CN114181086B - Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer - Google Patents

Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer Download PDF

Info

Publication number
CN114181086B
CN114181086B CN202111015745.1A CN202111015745A CN114181086B CN 114181086 B CN114181086 B CN 114181086B CN 202111015745 A CN202111015745 A CN 202111015745A CN 114181086 B CN114181086 B CN 114181086B
Authority
CN
China
Prior art keywords
water reducer
unsaturated carboxylic
unsaturated
water
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111015745.1A
Other languages
Chinese (zh)
Other versions
CN114181086A (en
Inventor
蒋卓君
林晓森
赵会
尤仁良
陈文山
姚良科
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kezhijie New Material Group Fujian Co ltd
Kezhijie New Material Group Co Ltd
Original Assignee
Kezhijie New Material Group Fujian Co ltd
Kezhijie New Material Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kezhijie New Material Group Fujian Co ltd, Kezhijie New Material Group Co Ltd filed Critical Kezhijie New Material Group Fujian Co ltd
Priority to CN202111015745.1A priority Critical patent/CN114181086B/en
Publication of CN114181086A publication Critical patent/CN114181086A/en
Application granted granted Critical
Publication of CN114181086B publication Critical patent/CN114181086B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/604—Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to the technical field of concrete additives, in particular to an esterified product for preparing a water reducer, a preparation method thereof, a high-workability polycarboxylate water reducer and a preparation method thereof, wherein the esterified product for preparing the water reducer is a mixture prepared by esterification reaction of excessive unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and phenoxyethanol and/or phenoxyisopropanol, and the esterified product for preparing the water reducer is provided by the invention, so that the main chain of the polycarboxylate water reducer is provided with phenoxyethanol and/or phenoxyisopropanol, fumarate and maleate structural units, the polycarboxylate water reducer with self corrosion resistance is obtained, the problem of uneven distribution caused by poor compatibility of a preservative and the polycarboxylate water reducer is avoided, and the final product is of a stable high-molecular structure and can resist high temperature higher than 50 ℃ and has more excellent high-temperature corrosion resistance.

