CN112708059B - Anti-corrosion polycarboxylic slump retaining agent and preparation method thereof - Google Patents
Anti-corrosion polycarboxylic slump retaining agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/67—Biocides
- C04B2103/69—Fungicides
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- Structural Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of building materials, in particular to an anticorrosive polycarboxylic slump retaining agent and a preparation method thereof, wherein the anticorrosive polycarboxylic slump retaining agent is prepared by carrying out polymerization reaction on a small monomer with an anticorrosive function, an unsaturated macromonomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and a slow-release slump retaining small monomer under the action of an initiator and a molecular weight regulator to generate the anticorrosive polycarboxylic slump retaining agent with the small monomer with the anticorrosive function linked on a molecular main chain.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to an anticorrosive polycarboxylic slump retaining agent and a preparation method thereof.
Background
The conventional method for solving the problem of mildew and odor of the polycarboxylic acid water reducing agent is a compound preservative, and some people also study the anti-corrosion polycarboxylic acid slump retaining agent.
The method for adding the preservative in the compounding process is the method which is the most widely applied in the prior art, but the compounded preservative generally has a small molecular weight, so that on one hand, the problem of nonuniform dispersion in the polycarboxylic acid water reducing agent can exist, and on the other hand, the problem of decomposition failure of the conventional compounded preservative used at present under the environment of higher than 50 ℃ also exists, and the application of the preservative is limited to a certain extent.
CN110642996A, published in 2020, 01, 03 days, discloses a self-preservation type polycarboxylate water reducer and a preparation method thereof, but monomers with preservation performance used by the self-preservation type polycarboxylate water reducer are any one or more of polymethacryloxyethyltrimethylammonium chloride, poly [2- (acryloyloxy) ethyl ] trimethylammonium bromide, poly (benzylethyltrimethylammonium chloride), polyallyltrimethylammonium chloride and poly (3-acrylamidopropyl) trimethylammonium bromide. However, these substances are already polymers, have no polymerization activity and cannot be connected into the molecular structure of the water reducing agent, so the method is also a method for compounding the preservative in nature.
CN110128048A, the disclosure time of which is 2019, 08 months and 16 days, discloses an antiseptic slump retaining polycarboxylate water reducer for summer and a preparation method thereof, and also realizes the antiseptic property by a method of compounding a bactericide (polyhexamethylene guanidine phosphate).
CN110015857A, the publication time is 2019, 07, 16, discloses a preparation method and application of a straw-starch-based mixed modified composite polycarboxylate water reducer, dimethyl fumarate is used as a preservative to be directly compounded into a patent product, but the water solubility of the dimethyl fumarate is not very good, a large amount of water is generally required to be compounded and added in the actual use process of the polycarboxylate water reducer, and the water content often exceeds 90%, so the effect of directly compounding and adding the dimethyl fumarate is not ideal.
CN109796561A, the disclosure time is 2019, 05, month and 24, and discloses a mother liquor of an aromatic ring polycarboxylic acid water reducing agent and a preparation method and application thereof.
CN109400819A, published in 2019, 03 and 01, discloses a viscosity-reduction-integrated antibacterial amphoteric polycarboxylate-type high-efficiency water reducing agent and a preparation method thereof.
CN108373526A, with the publication time of 07 days in 2018, 08 months, discloses an antifouling and antibacterial polycarboxylic acid water reducer and a preparation method thereof, wherein (meth) acrylic acid sulfobetaine and methacryloyloxyethyl trimethyl ammonium chloride are added during polymerization to achieve an antibacterial effect, but the cost of the two monomers is high.
CN107698721A, published in 2018, 16.02.2018, discloses a branched chain type antibacterial polycarboxylate superplasticizer, a preparation method and application thereof, but the preparation process is too complex and the production efficiency is low.
CN107265907A, the publication time is 10 months and 20 days in 2017, and discloses an amphiprotic antibacterial polycarboxylic acid high-efficiency water reducing agent and a preparation method thereof.
CN111592269A, the publication time is 28 days 08/2020, and discloses a preparation method of an antibacterial preservative for a polycarboxylic acid water reducer, which is characterized in that betaine and dimethyl fumarate monomers with antibacterial functions are introduced into polyoxyethylene ether with a similar structure of the polycarboxylic acid water reducer for free radical copolymerization reaction, so that the preservative is compatible with the polycarboxylic acid water reducer with a similar molecular structure. However, the product prepared by the patent only has an anti-corrosion effect and does not have a slump retaining effect, and the direct polymerization of the dimethyl fumarate monomer and the unsaturated monomer in a system has the problems of poor water solubility, phase separation in the polymerization process and low polymerization efficiency.
Disclosure of Invention
In order to solve the problem of how to provide a stable slump retaining agent with excellent anticorrosion effect in the background technology, the invention provides an anticorrosion polycarboxylic acid slump retaining agent, which is prepared by carrying out polymerization reaction on an anticorrosion small monomer, an unsaturated macromonomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and a slow-release slump retaining small monomer under the action of an initiator and a molecular weight regulator to generate an anticorrosion polycarboxylic acid water reducing agent with a molecule main chain connected with the anticorrosion small monomer;
the preservative functional small monomer is fumarate and/or maleate.
On the basis of the technical scheme, further, the slow-release slump-retaining small monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
On the basis of the technical scheme, the mass ratio range of the unsaturated macromonomer, the preservative functional small monomer, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and the slow-release slump retaining small monomer is 180: (1-15): (2-10): (10 to 30).
On the basis of the technical scheme, further, the using amount of the initiator is 0.5-3.0% of the total mass of the reactants; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the reactants.
On the basis of the technical scheme, in the polymerization reaction process, an initiator aqueous solution, a molecular weight regulator aqueous solution and an unsaturated carboxylic acid and/or unsaturated carboxylic anhydride aqueous solution are dropwise added within 0.5 to 6 hours, the reaction temperature is 10 to 90 ℃, and the temperature is kept for 0 to 3 hours after the dropwise addition.
On the basis of the technical scheme, the initiator further comprises a water-soluble redox initiation system or a water-soluble peroxide initiation system reagent; specifically, hydrogen peroxide-ascorbic acid, hydrogen peroxide-sodium formaldehyde sulfoxylate and ammonium persulfate can be adopted.
The molecular weight regulator comprises at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid and sodium hypophosphite.
On the basis of the technical scheme, the fumaric acid ester comprises monomethyl fumarate and monoethyl fumarate.
On the basis of the technical scheme, the maleate further comprises diethyl maleate, dimethyl maleate and dipropyl maleate.
On the basis of the technical scheme, the molecular weight of the unsaturated macromonomer is 600-6000.
On the basis of the technical scheme, the unsaturated macromonomer is at least one of methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
In addition to the above technical solutions, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid, and maleic anhydride.
The invention also provides a preparation method of the corrosion-resistant polycarboxylic slump retaining agent, which comprises the following steps:
adding unsaturated macromonomer, small monomer with anticorrosion function and water into a reactor for stirring, after the materials are uniformly mixed, dropwise adding unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, slow-release slump-retaining small monomer, initiator and molecular weight regulator for 0.5-6 h, wherein the reaction temperature is 10-90 ℃; and preserving the heat for 0-3 h after the dropwise addition is finished to obtain a copolymerization product, namely the anti-corrosion polycarboxylic acid slump retaining agent.
According to the anti-corrosion type polycarboxylic acid slump retaining agent provided by the invention, at least one monomer unit of fumarate and maleate is introduced into a product molecular structure in a way of copolymerizing an unsaturated macromonomer, an anti-corrosion functional small monomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and a slow-release slump retaining small monomer, so that the polycarboxylic acid slump retaining agent with anti-corrosion performance is obtained, a small-molecular preservative does not need to be compounded, the problem of uneven distribution caused by poor compatibility of the preservative and a polycarboxylic acid water reducing agent is solved, the formed final product is a stable high-molecular structure, can resist high temperature higher than 50 ℃, and is more excellent in high-temperature anti-corrosion performance.
The raw materials used in the invention have wide sources, low price and simple preparation process, so that the cost of the project product more meets the application requirement of the polycarboxylic acid slump retaining agent, and the polycarboxylic acid slump retaining agent has important practical application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides a preparation example of the anti-corrosion polycarboxylic slump retaining agent as shown in the following:
example 1
Adding 180.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400, 2.50g of monomethyl fumarate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, after the materials are uniformly mixed, beginning to dropwise add an aqueous solution of a mixed solution of acrylic acid and hydroxyethyl acrylate (wherein 6.00g of acrylic acid, 27.00g of hydroxyethyl acrylate and 20.00g of water), an aqueous solution of hydrogen peroxide (wherein 1.50g of hydrogen peroxide and 20.00g of water), an aqueous solution of mercaptopropionic acid (wherein 0.90g of mercaptopropionic acid and 20.00g of water), an aqueous solution of ascorbic acid (wherein 0.25 of ascorbic acid and 20.00g of water), starting to react at 30 ℃, dropwise adding time of 3.0h, dropwise adding process temperature of 30-50 ℃, and preserving heat at 45-50 ℃ for 0.5h after dropwise adding, thus obtaining the preservative type polycarboxylic acid slump-1.
