CN112851889A - Preparation method of graphene oxide modified TPEG type polycarboxylate superplasticizer - Google Patents
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- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B24/16—Sulfur-containing compounds
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- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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Abstract
本发明涉及混凝土化学外加剂技术，旨在提供一种氧化石墨烯改性TPEG型聚羧酸减水剂的制备方法。包括：以水溶剂体系内的四种单体原料，通过硫酸盐和氧化还原双引发体系进行自由基共聚反应制备获得减水剂；在反应过程中使用的原料组分包括：不饱和大单体TPEG、功能单体氧化石墨烯、功能单体对苯乙烯磺酸钠、小单体的丙烯酸、溶剂蒸馏水；以及引发剂过硫酸盐、氧化还原引发体系中的氧化剂和还原剂、中和剂。本发明使聚羧酸大分子通过共价键接枝到氧化石墨烯片层间，提高了氧化石墨烯的分散能力。可避免氧化石墨烯被还原成石墨烯，避免丙烯酸单体均聚。具有活化能低、引发速率快、诱导期短等特点，可在较低温环境下合成氧化石墨‑羧酸减水剂。
The invention relates to concrete chemical admixture technology, and aims to provide a preparation method of a graphene oxide modified TPEG type polycarboxylate water reducer. Including: four monomer raw materials in a water solvent system are used to prepare a water reducing agent through radical copolymerization reaction of sulfate and redox dual initiation system; the raw material components used in the reaction process include: unsaturated macromonomer TPEG, functional monomer graphene oxide, functional monomer sodium p-styrene sulfonate, small monomer acrylic acid, solvent distilled water; and initiator persulfate, oxidant, reducing agent and neutralizer in redox initiation system. In the present invention, the polycarboxylic acid macromolecules are grafted to the graphene oxide sheets through covalent bonds, and the dispersing ability of the graphene oxide is improved. It can avoid the reduction of graphene oxide into graphene and the homopolymerization of acrylic monomers. It has the characteristics of low activation energy, fast initiation rate and short induction period.
Description
Technical Field
The invention relates to a preparation method and application of a high-efficiency water reducing agent, in particular to a method for preparing a graphene oxide modified polycarboxylic acid high-performance water reducing agent at a lower temperature, and belongs to the technical field of concrete chemical admixtures.
Background
The development of infrastructure construction not only promotes the increase of the demand of high-performance concrete, but also puts higher requirements on the performance of the high-efficiency water reducing agent. Compared with other water reducing agents, the polycarboxylic acid high-performance water reducing agent has the advantages of low mixing amount, high water reducing rate, low slump loss, low shrinkage, low pollution in the production process and the like, and becomes one of the most active water reducing agents studied at home and abroad.
In some important concrete projects, in particular to projects such as high-speed railways, nuclear power hydropower, bridges and tunnels, the polycarboxylic acid water reducing agent is already applied in a large scale. In terms of the prior art, the polycarboxylic acid high-performance water reducing agent is the only high-performance water reducing agent capable of preparing C100 concrete. The main reason is that the molecular structure parameters of the polycarboxylate water reducer can be designed, and the modifiability of the chain structure and a large amount of polymerizable monomers are the basis of various types, multiple purposes and high performance of the polycarboxylate water reducer.
The polycarboxylic acid high-performance water reducing agent is a typical high molecular surfactant, and the molecule of the polycarboxylic acid high-performance water reducing agent often contains active groups such as carboxyl, hydroxyl, sulfonic group, ester group, polyoxyalkylene chain link and the like so as to provide anchoring, solubilization, electrostatic repulsion and steric hindrance repulsion, so that the polycarboxylic acid high-performance water reducing agent has strong adsorption and dispersion effects. The common polycarboxylic acid water reducing agent has less group amount and short side chain, and is difficult to greatly improve the water reducing rate, and the mechanical property of concrete cannot be obviously improved by doping the common water reducing agent, so that the modification of the common polycarboxylic acid water reducing agent is one of important means for improving the performance of the concrete.
Researches find that the graphene oxide nanophase sheet layer can regulate and control cement hydration reaction and form regular flower-shaped and polyhedral crystal structures, and has the effect of remarkably improving the strength and toughness of a cement matrix, but the graphene oxide is difficult to uniformly disperse and remarkably reduces the fluidity in alkaline cement slurry, and is serious. The problem that the dispersibility of the graphene oxide is not uniform enough can be improved to a certain extent by using an ultrasonic treatment method, but the long-chain molecular structure of the water reducing agent can be damaged by the ultrasonic process, and particularly when the main chain contains quaternary carbon atoms, the performance of the water reducing agent is seriously influenced.
Therefore, how to uniformly disperse the graphene oxide in the cement paste and simultaneously exert the original performance of the polycarboxylate superplasticizer so as to improve the mechanical property and durability of the cement-based material has important significance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a graphene oxide modified TPEG type polycarboxylic acid water reducing agent.
In order to solve the technical problems, the invention adopts the following solution:
the preparation method of the graphene oxide modified TPEG type polycarboxylate water reducer is provided, and the water reducer is prepared by carrying out free radical copolymerization on four monomer raw materials in a water solvent system through a double-initiation system; the double initiation system refers to a persulfate initiation system and a redox initiation system; the raw material components used in the reaction process and the mass ratio are as follows:
75.00-135.00 parts of TPEG serving as an unsaturated macromonomer;
30.00-75.00 parts of graphene oxide serving as a first functional monomer;
7.16-12.89 parts of sodium p-styrene sulfonate serving as a second functional monomer;
6.76-12.16 parts of acrylic acid serving as a small monomer;
75.00-120.00 parts of distilled water as a solvent in the reaction process;
and 1.125-2.025 parts of persulfate serving as an initiator; 3.75-6.75 parts of oxidant and 1.125-2.025 parts of reducer in the redox initiation system; 2.50-4.00 parts of a neutralizing agent.
In the invention, the graphene oxide is in a solution state, and the concentration is 7.6 g/L; the purity of the sodium p-styrene sulfonate is 90 percent.
In the invention, the persulfate initiator is ammonium persulfate; the oxidant in the redox initiation system is hydrogen peroxide solution with the mass percent concentration of 30 percent; the reducing agent is ascorbic acid; the neutralizer is sodium hydroxide.
The invention specifically comprises the following steps:
(1) weighing the raw material components according to the mass ratio;
(2) preparing a solution: dissolving a reducing agent in water to obtain solution A; mixing half of the small monomer with water to prepare a solution B; dissolving persulfate initiator in water to obtain solution C; dissolving a neutralizing agent in water to prepare solution D;
(3) adding unsaturated macromonomer, first functional monomer and distilled water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating, stirring to completely dissolve and uniformly mix;
(4) adding a second functional monomer, half of the small monomer and an oxidant into the four-neck flask, and continuously heating and stirring for 1 h;
(5) dripping the solution A into a four-neck flask for 0.5h while dripping the solution B for 0.4 h; after the dropwise addition is finished, continuously dropwise adding the liquid C for 0.5h, and after the dropwise addition is finished, continuously heating and stirring for 10 h;
(6) stopping heating, cooling, dropwise adding the solution D, and uniformly mixing to obtain the graphene oxide modified TPEG type polycarboxylate superplasticizer solution.
In the invention, in the step (3), the heating condition is 45 ℃, and the stirring speed is 300 r/min.
In the present invention, in the step (4), the stirring speed is 500 r/min.
Compared with the prior art, the invention has the technical effects that:
1. according to the invention, a free radical copolymerization method is adopted, so that polycarboxylic acid macromolecules are grafted between graphene oxide lamella layers through covalent bonds, and the dispersion capacity of graphene oxide is improved. The prepared graphite oxide-carboxylic acid water reducing agent has high water reducing rate and good dispersibility under low doping amount, can exert the potential of graphene oxide for enhancing the mechanical property of the cement-based material, and improves the strength of the cement matrix.
