CN112608421B - Preparation method of air-entraining ether polycarboxylate superplasticizer - Google Patents
Preparation method of air-entraining ether polycarboxylate superplasticizer Download PDFInfo
- Publication number
- CN112608421B CN112608421B CN201911166085.XA CN201911166085A CN112608421B CN 112608421 B CN112608421 B CN 112608421B CN 201911166085 A CN201911166085 A CN 201911166085A CN 112608421 B CN112608421 B CN 112608421B
- Authority
- CN
- China
- Prior art keywords
- acid
- unsaturated
- parts
- ether
- esterification product
- 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
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of an air-entraining ether polycarboxylic acid water reducer, which comprises the following steps: (1) preparing an esterification product; (2) carrying out copolymerization reaction; (3) and (4) neutralizing. The preparation method of the invention prepares the esterification product by esterifying the coconut diethanolamide and the unsaturated acid, and has the advantages of low cost and simple and convenient operation, and the prepared esterification product participates in the next copolymerization reaction to ensure that the main chain of the polycarboxylate water reducer has hydrophilic groups such as amide, and the prepared polycarboxylate water reducer has better air entraining and foam stabilizing properties, and improves the workability and strength of concrete.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of an air-entraining ether polycarboxylic acid water reducer.
Background
Along with the construction of national large-scale infrastructure, nuclear power, water conservancy, bridges and various large-scale projects, the requirements on the performance of concrete in all aspects are continuously improved, and particularly, the requirements on the strength, durability, workability and the like of the concrete are greatly improved in some major projects.
Although the excellent water reducing performance of the polycarboxylate superplasticizer has been widely accepted by the industry, the polycarboxylate superplasticizer has poor air entraining effect, so that the concrete workability is poor and the pumping is difficult when the polycarboxylate superplasticizer is applied to concrete due to high viscosity and low air entraining.
At present, the problem of poor air entrainment is solved by adopting a compound air entraining agent to improve the air entraining performance, but the dosage of the air entraining agent is small and is difficult to control in actual construction, and if the dosage is too large, the amount of air introduced into concrete is too large, so that the strength of the concrete is reduced; if the dosage is too small, the effect is weak, the problem of poor workability of the concrete is difficult to improve, the construction performance is influenced, the resistance of the concrete to climate change and chemical erosion is not increased much, and the improvement on the durability of the concrete is slight.
Patent CN 106380554A discloses a preparation method of an ester viscosity-reducing type polycarboxylate water reducer, which is published as 2017, 02/08.3.3.3.3.4.A polyethylene glycol monomethyl ether and methyl methacrylate are esterified to prepare an esterification product, and the esterification product, unsaturated sulfonic acid, a crosslinking monomer and a cationic monomer are subjected to polymerization reaction under the action of an emulsifier, an initiator and a chain transfer agent. At present, the research on the air-entraining type polycarboxylate superplasticizer is less, so that the development of the air-entraining type ether polycarboxylate superplasticizer does not need to be compounded with an air-entraining agent, and the method has important significance in directly improving the air-entraining performance of concrete.
Disclosure of Invention
The invention aims to provide a preparation method of an air-entraining ether polycarboxylic acid water reducer, which comprises the following steps:
1) and (3) copolymerization reaction: adding the esterification product, unsaturated polyoxyethylene ether and an emulsifier into a first reaction container, mixing, then respectively dropwise adding an initiator solution, a chain transfer agent solution, acrylic acid, a foam stabilizing functional monomer and an unsaturated ester monomer mixed solution, and reacting for 0.5-5 h at normal temperature;
2) and (3) neutralization reaction: after the reaction is finished, adding 10-50% of alkali liquor to adjust the pH value to 6-7 to obtain the air-entraining ether polycarboxylic acid water reducer,
the esterification product comprises an esterification product of a monomer with amide and dihydroxy and an unsaturated acid, and the foam stabilizing functional monomer is a monomer with double bonds, ester groups and sulfonic acid groups.
Optionally, after the copolymerization reaction is finished, keeping the temperature for a period of time, such as 0.5-2 h.