Example 2
Adding 180.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 3000, 3.50g of diethyl maleate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, starting to dropwise add acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate aqueous solution (wherein 4.00g of acrylic acid, 23.00g of hydroxyethyl acrylate, 5.00g of hydroxyethyl methacrylate and 20.00g of water), hydrogen peroxide aqueous solution (wherein 2.00g of hydrogen peroxide and 20.00g of water), thioglycolic acid aqueous solution (wherein 0.70g of thioglycolic acid and 20.00g of water), ascorbic acid aqueous solution (wherein 0.30 g of ascorbic acid and 20.00g of water) when the initial reaction temperature is 30 ℃, dropwise adding time is 2.5 hours, controlling the temperature in the dropwise adding process to be 30-50 ℃, and keeping the temperature at 45-50 ℃ for 0.5 hours after dropwise adding, thus obtaining the anti-corrosion polycarboxylic acid slump-retaining agent KZJ-2.
Example 3:
adding 150.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400, 30.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400, 3.00g of monoethyl fumarate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, starting dropwise adding a mixed aqueous solution of acrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate (6.00 g of acrylic acid, 10.00g of hydroxyethyl acrylate, 12.00g of hydroxypropyl acrylate and 20.00g of water), a hydrogen peroxide aqueous solution (1.80 g of hydrogen peroxide and 20.00g of water), a mercaptoethanol aqueous solution (0.70 g of mercaptoethanol and 20.00g of water), a rongalite aqueous solution (0.50 g of rongalite and 20.00g of water), starting the reaction temperature is 45 ℃, the dropwise adding time is 2.5h, the dropwise adding process temperature is controlled to be 43-47 ℃, and then keeping the temperature at 43-47 ℃ for 1h to obtain the anti-corrosion polycarboxylic acid slump-3 slump-3 slump.
Example 4:
adding 180.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 3000, 2.00g of monomethyl fumarate, 1.50g of diethyl maleate, 2.00g of sodium hypophosphite, 0.005g of ferrous sulfate and 150.00g of water into a reactor, starting a stirrer and a temperature control device, starting dropwise adding a mixed aqueous solution of acrylic acid, hydroxypropyl acrylate and hydroxyethyl methacrylate (wherein 3.00g of acrylic acid, 20.00g of hydroxypropyl acrylate, 5.00g of hydroxyethyl methacrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.80g of hydrogen peroxide and 20.00g of water), an ascorbic acid aqueous solution (wherein 0.30 g of ascorbic acid and 20.00g of water) when the initial reaction temperature is 10 ℃, the dropwise adding time is 1h, controlling the temperature of the material dropwise adding process to be less than or equal to 30 ℃, and keeping the temperature for 1h after the slump constant, thereby obtaining the anti-corrosion type polycarboxylic acid preservative KZJ-4.
Example 5:
adding 180.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 2.00g of monomethyl fumarate, 1.00g of diethyl maleate, 3.00g of sodium hypophosphite, 0.005g of ferrous sulfate and 150.00g of water into a reactor, starting a stirrer and a temperature control device, starting dropwise adding a mixed aqueous solution of acrylic acid and hydroxyethyl acrylate (8.00 g of acrylic acid, 15.00 g of hydroxyethyl acrylate and 20.00g of water), a hydrogen peroxide solution (1.20 g of hydrogen peroxide and 20.00g of water), an ascorbic acid aqueous solution (0.30 g of ascorbic acid and 20.00g of water), starting the reaction at 15 ℃, dropwise adding time of 1.0h, controlling the temperature of the material in the dropwise adding process to be less than or equal to 30 ℃, and preserving heat for 0.5h after dropwise adding is finished to obtain the anti-corrosion type polycarboxylic acid slump-retaining agent KZJ-5.
Comparative example 1:
adding 180.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400 and 145.00g of water into a reactor, starting a stirrer and a temperature control device, after the materials are uniformly mixed, dropwise adding an aqueous solution of a mixed solution of acrylic acid and hydroxyethyl acrylate (wherein 6.00g of acrylic acid, 27.00g of hydroxyethyl acrylate and 20.00g of water), an aqueous solution of hydrogen peroxide (wherein 1.50g of hydrogen peroxide and 20.00g of water), an aqueous solution of mercaptopropionic acid (wherein 0.90g of mercaptopropionic acid and 20.00g of water), an aqueous solution of ascorbic acid (wherein 0.25 g of ascorbic acid and 20.00g of water), controlling the initial reaction temperature to be 30 ℃, the dropwise adding time to be 3.0h, controlling the temperature in the dropwise adding process to be 30-50 ℃, and preserving the temperature at 45-50 ℃ for 0.5h after the dropwise adding is finished, thus obtaining a comparative sample PCE-1.
Comparative example 2:
PCE-1 and monomethyl fumarate are mixed according to a mass ratio of 176:1, compounding to obtain a comparison sample PCE-2.
Comparative example 3:
PCE-1 and
the K350 preservative is 176:1, compounding to obtain a comparison sample PCE-3.
Comparative example 4:
in the market under the name of Pasteur
The slump retaining agent 412 is comparative example 4: PCE-4.
Comparative example 5:
adding 180.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400, 2.77g of dimethyl fumarate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, after the materials are uniformly mixed, dropwise adding an aqueous solution of a mixed solution of acrylic acid and hydroxyethyl acrylate (6.00 g of acrylic acid, 27.00g of hydroxyethyl acrylate and 20.00g of water), an aqueous solution of hydrogen peroxide (1.50 g of hydrogen peroxide and 20.00g of water), an aqueous solution of mercaptopropionic acid (0.90 g of mercaptopropionic acid and 20.00g of water), an aqueous solution of ascorbic acid (0.25 g of ascorbic acid and 20.00g of water), starting the reaction temperature is 30 ℃, the dropwise adding time is 3.0h, the temperature in the dropwise adding process is controlled to be 30-50 ℃, and after the dropwise adding is finished, keeping the temperature at 45-50 ℃ for 0.5h to obtain the anti-corrosive polycarboxylic acid preservative type PCE-5.
And (3) performance detection:
1. testing of concrete Properties
The concrete raw materials and the mixing ratio shown in Table 1 and the additive formula shown in Table 2 are adopted to carry out performance tests on the anti-corrosion type polycarboxylic slump retaining agent prepared in the examples 1 to 5, the polycarboxylic acid slump retaining agent prepared in the comparative examples 1, 2, 3 and 5 and the polycarboxylic acid slump retaining agent prepared in the comparative example 4, the test environment temperature is 30 +/-2 ℃, and the test results are shown in Table 3:
TABLE 1 concrete mix proportion
TABLE 2 additive formulation
| Slump retaining agent | Water reducing agent | Air entraining agent | Defoaming agent | White sugar | Water (I) |
| 70.00 | 75.00 | 0.40 | 0.05 | 6.00 | 365.00 |
Note: the slump retaining agent is diluted to 20% of solid content, the water reducing agent is Kojek TS-8 mother liquor, the solid content is 50%, the air entraining agent is Kojek Y7 air entraining agent, and the defoaming agent is Kojek X1 defoaming agent.
TABLE 3 concrete performances of different slump retaining agents
As shown in Table 3, the comparison result of PCE-1 and KZJ-1 shows that after monomethyl fumarate in KZJ-1 is removed, the initial dispersion effect and the slump retaining ability of 1h, 2h and 3h of the product are not affected basically; the comparison result of the PCE-5 and the KZJ-1 shows that the initial dispersion effect of the product and the initial water reducing rate of the PCE-4 are slightly reduced by 1h, 2h and 3h slump retaining capability of the product after the amount of materials such as monomethyl fumarate in the KZJ-1 is changed into dimethyl fumarate are relatively large, but the slump retaining effect is not as good as that of the product synthesized according to the technical scheme of the patent.
2. Test of Corrosion resistance
The anti-corrosion polycarboxylic acid slump retaining agent prepared in the examples 1 to 5, the polycarboxylic acid slump retaining agent prepared in the comparative examples 1, 2, 3 and 5 and the slump retaining agent prepared in the comparative examples 4 are diluted to be 15% in concentration, 1% of white sugar and 2% of sodium gluconate are added to be compounded to obtain a final slump retaining agent finished product, 300g of each sample is placed in an open glass container with the same volume of 500ml, the sample is heated to 50 ℃ and kept at the constant temperature for 12 hours, then the sample is placed in a constant temperature cabinet with the temperature of 30 ℃ and kept for 15 days (d), 30d, 60d, 90d and 120d, the state of the sample (whether peculiar smell, turbidity or mildew exists) is observed at the corresponding time, so as to compare the anti-corrosion performance of the samples, and the specific test results are shown in table 4.
TABLE 4 Corrosion protection Performance test results
As can be seen from Table 4, PCE-1 had begun to develop off-flavor and long by 30 daysThe mildew phenomenon is caused, the antiseptic effect of the PCE-2 compounded with monomethyl fumarate is slightly better than that of the PCE-1, but peculiar smell and mildew phenomenon are caused at 60 days, and the compound is compounded
The anticorrosion effect of PCE-3 of K350 preservative is equivalent to that of PCE-2, the amount of materials such as monomethyl fumarate and the like in synthesis is changed into dimethyl fumarate PCE-5, PCE-4 begins to generate peculiar smell and mildew phenomenon in 90 days, and the anticorrosion effect of the anticorrosion type polycarboxylic acid slump retaining agent prepared in the embodiments 1 to 5 is obviously better than that of a comparative example in the environment of 50 ℃, so that the prepared anticorrosion type polycarboxylic acid slump retaining agent has a highly stable structure, can resist high temperature higher than 50 ℃ and has more excellent high-temperature anticorrosion performance by introducing the monomethyl fumarate into a product molecular structure in a polymerization mode through specific raw material and proportion matching.
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 (8)
1. An anti-corrosion polycarboxylic slump retaining agent is characterized in that: the corrosion-resistant polycarboxylic acid water reducer with the corrosion-resistant small monomer connected with the main molecular chain is generated by carrying out polymerization reaction on the corrosion-resistant small monomer, the unsaturated macromonomer, the unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride and the slow-release slump-retaining small monomer under the action of an initiator and a molecular weight regulator;
the preservative functional small monomer only contains fumarate or simultaneously contains fumarate and maleate;
the fumarate is at least one of monomethyl fumarate and monoethyl fumarate;
the mass ratio range of the unsaturated macromonomer, the preservative functional small monomer, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and the slow-release slump retaining small monomer is 180: (1-15): (2-10): (10 to 30);
the slow-release slump retaining small monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the unsaturated macromonomer is at least one of methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, allyl polyethylene glycol, 3-methyl-3-butylene-1-polyethylene glycol, 2-methyl allyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
2. The corrosion-resistant polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the dosage of the initiator is 0.5 to 3.0 percent of the total mass of the reactants; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the reactants.
3. The corrosion-resistant polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: in the polymerization reaction process, an initiator aqueous solution, a molecular weight regulator aqueous solution and an unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride aqueous solution are dropwise added within 0.5 to 6 hours, the reaction temperature is 10 to 90 ℃, and the temperature is kept for 0 to 3 hours after the dropwise addition.
4. The corrosion-resistant polycarboxylic acid slump retaining agent as claimed in claim 2, wherein: the initiator comprises a water-soluble redox initiation system or a water-soluble peroxide initiation system reagent;
the molecular weight regulator comprises at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid and sodium hypophosphite.
5. The corrosion-resistant polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the maleic acid ester is at least one of diethyl maleate, dimethyl maleate and dipropyl maleate.
6. The corrosion-resistant polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the molecular weight of the unsaturated macromonomer is 600-6000.
7. The corrosion-resistant polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
8. The preparation method of the corrosion-resistant polycarboxylic acid slump retaining agent as claimed in any one of claims 1 to 7, comprising the following steps:
adding unsaturated macromonomer, small monomer with anticorrosion function and water into a reactor for stirring, after the materials are uniformly mixed, dropwise adding unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, slow-release slump-retaining small monomer, initiator and molecular weight regulator for 0.5-6 h, wherein the reaction temperature is 10-90 ℃; and preserving the temperature for 0 to 3 hours after the dropwise addition is finished to obtain a copolymerization product, namely the anti-corrosion polycarboxylic acid slump retaining agent.
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| CN113698547B (en) * | 2021-08-31 | 2022-06-03 | 科之杰新材料集团有限公司 | High-performance polycarboxylate superplasticizer and preparation method thereof |
| CN114085334B (en) * | 2021-11-17 | 2023-08-25 | 科之杰新材料集团有限公司 | Slump-retaining polycarboxylate water reducer with vinyl ether ester mixed structure and preparation method thereof |
| CN114409854B (en) * | 2021-12-09 | 2024-04-23 | 重庆建研科之杰建材有限公司 | Polycarboxylic acid slump retaining agent and preparation method thereof |
| CN116496023A (en) * | 2023-04-23 | 2023-07-28 | 唐山冀东水泥外加剂有限责任公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN116903799A (en) * | 2023-09-13 | 2023-10-20 | 信丰华轩建材有限公司 | High-temperature slow-release type polycarboxylate superplasticizer and preparation method thereof |
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| CN104261722B (en) * | 2014-10-10 | 2016-06-29 | 科之杰新材料集团有限公司 | A kind of polycarboxylic acid slump retaining agent and preparation method thereof |
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