CN114409857B - Graphene oxide monomer, high-workability polycarboxylate superplasticizer and preparation method thereof - Google Patents

Graphene oxide monomer, high-workability polycarboxylate superplasticizer and preparation method thereof Download PDF

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CN114409857B
CN114409857B CN202111618938.6A CN202111618938A CN114409857B CN 114409857 B CN114409857 B CN 114409857B CN 202111618938 A CN202111618938 A CN 202111618938A CN 114409857 B CN114409857 B CN 114409857B
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graphene oxide
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workability
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CN114409857A (en
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李格丽
林志群
邵幼哲
吴传灯
方云辉
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Kezhijie New Material Group Co Ltd
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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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
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  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention relates to the field of concrete additives, and provides a graphene oxide monomer, a high-workability polycarboxylate superplasticizer and a preparation method thereof. The graphene oxide monomer is formed by polymerizing glycolic acid, graphene oxide and vinyl trimethoxy silane, and the glycolic acid is: graphene oxide: the mass ratio of the vinyl trimethoxy silane is 15-25: 3 to 5:36 to 61. The polycarboxylate water reducer is formed by reacting reactants comprising polyether monomer, functional monomer, unsaturated acid and graphene oxide monomer, wherein the polyether monomer is as follows: functional monomer: unsaturated acid: the mass ratio of the graphene oxide monomers is 150-200:1-5:10-30:1-5. The polycarboxylate water reducer prepared by the invention has the advantages that the ester group is introduced in a copolymerization function monomer mode, the carboxyl content is not reduced due to esterification, the preparation process is simple, the water reducing and defoaming effects are excellent, the biotoxicity is low, and the environmental protection performance is good.

Description

Graphene oxide monomer, high-workability polycarboxylate superplasticizer and preparation method thereof
Technical Field
The invention relates to the field of concrete additives, in particular to a graphene oxide monomer, a high-workability polycarboxylate superplasticizer and a preparation method thereof.
Background
The polycarboxylate water reducer has the advantages of low mixing amount, high water reducing rate, good compatibility with various building materials such as cement, environmental friendliness and the like, receives much attention of experts and scholars, and has more application in building industries such as municipal administration, bridges, roads and the like. However, with the continuous development of the engineering and building industry, higher and higher requirements are put forward on the quality and technology of concrete, and further new requirements are put forward on the quality of the polycarboxylate water reducer. However, the polycarboxylate water reducer has some problems in the application process, such as sensitivity to the mud content of sand and stone, improved compatibility to building materials such as cement, poor workability of concrete bleeding, bottom scraping and the like.
The Chinese patent with publication number of CN109369860A published in 2.22.2019 discloses a slow-release controllable polycarboxylate water reducer mother liquor and a preparation method thereof, wherein a large monomer TPEG, a monoester small monomer, a diester small monomer and a functional monomer are adopted as polymerization monomers, and a polycarboxylate water reducer polymer is subjected to partial hydrolysis by regulating the pH value to be strong alkaline, so that the slow release controllability of the polycarboxylate water reducer mother liquor is realized. However, the adopted diester small monomer has fewer functional groups with easy effects, and the adopted monoester small monomer has insufficient activity density, so that the mother solution and the workability of the polycarboxylate water reducer are limited.
Disclosure of Invention
In order to solve the defect of workability of the polycarboxylate water reducer in the prior art, the invention provides a graphene oxide monomer, wherein the graphene oxide monomer is formed by polymerizing glycolic acid, graphene oxide and vinyl trimethoxy silane, and the glycolic acid is as follows: the graphene oxide: the mass ratio of the vinyl trimethoxy silane is 15-25: 3 to 5:36 to 61, wherein the graphene oxide monomer contains a double bond.
In one embodiment, the hydroxyacetic acid is 15-25 parts, the graphene oxide is 3-5 parts, and the vinyltrimethoxysilane is 36-61 parts.
In one embodiment, the glycolic acid: graphene oxide: the mass ratio of the vinyl trimethoxy silane is 15-25: 3 to 5:36.4 to 60.6.