In the copolymerization reaction in the step 1), the preferable reaction time is 1-3 h, and in the neutralization reaction in the step 2), the used alkali liquor is any alkali liquor commonly used in the field, such as NaOH aqueous solution, KOH aqueous solution and the like, and the concentration of the alkali liquor is preferably 10-40%, and more preferably 20-40%.
In a preferred embodiment, the monomer having amide, dihydroxy groups is the following compound a:
wherein R is CH3～C18H37An alkyl group, a carboxyl group,
the esterification product of the monomer with amide and dihydroxy and unsaturated acid is prepared by the following method:
and (2) adding unsaturated acid and the compound A into a second reaction container, mixing, adding a catalyst and a polymerization inhibitor under the condition of nitrogen, adjusting the temperature to 50-200 ℃, preferably 80-120 ℃, and reacting for 0.5-10 h, preferably 4-6 h to obtain an esterification product of the monomer with amide and dihydroxy and the unsaturated acid.
Preferably, the unsaturated acid is acrylic acid, maleic anhydride or fumaric acid.
Preferably, the catalyst is selected from the group consisting of cerium sulfate, antimony trioxide, p-toluenesulfonic acid, and combinations thereof.
Preferably, the polymerization inhibitor is selected from the group consisting of 4-hydroxypiperidinol oxyl, 4-tert-butylcatechol, methyl hydroquinone, and combinations thereof.
The molar ratio of the unsaturated acid to the compound A can be 1-5: 1, preferably 1-2.5: 1.
The amount of the catalyst can be 0.1-10%, preferably 0.1-3.5% of the total mass of the unsaturated acid and the compound A.
The amount of the polymerization inhibitor can be 0.1-10%, preferably 0.1-2% of the total mass of the unsaturated acid and the compound A.
In another preferred embodiment, the foam stabilizing functional monomer having a double bond, an ester group and a sulfonate group is sodium oleoyl isethionate.
In yet another preferred embodiment, the unsaturated polyoxyethylene ether has a molecular weight of 500 to 15000, preferably 2000 to 5000, and is 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allylpolyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether or allylic alcohol polyoxyethylene ether.
In yet another preferred embodiment, the unsaturated ester monomer is methyl methacrylate, hydroxyethyl acrylate, or hydroxypropyl methacrylate.
In yet another preferred embodiment, the emulsifier is selected from sodium dodecylbenzene sulfonate, diethylene glycol monolaurate and a combination thereof, preferably the emulsifier is a combination of sodium dodecylbenzene sulfonate and diethylene glycol monolaurate, and the mass ratio of the sodium dodecylbenzene sulfonate to the diethylene glycol monolaurate is 1:10 to 10:1, preferably 1:5 to 5:1, more preferably 1:2 to 1:1, and most preferably 1:2 to 1: 3.
In yet another preferred embodiment, the initiator is selected from ammonium persulfate, sodium bisulfite, hydrogen peroxide, sodium hypophosphite, ascorbic acid and combinations thereof, preferably the initiator comprises 2 initiators, such as ammonium persulfate + sodium bisulfite, hydrogen peroxide + sodium hypophosphite, hydrogen peroxide + ascorbic acid, and the mass ratio of one initiator to another initiator is 1: 10-10: 1, preferably 1: 1-10: 1.
In yet another preferred embodiment, the chain transfer agent is a mercapto-containing chain transfer agent, preferably mercaptoacetic acid, mercaptopropionic acid, or n-butylmercaptan.
In still another preferred embodiment, the mass ratio of the esterification product, the unsaturated polyoxyethylene ether, the acrylic acid, the foam stabilizing functional monomer and the unsaturated ester monomer is 1-4: 100: 5-10: 0.4-3: 2-5.5.
In still another preferred embodiment, the amount of the emulsifier is 0.3-1.8% of the total mass of the unsaturated polyoxyethylene ether, the amount of the initiator is 0.8-4% of the total mass of the unsaturated polyoxyethylene ether, and the amount of the chain transfer agent is 1-2.5% of the total mass of the unsaturated polyoxyethylene ether.
