mercaptopropionic acid in 35g of water, and marking as liquid B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 21g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: putting 225g of polyethylene glycol monomethyl ether (MPEG) into a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 13g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into an alkali liquor tank, cooling after reacting for 1.5h, adding 33g of triethylene tetramine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; and continuously adding 78g of phosphorous acid into the three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 78g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 24g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40%, thereby obtaining the polyamine polyether modified water reducer containing the phosphoric acid structure.
Preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the ratio of 2.3:1 to obtain the anti-mud polycarboxylic acid water reducer.
Example 7
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: putting 340g of methallyl alcohol polyoxyethylene ether and 11g of maleic anhydride into a dry three-neck flask, adding 0.30g of azobisisobutyrimidazoline hydrochloride, introducing nitrogen and continuously stirring, heating to 60 ℃, continuously reacting for 3.5 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: sequentially adding 330g of 4-hydroxybutyl vinyl polyoxyethylene ether VPEG, 12g of the modified polyether monomer and 5g of acrylamide into a three-neck flask, adding 220g of water, continuously stirring until the components are completely dissolved, and adding 0.58g of hydrogen peroxide to obtain a base material; dissolving 31g of acrylic acid and 5g of hydroxyethyl acrylate in 33g of water, and marking as solution A; dissolving 0.45g of vitamin C and 1.75g of mercaptopropionic acid in 35g of water, and marking as liquid B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 23g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 235g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 15g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into a lye tank, cooling after reacting for 1.5h, adding 30g of tetraethylenepentamine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; and continuously adding 82g of phosphorous acid into the three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 76g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 25g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40% to obtain the polyamine polyether modified water reducer containing the phosphoric acid structure.
Preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the ratio of 2.3:1 to obtain the anti-mud polycarboxylic acid water reducer.
Example 8
The embodiment provides a mud-resistant polycarboxylate superplasticizer, which is obtained through the following steps:
preparing a modified polyether monomer: putting 330g of ethoxy vinyl polyglycol ether and 13g of succinic anhydride into a dry three-neck flask in sequence according to weight, adding 0.34g of azo-bis-isobutyramidine hydrochloride, introducing nitrogen and continuously stirring, heating to 65 ℃, continuously reacting for 4 hours, and after the reaction is finished, adding water to dilute to 60% of solid content to obtain a modified polyether monomer;
preparing a terminal group modified polycarboxylic acid water reducing agent: sequentially adding 330g of 4-hydroxybutyl vinyl polyoxyethylene ether VPEG, 14g of the modified polyether monomer and 6g of acrylamide into a three-neck flask, adding 230g of water, continuously stirring until the components are completely dissolved, and adding 0.6g of hydrogen peroxide to obtain a base material; 35g of acrylic acid and 7g of hydroxyethyl acrylate are dissolved in 33g of water and are marked as solution A; dissolving 0.4g of vitamin C and 1.8g of mercaptopropionic acid in 35g of water, and marking as a solution B; when the temperature of the base material in the flask rises to 25 ℃, dropwise adding the solution A and the solution B, finishing dripping the solution A after 3 hours, finishing dripping the solution B after 3.5 hours, keeping the temperature at 36-38 ℃ for 1 hour after finishing dripping, adding 23g of 32% NaOH, adjusting the pH to 7, adding water to dilute the product to 40%, and obtaining the end group modified polycarboxylic acid water reducer;
preparing a polyamine polyether modified water reducing agent: placing 230g of polyethylene glycol monomethyl ether (MPEG) in a dry three-neck flask, continuously stirring, slowly heating to 70 ℃, slowly adding 13g of thionyl chloride into the three-neck flask, adding within 20min, continuously introducing air, blowing tail gas into an alkali liquor tank, cooling after reacting for 1.5h, adding 32g of triethylene tetramine into the three-neck flask at one time, introducing air, slowly heating to 70 ℃, and reacting for 1.5h to obtain polyamine polyether; and (2) continuously adding 80g of phosphorous acid into the three-neck flask, uniformly stirring, heating to 100 ℃, slowly adding 77g of formaldehyde (omega is 37%), carrying out Mannich reaction, keeping the reaction for 2-3h, adding 25g of NaOH solution (32%) into the three-neck flask, and supplementing water until the mass concentration is 40%, thereby obtaining the polyamine polyether modified water reducer containing the phosphoric acid structure.
Preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylic acid water reducer and the polyamine polyether modified water reducer according to the proportion of 1.5:1 to obtain the anti-mud polycarboxylic acid water reducer.
Comparative example 1
This comparative example provides a terminal group-modified polycarboxylic acid water-reducing agent, the preparation process of which is completely identical to that of the terminal group-modified polycarboxylic acid water-reducing agent in example 1.
