CN110240697B - Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof - Google Patents
Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN110240697B CN110240697B CN201910533183.6A CN201910533183A CN110240697B CN 110240697 B CN110240697 B CN 110240697B CN 201910533183 A CN201910533183 A CN 201910533183A CN 110240697 B CN110240697 B CN 110240697B
- Authority
- CN
- China
- Prior art keywords
- parts
- acid
- anhydride
- functional monomer
- 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
Links
Classifications
-
- 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
- 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
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention provides a functional monomer and a preparation method thereof, a polycarboxylic acid water reducing agent and a preparation method and application thereof, and relates to the technical field of concrete admixtures. The preparation method of the functional monomer adopts alkylphenol ethoxylates, first acid anhydride, an acidic catalyst and an optional polymerization inhibitor to carry out esterification reaction to obtain the functional monomer, wherein the esterification reaction is carried out in an anhydrous environment, so that micromolecular water is not removed in the reaction process to promote the forward progress of the esterification reaction, and meanwhile, the preparation method has mild reaction conditions and is simple to operate; the invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the step of carrying out free radical polymerization reaction on the functional monomer, the polyether macromonomer, the second anhydride and unsaturated carboxylic acid and/or unsaturated carboxylic acid derivatives to obtain the polycarboxylate superplasticizer; the functional monomer is introduced into the molecular structure of the polycarboxylate superplasticizer, so that the polycarboxylate superplasticizer has good workability, and meanwhile, the polycarboxylate superplasticizer can improve the stability of concrete in high-salt and high-alkali environments.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a functional monomer and a preparation method thereof, and a polycarboxylic acid water reducing agent and a preparation method and application thereof.
Background
The concrete workability means that the concrete mixture is easy to construct and operate and can obtain the performance of uniform quality and compact forming. Workability is a comprehensive technical property, and includes three meanings of fluidity, cohesiveness and water retention, which are related to each other, but there are often contradictions. Fluidity refers to the property of a concrete mixture that it tends to flow, transport and fill concrete forms under the action of its own weight or mechanical vibration. Cohesiveness is the ability of concrete mixtures to maintain overall uniformity during construction. The good cohesiveness can ensure that the concrete mixture is not layered and separated in the processes of conveying, pouring, forming and the like, namely the internal structure of the hardened concrete is uniform. Water retention is the ability of concrete mixtures to retain water during construction. The good water retention can ensure that the concrete mixture does not generate large or serious bleeding in the processes of conveying, forming and condensing, not only can avoid a large amount of communicated capillary pores generated by bleeding, but also can avoid the interface bonding defect caused by the accumulation of water at the lower parts of the coarse aggregate and the reinforcing steel bars due to bleeding, and the water retention has great influence on the strength and the durability of the concrete.
Patent GB2380504B adopts 2-acrylamide-2-methylpropanesulfonic acid, maleic anhydride and unsaturated polyether macromonomer or (methyl) acrylate as comonomers to prepare a polymer water retention agent based on vinyl sulfonic acid, and the workability of the polymer is improved by utilizing the water retention effect, but the maleic anhydride used in the patent has lower polymerization activity, and the homopolymer of the 2-acrylamide-2-methylpropanesulfonic acid is easily obtained, so that the stability of the obtained polymer is poor in the environment of high salt and high alkali of concrete. Patent CN201310749293.9 discloses a water reducing agent with concrete workability adjusting function and a synthesis method thereof. The patent adopts prenyl alcohol polyoxyethylene ether, acrylic acid or methacrylic acid or a mixture of the prenyl alcohol polyoxyethylene ether and the acrylic acid or the methacrylic acid, maleic anhydride, sodium p-styrene sulfonate and sodium methallyl sulfonate as comonomers to prepare the water reducer with the workability regulation function. The water reducer has the water retention capacity, has the function of reducing the surface tension of concrete so as not to influence the viscosity and the fluidity of the concrete, and can also ensure the normal coagulation and the strength development of the concrete, but the salt tolerance of two monomers, namely sodium p-styrene sulfonate and sodium methyl propylene sulfonate, introduced into the water reducer is poor, and the stability of a polymer is easily reduced when the water reducer is used in a high-salt environment of the concrete, so that the performance of the water reducer is influenced.
In view of the above, a technical solution is proposed to solve at least one of the above problems.
Disclosure of Invention
The first purpose of the invention is to provide a functional monomer, which is introduced into a polycarboxylate superplasticizer to effectively improve the air entraining controllability of the polycarboxylate superplasticizer.
The second purpose of the invention is to provide a preparation method of the functional monomer, which has mild reaction conditions and simple operation process.
The third purpose of the invention is to provide a polycarboxylate water reducing agent which has the characteristic of controllable air entraining, and is applied to concrete so as to enable the concrete to have excellent workability and good stability in high-salt and high-alkali environments.
The fourth purpose of the invention is to provide a preparation method of the polycarboxylic acid water reducing agent.
The fifth purpose of the invention is to provide the application of the polycarboxylate superplasticizer.
The invention provides a functional monomer, which has a structure shown in a formula (I):
in formula (I), a is 4-8, b is 4-15, and R is an unsaturated organic residue having 2-5 carbon atoms.
Further, on the basis of the technical scheme, in the formula (I), a is 5-8, b is 5-15, and R is an unsaturated organic residue with 2-4 carbon atoms;
preferably, in formula (I), a is 8, b is 6 to 15, and R is vinyl, propenyl, or isobutenyl.
The invention also provides a preparation method of the functional monomer, which comprises the following steps:
mixing alkylphenol polyoxyethylene, first anhydride, acid catalyst and optional polymerization inhibitor to perform esterification reaction to obtain the functional monomer.
