CN113861405A - Polyether macromonomer and preparation method and application thereof - Google Patents
Polyether macromonomer and preparation method and application thereof Download PDFInfo
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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
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3348—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing nitrogen in addition to sulfur
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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
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33344—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carbamate group
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention provides a polyether macromonomer and a preparation method and application thereof, wherein the method comprises the following steps: 1) unsaturated alcohol containing active hydrogen and olefin oxide are used as raw materials, and ring-opening polymerization is carried out under heating under the condition of nitrogen and under the action of a catalyst to obtain a polyoxyethylene ether monomer intermediate; 2) mixing with a catalyst, continuously introducing olefin oxide under the condition of nitrogen, and performing curing and degassing treatment after the feeding is finished to obtain a polyoxyethylene ether monomer; 3) adding benzyl carbamate, and reacting under heating to obtain a formamide-terminated polyether macromonomer; 4) adding substituted sulfonyl isocyanate, heating for reaction, cooling, and adjusting pH to obtain the polyether macromonomer. Compared with the prior art, the polycarboxylic acid water reducing agent prepared from the polyether macromonomer synthesized by the method has the advantages of low mixing amount, high water reducing rate, good slump retaining performance and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyether macromonomer and a preparation method and application thereof.
Background
Concrete is widely applied to civil engineering as a building material, and a polycarboxylate water reducing agent as a fifth component of modern concrete is an essential component in concrete and plays a central role in the concrete production technology. The main raw material of the polycarboxylic acid water reducing agent is unsaturated polyether, which is a polyether monomer with a certain molecular weight obtained by directly carrying out polymerization reaction on allyl alcohol, methallyl alcohol, isopentenol and the like serving as raw materials and ethylene oxide anions.
With the reduction of natural high-quality sandstone aggregate resources and the application of industrial waste residues and machine-made sandstone in commercial concrete, the clay and stone powder content in the sandstone aggregate is increased, and the application problems of large fluctuation of water reducing performance, poor slump loss resistance and the like of the polycarboxylic acid water reducing agent synthesized by the polyether are more and more prominent. At present, polyether with different molecular weight is prepared by reacting different unsaturated alcohol and ethylene oxide, for example, Chinese patent CN102206335B, CN111848944A, etc., and the research on the aspect of polycarboxylic acid water reducing agent by the molecular structure is not reported. Therefore, the influence of the polyether structure on the polycarboxylate superplasticizer is deeply researched, and the development and synthesis of novel polyether for improving the performance of the polycarboxylate superplasticizer are of great significance.
The main stream raw materials for synthesizing the domestic polycarboxylate superplasticizer are methyl allyl polyoxyethylene ether and isopentenyl polyoxyethylene ether, the water reducer synthesized by the polyether is sensitive to the content of clay and stone powder in the aggregate of sandstone, so that the water reducing performance is reduced, and the slump retaining performance of the mixed concrete is deteriorated to cause pump blockage and the like.
Disclosure of Invention
The invention aims to provide a polyether macromonomer and a preparation method thereof, wherein the polyether macromonomer contains structures of carbamate and sulfonylurea, and can effectively solve a plurality of defects in the prior art.
The polyether macromonomer is used for preparing the polycarboxylate superplasticizer, free radical polymerization is carried out on the polyether macromonomer and unsaturated carboxylic acid, reaction can be carried out at room temperature, heating is not needed in the production process, production energy consumption is low, acid-ether ratio can be reduced by adopting the polyether to synthesize the polycarboxylate superplasticizer, slump retaining performance of the polycarboxylate superplasticizer is improved, and resources are saved.
The specific technical scheme of the invention is as follows:
a method for preparing a polyether macromonomer, comprising the steps of:
1) unsaturated alcohol containing active hydrogen and olefin oxide are used as raw materials, and ring-opening polymerization is carried out under heating under the condition of nitrogen and under the action of a catalyst to obtain a polyoxyethylene ether monomer intermediate;
2) mixing the polyoxyethylene ether monomer intermediate synthesized in the step 1) with a catalyst, continuously introducing olefin oxide to react under the condition of nitrogen, and performing heat preservation curing and vacuum degassing treatment after the feeding is finished to obtain a polyoxyethylene ether monomer;
3) adding benzyl carbamate into the polyoxyethylene ether monomer in the step 2), and reacting under heating to obtain a formamide-terminated polyether macromonomer;
4) adding substituted sulfonyl isocyanate into the formamide-terminated polyether macromonomer synthesized in the step 3), heating for reaction, and adjusting the pH after cooling to obtain the polyether macromonomer.
