CN115947907B - Graphene water reducer and preparation method and application thereof - Google Patents
Graphene water reducer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene water reducer and a preparation method and application thereof. The graphene water reducer comprises the following raw materials: isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate, graphene oxide, 3-mercaptopropionic acid, ascorbic acid, an initiator and water. The invention also provides a preparation method of the composite. Compared with the prior art, the graphene water reducer prepared by the invention has the water reducing performance, slump retaining, early strength and slow release performance, effectively disperses graphene oxide, has excellent adaptability to cement and concrete, improves the appearance of cement, stores the growth of cement-made products, ensures that the internal structure of cement mortar is compact, further improves the compression resistance and bending resistance of the cement mortar, and enables the star-shaped graphene water reducer prepared by the invention to be dissociated from a hydrolysis center so as to maintain good paste fluidity.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a graphene water reducer, a preparation method and application thereof.
Background
The water reducing agent is one of the additives for improving concrete mixing fluidity, plays a vital role in the development of concrete, and has high requirements in concrete application so as to improve the fluidity, durability, mechanical property and the like of the concrete. The polycarboxylate water reducer is a third-generation high-performance water reducer, has strong molecular structure designability, and has the functions of slump loss protection, early strength, mud resistance and the like besides the tax reduction performance so as to meet the requirements of different construction environments and sand quality.
CN111410451a discloses a raw material formulation of a graphene polycarboxylate water reducer and a preparation and use method of the water reducer, wherein in the raw material formulation of the water reducer, the weight ratio relation of the raw material components is as follows: 30-160 parts of graphene oxide dispersion liquid, 80-100 parts of propenyl polyoxyethylene ether, 5-15 parts of sodium p-styrenesulfonate, 2.5-7.5 parts of ascorbic acid, 7-9 parts of acrylic acid, 25-35 parts of sodium hydroxide solution, 8.7-27.8 parts of potassium persulfate and/or 1.1-3.5 parts of hydrogen peroxide serving as an oxidation initiator. The invention is used as an oxidant and a chain transfer agent to modify the space structure of the polycarboxylic acid water reducer in the synthesis process of the polycarboxylic acid water reducer, increases the side chain length of the polycarboxylic acid water reducer, enhances the steric hindrance effect and improves the carboxyl number. Not only can increase the water reducing rate and reduce the water for cement stirring, but also can reduce the adaptability of the water reducing agent and cement. The invention can improve the water reduction rate to more than 33%, can greatly reduce the water consumption and strengthen the mechanical property of cement-based materials. However, in the prior art, the compatibility of the graphene oxide and the polycarboxylate superplasticizer is poor, and the dispersibility of the graphene oxide is poor, so that the performance of cement and concrete is greatly improved.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a graphene water reducer, which is characterized in that: the preparation method comprises the following steps: isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate, graphene oxide, 3-mercaptopropionic acid, ascorbic acid and an initiator;
further, the graphene water reducer is prepared from the following raw materials in parts by weight: 60-80 parts of isopentenyl alcohol polyoxyethylene ether, 3-6 parts of isovaleryltetraacrylate, 1-5 parts of 2-acrylamide-1-methylpropanesulfonic acid, 1-3 parts of unsaturated phosphate, 8-12 parts of graphene oxide, 0.1-0.5 part of 3-mercaptopropionic acid, 0.5-1.5 parts of ascorbic acid and 2-3 parts of initiator.
The unsaturated phosphate is one or a mixture of 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, 9-octadecen-1-ol phosphate, dimethyl vinyl phosphate, allyl diethyl phosphate and triallyl phosphate.
The initiator is one or a mixture of more of potassium persulfate, ammonium persulfate, benzoyl peroxide and tert-butyl hydroperoxide.
The graphene oxide is introduced into cement to promote the growth of cement hydration products, and meanwhile, the internal structure of the cement mortar is compact, so that the compressive strength and durability of the cement mortar are improved. However, in the prior art, the compatibility of the graphene oxide and the polycarboxylate superplasticizer is poor, and the dispersibility of the graphene oxide is poor, so that the performance of cement and concrete is greatly improved.