In the preparation method of the present invention, it is preferable that the esterification product used is an esterification product of a monomer having amide and dihydroxy groups and an unsaturated acid, and it is more preferable that the esterification product is an esterification product of a monomer having amide and dihydroxy groups and an unsaturated acid, and in the monomer compound a having amide and dihydroxy groups, R is C11H23Alkyl, i.e. cocodiethanolamide used in the examples below.
It is another object of the present invention to provide an esterified product produced by the production method of the present invention.
The invention has the beneficial effects that:
1. the preparation method of the invention prepares the esterification product by esterifying the coconut diethanolamide and the unsaturated acid, and has the advantages of low cost and simple and convenient operation. The monomer obtained after partial dihydroxyl esterification is a crosslinking monomer, partial crosslinking is realized in the polymerization process, the steric hindrance effect of a system is increased, the hydrolysis of a crosslinking structure is slower than that of a water reducing agent obtained by copolymerization of monomers containing ester groups, acid anhydrides and other groups under the alkaline condition of cement, and carboxylic acid groups contributing to the water reducing effect are continuously released by gradual hydrolysis along with the extension of time, so that the lost water reducing rate is compensated, and the effect of maintaining slump is achieved;
2. according to the preparation method, the foam stabilizing functional monomer is introduced, so that the molecular main chain of the polycarboxylate water reducer is provided with the oleoyl isethionate sodium, the monomer is an anionic surfactant, the surface tension of the polycarboxylate water reducer can be reduced, the monomer is hydrated under the action of water dipoles around the polycarboxylate water reducer in water, and water in a bubble film is reserved so that bubbles are stable and do not break. The introduction of a large number of tiny and independent air bubbles can form a lubricating effect in the concrete, thereby greatly improving the workability of the concrete. And the introduction of sulfonic acid groups ensures that the prepared polycarboxylic acid water reducing agent has excellent dispersibility.
Detailed Description
The invention is further illustrated and described below by means of specific examples.
Example 1
(1) Preparing an esterification product: 40.97 parts of maleic anhydride and 100 parts of coconut diethanolamide are added into a first reaction vessel to be mixed, 0.5 part of cerium sulfate and 0.3 part of 4-hydroxypiperidinol oxygroup are added under the condition of nitrogen, the temperature is adjusted to 110 ℃, and the mixture is reacted for 4 hours, so that an esterification product of a monomer with amide and dihydroxy and an unsaturated acid is obtained;
(2) and (3) copolymerization reaction: adding 2.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 4000, 0.43 part by weight of sodium dodecyl benzene sulfonate, 1.07 part by weight of diethylene glycol monolaurate and 108 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.5 part of ascorbic acid, 1.5 parts of n-butylmercaptan and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 1.5 parts of sodium oleoyl isethionate, 2 parts of methyl methacrylate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and keeping the reaction for 0.5 h;
(3) and (3) neutralization reaction: and adding 15 parts by weight of 32% sodium hydroxide by mass to obtain the air-entraining ether polycarboxylic acid water reducer with the concentration of 40%.
Example 2
(1) Preparing an esterification product: 72.76 parts of fumaric acid and 100 parts of coconut diethanolamide are added into a first reaction vessel to be mixed, 1.2 parts of antimony trioxide and 1 part of methyl hydroquinone are added under the condition of nitrogen, the temperature is adjusted to 120 ℃, and the mixture reacts for 6 hours to obtain an esterification product of a monomer with amide and dihydroxy and an unsaturated acid;
(2) and (3) copolymerization reaction: adding 1 part by weight of the esterification product prepared in the step (1), 100 parts by weight of methylallyl alcohol polyoxyethylene ether with the molecular weight of 3000, 0.51 part by weight of sodium dodecyl benzene sulfonate, 1.28 parts by weight of diethylene glycol monolaurate and 106 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 2.3 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.7 part of ascorbic acid, 2.5 parts of mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 7 parts of acrylic acid, 3 parts of sodium oleoyl isethionate, 5.5 parts of hydroxyethyl acrylate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and keeping the reaction for 0.5 h;
(3) and (3) neutralization reaction: and adding 15 parts by weight of 32% sodium hydroxide by mass to obtain the air-entraining ether polycarboxylic acid water reducer with the concentration of 40%.