2. The invention adopts two measures to improve the degree of polymerization reaction: (1) when the redox initiator is added, the oxidant is added into the system firstly, so that the graphene oxide can be prevented from being reduced into graphene; (2) the acrylic monomer has high activity, and can avoid homopolymerization by adopting a sectional dripping mode.
3. Compared with high-temperature polymerization reaction, the single azo initiator and peroxy initiator cannot meet the polymerization reaction requirement of the system. The invention adopts a persulfate initiator and redox initiator dual-initiation system, and has the characteristics of low activation energy, high initiation rate, short induction period and the like, so that the graphite oxide-carboxylic acid water reducing agent can be synthesized in a lower temperature environment, the energy can be saved, and the production cost can be reduced.
Drawings
FIG. 1 is the FT-IR spectrum of the product of each example.
FIG. 2 is a graph comparing the compressive strength of the products of comparative example and example.
FIG. 3 is a graph comparing the flexural strength of the products of comparative example and example.
Detailed Description
The present invention will be further described with reference to the following examples.
Reagents used in the examples: TPEG is white lamellar and has a molecular weight of 2400.00. The graphene oxide is in a solution state, and the concentration is 7.60 g/L. The sodium p-styrene sulfonate is light yellow powder with the purity of 90 percent. Acrylic acid is colorless liquid with pungent odor and is analytically pure. Ascorbic acid was in the form of white granules and was analytically pure. The mass percentage concentration of the hydrogen peroxide solution is 30 percent. Ammonium persulfate as white particles, analytically pure. Sodium hydroxide was a white lamellar solid, analytically pure.
The parts mentioned in the following examples are all parts by mass.
Example 1
A low-temperature synthesis method for preparing a graphite oxide-carboxylic acid high-performance water reducing agent comprises the following steps:
step one, preparing a solution: dissolving 1.125 parts of ascorbic acid in 10.125 parts of water to obtain 11.25 parts of solution A; mixing 3.38 parts of acrylic acid and 7.89 parts of water to prepare 11.27 parts of liquid B; dissolving 1.125 parts of ammonium persulfate in 10.125 parts of water to obtain 11.25 parts of solution C; 2.50 parts of sodium hydroxide was dissolved in 3.75 parts of water to prepare 6.25 parts of solution D.
Secondly, weighing 75.00 parts of TPEG, 75.00 parts of graphene oxide solution and 75.00 parts of distilled water by mass, adding the TPEG, the graphene oxide solution and the distilled water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, heating the mixture in a water bath to 45 ℃, and stirring the mixture at a speed of 300r/min until the mixture is completely dissolved and uniformly mixed;
thirdly, adding 7.16 parts of sodium p-styrene sulfonate, 3.38 parts of acrylic acid and 3.75 parts of hydrogen peroxide solution into a four-neck flask, and continuously heating and stirring for 1h at the stirring speed of 500 r/min;
fourthly, dropwise adding the solution A into the four-neck flask at a constant speed and slowly for 0.5h while dropwise adding the solution B for 0.4 h; after the dropwise addition is finished, continuously dropwise adding the solution C for 0.5h, continuously stirring and keeping the temperature for 10 h;
and fifthly, stopping heating, cooling, dropwise adding the solution D, and uniformly mixing to obtain the graphene oxide modified polycarboxylate superplasticizer solution.
Example 2
A low-temperature synthesis method for preparing a graphite oxide-carboxylic acid high-performance water reducing agent comprises the following steps:
step one, preparing a solution: dissolving 1.35 parts of ascorbic acid in 12.15 parts of water to obtain 13.50 parts of solution A; mixing 4.05 parts of acrylic acid and 9.45 parts of water to prepare 13.50 parts of liquid B; dissolving 1.35 parts of ammonium persulfate in 12.15 parts of water to obtain 13.50 parts of liquid C; 3.00 parts of sodium hydroxide was dissolved in 4.50 parts of water to prepare 7.50 parts of solution D.
