CN111560104B - Star polycarboxylic acid water reducing agent prepared by using tannic acid azo compound as initiator - Google Patents
Star polycarboxylic acid water reducing agent prepared by using tannic acid azo compound as initiator Download PDFInfo
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- CN111560104B CN111560104B CN202010606070.7A CN202010606070A CN111560104B CN 111560104 B CN111560104 B CN 111560104B CN 202010606070 A CN202010606070 A CN 202010606070A CN 111560104 B CN111560104 B CN 111560104B
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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
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates 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
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a star polycarboxylic acid water reducing agent prepared by using a tannic acid azo compound as an initiator, which is a copolymer prepared by polymerizing unsaturated polyether macromonomer and acrylic acid serving as raw materials through free radical copolymerization reaction in the presence of an initiator and a chain transfer agent; the unsaturated polyether macromonomer is selected from one or two of APEG, HPEG or TPEG; the chain transfer agent is at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, mercaptoethylamine, sodium methallyl sulfonate or sodium propylene sulfonate. The star-shaped polycarboxylate superplasticizer designed and synthesized by the invention has many molecular branched chains, low viscosity, small hydrodynamic volume and rich surface functional groups, and tannin molecules have a large amount of hydroxyl groups, so that cement particles are fully dispersed and wetted; meanwhile, the long hydrophobic chains and a large number of hydrophobic aromatic ring cores contained on the star-shaped polycarboxylate superplasticizer arm provide larger steric hindrance for cement particles, so that the cement particles are uniformly dispersed.
Description
Technical Field
The invention belongs to the technical field of building material additives, and particularly relates to a method for preparing a star polycarboxylic acid water reducer by using a tannic acid azo compound as an initiator.
Background
In recent years, building construction techniques have been rapidly developed, and higher standards have been proposed for the performance of concrete as a main building material. High-performance concrete requires not only excellent fluidity of fresh concrete but also good retention of fluidity over time. Therefore, the water reducing agent is one of the essential important components for preparing high-performance, high-fluidity and high-fluidity retention capability over time and green concrete, and the water reducing agent can reduce the water consumption of the concrete in the using process, improve the service durability of the concrete, improve the slump retention property, change the property of the concrete and improve the strength. The polycarboxylic acid high-performance water reducing agent has the advantages of low mixing amount, high water reducing rate, good collapse protection performance, strong molecular structure adjustability and the like, becomes a hot spot in research and development key points and markets of concrete water reducing agents at home and abroad, has wide application prospect, and is widely applied to key projects such as dams, bridges, tunnels, high-speed rails and the like. The polycarboxylic acid high-performance water reducing agent has only decades of development history, is not enough abundant and perfect in molecular structure and product variety, and cannot completely meet the theoretical and application requirements of the current concrete. At present, researchers mainly focus on solving the problems of concrete dispersibility, dispersion retention and the like by preparing a comb-type polycarboxylate superplasticizer through molecular structure design, but the problems of single molecular structure, complex preparation process, high production cost and the like exist. Therefore, the research and development of the polycarboxylate superplasticizer with a novel molecular structure are imperative, and the polycarboxylate superplasticizer has important significance for the development of concrete admixtures and the concrete industry.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a novel star-shaped polycarboxylate superplasticizer which has the advantages of multiple branched chains, low viscosity, small hydrodynamic volume, rich surface functional groups and good adaptability.
The second technical problem to be solved by the invention is to provide a preparation method of the star polycarboxylic acid water reducer, which has the advantages of simple preparation process, easy operation, low cost, no pollution in the preparation process by using the tannin azo compound as the initiator.
The technical scheme of the invention is as follows: a star-shaped polycarboxylic acid water reducing agent prepared by using a tannic acid azo compound as an initiator has a chemical structural general formula shown as the following formula (I):
wherein R is 1 is-H or-CH 3 ；R 2 is-CH 2 -or-CH 2 CH 2 -; y, x and n are all non-0 integers.
The preferable star-shaped polycarboxylic acid water reducing agent has the structure shown in the formula (I), and the molecular weight of the unsaturated polyether macromonomer is 1000-3000; and most preferably 2400.