In one embodiment, the hydroxyacetic acid is 15-25 parts, the graphene oxide is 3-5 parts, and the vinyltrimethoxysilane is 36.4-60.6 parts.
The invention also provides a preparation method of the graphene oxide monomer in any technical scheme, which comprises the following specific steps: mixing 15-25 parts of glycolic acid, 3-5 parts of graphene oxide, 400-500 parts of toluene and 0.2-0.3 part of phosphomolybdic acid in a first container, heating, condensing, refluxing, distilling under reduced pressure to remove toluene, cooling to room temperature, washing and filtering with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, and drying at 50-60 ℃ to obtain a first product; mixing 400 parts of deionized water and 400 parts of absolute ethyl alcohol, regulating the pH value of the solution to 4-5, then adding 0.4 part of vinyltrimethoxysilane, pre-hydrolyzing in a water bath at 30-40 ℃ for 30-60 min, adding 0.2 part of the first product, heating to 70-80 ℃, stirring for 3-5 h, cooling to room temperature after the reaction is finished, filtering, washing and drying at 50-60 ℃ to obtain the graphene oxide monomer.
In one embodiment of the preparation method, glacial acetic acid is used to adjust the pH of the solution.
In one embodiment of the preparation method, the filter is washed with 50% by mass aqueous ethanol.
In one example of the preparation process, the reflux temperature of the heating and condensing is 100℃for 4 hours.
In one embodiment of the method, the number of washes is 3 to 5.
In one embodiment of the method of preparation, the room temperature is 25 ℃ to 28 ℃.
In a preferred embodiment of the method of preparation, the room temperature is 25 ℃.
The invention also provides a high-workability polycarboxylate water reducer, which is prepared by free radical polymerization of a polyether monomer, a functional monomer, unsaturated acid and the graphene oxide monomer in any technical scheme, wherein the polyether monomer is as follows: the functional monomer comprises the following components: the unsaturated acid: the mass ratio of the graphene oxide monomers is 150-200:1-5:10-30:1-5;
the structural formula of the functional monomer is as follows:
wherein R is 1 is-H or-CH 3 ，m＝8～12，n＝10～20M and n are positive integers.
In one embodiment, the polyether monomer is one of methallyl polyoxyethylene ether (HPEG), isopentenyl alcohol polyoxyethylene ether (TPEG) or ethylene glycol monovinyl polyethylene glycol ether (EPEG).
In a preferred embodiment, the polyether monomer has a molecular weight of 1200 to 5000.
In one embodiment, the unsaturated acid is methacrylic acid or acrylic acid.
In one embodiment, the polyether monomer is 150-200 parts, the functional monomer is 1-5 parts, the unsaturated acid is 10-30 parts, and the graphene oxide monomer is 1-5 parts.
In one embodiment, the composition further comprises 1-5 parts of initiator, 1-5 parts of reducing agent, 0.5-1 part of chain transfer agent and 300-350 parts of deionized water.
The invention also provides a preparation method of the high-workability polycarboxylate superplasticizer, which is characterized by comprising the following specific steps: dissolving a reducing agent in deionized water to obtain a solution A; dissolving the unsaturated acid and the graphene oxide monomer in deionized water to obtain a solution B; dissolving a chain transfer agent in deionized water to obtain a solution C; mixing the polyether monomer, the functional monomer, the initiator and deionized water at room temperature, uniformly stirring, and then simultaneously dropwise adding A, B and C solution for t time 1 Preserving heat t after the end of dripping 2 And finally, regulating the pH value of the reaction product to n to obtain the high-workability polycarboxylate superplasticizer.
In one embodiment of the method of preparation, the room temperature is 25 ℃ to 28 ℃.
In a preferred embodiment of the method of preparation, the room temperature is 25 ℃.
In one embodiment of the preparation process, t 1 Is 2 to 4 hours, t 2 1 to 2 hours, and n is 4.0 to 6.0.
In a preferred embodiment of the preparation method, 150-200 parts of the polyether monomer, 1-5 parts of the functional monomer, 10-30 parts of the unsaturated acid, 1-5 parts of the graphene oxide monomer, 1-5 parts of the initiator, 1-5 parts of the reducing agent, 0.5-1 part of the chain transfer agent and 300-350 parts of the deionized water.
In a preferred embodiment of the preparation method, the deionized water dissolving the reducing agent is 30-50 parts, the deionized water dissolving the unsaturated acid and the graphene oxide monomer is 10-20 parts, the deionized water dissolving the chain transfer agent is 30-50 parts, and the rest of deionized water is mixed with the polyether monomer, the graphene oxide monomer and the initiator.
In one embodiment of the preparation method, the reducing agent is one of L-ascorbic acid, sodium hypophosphite and sodium formaldehyde sulfoxylate.
In one embodiment of the method, the initiator is one of hydrogen peroxide, sodium persulfate, or ammonium persulfate.
In one embodiment of the method of preparation, the chain transfer agent is one of thioglycolic acid, mercaptopropionic acid, or mercaptoethanol.
In one embodiment of the preparation process, the pH of the reaction product is adjusted using a liquid base.
In one embodiment of the preparation method, the liquid-alkali mass fraction is 30% -32%.
Based on the above, compared with the prior art, the functional monomer used in the invention has the structure containing the ethoxy group and the isobutoxy group which have the defoaming effect and the water reducing effect, so that the synthesized polycarboxylate water reducer has better defoaming performance and water reducing performance and better workability, and is a product of the polyol with two hydroxyl groups activated by ester groups, the reaction activity is higher, more active sites can be provided in the synthesis process of the polycarboxylate water reducer, and the synthesized polycarboxylate water reducer has better dispersion performance and working performance. The isobutoxy group contained in the modified polyurethane foam has smaller surface tension, can increase the rigidity of a liquid film, reduce the stability of bubbles, ensure that more alkoxy structural units of the polycarboxylate water reducer are involved in synthesis, obviously reduce the air content and achieve the defoaming effect.
The graphene oxide monomer used in the invention contains a large number of hydroxyl groups and carboxyl groups in the structure, so that the graphene oxide monomer can provide higher charge density when participating in oxidation reaction and carboxylation reaction, and the synthesized polycarboxylate water reducer has higher steric hindrance effect and higher dispersion capability. In the invention, the environment for synthesizing the polycarboxylate superplasticizer is an acidic environment, the graphene oxide monomer hydrolyzes more carboxyl than the reaction in an alkaline environment, and the workability of the polycarboxylate superplasticizer is improved through anchoring.
The polycarboxylate water reducer prepared by the invention has the advantages that the ester group is introduced in a copolymerization function monomer mode, the carboxyl content is not reduced due to esterification, the preparation process is simple, the water reducing and defoaming effects are excellent, the biotoxicity is low, and the environmental protection performance is good.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The present invention provides the following examples and comparative examples:
example 1
Weighing the following raw material components in parts by weight: HPEG-2400 150 parts, 1 part of functional monomer, 15 parts of acrylic acid, 1 part of graphene oxide monomer, 2 parts of hydrogen peroxide, 1 part of L-ascorbic acid, 0.6 part of thioglycollic acid, 300 parts of water and 20 parts of 30-32% liquid alkali.
The functional monomer R 1 H, m is 9, n is 10.
Dissolving L-ascorbic acid in 35 parts of deionized water to obtain a solution A; dissolving acrylic acid and graphene oxide monomers in 10 parts of deionized water to obtain a solution B; dissolving mercaptoacetic acid in 30 parts of deionized water to obtain a solution C; mixing HPEG-2400, functional monomer, hydrogen peroxide and the rest water, uniformly stirring, dripping A, B and C solution for 2.5h, and preserving heat for 1h after dripping. And after the reaction is finished, regulating the pH value of the reaction product to 4.0-6.0 by using 30-32% liquid alkali by mass concentration to obtain the polycarboxylate water reducer.