The mass ratio of the unsaturated alcohol containing active hydrogen to the olefin oxide in the step 1) is 1.0: 0.1-8.0;
the unsaturated alcohol containing active hydrogen in the step 1) is unsaturated alcohol, and comprises one of allyl alcohol, methallyl alcohol, isopentenol and ethylene glycol monovinyl ether.
The alkylene oxide in the step 1) is alkylene oxide which comprises one or two of ethylene oxide and propylene oxide.
Preferably, the mass ratio of the unsaturated alcohol containing active hydrogen to the olefin oxide in the step 1) is 1.0: 0.1-5.0,
preferably, the catalyst in step 1) comprises one of sodium hydroxide, metallic sodium, sodium hydride, sodium methoxide, potassium hydroxide, potassium methoxide or potassium tert-butoxide, and the dosage of the catalyst is 0.1-5% of the total mass of the unsaturated alcohol containing active hydrogen and the olefin oxide.
Preferably, the reaction temperature in the step 1) is between 100 and 120 ℃, and the reaction pressure is less than or equal to 0.5 MPa.
In the step 2), the mass ratio of the polyoxyethylene ether monomer intermediate to the oxyalkylene is 1.0: 1.0-5.0; preferably, the mass ratio of the polyoxyethylene ether monomer intermediate to the oxyalkylene is 1.0: 1.0-3.0.
The alkylene oxide in the step 2) is alkylene oxide which comprises one or two of ethylene oxide and propylene oxide.
The catalyst in the step 2) comprises one of sodium hydroxide, metal sodium, sodium hydride, sodium methoxide, potassium hydroxide, potassium methoxide or potassium tert-butoxide, and the dosage of the catalyst is 0.1-5% of the total mass of the polyoxyethylene ether monomer intermediate;
in the step 2), the reaction temperature is 120-140 ℃, and the reaction pressure is less than or equal to 0.6 MPa.
In the step 3), the dosage of the benzyl carbamate is 3-8% of the mass of the polyoxyethylene ether monomer;
the reaction temperature in the step 3) is 80-110 ℃.
The substituted sulfonyl isocyanate in the step 4) comprises one of chlorosulfonyl isocyanate and aryl sulfonyl isocyanate;
the reaction temperature in the step 4) is 80-110 ℃;
and (4) after the reaction is finished, cooling to 60-70 ℃, adding acetic acid to adjust the pH to 6-8, and thus obtaining the polyether macromonomer.
The polyether macromonomer provided by the invention is prepared by the method, and the structural formula of the polyether macromonomer is as follows:
wherein R is1One selected from allyl alcohol group, methyl allyl alcohol group, isoamylene alcohol group and ethylene glycol monovinyl ether group; r2One selected from chlorine, phenyl and substituted phenyl.
The invention provides application of a polyether macromonomer to preparation of a polycarboxylic acid water reducing agent.
The specific application method comprises the following steps: the polyether macromonomer synthesized by the method is used as a raw material to polymerize with acrylic acid to synthesize the polycarboxylic acid water reducing agent, and the synthesis process comprises the following steps:
A. weighing 300 parts of the polyether macromonomer synthesized by the method according to the parts by weight, and adding water to dilute the polyether macromonomer to 60% of mass solid content; then adding 3 parts of hydrogen peroxide (with the mass concentration of 30 percent), stirring the mixture until the mixture is clear and transparent solution,
B. weighing 28 parts of acrylic acid and 1.5 parts of mercaptopropionic acid by weight, adding 50 parts of water, and uniformly mixing to obtain a dropwise added solution A;
C. weighing 510.8 parts of reducing agent E and 60 parts of water according to the parts by weight to obtain dropwise added solution B;
D. setting the dropping time of the dropping solution A to be 2-2.5h, setting the dropping time of the dropping solution B to be 3h, naturally heating in the dropping process, and continuously preserving heat for 1h after the dropping is finished; and (4) neutralizing by using 20% liquid caustic soda by mass until the pH value is 6 to obtain a viscous polycarboxylic acid water reducing agent finished product.
The liquid alkali is sodium hydroxide solution.