The preferable star-shaped polycarboxylate superplasticizer of the invention has the structure shown in the formula (I), and R is 1 is-CH 3 And R is 2 is-CH 2 CH 2 -。
The preferred star polycarboxylic acid water reducing agent is a copolymer prepared by polymerizing unsaturated polyether macromonomer and acrylic acid serving as raw materials through free radical copolymerization reaction in the presence of an initiator and a chain transfer agent; the unsaturated polyether macromonomer is selected from any one or two of Allyl Polyoxyethylene Ether (APEG), isobutenol polyoxyethylene ether (HPEG) or isoamylene polyoxyethylene ether (TPEG); the chain transfer agent is selected from at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, mercaptoethylamine, sodium methallylsulfonate or sodium propylene sulfonate. The structure of the initiator tannic acid azo compound is shown as the following formula (II).
The preferable preparation method of the star-shaped polycarboxylic acid water reducing agent comprises the following steps:
1) Taking the unsaturated polyether macromonomer, acrylic acid, an initiator and a chain transfer agent to perform copolymerization reaction with water at 50-80 ℃ for 3-5 hours to obtain a copolymer solution; wherein, the molar percentages of the raw materials in the total reaction system are respectively as follows: 10-35% of unsaturated polyether macromonomer, 60-80% of acrylic acid, 0.5-5% of initiator, 0.1-3% of chain transfer agent and the balance of water;
2) Cooling the copolymer solution obtained in the step 1) to below 40 ℃, and then adjusting the pH value to be within the range of 5.0-7.0 by using an alkaline substance to obtain a reddish brown solution, namely the star polycarboxylic acid water reducer.
In a preferable scheme of the invention, the molecular weight of the Allyl Polyoxyethylene Ether (APEG), the isobutenol polyoxyethylene ether (HPEG) or the isoamylene polyoxyethylene ether (TPEG) is 1000-3000.
In a further preferred embodiment of the present invention, the copolymerization reaction temperature in 1) is 63 to 65 ℃.
Compared with the existing polycarboxylic acid water reducing agent, the polycarboxylic acid water reducing agent has the following advantages: the star-shaped polycarboxylic acid water reducing agent has the advantages of novel structure, reasonable design, more molecular branched chains, low viscosity, small hydrodynamic volume, rich surface functional groups, and a large amount of hydroxyl groups on tannin molecules, and the rich polar groups have stronger hydrophilic action with the polar surfaces of cement particles, so that hydration films can be generated on the surfaces of the cement particles, and the cement particles are fully dispersed and wetted; meanwhile, the long hydrophobic chains and a large number of hydrophobic aromatic nucleus contained on the star polycarboxylic acid water reducing agent arm can provide larger steric hindrance for cement particles, so that the cement particles are uniformly dispersed.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
Example 1
A preparation method of a star-shaped polycarboxylic acid water reducing agent comprises the following steps:
250g of water and 300g of polyether macromonomer APEG are added into a 1000mL four-neck round bottom flask provided with a thermometer, an electric stirrer, a constant temperature electric heating jacket and a peristaltic pump, the molecular weight of the APEG is 2400, the mixture is stirred and heated to 58 ℃, after the mixture is dissolved uniformly, a mixed solution of 12g of tannin azo compound initiator and 20g of water is directly added, and the mixture is stirred for 10 minutes to be fully dissolved. Respectively dropwise adding a mixed aqueous solution consisting of 45g of acrylic acid and 76g of water and a mixed solution consisting of 1.8g of mercaptopropionic acid and 90g of water within 3 hours, and keeping the temperature between 63 and 65 ℃; after the dropwise addition is finished, the reaction is continued for 2 hours, then the temperature is reduced to 30-35 ℃, and 30% of sodium hydroxide solution and dilution water are added to obtain the star polycarboxylic acid water reducing agent with the pH value of 5-7 and the concentration of about 40%, wherein the structural formula of the star polycarboxylic acid water reducing agent is shown as the following formula:
example 2
A preparation method of a star-shaped polycarboxylic acid water reducing agent comprises the following steps:
250g of water and 300g of polyether macromonomer HPEG are added into a 1000mL four-neck round bottom flask provided with a thermometer, an electric stirrer, a constant temperature electric heating jacket and a peristaltic pump, the molecular weight of the used HPEG is 2400, the mixture is stirred and heated to 58 ℃, after uniform dissolution, a mixed solution of 12g of tannin azo compound initiator and 20g of water is directly added, and the mixture is stirred for 10 minutes to be fully dissolved. Respectively dropwise adding a mixed aqueous solution consisting of 45g of acrylic acid and 76g of water and a mixed solution consisting of 1.8g of mercaptopropionic acid and 90g of water within 3 hours, and keeping the temperature between 63 and 65 ℃; after the dropwise addition is finished, the reaction is continued for 2 hours, then the temperature is reduced to 30-35 ℃, and 30% of sodium hydroxide solution and dilution water are added to obtain the star polycarboxylic acid water reducing agent with the pH value of 5-7 and the concentration of about 40%, wherein the structural formula of the star polycarboxylic acid water reducing agent is shown as the following formula:
example 3
A preparation method of a star-shaped polycarboxylic acid water reducing agent comprises the following steps:
250g of water and 300g of polyether macromonomer TPEG are added into a 1000mL four-neck round bottom flask provided with a thermometer, an electric stirrer, a constant temperature electric heating jacket and a peristaltic pump, the molecular weight of the used TPEG is 2400, the temperature is raised to 58 ℃ by stirring, after uniform dissolution, a mixed solution of 12g of tannin azo compound initiator and 20g of water is directly added, and the mixture is stirred for 10 minutes to be fully dissolved. Respectively dropwise adding a mixed aqueous solution consisting of 45g of acrylic acid and 76g of water and a mixed solution consisting of 1.8g of mercaptopropionic acid and 90g of water within 3 hours, and keeping the temperature between 63 and 65 ℃; after the dropwise addition is finished, the reaction is continued for 2 hours, then the temperature is reduced to 30-35 ℃, and 30% of sodium hydroxide solution and dilution water are added to obtain the star polycarboxylic acid water reducing agent with the pH value of 5-7 and the concentration of about 40%, wherein the structural formula of the star polycarboxylic acid water reducing agent is shown as the following formula:
example 4
A preparation method of a star-shaped polycarboxylic acid water reducing agent comprises the following steps:
250g of water and 300g of polyether macromonomer TPEG are added into a 1000mL four-neck round bottom flask provided with a thermometer, an electric stirrer, a constant temperature electric heating jacket and a peristaltic pump, the molecular weight of the used TPEG is 2400, the temperature is raised to 58 ℃ by stirring, after uniform dissolution, a mixed solution of 12g of tannin azo compound initiator and 20g of water is directly added, and the mixture is stirred for 10 minutes to be fully dissolved. Respectively dropwise adding a mixed aqueous solution consisting of 45g of acrylic acid and 76g of water and a mixed solution consisting of 2.8g of sodium hypophosphite and 90g of water within 3 hours, and keeping the temperature between 63 and 65 ℃; after the dropwise addition is finished, the reaction is continued for 2 hours, then the temperature is reduced to 30-35 ℃, and 30% of sodium hydroxide solution and dilution water are added to obtain the star polycarboxylic acid water reducing agent with the pH value of 5-7 and the concentration of about 40%, wherein the structural formula of the star polycarboxylic acid water reducing agent is shown as the following formula:
comparative example
The preparation method of the conventional polycarboxylic acid water reducing agent comprises the following steps:
250g of water and 300g of polyether macromonomer HPEG are added into a 1000mL four-neck round-bottom flask provided with a thermometer, an electric stirrer, an electric heating jacket and a peristaltic pump, the molecular weight of the used HPEG is 2400, and after the HPEG is uniformly stirred and dissolved, 3.9g of hydrogen peroxide solution is directly added and stirred for 10 minutes to be fully dissolved. Respectively dropwise adding a mixed aqueous solution consisting of 45g of acrylic acid and 60g of water and a mixed solution consisting of 1.6g of ascorbic acid, 2.0g of mercaptopropionic acid and 60g of water within 3 hours and 3.5 hours, and dropwise adding at normal temperature; after the dropwise addition is finished, continuing the reaction for 1 hour, and adding 30% sodium hydroxide solution and dilution water to obtain the conventional polycarboxylate superplasticizer with pH of 6-7 and concentration of about 40%, wherein the structural formula is shown as the following formula:
application examples
The star polycarboxylic acid water reducing agent is used for measuring the net slurry flow according to GB/T8000-2000 'test method for homogeneity of concrete admixture', and the cement is reference cement. The test results are shown in Table 1.
TABLE 1 Cement paste fluidity test results
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modifications, equivalent variations and modifications made on the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention without departing from the technical solution of the present invention.
Claims (8)
1. A star-shaped polycarboxylic acid water reducing agent prepared by using a tannic acid azo compound as an initiator is characterized in that: the chemical structural general formula is shown as the following formula (I):
wherein R is 1 is-H or-CH 3 ；R 2 is-CH 2 -or-CH 2 CH 2 -; y, x and n are all non-0 integers.