Further preferably, the graphene water reducer is prepared from the following raw materials in parts by weight: 60-80 parts of isopentenyl alcohol polyoxyethylene ether, 3-6 parts of isovaleryltetraacrylate, 1-5 parts of 2-acrylamide-1-methylpropanesulfonic acid, 1-3 parts of unsaturated phosphate, 8-12 parts of modified graphene, 0.1-0.5 part of 3-mercaptopropionic acid, 0.5-1.5 parts of ascorbic acid and 2-3 parts of initiator.
The preparation method of the modified graphene comprises the following steps:
(1) Adding 5-10 parts by weight of graphene oxide and 3-8 parts by weight of double bond-containing silane coupling agent into 50-100 parts by weight of water, uniformly mixing, heating to 70-90 ℃ for reaction for 1-3 hours, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain double bond-containing graphene oxide; adding 4-6 parts by weight of graphene containing double bonds, 1-3 parts by weight of fumaric acid and 1-3 parts by weight of amide containing unsaturated groups into 50-100 parts by weight of water, uniformly mixing, heating to 50-70 ℃ for reacting for 5-20min, then adding 0.05-0.2 part by weight of initiator and 0.1-0.5 part by weight of surfactant, adding 0.1-0.5 part by weight of polyvinyl alcohol, keeping the temperature of 50-70 ℃ for reacting for 1-5h, and adopting 0.5-1mol/L sodium hydroxide aqueous solution to adjust pH to be neutral to obtain a graphene-containing mixed material; adding 0.1-0.5 part by weight of mercapto silane coupling agent into 50-80 parts by weight of ethyl acetate, uniformly mixing, adding 30-50 parts by weight of tetraethoxysilane, and uniformly stirring to obtain mercapto compound; uniformly mixing the graphene-containing mixed material and the sulfhydryl-containing mixed material, regulating the pH to 8-9 by adopting 20-25wt% ammonia water, stirring for 30-120min at 1000-5000r/min, standing for 4-6h, centrifuging to obtain precipitate, washing and drying after the reaction is finished, so as to obtain sulfhydryl-containing pretreated graphene;
(2) Adding 5-6 parts by weight of the sulfhydryl-containing pretreated graphene and 8-10 parts by weight of 2, 2-diallyl bisphenol A into 100-200 parts by weight of ethyl acetate, uniformly mixing, then adding 0.1-0.5 part by weight of benzoin dimethyl ether, uniformly mixing, reacting for 20-40min at room temperature under 365nm ultraviolet light, washing and drying after the reaction is finished, and obtaining the modified graphene.
The double bond-containing silane coupling agent in the step (1) is one or more of vinyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and vinyl tri (2-methoxyethoxy) silane.
The sulfhydryl-containing silane coupling agent in the step (1) is mercaptopropyl triethoxysilane.
The amide containing unsaturated groups in the step (1) is one or a mixture of more of N, N-methylene bisacrylamide, N-vinyl caprolactam, N-vinyl formamide, 2-methyl acrylamide and N- (3-dimethylaminopropyl) methyl acrylamide.
The initiator in the step (1) is one or a mixture of more of potassium persulfate, ammonium persulfate, benzoyl peroxide and tert-butyl hydroperoxide.
The surfactant in the step (1) is one or a mixture of more of sodium Alcohol Ether Sulfate (AES), secondary alkyl sodium sulfonate (SAS) and fatty acid methyl ester ethoxylate sodium sulfonate (FMES).
