CN107325234B - Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof - Google Patents
Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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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
Abstract
The invention discloses an anti-mud phosphate modified polycarboxylate superplasticizer and a preparation method thereof, and the preparation method comprises the following steps: carrying out oxidation-reduction free radical polymerization on an unsaturated carboxylic acid small monomer and an unsaturated polyether large monomer under the action of an initiator, a reducing agent and a chain transfer agent to obtain a carboxyl-containing polycarboxylate water reducer prepolymer; and (2) carrying out partial modification on the carboxyl-containing polycarboxylate water reducer prepolymer by using diphenylphosphoryl chloride to obtain a phosphate-group-containing copolymerization product, adjusting the pH value to 6-7 after the reaction is finished, and adding water to obtain the polycarboxylate water reducer. According to the invention, the side chain of the polycarboxylate superplasticizer is modified into the phosphate group containing two benzene rings, the phosphate functional group enters the polycarboxylate superplasticizer comb-shaped molecule, the sulfate resistance and the mud resistance of the polycarboxylate superplasticizer are improved, the physical size of the polycarboxylate superplasticizer side chain is greatly increased by introducing the benzene rings, and the polycarboxylate superplasticizer side chain is not easily inserted into a clay layered structure, so that the mud resistance effect is achieved without affecting the inherent function of the polycarboxylate superplasticizer.
Description
Technical Field
The invention relates to the technical field of polycarboxylic acid water reducing agents for cement concrete, in particular to an anti-mud polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylic acid water reducing agent has the excellent performances of high water reducing rate, good slump retaining property, low mixing amount, strong molecular structure adjustability, environmental protection and the like, and is increasingly and widely applied to concrete engineering. However, a large number of engineering examples and researches show that compared with traditional naphthalene-based, melamine-based and sulfamic acid-based water reducers, polycarboxylic acid-based water reducers are more sensitive to the mud content of aggregates, the mud in the aggregates can adsorb the polycarboxylic acid water reducers, and the water reducing and dispersing capacity of the polycarboxylic acid-based water reducers is seriously reduced and the slump retaining effect is poor along with the increase of the mud content, so that the workability of fresh concrete is greatly reduced. With the rapid development of the building industry, high-quality sandstone resources are gradually consumed, sandstone resources in various places tend to be deteriorated, and particularly, the used sandstone has a high mud content in large and medium-sized cities. When the aggregate content is high, even if the mixing amount of the polycarboxylic acid water reducing agent is increased, the initial fluidity is improved, but the problems of water reducing rate, slump retention and the like cannot be solved, and the excessive mixing of the polycarboxylic acid causes the cost to be increased, and on the other hand, the problems of serious initial segregation, overlong setting time and the like of concrete are caused. Therefore, starting from the molecular structure of the polycarboxylate superplasticizer, the clay adsorption reducing functional groups are introduced to develop the anti-mud polycarboxylate superplasticizer, so that the nationwide applicability of the polycarboxylate superplasticizer can be greatly improved, and the polycarboxylate superplasticizer has important significance for the development of the building industry.
The existing research shows that the Ca in the cement can be neutralized by using small molecular phosphate2+Form complex to delay cement hydration, and simultaneously can compete with carboxyl in the polycarboxylate water reducing agent for adsorption, and can reduce adsorption of clay and the like to carboxyl, thereby ensuring the performance of the polycarboxylate water reducing agent (and steel and the like]The fifth national academy of special concrete technologies, 2014, chengdu).
Patent WO2010/040611a1 discloses a preparation method of introducing a phosphoric acid group into a linear condensation type water reducing agent. It is prepared by the condensation reaction of the esterification product of ethylene glycol phenyl ether and phosphoric acid, polyoxyethylene monophenyl ether and formaldehyde at 105 ℃. The method is used for straight-chain type condensed water reducing agents, and the water reducing rate and the retention property of the condensed water reducing agents are relatively poorer than those of comb-shaped polycarboxylic acid water reducing agents.
Chinese patent document CN 105418857 a reports a preparation method of a phosphate group-containing polycarboxylic acid water reducer, which comprises copolymerizing unsaturated polyether macromonomer, unsaturated carboxylic acid ester, and unsaturated alcohol in an organic solvent to obtain a polycarboxylic acid water reducer prepolymer, then subjecting the polycarboxylic acid water reducer prepolymer to phosphorylation modification, hydrolyzing carboxylic acid ester groups on the phosphorylation modified product in the presence of an acidic aqueous solution, removing the organic solvent, and finally neutralizing to obtain the phosphate group-containing polycarboxylic acid water reducer.
Patent US2014/0039098 discloses the preparation of a medium diphosphate based water reducer that has certain sulfate ion and mud resistance properties. The preparation method is characterized in that polyacrylic acid, polyethylene glycol monomethyl ether and hydroxyethylidene diphosphonic acid are reacted at 175 ℃ and 20mBar vacuum degree to prepare the modified polyethylene glycol. The method has long reaction time, harsh industrial conditions, low esterification yield and high investment on early-stage industrial production equipment.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a mud-resistant phosphate-modified polycarboxylate superplasticizer, which improves mud resistance on the premise of reducing water.
The technical scheme of the invention is as follows: the mud-resistant phosphate modified polycarboxylate superplasticizer is characterized by having the following molecular structural formula:
wherein R is1、R3Each independently is a hydrogen atom, a methyl group or COOM, M represents a monovalent metal atom; r2Is H or an alkyl, phenyl or phenyl derivative containing 1 to 4 carbon atoms; r4H or an alkyl, phenyl or phenyl derivative having 1 to 5 carbon atoms; a is 1 or 2; b is 5 to 200; c is 0 to 100; x and y are each independently 500 to 1000; z is 250 to 500.
The invention also provides a preparation method of the anti-mud phosphate modified polycarboxylate superplasticizer, which comprises the following steps:
1) under the action of an initiator, a reducing agent and a chain transfer agent, an unsaturated carboxylic acid small monomer and an unsaturated polyether large monomer are kept at 20-60 ℃ for free radical polymerization reaction for 3-5 h to obtain a carboxyl-containing polycarboxylate water reducer prepolymer, wherein the molecular structural formula of the prepolymer is as follows:
wherein w is 1000-2000.
2) Preparing the anti-mud phosphate modified polycarboxylate superplasticizer: partially modifying the carboxyl-containing polycarboxylate water reducer prepolymer by using diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6-7 by using alkali liquor, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 5-60%, wherein the molar ratio of the carboxyl-containing polycarboxylate water reducer prepolymer to the diphenyl phosphoryl chloride is 1: (0.1-0.9).
Preferably, the molecular structural formula of the unsaturated carboxylic acid small monomer in the step 1) is as follows:
wherein R is1、R3Is independently a hydrogen atom, a methyl group or a COOM, M represents H or a monovalent metal atom; r2Is H or an alkyl, phenyl or phenyl derivative containing 1 to 4 carbon atoms.
The molecular structural formula of the unsaturated polyether macromonomer in the step 1) is as follows:
wherein R is4H or an alkyl, phenyl or phenyl derivative having 1 to 5 carbon atoms; a is 1 or 2; b is 5 to 200; c is 0 to 100.
Preferably, the unsaturated carboxylic small monomer in the step 1) is one or more of acrylic acid, methacrylic acid, fumaric acid, maleic acid, 2-methyl-2-butenoic acid and 3-methyl-2-butenoic acid.
Preferably, the unsaturated polyether macromonomer in the step 1) is one or more of methyl allyl polyoxyethylene ether, methyl allyl polyoxyethylene allyl ether, prenyl polyoxyethylene ether and prenyl polyoxyethylene allyl ether.
Preferably, the initiator in the step 1) is one or more of hydrogen peroxide, potassium persulfate, ammonium persulfate and sodium persulfate; the reducing agent is one or more of sodium formaldehyde sulfoxylate, sodium sulfite, sodium pyrosulfite, sodium bisulfite, ferrous pyrophosphate, ferrous sulfate, sodium hypophosphite or sodium ascorbate; the chain transfer agent is one or the combination of more than two of mercaptoethanol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, sodium methyl propenyl sulfonate or dodecanethiol.
Preferably, the alkali liquor in the method is any one or the combination of more than two of potassium hydroxide, sodium hydroxide or calcium hydroxide.
Preferably, the molar ratio of the unsaturated carboxylic acid small monomer, the unsaturated polyether large monomer, the initiator, the reducing agent and the chain transfer agent is 1: (1.2-10): (0.01-0.1): (0.03-0.2): (0.005-0.1); wherein the molar ratio of the carboxyl-containing polycarboxylate superplasticizer prepolymer to the diphenyl phosphoryl chloride is 1: (0.1-0.9).
According to the method, the molecular structure of the water reducing agent is introduced with the phosphate groups containing two benzene rings, the adsorption capacity of the phosphate groups is stronger than that of the carboxylic acid groups, the phosphate groups can be preferentially adsorbed to the surface of clay in the aggregate, and the adsorption of the clay to the carboxylic acid groups is reduced, so that the sensitivity of the polycarboxylic acid water reducing agent to the mud content of the aggregate is reduced; and the introduction of the phosphate group enables the polycarboxylic acid water reducing agent to have stronger adsorption capacity than that of the traditional polycarboxylic acid water reducing agent, so that competitive adsorption of sulfate and the like on the polycarboxylic acid water reducing agent in cement can be resisted, the performance of the polycarboxylic acid water reducing agent is not affected by sulfate and the like, and the dispersing capacity of the polycarboxylic acid water reducing agent is greatly improved. In addition, the introduction of the benzene ring structure greatly increases the physical size of the side chain of the polycarboxylic acid water reducing agent, increases the steric hindrance, weakens the interpenetration adsorption effect of molecules on clay minerals, ensures that the clay minerals are not easily inserted into the layered structure of clay, and solves the problems of high mud content, high mixing amount of the mud-resistant water reducing agent and over-rapid concrete loss over time.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) according to the invention, the side chain of the polycarboxylate superplasticizer is modified into the phosphate group containing two benzene rings to synthesize the mud-resistant polycarboxylate superplasticizer, the process is simple, the problem that the polycarboxylate superplasticizer has high sensitivity to sand and stone mud content is solved, and the mud-resistant function of the polycarboxylate superplasticizer is effectively improved.
(2) According to the method, diphenyl phosphoryl chloride is used for modifying the water reducing agent molecules to introduce phosphate groups, so that the defect that the structure and the molecular weight of the water reducing agent cannot be accurately controlled due to the chain transfer effect caused by the fact that unsaturated phosphate monomers containing the phosphate groups directly participate in the copolymerization reaction of the water reducing agent is overcome.
(3) The phosphate group modified polycarboxylate superplasticizer product prepared by the method has mud resistance on the premise of reducing water and protecting slump.
(4) The anti-mud phosphate modified polycarboxylate superplasticizer prepared by the method has stable performance after being prepared into an aqueous solution, does not delaminate or precipitate during storage, and is convenient to transport.
(5) The anti-mud phosphate modified polycarboxylate superplasticizer product prepared by the method solves the problem of mud content of engineering building materials, and can ensure slump loss under low doping amount.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
1mol of acrylic acid and 5mol of methyl allyl polyoxyethylene ether are kept at 20 ℃ for free radical polymerization reaction for 5h under the action of 0.05mol of hydrogen peroxide, 0.1mol of sodium formaldehyde sulfoxylate and 0.05mol of thioglycollic acid to obtain a carboxyl-containing polycarboxylate superplasticizer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.1mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6.5 by using sodium hydroxide, and adding water to obtain the polycarboxylate water reducer with the mass concentration of 40%.
Example 2
1mol of methacrylic acid and 1.2mol of prenyl polyoxyethylene ether are kept at 50 ℃ for free radical polymerization reaction for 3h under the action of 0.01mol of ammonium persulfate, 0.03mol of sodium metabisulfite and 0.005mol of sodium methyl propenyl sulfonate to obtain a carboxyl-containing polycarboxylate water reducer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.4mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 7 by potassium hydroxide, and adding water to obtain a 10 mass percent polycarboxylate water reducer.
Example 3
1mol of maleic acid and 8mol of methyl allyl polyoxyethylene allyl ether are kept at 25 ℃ for free radical polymerization reaction for 3.5h under the action of 0.1mol of sodium persulfate, 0.2mol of sodium ascorbate and 0.1mol of 2-mercaptopropionic acid to obtain a carboxyl-containing polycarboxylate water reducer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.9mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6.5 by using sodium hydroxide, and adding water to obtain the polycarboxylate water reducer with the mass concentration of 45%.
Example 4
1mol of fumaric acid and 10mol of prenyl polyoxyethylene ether are subjected to free radical polymerization reaction for 3h at 45 ℃ under the action of 0.05mol of hydrogen peroxide, 0.1mol of ferrous pyrophosphate and 0.05mol of 3-mercaptopropionic acid to obtain a carboxyl-containing polycarboxylate water reducer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.5mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6 by using calcium hydroxide, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 35%.
Example 5
Carrying out free radical polymerization reaction on 1mol of 2-methyl-2-butenoic acid and 4mol of methyl allyl polyoxyethylene ether for 4h at 30 ℃ under the action of 0.01mol of potassium persulfate, 0.05mol of sodium bisulfite and 0.005mol of dodecyl mercaptan to obtain a carboxyl-containing polycarboxylic acid water reducing agent prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.3mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 7 by potassium hydroxide, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 60%.
Example 6
Carrying out free radical polymerization reaction on 1mol of 3-methyl-2-butenoic acid and 2mol of prenyl polyoxyethylene allyl ether at 40 ℃ for 4.5h under the action of 0.02mol of ammonium persulfate, 0.05mol of ferrous sulfate and 0.01mol of dodecyl mercaptan to obtain a carboxyl-containing polycarboxylate water reducer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.6mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6 by using calcium hydroxide, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 25%.
Example 7
1mol of acrylic acid, 4mol of methallyl polyoxyethylene allyl ether, 0.05mol of sodium persulfate,
under the action of 0.2mol of sodium sulfite and 0.05mol of mercaptoethanol, free radical polymerization is carried out for 3.5h at 35 ℃ to obtain a carboxyl-containing polycarboxylate superplasticizer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.8mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6.5 by using sodium hydroxide, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 50%.
Example 8
1mol of methacrylic acid and 1.2mol of prenyl polyoxyethylene ether are kept at 50 ℃ for free radical polymerization reaction for 5h under the action of 0.01mol of potassium persulfate, 0.03mol of sodium formaldehyde sulfoxylate and 0.01mol of thioglycolic acid to obtain a carboxyl-containing polycarboxylate water reducer prepolymer; modifying 1mol of carboxyl-containing polycarboxylate water reducer prepolymer by 0.2mol of diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 7 by potassium hydroxide, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 15%.
Effects of the implementation
And (3) testing the net slurry fluidity: reference GB8077-2000 concrete additionMethod of homogeneity test of agent the samples obtained in examples 1 to 8 were tested for net slurry fluidity. W/C is 0.29, the folded and fixed mixing amount of the admixture is 0.21 percent of the cement dosage, and montmorillonite is 2 percent. As can be seen from the table below, the anti-mud agent is compatible with commercially available anti-mud agents
By comparison, the samples obtained in examples 1 to 8 added with the admixture have obvious advantages in net slurry fluidity, which shows that the mud-resistant polycarboxylate superplasticizer has obvious effect on mud resistance and the loss of the net slurry fluidity is small with time.
TABLE 1 Net pulp fluidity and loss over time for different samples
Testing the performance of the concrete: the samples obtained in examples 1 to 8 were tested for slump loss and concrete strength with reference to GB8076-2008 "concrete Admixture". When the folded-in amount of the admixture is 1.8% (relative to the amount of cement), it can be seen from the following table that the admixture is compatible with a commercially available anti-mud agent
Compared with the samples obtained in examples 1 to 8 added with the montmorillonite, the slump loss is obviously improved, which shows that the mud resistance effect of the mud resistance type water reducing agent is obviously improved compared with that of the commercial mud resistance agent.
TABLE 2 concrete testing of different samples
Claims (9)
1. The mud-resistant phosphate modified polycarboxylate superplasticizer is characterized by having the following molecular structural formula:
wherein R is1、R3Each independently is a hydrogen atom, a methyl group or COOM, M represents a monovalent metal atom; r2Is H or an alkyl, phenyl or phenyl derivative containing 1 to 4 carbon atoms; r4H or an alkyl, phenyl or phenyl derivative having 1 to 5 carbon atoms; a is 1 or 2; b is 5 to 200; c is 0 to 100; x and y are each independently 500 to 1000; z is 250 to 500.
2. The preparation method of the anti-mud phosphate modified polycarboxylate superplasticizer according to claim 1, characterized by comprising the following steps:
1) under the action of an initiator, a reducing agent and a chain transfer agent, an unsaturated carboxylic acid small monomer and an unsaturated polyether large monomer are kept at 20-60 ℃ for free radical polymerization reaction for 3-5 h to obtain a carboxyl-containing polycarboxylate water reducer prepolymer, wherein the molecular structural formula of the prepolymer is as follows:
wherein w is 1000-2000;
2) preparing the anti-mud phosphate modified polycarboxylate superplasticizer: partially modifying the carboxyl-containing polycarboxylate water reducer prepolymer by using diphenyl phosphoryl chloride to obtain a copolymerization product containing a phosphate group, adjusting the pH value of the copolymerization product to 6-7 by using alkali liquor, and adding water to obtain a polycarboxylate water reducer with the mass concentration of 5-60%, wherein the molar ratio of the carboxyl-containing polycarboxylate water reducer prepolymer to the diphenyl phosphoryl chloride is 1: (0.1-0.9).
3. The preparation method according to claim 2, characterized in that the molecular structural formula of the unsaturated carboxylic acid small monomer in step 1) is:
wherein R is1、R3Is independently a hydrogen atom, a methyl group or a COOM, M represents H or a monovalent metal atom; r2Is H or an alkyl, phenyl or phenyl derivative containing 1 to 4 carbon atoms.
4. The method of claim 2, wherein the molecular formula of the unsaturated polyether macromonomer in step 1) is:
wherein R is4H or an alkyl, phenyl or phenyl derivative having 1 to 5 carbon atoms; a is 1 or 2; b is 5 to 200; c is 0 to 100.
5. The preparation method according to claim 2, characterized in that the unsaturated carboxylic small monomer in step 1) is one or more of acrylic acid, methacrylic acid, fumaric acid, maleic acid, 2-methyl-2-butenoic acid and 3-methyl-2-butenoic acid.
6. The preparation method of claim 2 or 4, wherein the unsaturated polyether macromonomer used in step 1) is one or more selected from methallyl polyoxyethylene ether and methallyl polyoxyethylene allyl ether.
7. The preparation method according to claim 2, wherein the initiator in the step 1) is one or a combination of two or more of hydrogen peroxide, potassium persulfate, ammonium persulfate and sodium persulfate; the reducing agent is one or more of sodium formaldehyde sulfoxylate, sodium sulfite, sodium pyrosulfite, sodium bisulfite, ferrous pyrophosphate, ferrous sulfate, sodium hypophosphite or sodium ascorbate; the chain transfer agent is one or the combination of more than two of mercaptoethanol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, sodium methyl propenyl sulfonate or dodecanethiol.
8. The method according to claim 2, wherein the alkali solution in step 2) is any one or a combination of two or more of potassium hydroxide, sodium hydroxide or calcium hydroxide.
9. The method according to claim 2, wherein the molar ratio of the unsaturated carboxylic acid small monomer, the unsaturated polyether macromonomer, the initiator, the reducing agent and the chain transfer agent is 1: (1.2-10): (0.01-0.1): (0.03-0.2): (0.005-0.1); wherein the molar ratio of the carboxyl-containing polycarboxylate superplasticizer prepolymer to the diphenyl phosphoryl chloride is 1: (0.1-0.9).
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| CN108047390B (en) * | 2017-12-11 | 2020-07-07 | 广西壮族自治区水利科学研究院 | Preparation method of anti-mud-reduction type polycarboxylate superplasticizer |
| CN108623745B (en) * | 2018-06-08 | 2020-03-06 | 科之杰新材料集团有限公司 | Phosphorus-containing polycarboxylate superplasticizer and preparation method thereof |
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| CN111961147A (en) * | 2020-07-16 | 2020-11-20 | 佳化化学（茂名）有限公司 | Polycarboxylate superplasticizer powder containing phosphate ester and preparation method thereof |
| CN112062910A (en) * | 2020-09-09 | 2020-12-11 | 安徽海螺新材料科技有限公司 | Micro-crosslinking anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN114349914B (en) * | 2021-02-02 | 2024-01-19 | 江苏奥莱特新材料股份有限公司 | Ferrocene modified anti-mud polycarboxylate water reducer and preparation method thereof |
| CN116102283B (en) * | 2023-02-27 | 2023-08-08 | 广西云鹰新材料科技有限公司 | Super-temperature-resistant high MB-value-resistant adsorption type polycarboxylate superplasticizer and preparation method thereof |
| CN116731275B (en) * | 2023-07-06 | 2024-01-26 | 湖北腾辰科技股份有限公司 | Mud-resistant modified naphthalene water reducer and preparation method thereof |
| CN117024669B (en) * | 2023-08-21 | 2024-04-09 | 湖北腾辰科技股份有限公司 | Mud-resistant polycarboxylate superplasticizer and preparation method thereof |
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