The graphene oxide monomer is prepared by the following method: mixing 15 parts of glycolic acid, 5 parts of graphene oxide, 400 parts of toluene and 0.3 part of phosphomolybdic acid, placing the mixture into a first container, heating, condensing and refluxing for 4 hours at 100 ℃, distilling under reduced pressure to remove toluene, cooling, washing and filtering the mixture by using a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution, and drying the mixture at 50 ℃ to obtain a first product; mixing 400 parts of deionized water and 400 parts of absolute ethyl alcohol, regulating the pH value of the solution to 4-5 by glacial acetic acid, then adding 0.4 part of vinyltrimethoxysilane, carrying out prehydrolysis for 30min in a water bath at 30 ℃, adding 0.2 part of the first product, heating to 70 ℃, stirring for 5h, cooling to room temperature after the reaction is finished, filtering, washing 3 times by using a 50% ethanol aqueous solution, and drying at 60 ℃ to obtain the graphene oxide monomer.
Example 2
Weighing the following raw material components in parts by weight: TPEG-2400 200 parts, 3 parts of functional monomer, 20 parts of methacrylic acid, 5 parts of graphene oxide monomer, 3 parts of sodium persulfate, 2 parts of sodium hypophosphite, 0.8 part of mercaptopropionic acid, 320 parts of water and 25 parts of 30-32% liquid alkali with mass concentration.
The functional monomer R 1 Is CH 3 M is 9, n is 12.
Dissolving sodium hypophosphite in 40 parts of deionized water to obtain solution A; dissolving methacrylic acid and graphene oxide monomers in 15 parts of deionized water to obtain a solution B; dissolving mercaptopropionic acid in 40 parts of deionized water to obtain a solution C; mixing TPEG-2400, functional monomer, sodium persulfate and the rest water, uniformly stirring, dripping A, B and C solution for 3h, and preserving heat for 1.5h after dripping. And after the reaction is finished, regulating the pH value of the reaction product to 4.0-6.0 by using 30-32% liquid alkali by mass concentration to obtain the polycarboxylate water reducer.
The double bond-containing modified graphene oxide is prepared by the following method: mixing 25 parts of glycolic acid, 3 parts of graphene oxide, 500 parts of toluene and 0.2 part of phosphomolybdic acid, placing the mixture into a first container, heating, condensing and refluxing for 4 hours at 100 ℃, distilling under reduced pressure to remove the toluene, cooling, washing and filtering the mixture by using a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution, and drying the mixture at 60 ℃ to obtain a first product; mixing 400 parts of deionized water and 400 parts of absolute ethyl alcohol, regulating the pH value of the solution to 4-5 by glacial acetic acid, then adding 0.4 part of vinyltrimethoxysilane, carrying out prehydrolysis for 60min in a water bath at 40 ℃, adding 0.2 part of the first product, heating to 80 ℃, stirring for 3h, cooling to room temperature after the reaction is finished, filtering, washing for 3 times by using a 50% ethanol aqueous solution, and drying at 60 ℃ to obtain the graphene oxide monomer.
Example 3
Weighing the following raw material components in parts by weight: EPEG-3600 170 parts, 5 parts of functional monomer, 30 parts of methacrylic acid, 2 parts of graphene oxide monomer, 2 parts of ammonium persulfate, 3 parts of formaldehyde sodium bisulfate, 1 part of mercaptoethanol, 350 parts of water and 15 parts of 30-32% liquid alkali with mass concentration.
The functional monomer R 1 Is CH 3 M is 12 and n is 18.
Dissolving formaldehyde sodium bisulfate in 30 parts of deionized water to obtain a solution A; dissolving methacrylic acid and graphene oxide monomers in 15 parts of deionized water to obtain a solution B; dissolving mercaptoethanol in 50 parts of deionized water to obtain a solution C; EPEG-3600, functional monomer, ammonium persulfate and the rest water are mixed together and stirred uniformly, meanwhile, A, B and C solution are added dropwise for 3.5h, and the temperature is kept for 2h after the addition is finished. And after the reaction is finished, regulating the pH value of the reaction product to 4.0-6.0 by using 30-32% liquid alkali by mass concentration to obtain the polycarboxylate water reducer.