The graphene water reducer prepared by the method comprises isopentenyl alcohol polyoxyethylene ether, isovaleryl tetra-acrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate and modified graphene raw materials, wherein the prepared graphene water reducer is a star-shaped macromolecular substance, contains phosphate groups, sulfonic acid groups, phenyl groups and amide groups, and meanwhile, the core of the modified graphene is a polymer containing graphene, and a large amount of hydrophilic groups contained in the graphene-containing polymer are easy to absorb water and swell and break shells to release interaction between the graphene-containing polymer and the graphene water reducer, so that the water reducer has excellent adaptability to cement and concrete, improves the appearance of cement, stores the growth of water-containing hydration products, enables the internal structure of the cement mortar to be compact, and further improves the compression resistance and bending resistance of the cement mortar.
The invention introduces the isopentyl tetraacrylate as the reaction monomer, so that the prepared graphene water reducer has larger steric hindrance, and has better dispersion performance in cement slurry. The introduced carboxyl has electrostatic repulsive force with negative electricity, maintains stable steric hindrance effect, plays a role in dispersion, and greatly improves concrete slump; the introduction of the sulfonic group improves the initial adsorption capacity of graphene water reducer molecules on the surface of cement particles, so that the fluidity retention of the graphene water reducer molecules is improved, and the graphene water reducer has good water reducing performance; the introduction of the amide group has good promotion effect on the development of concrete, and shows excellent drought strength performance; the phosphate band has negative charge and has stronger complexing ability to calcium ions, so that in a cement system, the phosphate group can be adsorbed on the surface of cement particles faster, more preferentially and more, and the polyether long side chain in the water reducing agent provides steric hindrance, so that the dispersibility is enhanced; the modified graphene contains 2 phenyl groups, and the introduction of the phenyl groups can further reduce the drying shrinkage of concrete, so that the prepared graphene water reducer has higher water reducing rate, has the function of reducing the drying shrinkage of hardened concrete, and also has obvious slump retaining performance.
Based on the above, the inventors modified graphene, and modified graphene oxide with a double bond-containing silane coupling agent to prepare double bond-containing graphene oxide. Preparing a core-shell modified graphene by reacting a mixed material prepared by double bond-containing graphene oxide, fumaric acid, unsaturated group-containing amide and polyvinyl alcohol under the action of an initiator and a surfactant with a sulfhydryl-containing mixed material, wherein a graphene-containing polymer is used as a core, and sulfhydryl-containing silicon dioxide is used as a shell; the preparation method comprises the steps of (1) carrying out a thiol-containing pretreatment graphene and 2, 2-diallyl bisphenol A under the action of benzoin dimethyl ether, and carrying out a alkene-thiol clicking chemical reaction under the irradiation of ultraviolet light, so that the graphene is improved to contain double bonds, and simultaneously, phenyl is introduced; preparing a graphene water reducer by reacting modified graphene with isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid and unsaturated phosphate; the modified graphene has the advantages that the core is a graphene-containing polymer, contains a large amount of hydrophilic groups, is easy to absorb water and swell, releases the graphene-containing polymer, improves the dispersion performance of graphene, and further improves the problem of poor adaptability of graphene in cement and concrete due to interaction between the released graphene-containing polymer and a water reducer.
The invention also discloses a preparation method of the graphene water reducer.
The preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isotetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate and graphene oxide raw materials according to parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate, graphene oxide, 3-mercaptopropionic acid and ascorbic acid into water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding an initiator into water, and uniformly mixing to obtain an initiator solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the initiator solution, heating to 80-90 ℃ for reaction for 1-5h, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 10-20wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
The invention also provides application of the graphene water reducer as a cement and concrete dispersing agent. The graphene water reducer prepared by the invention has the doping amount of 0.05-0.3% of the total cementing material, wherein the doping amount is pure solid doping amount, and the percentage is weight percentage.
The invention has the beneficial effects that:
the graphene water reducer prepared by the method comprises isopentenyl alcohol polyoxyethylene ether, isovaleryl tetra-acrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate and modified graphene raw materials, wherein the prepared graphene water reducer is a star-shaped macromolecular substance, contains phosphate groups, sulfonic acid groups, phenyl groups and amide groups, and meanwhile, the core of the modified graphene is a polymer containing graphene, and a large amount of hydrophilic groups contained in the graphene-containing polymer are easy to absorb water and swell and break shells to release interaction between the graphene-containing polymer and the graphene water reducer, so that the water reducer has excellent adaptability to cement and concrete, improves the appearance of cement, stores the growth of water-containing hydration products, enables the internal structure of the cement mortar to be compact, and further improves the compression resistance and bending resistance of the cement mortar.