Secondly, weighing 90.00 parts of TPEG, 60.00 parts of graphene oxide solution and 90.00 parts of distilled water by mass, adding the TPEG, the 60.00 parts of graphene oxide solution and the 90.00 parts of distilled water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating the mixture in a water bath to 45 ℃, and stirring the mixture at a speed of 300r/min until the mixture is completely dissolved and uniformly mixed;
thirdly, adding 8.59 parts of sodium p-styrene sulfonate, 4.05 parts of acrylic acid and 4.50 parts of hydrogen peroxide solution into a four-neck flask, and continuously heating and stirring for 1h at the stirring speed of 500 r/min;
fourthly, dropwise adding the solution A into the four-neck flask at a constant speed and slowly for 0.5h while dropwise adding the solution B for 0.4 h; after the dropwise addition is finished, continuously dropwise adding the solution C for 0.5h, continuously stirring and keeping the temperature for 10 h;
and fifthly, stopping heating, cooling, dropwise adding the solution D, and uniformly mixing to obtain the graphene oxide modified polycarboxylate superplasticizer solution.
Example 3
A low-temperature synthesis method for preparing a graphite oxide-carboxylic acid high-performance water reducing agent comprises the following steps:
step one, preparing a solution: dissolving 1.80 parts of ascorbic acid in 16.20 parts of water to obtain 18.00 parts of solution A; mixing 5.40 parts of acrylic acid and 12.60 parts of water to prepare 18.00 parts of liquid B; dissolving 1.80 parts of ammonium persulfate in 16.20 parts of water to obtain 18.00 parts of solution C; 3.50 parts of sodium hydroxide was dissolved in 5.25 parts of water to prepare 8.75 parts of solution D.
Secondly, weighing 120.00 parts of TPEG, 40.00 parts of graphene oxide solution and 110.00 parts of distilled water by mass, adding the TPEG, the graphene oxide solution and the 110.00 parts of distilled water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating the mixture in a water bath to 45 ℃, and stirring the mixture at a speed of 300r/min until the mixture is completely dissolved and uniformly mixed;
thirdly, adding 11.46 parts of sodium p-styrene sulfonate, 5.40 parts of acrylic acid and 6.00 parts of hydrogen peroxide solution into a four-neck flask, and continuously heating and stirring for 1 hour at the stirring speed of 500 r/min;
fourthly, dropwise adding the solution A into the four-neck flask at a constant speed and slowly for 0.5h while dropwise adding the solution B for 0.4 h; after the dropwise addition is finished, continuously dropwise adding the solution C for 0.5h, continuously stirring and keeping the temperature for 10 h;
and fifthly, stopping heating, cooling, dropwise adding the solution D, and uniformly mixing to obtain the graphene oxide modified polycarboxylate superplasticizer solution.
Example 4
A low-temperature synthesis method for preparing a graphite oxide-carboxylic acid high-performance water reducing agent comprises the following steps:
step one, preparing a solution: dissolving 2.025 parts of ascorbic acid in 18.225 parts of water to obtain 20.25 parts of solution A; mixing 6.08 parts of acrylic acid and 14.19 parts of water to prepare 20.27 parts of liquid B; dissolving 2.025 parts of ammonium persulfate in 18.225 parts of water to obtain 20.25 parts of solution C; 4.00 parts of sodium hydroxide was dissolved in 6.00 parts of water to prepare 10.00 parts of solution D.
Secondly, weighing 135.00 parts of TPEG, 30.00 parts of graphene oxide solution and 120.00 parts of distilled water by mass, adding the TPEG, the graphene oxide solution and the 120.00 parts of distilled water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating the mixture in a water bath to 45 ℃, and stirring the mixture at a speed of 300r/min until the mixture is completely dissolved and uniformly mixed;
thirdly, adding 12.89 parts of sodium p-styrene sulfonate, 6.08 parts of acrylic acid and 6.75 parts of hydrogen peroxide solution into a four-neck flask, and continuously heating and stirring for 1h at the stirring speed of 500 r/min;
fourthly, dropwise adding the solution A into the four-neck flask at a constant speed and slowly for 0.5h while dropwise adding the solution B for 0.4 h; after the dropwise addition is finished, continuously dropwise adding the solution C for 0.5h, continuously stirring and keeping the temperature for 10 h;
and fifthly, stopping heating, cooling, dropwise adding the solution D, and uniformly mixing to obtain the graphene oxide modified polycarboxylate superplasticizer solution.
