CN113336902A - Tea saponin modified compound water reducing agent and preparation method and application thereof - Google Patents
Tea saponin modified compound water reducing agent and preparation method and application thereof Download PDFInfo
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- CN113336902A CN113336902A CN202110905307.6A CN202110905307A CN113336902A CN 113336902 A CN113336902 A CN 113336902A CN 202110905307 A CN202110905307 A CN 202110905307A CN 113336902 A CN113336902 A CN 113336902A
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- tea saponin
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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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C04B2103/302—Water reducers
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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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention discloses a tea saponin modified composite water reducing agent and a preparation method thereof, belonging to the technical field of concrete admixtures. According to the invention, the tea saponin structure is introduced into the main chain of the polymer molecule, so that the polymer has high air-entraining and foam-stabilizing properties of the tea saponin molecule, and is compounded with the polycarboxylic acid, so that the water-reducing effect of the polycarboxylic acid is better, and the strength and the fluidity of concrete are improved. The product of the invention has simple preparation method, controllable structure and low cost, and the product performance can be flexibly regulated and controlled according to the actual industrial requirements through the characteristics and the use amount of the tea saponin.
Description
Technical Field
The invention relates to the field of concrete, in particular to a tea saponin modified composite water reducing agent and a preparation method and application thereof.
Background
Cracking caused by various shrinkage of concrete is a worldwide problem of the concrete structural engineering world and is a key and difficult point of control, and severe shrinkage cracking has great negative effects on the safety and the service life of buildings. One of the major trends in the development of concrete is high performance and high strength, which are generally achieved by adding water reducing agents, which have become essential components of concrete, to reduce the water-cement ratio. However, the addition of the water reducing agent can increase the drying shrinkage of concrete, so the development of the high-performance water reducing agent becomes a research and development focus of the concrete admixture. At present, the polycarboxylate superplasticizer is a commonly used water reducer in cement-based materials, has a comb-shaped structure, can introduce some functional monomers and structures based on the designability of the molecular structure of the polycarboxylate superplasticizer, and endows the polycarboxylate superplasticizer with more and new functions, such as slump retaining performance, air entraining performance, shrinkage reducing performance, slow release performance and the like. At present, practical engineering focuses on the working performance and mechanical property of concrete doped with a polycarboxylate superplasticizer, and ignores the long-term and durable performances of concrete. Numerous researches show that the hardening pore structure of the concrete can be improved by introducing a proper amount of tiny, uniform, closed and stable bubbles into the concrete, and the durability of the concrete is greatly improved. The traditional air entraining mode is to add an air entraining agent in the concrete stirring process or adopt a common lignosulfonate water reducing agent with an air entraining function, but the two modes have certain defects in the using effect in actual engineering. The air entraining agent, especially the shared air entraining agent and the saponin air entraining agent are compounded in the additive, so that the incompatibility problem of the air entraining agent and other additive systems is easy to occur, the additive layering phenomenon is caused, and the use efficiency of the additive is influenced. The existing conventional water reducing agent is poor in water reducing effect, so that a large-dosage lignosulfonate water reducing agent is used for meeting the working performance of engineering concrete, excessive slow setting of the concrete is easily caused, and the construction progress and the engineering quality of the concrete are influenced. And by adopting the polyether water reducing agent, part of monomers are low in solubility or insoluble in water, and the oil-soluble functional monomers are difficult to be completely polymerized and are easy to have the problem of floating and layering in the polymerization process, so that the product performance and the concrete performance are influenced.
Patent CN111116844 discloses an air-entraining type polycarboxylic acid water reducing agent and a preparation method thereof, wherein the water reducing agent comprises the following raw materials: 20-40 parts of polyether macromonomer, 5-20 parts of vinyl small monomer, 1-10 parts of tea saponin, 0.1-0.5 part of catalyst, 1-6 parts of initiator and the balance of water. The air-entraining type polycarboxylate superplasticizer provided by the invention is prepared by reacting tea saponin molecules with vinyl small monomers to form an active intermediate containing tea saponin through esterification reaction, and then polymerizing the active intermediate and polycarboxylic acid molecules into an integral polymer through free radical polymerization, so that the product not only can play the high dispersibility of the polycarboxylate superplasticizer, but also can retain the high air-entraining and strong foam stabilizing properties of the tea saponin molecules. However, in the invention, the esterification reaction is carried out through hydroxyl on the tea saponin molecule and carboxyl or ester group of the alkenyl small monomer, and the hydroxyl on the tea saponin molecule has a plurality of sites, and a plurality of alkenyl small monomers are bonded on the tea saponin, so that a cross-linked structure is easily formed when the tea saponin molecule reacts with a polyether monomer, and the tea saponin molecule is easy to agglomerate, the dispersibility of the polycarboxylic acid is weakened, and the air entraining and foam stabilizing performance of the tea saponin molecule is also influenced. The structural formula of the tea saponin is as follows
Disclosure of Invention
Aiming at the problems, the invention provides a tea saponin modified composite concrete water reducer and a preparation method thereof, which mainly utilize only one double bond on tea saponin to carry out direct free radical polymerization with acrylic monomers and alkenyl polyether monomers through active controllable free radical polymerization to form a modified polycarboxylic acid water reducer with a tea saponin structure on a main chain. By introducing the tea saponin into the main chain of the polymer molecule, the product has high air-entraining and foam-stabilizing performances of the tea saponin molecule, thereby better promoting the water-reducing performance of the polycarboxylate superplasticizer. And the main chain structure of the molecule can be accurately regulated and controlled through active free radical polymerization, and the polymer structure can be further regulated and controlled by introducing monomers with different functions and regulating and controlling the content of different monomers, so that a series of water reducing agents with different target properties can be obtained. Meanwhile, the tea saponin modified compound polycarboxylate superplasticizer also avoids the problems of compatibility and layering between the air entraining agent and the water reducing agent.
In order to achieve the purpose, the invention provides a tea saponin modified composite water reducing agent which is mainly characterized in that: the polymer for the water reducer is prepared by living radical polymerization, wherein the raw materials for the polymer comprise a tea saponin monomer, an acrylic acid and derivative monomer thereof, an alkenyl polyether monomer, a chain transfer agent, an initiator and a solvent.
The tea saponin modified composite water reducing agent is characterized in that the active free radical polymerization is a reversible addition-fragmentation chain transfer polymerization (RAFT) method.
The tea saponin modified composite water reducing agent is characterized in that the acrylic acid and derivative monomers thereof are one or more monomers selected from acrylic acid, sodium acrylate, sodium allyl sulfonate and methacrylate monomers.
The tea saponin modified composite water reducing agent is characterized in that the alkenyl polyether monomer is one or more selected from isopentenyl polyoxyethylene ether (TPEG), methyl allyl polyoxyethylene ether (HPEG), ethylene glycol monovinyl polyethylene glycol ether (EPEG) and Allyl Polyoxyethylene Ether (APEG), and the number average molecular weight of the alkenyl polyether monomer is preferably 1000-3000.
The tea saponin modified compound water reducing agent comprises the following preparation raw materials in parts by mass: 5-40 parts of tea saponin, 20-60 parts of acrylic acid and derivative monomers thereof, 500 parts of alkenyl polyether monomers, 1-5 parts of chain transfer agent, 0.1-1 part of initiator and 1000 parts of solvent; preferably, 5-10 parts of tea saponin, 30-40 parts of acrylic acid, 500 parts of alkenyl polyether monomer, 1-5 parts of chain transfer agent, 0.1-1 part of initiator and 1000 parts of solvent.
In order to achieve the purpose, the invention also provides a preparation method of the tea saponin modified compound water reducing agent, which is characterized by comprising the following steps:
dissolving a tea saponin monomer, an alkenyl polyether monomer and an initiator in a solvent, stirring and mixing, vacuumizing, heating in an oil bath to 60-90 ℃, dropwise adding an acrylic acid and derivative monomer at a constant speed, reacting for 1-48 hours under the protection of nitrogen, dropwise adding a chain transfer agent, continuing to react for 0.5-1 hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating to obtain a polymer, cleaning the polymer with the solvent for three times, precipitating again, and drying in vacuum to obtain a target product.
Alternatively, the preparation method comprises the following steps:
dissolving an alkenyl polyether monomer and an initiator in a solvent, stirring and mixing, vacuumizing, heating in an oil bath to 60-90 ℃, dropwise adding acrylic acid and derivative monomers thereof at a constant speed, adding an esterified tea saponin monomer (preferably 3-5 times) in batches, reacting for 1-48 hours under the protection of nitrogen, dropwise adding a chain transfer agent, continuing to react for 0.5-1 hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating a polymer, cleaning the polymer with the solvent for three times, precipitating again, and drying in vacuum to obtain a target product.
The preparation method is characterized in that the solvent is selected from methanol, ethanol, N, N Dimethylformamide (DMF), acetone, toluene, chloroform, dimethyl sulfoxide (DMSO), water or a mixture thereof, and preferably a mixed solvent of water and alcohol, such as water and ethanol.
Preferably, wherein the initiator is selected from azo compounds or organic peroxides, preferably Azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO) or potassium persulfate (K)2S2O8)。
Preferably, wherein the chain transfer agent is selected from the group consisting of dithioesters, isobutyronitrile ester of α -dithionaphthoic acid (CPDN), 2-cyanoisopropyl dithiobenzoate (CPDB), 1-phenethyldithiophenylacetate (PEPTDA), tert-butyl dithiobenzoate (CDB), 2-ethoxycarbonyl-propyl-2-bisthiobenzoate (EPDB), 2- (ethoxyformyl) -2-propyl dithiobenzoate.
In order to realize the purpose, the invention also discloses concrete with the tea saponin modified polycarboxylate water reducer, which mainly comprises cement, sand stone, fly ash, a blending material, the tea saponin modified compound water reducer and water.
Preferably, wherein the blend comprises predominantly graphene oxide, preferably carboxylated graphene oxide. The amount is preferably 0.05-0.5wt.% of the total amount of concrete.
According to the invention, the tea saponin structure is introduced into the main chain of the polymer molecule, so that the product can better introduce the high air-entraining and strong foam-stabilizing properties of the tea saponin molecule into the polycarboxylic acid polymer, and the problems of compatibility and layering between the air-entraining agent and the water reducing agent are avoided, so that the product has a better water reducing effect. The product of the invention has simple preparation method, controllable structure and low cost, and the product performance can be adjusted by flexibly regulating and controlling the characteristics and the use amount of the tea saponin according to the actual industrial requirements, thereby having important economic value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments. The experimental raw materials are all commercial products and are not subjected to secondary processing.
The preparation method of the tea saponin modified compound water reducing agent of the present invention is further described with reference to the following specific examples.
Tea saponin, CAS number, selected in the following examples: 8047-15-2, and density of 1.015-1.020 g/ml.
Isopentenyl polyoxyethylene ether (TPEG, number average molecular weight 2000), methallyl polyoxyethylene ether (HPEG, number average molecular weight 2400), and ethylene glycol monovinyl polyethylene glycol ether (EPEG, number average molecular weight 2000) are all technical grades. The other raw material components are also commercial products and are not subjected to secondary processing. In the experiment, the raw material components are calculated according to the parts by weight.
Example 1
Dissolving 10 parts of tea saponin monomer, 500 parts of methyl allyl polyoxyethylene ether (HPEG) and 3 parts of potassium persulfate in 1000 parts of deionized water/ethanol (mass ratio of 9: 1), stirring at room temperature for 30min to dissolve uniformly, vacuumizing, heating an oil bath to 70 ℃, dripping 40 parts of acrylic acid monomer at a constant speed, reacting for 8 hours under the protection of nitrogen, dripping 1 part of double thioester chain transfer agent, continuing to react for half an hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating a polymer in n-hexane, washing the polymer with methanol for three times, precipitating again, and drying in vacuum to obtain a target product.
Example 2
Dissolving 5 parts of tea saponin monomer, 500 parts of methyl allyl polyoxyethylene ether (HPEG) and 3 parts of potassium persulfate in 1000 parts of deionized water/ethanol (mass ratio of 9: 1), stirring at room temperature for 30min to dissolve uniformly, vacuumizing, heating an oil bath to 70 ℃, dripping 40 parts of acrylic acid monomer at a constant speed, reacting for 8 hours under the protection of nitrogen, dripping 1 part of double thioester chain transfer agent, continuing to react for half an hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating a polymer in n-hexane, washing the polymer with methanol for three times, precipitating again, and drying in vacuum to obtain a target product.
Example 3
Dissolving 20 parts of tea saponin monomer, 500 parts of methyl allyl polyoxyethylene ether (HPEG) and 3 parts of potassium persulfate in 1000 parts of deionized water/ethanol (mass ratio of 9: 1), stirring at room temperature for 30min to dissolve uniformly, vacuumizing, heating an oil bath to 70 ℃, dripping 40 parts of acrylic acid monomer at a constant speed, reacting for 8 hours under the protection of nitrogen, dripping 1 part of double thioester chain transfer agent, continuing to react for half an hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating a polymer in n-hexane, washing the polymer with methanol for three times, precipitating again, and drying in vacuum to obtain a target product.
Example 4
The other conditions were the same as in example 1 except that 4 parts of tea saponin monomer was added at the beginning of the reaction, followed by reaction under nitrogen for 3 hours, 3 parts of it was added, followed by reaction for 3 hours, then 3 parts of it was added, followed by reaction for 2 hours and then chain transfer agent was added.
Example 5
The other conditions were the same as in example 1 except that the tea saponin monomer was not added at the beginning, reacted under nitrogen for 3 hours, 5 parts was added, reacted for 3 hours, then 5 parts was added, and then a chain transfer agent was added after 2 hours of the reaction.
Example 6
The other conditions were the same as in example 1 except that the tea saponin monomer was not added at the beginning, reacted under nitrogen for 2 hours, 4 parts was added, reacted for 2 hours, then 3 parts was added, and then chain transfer agent was added after 2 hours of reaction.
Example 7
The other conditions were the same as in example 5 except that isopentenyl polyoxyethylene ether (TPEG) was used in place of methallyl polyoxyethylene ether (HPEG).
Example 8
The other conditions were the same as in example 1 except that ethylene glycol monovinyl polyethylene glycol ether (EPEG) was used in place of methallyl polyoxyethylene ether (HPEG).
Application examples 1 to 8
The concrete mainly comprises 300kg of cement (PO 42.5), 800kg of sand, 1100kg of stones, 100kg of fly ash, 2kg of admixture (carboxymethyl cellulose) and 3kg of water reducing agent. The water reducing agent was prepared as described in examples 1-8. The admixture is sodium carboxymethyl cellulose.
Application example 9
The main components of the concrete are the same as in application example 1. Except that the blend was carboxylated graphene oxide.
Application example 10
The concrete was mainly composed in the same manner as in application example 4. Except that the blend was carboxylated graphene oxide.
Comparative example 1
The concrete components are the same as those in application example 4, except that the water reducing agent is a polycarboxylic acid water reducing agent polymer disclosed in CN 111116844.
Comparative example 2
Dissolving 500 parts of methyl allyl polyoxyethylene ether (HPEG) and 3 parts of potassium persulfate in 1000 parts of deionized water/ethanol (mass ratio of 9: 1), stirring for 30min at room temperature to uniformly dissolve, vacuumizing, heating an oil bath to 70 ℃, dropping 40 parts of acrylic monomer at a constant speed, reacting for 8 hours under the protection of nitrogen, dropping 1 part of dithioester chain transfer agent, continuing the reaction for half an hour, cooling in an ice bath to terminate the reaction after the reaction is ended, precipitating the polymer in n-hexane, washing the polymer with methanol for three times, precipitating again, and drying in vacuum to obtain the target product.
The concrete of application examples 1-10 and comparative examples 1 and 2 of the invention were subjected to water reducing rate and air content tests (refer to GB8076-2008 "concrete admixture"), compressive strength tests (refer to GB/T50081-2019 "common concrete mechanical property test method") and extension tests (refer to GB50080-2002 "common concrete mixture property test method standard"). The performance results are shown in Table 1.
TABLE 1 Properties of application examples 1-10 and comparative examples 1-2
TABLE 2 concrete expansion (unit: mm) using examples 1-10 and comparative examples 1-2
The above-described embodiments are merely illustrative of the present invention, and not restrictive, and any modifications, equivalents, improvements, etc. that come within the spirit and scope of the invention are intended to be included therein.