Detailed Description
Parameters of specific chemicals were used in the examples, sources:
the isopentenol polyoxyethylene ether is of the type of TPEG-2400 and is purchased from the sea-Ann petrochemical plant in Jiangsu province.
The graphene oxide has an average thickness of 1-3nm, a diameter of 4-7 μm, a layer number of 2-5 layers and a specific surface area of 20-50m 2 And/g, purchased from intelligent titanium purification technology power suppliers.
Polyvinyl alcohol, mw=27000, purchased from Shanghai microphone biochemistry technologies limited.
Comparative example 1
The graphene water reducer is prepared from the following raw materials in parts by weight: 65 parts by weight of isopentenyl alcohol polyoxyethylene ether, 3.5 parts by weight of 2-acrylamide-1-methylpropanesulfonic acid, 2 parts by weight of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 10 parts by weight of graphene oxide, 0.4 part by weight of 3-mercaptopropionic acid, 0.9 part by weight of ascorbic acid and 2.5 parts by weight of tert-butyl hydroperoxide.
The preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, graphene oxide, 3-mercaptopropionic acid, ascorbic acid, tert-butyl hydroperoxide and water raw materials in parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into 30 parts by weight of water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, graphene oxide, 3-mercaptopropionic acid and ascorbic acid into 50 parts by weight of water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding the tert-butyl hydroperoxide into 20 parts by weight of water, and uniformly mixing to obtain a tert-butyl hydroperoxide solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the tert-butyl hydroperoxide solution, heating to 85 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 15wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
Example 1
The graphene water reducer is prepared from the following raw materials in parts by weight: 65 parts by weight of isopentenyl alcohol polyoxyethylene ether, 5 parts by weight of isovaleryltetra tetraacrylate, 3.5 parts by weight of 2-acrylamide-1-methylpropanesulfonic acid, 2 parts by weight of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 10 parts by weight of graphene oxide, 0.4 part by weight of 3-mercaptopropionic acid, 0.9 part by weight of ascorbic acid and 2.5 parts by weight of tert-butyl hydroperoxide.
The preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, graphene oxide, 3-mercaptopropionic acid, ascorbic acid, tert-butyl hydroperoxide and water raw materials in parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into 30 parts by weight of water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, graphene oxide, 3-mercaptopropionic acid and ascorbic acid into 50 parts by weight of water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding the tert-butyl hydroperoxide into 20 parts by weight of water, and uniformly mixing to obtain a tert-butyl hydroperoxide solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the tert-butyl hydroperoxide solution, heating to 85 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 15wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
Example 2
The graphene water reducer is prepared from the following raw materials in parts by weight: 65 parts by weight of isopentenyl alcohol polyoxyethylene ether, 5 parts by weight of isovaleryltetra tetraacrylate, 3.5 parts by weight of 2-acrylamide-1-methylpropanesulfonic acid, 2 parts by weight of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 10 parts by weight of modified graphene, 0.4 part by weight of 3-mercaptopropionic acid, 0.9 part by weight of ascorbic acid and 2.5 parts by weight of tert-butyl hydroperoxide.
The preparation method of the modified graphene comprises the following steps:
(1) Adding 10 parts by weight of graphene oxide and 8 parts by weight of gamma-methacryloxypropyl trimethoxy silane into 100 parts by weight of water, uniformly mixing, heating to 80 ℃ for reaction for 3 hours, centrifuging after the reaction is finished, taking precipitate, washing, and drying to obtain graphene oxide containing double bonds; adding 5 parts by weight of graphene oxide containing double bonds, 2 parts by weight of fumaric acid and 3 parts by weight of N- (3-dimethylaminopropyl) methacrylamide into 80 parts by weight of water, uniformly mixing, heating to 55 ℃ for reaction for 10min, then adding 0.1 part by weight of benzoyl peroxide and 0.5 part by weight of sodium fatty acid methyl ester ethoxylate sulfonate (FMES), adding 0.5 part by weight of polyvinyl alcohol, keeping the temperature of 55 ℃ for reaction for 2h, and adopting a 1mol/L sodium hydroxide aqueous solution to adjust the pH value to be neutral to obtain a graphene-containing mixed material; adding 0.5 weight part of mercaptopropyl triethoxysilane into 50 weight parts of ethyl acetate, uniformly mixing, adding 50 weight parts of tetraethoxysilane, and uniformly stirring to obtain a mercapto-containing mixed material; uniformly mixing the graphene-containing mixed material and the sulfhydryl-containing mixed material, regulating the pH to 8.5 by adopting 25wt% ammonia water, stirring for 60min at 5000r/min, standing for 4h, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain sulfhydryl-containing pretreated graphene;
(2) Adding 5 parts by weight of the mercapto pretreatment graphene and 10 parts by weight of 2, 2-diallyl bisphenol A into 200 parts by weight of ethyl acetate, uniformly mixing, then adding 0.3 part by weight of benzoin dimethyl ether, uniformly mixing, reacting for 30min at room temperature under 365nm ultraviolet light, and washing and drying after the reaction is finished to obtain the modified graphene.
The preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid, ascorbic acid, tert-butyl hydroperoxide and water raw materials in parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into 30 parts by weight of water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid and ascorbic acid into 50 parts by weight of water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding the tert-butyl hydroperoxide into 20 parts by weight of water, and uniformly mixing to obtain a tert-butyl hydroperoxide solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the tert-butyl hydroperoxide solution, heating to 85 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 15wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
Example 3
The graphene water reducer is prepared from the following raw materials in parts by weight: 65 parts by weight of isopentenyl alcohol polyoxyethylene ether, 5 parts by weight of isovaleryltetra tetraacrylate, 3.5 parts by weight of 2-acrylamide-1-methylpropanesulfonic acid, 2 parts by weight of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 10 parts by weight of modified graphene, 0.4 part by weight of 3-mercaptopropionic acid, 0.9 part by weight of ascorbic acid and 2.5 parts by weight of tert-butyl hydroperoxide.
The preparation method of the modified graphene comprises the following steps: adding 10 parts by weight of graphene oxide and 8 parts by weight of gamma-methacryloxypropyl trimethoxy silane into 100 parts by weight of water, uniformly mixing, heating to 80 ℃ for reaction for 3 hours, centrifuging after the reaction is finished, taking precipitate, washing, and drying to obtain the modified graphene.
The preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid, ascorbic acid, tert-butyl hydroperoxide and water raw materials in parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into 30 parts by weight of water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid and ascorbic acid into 50 parts by weight of water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding the tert-butyl hydroperoxide into 20 parts by weight of water, and uniformly mixing to obtain a tert-butyl hydroperoxide solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the tert-butyl hydroperoxide solution, heating to 85 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 15wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
Example 4
The graphene water reducer is prepared from the following raw materials in parts by weight: 65 parts by weight of isopentenyl alcohol polyoxyethylene ether, 5 parts by weight of isovaleryltetra tetraacrylate, 3.5 parts by weight of 2-acrylamide-1-methylpropanesulfonic acid, 2 parts by weight of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 10 parts by weight of modified graphene, 0.4 part by weight of 3-mercaptopropionic acid, 0.9 part by weight of ascorbic acid and 2.5 parts by weight of tert-butyl hydroperoxide.