Example 3
(1) Preparing an esterification product: adding 37.64 parts by weight of acrylic acid and 100 parts by weight of coconut diethanolamide into a first reaction vessel, mixing, adding 2.5 parts by weight of antimony trioxide and 1.5 parts by weight of methyl hydroquinone under the condition of nitrogen, adjusting the temperature to 80 ℃, and reacting for 5 hours to obtain an esterification product of a monomer with amide and dihydroxy and an unsaturated acid;
(2) and (3) copolymerization reaction: adding 4 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of methylallyl polyoxyethylene polyoxypropylene ether with the molecular weight of 5000, 0.28 part by weight of sodium dodecyl benzene sulfonate, 0.72 part by weight of diethylene glycol monolaurate and 115 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 1.2 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.8 part of sodium hypophosphite, 1.8 parts of mercaptopropionic acid and 20 parts of water are uniformly mixed in a second dripping device; 8.5 parts of acrylic acid, 0.4 part of sodium oleoyl isethionate, 4 parts of hydroxypropyl methacrylate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dropping materials in the first dropping device, the second dropping device and the third dropping device into the second reaction container, respectively dropping the materials in the third dropping device, the second dropping device and the first dropping device within 2 hours, and keeping the reaction for 0.5 hour;
(3) and (3) neutralization reaction: and adding 15 parts by weight of 32% sodium hydroxide by mass to obtain the air-entraining ether polycarboxylic acid water reducer with the concentration of 40%.
Example 4
(1) Preparing an esterification product: adding 62.7 parts by weight of acrylic acid and 100 parts by weight of coconut diethanolamide into a first reaction vessel, mixing, adding 3.5 parts by weight of p-toluenesulfonic acid and 2 parts by weight of 4-tert-butyl catechol under the condition of nitrogen, adjusting the temperature to 100 ℃, and reacting for 4 hours to obtain an esterification product of a monomer with amide and dihydroxy and an unsaturated acid;
(2) and (3) copolymerization reaction: adding 3 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of allyl polyoxyethylene polyoxypropylene ether with the molecular weight of 4000, 0.09 part by weight of sodium dodecyl benzene sulfonate, 0.21 part by weight of diethylene glycol monolaurate and 112 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 0.4 part by weight of ammonium persulfate and 20 parts by weight of water in a first dripping device; 0.4 part of sodium bisulfite, 1 part of thioglycolic acid and 20 parts of water are uniformly mixed in a second dripping device; uniformly mixing 10 parts of acrylic acid, 2.5 parts of sodium oleoyl isethionate, 3 parts of methyl methacrylate and 20 parts of water in a third dripping device; at normal temperature, sequentially dropping materials in the first dropping device, the second dropping device and the third dropping device into the second reaction container, respectively dropping the materials in the third dropping device, the second dropping device and the first dropping device within 2 hours, and keeping the reaction for 0.5 hour;
(3) and (3) neutralization reaction: and adding 15 parts by weight of 32% sodium hydroxide by mass to obtain the air-entraining ether polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 1:
(1) and (3) copolymerization reaction: adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 4000, 0.43 part by weight of sodium dodecyl benzene sulfonate, 1.07 part by weight of diethylene glycol monolaurate and 108 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.5 part of ascorbic acid, 1.5 parts of n-butylmercaptan and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 1.5 parts of sodium oleoyl isethionate, 2 parts of methyl methacrylate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and keeping the reaction for 0.5 h;
(2) and (3) neutralization reaction: adding 15 parts by weight of sodium hydroxide with the mass concentration of 32% to obtain the ether polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 2:
(1) preparing an esterification product: 40.97 parts of maleic anhydride and 100 parts of coconut diethanolamide are added into a first reaction vessel to be mixed, 0.5 part of cerium sulfate and 0.3 part of 4-hydroxypiperidinol oxygroup are added under the condition of nitrogen, the temperature is adjusted to 110 ℃, and the mixture is reacted for 4 hours, so that an esterification product of a monomer with amide and dihydroxy and an unsaturated acid is obtained;
(2) and (3) copolymerization reaction: adding 2.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 4000, 0.43 part by weight of sodium dodecyl benzene sulfonate, 1.07 part by weight of diethylene glycol monolaurate and 106 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.5 part of ascorbic acid, 1.5 parts of n-butylmercaptan and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 2 parts of methyl methacrylate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and keeping the reaction for 0.5 h;
(3) and (3) neutralization reaction: adding 15 parts by weight of sodium hydroxide with the mass concentration of 32% to obtain the ether polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 3:
(1) preparing an esterification product: 40.97 parts of maleic anhydride and 100 parts of coconut diethanolamide are added into a first reaction vessel to be mixed, 0.5 part of cerium sulfate and 0.3 part of 4-hydroxypiperidinol oxygroup are added under the condition of nitrogen, the temperature is adjusted to 110 ℃, and the mixture is reacted for 4 hours, so that an esterification product of a monomer with amide and dihydroxy and an unsaturated acid is obtained;
(2) and (3) copolymerization reaction: adding 2.5 parts by weight of the esterification product prepared in the step (1), 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 4000, 0.43 part by weight of sodium dodecyl benzene sulfonate, 1.07 part by weight of diethylene glycol monolaurate and 106 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.5 part of ascorbic acid, 1.5 parts of n-butylmercaptan and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 1.5 parts of sodium oleoyl isethionate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and keeping the reaction for 0.5 h;
(3) and (3) neutralization reaction: adding 15 parts by weight of sodium hydroxide with the mass concentration of 32% to obtain the ether polycarboxylic acid water reducer with the concentration of 40%.
Comparative example 4:
(1) and (3) copolymerization reaction: adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether with the molecular weight of 4000, 0.43 part by weight of sodium dodecyl benzene sulfonate, 1.07 part by weight of diethylene glycol monolaurate and 102 parts by weight of water into a second reaction vessel, uniformly stirring, and uniformly mixing 3.5 parts by weight of hydrogen peroxide and 20 parts by weight of water in a first dripping device; 0.5 part of ascorbic acid, 1.5 parts of n-butylmercaptan and 20 parts of water are uniformly mixed in a second dripping device; 5 parts of acrylic acid, 2 parts of methyl methacrylate and 20 parts of water are uniformly mixed in a third dripping device; at normal temperature, sequentially dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction container, dripping the materials in the third dripping device, the second dripping device and the first dripping device in 1.5h, and keeping the reaction for 0.5 h;
(2) and (3) neutralization reaction: adding 15 parts by weight of sodium hydroxide with the mass concentration of 32% to obtain the ether polycarboxylic acid water reducer with the concentration of 40%.
Comparing the air-entraining ether polycarboxylic acid water reducing agent of the embodiments 1-4 with the water reducing agent of the comparative examples 1-4, adopting standard cement, and measuring the air content, the slump, the expansion degree and the strength of the concrete at each age according to GB 8076 plus 2008 concrete admixture by using the mixing amount of 0.2 percent (converted into solid parts) of the cement. The concrete mixing proportion is as follows: cement 360kg/m3803kg/m of sand3982kg/m stone3The initial slump was controlled to 190. + -. 10mm, and the concrete test results are shown in Table 1.
The foam-inducing and foam-stabilizing capabilities of the air-entraining ether polycarboxylic acid water reducing agents of examples 1 to 4 and the water reducing agents of comparative examples 1 to 4 were measured by a cement slurry foam shaking method, as shown in tables 1 and 2. The experimental method is as follows:
mixing 30mL of water, 10mL of water reducing agent (10% solution by mass concentration) and 5g of ordinary portland cement, pouring the mixture into a 1L measuring cylinder, oscillating the mixture for 30 times to generate foam, and respectively recording the volume of the foam and the corresponding time. For convenience of quantitative studies, the foam stabilizing rate was calculated as follows:
V＝(V0-V1)/t
wherein V is the bubble stabilizing rate;
t is time in min;
V0initial foam volume in mL;
V1foam volume in mL for time t.
Table 1: the performances of the air-entraining ether polycarboxylate superplasticizer disclosed by the invention are compared with those of the water reducers in comparative examples 1-4
Table 2: measurement results of foam stabilizing ability and surface tension
As can be seen from the results in Table 1, compared with comparative examples, the air-entraining ether polycarboxylic acid water reducing agent for concrete prepared by the invention (examples 1 to 4) has the advantages that the air content of the mixed concrete is high, the workability is good, the initial dispersing performance and the slump retaining performance are good, and the strength of the concrete is not influenced or slightly improved.
As can be seen from the results in tables 1 and 2, the concrete incorporating comparative example 1 (without esterified product) has good foam stabilizing properties, but slightly lower air content and poorer workability; the concrete doped with the comparative example 2 (without foam stabilizing functional monomer) has poor foam stabilizing performance and poor concrete workability; although the concrete doped with the unsaturated ester monomer in the comparative example 3 has good foam stability and high gas content, the initial dispersion performance and slump retaining performance of the concrete are reduced; the concrete doped with comparative example 4 (without esterification product and foam stabilizing functional monomer) has good initial dispersing performance and slump retaining performance, but the concrete has poor foam stabilizing performance and low air content, which results in poor workability.
Finally, it should be noted that: the above examples are intended to illustrate the invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments and examples, it will be understood by those of ordinary skill in the art that: it is also possible to modify the embodiments described above or to substitute them in part or in whole with equivalents; and such modifications or alterations do not depart from the spirit of the invention.
Claims (14)
1. A preparation method of an air-entraining ether polycarboxylic acid water reducer is characterized by comprising the following steps: the method comprises the following steps:
1) and (3) copolymerization reaction: adding the esterification product, unsaturated polyoxyethylene ether and an emulsifier into a first reaction container, mixing, then respectively dropwise adding an initiator solution, a chain transfer agent solution, acrylic acid, a foam stabilizing functional monomer and an unsaturated ester monomer mixed solution, and reacting for 0.5-5 h at normal temperature;
2) and (3) neutralization reaction: after the reaction is finished, adding 10-50% of alkali liquor to adjust the pH value to 6-7 to obtain the air-entraining ether polycarboxylic acid water reducer,
wherein the esterification product comprises an esterification product of coconut diethanolamide and unsaturated acid, and the foam stabilizing functional monomer is a monomer with double bonds, ester groups and sulfonic acid groups.
2. The process according to claim 1, characterized in that the esterification product of coconut diethanolamide with unsaturated acids is prepared by:
and adding unsaturated acid and coconut oil acid diethanolamide into a second reaction vessel for mixing, adding a catalyst and a polymerization inhibitor under the condition of nitrogen, adjusting the temperature to 50-200 ℃, and reacting for 0.5-10 h to obtain an esterification product of the coconut oil acid diethanolamide and the unsaturated acid.
3. The method of claim 2, wherein: the unsaturated acid is acrylic acid, maleic anhydride or fumaric acid.
4. The method of claim 2, wherein: the catalyst is selected from the group consisting of cerium sulfate, antimony trioxide, p-toluenesulfonic acid, and combinations thereof.
5. The method of claim 2, wherein: the polymerization inhibitor is selected from 4-hydroxypiperidinol oxygen free radical, 4-tert-butylcatechol, methyl hydroquinone and combination thereof.
6. The method of claim 2, wherein: the molar ratio of the unsaturated acid to the coconut oil acid diethanolamide is 1-2.5: 1, the dosage of the catalyst is 0.1-10% of the total mass of the unsaturated acid and the coconut oil acid diethanolamide, and the dosage of the polymerization inhibitor is 0.1-10% of the total mass of the unsaturated acid and the coconut oil acid diethanolamide.
7. The preparation method according to claim 2, wherein the foam stabilizing functional monomer is sodium oleoyl isethionate.
8. The method of claim 2, wherein: the molecular weight of the unsaturated polyoxyethylene ether is 500-15000, and the unsaturated polyoxyethylene ether is 4-hydroxybutyl vinyl ether polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether or allyl alcohol polyoxyethylene ether.
9. The method of claim 2, wherein: the unsaturated ester monomer is methyl methacrylate, hydroxyethyl acrylate or hydroxypropyl methacrylate.
10. The method of claim 2, wherein: the emulsifier is selected from sodium dodecyl benzene sulfonate, diethylene glycol monolaurate and combinations thereof.
11. The method of claim 2, wherein: the initiator is selected from ammonium persulfate, sodium bisulfite, hydrogen peroxide, sodium hypophosphite, ascorbic acid and combinations thereof.
12. The method of claim 2, wherein: the chain transfer agent is a mercapto-containing chain transfer agent.
13. The method of claim 2, wherein: the mass ratio of the esterification product to the unsaturated polyoxyethylene ether to the acrylic acid to the foam stabilizing functional monomer to the unsaturated ester monomer is 1-4: 100: 5-10: 0.4-3: 2-5.5.
14. The method of claim 2, wherein: the dosage of the emulsifier is 0.3-1.8% of the total mass of the unsaturated polyoxyethylene ether, the dosage of the initiator is 0.8-4% of the total mass of the unsaturated polyoxyethylene ether, and the dosage of the chain transfer agent is 1-2.5% of the total mass of the unsaturated polyoxyethylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911166085.XA CN112608421B (en) | 2019-11-25 | 2019-11-25 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911166085.XA CN112608421B (en) | 2019-11-25 | 2019-11-25 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112608421A CN112608421A (en) | 2021-04-06 |
| CN112608421B true CN112608421B (en) | 2022-02-18 |
Family
ID=75224309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911166085.XA Active CN112608421B (en) | 2019-11-25 | 2019-11-25 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608421B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608420B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN114349902B (en) * | 2021-12-14 | 2023-05-12 | 云南森博混凝土外加剂有限公司 | Stable foam type concrete air entraining agent and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1015399A1 (en) * | 1997-07-09 | 2000-07-05 | ARCO Chemical Technology, L.P. | Method of making a water reducing additive for cement |
| CN102351999A (en) * | 2011-07-15 | 2012-02-15 | 清华大学 | Method for preparing nanoparticle water reducing agent |
| CN106116228A (en) * | 2016-06-24 | 2016-11-16 | 桂林华越环保科技有限公司 | A kind of concrete antifreezing pumping aid |
| CN106145745A (en) * | 2016-06-24 | 2016-11-23 | 桂林华越环保科技有限公司 | A kind of compensating shrinkage of concrete pumping admixture |
| CN106380554A (en) * | 2016-08-26 | 2017-02-08 | 科之杰新材料集团有限公司 | Preparation method of ester type viscosity reduction type polycarboxylate superplasticizer |
| CN108047388A (en) * | 2017-12-07 | 2018-05-18 | 科之杰新材料集团有限公司 | A kind of preparation method of shrinkage type concrete mobility stabilizer |
| CN108192040A (en) * | 2017-12-28 | 2018-06-22 | 科之杰新材料集团有限公司 | A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent |
| CN108484841A (en) * | 2018-03-30 | 2018-09-04 | 湖北工业大学 | A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization |
| CN109354654A (en) * | 2018-08-30 | 2019-02-19 | 济南大学 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN109575198A (en) * | 2018-11-15 | 2019-04-05 | 福建路桥翔通建材科技有限公司 | A kind of reinforcing type polycarboxylic acid water-reducing agent and preparation method thereof |
| CN109627396A (en) * | 2018-12-24 | 2019-04-16 | 科之杰新材料集团有限公司 | A kind of preparation method for the ether-ether copoly type polycarboxylate water-reducer improving rheological behavior |
| CN109970922A (en) * | 2019-01-29 | 2019-07-05 | 武汉苏博新型建材有限公司 | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process |
| CN110003402A (en) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN113292686A (en) * | 2020-12-30 | 2021-08-24 | 云南森博混凝土外加剂有限公司 | Multifunctional concrete water-retaining agent and preparation method thereof |
-
2019
- 2019-11-25 CN CN201911166085.XA patent/CN112608421B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1015399A1 (en) * | 1997-07-09 | 2000-07-05 | ARCO Chemical Technology, L.P. | Method of making a water reducing additive for cement |
| CN102351999A (en) * | 2011-07-15 | 2012-02-15 | 清华大学 | Method for preparing nanoparticle water reducing agent |
| CN106116228A (en) * | 2016-06-24 | 2016-11-16 | 桂林华越环保科技有限公司 | A kind of concrete antifreezing pumping aid |
| CN106145745A (en) * | 2016-06-24 | 2016-11-23 | 桂林华越环保科技有限公司 | A kind of compensating shrinkage of concrete pumping admixture |
| CN106380554A (en) * | 2016-08-26 | 2017-02-08 | 科之杰新材料集团有限公司 | Preparation method of ester type viscosity reduction type polycarboxylate superplasticizer |
| CN108047388A (en) * | 2017-12-07 | 2018-05-18 | 科之杰新材料集团有限公司 | A kind of preparation method of shrinkage type concrete mobility stabilizer |
| CN108192040A (en) * | 2017-12-28 | 2018-06-22 | 科之杰新材料集团有限公司 | A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent |
| CN108484841A (en) * | 2018-03-30 | 2018-09-04 | 湖北工业大学 | A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization |
| CN109354654A (en) * | 2018-08-30 | 2019-02-19 | 济南大学 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN109575198A (en) * | 2018-11-15 | 2019-04-05 | 福建路桥翔通建材科技有限公司 | A kind of reinforcing type polycarboxylic acid water-reducing agent and preparation method thereof |
| CN109627396A (en) * | 2018-12-24 | 2019-04-16 | 科之杰新材料集团有限公司 | A kind of preparation method for the ether-ether copoly type polycarboxylate water-reducer improving rheological behavior |
| CN109970922A (en) * | 2019-01-29 | 2019-07-05 | 武汉苏博新型建材有限公司 | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process |
| CN110003402A (en) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and its low temperature preparation method of lower shrinkage high-adaptability |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN113292686A (en) * | 2020-12-30 | 2021-08-24 | 云南森博混凝土外加剂有限公司 | Multifunctional concrete water-retaining agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 减缩型聚羧酸减水剂的制备与作用机理研究;路芳;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅱ辑》;20140315;C038-546页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112608421A (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112708042B (en) | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN112608420B (en) | Preparation method of air-entraining type ester polycarboxylate superplasticizer | |
| CN111607039A (en) | Slow-release high slump loss resistant polycarboxylic acid concrete water reducer and preparation method thereof | |
| CN109705282A (en) | A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer | |
| CN107652405B (en) | Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof | |
| CN110358026B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN107337769B (en) | Slump-retaining type polycarboxylate superplasticizer and preparation method thereof | |
| CN109776742A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer of phosphate ester-containing and preparation method thereof | |
| CN107325236A (en) | A kind of non-soil responsive type polycarboxylate water-reducer and preparation method thereof | |
| CN112608421B (en) | Preparation method of air-entraining ether polycarboxylate superplasticizer | |
| CN111548459A (en) | Preparation method of high slump loss resistant polycarboxylate superplasticizer | |
| CN115960322A (en) | Polycarboxylic acid viscosity reducer and preparation method thereof | |
| CN111439947A (en) | Low-air-entraining slow-setting type polycarboxylate superplasticizer and preparation method thereof | |
| CN106397683A (en) | Polycarboxylate superplasticizer for reducing viscosity of high-grade concrete and preparation method thereof | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN113929837B (en) | Shrinkage-reducing polycarboxylic acid water reducing agent, and preparation method and application thereof | |
| CN112708041B (en) | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof | |
| CN112608423B (en) | Preparation method of viscosity-reducing and mud-resisting polycarboxylate superplasticizer | |
| CN109320668B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN112194762A (en) | Preparation method of non-crosslinked reticular polycarboxylic acid water reducing agent | |
| CN106883358B (en) | Four arm star polycarboxylic acid super-plasticizers of one kind and its preparation method and application | |
| WO2023184785A1 (en) | Crosslinked polycarboxylic acid water reducer and preparation method therefor | |
| CN114702683A (en) | Hyperbranched polycarboxylic acid water reducer and preparation method thereof | |
| CN114163578A (en) | Viscosity-controlled polycarboxylate superplasticizer and preparation method thereof | |
| CN109880018B (en) | One-step method for preparing polycarboxylic acid high-efficiency water reducing agent with four-arm branched structure |
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 |