Further, on the basis of the technical scheme, the molar ratio of the alkylphenol ethoxylate to the first anhydride is 1:1-1: 3;
and/or, the mole number of the acid catalyst accounts for 0.5-8% of the total mole number of the alkylphenol polyoxyethylene and the first anhydride;
and/or the mole number of the polymerization inhibitor accounts for 0.7-5% of the total mole number of the alkylphenol polyoxyethylene and the first anhydride;
and/or the esterification reaction temperature is 65-90 ℃, and the esterification reaction time is 3-5 h;
and/or the alkylphenol polyoxyethylene ether comprises any one or the combination of at least two of nonylphenol polyoxyethylene ether, isoamyl phenol polyoxyethylene ether or octyl phenol polyoxyethylene ether;
and/or the first anhydride comprises any one of maleic anhydride, fumaric acid, acrylic anhydride or isobutylene anhydride or a combination of at least two of the maleic anhydride, the fumaric acid, the acrylic anhydride or the isobutylene anhydride;
and/or, the acidic catalyst comprises concentrated sulfuric acid and/or p-toluenesulfonic acid;
and/or the polymerization inhibitor comprises hydroquinone and/or phenothiazine.
The invention also provides a polycarboxylate superplasticizer which comprises the following raw materials in parts by weight:
1-10 parts of functional monomer, 500-600 parts of polyether macromonomer, 40-60 parts of second anhydride, 10-30 parts of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, 15-40 parts of initiator, 1-4 parts of chain transfer agent and 850 parts of water 440-;
wherein the functional monomer is the functional monomer or the functional monomer prepared by the preparation method of the functional monomer.
Further, on the basis of the technical scheme, the polycarboxylic acid water reducing agent comprises the following raw materials in parts by weight:
1.5-9 parts of functional monomer, 590 parts of polyether macromonomer 510-;
preferably, the polycarboxylate superplasticizer comprises the following raw materials in parts by weight:
2-8 parts of functional monomer, 580 parts of polyether macromonomer 520-containing material, 45-56 parts of second anhydride, 14-25 parts of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, 18-35 parts of initiator, 2-3 parts of chain transfer agent and 820 parts of water 460-containing material;
preferably, the molecular weight of the polycarboxylic acid water reducing agent is 20000-70000.
Further, on the basis of the above technical scheme, the polyether macromonomer comprises any one or a combination of at least two of allyl polyoxyethylene ether, methallyl polyoxyethylene ether, isoamyl polyoxyethylene ether or 2-hydroxyethyl vinyl polyoxyethylene ether with weight average molecular weights of 1000-4000;
and/or the second anhydride comprises maleic anhydride and/or fumaric acid;
and/or the unsaturated carboxylic acid comprises any one or a combination of at least two of acrylic acid, methacrylic acid, itaconic acid or aconitic acid; the unsaturated carboxylic acid derivative comprises any one or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate;
and/or, the chain transfer agent is a thiol chain transfer agent; preferably, the chain transfer agent comprises any one or a combination of at least two of 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, thioglycolic acid, mercaptoethanol, dimercaprol, 2-mercaptoethanesulfonic acid, isopropanol, diphosphonic acid and metal salts thereof, hypophosphorous acid and metal salts thereof, or sodium methallylsulfonate;
and/or the initiator is a persulfate initiator.
The invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
mixing functional monomers, polyether macromonomers, second anhydride, unsaturated carboxylic acid and/or unsaturated carboxylic acid derivatives, an initiator, a chain transfer agent and water according to the formula ratio, and carrying out free radical polymerization reaction to obtain a polycarboxylic acid water reducer;
preferably, the preparation method of the polycarboxylate superplasticizer comprises the following steps:
providing a solution A of a formulated amount of a functional monomer, a polyether macromonomer, a second anhydride and a portion of the formulated amount of water, a solution B of a formulated amount of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative, a chain transfer agent and another portion of the formulated amount of water, and a solution C of an initiator and the remaining formulated amount of water;
and mixing the solution A, the solution B and the solution C to perform free radical polymerization reaction to obtain the polycarboxylic acid water reducing agent.
Further, on the basis of the technical scheme, dropwise adding the solution B and the solution C into the heated solution A to perform free radical polymerization reaction to obtain the polycarboxylic acid water reducing agent;
preferably, the temperature of the heated solution A is 30-85 ℃, preferably 50-80 ℃;
preferably, the dropping time is 2-5 h;
preferably, the free radical polymerization reaction temperature is 30-85 ℃, and the free radical polymerization reaction time is 2-5 h;
preferably, cooling a product obtained by the free radical polymerization reaction to below 30 ℃ and adjusting the pH value to be neutral to obtain the polycarboxylic acid water reducing agent;
preferably, in the solution A, the weight ratio of the functional monomer, the polyether macromonomer, the second anhydride and the water is (1-10): 500-600): 40-60): 200-300);
preferably, in the solution B, the weight ratio of the unsaturated carboxylic acid and/or the unsaturated carboxylic acid derivative, the chain transfer agent and the water is (10-30): (1-4): (40-150);
preferably, in the solution C, the weight ratio of the initiator to the water is (15-40): 200-400).
The invention also provides application of the polycarboxylate superplasticizer or the polycarboxylate superplasticizer prepared by the preparation method of the polycarboxylate superplasticizer in concrete construction.
Compared with the prior art, the functional monomer and the preparation method thereof, and the polycarboxylate superplasticizer and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the functional monomer provided by the invention is an amphoteric monomer, one end of the functional monomer has hydrophilicity, and the other end of the functional monomer has hydrophobicity, and the functional monomer is introduced into the polycarboxylic acid water reducing agent, so that the surface tension of the polycarboxylic acid can be greatly reduced, and the polycarboxylic acid water reducing agent has an effect of controllable air entraining.
(2) According to the preparation method of the functional monomer, alkylphenol ethoxylates, first acid anhydride, an acidic catalyst, an optional polymerization inhibitor and the like are used as raw materials for esterification reaction, and the esterification reaction is carried out in an anhydrous environment, so that micromolecular water is not removed in the esterification process to promote the forward progress of the esterification reaction;
in addition, the preparation method has mild reaction conditions and simple operation process, and is suitable for industrial production.
(3) The polycarboxylate superplasticizer provided by the invention has good and easily-adjustable functions, can introduce stable, tiny and uniform bubbles into concrete when being applied to the concrete, and can effectively reduce the surface tension of cement paste, thereby achieving the purpose of adjusting the workability of the concrete and avoiding the application problems of bleeding, water bleeding, layering and the like of the concrete; meanwhile, the polycarboxylate superplasticizer can obviously improve the chloride ion permeability resistance of concrete, so that the stability of the concrete in high-salt and high-alkali environments is improved.
(4) According to the preparation method of the polycarboxylate water reducer, the polycarboxylate water reducer is obtained by performing free radical polymerization on a functional monomer, a polyether macromonomer, a second anhydride, unsaturated carboxylic acid and/or unsaturated carboxylic acid derivatives and water; the polycarboxylic acid water reducing agent has good and easily-adjustable functions by introducing the functional monomer into the molecular structure of the polycarboxylic acid water reducing agent, and can obviously improve the workability and the stability of concrete in high-salt and high-alkali environments;
the preparation method has simple operation process and is suitable for industrial production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
According to a first aspect of the present invention, there is provided a functional monomer, the structure of the functional monomer is shown in formula (I):
in formula (I), a is 4-8, b is 4-15, and R is an unsaturated organic residue having 2-5 carbon atoms.
In the present invention, a is typically but not limited to 4, 5, 6, 7 or 8, b is typically but not limited to 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, and R is an unsaturated organic residue of 2 to 5 carbon atoms, which may typically but not limited to vinyl, propenyl or isobutenyl.
The functional monomer provided by the invention is an amphoteric monomer, one end containing an aliphatic long chain is hydrophobic, and one end containing polyoxyalkenyl ether is hydrophilic, and the functional monomer is introduced into the polycarboxylic acid water reducing agent, so that the surface tension of polycarboxylic acid can be greatly reduced, and the polycarboxylic acid water reducing agent has a good effect of controllable air entraining.
As an alternative embodiment of the invention, in formula (I), a is 5 to 8, b is 5 to 15, R is an unsaturated organic residue having 2 to 4 carbon atoms;
preferably, in formula (I), a is 8, b is 6 to 15, R is vinyl, propenyl or isobutenyl;
more preferably, when in formula (I), a is 8, b is 6 to 15, R is vinyl, and the specific structure of the functional monomer is shown as (II):
the concrete structure of the functional monomer is limited, so that the polycarboxylic acid water reducing agent is endowed with better air-entraining controllable performance.
According to the second aspect of the present invention, there is also provided a method for preparing a functional monomer, comprising the steps of:
mixing alkylphenol polyoxyethylene, first anhydride, acid catalyst and optional polymerization inhibitor to perform esterification reaction to obtain the functional monomer.
The method adopts alkylphenol ethoxylates, first acid anhydride, an acidic catalyst and other raw materials to carry out esterification reaction, and the esterification reaction is carried out in an anhydrous environment, so that small molecular water is not excluded in the esterification process to promote the forward progress of the esterification reaction;
in addition, the preparation method has mild reaction conditions and simple operation process, and is suitable for industrial production.
As an alternative embodiment of the present invention, the method for preparing the functional monomer comprises the steps of:
mixing alkylphenol polyoxyethylene, first anhydride, acid catalyst and polymerization inhibitor to carry out esterification reaction to obtain the functional monomer.
The alkylphenol polyoxyethylene and the first anhydride are subjected to esterification reaction under the action of an acid catalyst, and the polymerization inhibitor is added mainly for preventing the first anhydride from self polymerization so as to influence the esterification reaction.
As an alternative embodiment of the present invention, the molar ratio of alkylphenol ethoxylate to first anhydride is 1:1 to 1:3, preferably; typical but non-limiting molar ratios of alkylphenol ethoxylates to the first anhydride are 1:1, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:2.8, or 1: 3.
As an alternative embodiment of the invention, the mole number of the acid catalyst accounts for 0.5-8% of the total mole number of the alkylphenol polyoxyethylene ether and the first anhydride; typical, but non-limiting, ratios of the acidic catalyst to the total moles of alkylphenol ethoxylate and primary anhydride are 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%.
As an optional embodiment of the invention, the mole number of the polymerization inhibitor accounts for 0.7-5% of the total mole number of the alkylphenol polyoxyethylene ether and the first anhydride; typical but non-limiting proportions of inhibitor to the total moles of alkylphenol ethoxylate and primary anhydride are 0.7%, 1%, 2%, 3%, 4% or 5%.
The dosage of each raw material is limited, so that the dosage of each raw material can reach reasonable proportion.
As an optional embodiment of the invention, the esterification reaction temperature is 65-90 ℃ and the esterification reaction time is 3-5 h.
Typical but non-limiting esterification reaction temperatures are 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃; typical but non-limiting esterification reaction times are 3h, 3.5h, 4h, 4.5h or 5 h.
As an optional embodiment of the present invention, the alkylphenol ethoxylate includes any one of nonylphenol ethoxylate, isopentylphenol ethoxylate, or octylphenol ethoxylate, or a combination of at least two thereof.
As an alternative embodiment of the present invention, the first anhydride comprises any one of maleic anhydride, fumaric acid, acrylic anhydride or isobutylene anhydride or a combination of at least two thereof;
as an alternative embodiment of the present invention, the acidic catalyst comprises concentrated sulfuric acid and/or p-toluenesulfonic acid;
as an alternative embodiment of the invention, the polymerization inhibitor comprises hydroquinone and/or phenothiazine.
The method is beneficial to the smooth proceeding of the esterification reaction by limiting the types of the specific materials of the raw materials and the reaction parameters.
According to the third aspect of the invention, the polycarboxylate superplasticizer is also provided, and comprises the following raw materials in parts by weight:
1-10 parts of functional monomer, 500-600 parts of polyether macromonomer, 40-60 parts of second anhydride, 10-30 parts of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, 15-40 parts of initiator, 1-4 parts of chain transfer agent and 850 parts of water 440-;
wherein the functional monomer is the functional monomer or the functional monomer prepared by the preparation method of the functional monomer.
Typical but non-limiting parts by weight of functional monomer are 1 part, 1.5 parts, 2 parts, 4 parts, 5 parts, 6 parts, 8 parts, 9 parts or 10 parts; typical but non-limiting parts by weight of the polyether macromonomer are 510 parts, 520 parts, 530 parts, 540 parts, 550 parts, 560 parts, 570 parts, 580 parts, 590 parts, or 600 parts; typical but non-limiting parts by weight of the second anhydride are 40 parts, 42 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 55 parts, 56 parts, 58 parts or 60 parts; typical but non-limiting parts by weight of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative are 10 parts, 12 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts or 30 parts; typical but non-limiting parts by weight of the initiator are 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts, or 40 parts; typical but non-limiting parts by weight of chain transfer agent are 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 3.6 parts, 3.8 parts, or 4 parts; water is typically, but not limited to, 440 parts, 450 parts, 480 parts, 500 parts, 550 parts, 580 parts, 600 parts, 650 parts, 680 parts, 700 parts, 750 parts, 780 parts, 800 parts, 820 parts, 840 parts, or 850 parts by weight.
The polycarboxylate superplasticizer has good workability and regulation functions, can effectively improve the workability of concrete when being applied to the concrete construction process, and can improve the stability of the concrete in high-salt and high-alkali environments.
The term "comprising" as used herein means that it may include, in addition to the raw materials, other raw materials which impart different characteristics to the polycarboxylic acid water-reducing agent. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
As an optional embodiment of the invention, the polycarboxylic acid water reducing agent comprises the following raw materials in parts by weight:
1.5-9 parts of functional monomer, 590 parts of polyether macromonomer 510-;
preferably, the polycarboxylate superplasticizer comprises the following raw materials in parts by weight:
2-8 parts of functional monomer, 580 parts of polyether macromonomer 520-containing material, 45-56 parts of second anhydride, 14-25 parts of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, 18-35 parts of initiator, 2-3 parts of chain transfer agent and 820 parts of water 460-containing material.
The product quality of the prepared polycarboxylate superplasticizer is better by further limiting the use amount of each raw material of the polycarboxylate superplasticizer.
As an alternative embodiment of the invention, the molecular weight of the polycarboxylic acid water reducing agent is 20000-70000.
Polycarboxylic acid water reducing agents typically, but not by way of limitation, have a molecular weight of 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000 or 70000. The molecular weight of the polycarboxylate superplasticizer is further limited, so that the polycarboxylate superplasticizer has good comprehensive performance.
If the molecular weight of the polycarboxylate superplasticizer is too small and is lower than 20000, the obtained polycarboxylate superplasticizer is added into concrete, the later-stage retention effect of the concrete is poor, and the water reducing rate is low; if the molecular weight of the polycarboxylic acid water-reducing agent is too high, higher than 70000, the polycarboxylic acid water-reducing agent becomes tacky, resulting in poor workability thereof.
As an optional embodiment of the invention, the polyether macromonomer comprises any one or a combination of at least two of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, isoamyl polyoxyethylene ether or 2-hydroxyethyl vinyl polyoxyethylene ether with the weight average molecular weight of 1000-4000;
and/or, the second anhydride comprises maleic anhydride and/or fumaric acid;
and/or the unsaturated carboxylic acid comprises any one or a combination of at least two of acrylic acid, methacrylic acid, itaconic acid or aconitic acid; the unsaturated carboxylic acid derivative comprises any one or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate;
and/or the chain transfer agent is a mercaptan chain transfer agent; preferably, the chain transfer agent comprises any one or a combination of at least two of 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, thioglycolic acid, mercaptoethanol, dimercaprol, 2-mercaptoethanesulfonic acid, isopropanol, diphosphonic acid and metal salts thereof, hypophosphorous acid and metal salts thereof, or sodium methallylsulfonate; wherein, the diphosphoric acid and the metal salt thereof can be diphosphonic acid, potassium diphosphate and/or sodium diphosphate, and the hypophosphorous acid and the metal salt thereof can be hypophosphorous acid, potassium hypophosphite and/or sodium hypophosphite;
and/or the initiator is a persulfate initiator.
Through the limitation of the specific types of the raw materials, the free radical polymerization reaction is carried out more smoothly, and the obtained polycarboxylic acid water reducing agent has a good molecular structure.
According to the fourth aspect of the invention, the preparation method of the polycarboxylic acid water reducing agent is also provided, and comprises the following steps:
mixing functional monomers, polyether macromonomers, second anhydride, unsaturated carboxylic acid and/or unsaturated carboxylic acid derivatives, an initiator, a chain transfer agent and water according to the formula ratio, and carrying out free radical polymerization reaction to obtain a polycarboxylic acid water reducer;
preferably, the preparation method of the polycarboxylic acid water reducing agent comprises the following steps:
providing a solution A of a formulated amount of a functional monomer, a polyether macromonomer, a second anhydride and a portion of the formulated amount of water, a solution B of a formulated amount of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative, a chain transfer agent and another portion of the formulated amount of water, and a solution C of an initiator and the remaining formulated amount of water;
and mixing the solution A, the solution B and the solution C to perform free radical polymerization reaction to obtain the polycarboxylic acid water reducing agent.
The preparation method of the polycarboxylic acid water reducing agent mainly comprises the steps of enabling a functional monomer, a polyether macromonomer, a second anhydride and unsaturated carboxylic acid and/or unsaturated carboxylic acid derivatives to form free radicals under the action of an initiator so as to generate addition polymerization, and controlling the molecular weight through a chain transfer agent to obtain the polycarboxylic acid water reducing agent with proper molecular weight; the functional monomer is introduced into the molecular structure of the polycarboxylate superplasticizer, so that the polycarboxylate superplasticizer has good and easily-adjustable functions.
Moreover, the preparation method has simple operation process and is suitable for industrial production.
As an optional embodiment of the invention, the solution B and the solution C are added dropwise to the heated solution a to perform a radical polymerization reaction, thereby obtaining a polycarboxylic acid water reducing agent;
the solution A is kept at a certain temperature, so that after the solution B and the solution C are dripped into the solution A, free radical polymerization can be carried out between the solution B and the solution C.
As an alternative embodiment of the invention, the temperature of the heated solution A is between 30 ℃ and 85 ℃, preferably between 50 ℃ and 80 ℃, and the typical but non-limiting temperature of the heated solution A is between 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃;
and/or, the dropping time is 2-5 h; typical but non-limiting dropping times are 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h.
And/or the free radical polymerization reaction temperature is 30-85 ℃, and the free radical polymerization reaction time is 2-5 h; typical but not limiting free radical polymerization temperatures are 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃; typical but non-limiting free radical polymerization reaction times are 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h.
The quality of the polycarboxylic acid water reducing agent obtained by the reaction is in a better level through the limitation of each reaction parameter during the dripping and free radical polymerization reaction of each raw material.
As an optional embodiment of the invention, the product obtained by the free radical polymerization reaction is cooled to below 30 ℃ and the pH value is adjusted to be neutral, so as to obtain the polycarboxylic acid water reducing agent.
Since the product obtained by the free radical polymerization reaction is acidic, the pH value of the product is adjusted in order to prevent the product from corroding subsequent pipeline containers and reduce the risk of injury to operators. The product obtained by free radical polymerization can be subjected to pH value adjustment by using alkaline substances.
As an alternative embodiment of the invention, in the solution A, the weight ratio of the functional monomer, the polyether macromonomer, the second anhydride and the water is (1-10): 500-600): 40-60): 200-300), preferably; typical but non-limiting weight ratios of functional monomer, polyether macromonomer, second anhydride and water are 1:500:40:200, 5:550:50:300, 7:600:60:200, 10:500:40:250, 1:550:40:300, 5:500:40:250, 7:500:50:300, 10:500:40:200, 2: 600:50:300, 4:520:45:280, 6:520:55:300, 8:580:60:200 or 10:500:40: 200.
As an alternative embodiment of the present invention, in the solution B, the weight ratio of the unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, the chain transfer agent and water is (10-30): 1-4: 40-150, preferably; the unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, chain transfer agent and water are typically, but not limited to, in a weight ratio of 10:1:40, 10:2:60, 10:3:80, 15:1:100, 15:2:40, 15:2: 100, 15:3:150, 20:1:40, 20:2:60, 20:3:80, 20:1:100, 30:2:40, 30:4:120 or 30:2: 150.
And/or in solution C, the weight ratio of initiator to water is (15-40): 200-400), and the typical but non-limiting weight ratio of initiator to water is 15:200, 15:300, 15:400, 20:200, 20:300, 20:400, 30:400, 20:300 or 40: 300.
Through specific limitation on the composition and the use amount of the raw materials in the solution A, the solution B and the solution C, the free radical polymerization reaction among the solution A, the solution B and the solution C is more sufficient, and the obtained polycarboxylic acid water reducing agent has a good air entraining controllable function and an easy adjustment function.
A typical, but non-limiting, method for preparing a polycarboxylate water reducer comprises the steps of:
(a) providing a solution A of a formulated amount of a functional monomer, a polyether macromonomer, a second anhydride and a portion of the formulated amount of water, a solution B of a formulated amount of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative, a chain transfer agent and another portion of the formulated amount of water, and a solution C of an initiator and the remaining formulated amount of water;
(b) and heating the solution A to 30-85 ℃, dropwise adding the solution B and the solution C into the solution A for 2-5h, continuing to perform free radical polymerization for 2-5h after dropwise adding, cooling a product obtained by the free radical polymerization to below 40 ℃ after the reaction is finished, and adjusting the pH to be neutral by adopting an alkaline substance to obtain the polycarboxylic acid water reducer.
According to the fifth aspect of the invention, the application of the polycarboxylate superplasticizer or the polycarboxylate superplasticizer prepared by the preparation method of the polycarboxylate superplasticizer in concrete construction is also provided.
The polycarboxylate superplasticizer provided by the invention can introduce stable, tiny and uniform bubbles in concrete application, and can effectively reduce the surface tension of cement paste, thereby achieving the purpose of adjusting the workability of concrete and avoiding the application problems of bleeding, water bleeding, layering and the like of concrete.
In order that the invention may be better understood, reference will now be made to the following examples.
Example 1
The embodiment provides a functional monomer, the structure of which is as follows:
wherein a is 8, b is 6, and R is vinyl;
the preparation method of the functional monomer comprises the following steps:
in a four-neck flask equipped with a stirring bar and a thermometer, 12 parts by weight of maleic anhydride, 60 parts by weight of nonylphenol polyoxyethylene ether (b ═ 6), 2 parts by weight of p-toluenesulfonic acid and 0.9 part by weight of hydroquinone were charged, heated to 65 ℃, stirred and reacted for 5 hours to obtain a functional monomer.
Example 2
The embodiment provides a functional monomer, the structure of which is as follows:
wherein a is 4, b is 9, and R is propenyl;
the preparation method of the functional monomer comprises the following steps:
in a four-neck flask equipped with a stirring bar and a thermometer, 12 parts by weight of maleic anhydride, 75 parts by weight of isoamyl phenol polyoxyethylene ether (b ═ 9), 0.8 parts by weight of concentrated sulfuric acid, and 0.35 parts by weight of phenothiazine were charged, heated to 70 ℃, stirred, and reacted for 4 hours to obtain a functional monomer.
Example 3
The embodiment provides a functional monomer, the structure of which is as follows:
wherein a is 8, b is 12, and R is isobutene;
the preparation method of the functional monomer comprises the following steps:
in a four-neck flask equipped with a stirring bar and a thermometer, 12 parts by weight of maleic anhydride, 110 parts by weight of nonylphenol polyoxyethylene ether (b ═ 12), 3.5 parts by weight of p-toluenesulfonic acid and 1.5 parts by weight of hydroquinone were charged, heated to 90 ℃, stirred and reacted for 3 hours to obtain a functional monomer.
Example 4
The embodiment provides a functional monomer, the structure of which is as follows:
wherein a is 8, b is 15, and R is vinyl;
the preparation method of the functional monomer comprises the following steps:
in a four-neck flask equipped with a stirring bar and a thermometer, 12 parts by weight of maleic anhydride, 38 parts by weight of nonylphenol polyoxyethylene ether (b ═ 15), 1.1 parts by weight of p-toluenesulfonic acid and 0.7 part by weight of hydroquinone were charged, heated to 80 ℃, stirred and reacted for 4 hours to obtain a functional monomer.
Example 5
This example provides a functional monomer, which has the same steps and process parameters as example 1, except that the part by weight of nonylphenol polyoxyethylene ether (b ═ 6) in the preparation process is 55 parts.
Example 6
This example provides a functional monomer, which has the same steps and process parameters as example 1, except that maleic anhydride is replaced with fumaric acid in the preparation method.
Comparative example 1
The comparative example provides a functional monomer, except that nonylphenol polyoxyethylene ether was replaced with methoxypolyoxyethylene ether in the preparation method, the remaining steps and process parameters were the same as those of example 1.
Example 7
The embodiment provides a preparation method of a polycarboxylate water reducer, which adopts the functional monomer provided in embodiment 1 as a raw material and comprises the following steps:
(a) adding 1 weight part of functional monomer, 500 weight parts of allyl polyoxyethylene ether, 40 weight parts of maleic anhydride and 200 weight parts of water into a four-neck flask provided with a stirring rod, a constant-pressure dropping funnel and a thermometer, heating to 80 ℃, and stirring for dissolving to obtain a solution A;
mixing 10 parts by weight of acrylic acid, 2-mercaptopropionic acid and 60 parts by weight of water to obtain a solution B;
mixing 40 parts by weight of ammonium persulfate and 400 parts by weight of water to obtain a solution C;
(b) dropwise adding the solution B and the solution C into the solution A through a constant-pressure dropping funnel, finishing dropwise adding within 5h, and continuing to perform free radical polymerization reaction for 5h at 80 ℃ after dropwise adding;
and after the reaction is finished, cooling to below 30 ℃, neutralizing with a sodium hydroxide aqueous solution, and adjusting the pH to be neutral to obtain the polycarboxylic acid water reducing agent.
Example 8
The embodiment provides a preparation method of a polycarboxylate water reducer, which adopts the functional monomer provided in embodiment 2 as a raw material and comprises the following steps:
(a) adding 3 parts by weight of functional monomer, 520 parts by weight of 2-hydroxyethyl vinyl polyoxyethylene ether, 42 parts by weight of maleic anhydride and 250 parts by weight of water into a four-neck flask provided with a stirring rod, a constant-pressure dropping funnel and a thermometer, heating to 30 ℃, and stirring for dissolving to obtain a solution A;
mixing 12 parts by weight of acrylic acid, 2 parts by weight of thioglycolic acid and 90 parts by weight of water to obtain a solution B;
mixing 15 parts by weight of ammonium persulfate and 200 parts by weight of water to obtain a solution C;
(b) dropwise adding the solution B and the solution C into the solution A through a constant-pressure dropping funnel, finishing dropping in 2 hours, and continuing performing free radical polymerization reaction for 2 hours at 30 ℃ after finishing dropping;
and (4) neutralizing with a sodium hydroxide aqueous solution after the reaction is finished, and adjusting the pH value to be neutral to obtain the polycarboxylic acid water reducing agent.
Example 9
The embodiment provides a preparation method of a polycarboxylate water reducer, which adopts the functional monomer provided in embodiment 3 as a raw material and comprises the following steps:
(a) adding 6 parts by weight of functional monomer, 560 parts by weight of isoprene polyoxyethylene ether, 50 parts by weight of maleic anhydride and 270 parts by weight of water into a four-neck flask provided with a stirring rod, a constant-pressure dropping funnel and a thermometer, mixing, heating to 40 ℃, and stirring for dissolving to obtain a solution A;
mixing 15 parts by weight of acrylic acid, 3 parts by weight of 3-mercaptopropionic acid and 120 parts by weight of water to obtain a solution B;
mixing 25 parts by weight of ammonium persulfate and 300 parts by weight of water to obtain a solution C;
(b) dropwise adding the solution B and the solution C into the solution A through a constant-pressure dropping funnel, finishing dropwise adding within 3h, and continuing to perform free radical polymerization reaction for 2h at 40 ℃ after dropwise adding;
and after the reaction is finished, cooling to below 40 ℃, neutralizing with a sodium hydroxide aqueous solution, and adjusting the pH to be neutral to obtain the polycarboxylic acid water reducing agent.
Example 10
The embodiment provides a preparation method of a polycarboxylate water reducer, which adopts the functional monomer provided in embodiment 4 as a raw material and comprises the following steps:
(a) adding 10 parts by weight of functional monomer, 600 parts by weight of methyl propenyl polyoxyethylene ether, 60 parts by weight of maleic anhydride and 300 parts by weight of water into a four-neck flask provided with a stirring rod, a constant-pressure dropping funnel and a thermometer, mixing, heating to 60 ℃, and stirring for dissolving to obtain a solution A;
mixing 30 parts by weight of acrylic acid, 4 parts by weight of 2-mercaptoethanesulfonic acid and 150 parts by weight of water to obtain a solution B;
mixing 30 parts by weight of potassium persulfate and 300 parts by weight of water to obtain a solution C;
(b) dropwise adding the solution B and the solution C into the solution A through a constant-pressure dropping funnel, finishing dropwise adding within 3h, and continuing to perform free radical polymerization reaction for 2h at 60 ℃ after dropwise adding;
and after the reaction is finished, cooling to below 40 ℃, neutralizing with a potassium hydroxide aqueous solution, and adjusting the pH to be neutral to obtain the polycarboxylic acid water reducing agent.
Example 11
The embodiment provides a preparation method of a polycarboxylate water reducer, which adopts the functional monomer provided in the embodiment 5 as a raw material, and the specific preparation method is the same as that in the embodiment 7.
Example 12
The embodiment provides a preparation method of a polycarboxylate water reducer, which adopts the functional monomer provided in the embodiment 6 as a raw material, and the specific preparation method is the same as that in the embodiment 7.
Comparative example 2
The comparative example provides a preparation method of a polycarboxylate water reducer, the functional monomer provided in the comparative example 1 is used as a raw material, and the specific preparation method is the same as that in example 7.
To further illustrate the technical effects of the above examples, the following experimental examples are specified.
Experimental example 1
The polycarboxylate superplasticizers provided in examples 7-12 and comparative example 2 were added to concrete, and table 1 shows the mixture ratio of the raw materials in the concrete, wherein the polycarboxylate superplasticizers (calculated by the effective solid content) are all 0.2% of the mass of the cementitious material (cement + mineral powder + fly ash).
TABLE 1
Concrete corresponding to examples 7-12 and comparative example 2 was tested according to the homogeneity test method of GB/T8077-2012 concrete admixture, and the specific results are shown in Table 2. Meanwhile, the stability of the concrete corresponding to examples 7-12 and comparative example 2 is tested according to the test method standard of the long-term performance and the durability of the GB/T50082-2009 common concrete, and the specific result is shown in Table 3.
TABLE 2
TABLE 3
As can be seen from the data in Table 2, after the polycarboxylate superplasticizer provided by the invention is adopted, the water reducing rate of concrete is more than 30%, the gas content is between 2.0 and 4.0%, and the compressive strength ratio in 28 days is not less than 133%.
As can be seen from the data in Table 3, the water reducing agent for polycarboxylic acid provided by the invention has the advantages that the chlorine ion permeation resistance of concrete is obviously improved, and the stability of concrete in high-salt and high-alkali environments can be obviously improved.
In conclusion, on the premise of not influencing the water reducing effect, the polycarboxylate water reducing agent provided by the invention endows the water reducing agent with a function of controllable air entraining, namely, on the basis of ensuring the fluidity and the constructability of the prepared concrete, the content of residual air bubbles in the concrete is controllable, and the stability of the concrete in a high-salt and high-alkali environment can be improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (21)
1. The polycarboxylate superplasticizer is characterized by comprising the following raw materials in parts by weight:
1-10 parts of functional monomer, 500-600 parts of polyether macromonomer, 40-60 parts of second anhydride, 10-30 parts of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, 15-40 parts of initiator, 1-4 parts of chain transfer agent and 850 parts of water 440-;
wherein the structure of the functional monomer is shown as the formula (I):
in formula (I), a is 4-8, b is 4-15, R is unsaturated organic residue with 2-5 carbon atoms;
the preparation method of the functional monomer comprises the following steps: mixing alkylphenol polyoxyethylene, first anhydride, acid catalyst and optional polymerization inhibitor to perform esterification reaction to obtain the functional monomer.
2. The polycarboxylate water reducer according to claim 1, characterized in that in formula (I), a is 5-8, b is 5-15, and R is an unsaturated organic residue having 2-4 carbon atoms.
3. The polycarboxylate water reducer according to claim 1, characterized in that in formula (I), a is 8, b is 6-15, and R is vinyl, propenyl or isobutenyl.
4. The polycarboxylate water reducer according to claim 1, characterized in that the molar ratio of alkylphenol ethoxylates to first acid anhydride is 1:1-1: 3;
and/or, the mole number of the acid catalyst accounts for 0.5-8% of the total mole number of the alkylphenol polyoxyethylene and the first anhydride;
and/or the mole number of the polymerization inhibitor accounts for 0.7-5% of the total mole number of the alkylphenol polyoxyethylene and the first anhydride;
and/or the esterification reaction temperature is 65-90 ℃, and the esterification reaction time is 3-5 h;
and/or the alkylphenol polyoxyethylene ether comprises any one or the combination of at least two of nonylphenol polyoxyethylene ether, isoamyl phenol polyoxyethylene ether or octyl phenol polyoxyethylene ether;
and/or the first anhydride comprises any one of maleic anhydride, fumaric acid, acrylic anhydride or isobutylene anhydride or a combination of at least two of the maleic anhydride, the fumaric acid, the acrylic anhydride or the isobutylene anhydride;
and/or, the acidic catalyst comprises concentrated sulfuric acid and/or p-toluenesulfonic acid;
and/or the polymerization inhibitor comprises hydroquinone and/or phenothiazine.
5. The polycarboxylate superplasticizer according to claim 1, characterized by comprising the following raw materials in parts by weight:
1.5-9 parts of functional monomer, 590 parts of polyether macromonomer 510-.
6. The polycarboxylate water reducer according to claim 1, characterized by comprising the following raw materials in parts by weight:
2-8 parts of functional monomer, 580 parts of polyether macromonomer 520-containing material, 45-56 parts of second anhydride, 14-25 parts of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, 18-35 parts of initiator, 2-3 parts of chain transfer agent and 820 parts of water 460-containing material.
7. The polycarboxylate water reducer as set forth in claim 1, characterized in that the molecular weight of said polycarboxylate water reducer is 20000-70000.
8. The polycarboxylate water reducer as claimed in claim 1 or 5, wherein the polyether macromonomer comprises any one or a combination of at least two of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, isoamyl polyoxyethylene ether or 2-hydroxyethyl vinyl polyoxyethylene ether with weight average molecular weight of 1000-4000;
and/or the second anhydride comprises maleic anhydride and/or fumaric acid;
and/or the unsaturated carboxylic acid comprises any one or a combination of at least two of acrylic acid, methacrylic acid, itaconic acid or aconitic acid; the unsaturated carboxylic acid derivative comprises any one or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate;
and/or, the chain transfer agent is a thiol chain transfer agent;
and/or the initiator is a persulfate initiator.
9. The polycarboxylate water reducer according to claim 8, wherein the chain transfer agent comprises any one or a combination of at least two of 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, thioglycolic acid, mercaptoethanol, dimercaprol, 2-mercaptoethanesulfonic acid, isopropanol, diphosphonic acid and metal salts thereof, hypophosphorous acid and metal salts thereof, or sodium methallylsulfonate.
10. The method for preparing the polycarboxylic acid water reducing agent according to any one of claims 1 to 9, characterized by comprising the steps of:
mixing the functional monomer, the polyether macromonomer, the second anhydride, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid derivative, the initiator, the chain transfer agent and water according to the formula ratio, and carrying out free radical polymerization reaction to obtain the polycarboxylic acid water reducing agent.
11. The preparation method of the polycarboxylate water reducer as claimed in claim 10, characterized by comprising the following steps:
providing a solution A of a formulated amount of a functional monomer, a polyether macromonomer, a second anhydride and a portion of the formulated amount of water, a solution B of a formulated amount of an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative, a chain transfer agent and another portion of the formulated amount of water, and a solution C of an initiator and the remaining formulated amount of water;
and mixing the solution A, the solution B and the solution C to perform free radical polymerization reaction to obtain the polycarboxylic acid water reducing agent.
12. The preparation method of the polycarboxylate water reducer as set forth in claim 11, characterized by comprising the steps of:
and dropwise adding the solution B and the solution C into the heated solution A to perform free radical polymerization reaction, thereby obtaining the polycarboxylic acid water reducing agent.