Comparative example 2
The comparative example provides a polyamine polyether modified water reducing agent, and the preparation process of the polyamine polyether modified water reducing agent is completely consistent with that of the polyamine polyether modified water reducing agent in example 1.
Comparative example 3
The comparative example provides a polycation anti-mud polycarboxylate superplasticizer, which is obtained by the following steps:
174g of hydroxyethyl acrylate is put into a reactor, hydrochloric acid solution containing 142g of tetraethylenepentamine is dripped at the temperature of 30 ℃, and the unsaturated anti-mud monomer C is obtained after 1 hour of dripping; 2400g of prenyl polyoxyethylene ether is placed in a reactor, water is added for dissolution, 144g of acrylic acid and the prepared unsaturated anti-mud monomer C are mixed and dissolved, and the mixture is marked as component X; diluting 16g of hydrogen peroxide with water, and recording the diluted solution as a Y component; dissolving 6g vitamin C in water, and recording as Z component; diluting 10g of mercaptopropionic acid with water, and recording as a component D; controlling the temperature to be 40 ℃ at constant temperature, simultaneously dropwise adding for 2.5h, 3h and 3h, keeping the temperature for 1.5h after dropwise adding, adding sodium hydroxide to adjust the pH value to 5, and supplementing water to 40% of solid content to obtain the polycation anti-mud polycarboxylic acid water reducer.
Comparative example 4
The comparative example provides a mud-resistant polycarboxylate superplasticizer, which is obtained by the following steps:
adding 137g of epibromohydrin, 400g of ethanol and 98.2g of water into a four-neck flask provided with a thermometer, a stirrer, a constant-pressure funnel, a nitrogen inlet pipe and a reflux condenser, performing nitrogen replacement under stirring, heating to 30-35 ℃, slowly dropwise adding 236g of trimethylamine solution (30%) within 1h, stirring at a low speed, adding 23g of phosphoric acid to adjust the pH to 1-2, adding a composite initiator consisting of 0.8g of ammonium persulfate, 5g of sodium hypophosphite and 100g of water, heating the solution to 65-70 ℃, reacting for 5.5 h, stopping, and performing reduced pressure distillation on the reaction solution at the vacuum degree of 70Kpa and the temperature of 90 ℃ to obtain a quaternary ammonium salt oligomer A; 19.2g of the quaternary ammonium salt oligomer A, 400g of prenol polyoxyethylene ether, 24.8g of aminotrimethylene phosphoric acid and 300g of water are added into a four-neck flask provided with a thermometer, a stirrer, a constant pressure funnel and a reflux condenser, heated to 50 ℃ under stirring, and 4.4g of ammonium persulfate is added; 44.2g of acrylic acid, 1.5g of mercaptopropionic acid and 180g of mercaptopropionic acid are hydrated and uniform, the dripping is finished at a constant speed within 3h, the constant temperature of 50 ℃ is kept for 1h, the polymerization reaction is finished, the temperature is cooled to 30 ℃, and 25.4g of sodium hydroxide is used for neutralizing to obtain the anti-mud polycarboxylic acid water reducing agent.
Comparative example 5
The comparative example provides a silane modified polycarboxylate water reducer, which is obtained by the following steps:
adding 70g of allyl polyoxyethylene ether with the molecular weight of 2400, 5g of hydrogen peroxide and 70g of water into a reaction device; uniformly mixing 5g of acrylic acid, 5g of vinyltriethoxysilane, 20g of hydroxyethyl acrylate, 0.1g of mercaptoethanol, 0.1g of vitamin C and 40g of water, dropwise adding, after 4h of dropwise adding is finished, reacting at 60 ℃, keeping the total time for 12 hours, cooling to 30-40 ℃ after the reaction is finished, adding sodium hydroxide to adjust the pH value, and adding water to adjust the solid content to 40% to obtain the silane modified polycarboxylic acid water reducer.
Detection example 1
The water reducing agents in the embodiments 1 to 8 and the water reducing agent samples in the comparative examples 1 to 5 are subjected to a net slurry fluidity test with reference to GB/T8077-2012 'concrete admixture homogeneity test method'. Wherein, the W/C is 0.29, the bending and fixing admixture amount of the water reducing agent is 0.18 percent of the cement dosage, 10g of bentonite, and the detection results are shown in the table 1:
TABLE 1 Net pulp fluidity and loss over time for different samples
As can be seen from Table 1, compared with comparative examples 1 to 5, the anti-mud polycarboxylic acid water reducing agent obtained in examples 1 to 8 of the invention has better dispersing performance on cement, and the loss of the fluidity of the net slurry is smaller after 1 hour, which indicates that the anti-mud polycarboxylic acid water reducing agent obtained in examples 1 to 8 of the invention has good adaptability to cement, and the fluidity and the slump retaining performance in the net slurry are both better; meanwhile, the net slurry fluidity and slump retention of the water reducing agent obtained in the comparative examples 1-2 are also superior to those of the water reducing agent obtained in the comparative examples 3-5, which shows that the end group modified polycarboxylic acid water reducing agent and the polyamine polyether modified water reducing agent obtained by the method have better net slurry fluidity and slump retention, and the net slurry fluidity and slump retention are better after the two are compounded in proportion.
Detection example 2
Concrete slump and strength of the water reducing agent in the embodiments 1-8 and the water reducing agent samples in the comparative examples 1-5 are detected by referring to GB8076-2008 concrete admixture. Materials used for the experiments: cement, huaxin p.o 42.5 cement; mineral powder grade S95; coal ash grade I; river sand, the mud content is 5%; machine-made sand with a mud content of 10%; stone, continuous graded broken stone with the particle size of 5-30mm, and the mud content of 7 percent; sodium gluconate: shandong Fuyang Biotechnology Ltd; and (3) organic silicon defoaming agent: nanjing chess, a new materials Co.Ltd; air entraining agent 601: shanghai Shunqi International trade, Inc.; the water-reducing mother liquor M11 with the water-reducing rate of more than or equal to 40 percent and the slow-release slump-retaining mother liquor M21 are commercially available, and the solid content is 40 percent (produced by Wuhan Sanyuan Special building materials, Limited liability company). The mixing amount of the water reducing agent is 1.5 percent of the total using amount of the cementing material.
TABLE 2 concrete mix ratio/kg/m3
| Strength grade | Cement | Mineral powder | Fly ash | Stone | Machine-made sand | River sand | Water (W) |
| C30 | 225 | 80 | 70 | 1030 | 370 | 430 | 165 |
| C60 | 375 | 75 | 75 | 1090 | 320 | 350 | 160 |
TABLE 3 Water reducing agent formulation
It should be noted that the anti-sludge mother liquor in Table 3 refers to the water reducing agents obtained by comparative examples 1 to 5 and examples 1 to 8, respectively.
TABLE 4 concrete application Properties of different samples (C30)
TABLE 5 concrete application Properties of different samples (C60)
As can be seen from tables 4 and 5, in the concrete (C30, C60) with different strength grades, the mud resistance effect and the slump retaining effect of the water reducing agent obtained in the examples 1-8 are obviously better than those of the water reducing agent obtained in the comparative examples 1-5, and the compressive strength of the concrete is higher than those of the concrete obtained in the comparative examples 1-5; meanwhile, the mud resistance effect and the slump retaining effect of the water reducing agent obtained in the comparative examples 1-2 are also superior to those of the water reducing agent in the comparative examples 3-5, which shows that the end group modified polycarboxylic acid water reducing agent and the polyamine polyether modified water reducing agent obtained by the method have better mud resistance effect and slump retaining effect, and the mud resistance effect and slump retaining effect are better after the two are compounded in proportion. The reasons for the above results are: the polycarboxylic acid water reducing agent synthesized by the modified monomer weakens the intercalation adsorption effect in soil, so that the anti-soil effect is generated, the tail end of the modified monomer is changed into an ester group, and the ester group is hydrolyzed in the cement alkaline environment to slowly release carboxyl, so that a certain slump retaining effect is achieved; the synthesized single-chain structure modified water reducing agent can effectively weaken the adsorption between water reducing agent molecules and clay layers by introducing phosphate groups through specific steric hindrance, and also has a certain mud resistance effect. By compounding the two water reducing agents with the anti-mud effect in proportion, the anti-mud effect of the water reducing agent is greatly improved due to the intermolecular synergistic effect on the premise of ensuring the water reducing effect. Meanwhile, as can be seen from the above table, for the concrete with a large mud content in sand, the dosage of the polycarboxylic acid water reducing agent can be reduced by 10-20%, and the workability and compressive strength of the concrete can be remarkably improved.
Compared with the prior art, the mud-resistant polycarboxylate superplasticizer provided by the invention has excellent dispersing effect and good mud slump loss resistance, and can reduce the using amount of the polycarboxylate superplasticizer by 10-20% for concrete with high mud content in sand and stone;
the mud-resistant polycarboxylate superplasticizer provided by the invention can improve the workability of concrete and improve the compressive strength of the concrete.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (5)
1. The mud-resistant polycarboxylate superplasticizer is characterized by comprising a polycarboxylate superplasticizer modified by end groups and a polyamine polyether modified superplasticizer; wherein,
the end group modified polycarboxylate superplasticizer is prepared by reacting the following raw materials: bottom materials, A liquid, B liquid, neutralizing liquid and water; the base material is prepared by reacting the following raw materials in parts by weight: 10-15 parts of modified polyether monomer, 360 parts of unsaturated polyoxyethylene ether 320-containing organic silicon, 4-8 parts of unsaturated amide, 240 parts of water 210-containing organic silicon and 0.4-0.6 part of initiator; the solution A is prepared by the following raw materials in parts by weight: 27-39 parts of unsaturated carboxylic acid, 5-8 parts of unsaturated carboxylic ester and 30-35 parts of water; the liquid B is prepared by the following raw materials in parts by weight: 0.3-0.5 part of reducing agent, 1.6-2.0 parts of chain transfer agent and 30-35 parts of water; the neutralization solution is one or two of sodium hydroxide or potassium hydroxide aqueous solution; the modified polyether monomer is obtained by performing esterification reaction on the following raw materials in parts by weight: 300-360 parts of polyether macromonomer, 10-15 parts of anhydride small monomer and 0.25-0.35 part of catalyst; the polyether macromonomer is one or more of methallyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether and ethylene glycol monovinyl polyethylene glycol ether, and the number average molecular weight of the polyether macromonomer is 2400-4000; the acid anhydride small monomer is one or more of maleic anhydride, phthalic anhydride and succinic anhydride; the catalyst is one or more of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride and azodicyano valeric acid;
the raw materials of the polyamine polyether modified water reducing agent comprise the following components in parts by weight: 240 parts of polyethylene glycol monomethyl ether 220-15 parts, 12-15 parts of thionyl chloride, 30-33 parts of polyethylene polyamine, 75-85 parts of phosphorous acid, 75-80 parts of formaldehyde and 22-25 parts of neutralizing solution;
the weight ratio of the end group modified polycarboxylic acid water reducer to the polyamine polyether modified water reducer is (1-3) to 1.
2. The mud-resistant polycarboxylate superplasticizer according to claim 1, wherein said unsaturated polyoxyethylene ether is 4-hydroxybutyl vinyl polyoxyethylene ether, and the number average molecular weight of said 4-hydroxybutyl vinyl polyoxyethylene ether is 3000;
the unsaturated amide is acrylamide;
the unsaturated carboxylic acid is acrylic acid;
the unsaturated carboxylic ester is one or two of hydroxyethyl acrylate and ethyl acrylate.
3. The anti-mud type polycarboxylate water reducer as defined in claim 1, wherein the number average molecular weight of said polyethylene glycol monomethyl ether is 1000-2000;
the polyethylene polyamine is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine.
4. A preparation method of the anti-mud polycarboxylate superplasticizer according to any one of claims 1 to 3, characterized by comprising the following steps: preparing a modified polyether monomer, preparing a terminal group modified polycarboxylic acid water reducing agent, preparing a polyamine polyether modified water reducing agent and preparing an anti-mud polycarboxylic acid water reducing agent; wherein,
the preparation of the modified polyether monomer comprises the following steps: mixing a polyether macromonomer and an anhydride small monomer, adding a catalyst, and reacting to obtain the modified polyether monomer;
the preparation of the end group modified polycarboxylate superplasticizer comprises the following steps: mixing and stirring the modified polyether monomer, unsaturated polyoxyethylene ether, unsaturated amide and water until the modified polyether monomer, the unsaturated polyoxyethylene ether, the unsaturated amide and the water are dissolved, and adding an initiator to obtain a base material; dropwise adding the solution A and the solution B into the base material, reacting after the dropwise adding is finished, and adding a neutralizing solution to obtain the end group modified polycarboxylic acid water reducer;
the preparation method of the polyamine polyether modified water reducing agent comprises the following steps: adding thionyl chloride into polyethylene glycol monomethyl ether, adding polyethylene polyamine after the reaction is finished, and continuing the reaction to obtain polyamine polyether; continuously adding phosphorous acid and formaldehyde to carry out Mannich reaction, and adding a neutralization solution after the reaction is finished to obtain a polyamine polyether modified water reducing agent containing a phosphoric acid structure;
preparing the anti-mud polycarboxylic acid water reducer: and mixing the end group modified polycarboxylate superplasticizer and the polyamine polyether modified polycarboxylate superplasticizer according to a certain proportion to obtain the anti-mud polycarboxylate superplasticizer.
5. The preparation method of the anti-mud type polycarboxylate superplasticizer according to claim 4, wherein the solution A is obtained by the following steps: dissolving unsaturated carboxylic acid and unsaturated carboxylic ester in water to obtain solution A;
the solution B is obtained by the following steps: and dissolving a reducing agent and a chain transfer agent in water to obtain solution B.
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| CN113321776B (en) * | 2021-06-21 | 2023-08-25 | 山西宝路加交通科技有限公司 | Mud-resistant polycarboxylate water reducer |
| CN113861352B (en) * | 2021-09-14 | 2023-08-29 | 科之杰新材料集团有限公司 | Ligand, conductive water reducer, conductive cement-based composite material and preparation method thereof |
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