Description

Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer
Technical Field
The invention relates to the technical field of concrete additives, in particular to an esterified product for preparing a water reducer, a preparation method of the esterified product, a high-workability polycarboxylate water reducer and a preparation method of the high-workability polycarboxylate water reducer.
Background
At present, the problem of mildew and odor of the polycarboxylate water reducer usually occurs in the application process, and although the application performance of the polycarboxylate water reducer is not greatly influenced, the problem of inconvenient use is brought to application units, the conventional method for solving the problem of mildew and odor of the polycarboxylate water reducer is a compound preservative, and some personnel research the corrosion-resistant polycarboxylate water reducer.
The method of adding the preservative in a compounding way is the method with the widest practical application at present, but the compounded preservative is generally smaller in molecular weight, so that on one hand, the problem of uneven dispersion in the polycarboxylate water reducer is likely to exist, and on the other hand, the problem of decomposition failure of the compounded preservative which is conventionally used at present also exists in an environment higher than 50 ℃, so that the application of the compounded preservative is limited to a certain extent.
The patent document with publication number CN110642996A discloses a self-corrosion-preventing polycarboxylic acid water reducing agent and a preparation method thereof, but the monomer with corrosion resistance is any one or more of polymethyl methacrylate acyloxy ethyl trimethyl ammonium chloride, poly [2- (acryloyloxy) ethyl ] trimethyl ammonium bromide, poly benzyl ethyl trimethyl ammonium chloride, polyallyl trimethyl ammonium chloride and poly (3-acrylamide propyl) trimethyl ammonium bromide. However, these materials are already polymers, have no polymerization activity, cannot be incorporated into the molecular structure of the water reducing agent, and tend to have a problem of uneven dispersion in the polycarboxylic acid water reducing agent.
As another example, patent document CN109796561a discloses an aromatic ring type polycarboxylate water reducer mother liquor, and a preparation method and application thereof, wherein aryl conjugated unsaturated carboxylic acid is used as an anti-corrosion monomer to prepare a polycarboxylate water reducer with self-corrosion resistance, but the aryl conjugated unsaturated carboxylic acid has large steric hindrance during polymerization, which can cause the problem of unsatisfactory polymerization effect and finally affect the performance of the product.
Further, as disclosed in the patent document with publication number CN107265907a, an amphoteric antibacterial polycarboxylic acid type high efficiency water reducing agent and a preparation method thereof are disclosed, and the process is complicated by copolymerizing first and then sequentially reacting with an unsaturated polyester macromonomer and a halogen-terminated polyether, and the product conversion rate is limited due to the reaction of a large molecular weight and a large molecule, so that the product performance is affected.
Therefore, the development of the water reducer with convenient production, high cost performance and excellent anti-corrosion effect is very important.
Disclosure of Invention
In order to solve the problem of performance reduction of the water reducer caused by compounding of the preservative with the water reducer in the prior art, the invention provides an esterification product for preparing the water reducer, wherein the esterification product is a mixture prepared by esterification reaction of excessive first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and phenoxyethanol and/or phenoxyisopropanol.
The invention also provides a preparation method of the esterified product for preparing the water reducer, which is any of the above, wherein,
and (3) mixing excessive first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride with phenoxyethanol and/or phenoxyisopropanol and a polymerization inhibitor, heating to 70-90 ℃ in a protective gas atmosphere, adding a catalyst for heat preservation reaction, and cooling to room temperature after the reaction is finished to obtain a mixture, namely the esterified product.
Preferably, the protective gas is nitrogen, the reaction time is 1.0-3.0 h, and water is removed by vacuumizing or nitrogen with water during the reaction.
In one embodiment, the total mass of the phenoxyethanol and/or phenoxyisopropanol is M 1 The total mass of the first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is M 2 ，M 1 And M is as follows 2 The ratio range of (2) is 1: (1-3).
In one embodiment, the catalyst is concentrated sulfuric acid, at least one of benzenesulfonic acid, p-toluenesulfonic acid and ethylsulfonic acid; the polymerization inhibitor is at least one of 4-hydroxy-2, 6-tetramethyl piperidine-1-oxygen free radical, hydroquinone, phenothiazine and p-hydroxyanisole.
In one embodiment, the polymerization inhibitor is added in an amount of 0.2 to 3.0% of the total mass of the reactants, and the catalyst is added in an amount of 0.03 to 0.3% of the total mass of the reactants.
The invention provides a high-workability polycarboxylate water reducer, which also comprises the following components: esterified products, unsaturated ether macromers, unsaturated ester macromers, preservative functional monomers, second unsaturated carboxylic acids and/or unsaturated carboxylic anhydrides;
wherein the esterification product is a mixture prepared by reacting excessive first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride with phenoxyethanol and/or phenoxyisopropanol.
In one embodiment, the unsaturated ether type macromer has a molecular weight of 600 to 6000 and is at least one of 3-methyl-3-butene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
In one embodiment, the unsaturated ester macromer is at least one of acrylic acid or methacrylic acid and an esterification product of methoxy polyethylene glycol with a molecular weight of 600 to 2400.
In an embodiment, the small antiseptic monomer is at least one of diethyl maleate, monomethyl fumarate, dimethyl maleate, dipropyl maleate, monoethyl fumarate, and dimethyl fumarate.
In an embodiment, the first unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, the second unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride are at least one of acrylic acid, methacrylic acid, and maleic anhydride, respectively.
The invention also provides a preparation method of the high-workability polycarboxylate superplasticizer, wherein,
and mixing the esterification product, the unsaturated ether macromonomer, the unsaturated ester macromonomer, the antiseptic function small monomer, the second unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride, and obtaining the high-workability polycarboxylate water reducer through polymerization reaction.
In one embodiment, the polymerization is carried out in the presence of an initiator and a molecular weight regulator.
In one embodiment, the unsaturated ether macromonomer, the unsaturated ester macromonomer, the esterification product and the small antiseptic monomer are mixed and dissolved in water, and an initiator aqueous solution, a chain transfer agent aqueous solution, a second unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride aqueous solution are respectively dripped at 5-50 ℃, and the temperature is kept for 0-2 hours after the dripping is completed for 0.5-3.0 hours, so that the high-workability polycarboxylate water reducer is obtained.
In one embodiment, the mass ratio of the unsaturated ether-based macromer, the unsaturated ester-based macromer, the esterification product, the preservative functional monomer, the second unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride is in the range of 300: (20-110): (1-10): (1-10): (35-50).
In one embodiment, the initiator is used in an amount of 0.5% to 3.0% of the total mass of the reactants; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the reactants.
In one embodiment, the initiator is a redox initiation system consisting of ferrous sulfate heptahydrate, hydrogen peroxide and sodium hypochlorite, and the molecular weight regulator is sodium hypophosphite.
Based on the above, compared with the prior art, the invention has the following beneficial effects:
according to the esterified product for preparing the water reducer, the phenoxyethanol and/or phenoxyisopropanol and unsaturated acid (anhydride) are esterified to prepare the unsaturated monomer with the phenoxyethanol and/or phenoxyisopropanol ester structure to participate in the next reaction, so that the main chain of the polycarboxylic acid water reducer is provided with the phenoxyethanol and/or phenoxyisopropanol, the fumarate and the maleate structural units, the polycarboxylic acid water reducer with the self anti-corrosion performance is obtained, a small-molecule preservative is not required to be compounded, the problem of uneven distribution caused by poor compatibility of the preservative and the polycarboxylic acid water reducer is avoided, and the final product is of a stable high-molecular structure, can resist high temperature higher than 50 ℃, and is more excellent in high-temperature anti-corrosion performance.
According to the preparation method of the esterified product for preparing the water reducer, the esterified product is prepared by esterifying the phenoxyethanol and/or phenoxyisopropanol with the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, so that the preparation method has the advantages of low cost and simplicity and convenience in operation, and the anti-corrosion performance of the water reducer can be effectively improved by introducing the esterified product into the polycarboxylic acid water reducer.
The invention provides a high-workability polycarboxylate water reducer, which is prepared by introducing phenoxyethanol and/or phenoxyisopropanol and fumarate and maleate structural units into a molecular structure of a product in a mode of copolymerizing a monomer with phenoxyethanol and/or phenoxyisopropanol ester structure with an unsaturated macromonomer, a small anti-corrosion functional monomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, so that the polycarboxylate water reducer with self anti-corrosion performance is obtained, a small-molecule preservative is not required to be compounded, and the prepared product has both the high water reducing performance of an ether product and the high workability of the ester product through copolymerization of an ester and an ether macromonomer.
According to the preparation method of the high-workability polycarboxylate superplasticizer, disclosed by the invention, the raw materials are widely available, the price is low, the preparation process is simple, the synthesis time is short, the polymerization rate is high, and the mechanical property and strength of the interior of the concrete are improved on the premise of improving the corrosion resistance, so that the cost of the product meets the application requirements of the polycarboxylate superplasticizer.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in conjunction with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; 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 the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention also provides the following embodiments:
example 1
(1) Preparation of esterification products: 150.00g of acrylic acid, 140.00g of phenoxyethanol and 2.00g of hydroquinone are mixed, the temperature is raised to 90 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the reaction is carried out for 2.0h under the heat preservation, the water is removed by a method of vacuumizing or introducing nitrogen with water, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterified product A-1.
(2) Copolymerization reaction: 300.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400, 100g of acrylic acid and an esterification product of methoxy polyethylene glycol with the molecular weight of 1200, 8.00g of esterification product A-1, 3.00g of monomethyl fumarate, 0.08g of ferrous sulfate heptahydrate, 10.00g of sodium hypophosphite and 278.00g of water are added into a reactor, a stirrer is started, and after the materials are uniformly mixed, dropwise adding of an acrylic acid aqueous solution (45.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.50 g of hydrogen peroxide and 30.00g of water) and a white hanging block aqueous solution (3.00 g of white hanging block and 30.00g of water) is started, the initial reaction temperature is 30 ℃, the dropwise adding time is 2.5h, the material temperature is controlled to be less than or equal to 50 ℃, and after the dropwise adding is finished, the high-workability polycarboxylate water reducer B-1 is obtained.
Example 2
(1) Preparation of esterification products: 180.00g of methacrylic acid, 140.00g of phenoxyethanol and 2.50g of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen free radical are mixed, the temperature is raised to 90 ℃ under the protection of nitrogen, 1.30g of concentrated sulfuric acid is added, the reaction is kept for 2.5 hours, water is removed by vacuumizing or introducing nitrogen and water, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterified product A-2.
(2) Copolymerization reaction: 300.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400, 30g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 30g of esterification product of methacrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 4.00g of esterification product A-2, 4.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 285.00g of water are added into a reactor, a stirrer is started, after materials are uniformly mixed, dropwise adding of an acrylic acid aqueous solution (35.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.40 g of hydrogen peroxide and 20.00g of water) and a mercaptopropionic acid aqueous solution (1.40 g of mercaptopropionic acid and 20.00g of water) and ascorbic acid aqueous solution (wherein the ascorbic acid 1.60g and the water 20.00 g) are started, the initial reaction temperature is 20 ℃ and the dropwise adding time is 3.0h, the material temperature is controlled to be less than or equal to 45 ℃, and after dropwise adding is completed, the high-workability polycarboxylate water reducer B-2 is obtained.
Example 3
(1) Preparation of esterification products: 100.00g of maleic anhydride, 70.00g of acrylic acid, 150.00g of phenoxyisopropanol, 1.00g of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the reaction is carried out for 2.5 hours under the heat preservation, water is removed by a method of vacuumizing or introducing nitrogen with water, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterified product A-3.
(2) Copolymerization reaction: 300.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 3000, 50g of esterification product of acrylic acid and methoxypolyethylene glycol with the molecular weight of 600, 50g of esterification product of acrylic acid and methoxypolyethylene glycol with the molecular weight of 1200, 6.00g of esterification product A-3, 1.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 280.00g of water are added into a reactor, a stirrer is started, after the materials are uniformly mixed, dropwise adding of an acrylic acid aqueous solution (40.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.30 g of hydrogen peroxide and 20.00g of water), a mercaptoethanol aqueous solution (1.20 g of mercaptoethanol and 20.00g of water) and a reducing agent E51 aqueous solution (2.00 g of reducing agent E51 and 20.00g of water) is started, the initial reaction temperature is 8 ℃, the dropwise adding time is 1.2h, the dropwise adding process control material temperature is less than or equal to 35 ℃, and after the dropwise adding is completed, the material is dropwise added for 0.5h, so that the polycarboxylic acid water reducer is obtained.
Example 4
(1) Preparation of esterification products: 90.00g of methacrylic acid, 70.00g of acrylic acid, 70.00g of phenoxyethanol, 80.00g of phenoxyisopropanol, 1.50g of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 85 ℃ under the protection of nitrogen, 0.80g of concentrated sulfuric acid and 0.50g of p-toluenesulfonic acid are added, the reaction is carried out for 1.5 hours under the heat preservation, the water is removed by a method of vacuumizing or introducing nitrogen and water, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterified product A-4;
(2) Copolymerization reaction: 300.00g of ethylene glycol monoethyl polyethylene glycol ether with the molecular weight of 3000, 100g of methacrylic acid and an esterification product of methoxy polyethylene glycol with the molecular weight of 1200, 5.00g of esterification product A-4, 2.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.08g of ferrous sulfate heptahydrate, 8.00g of sodium hypophosphite and 280.00g of water are added into a reactor, a stirrer is started, and after materials are uniformly mixed, dropwise adding of an acrylic acid aqueous solution (36.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.00 g of hydrogen peroxide and 30.00g of water) and a reducing agent E51 aqueous solution (2.20 g of reducing agent E51 and 30.00g of water) is started, the initial reaction temperature is 10 ℃, the dropwise adding time is 1.0h, the dropwise adding process control material temperature is less than or equal to 30 ℃, and after dropwise adding is completed, the high-workability polycarboxylate water reducer B-4 is obtained.
Comparative example 1
300.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400, 100g of acrylic acid and an esterification product of methoxy polyethylene glycol with the molecular weight of 1200, 3.00g of monomethyl fumarate, 0.08g of ferrous sulfate heptahydrate, 10.00g of sodium hypophosphite and 278.00g of water are added into a reactor, a stirrer is started, and after materials are uniformly mixed, dropwise adding of an aqueous acrylic acid solution (45.00 g of acrylic acid and 20.00g of water), an aqueous hydrogen peroxide solution (3.50 g of hydrogen peroxide and 30.00g of water) and an aqueous hanging white block solution (3.00 g of hanging white block and 30.00g of water) is started, the initial reaction temperature is 30 ℃, the dropwise adding time is 2.5h, the dropwise adding process control material temperature is less than or equal to 50 ℃, and the dropwise adding is kept for 1h after the dropwise adding is completed, so as to obtain a comparative sample C-1.
Comparative example 2
300.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400, 100g of acrylic acid and an esterification product of methoxy polyethylene glycol with the molecular weight of 1200, 0.08g of ferrous sulfate heptahydrate, 10.00g of sodium hypophosphite and 278.00g of water are added into a reactor, a stirrer is started, an acrylic acid aqueous solution (45.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.50 g of hydrogen peroxide and 30.00g of water) and a white suspending block aqueous solution (3.00 g of white suspending block and 30.00g of water) are started to be mixed uniformly, the initial reaction temperature is 30 ℃, the dripping time is 2.5h, the temperature of a dripping process control material is less than or equal to 50 ℃, and the temperature is kept for 1h after the dripping is finished, so as to obtain a comparison sample C-2.
Comparative example 3
(1) Preparation of esterification products: 180.00g of methacrylic acid, 154.00g of 3-phenoxy-1-propanol and 2.50g of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen free radical are mixed, the temperature is raised to 90 ℃ under the protection of nitrogen, 1.30g of concentrated sulfuric acid is added, the reaction is kept for 2.5 hours, water is removed by a vacuum pumping or nitrogen water charging method, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterification product D-1.
(2) Copolymerization reaction: 300.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400, 30g of esterification product of acrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 30g of esterification product of methacrylic acid and methoxy polyethylene glycol with the molecular weight of 1200, 4.00g of esterification product D-1, 4.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 285.00g of water are added into a reactor, a stirrer is started, after materials are uniformly mixed, dropwise adding of an acrylic acid aqueous solution (35.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.40 g of hydrogen peroxide and 20.00g of water) and a mercaptopropionic acid aqueous solution (1.40 g of mercaptopropionic acid and 20.00g of water) and ascorbic acid aqueous solution (wherein the ascorbic acid 1.60g and the water 20.00 g) are started, the initial reaction temperature is 20 ℃ and the dropwise adding time is 3.0h, the material temperature is controlled to be less than or equal to 45 ℃, and after dropwise adding is completed, the high-workability polycarboxylate water reducer C-3 is obtained.
Comparative example 4
(1) Preparation of esterification products: 100.00g of maleic anhydride, 70.00g of acrylic acid, 150.00g of phenoxyisopropanol, 1.00g of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the reaction is carried out for 2.5 hours under the heat preservation, water is removed by a method of vacuumizing or introducing nitrogen with water, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterified product A-3.
(2) Copolymerization reaction: 350g of acrylic acid and methoxy polyethylene glycol esterification product with molecular weight of 600, 50g of acrylic acid and methoxy polyethylene glycol esterification product with molecular weight of 1200, 6.00g of esterification product A-3, 1.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 280.00g of water are added into a reactor, a stirrer is started, and after the materials are uniformly mixed, dropwise adding of an acrylic acid aqueous solution (40.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (3.30 g of hydrogen peroxide and 20.00g of water), a mercaptoethanol aqueous solution (1.20 g of mercaptoethanol and 20.00g of water) and a reducing agent E51 aqueous solution (2.00 g of reducing agent E51 and 20.00g of water) is started, the initial reaction temperature is 8 ℃, the dropwise adding process control material temperature is less than or equal to 35 ℃, and after dropwise adding is completed, the high-workability polycarboxylate water reducer C-4 is obtained.
Comparative example 5
(1) Preparation of esterification products: 100.00g of maleic anhydride, 70.00g of acrylic acid, 150.00g of phenoxyisopropanol, 1.00g of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen free radical and 1.0g of hydroquinone are mixed, the temperature is raised to 75 ℃ under the protection of nitrogen, 1.30g of p-toluenesulfonic acid is added, the reaction is carried out for 2.5 hours under the heat preservation, water is removed by a method of vacuumizing or introducing nitrogen with water, and the temperature is reduced to room temperature after the reaction is finished, so that the obtained mixture is an esterified product A-3.
(2) Copolymerization reaction: 350.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with a molecular weight of 3000, 50g of esterification product of acrylic acid and methoxy polyethylene glycol with a molecular weight of 1200, 6.00g of esterification product A-3, 1.00g of monomethyl fumarate, 2.00g of diethyl maleate, 0.09g of ferrous sulfate heptahydrate and 280.00g of water are added into a reactor, a stirrer is started, an aqueous solution of acrylic acid (40.00 g of acrylic acid and 20.00g of water) is started to be mixed uniformly, an aqueous solution of hydrogen peroxide (3.30 g of hydrogen peroxide and 20.00g of water) and an aqueous solution of mercaptoethanol (1.20 g of mercaptoethanol and 20.00g of water) are added, an initial reaction temperature is 8 ℃, a dripping time is 1.2h, a dripping process is controlled, the temperature of the material is 35 ℃, and after dripping is finished, the temperature is kept for 0.5h, so that the high-workability polycarboxylate water reducer C-5 is obtained.
The above preparation methods, the brands of the raw materials and other technical indexes adopted in the examples and comparative examples can be selected according to the prior art, and if the technical indexes are specified in the invention, the technical indexes are selected within the specified range of the invention, so that the technical effects of the invention are not affected.
1. Concrete performance test
The water reducer samples prepared in the examples and the comparative examples were subjected to concrete performance test according to GB/T8076-2008 at a fold-solid mixing amount of 0.20%, and the test results are shown in Table 1:
table 1 concrete test results
As can be seen from the test results in Table 1, the performance test of the examples is superior to that of the comparative examples, as the comparison between the example 1 and the comparative example 1 shows that the water reduction rate and the 3d, 7d and 28d compressive strength ratio of the esterified product A-1 in the example 1 are slightly reduced after the esterified product A-1 is removed, and the product synthesized according to the technical scheme of the patent has higher water reduction rate and the 3d, 7d and 28d compressive strength ratio. However, comparative example 5 synthesized using the ether macromonomer alone was slightly inferior in workability as compared to the concrete of examples 1 to 4.
2. Corrosion resistance test
The high workability polycarboxylate water reducer samples prepared in the examples and the comparative samples prepared in the comparative examples were diluted to 15% concentration, and 1% white sugar and 2% sodium gluconate were added to compound to obtain final water reducer products, 300g of each of these final water reducer samples was placed in the same open glass container having a volume of 500ml, heated to 50 ℃ for 12 hours, placed in a 30 ℃ incubator, and placed for 15 days (d), 30d, 60d, 90d, 120d, 180d, and the state of the samples (whether there was an odor, turbidity, or mold growth) was observed at the corresponding time to compare the corrosion resistance of the above samples, and the specific test results are shown in table 2.
TABLE 2 test results of anti-corrosive Properties
As can be seen from the test results of Table 2, comparative example 2 has already started to develop the off-flavor and mold growth phenomenon at 30 days, comparative example 1, to which monomethyl fumarate was added during copolymerization, has slightly better preservative effect, but also developed the off-flavor and mold growth phenomenon at 120 days, comparative example 3, which used 3-phenoxy-1-propanol instead of phenoxyethanol and/or phenoxyisopropanol, developed the off-flavor and mold growth phenomenon at 120 days, indicating that phenoxyethanol and/or phenoxyisopropanol were significantly better in preservative effect than 3-phenoxy-1-propanol even though it was phenoxyethanol;
furthermore, the test results of comparative example 4 demonstrate that the use of ester macromers alone also resulted in off-flavors at a later stage. From this, the anticorrosive high-efficiency polycarboxylate water reducer prepared in examples 1 to 4 of the present invention has significantly better anticorrosive effect than the comparative examples.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (5)

1. The utility model provides a high workability polycarboxylate water reducing agent which characterized in that: the preparation method comprises the following steps: esterified products, unsaturated ether macromers, unsaturated ester macromers, preservative functional monomers, second unsaturated carboxylic acids and/or unsaturated carboxylic anhydrides;
wherein the esterification product is a mixture prepared by reacting excessive first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride with phenoxyethanol and/or phenoxyisopropanol;
the small antiseptic monomer is at least one of diethyl maleate, monomethyl fumarate, dimethyl maleate, dipropyl maleate, monoethyl fumarate and dimethyl fumarate;
the mass ratio range of the unsaturated ether macromonomer, the unsaturated ester macromonomer, the esterification product, the small antiseptic function monomer, the second unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride is 300: (20-110): (1-10): (1-10): (35-50).
2. The high workability polycarboxylate superplasticizer as set forth in claim 1, wherein: the molecular weight of the unsaturated ether macromonomer is 600-6000, and the unsaturated ether macromonomer is at least one of 3-methyl-3-butene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
3. The high workability polycarboxylate superplasticizer as set forth in claim 1, wherein: the unsaturated ester macromer is at least one of acrylic acid or methacrylic acid and methoxy polyethylene glycol esterification products with molecular weight of 600-2400.
4. The high workability polycarboxylate superplasticizer as set forth in claim 1, wherein: the first unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and the second unsaturated carboxylic acid and/or unsaturated carboxylic anhydride are at least one of acrylic acid, methacrylic acid and maleic anhydride respectively.
5. A method for preparing the high workability polycarboxylate superplasticizer as described in any one of claims 1 to 4, characterized in that:
and mixing the esterification product, the unsaturated ether macromonomer, the unsaturated ester macromonomer, the antiseptic functional small monomer, the unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride, and obtaining the high-workability polycarboxylate water reducer through polymerization reaction.
CN202111015745.1A 2021-08-31 2021-08-31 Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer Active CN114181086B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111015745.1A CN114181086B (en) 2021-08-31 2021-08-31 Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111015745.1A CN114181086B (en) 2021-08-31 2021-08-31 Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer

Publications (2)

Publication Number Publication Date
CN114181086A CN114181086A (en) 2022-03-15
CN114181086B true CN114181086B (en) 2023-08-29

Family

ID=80601337

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111015745.1A Active CN114181086B (en) 2021-08-31 2021-08-31 Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer

Country Status (1)

Country Link
CN (1) CN114181086B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240056852A (en) * 2022-10-21 2024-05-02 주식회사 실크로드시앤티 Additive for concrete comprising polycarboxylate ether-based copolymer compound prepared by reacting different macro monomers and chemical admixture for concrete comprising the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1008959A (en) * 1961-05-16 1965-11-03 Beck & Co Gmbh Dr Method of producing unsaturated polyester resins
CN111378077A (en) * 2018-12-29 2020-07-07 江苏苏博特新材料股份有限公司 Low-temperature-sensitivity polycarboxylic acid superplasticizer and preparation method thereof
CN111607040A (en) * 2020-06-24 2020-09-01 南宁新泰瑞科建材股份有限公司 Super-slow release type polycarboxylic slump retaining agent and preparation method thereof
CN112708055A (en) * 2020-10-30 2021-04-27 科之杰新材料集团(贵州)有限公司 Ester ether copolymerization viscosity-reducing hydration regulator and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1008959A (en) * 1961-05-16 1965-11-03 Beck & Co Gmbh Dr Method of producing unsaturated polyester resins
CN111378077A (en) * 2018-12-29 2020-07-07 江苏苏博特新材料股份有限公司 Low-temperature-sensitivity polycarboxylic acid superplasticizer and preparation method thereof
CN111607040A (en) * 2020-06-24 2020-09-01 南宁新泰瑞科建材股份有限公司 Super-slow release type polycarboxylic slump retaining agent and preparation method thereof
CN112708055A (en) * 2020-10-30 2021-04-27 科之杰新材料集团(贵州)有限公司 Ester ether copolymerization viscosity-reducing hydration regulator and preparation method thereof

Also Published As

Publication number Publication date
CN114181086A (en) 2022-03-15

Similar Documents

Publication Publication Date Title
WO2022095232A1 (en) Ether-type anti-corrosive polycarboxylic acid water reducer and preparation method therefor
CN112708060B (en) Novel anti-corrosion polycarboxylate superplasticizer and preparation method thereof
CN110845672B (en) Polycarboxylic acid type concrete glue reducing agent and preparation method thereof
CN111234095B (en) Method for preparing polycarboxylate superplasticizer by using C6 monomer
CN112708059B (en) Anti-corrosion polycarboxylic slump retaining agent and preparation method thereof
CN113121751B (en) High-adaptability concrete superplasticizer, preparation method and application thereof
CN109627433B (en) Mud-resistant slump-retaining multifunctional unsaturated monomer for production of polycarboxylic acid slump-retaining mother liquor
CN112708045B (en) Low-sensitivity super-early-strength polycarboxylate superplasticizer and preparation method thereof
CN114181086B (en) Esterified product for preparing water reducer, preparation method of esterified product, high-workability polycarboxylate water reducer and preparation method of polycarboxylate water reducer
WO2014059674A1 (en) Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same
CN102627743A (en) Preparation method of polycarboxylic copolymer with high solid content
CN106632881A (en) Low water-reducing and high slump loss resistant type polycarboxylate superplasticizer master batch
CN106496441B (en) A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method
CN112708057B (en) High-temperature-resistant anti-corrosion long-acting polycarboxylic acid slump retaining agent and preparation method thereof
CN110698609A (en) High-performance polycarboxylic acid water reducing agent synthesized at normal temperature, preparation method and application thereof
CN113698547B (en) High-performance polycarboxylate superplasticizer and preparation method thereof
CN114195953B (en) Low-sensitivity high-water-retention polycarboxylate superplasticizer and preparation method thereof
CN112708065B (en) Polyhydroxy air entraining retarding water reducing agent and preparation method thereof
CN114085334A (en) Slump-retaining type polycarboxylate superplasticizer with vinyl ether ester mixed structure and preparation method thereof
CN113773450A (en) Low-temperature low-sensitivity strong-adsorption type polycarboxylate superplasticizer and preparation method thereof
CN114516938A (en) Non-chlorine double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof
WO2022110325A1 (en) Polycarboxylate water reducer and preparation method therefor
CN114479057B (en) Ester monomer, polycarboxylate water reducer and preparation method thereof
CN115197413B (en) Polycarboxylate water reducing agent anti-mud functional monomer
CN113912833B (en) Esterified monomer, esterified product, high-adaptability polycarboxylic acid slump retaining agent and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant