CN110467705B - Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof - Google Patents
Shrinkage-reducing 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
- 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
- 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
- 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
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
- C08G65/3355—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus having phosphorus bound to carbon and oxygen
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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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- Ceramic Engineering (AREA)
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Abstract
The invention relates to the technical field of building additives, in particular to a reduction type polycarboxylate water reducer and a preparation method thereof, wherein the preparation method of the reduction type polycarboxylate water reducer comprises the following steps: adding the shrinkage-reducing functional macromonomer and water into a reaction kettle, controlling the temperature at 20-60 ℃, then respectively adding an initiator aqueous solution, a chain transfer agent aqueous solution and an unsaturated acid aqueous solution for reaction to obtain a reaction product, and adjusting the pH to 6.0-7.0 by using an alkaline substance to obtain the shrinkage-reducing polycarboxylic acid water reducer. The molecular structure of the prepared shrinkage-reducing polycarboxylate superplasticizer has hyperbranched shrinkage-reducing functional chain segment, steric hindrance chain segment and adsorption group chain segment, so that the shrinkage reduction and the dispersion performance are unified under low doping amount, and concrete can be prevented from shrinkage cracking, thereby improving the durability of the concrete.
Description
Technical Field
The invention relates to the technical field of building additives, in particular to a reduction type polycarboxylate superplasticizer and a preparation method thereof.
Background
The brittleness and shrinkage problems of concrete are important factors influencing the performance of the concrete, the shrinkage causes cracks inside the concrete, the strength of the concrete is reduced, and the durability of the concrete is adversely affected. Therefore, the shrinkage of the concrete is reduced, and the control of the generation of internal defects of the concrete is important for improving the application performance of the concrete.
The way by which shrinkage of concrete is reduced has become the focus of current engineering research. The addition of concrete expanding agents is commonly used at home and abroad to compensate the drying shrinkage of concrete. The mixing amount of the expanding agent is generally 6-15% of the total amount of the cementing material, the mixing amount is large, and the concrete must be sufficiently moisturized and cured. The concrete shrinkage reducing agent reduces the shrinkage of concrete by reducing the surface tension of water in concrete capillary pores and reducing the shrinkage force in the water evaporation process, so as to achieve the purpose of reducing concrete cracks. However, the shrinkage-reducing agent has the problem of influencing the strength of concrete and is high in price, and the shrinkage-reducing agent is not popularized and used in a large area at present. The polycarboxylic acid superplasticizer is a concrete admixture with better comprehensive performance in the current market, has the advantages of high water reducing rate, small slump loss and the like, can obviously improve the performance of concrete mixtures, and is one of the most hot subjects studied in recent years. Researches indicate that when the water-cement ratio is 0.28, the mixing amount of the polycarboxylic acid water reducing agent is increased within the range of 0.15-0.23 percent, the initial cracking time of the high-strength concrete is delayed, and the plastic shrinkage value is in a decreasing trend. Under the condition of ensuring that the slump of the mixture is consistent, different additives have obvious influence on the plastic shrinkage and crack resistance of the concrete, the naphthalene series, sulfamate series and aliphatic series water reducing agents increase early shrinkage and total shrinkage, and compared with the naphthalene series water reducing agent and the sulfamate series water reducing agent, the high-strength concrete doped with the polycarboxylic acid water reducing agent has small plastic shrinkage and good crack resistance, but the reduction amplitude is far from enough, and the shrinkage reduction effect is difficult to compare with that of the shrinkage reducing agent. In order to overcome the above problems, it is necessary to study a reduction type polycarboxylic acid water reducing agent.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a preparation method of a shrinkage-reducing polycarboxylic acid water reducer, which comprises the following steps:
adding a shrinkage-reducing functional macromonomer and water into a reaction kettle together, controlling the temperature to be 20-60 ℃, then respectively adding an initiator aqueous solution, a chain transfer agent aqueous solution and an unsaturated acid aqueous solution for reaction, wherein the addition of the initiator aqueous solution, the chain transfer agent aqueous solution and the unsaturated acid aqueous solution is preferably in a dropwise adding mode and is completed within 1-4 h, after the dropwise addition is completed, preferably preserving heat for 1-3 h, and further obtaining a reaction product, preferably controlling the mass concentration of the reaction product to be 40-50%, and adjusting the pH to be 6.0-7.0 through an alkaline substance, so as to obtain the shrinkage-reducing polycarboxylic acid water reducer;
the structural formula of the shrinkage reducing functional macromonomer is as follows:
wherein m is 50-90, and n is 2 or 3.
