CN116655865B - Preparation process and application of modified polycarboxylic acid type high-efficiency water reducer - Google Patents

Preparation process and application of modified polycarboxylic acid type high-efficiency water reducer Download PDF

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CN116655865B
CN116655865B CN202310955916.1A CN202310955916A CN116655865B CN 116655865 B CN116655865 B CN 116655865B CN 202310955916 A CN202310955916 A CN 202310955916A CN 116655865 B CN116655865 B CN 116655865B
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polyoxyethylene ether
type high
mass
polycarboxylic acid
glycol monomethyl
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CN116655865A (en
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南春明
李红伟
乔金宁
杨保旺
李庆宏
侯军岐
蔡艳辉
任兴兴
周扬
张亚运
霍艳艳
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Xingtai Jiangong Commercial Concrete Co ltd
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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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Polyethers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a preparation process and application of a modified polycarboxylic acid type high-efficiency water reducer, and relates to the technical field of building materials. When the modified polycarboxylic acid type high-efficiency water reducer is prepared, methyl allyl polyoxyethylene ether and 4-valeric acid are reacted to prepare alkynylated methyl allyl polyoxyethylene ether; reacting alkynylated methallyl polyoxyethylene ether with 2-azidoacetamide to prepare aminated methallyl polyoxyethylene ether; reacting thionyl chloride with polyethylene glycol monomethyl ether to prepare chloro polyethylene glycol monomethyl ether; reacting chloro polyethylene glycol monomethyl ether with aminated methyl allyl polyoxyethylene ether to prepare a branched macromonomer; and (3) carrying out polymerization reaction on the branched macromonomer and acrylic acid to obtain the modified polycarboxylic acid type high-efficiency water reducer. The modified polycarboxylic acid type high-efficiency water reducer prepared by the invention has good dispersibility and wettability.

Description

Preparation process and application of modified polycarboxylic acid type high-efficiency water reducer
Technical Field
The invention relates to the technical field of building materials, in particular to a preparation process and application of a modified polycarboxylic acid type high-efficiency water reducer.
Background
Polycarboxylic acid water reducers are one of the most important water reducers for concrete because of their excellent properties, they fluidize cement even in the case of low cement content, require relatively low dosage, and exhibit long slump retention ability, as compared with other products such as polycondensates. The high dispersion efficiency of polycarboxylate water reducers can be attributed to the nonionic side chains, which extend into the pore solution and act as a spatial barrier to keep the cement particles separated. In addition, since the polycarboxylate water reducer is adsorbed on the surfaces of cement particles, negative charges are generated on the surfaces of cement particles, which also causes electrostatic repulsion between cement particles. However, a key parameter for effective dispersion is the thickness of the adsorbed layer of the polycarboxylate water reducer on the cement surface.
According to the Ottewill-Walker equation, a high dimensional stability of the particle suspension can be achieved in particular by polymers which form particularly thick adsorption layers. The results of the studies indicate that branched structures appear to be very beneficial for steric stabilization, which is why these hyperbranched structures are attractive elements for the development of novel water reducers, and their preparation, unfortunately, generally involves cumbersome and time-consuming multiple synthetic steps. Therefore, the polycarboxylate water reducer with the hyperbranched structure and good water reducing and dispersing properties is developed, and has great market prospect.
Disclosure of Invention
The invention aims to provide a preparation process and application of a modified polycarboxylic acid type high-efficiency water reducer, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation process of the modified polycarboxylic acid type high-efficiency water reducer comprises the following preparation steps:
(1) Reacting methyl allyl polyoxyethylene ether with 4-pentynoic acid to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Reacting alkynylated methallyl polyoxyethylene ether with 2-azidoacetamide to prepare aminated methallyl polyoxyethylene ether;
(3) Reacting the sulfoxide chloride solution with polyethylene glycol monomethyl ether to prepare chlorinated polyethylene glycol monomethyl ether;
(4) Reacting chloro polyethylene glycol monomethyl ether with aminated methyl allyl polyoxyethylene ether to prepare a branched macromonomer;
(5) And (3) carrying out polymerization reaction on the branched macromonomer and acrylic acid to obtain the modified polycarboxylic acid type high-efficiency water reducer.
Further, the preparation method comprises the following preparation steps:
(1) Uniformly mixing methyl allyl polyoxyethylene ether, 4-valeric acid, 4-dimethylaminopyridine and methylene dichloride according to the mass ratio of 1:0.07-0.08:0.05-0.06:5-7, stirring for 6-8 min at 20-30 ℃ at 200-300 r/min, adding N, N' -dicyclohexylcarbodiimide with the mass of 0.15-0.16 times that of the methyl allyl polyoxyethylene ether, continuously stirring for reacting for 20-24 h, filtering to remove the precipitate, placing in N-hexane at-10 to-5 ℃ for precipitation, filtering to obtain the precipitate, and drying at 20-30 ℃ at 10-20 Pa for 6-8 h to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Uniformly mixing 2-azidoethylamine, alkynylated methyl allyl polyoxyethylene ether, dimethyl sulfoxide and water according to the mass ratio of 1:4:20-30, adding copper sulfate with the mass of 0.01-0.02 times of the 2-azidoethylamine and sodium ascorbate with the mass of 0.01-0.02 times of the 2-azidoethylamine, stirring at 65-70 ℃ for reacting for 20-24 h at 200-300 r/min, placing in n-hexane at-10 to-5 ℃ for precipitation, filtering, taking the precipitate, placing at 20-30 ℃ and drying at 10-20 Pa for 6-8 h to obtain the aminated methyl allyl polyoxyethylene ether;
(3) Uniformly mixing polyethylene glycol monomethyl ether and methylene dichloride according to a mass ratio of 1:2-3, dropwise adding a sulfoxide chloride solution with the mass of 0.3-0.4 times of that of the polyethylene glycol monomethyl ether at a constant speed within 40-60 min under the stirring condition of 43-45 ℃ and 200-300 r/min, continuously stirring and refluxing for 20-24 h after the dropwise adding, naturally cooling to room temperature, and then placing the mixture at 20-30 ℃ and drying at 10-20 Pa for 6-8 h to obtain chlorinated polyethylene glycol monomethyl ether;
(4) Uniformly mixing chloropolyethylene glycol monomethyl ether, acetonitrile, potassium carbonate and potassium iodide according to the mass ratio of 1:2-3:0.1-0.2:0.01-0.02, adding amino methyl allyl polyoxyethylene ether with the mass of 2.4-2.6 times that of the chloropolyethylene glycol monomethyl ether under the condition of avoiding light in a nitrogen atmosphere, stirring and refluxing for 20-24 hours at 70-80 ℃ and 200-300 r/min, placing in normal hexane at-10 to-5 ℃ for precipitation, filtering, taking the precipitate, and drying for 6-8 hours at 10-20 Pa at 20-30 ℃ to obtain a branched macromolecular monomer;
(5) Uniformly mixing the branched macromer and pure water according to the mass ratio of 1:4-5, heating to 60-65 ℃, adding hydrogen peroxide with the mass fraction of 0.3-0.4 times of the mass fraction of the branched macromer, dropwise adding acrylic acid with the mass of 2-3 times of the branched macromer and ascorbic acid with the mass of 0.04-0.06 times of the branched macromer at a uniform speed within 3 hours under stirring at 600-800 r/min, continuing stirring for reacting for 6-8 hours after the dropwise adding, cooling to room temperature, adjusting the PH to 6.8-7.2 by using sodium hydroxide with the mass fraction of 25-30%, and drying for 6-8 hours at 20-30 ℃ under 10-20 Pa to obtain the modified polycarboxylic acid type high-efficiency water reducer.
Further, the model of the methallyl polyoxyethylene ether in the step (1) is HPEG-2400.
Further, the sulfoxide chloride solution in the step (3) is prepared by uniformly mixing sulfoxide chloride and methylene dichloride according to a mass ratio of 1:1.6-1.8.