13. The preparation method of the polycarboxylate water reducer as claimed in claim 12, wherein the temperature of the heated solution A is 30-85 ℃.
14. The preparation method of the polycarboxylate water reducer as claimed in claim 12, wherein the temperature of the heated solution A is 50-80 ℃.
15. The preparation method of the polycarboxylate water reducer as claimed in claim 12, characterized in that the dropping time is 2-5 h.
16. The preparation method of the polycarboxylate water reducer according to claim 12, characterized in that the free radical polymerization reaction temperature is 30-85 ℃ and the free radical polymerization reaction time is 2-5 h.
17. The preparation method of the polycarboxylate water reducer according to claim 12, characterized by cooling the product obtained by the radical polymerization to below 30 ℃ and adjusting the pH to neutral to obtain the polycarboxylate water reducer.
18. The method for preparing a polycarboxylate water reducer as claimed in claim 12, wherein the weight ratio of the functional monomer, the polyether macromonomer, the second anhydride and the water in the solution A is (1-10): 500- > 600): 40-60): 200- > 300.
19. The method for preparing a polycarboxylic acid water reducing agent according to claim 12, characterized in that the weight ratio of unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative, chain transfer agent and water in the solution B is (10-30): (1-4): (40-150).
20. The method for preparing a polycarboxylate water reducer as claimed in claim 12, wherein the weight ratio of the initiator to the water in the solution C is (15-40): 200-400).
21. The use of a polycarboxylate water reducer as defined in any one of claims 1 to 9 or prepared by the method of preparing a polycarboxylate water reducer as defined in any one of claims 10 to 20 in concrete construction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910533183.6A CN110240697B (en) | 2019-06-19 | 2019-06-19 | Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910533183.6A CN110240697B (en) | 2019-06-19 | 2019-06-19 | Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110240697A CN110240697A (en) | 2019-09-17 |
| CN110240697B true CN110240697B (en) | 2020-06-12 |
Family
ID=67888186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910533183.6A Active CN110240697B (en) | 2019-06-19 | 2019-06-19 | Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110240697B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645630B (en) * | 2020-12-19 | 2023-02-10 | 厦门宏发先科新型建材有限公司 | Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete |
| CN113461872A (en) * | 2021-07-01 | 2021-10-01 | 石家庄市长安育才建材有限公司 | Foam control monomer, polycarboxylate superplasticizer and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160159B (en) * | 2011-12-09 | 2014-07-30 | 东莞市绿微康生物科技有限公司 | Surfactant for wastepaper deinking, and preparation method thereof |
| CN103359971B (en) * | 2013-07-22 | 2015-03-04 | 中核混凝土股份有限公司 | Nuclear-power concrete air-entraining polycarboxylic acid additive |
| CN106587709B (en) * | 2016-12-07 | 2018-11-20 | 广西金洪混凝土有限公司 | Polycarboxylate water-reducer and preparation method thereof |
| CN107265906B (en) * | 2017-06-15 | 2018-02-23 | 广东瑞安科技实业有限公司 | A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof |
| CN107325293B (en) * | 2017-06-30 | 2020-08-11 | 中国石油大学(华东) | Styrene-maleic anhydride alkylphenol polyoxyethylene ether copolymer and preparation method and application thereof |
| CN108117626A (en) * | 2017-12-07 | 2018-06-05 | 浙江老虎山建材有限公司 | A kind of high performance water reducing agent of polyocarboxy acid |
| CN109627397B (en) * | 2018-12-24 | 2021-11-30 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer for improving rheological property of cement paste and preparation method thereof |
-
2019
- 2019-06-19 CN CN201910533183.6A patent/CN110240697B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110240697A (en) | 2019-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100481059B1 (en) | Copolymer for cement admixtures and its production process and use | |
| EP2181079B1 (en) | A liquid admixture composition | |
| KR101288145B1 (en) | Ultrarapid hardening cement composition and dispersant for ultrarapid hardening cement composition | |
| JPH0511057B2 (en) | ||
| JP4233294B2 (en) | Cement admixture, cement composition, and method for producing cement admixture | |
| JP2004519406A (en) | Cement admixture and cement composition | |
| WO2009139328A1 (en) | Method for producing polycarboxylic acid copolymer and copolymer composition for cement admixture | |
| WO2011034142A1 (en) | Cement admixture, cement composition, and polycarboxylic acid copolymer for cement admixture | |
| CN105218757B (en) | Early-strength polycarboxylate superplasticizer with slump retaining function and preparation method thereof | |
| JP2003221266A (en) | Cement admixture | |
| WO2006011182A1 (en) | Cement dispersant and concrete composition containing the dispersant | |
| CN110240697B (en) | Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof | |
| JP4947856B2 (en) | Cement dispersant and cement composition using the same | |
| JP2012166978A (en) | Cement admixture and cement composition | |
| JP2002121055A (en) | Cement dispersant and cement composition using the same | |
| WO2012105239A1 (en) | Hydraulic material dispersing agent and hydraulic material composition | |
| JP2013139351A (en) | Copolymer for cement admixture, method for producing the same, and cement admixture containing copolymer | |
| JP2007076970A (en) | Admixture composition for hydraulic material | |
| JP4877691B2 (en) | Method of constructing cement admixture and cement composition | |
| JP3780456B2 (en) | Cement dispersant and concrete composition containing the dispersant | |
| JP4448274B2 (en) | Method of constructing cement admixture and cement composition | |
| CN114685085B (en) | Wet-mixed mortar additive and preparation method thereof | |
| JP2003002719A (en) | Admixture for extruded formed body | |
| JP2010006701A (en) | Method for producing cement admixture | |
| JP4822613B2 (en) | Cement admixture and cement composition |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191030 Address after: 102400 No. 1 Qianjie, Liulihe Town Station, Fangshan District, Beijing Applicant after: Beijing Bbmg Cement Energy Technology Co., Ltd. Applicant after: Tangshan Jidong Cement Admixture Co., Ltd. Address before: 102400 No. 1 Qianjie, Liulihe Town Station, Fangshan District, Beijing Applicant before: Beijing Bbmg Cement Energy Technology Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |