CN110684161A - Preparation method of polycarboxylate superplasticizer containing phosphate - Google Patents
Preparation method of polycarboxylate superplasticizer containing phosphate Download PDFInfo
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- CN110684161A CN110684161A CN201911096750.2A CN201911096750A CN110684161A CN 110684161 A CN110684161 A CN 110684161A CN 201911096750 A CN201911096750 A CN 201911096750A CN 110684161 A CN110684161 A CN 110684161A
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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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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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 a preparation method of a polycarboxylate superplasticizer containing phosphate ester, which comprises the following steps: firstly, taking glycidol or alcohol with a structural formula of A and maleic anhydride as reactants, and carrying out esterification reaction in deionized water under the action of a catalyst and at a reaction temperature of 60-70 ℃ to obtain an intermediate solution; adding alkali into the intermediate solution to adjust the pH value to 9-10, and carrying out hydrolysis reaction for 0.5-1h at the temperature of 25-40 ℃ to obtain maleic acid hydroxy ester; adding a phosphorylation reagent into maleic acid hydroxy ester, and carrying out phosphorylation reaction at 60-80 ℃ to obtain unsaturated phosphate; and polymerizing unsaturated phosphate, unsaturated carboxylic acid and allyl alcohol polyoxyethylene ether to obtain the polycarboxylate water reducer containing phosphate. In the preparation method, the problem of generating diester or polybasic ester is avoided in the preparation process of the unsaturated phosphate, the content of the unsaturated phosphate is increased, and the generation of a cross-linking structure in the polycarboxylic acid water reducing agent is reduced.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a preparation method of an allyl alcohol polyoxyethylene ether type polycarboxylate superplasticizer containing phosphate.
Background
Since concrete plays an important indispensable role in various engineering fields, concrete technology is required to be continuously improved in basic functions and developed toward high-tech. The concrete admixture is a key material for the development of the concrete technology to the high-tech field, and the water reducing agent is the admixture with the largest use amount and the widest application range. As a new generation high-performance water reducing agent, the polycarboxylate water reducing agent has the advantages of high water reducing rate, high slump loss resistance, super-dispersibility, super-stability and the like, and has become a hot point of domestic and foreign research in recent years.
However, the polycarboxylate superplasticizer is sensitive to low-quality aggregates such as silt-containing sand, machine-made sand and the like due to low mixing amount, and needs to increase the mixing amount or increase the water consumption for compensation,and the phenomena of poor working performance, segregation, bleeding and the like of concrete are easily caused. The existing research shows that the phosphorus-containing group can react with Ca in cement2+And complexing is carried out to delay cement hydration, and the cement hydration and carboxyl in the polycarboxylate superplasticizer form competitive adsorption, so that the adsorption of clay to the superplasticizer is reduced, and the performance of the superplasticizer is improved.
Patent CN 106008593A discloses a phosphate ester functional monomer for preparing a high slump retaining type polycarboxylate water reducer. The functional monomer is prepared by carrying out esterification reaction on unsaturated acid or anhydride and alcohol, and then carrying out phosphorylation reaction on unsaturated ester and a phosphorylation reagent to obtain the phosphate functional monomer. The polycarboxylic acid water reducing agent prepared from the functional monomer has the characteristics of low mixing amount, high water reducing rate, strong slump retaining performance, good adaptability to cement and the like. Patent CN 109467649 a discloses another preparation method of phosphate functional monomer. Compared with CN 106008593A, the patent uses maleic anhydride, polyethylene glycol, polypropylene glycol, small molecular alcohol or alcohol amine and a phosphorylation reagent to carry out 'one-pot' reaction to obtain the phosphate functional monomer. The water reducer prepared by the functional monomer has good water reducing performance and obvious viscosity reducing effect on high-strength concrete.
In the two patent documents, the process flow is simplified by a method of preparing an unsaturated phosphate functional monomer and then copolymerizing the unsaturated phosphate functional monomer with a polyether monomer; however, the alcohol used in the esterification reaction in the process of preparing the unsaturated phosphate ester is diol or polyol, which is easy to generate diester or polyester compounds, the compounds cannot generate subsequent phosphorylation reaction, the content of the unsaturated phosphate ester functional monomer is reduced, and the unsaturated phosphate ester functional monomer and the polyether monomer are easy to form a cross-linking structure, which affects the performance of the water reducing agent.
Disclosure of Invention
The invention aims to solve the problem that in the preparation method of the polycarboxylate superplasticizer, diester or polyester compounds are easily generated in the unsaturated phosphate synthesis process, so that the compounds cannot generate subsequent phosphorylation reaction; provides a new method for preparing a polycarboxylate superplasticizer containing phosphate ester.
The preparation method of the polycarboxylate superplasticizer containing phosphate ester provided by the invention comprises the following steps:
s1, preparing an unsaturated phosphate functional monomer, and comprising the following detailed steps:
s11, adding glycidol or alcohol with the structural formula of A, solvent deionized water and a catalyst into a reaction container, heating to 60-70 ℃, then dropwise adding a maleic anhydride solution, completing dropwise adding within 0.5-1h, and then carrying out constant temperature reaction for 1h to obtain an intermediate solution. The structural formula A is as follows:
in the formula, R1Is C2H4Or C3H6；
R2Is TMS, TBDMS or TBDPS; the structure is as follows:
the catalyst is one of concentrated sulfuric acid, p-toluenesulfonic acid and 4-dimethylaminopyridine, and the amount of the catalyst is 0.01-0.1% of the weight of maleic anhydride. The glycidol and the alcohol with the structural formula of A contain an alcoholic hydroxyl protecting group, so that the generation of maleic diester is avoided.
S12, adding alkali into the intermediate solution obtained in the step S11 to adjust the pH value to 9-10, and carrying out hydrolysis reaction for 0.5-1h at the temperature of 25-40 ℃ to obtain maleic acid hydroxy ester; the hydrolysis reaction is a step of removing the protecting group, because the epoxy ethane ring tension in glycidol is larger, the activity of the silicon alcohol ether bond in the structural formula A is high, and the epoxy ethane ring tension and the silicon alcohol ether bond in the structural formula A are easy to hydrolyze under an alkaline condition, therefore, the hydrolysis condition needs to control the reaction temperature to be between 25 and 40 ℃, and meanwhile, the pH value cannot be too high, so that the protecting group is removed under the condition that an ester group is not hydrolyzed.
S13, adding a phosphorylation reagent into the maleic acid hydroxyl ester, and carrying out phosphorylation reaction at 60-80 ℃ to obtain unsaturated phosphate. The phosphorylation reaction is that the phosphorylation reagent and maleic acid hydroxyl ester are subjected to esterification reaction in an acidic environment to obtain unsaturated phosphate ester, wherein the acidic environment is provided by the excessive phosphorylation reagent.
S2, polymerizing unsaturated phosphate, unsaturated carboxylic acid and allyl alcohol polyoxyethylene ether to obtain the polycarboxylic acid water reducing agent. The specific operation is as follows:
s21, adding allyl alcohol polyoxyethylene ether, unsaturated phosphate ester and deionized water into a reactor which is replaced by nitrogen, stirring at room temperature to dissolve, and taking the solution as a bottom material;
s22, preparing a material A from unsaturated carboxylic acid and deionized water; preparing a material B from a chain transfer agent and deionized water; dissolving an initiator and deionized water to prepare a material C;
s23, firstly, dropwise adding the material C into the base material, then, dropwise adding the material A and the material B simultaneously, wherein the dropwise adding time is 1.5-4 h, after the dropwise adding is finished, keeping the temperature at 60-80 ℃ for reaction for 1-2h, then, cooling to room temperature, and adding an alkali liquor to adjust the pH value to 6-7, so that the polycarboxylate superplasticizer containing the phosphate ester is obtained. Wherein the components are used in the following mass percentage:
1-10% of unsaturated phosphate, 6-18% of unsaturated carboxylic acid, 75-90% of allyl polyoxyethylene ether, 0.5-1.5% of initiator and 0.2-0.8% of chain transfer agent, wherein the sum of the mass percentages is 100%. Wherein the unsaturated phosphate is an unsaturated phosphate aqueous solution with the mass percentage concentration of 10 percent
Preferably, in the step S11, the molar ratio of glycidol or the alcohol of formula A to maleic anhydride is 1 (1.0-1.5).
Preferably, in step S12, the alkali is one of sodium hydroxide, potassium hydroxide, and ammonia water.
Preferably, in step S13, the phosphorylating reagent is one of phosphoric acid, polyphosphoric acid, phosphorus pentoxide, and pyrophosphoric acid, and the molar ratio of the phosphoric acid group to the alcoholic hydroxyl group of the maleic acid hydroxy ester in the phosphorylating reagent is (1.0 to 1.5): 1.
preferably, the unsaturated carboxylic acid is one or a mixture of acrylic acid, methacrylic acid, itaconic acid and salts thereof.
Preferably, the molecular weight of the allyl alcohol polyoxyethylene ether is 1100-3000.
The chain transfer agent is one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, sodium methallyl sulfonate and sodium hypophosphite.
The initiator is at least one of ammonium persulfate, potassium persulfate and hydrogen peroxide.
The structural formula of the unsaturated phosphate functional monomer prepared in the step S1 is as follows:
in the formula, R' is CH2CH2、CH2CH2CH2、CH2CH2OHCH2One kind of (1).
The structural formula of the polycarboxylic acid water reducing agent finally prepared in the step S2 is as follows:
in the formula, R' is CH2CH2、CH2CH2CH2、CH2CH2OHCH2One kind of (1). R is H or CH3。
a. b, c and n are positive integers, a, b and c are 1-50, and n is 30-100.
Compared with the prior art, the invention has the advantages that:
in the process of preparing the unsaturated phosphate ester functional monomer, glycidol or alcohol with the structural formula of A is used as a raw material, so that the generation of maleic acid diester is reduced and even avoided, and the generation of a cross-linked structure in the polycarboxylic acid water reducing agent is reduced; meanwhile, the phosphorylation reaction is fully carried out, more phosphate groups are connected to the main chain, the adsorption efficiency of the water reducing agent on cement can be improved, and ester groups are subjected to water interpretation under an alkaline condition to release carboxyl groups, so that the adsorption of the water reducing agent on the cement is increased, and the water reducing and slump retaining performance of the water reducing agent is improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
A preparation method of a polycarboxylate superplasticizer containing phosphate ester comprises the following steps:
s1, preparing an unsaturated phosphate functional monomer, and comprising the following detailed steps:
s11, adding 0.11mol of glycidol, 0.001mol of p-toluenesulfonic acid and 200g of deionized water into a 500ml four-neck flask provided with a heating device, a stirring device and a reflux condenser, heating to 70 ℃, dropwise adding a 50% maleic anhydride aqueous solution (0.1mol), finishing dropping for 0.5h, and carrying out heat preservation reaction for 1h to obtain an intermediate solution.
S12, adding sodium hydroxide into the intermediate solution obtained in the step S11 to adjust the pH value to 9-10, and carrying out hydrolysis reaction for 0.5h at 40 ℃ to obtain maleic acid hydroxy ester;
s13, adding polyphosphoric acid (0.15 mol based on phosphoric acid) into maleic acid hydroxy ester, carrying out phosphorylation reaction for 1h at 60 ℃, and cooling to normal temperature to obtain brown liquid, namely the unsaturated phosphate ester maleic acid phosphoglyceride functional monomer. The specific reaction process is as follows:
s2, polymerizing unsaturated phosphate, unsaturated carboxylic acid and allyl alcohol polyoxyethylene ether to obtain the polycarboxylic acid water reducing agent. The specific operation is as follows:
s21, weighing 10g of maleic acid phosphoglyceride aqueous solution (the mass percentage concentration is 10%), 75g of allyl alcohol polyoxyethylene ether with the molecular weight of 1100 and 150g of deionized water, adding the weighed materials into a reaction vessel with nitrogen replaced and air removed, stirring at room temperature to dissolve, and taking the solution as a bottom material.
S22, preparing a material A from 12.7g of acrylic acid and 35g of water; 0.8g of mercaptoacetic acid and 15g of water are used to prepare material B. 1.5g of potassium persulfate was dissolved in 20g of water to prepare a material C.
S23, firstly, dropwise adding the material C into the backing material, then, dropwise adding the material A and the material B at the same time, wherein the dropwise adding time is 2 hours, reacting for 1.5 hours at 60 ℃ after the dropwise adding is finished, then, cooling to room temperature, adding alkali to neutralize and regulate the pH value to 6-7, and adding a certain amount of water to adjust to obtain the phosphate-containing polycarboxylate water reducer with the solid content of 50%. The structural formula is as follows:
wherein the ratio of a, b and c is 48:1:20, and n is equal to 23.
Example 2
A preparation method of a polycarboxylate superplasticizer containing phosphate ester comprises the following steps:
s1, preparing an unsaturated phosphate functional monomer, and comprising the following detailed steps:
s11, adding 0.11mol of alcohol with the structural formula A, 0.01mol of concentrated sulfuric acid and 200g of deionized water into a 500ml four-neck flask provided with a heating device, a stirring device and a reflux condenser pipe, heating to 60 ℃, dropwise adding a 50% maleic anhydride aqueous solution (0.1mol), finishing dropping for 0.5h, and carrying out heat preservation reaction for 1h to obtain an intermediate solution.
The structural formula A is as follows:
in the formula, R1Is C2H4；R2Is a TMS, and the TMS is a TMS,
s12, adding sodium hydroxide into the intermediate solution obtained in the step S11 to adjust the pH value to 9-10, and carrying out hydrolysis reaction for 1h at the temperature of 25 ℃ to obtain maleic acid hydroxy ester;
s13, adding polyphosphoric acid (0.15 mol based on phosphoric acid) into the maleic acid hydroxyl ester, carrying out phosphorylation reaction for 1h at 80 ℃, and cooling to normal temperature to obtain the unsaturated phosphate ester maleic acid glycerol phosphate functional monomer. The specific reaction process is as follows:
s2, polymerizing unsaturated phosphate, unsaturated carboxylic acid and allyl alcohol polyoxyethylene ether to obtain the polycarboxylic acid water reducing agent. The specific operation is as follows:
s21, weighing 10g of maleic acid phosphoglyceride aqueous solution (10 percent by mass concentration), 75g of allyl alcohol polyoxyethylene ether with the molecular weight of 1100 and 150g of deionized water, adding into a reaction vessel which is subjected to nitrogen replacement and air removal, stirring at room temperature for dissolution, and taking the solution as a bottom material.
S22, preparing a material A from 12.7g of acrylic acid and 35g of water; 0.8g of mercaptoacetic acid and 15g of water are used to prepare material B. 1.5g of potassium persulfate was dissolved in 20g of water to prepare a material C.
S23, firstly, dropwise adding the material C into the backing material, then, dropwise adding the material A and the material B at the same time, wherein the dropwise adding time is 2 hours, reacting for 1.5 hours at 60 ℃ after the dropwise adding is finished, then, cooling to room temperature, adding alkali to neutralize and regulate the pH value to 6-7, and adding a certain amount of water to adjust to obtain the phosphate-containing polycarboxylate water reducer with the solid content of 50%. The structural formula is as follows:
Wherein the ratio of a, b and c is 47:1:18, and n is equal to 23.
Example 3
The preparation method of the polycarboxylate superplasticizer containing phosphate ester comprises the same operation steps as the example 2. Except that the alcohol of formula a has the following structure:
in the formula, R1Is C3H6；R2Is TBDPS.
Example 4
A preparation method of a polycarboxylate superplasticizer containing phosphate ester comprises the following steps:
step S1, preparation of unsaturated phosphate ester functional monomer, same as step S1 of example 1.
S2, polymerizing unsaturated phosphate, unsaturated carboxylic acid and allyl alcohol polyoxyethylene ether to obtain the polycarboxylic acid water reducing agent. The specific operation is as follows:
s21, weighing 2.3g of maleic acid phosphoglyceride aqueous solution (10 percent by mass concentration), 90g of allyl alcohol polyoxyethylene ether with the molecular weight of 3000 and 150g of deionized water, adding into a reaction vessel which is displaced by nitrogen and excludes air, stirring at room temperature for dissolving, and taking the solution as a bottom material.
S22, preparing a material A from 7g of itaconic acid and 35g of water; 0.2g of sodium methallyl sulfonate and 15g of water are prepared into a material B. 0.5g of hydrogen peroxide was dissolved in 20g of water to prepare a feed C.
S23, firstly, dropwise adding the material C into the backing material, then, dropwise adding the material A and the material B at the same time, wherein the dropwise adding time is 2 hours, reacting for 1.5 hours at 60 ℃ after the dropwise adding is finished, then, cooling to room temperature, adding alkali to neutralize and regulate the pH value to 6-7, and adding a certain amount of water to adjust to obtain the phosphate-containing polycarboxylate water reducer with the solid content of 50%.
The polycarboxylate superplasticizer containing phosphate ester obtained in the embodiments 1 to 4 of the invention and similar water reducers sold in the market are subjected to concrete working performance and mechanical property tests. The performance of the concrete mixture is tested by referring to the standard GB/T50080-2002 of the test method for the performance of the common concrete mixture, the standard GB/T50081-2002 of the test method for the mechanical property of the common concrete, and the technical specification JGJ/T283-2012 of the self-compacting concrete application, CECS 203-. The test results are shown in Table 1.
The concrete comprises the following components in percentage by weight: 490kg of Lafaji P. 042.5 cement, 90kg of industrial fly ash, 730kg of Hanwang machine sand (fineness modulus is 2.9), 1000kg of stones and 0.250 of water-cement ratio.
TABLE 1 comparative data on concrete Properties
The average change rate of the spread: and adjusting the doping amount by 10 percent up and down by taking the expansion degree reaching 550 +/-10 mm as a reference, testing again, then averaging the expansion degrees of 3 doping amount points, calculating the change rate of the expansion degree and the average value of each doping amount point, and averaging the three change rates to obtain the average change rate of the expansion degree.
As can be seen from Table 1, the water reducing rate of the polycarboxylic acid water reducing agent prepared by the method is superior to that of the commercial product, the change rate of the mixing amount is smaller than that of the commercial product, and the sensitivity to the mixing amount is low.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the polycarboxylate superplasticizer containing phosphate ester is characterized by comprising the following steps:
s1, preparing an unsaturated phosphate functional monomer, which comprises the following steps:
s11, taking glycidol or alcohol with the structural formula of A and maleic anhydride as reactants, and reacting in a deionized water solvent under the action of a catalyst at the temperature of 60-70 ℃ to perform esterification reaction to obtain an intermediate solution; the structural formula A is as follows:
in the formula, R1Is C2H4Or C3H6；
R2Is TMS, TBDMS or TBDPS; the structure is as follows:
s12, adding alkali into the intermediate solution to adjust the pH value to 9-10, and carrying out hydrolysis reaction for 0.5-1h at the temperature of 25-40 ℃ to obtain maleic acid hydroxy ester;
s13, adding a phosphorylation reagent into the maleic acid hydroxy ester, and carrying out phosphorylation reaction at 60-80 ℃ to obtain unsaturated phosphate;
s2, polymerizing unsaturated phosphate, unsaturated carboxylic acid and allyl alcohol polyoxyethylene ether to obtain the polycarboxylic acid water reducing agent.
2. The method for preparing the phosphate-containing polycarboxylate superplasticizer according to claim 1, wherein the step S11 specifically comprises the following steps: adding glycidol or alcohol with a structural formula of A, deionized water and a catalyst into a reaction container, heating to 40-70 ℃, then dropwise adding maleic anhydride, finishing dropwise adding within 0.5-1h, and then reacting for 1h at constant temperature.
3. The method for preparing the phosphate-containing polycarboxylate superplasticizer according to claim 2, wherein the catalyst is one of concentrated sulfuric acid, p-toluenesulfonic acid and 4-dimethylaminopyridine, and the amount of the catalyst is 0.01-0.1% of the weight of maleic anhydride.
4. The method for preparing the phosphate-containing polycarboxylate superplasticizer according to claim 2, wherein in step S11, the molar ratio of glycidol or the alcohol with the structural formula A to maleic anhydride is 1 (1.0-1.5).
5. The method for preparing the phosphate-containing polycarboxylate superplasticizer according to claim 1, wherein in step S12, the alkali is one of sodium hydroxide, potassium hydroxide and ammonia water.
6. The method for preparing a phosphate-containing polycarboxylate water reducer according to claim 1, wherein in step S13, the phosphorylating reagent is one of phosphoric acid, polyphosphoric acid, phosphorus pentoxide and pyrophosphoric acid, and the molar ratio of the phosphoric acid group in the phosphorylating reagent to the alcoholic hydroxyl group of the maleic acid hydroxy ester is (1.0-1.5): 1.
7. the method for preparing the phosphate-containing polycarboxylate superplasticizer according to claim 1, wherein the step S2 is as follows:
s21, adding allyl alcohol polyoxyethylene ether, unsaturated phosphate ester and deionized water into a reactor which is replaced by nitrogen, stirring at room temperature to dissolve, and taking the solution as a bottom material;
s22, preparing a material A from unsaturated carboxylic acid and deionized water; preparing a material B from a chain transfer agent and deionized water; dissolving an initiator and deionized water to prepare a material C;
s23, firstly, dropwise adding the material C into the base material, then, dropwise adding the material A and the material B simultaneously, wherein the dropwise adding time is 1.5-4 h, after the dropwise adding is finished, keeping the temperature at 60-80 ℃ for reaction for 1-2h, then, cooling to room temperature, and adding an alkali liquor to adjust the pH value to 6-7, so that the polycarboxylate superplasticizer containing the phosphate ester is obtained.
8. The preparation method of the phosphate-containing polycarboxylate superplasticizer according to claim 7, wherein the components are used in the following mass percentages:
1-10% of unsaturated phosphate, 6-18% of unsaturated carboxylic acid, 75-90% of allyl polyoxyethylene ether, 0.5-1.5% of initiator and 0.2-0.8% of chain transfer agent, wherein the sum of the mass percentages is 100%; the unsaturated phosphate is an unsaturated phosphate aqueous solution with the mass percentage concentration of 10%.
9. The method for preparing the phosphate-containing polycarboxylate water reducer according to claim 8, wherein the unsaturated carboxylic acid is one or a mixture of acrylic acid, methacrylic acid, itaconic acid and salts thereof.
10. The method for preparing a phosphate-containing polycarboxylate water reducer according to claim 8, wherein the molecular weight of the allyl alcohol polyoxyethylene ether is 1100-3000.
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