The graphene oxide monomer is prepared by the following method: mixing 20 parts of glycolic acid, 4 parts of graphene oxide, 450 parts of toluene and 0.25 part of phosphomolybdic acid, placing the mixture into a first container, heating, condensing and refluxing for 4 hours at 100 ℃, distilling under reduced pressure to remove the toluene, cooling, washing and filtering the mixture by using a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution, and drying the mixture at 55 ℃ to obtain a first product; mixing 400 parts of deionized water and 400 parts of absolute ethyl alcohol, regulating the pH value of the solution to 4-5 by glacial acetic acid, then adding 0.4 part of vinyltrimethoxysilane, carrying out prehydrolysis in a water bath at 35 ℃ for 40min, adding 0.2 part of the first product, heating to 75 ℃, stirring for 4h, cooling to room temperature after the reaction is finished, filtering, washing with a 50% ethanol water solution for 3 times, and drying at 55 ℃ to obtain the graphene oxide monomer.
Example 4
Weighing the following raw material components in parts by weight: EPEG-5000 180 parts, 4 parts of functional monomer, 30 parts of acrylic acid, 2 parts of graphene oxide monomer, 5 parts of hydrogen peroxide, 5 parts of formaldehyde sodium bisulfate, 1 part of mercaptoethanol, 350 parts of water and 15 parts of 30-32% liquid alkali with mass concentration.
The functional monomer R 1 H, m is 10, and n is 20.
Dissolving formaldehyde sodium bisulfate in 45 parts of deionized water to obtain a solution A; dissolving methacrylic acid and graphene oxide monomers in 15 parts of deionized water to obtain a solution B; dissolving mercaptoethanol in 30 parts of deionized water to obtain a solution C; mixing EPEG-5000, functional monomer, hydrogen peroxide and the rest water, uniformly stirring, dripping A, B and C solution for 3h, and preserving heat for 2h after dripping. And after the reaction is finished, regulating the pH value of the reaction product to 4.0-6.0 by using 30-32% liquid alkali by mass concentration to obtain the polycarboxylate water reducer.
The graphene oxide monomer is prepared by the following method: mixing 20 parts of glycolic acid, 4 parts of graphene oxide, 450 parts of toluene and 0.25 part of phosphomolybdic acid, placing the mixture into a first container, heating, condensing and refluxing for 4 hours at 100 ℃, distilling under reduced pressure to remove the toluene, cooling, washing and filtering the mixture by using a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution, and drying the mixture at 55 ℃ to obtain a first product; mixing 400 parts of deionized water and 400 parts of absolute ethyl alcohol, regulating the pH value of the solution to 4-5 by glacial acetic acid, then adding 0.4 part of vinyltrimethoxysilane, carrying out prehydrolysis in a water bath at 35 ℃ for 40min, adding 0.2 part of the first product, heating to 75 ℃, stirring for 4h, cooling to room temperature after the reaction is finished, filtering, washing with a 50% ethanol water solution for 3 times, and drying at 55 ℃ to obtain the graphene oxide monomer.
Comparative example 1
Comparative example 1 differs from example 1 in that polyethylene glycol diacrylate was used instead of the functional monomer in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that hydroxyethyl acrylate was used instead of the graphene oxide monomer in example 1.
Comparative example 3
Comparative example 3 is different from example 1 in that 0.5 parts of graphene oxide monomer and 300.5 parts of water are used.
Comparative example 4
Comparative example 4 differs from example 1 in that 6 parts of graphene oxide monomer and 295 parts of water were used.
Comparative example 5
Comparative example 5 differs from example 1 in that 0.5 parts of functional monomer and 300.5 parts of water were used.
Comparative example 6
Comparative example 6 differs from example 1 in that 6 parts of functional monomer and 295 parts of water were used.