2. A star polycarboxylic acid water reducing agent prepared by using tannic acid azo compound as initiator according to claim 1, characterized in that: the structure is shown in the formula (I), wherein the molecular weight of the unsaturated polyether macromonomer is 1000-3000.
3. The star polycarboxylic acid water reducing agent prepared using a tannic acid azo compound as an initiator according to claim 1, wherein: the structure is shown in the formula (I), wherein the molecular weight of the unsaturated polyether macromonomer is 2400.
4. The star polycarboxylic acid water reducing agent prepared using a tannic acid azo compound as an initiator according to claim 1, wherein: the structure is shown in the formula (I), and R is 1 is-CH 3 And R is 2 is-CH 2 CH 2 -。
5. The star polycarboxylic acid water reducing agent prepared using a tannic acid azo compound as an initiator according to claim 1, wherein: the star polycarboxylic acid water reducing agent is a copolymer which is polymerized by taking unsaturated polyether macromonomer and acrylic acid as raw materials through free radical copolymerization reaction in the presence of an initiator and a chain transfer agent; the unsaturated polyether macromonomer is selected from any one or two of Allyl Polyoxyethylene Ether (APEG), isobutenol polyoxyethylene ether (HPEG) or isoamylene polyoxyethylene ether (TPEG); the chain transfer agent is selected from at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, mercaptoethylamine, sodium methallylsulfonate or sodium propylene sulfonate; the structure of the initiator tannic acid azo compound is shown as the following formula (II):
6. a preparation method of a star polycarboxylic acid water reducing agent prepared by using a tannic acid azo compound as an initiator is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking unsaturated polyether macromonomer, acrylic acid, an initiator, a chain transfer agent and water to carry out copolymerization reaction for 3-5 hours at 50-80 ℃ to obtain a copolymer solution; wherein, the molar percentages of the raw materials in the total reaction system are respectively as follows: 10-35% of unsaturated polyether macromonomer, 60-80% of acrylic acid, 0.5-5% of initiator, 0.1-3% of chain transfer agent and the balance of water;
(2) And (2) cooling the copolymer solution obtained in the step (1) to below 40 ℃, and then adjusting the pH value to be within the range of 5.0-7.0 by using an alkaline substance to obtain a reddish brown solution, namely the star polycarboxylic acid water reducer.
7. The method for producing a star polycarboxylic acid water reducing agent produced using a tannic acid azo compound as an initiator according to claim 6, wherein: the unsaturated polyether macromonomer is selected from any one or two of Allyl Polyoxyethylene Ether (APEG), isobutenol polyoxyethylene ether (HPEG) or isoamylene polyoxyethylene ether (TPEG); the molecular weight of the Allyl Polyoxyethylene Ether (APEG), the isobutenol polyoxyethylene ether (HPEG) or the isoamylene polyoxyethylene ether (TPEG) is 1000-3000.
8. The method for producing a star polycarboxylic acid water reducing agent produced using a tannic acid azo compound as an initiator according to claim 6, comprising: the copolymerization reaction temperature in the step (1) is 63-65 ℃.
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| CN106519143A (en) * | 2016-12-19 | 2017-03-22 | 贵州石博士科技有限公司 | Preparation method of star-shaped polycarboxylate water reducer |
| CN106750076A (en) * | 2017-01-24 | 2017-05-31 | 福州大学 | A kind of preparation method and applications of cement water reducing agent |
| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
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| KR100950719B1 (en) * | 2005-09-27 | 2010-03-31 | 니폰 쇼쿠바이 컴파니 리미티드 | Novel polymer and cement admixture using the same |
| US8097687B2 (en) * | 2009-02-09 | 2012-01-17 | Nalco Company | Multifunctional azo initiators for free radical polymerizations: uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106519143A (en) * | 2016-12-19 | 2017-03-22 | 贵州石博士科技有限公司 | Preparation method of star-shaped polycarboxylate water reducer |
| CN106750076A (en) * | 2017-01-24 | 2017-05-31 | 福州大学 | A kind of preparation method and applications of cement water reducing agent |
| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
Non-Patent Citations (2)
| Title |
|---|
| No AccessSynthesis of star-comb PCE superplasticiser towards an understanding of its properties in cement pastes;Shentong Li 等;《Advances in Cement Research》;20190123;第31卷(第2期);第58-68页 * |
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