And (3) product testing:
through the structural test of the product in the above embodiment, the FT-IR spectra of the graphene oxide-polycarboxylic acid water reducing agent are respectively shown in fig. 1. In the figure, 1, 2, 3 and 4 are maps of the graphene oxide modified polycarboxylate superplasticizer obtained in example 1, example 2, example 3 and example 4, respectively.
The product using method comprises the following steps:
the graphene oxide modified polycarboxylate superplasticizer prepared by the method is in a liquid state. When cement mortar is prepared, the water reducing agent is firstly mixed with water, ultrasonic treatment is carried out for 30min, and then the mixed solution, cement and standard sand are mixed and cured. The amounts of cement, standard sand and water are carried out with reference to the specifications of the cement mortar preparation standard, and the addition amount of the water reducing agent is carried out at 0.1% by mass of the cement (in terms of mass of solids).
And (3) product performance testing:
the performance test was performed on the graphite oxide-carboxylic acid water reducing agent synthesized in 4 examples. The compression and bending strength test is carried out according to the standard GB/T176-1999 method for testing the strength of cement mortar (ISO method). The flexural strength and the compressive strength of the cement mortar at the hydration ages of 3d, 7d and 28d are respectively tested. The mortar is prepared by mixing and solidifying 450 g of cement, 1350 g of standard sand, 202.5 g of water and 0.1% of water reducing agent (calculated by solid mass).
In the comparative example, 0.1% (by mass of solids) of a commercially available polycarboxylic acid water reducer type M18 was added.
The test results of the comparative and each example are shown in fig. 2 and 3:
as can be seen from the figures 2 and 3, the high efficiency water reducing agent of the invention can obviously improve the compression strength and the rupture strength of cement mortar.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention in any way.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113717329A (en) * | 2021-10-09 | 2021-11-30 | 湖南先锋建材有限公司 | Mud-blocking concrete water reducing agent and preparation method thereof |
| CN114591471A (en) * | 2022-03-09 | 2022-06-07 | 陕西友邦新材料科技有限公司 | A kind of polycarboxylate water reducer based on double redox system and preparation method thereof |
| CN116283038A (en) * | 2023-03-28 | 2023-06-23 | 上海珊凝建筑工程有限公司 | Solid concrete water reducer and manufacturing method thereof |
| CN116477872A (en) * | 2023-04-27 | 2023-07-25 | 上海珊凝建筑工程有限公司 | Concrete water reducer and preparation method thereof |
| CN118146467A (en) * | 2023-12-04 | 2024-06-07 | 湖北省路桥集团华晟通建设工程有限公司 | Concrete admixture with anti-seepage and anti-cracking functions and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717329A (en) * | 2021-10-09 | 2021-11-30 | 湖南先锋建材有限公司 | Mud-blocking concrete water reducing agent and preparation method thereof |
| CN114591471A (en) * | 2022-03-09 | 2022-06-07 | 陕西友邦新材料科技有限公司 | A kind of polycarboxylate water reducer based on double redox system and preparation method thereof |
| CN116283038A (en) * | 2023-03-28 | 2023-06-23 | 上海珊凝建筑工程有限公司 | Solid concrete water reducer and manufacturing method thereof |
| CN116477872A (en) * | 2023-04-27 | 2023-07-25 | 上海珊凝建筑工程有限公司 | Concrete water reducer and preparation method thereof |
| CN118146467A (en) * | 2023-12-04 | 2024-06-07 | 湖北省路桥集团华晟通建设工程有限公司 | Concrete admixture with anti-seepage and anti-cracking functions and preparation method thereof |
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Application publication date: 20210528 |