Further, the model of the polyethylene glycol monomethyl ether in the step (3) is MPEG500.
Compared with the prior art, the invention has the following beneficial effects:
the modified polycarboxylic acid type high-efficiency water reducer is prepared by carrying out polymerization reaction on branched macromer and acrylic acid.
Firstly, reacting methyl allyl polyoxyethylene ether with 4-pentynoic acid to obtain alkynylated methyl allyl polyoxyethylene ether; reacting alkynylated methallyl polyoxyethylene ether with 2-azidoacetamide to prepare aminated methallyl polyoxyethylene ether; reacting thionyl chloride with polyethylene glycol monomethyl ether to prepare chloro polyethylene glycol monomethyl ether; reacting chloro polyethylene glycol monomethyl ether with aminated methyl allyl polyoxyethylene ether to prepare a branched macromonomer; the branched macromonomer enables the modified polycarboxylic acid type high-efficiency water reducer prepared by polymerization to form a hyperbranched structure, and meanwhile, the branched molecular chain is a polyethylene glycol chain segment, so that the modified polycarboxylic acid type high-efficiency water reducer has good flexibility and hydrophilicity, and the dispersibility and wettability are improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the details, and the test methods of each index of the modified polycarboxylic acid type high efficiency water reducer prepared in the following examples are as follows:
dispersion properties: the materials obtained in each of the examples and comparative examples were tested for average diffusion diameter as fluidity according to GB8077-2012, "concrete admixture homogeneity test and method".
Infiltration performance: the materials obtained in each example and comparative example were mixed with pure water at a mass ratio of 1:10, and the equilibrium surface tension was measured at 25℃by the German KRUSS automatic tensiometer platinum plate method.
Example 1
(1) Uniformly mixing methyl allyl polyoxyethylene ether HPEG-2400, 4-valeric acid, 4-dimethylaminopyridine and methylene dichloride according to the mass ratio of 1:0.07:0.05:5, stirring for 8min at 20 ℃ and 200r/min, adding N, N' -dicyclohexylcarbodiimide with the mass of 0.15 times that of the methyl allyl polyoxyethylene ether HPEG-2400, continuously stirring for reacting for 24h, filtering to remove sediment, placing in N-hexane at-10 ℃ for precipitation, filtering to obtain sediment, placing in 20 ℃ and drying for 8h at 10Pa to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Uniformly mixing 2-azidoethylamine, alkynylated methallyl polyoxyethylene ether, dimethyl sulfoxide and water according to a mass ratio of 1:4:20, adding copper sulfate with the mass of 0.01 times of the 2-azidoethylamine and sodium ascorbate with the mass of 0.01 times of the 2-azidoethylamine, stirring at 65 ℃ for 24 hours at 200/min, placing in normal hexane with the temperature of minus 10 ℃ for precipitation, filtering, taking the precipitate, placing at 20 ℃ and drying at 10Pa for 8 hours to obtain the aminated methallyl polyoxyethylene ether;
(3) Uniformly mixing thionyl chloride and methylene dichloride according to a mass ratio of 1:1.6 to prepare a thionyl chloride solution, uniformly mixing polyethylene glycol monomethyl ether MPEG500 and methylene dichloride according to a mass ratio of 1:2, dropwise adding the thionyl chloride solution which is 0.3 times of the polyethylene glycol monomethyl ether MPEG500 at a uniform speed within 40min under the stirring condition of 43 ℃ and 200r/min, continuously stirring and refluxing for 24 hours after the dropwise adding is finished, naturally cooling to room temperature, and then placing the mixture at 20 ℃ and drying for 8 hours under 10Pa to prepare the chlorinated polyethylene glycol monomethyl ether;
(4) Uniformly mixing chloropolyethylene glycol monomethyl ether, acetonitrile, potassium carbonate and potassium iodide according to the mass ratio of 1:2:0.1:0.01, adding aminated methyl allyl polyoxyethylene ether with the mass of 2.4 times that of the chloropolyethylene glycol monomethyl ether under the condition of avoiding light, stirring and refluxing for 24 hours at 70 ℃ and 200r/min, placing in normal hexane at-10 ℃ for precipitation, filtering, taking the precipitate, placing at 20 ℃ and drying at 10Pa for 8 hours to obtain a branched macromolecular monomer;
(5) Uniformly mixing the branched macromer and pure water according to the mass ratio of 1:4, heating to 60 ℃, adding hydrogen peroxide with the mass fraction of 30% which is 0.3 times that of the branched macromer, dropwise adding acrylic acid with the mass of 2 times that of the branched macromer and ascorbic acid with the mass of 0.04 times that of the branched macromer at a constant speed within 3 hours under the stirring of 600r/min, continuing stirring for reacting for 8 hours after the dropwise adding is finished, cooling to room temperature, adjusting the PH to 6.8 by using sodium hydroxide with the mass fraction of 25%, placing at 20 ℃, and drying for 8 hours under 10Pa, thus obtaining the modified polycarboxylic acid type high-efficiency water reducer.
Example 2
(1) Uniformly mixing methyl allyl polyoxyethylene ether HPEG-2400, 4-valeric acid, 4-dimethylaminopyridine and methylene dichloride according to the mass ratio of 1:0.075:0.055:6, stirring for 7min at 25 ℃ and 250r/min, adding N, N' -dicyclohexylcarbodiimide which is 0.155 times of the mass of methyl allyl polyoxyethylene ether HPEG-2400, continuously stirring for reacting for 22h, filtering to remove sediment, precipitating in normal hexane at-7.5 ℃, filtering to obtain sediment, drying for 7h at 25 ℃ and 15Pa to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Uniformly mixing 2-azidoethyl amine, alkynylated methyl allyl polyoxyethylene ether, dimethyl sulfoxide and water according to the mass ratio of 1:4:25, adding copper sulfate with the mass of 0.015 times of the 2-azidoethyl amine and sodium ascorbate with the mass of 0.015 times of the 2-azidoethyl amine, stirring at 67.5 ℃ for reacting for 22 hours at 250r/min, placing in normal hexane at-7.5 ℃ for precipitation, filtering, taking out the precipitate, placing at 25 ℃ and drying at 15Pa for 7 hours to obtain the aminated methyl allyl polyoxyethylene ether;
(3) Uniformly mixing thionyl chloride and methylene dichloride according to the mass ratio of 1:1.7 to prepare a thionyl chloride solution, uniformly mixing polyethylene glycol monomethyl ether MPEG500 and methylene dichloride according to the mass ratio of 1:2.5, dropwise adding the thionyl chloride solution which is 0.35 times of the polyethylene glycol monomethyl ether MPEG500 at a uniform speed within 50min under the stirring condition of 44 ℃ and 250r/min, continuously stirring and refluxing for 22h after the dropwise adding is finished, naturally cooling to room temperature, and drying for 7h at the temperature of 25 ℃ under the pressure of 15Pa to prepare the chlorinated polyethylene glycol monomethyl ether;
(4) Uniformly mixing chloropolyethylene glycol monomethyl ether, acetonitrile, potassium carbonate and potassium iodide according to the mass ratio of 1:2.5:0.15:0.015, adding aminated methyl allyl polyoxyethylene ether with the mass of 2.5 times that of the chloropolyethylene glycol monomethyl ether under the condition of avoiding light in a nitrogen atmosphere, stirring and refluxing for 22 hours at 75 ℃ and 250r/min, placing in normal hexane at-7.5 ℃ for precipitation, filtering, taking the precipitate, placing in 25 ℃ and drying for 7 hours at 15Pa to prepare a branched macromolecular monomer;
(5) Uniformly mixing the branched macromer and pure water according to the mass ratio of 1:4.5, heating to 62.5 ℃, adding hydrogen peroxide with the mass fraction of 0.35 times of the mass of the branched macromer, dropwise adding acrylic acid with the mass of 2.5 times of the branched macromer and ascorbic acid with the mass of 0.05 times of the branched macromer at a uniform speed within 3 hours under the stirring of 700r/min, continuing stirring for reacting for 7 hours after the dropwise adding, cooling to room temperature, adjusting the PH to 7 by using sodium hydroxide with the mass fraction of 27.5%, and drying for 7 hours at the temperature of 25 ℃ under the pressure of 15Pa, thus obtaining the modified polycarboxylic acid type high-efficiency water reducer.
Example 3
(1) Uniformly mixing methyl allyl polyoxyethylene ether HPEG-2400, 4-valeric acid, 4-dimethylaminopyridine and methylene dichloride according to the mass ratio of 1:0.08:0.06:7, stirring for 6min at 30 ℃ and 300r/min, adding N, N' -dicyclohexylcarbodiimide with the mass of 0.16 times that of the methyl allyl polyoxyethylene ether HPEG-2400, continuously stirring for reacting for 20h, filtering to remove sediment, placing in N-hexane at-5 ℃ for precipitation, filtering to obtain sediment, placing in 30 ℃ and drying for 6h at 20Pa to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Uniformly mixing 2-azidoethylamine, alkynylated methallyl polyoxyethylene ether, dimethyl sulfoxide and water according to a mass ratio of 1:4:30, adding copper sulfate with the mass of 0.02 times of the 2-azidoethylamine and sodium ascorbate with the mass of 0.02 times of the 2-azidoethylamine, stirring at 70 ℃ and 300r/min for reaction for 20 hours, placing in n-hexane at-5 ℃ for precipitation, filtering, taking the precipitate, placing at 30 ℃ and drying at 20Pa for 6 hours to obtain the aminated methallyl polyoxyethylene ether;
(3) Uniformly mixing thionyl chloride and methylene dichloride according to a mass ratio of 1:1.8 to prepare a thionyl chloride solution, uniformly mixing polyethylene glycol monomethyl ether MPEG500 and methylene dichloride according to a mass ratio of 1:3, dropwise adding the thionyl chloride solution which is 0.4 times of the polyethylene glycol monomethyl ether MPEG500 at a uniform speed within 60 minutes under the stirring condition of 45 ℃ and 300r/min, continuously stirring and refluxing for 20 hours after the dropwise adding is finished, naturally cooling to room temperature, and drying at 30 ℃ under 20Pa for 6 hours to prepare chlorinated polyethylene glycol monomethyl ether;
(4) Uniformly mixing chloropolyethylene glycol monomethyl ether, acetonitrile, potassium carbonate and potassium iodide according to the mass ratio of 1:3:0.2:0.02, adding aminated methyl allyl polyoxyethylene ether with the mass of 2.6 times that of the chloropolyethylene glycol monomethyl ether under the condition of avoiding light, stirring and refluxing for 20 hours at 80 ℃ and 300r/min, placing in normal hexane with the temperature of minus 10 ℃ to minus 5 ℃ for precipitation, filtering, taking the precipitate, and drying for 6 hours at 30 ℃ and 20Pa to obtain a branched macromolecular monomer;
(5) Uniformly mixing the branched macromer and pure water according to the mass ratio of 1:5, heating to 65 ℃, adding hydrogen peroxide with the mass fraction of 30% which is 0.4 times that of the branched macromer, dropwise adding acrylic acid with the mass of 3 times that of the branched macromer and ascorbic acid with the mass of 0.06 times that of the branched macromer at a uniform speed within 3 hours under the stirring of 800r/min, continuously stirring for reaction for 6 hours after the dropwise adding is finished, cooling to room temperature, regulating the PH to 7.2 by using sodium hydroxide with the mass fraction of 30%, placing at 30 ℃ and drying at 20Pa for 6 hours, thus obtaining the modified polycarboxylic acid type high-efficiency water reducer.
Comparative example 1
(1) Uniformly mixing methyl allyl polyoxyethylene ether HPEG-2400 and pure water according to a mass ratio of 1:4.5, heating to 62.5 ℃, adding hydrogen peroxide with a mass fraction of 30% and with a mass fraction of 0.35 times that of the methyl allyl polyoxyethylene ether, dropwise adding acrylic acid with a mass fraction of 2.5 times that of the methyl allyl polyoxyethylene ether and ascorbic acid with a mass fraction of 0.05 times that of the methyl allyl polyoxyethylene ether at a constant speed within 3 hours under stirring at 700r/min, continuing stirring for reacting for 7 hours after the dropwise adding, cooling to room temperature, adjusting the PH to 7 by using sodium hydroxide with a mass fraction of 27.5%, and drying for 7 hours at 25 ℃ and 15Pa to obtain the modified polycarboxylic acid type high-efficiency water reducer.
Effect example
The following table 1 shows the analysis results of dispersibility and wettability of the modified polycarboxylic acid type high efficiency water reducing agent prepared by using examples 1 to 3 of the present invention and comparative example 1.
TABLE 1
Fluidity of flow Surface tension Fluidity of flow Surface tension
Example 1 316mm 34mN/m Comparative example 1 239mm 48mN/m
Example 2 312mm 35mN/m
Example 3 310mm 35mN/m
From table 1, it can be found that the modified polycarboxylic acid type high efficiency water reducing agents prepared in examples 1, 2 and 3 have good dispersibility and wettability.
From the comparison of experimental data of examples 1, 2 and 3 and comparative example 1, it can be found that the branched macromer is prepared by reaction based on the methallyl polyoxyethylene ether, so that the modified polycarboxylic acid type high-efficiency water reducer prepared by polymerization forms a hyperbranched structure, and meanwhile, the branched molecular chain is a polyethylene glycol chain segment, so that the dispersibility and the wettability are improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (6)

1. The preparation process of the modified polycarboxylic acid type high-efficiency water reducer is characterized by comprising the following preparation steps:
(1) Reacting methyl allyl polyoxyethylene ether with 4-pentynoic acid to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Reacting alkynylated methallyl polyoxyethylene ether with 2-azidoacetamide to prepare aminated methallyl polyoxyethylene ether;
(3) Reacting the sulfoxide chloride solution with polyethylene glycol monomethyl ether to prepare chlorinated polyethylene glycol monomethyl ether;
(4) Reacting chloro polyethylene glycol monomethyl ether with aminated methyl allyl polyoxyethylene ether to prepare a branched macromonomer;
(5) And (3) carrying out polymerization reaction on the branched macromonomer and acrylic acid to obtain the modified polycarboxylic acid type high-efficiency water reducer.
2. The process for preparing the modified polycarboxylic acid type high efficiency water reducing agent according to claim 1, which is characterized by comprising the following preparation steps:
(1) Uniformly mixing methyl allyl polyoxyethylene ether, 4-valeric acid, 4-dimethylaminopyridine and methylene dichloride according to the mass ratio of 1:0.07-0.08:0.05-0.06:5-7, stirring for 6-8 min at 20-30 ℃ at 200-300 r/min, adding N, N' -dicyclohexylcarbodiimide with the mass of 0.15-0.16 times that of the methyl allyl polyoxyethylene ether, continuously stirring for reacting for 20-24 h, filtering to remove the precipitate, placing in N-hexane at-10 to-5 ℃ for precipitation, filtering to obtain the precipitate, and drying at 20-30 ℃ at 10-20 Pa for 6-8 h to obtain alkynylated methyl allyl polyoxyethylene ether;
(2) Uniformly mixing 2-azidoethylamine, alkynylated methyl allyl polyoxyethylene ether, dimethyl sulfoxide and water according to the mass ratio of 1:4:20-30, adding copper sulfate with the mass of 0.01-0.02 times of the 2-azidoethylamine and sodium ascorbate with the mass of 0.01-0.02 times of the 2-azidoethylamine, stirring at 65-70 ℃ for reacting for 20-24 h at 200-300 r/min, placing in n-hexane at-10 to-5 ℃ for precipitation, filtering, taking the precipitate, placing at 20-30 ℃ and drying at 10-20 Pa for 6-8 h to obtain the aminated methyl allyl polyoxyethylene ether;
(3) Uniformly mixing polyethylene glycol monomethyl ether and methylene dichloride according to a mass ratio of 1:2-3, dropwise adding a sulfoxide chloride solution with the mass of 0.3-0.4 times of that of the polyethylene glycol monomethyl ether at a constant speed within 40-60 min under the stirring condition of 43-45 ℃ and 200-300 r/min, continuously stirring and refluxing for 20-24 h after the dropwise adding, naturally cooling to room temperature, and then placing the mixture at 20-30 ℃ and drying at 10-20 Pa for 6-8 h to obtain chlorinated polyethylene glycol monomethyl ether;
(4) Uniformly mixing chloropolyethylene glycol monomethyl ether, acetonitrile, potassium carbonate and potassium iodide according to the mass ratio of 1:2-3:0.1-0.2:0.01-0.02, adding amino methyl allyl polyoxyethylene ether with the mass of 2.4-2.6 times that of the chloropolyethylene glycol monomethyl ether under the condition of avoiding light in a nitrogen atmosphere, stirring and refluxing for 20-24 hours at 70-80 ℃ and 200-300 r/min, placing in normal hexane at-10 to-5 ℃ for precipitation, filtering, taking the precipitate, and drying for 6-8 hours at 10-20 Pa at 20-30 ℃ to obtain a branched macromolecular monomer;
(5) Uniformly mixing the branched macromer and pure water according to the mass ratio of 1:4-5, heating to 60-65 ℃, adding hydrogen peroxide with the mass fraction of 0.3-0.4 times of the mass fraction of the branched macromer, dropwise adding acrylic acid with the mass of 2-3 times of the branched macromer and ascorbic acid with the mass of 0.04-0.06 times of the branched macromer at a uniform speed within 3 hours under stirring at 600-800 r/min, continuing stirring for reacting for 6-8 hours after the dropwise adding, cooling to room temperature, adjusting the PH to 6.8-7.2 by using sodium hydroxide with the mass fraction of 25-30%, and drying for 6-8 hours at 20-30 ℃ under 10-20 Pa to obtain the modified polycarboxylic acid type high-efficiency water reducer.
3. The process for preparing the modified polycarboxylic acid type high-efficiency water reducer according to claim 1, wherein the type of the methallyl polyoxyethylene ether in the step (1) is HPEG-2400.
4. The preparation process of the modified polycarboxylic acid type high-efficiency water reducer according to claim 1 is characterized in that the thionyl chloride solution in the step (3) is prepared by uniformly mixing thionyl chloride and methylene dichloride according to a mass ratio of 1:1.6-1.8.
5. The process for preparing the modified polycarboxylic acid type high-efficiency water reducer according to claim 1, wherein the model of the polyethylene glycol monomethyl ether in the step (3) is MPEG500.
6. The application of the modified polycarboxylic acid type high-efficiency water reducer prepared by adopting the preparation process of the modified polycarboxylic acid type high-efficiency water reducer according to any one of claims 1-5 in concrete.
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CN112794958A (en) * 2021-01-21 2021-05-14 江苏奥莱特新材料股份有限公司 Antibacterial polycarboxylate superplasticizer and preparation method thereof
CN116041630A (en) * 2022-12-16 2023-05-02 科之杰新材料集团有限公司 Quaternary ammonium salt polyether ester monomer, EPEG type polycarboxylate superplasticizer and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN104945632A (en) * 2015-06-02 2015-09-30 江苏奥莱特新材料有限公司 Preparation method of microspheric polycarboxylic acid water-reducer
CN105330834A (en) * 2015-10-29 2016-02-17 江苏中铁奥莱特新材料有限公司 Preparing method for polycarboxylate-type anti-mud water reducer with modified side chain terminal group
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