According to the invention, polyether molecules are branched and terminated, polyether terminal hydroxyl is esterified by benzyl carbamate, formed terminal amino is sulfonylated by sulfonyl ester to form sulfonylurea, and a structure containing carbamate and sulfonylurea is introduced into unsaturated polyether.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some 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.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A method for preparing a polyether macromonomer, comprising the steps of:
under the protection of nitrogen, 200 parts by weight of methallyl alcohol and 5 parts by weight of catalyst metal sodium are mixed at the temperature of 55 ℃, then the temperature is raised to 110 ℃, 1000 parts by weight of first part of ethylene oxide is added under the pressure of 0.1-0.5MPa, and the first reaction mixture is cured at the temperature of 110 ℃ to obtain an intermediate product; taking 200 parts of intermediate product, mixing 2 parts of catalyst metal sodium and 200 parts of the intermediate product at the temperature of 80 ℃ in the nitrogen atmosphere, adding 800 parts by weight of second part of ethylene oxide under the pressure of 0.1-0.5MPa, and curing at the temperature of 120 ℃ until the pressure is not reduced any more to obtain 1000 parts of polyether product; slowly dripping 60 parts by weight of benzyl carbamate into a reactor containing 1000 parts of polyether product at a constant speed under the protection of nitrogen, controlling the reaction temperature to be about 90 ℃, dripping for 60min, preserving heat and curing for 1h after dripping to obtain polyether with an amino end cap, slowly dripping 60 parts by weight of chlorosulfonyl isocyanate into the reactor at a constant speed under the protection of nitrogen, dripping for 60min, preserving heat and curing for 1h after dripping, vacuumizing and degassing, cooling to 60-70 ℃, adding acetic acid to adjust the pH value to 6-8 to obtain a polyether macromonomer, wherein the structural formula is as follows:
weighing 300 parts of the polyether macromonomer synthesized by the method, and adding water to dilute the polyether macromonomer to 60% of solid content; then adding 3 parts of hydrogen peroxide (30%); weighing 28 parts of acrylic acid and 1.5 parts of mercaptopropionic acid, and adding 50 parts of water to uniformly mix to obtain a dropwise added solution A; weighing 510.8 parts of reducing agent E, and adding 60 parts of water to obtain dropwise added solution B; setting the dropping time of the dropping solution A to be 2 hours, setting the dropping time of the dropping solution B to be 3 hours, naturally heating in the dropping process, and continuously preserving the heat for 1 hour after the dropping is finished; and (4) neutralizing the mixture by using 20% sodium hydroxide solution until the pH value is 6 to obtain a viscous polycarboxylic acid water reducing agent finished product.
Example 2
A method for preparing a polyether macromonomer, comprising the steps of:
under the protection of nitrogen, 200 parts by weight of methallyl alcohol and 5 parts by weight of catalyst metal sodium are mixed at the temperature of 55 ℃, then the temperature is raised to 110 ℃, 1000 parts by weight of first part of ethylene oxide is added under the pressure of 0.1-0.5MPa, and the first reaction mixture is cured at the temperature of 110 ℃ to obtain an intermediate product; taking 200 parts of intermediate product, mixing 2 parts of catalyst metal sodium and 200 parts of the intermediate product at the temperature of 80 ℃ in the nitrogen atmosphere, adding 800 parts by weight of second part of ethylene oxide under the pressure of 0.1-0.5MPa, and curing at the temperature of 120 ℃ until the pressure is not reduced any more to obtain 1000 parts of polyether product; slowly dripping 60 parts by weight of benzyl carbamate into a reactor containing 1000 parts of polyether product at a constant speed under the protection of nitrogen, controlling the reaction temperature to be about 90 ℃, dripping for 60min, preserving heat and curing for 1h after dripping to obtain polyether with an amino end cap, slowly dripping 35 parts by weight of phenyl sulfonyl isocyanate into the reactor at a constant speed under the protection of nitrogen, dripping for 60min, preserving heat and curing for 1h after dripping, vacuumizing and degassing, cooling to 60-70 ℃, adding acetic acid to adjust the pH value to 6-8 to obtain a polyether macromonomer, wherein the structural formula is as follows:
weighing 300 parts of the polyether macromonomer synthesized by the method, and adding water to dilute the polyether macromonomer to 60% of solid content; then adding 3 parts of hydrogen peroxide (30%); weighing 28 parts of acrylic acid and 1.5 parts of mercaptopropionic acid, and adding 50 parts of water to uniformly mix to obtain a dropwise added solution A; weighing 510.8 parts of reducing agent E, and adding 60 parts of water to obtain dropwise added solution B; setting the dropping time of the dropping solution A to be 2 hours, setting the dropping time of the dropping solution B to be 3 hours, naturally heating in the dropping process, and continuously preserving the heat for 1 hour after the dropping is finished; and (4) neutralizing the mixture by using 20% sodium hydroxide solution until the pH value is 6 to obtain a viscous polycarboxylic acid water reducing agent finished product.
Example 3
A method for preparing a polyether macromonomer, comprising the steps of:
under the protection of nitrogen, 200 parts by weight of isopentenol and 5 parts by weight of catalyst metal sodium are mixed at the temperature of 55 ℃, then the temperature is raised to 110 ℃, 1000 parts by weight of first part of ethylene oxide is added under the pressure of 0.1-0.5MPa, and the first reaction mixture is cured at the temperature of 110 ℃ to obtain an intermediate product; taking 200 parts of intermediate product, mixing 2 parts of catalyst metal sodium and 200 parts of the intermediate product at the temperature of 80 ℃ in the nitrogen atmosphere, adding 800 parts by weight of second part of ethylene oxide under the pressure of 0.1-0.5MPa, and curing at the temperature of 120 ℃ until the pressure is not reduced any more to obtain 1000 parts of polyether product; slowly dripping 60 parts by weight of benzyl carbamate into a reactor containing 1000 parts of polyether product at a constant speed under the protection of nitrogen, controlling the reaction temperature to be about 90 ℃, dripping for 60min, preserving heat and curing for 1h after dripping to obtain polyether with an amino end cap, slowly dripping 60 parts by weight of chlorosulfonyl isocyanate into the reactor at a constant speed under the protection of nitrogen, dripping for 60min, preserving heat and curing for 1h after dripping, vacuumizing and degassing, cooling to 60-70 ℃, adding acetic acid to adjust the pH value to 6-8 to obtain a polyether macromonomer, wherein the structural formula is as follows:
weighing 300 parts of the polyether macromonomer synthesized by the method, and adding water to dilute the polyether macromonomer to 60% of solid content; then adding 3 parts of hydrogen peroxide (30%); weighing 28 parts of acrylic acid and 1.5 parts of mercaptopropionic acid, and adding 50 parts of water to uniformly mix to obtain a dropwise added solution A; weighing 510.8 parts of reducing agent E, and adding 60 parts of water to obtain dropwise added solution B; setting the dropping time of the dropping solution A to be 2 hours, setting the dropping time of the dropping solution B to be 3 hours, naturally heating in the dropping process, and continuously preserving the heat for 1 hour after the dropping is finished; and (4) neutralizing the mixture by using 20% sodium hydroxide solution until the pH value is 6 to obtain a viscous polycarboxylic acid water reducing agent finished product.
Example 4
A method for preparing a polyether macromonomer, comprising the steps of:
under the protection of nitrogen, 200 parts by weight of isopentenol and 5 parts by weight of catalyst metal sodium are mixed at the temperature of 55 ℃, then the temperature is raised to 110 ℃, 1000 parts by weight of first part of ethylene oxide is added under the pressure of 0.1-0.5MPa, and the first reaction mixture is cured at the temperature of 110 ℃ to obtain an intermediate product; taking 200 parts of intermediate product, mixing 2 parts of catalyst metal sodium and 200 parts of the intermediate product at the temperature of 80 ℃ in the nitrogen atmosphere, adding 800 parts by weight of second part of ethylene oxide under the pressure of 0.1-0.5MPa, and curing at the temperature of 120 ℃ until the pressure is not reduced any more to obtain 1000 parts of polyether product; slowly dripping 60 parts by weight of benzyl carbamate into a reactor containing 1000 parts of polyether product at a constant speed under the protection of nitrogen, controlling the reaction temperature to be about 90 ℃, dripping for 60min, preserving heat and curing for 1h after dripping to obtain polyether with an amino end cap, slowly dripping 35 parts by weight of phenyl sulfonyl isocyanate into the reactor at a constant speed under the protection of nitrogen, dripping for 60min, preserving heat and curing for 1h after dripping, vacuumizing and degassing, cooling to 60-70 ℃, adding acetic acid to adjust the pH value to 6-8 to obtain a polyether macromonomer, wherein the structural formula is as follows:
weighing 300 parts of the polyether macromonomer synthesized by the method, and adding water to dilute the polyether macromonomer to 60% of solid content; then adding 3 parts of hydrogen peroxide (30%); weighing 28 parts of acrylic acid and 1.5 parts of mercaptopropionic acid, and adding 50 parts of water to uniformly mix to obtain a dropwise added solution A; weighing 510.8 parts of reducing agent E, and adding 60 parts of water to obtain dropwise added solution B; setting the dropping time of the dropping solution A to be 2 hours, setting the dropping time of the dropping solution B to be 3 hours, naturally heating in the dropping process, and continuously preserving the heat for 1 hour after the dropping is finished; and (4) neutralizing by using 20% liquid alkali to pH 6 to obtain a viscous polycarboxylic acid water reducing agent finished product.
In the application embodiment of the invention, except for special description, all the adopted cements are ordinary portland cement (p.o42.5), in order to compare the dispersing performance and the dispersion retention performance of the water reducing agent prepared by the invention, a cement paste fluidity test is carried out according to the standard GB8077-2012, 300g of cement and 87g of water are added, the cement paste fluidity is measured on flat glass after stirring for 4 minutes, and the paste fluidity at different times is tested. The test data are shown in table 1.
TABLE 1 Cement paste fluidity test
The solid content of the water reducing agent prepared by the method is 50 percent; the folding and fixing amount of the water reducing agent is the percentage of the folding and fixing amount of the water reducing agent to the mass of the cement.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
The polyether macromonomer structure of the invention introduces the structure of carbamate and sulfonylurea, thereby increasing the water reducing and dispersing effects of the synthetic water reducing agent and improving the slump retaining performance; the raw materials used in the invention are simple and easy to obtain, and the prepared polycarboxylate superplasticizer mother liquor synthesized by the polyether macromonomer has stable performance.
Claims (10)
1. A preparation method of a polyether macromonomer is characterized by comprising the following steps:
1) unsaturated alcohol containing active hydrogen and olefin oxide are used as raw materials, and ring-opening polymerization is carried out under heating under the condition of nitrogen and under the action of a catalyst to obtain a polyoxyethylene ether monomer intermediate;
2) mixing the polyoxyethylene ether monomer intermediate synthesized in the step 1) with a catalyst, continuously introducing olefin oxide under the condition of nitrogen, and performing curing and degassing treatment after the feeding is finished to obtain a polyoxyethylene ether monomer;
3) adding benzyl carbamate into the polyoxyethylene ether monomer in the step 2), and reacting under heating to obtain a formamide-terminated polyether macromonomer;
4) adding substituted sulfonyl isocyanate into the formamide-terminated polyether macromonomer synthesized in the step 3), heating for reaction, and adjusting the pH after cooling to obtain the polyether macromonomer.
2. The preparation method according to claim 1, wherein the mass ratio of the unsaturated alcohol containing active hydrogen to the olefin oxide in the step 1) is 1.0: 0.1-8.0.
3. The preparation method of claim 1, wherein the reaction temperature in step 1) is 100-120 ℃ and the reaction pressure is less than or equal to 0.5 MPa.
4. The preparation method according to claim 1, wherein the mass ratio of the polyoxyethylene ether monomer intermediate to the oxyalkylene in the step 2) is 1.0: 1.0-5.0.
5. The preparation method of claim 1, wherein the reaction temperature in the step 2) is 120-140 ℃, and the reaction pressure is less than or equal to 0.6 MPa.
6. The preparation method according to claim 1, wherein the amount of benzyl carbamate used in step 3) is 3-8% of the mass of the polyoxyethylene ether monomer.
7. The method according to claim 1, wherein the reaction temperature in the step 3) is 80 to 110 ℃.
8. The preparation method of claim 1, wherein the temperature is reduced to 60-70 ℃ after the reaction in the step 4) is finished, and acetic acid is added to adjust the pH to 6-8, so as to obtain the polyether macromonomer.
9. A polyether macromonomer prepared by the process according to any one of claims 1 to 8, wherein the polyether macromonomer has the structural formula:
10. Use of a polyether macromonomer prepared by the process according to any one of claims 1 to 8 for the preparation of a polycarboxylic acid water reducing agent.
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