The above preparation methods, the brands of the raw materials and other technical indexes adopted in the examples and comparative examples can be selected according to the prior art, and if the technical indexes are specified in the invention, the technical indexes are selected within the specified range of the invention, so that the technical effects of the invention are not affected.
The polycarboxylate water reducers synthesized in the examples and the comparative examples utilize automatic world/surface tensionMeasuring a surface tension value by a force meter; the standard cement is adopted, the mixing amount is 0.20 percent (folded into solid) according to the mass of the cement, and the slump, the slump loss with time and the air content of the concrete are measured according to GB 8076-2008 concrete admixture. The concrete mixing ratio is as follows: 360kg/m of cement 3 790kg/m sand 3 Stone 1060kg/m 3 The results obtained are shown in Table 1.
TABLE 1
In summary, the performance of the examples is superior to that of the comparative examples, and in comparative example 1, the surface tension value of comparative example 1 is greater than that of example 1; the gas content, 0h,1h slump and expansion were smaller than those of example 1, because the polyethylene glycol diacrylate of comparative example 1 did not contain a polyhydroxy structure, and the water-reducing property and defoaming property were lowered; the hydroxyethyl acrylate of comparative example 2, since its hydroxyl group and double bond are smaller than those of the graphene oxide monomer, cannot release as many hydroxyl groups and ester groups as the graphene oxide monomer, and the water reducing property and defoaming property are lowered; the graphene oxide monomer in comparative example 3 is too small, the released ester group and hydroxyl group are insufficient, the graphene oxide monomer in comparative example 4 is too large, the released ester group and hydroxyl group are too large, and the cement viscosity is too large, so that the water reducing performance and the defoaming performance are reduced. Too little functional monomer in comparative example 5, too little ethoxy group and iso-butoxy group for defoaming and water-reducing, resulting in deterioration of water-reducing property, defoaming property and workability, too much functional monomer in comparative example 6, also inhibits release of ethoxy group and iso-butoxy group, resulting in deterioration of water-reducing property and defoaming property.
In summary, compared with the prior art, the functional monomer used in the invention has the structure containing the ethoxy group and the isobutoxy group which have the defoaming effect and the water reducing effect, so that the synthesized polycarboxylate water reducer has better defoaming performance and water reducing performance and better workability, and is a product of the polyol with two hydroxyl groups activated by ester groups, the reaction activity is higher, more active sites can be provided in the synthesis process of the polycarboxylate water reducer, and the synthesized polycarboxylate water reducer has better dispersion performance and working performance. The surface tension of the alkoxy groups contained in the polycarboxylate superplasticizer is smaller, so that the rigidity of a liquid film can be increased, the stability of bubbles is reduced, the air content of the concrete of the synthesized polycarboxylate superplasticizer is obviously reduced, and the defoaming effect is achieved.
The graphene oxide monomer used in the invention contains a large number of hydroxyl groups and carboxyl groups in the structure, so that the graphene oxide monomer can provide higher charge density when participating in oxidation reaction and carboxylation reaction, and the synthesized polycarboxylate water reducer has higher steric hindrance effect and higher dispersion capability. In the invention, the environment for synthesizing the polycarboxylate superplasticizer is an acidic environment, the graphene oxide monomer hydrolyzes more carboxyl than the reaction in an alkaline environment, and the workability of the polycarboxylate superplasticizer is improved through anchoring.
The polycarboxylate water reducer prepared by the invention has the advantages that the ester group is introduced in a copolymerization function monomer mode, the carboxyl content is not reduced due to esterification, the preparation process is simple, the water reducing and defoaming effects are excellent, the biotoxicity is low, and the environmental protection performance is good.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as unsaturated acid, polyether monomer, graphene oxide monomer, functional monomer, etc. are more used herein, the possibility of using other terms is not excluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A graphene oxide monomer, characterized in that: is polymerized from glycolic acid, graphene oxide and vinyltrimethoxysilane, wherein the glycolic acid is prepared by the following steps: the graphene oxide: the mass ratio of the vinyl trimethoxy silane is 15-25: 3 to 5:36 to 61.
2. The graphene oxide monomer of claim 1, wherein: 15-25 parts of glycolic acid, 3-5 parts of graphene oxide and 36-61 parts of vinyl trimethoxy silane.
3. A method for preparing the graphene oxide monomer according to claim 1 or 2, wherein: mixing 15-25 parts of glycolic acid, 3-5 parts of graphene oxide, 400-500 parts of toluene and 0.2-0.3 part of phosphomolybdic acid, heating, condensing, refluxing, distilling under reduced pressure to remove toluene, cooling to room temperature, washing and filtering with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, and drying at 50-60 ℃ to obtain a first product; mixing 400 parts of deionized water and 400 parts of absolute ethyl alcohol, regulating the pH value of the solution to 4-5, then adding 0.4 part of vinyltrimethoxysilane, pre-hydrolyzing in a water bath at 30-40 ℃ for 30-60 min, adding 0.2 part of the first product, heating to 70-80 ℃, stirring for 3-5 h, cooling to room temperature after the reaction is finished, filtering, washing and drying at 50-60 ℃ to obtain the graphene oxide monomer.
4. The utility model provides a high workability polycarboxylate water reducing agent which characterized in that: generated by radical polymerization of a polyether monomer, a functional monomer, an unsaturated acid and the graphene oxide monomer of claim 1 or 2, wherein the polyether monomer: the functional monomer comprises the following components: the unsaturated acid: the mass ratio of the graphene oxide monomers is 150-200:1-5:10-30:1-5;
the structural formula of the functional monomer is as follows:
wherein R is 1 is-H or-CH 3 M=8 to 12, n=10 to 20, and m and n are positive integers.
5. The high workability polycarboxylate superplasticizer as set forth in claim 4, wherein: the polyether monomer is one of methyl allyl polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether or ethylene glycol monovinyl polyethylene glycol ether.
6. The high workability polycarboxylate superplasticizer as set forth in claim 5, characterized in that: the molecular weight of the polyether monomer is 1200-5000.
7. The high workability polycarboxylate superplasticizer as set forth in claim 4, wherein: the unsaturated acid is methacrylic acid or acrylic acid.
8. The high-workability polycarboxylate superplasticizer as set forth in any one of claims 4 to 7, characterized in that: 150-200 parts of polyether monomer, 1-5 parts of functional monomer, 10-30 parts of unsaturated acid and 1-5 parts of graphene oxide monomer.
9. Root of Chinese characterThe method for producing a high-workability polycarboxylate superplasticizer as claimed in any one of claims 4 to 8, characterized in that: dissolving a reducing agent in deionized water to obtain a solution A; dissolving unsaturated acid and the graphene oxide monomer in deionized water to obtain a solution B; dissolving a chain transfer agent in deionized water to obtain a solution C; mixing the polyether monomer, the functional monomer, the initiator and deionized water at room temperature, uniformly stirring, and then simultaneously dropwise adding A, B and C solution for t time 1 Preserving heat t after the end of dripping 2 Finally, regulating the pH value of the reaction product to n to obtain the high-workability polycarboxylate superplasticizer;
t 1 is 2 to 4 hours, t 2 1 to 2 hours, and n is 4.0 to 6.0.
10. The method for preparing the high-workability polycarboxylate superplasticizer as claimed in claim 7, wherein: the reducing agent is one of L-ascorbic acid, sodium hypophosphite and formaldehyde sodium bisulfate, the initiator is one of hydrogen peroxide, sodium persulfate or ammonium persulfate, the chain transfer agent is one of thioglycollic acid, mercaptopropionic acid or mercaptoethanol, pH of a reaction product is adjusted by adopting liquid alkali, and the mass fraction of the liquid alkali is 30% -32%.
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CN105367720A (en) * 2015-11-25 2016-03-02 科之杰新材料集团有限公司 Water-reducing slump-retaining type polycarboxylic acid water reducing agent and preparing method thereof
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