Claims (10)
1. A tea saponin modified compound water reducing agent is characterized in that: the polymer for the water reducer is prepared by living radical polymerization, wherein the raw materials for the polymer comprise a tea saponin monomer, an acrylic acid and derivative monomer thereof, an alkenyl polyether monomer, a chain transfer agent, an initiator and a solvent.
2. The tea saponin modified compound water reducer of claim 1, wherein the living radical polymerization is a reversible addition-fragmentation chain transfer polymerization (RAFT) process.
3. The tea saponin modified composite water reducing agent of claim 1, wherein the acrylic acid and its derivative monomer is selected from one or more of acrylic acid, sodium acrylate, sodium allyl sulfonate and methacrylate monomers.
4. The tea saponin modified composite water reducing agent of claim 1, wherein the alkenyl polyether monomer is selected from one or more of isopentenyl polyoxyethylene ether (TPEG), methyl allyl polyoxyethylene ether (HPEG), ethylene glycol monovinyl polyethylene glycol ether (EPEG), and Allyl Polyoxyethylene Ether (APEG).
5. The tea saponin modified compound water reducing agent of claim 1, which comprises the following raw materials in parts by weight: 5-40 parts of tea saponin, 20-60 parts of acrylic acid and derivative monomers thereof, 500 parts of alkenyl polyether monomers, 1-5 parts of chain transfer agent, 0.1-1 part of initiator and 1000 parts of solvent.
6. The preparation method of the tea saponin modified compound water reducing agent as claimed in any one of claims 1 to 5, characterized by comprising the following steps: dissolving a tea saponin monomer, an alkenyl polyether monomer and an initiator in a solvent, stirring and mixing, vacuumizing, heating to 60-90 ℃ in an oil bath, dropwise adding an acrylic acid and derivative monomer at a constant speed, reacting for 1-48 hours under the protection of nitrogen, dropwise adding a chain transfer agent, continuing to react for 0.5-1 hour, cooling in an ice bath to terminate the reaction after the reaction is finished, precipitating a polymer, cleaning the polymer with the solvent for three times, precipitating again, and drying in vacuum to obtain a target product;
alternatively, the preparation method comprises the following steps:
dissolving an alkenyl polyether monomer and an initiator in a solvent, stirring and mixing, vacuumizing and heating in an oil bath to 60-90 ℃, dropwise adding acrylic acid and derivative monomers thereof at a constant speed, adding the tea saponin monomer in batches, reacting for 1-48 hours under the protection of nitrogen, dropwise adding a chain transfer agent, continuing to react for 0.5-1 hour, cooling in an ice bath to terminate the reaction after the reaction is ended, precipitating to obtain a polymer, cleaning the polymer with the solvent for three times, precipitating again, and drying in vacuum to obtain a target product.
7. The method according to claim 6, wherein the solvent is selected from the group consisting of methanol, ethanol, N, N Dimethylformamide (DMF), acetone, toluene, chloroform, Dimethylsulfoxide (DMSO), water and a mixed solvent of water and alcohol; the initiator is selected from azo compounds or organic peroxides; the chain transfer agent is selected from the group consisting of dithioesters, alpha-dithionaphthoic acid isobutyronitrile ester (CPDN), dithiobenzoic acid-2-cyanoisopropyl ester (CPDB), 1-phenethyldithiophenylacetate (PEPTTA), dithiobenzoic acid tert-butyl ester (CDB), dithiobenzoic acid (2-ethoxycarbonyl) propyl-2-Ester (EPDB), dithiobenzoic acid 2- (ethoxyformyl) -2-propyl ester.
8. A concrete mainly comprises cement, sand, stones, fly ash, admixtures and the tea saponin modified compound water reducing agent as claimed in any one of claims 1 to 5.
9. The concrete of claim 8, wherein the admixture is sodium carboxymethylcellulose or graphene oxide.
10. The concrete of claim 8, wherein the admixture is carboxylated graphene oxide.
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| CN114349386A (en) * | 2021-12-28 | 2022-04-15 | 重庆建研科之杰新材料有限公司 | Concrete water reducing agent and preparation method and application thereof |
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