On the basis of the above scheme, preferably, the preparation method of the reducing functional macromonomer is:
adding polyethylene glycol monomethyl ether, maleic anhydride, polyphosphate, a catalyst and a polymerization inhibitor into a reaction kettle, under the condition of protective gas, preferably selecting nitrogen as the protective gas, carrying out constant-temperature reaction at 40-100 ℃, preferably selecting 4-6 h as the constant-temperature reaction time, and thus obtaining the shrinkage-reducing functional macromonomer;
the structural formula of the polyphosphate ester is as follows:
wherein n is 2 or 3.
In the above schemeBased on the fact that the catalyst is FeCl3·6H2O、SnCl2·2H2O、NaHSO4·H2O、CuSO4·5H2And O is one of the compounds.
On the basis of the scheme, the polymerization inhibitor is preferably tert-butyl phenol or phenothiazine.
On the basis of the scheme, preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2400-4000; the dosage of the catalyst is 0.3-1.5% of the mass of the polyethylene glycol monomethyl ether; the dosage of the polymerization inhibitor is 0.3 to 1.2 percent of the mass of the polyethylene glycol monomethyl ether; the molar ratio of the polyethylene glycol monomethyl ether to the polyphosphate to the maleic anhydride is 1: (1-2): 1.
on the basis of the above scheme, preferably, the preparation method of the polyphosphate ester is as follows:
under the condition of protective gas, preferably nitrogen, adding trimethylolpropane into a reaction kettle, cooling in an ice water bath for preferably 0.5-1 h, adding triethylamine, adding a dichloromethane solution of ethyl dichlorophosphate, heating to 40-50 ℃ and reacting, preferably for 12-24 h; and after the reaction is finished, standing for suction filtration, wherein the standing time is preferably 12 hours, collecting filtrate, and distilling to remove the solvent to obtain the polyphosphate.
On the basis of the scheme, the molar ratio of the trimethylolpropane to the ethyl dichlorophosphate is preferably 1: 1.
on the basis of the above scheme, preferably, the initiator is a redox system, and comprises an oxidizing agent and a reducing agent, the oxidizing agent is one of ammonium persulfate, potassium persulfate and hydrogen peroxide, and the reducing agent is one of ascorbic acid, sodium formaldehyde sulfoxylate, Mohr's salt, sodium hypophosphite and Bruggolit FF 6.
On the basis of the above scheme, preferably, the unsaturated acid is at least one of acrylic acid, methacrylic acid, itaconic acid and allyl succinic acid.
On the basis of the scheme, preferably, the chain transfer agent is thioglycolic acid, isopropanol, sodium formate, isooctyl 3-mercaptopropionate, dodecyl mercaptan or 3-mercaptopropionic acid.
On the basis of the above scheme, preferably, the alkaline substance is at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, ammonia water and triethanolamine.
On the basis of the above scheme, preferably, the amount of the unsaturated acid is 5 to 10% of the mass of the reduction functional macromonomer, the amount of the initiator is 1.0 to 5.0% of the mass of the reduction functional macromonomer, and the amount of the chain transfer agent is 0.5 to 1.0% of the mass of the reduction functional macromonomer.
The invention also provides the reduction type polycarboxylate water reducer prepared by the preparation method of the reduction type polycarboxylate water reducer.
The preparation method and the shrinkage-reducing polycarboxylate superplasticizer prepared by the preparation method have the following technical principles and beneficial effects:
1. the self-made shrinkage-reducing functional macromonomer has a hyperbranched structure, contains ethoxy and alkyl chain, has the shrinkage-reducing function and the steric hindrance function, and also contains a phosphate ester adsorption group;
2. according to the invention, a large amount of shrinkage-reducing functional macromonomers are introduced into a polycarboxylic acid molecular structure through copolymerization, so that the polycarboxylic acid molecular structure has a shrinkage-reducing functional chain segment, a steric hindrance chain segment and an adsorption group chain segment, the hyperbranched structure overcomes the problem that the linear chain shrinkage-reducing agent is easily adsorbed by concrete to influence the shrinkage-reducing performance, meanwhile, the hyperbranched structure has larger steric hindrance, has better dispersing performance when applied to the concrete, and the phosphate adsorption group contained in the hyperbranched structure can further improve the dispersing performance of the concrete and simultaneously solve the problem that the shrinkage-reducing agent reduces the strength of the concrete.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the following embodiments:
example 1
(1) Preparing polyphosphate ester: under the protection of nitrogen, 10mol of trimethylolpropane is added into a first reaction device, the mixture is cooled for 1h in an ice-water bath, 500ml of triethylamine is added, 100ml of dichloromethane solution of ethyl dichlorophosphate (the solution concentration is 100mol/L) is dripped under the condition of rapid stirring, the dripping time is 1h, and the temperature is slowly raised to 45 ℃ after the dripping is finished to react for 24 h. Standing for 12h, performing suction filtration, collecting filtrate, and distilling to remove the solvent to obtain the polyphosphate.
(2) Preparing a reducing functional macromonomer: 100g of polyethylene glycol monomethyl ether with the molecular weight of 2400, 4.1g of maleic anhydride, 19g of polyphosphate prepared in the step (1) and 0.5g of SnCl2·2H2O and 0.6g of O-tert-butylphenol are added into a second reaction device and react for 5 hours at the constant temperature of 90 ℃ under the protection of nitrogen, thus obtaining the shrinkage reducing functional macromonomer.
(3) Preparing a reduction type polycarboxylate superplasticizer: adding 100g of the shrinkage reducing functional macromonomer prepared in the step (2), 1g of hydrogen peroxide and water into a reaction kettle, controlling the temperature at 40 ℃, then respectively dropwise adding a sodium formaldehyde sulfoxylate aqueous solution, a thioglycolic acid aqueous solution and an acrylic acid aqueous solution within 3h, and preserving heat for 1h after dropwise adding to obtain a reaction product, wherein the concentration is controlled to be 50%;
and adjusting the pH of the reaction product to 6.0-7.0 by using sodium hydroxide to obtain the shrinkage-reducing polycarboxylic acid water reducer. Wherein 0.5g of sodium formaldehyde sulfoxylate aqueous solution is dissolved in 150g of water, 0.5g of thioglycolic acid aqueous solution is dissolved in 150g of water, and 5g of acrylic acid aqueous solution is dissolved in 180g of water.
Example 2
(1) Preparing polyphosphate ester: under the protection of nitrogen, 10mol of trimethylolpropane is added into a first reaction device, the mixture is cooled for 1h in an ice-water bath, 500ml of triethylamine is added, 100ml of dichloromethane solution of ethyl dichlorophosphate (the solution concentration is 100mol/L) is dripped under the condition of rapid stirring, the dripping time is 1h, and the temperature is slowly raised to 45 ℃ after the dripping is finished to react for 24 h. Standing for 12h, performing suction filtration, collecting filtrate, and distilling to remove the solvent to obtain the polyphosphate.
(2) Preparing a reducing functional macromonomer: 100g of polyethylene glycol monomethyl ether with the molecular weight of 3000, 3.3g of maleic anhydride, 25g of polyphosphate prepared in the step (1), and 1g of NaHSO4·H2And adding O and 0.8g of phenothiazine into a second reaction device, and reacting for 6 hours at a constant temperature of 100 ℃ under the protection of nitrogen to obtain the shrinkage-reducing functional macromonomer.
(3) Preparing a reduction type polycarboxylate superplasticizer: adding 100g of the shrinkage-reducing functional macromonomer prepared in the step (2), 1.5g of ammonium persulfate and water into a reaction kettle, controlling the temperature at 50 ℃, then respectively dropwise adding an ascorbic acid aqueous solution, a 3-isooctyl mercaptopropionate aqueous solution and an itaconic acid aqueous solution within 2h, and preserving heat for 1.5h after dropwise adding to obtain a reaction product, wherein the concentration is controlled to be 50%;
and adjusting the pH of the reaction product to 6.0-7.0 by using potassium hydroxide to obtain the shrinkage-reducing polycarboxylic acid water reducer. Wherein 0.4g ascorbic acid aqueous solution is dissolved in 150g water, 0.8g isooctyl 3-mercaptopropionate aqueous solution is dissolved in 150g water, and 8g itaconic acid aqueous solution is dissolved in 180g water.
Example 3
(1) Preparing polyphosphate ester: under the protection of nitrogen, 10mol of trimethylolpropane is added into a first reaction device, the mixture is cooled for 1h in an ice-water bath, 500ml of triethylamine is added, 100ml of dichloromethane solution of ethyl dichlorophosphate (the solution concentration is 100mol/L) is dripped under the condition of rapid stirring, the dripping time is 1h, and the temperature is slowly raised to 45 ℃ after the dripping is finished to react for 24 h. Standing for 12h, performing suction filtration, collecting filtrate, and distilling to remove the solvent to obtain the polyphosphate.
(2) Preparing a reducing functional macromonomer: 100g of polyethylene glycol monomethyl ether with the molecular weight of 4000, 2.45g of maleic anhydride, 15g of polyphosphate prepared in the step (1), and 1.2g of FeCl3·6H2And adding O and 1.0g of phenothiazine into a second reaction device, and reacting for 4 hours at the constant temperature of 80 ℃ under the protection of nitrogen to obtain the shrinkage-reducing functional macromonomer.
(3) Preparing a reduction type polycarboxylate superplasticizer: adding 100g of the shrinkage-reducing functional macromonomer prepared in the step (2), 1.8g of potassium persulfate and water into a reaction kettle, controlling the temperature at 45 ℃, then respectively dropwise adding a sodium hypophosphite aqueous solution, a dodecyl mercaptan aqueous solution and an allyl succinic acid aqueous solution within 2.5h, and preserving heat for 3h after dropwise adding to obtain a reaction product, wherein the concentration is controlled to be 50%;
and regulating the pH of the reaction product to 6.0-7.0 by using triethanolamine to obtain the shrinkage-reducing polycarboxylic acid water reducer. Wherein the sodium hypophosphite aqueous solution 0.6g is dissolved in 150g of water, the dodecyl mercaptan aqueous solution 0.7g is dissolved in 150g of water, and the allyl succinic acid aqueous solution 10g is dissolved in 180g of water.
Comparative example
(1) Preparation of macromonomer: 100g of polyethylene glycol monomethyl ether with molecular weight of 4000, 2.45g of maleic anhydride and 1.2g of FeCl3·6H2And adding O and 1.0g of phenothiazine into a second reaction device, and reacting for 4 hours at the constant temperature of 80 ℃ under the protection of nitrogen to obtain the shrinkage-reducing functional macromonomer.
(2) Preparing a polycarboxylic acid water reducing agent: adding 100g of the macromonomer prepared in the step (1), 1.8g of potassium persulfate and water into a reaction kettle, controlling the temperature at 45 ℃, then respectively dropwise adding a sodium hypophosphite aqueous solution, a dodecyl mercaptan aqueous solution and an allyl succinic acid aqueous solution within 2.5h, and preserving heat for 3h after dropwise adding is finished to obtain a reaction product with the concentration of 50%;
and regulating the pH value of the reaction product to 6.0-7.0 by using triethanolamine to obtain the polycarboxylic acid water reducer. Wherein the sodium hypophosphite aqueous solution 0.6g is dissolved in 150g of water, the dodecyl mercaptan aqueous solution 0.7g is dissolved in 150g of water, and the allyl succinic acid aqueous solution 10g is dissolved in 180g of water.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
The shrinkage ratio and other properties of the concrete were measured using a commercially available BHY-2A type concrete shrinkage reducing agent, the polycarboxylic acid water reducing agents obtained in examples 1 to 3 and comparative examples, and standard cement according to GB 8076-. The results obtained are shown in table 1.
Table 1 comparison of the properties of the examples
The test result shows that compared with the comparative example, the invention introduces the shrinkage reducing functional macromonomer into the polycarboxylic acid molecular structure through copolymerization, so that the polycarboxylic acid molecular structure has a shrinkage reducing functional chain segment, a steric hindrance chain segment and an adsorption group chain segment, the shrinkage reducing functional chain segment of the hyperbranched structure reduces the shrinkage of concrete, improves the dispersibility of the concrete, and further improves the dispersibility of the concrete through the contained phosphate adsorption group. The commercial BHY-2A type concrete shrinkage reducing agent can improve the shrinkage reducing performance of concrete, but influences the strength of the concrete, the shrinkage reducing functional chain segment of the hyperbranched structure overcomes the problem that the linear chain shrinkage reducing agent is easily adsorbed by the concrete to influence the shrinkage reducing performance, the shrinkage reducing performance of the concrete is further improved, and meanwhile, the phosphate adsorption group can further improve the dispersing performance of the concrete without influencing the strength of the concrete.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (13)
1. The preparation method of the reduction type polycarboxylate superplasticizer is characterized by comprising the following steps:
adding a shrinkage-reducing functional macromonomer and water into a reaction kettle, controlling the temperature at 20-60 ℃, then respectively adding an initiator aqueous solution, a chain transfer agent aqueous solution and an unsaturated acid aqueous solution for reaction to obtain a reaction product, and adjusting the pH to 6.0-7.0 by using an alkaline substance to obtain a shrinkage-reducing polycarboxylic acid water reducer;
the structural formula of the shrinkage reducing functional macromonomer is as follows:
wherein m is 50-90, and n is 2 or 3.
2. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 1, wherein the preparation method of the reduction functional macromonomer comprises the following steps:
adding polyethylene glycol monomethyl ether, maleic anhydride, polyphosphate, a catalyst and a polymerization inhibitor into a reaction kettle, and carrying out constant-temperature reaction at 40-100 ℃ under the condition of protective gas to obtain a shrinkage-reducing functional macromonomer;
the structural formula of the polyphosphate ester is as follows:
wherein n is 2 or 3.
3. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 2, characterized by comprising the following steps: the catalyst is FeCl3·6H2O、SnCl2·2H2O、NaHSO4·H2O、CuSO4·5H2And O is one of the compounds.
4. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 2, characterized by comprising the following steps: the polymerization inhibitor is o-tert-butylphenol or phenothiazine.
5. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 2, characterized by comprising the following steps: the molecular weight of the polyethylene glycol monomethyl ether is 2400-4000; the dosage of the catalyst is 0.3-1.5% of the mass of the polyethylene glycol monomethyl ether; the dosage of the polymerization inhibitor is 0.3 to 1.2 percent of the mass of the polyethylene glycol monomethyl ether; the molar ratio of the polyethylene glycol monomethyl ether to the polyphosphate to the maleic anhydride is 1: (1-2): 1.
6. the preparation method of the reduction type polycarboxylate superplasticizer according to claim 2, wherein the preparation method of the polyphosphate ester is as follows:
under the condition of protective gas, adding trimethylolpropane into a reaction kettle, cooling in an ice-water bath, adding triethylamine, adding a dichloromethane solution of ethyl dichlorophosphate, heating to 40-50 ℃ and reacting; and after the reaction is finished, standing, performing suction filtration, collecting filtrate, and distilling to remove the solvent to obtain the polyphosphate.
7. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 6, characterized by comprising the following steps: the molar ratio of the trimethylolpropane to the ethyl dichlorophosphate is 1: 1.
8. the preparation method of the reduction type polycarboxylate superplasticizer according to claim 1, characterized by comprising the following steps: the initiator is a redox system and comprises an oxidant and a reducing agent, the oxidant is one of ammonium persulfate, potassium persulfate and hydrogen peroxide, and the reducing agent is one of ascorbic acid, sodium formaldehyde sulfoxylate, Mohr's salt, sodium hypophosphite and Brugolit FF 6.
9. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 1, characterized by comprising the following steps: the unsaturated acid is at least one of acrylic acid, methacrylic acid, itaconic acid and allyl succinic acid.
10. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 1, characterized by comprising the following steps: the chain transfer agent is thioglycolic acid, isopropanol, sodium formate, isooctyl 3-mercaptopropionate, dodecyl mercaptan or 3-mercaptopropionic acid.
11. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 1, characterized by comprising the following steps: the alkaline substance is at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, ammonia water and triethanolamine.
12. The preparation method of the reduction type polycarboxylate superplasticizer according to claim 1, characterized by comprising the following steps: the dosage of the unsaturated acid is 5 to 10 percent of the mass of the reducing functional macromonomer, the dosage of the initiator is 1.0 to 5.0 percent of the mass of the reducing functional macromonomer, and the dosage of the chain transfer agent is 0.5 to 1.0 percent of the mass of the reducing functional macromonomer.
13. The reduction type polycarboxylate water reducer prepared by the preparation method of the reduction type polycarboxylate water reducer according to any one of claims 1-12.
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WO2004076376A2 (en) * | 2003-02-26 | 2004-09-10 | Construction Research & Technology Gmbh | Strength improvement admixture |
CN107140866A (en) * | 2017-05-31 | 2017-09-08 | 徐州铸建建材科技有限公司 | A kind of pervasive anti-chamotte mould polycarboxylate water-reducer and preparation method thereof |
CN109265627A (en) * | 2018-09-27 | 2019-01-25 | 武汉奥克化学有限公司 | A kind of ester ether copoly type polycarboxylate water-reducer and preparation method thereof |
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