The preparation method of the modified graphene comprises the following steps: adding 10 parts by weight of graphene oxide and 8 parts by weight of gamma-methacryloxypropyl trimethoxy silane into 100 parts by weight of water, uniformly mixing, heating to 80 ℃ for reaction for 3 hours, centrifuging after the reaction is finished, taking precipitate, washing, and drying to obtain graphene oxide containing double bonds; adding 5 parts by weight of graphene oxide containing double bonds, 2 parts by weight of fumaric acid and 3 parts by weight of N- (3-dimethylaminopropyl) methacrylamide into 80 parts by weight of water, uniformly mixing, heating to 55 ℃ for reaction for 10min, then adding 0.1 part by weight of benzoyl peroxide and 0.5 part by weight of sodium fatty acid methyl ester ethoxylate sulfonate (FMES), adding 0.5 part by weight of polyvinyl alcohol, keeping the temperature of 55 ℃ for reaction for 2h, and adopting a 1mol/L sodium hydroxide aqueous solution to adjust the pH value to be neutral to obtain a graphene-containing mixed material; adding 0.5 weight part of mercaptopropyl triethoxysilane into 50 weight parts of ethyl acetate, uniformly mixing, adding 50 weight parts of tetraethoxysilane, and uniformly stirring to obtain a mercapto-containing mixed material; uniformly mixing a graphene-containing mixed material and a sulfhydryl-containing mixed material, regulating the pH to 8.5 by adopting 25wt% ammonia water, stirring for 60min at 5000r/min, standing for 4h, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain modified graphene;
the preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid, ascorbic acid, tert-butyl hydroperoxide and water raw materials in parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into 30 parts by weight of water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid and ascorbic acid into 50 parts by weight of water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding the tert-butyl hydroperoxide into 20 parts by weight of water, and uniformly mixing to obtain a tert-butyl hydroperoxide solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the tert-butyl hydroperoxide solution, heating to 85 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 15wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
Example 5
The graphene water reducer is prepared from the following raw materials in parts by weight: 65 parts by weight of isopentenyl alcohol polyoxyethylene ether, 5 parts by weight of isovaleryltetra tetraacrylate, 3.5 parts by weight of 2-acrylamide-1-methylpropanesulfonic acid, 2 parts by weight of 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate, 10 parts by weight of modified graphene, 0.4 part by weight of 3-mercaptopropionic acid, 0.9 part by weight of ascorbic acid and 2.5 parts by weight of tert-butyl hydroperoxide.
The preparation method of the modified graphene comprises the following steps: (1) Adding 5 parts by weight of graphene oxide, 2 parts by weight of fumaric acid and 3 parts by weight of N- (3-dimethylaminopropyl) methacrylamide into 80 parts by weight of water, uniformly mixing, heating to 55 ℃ for reaction for 10min, then adding 0.1 part by weight of benzoyl peroxide and 0.5 part by weight of fatty acid methyl ester ethoxylate sodium sulfonate (FMES), adding 0.5 part by weight of polyvinyl alcohol, keeping the temperature of 55 ℃ for reaction for 2h, and adopting a 1mol/L sodium hydroxide aqueous solution to adjust the pH value to be neutral to obtain a graphene-containing mixed material; adding 0.5 weight part of mercaptopropyl triethoxysilane into 50 weight parts of ethyl acetate, uniformly mixing, adding 50 weight parts of tetraethoxysilane, and uniformly stirring to obtain a mercapto-containing mixed material; uniformly mixing the graphene-containing mixed material and the sulfhydryl-containing mixed material, regulating the pH to 8.5 by adopting 25wt% ammonia water, stirring for 60min at 5000r/min, standing for 4h, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain sulfhydryl-containing pretreated graphene;
(2) Adding 5 parts by weight of the mercapto pretreatment graphene and 10 parts by weight of 2, 2-diallyl bisphenol A into 200 parts by weight of ethyl acetate, uniformly mixing, then adding 0.3 part by weight of benzoin dimethyl ether, uniformly mixing, reacting for 30min at room temperature under 365nm ultraviolet light, and washing and drying after the reaction is finished to obtain the modified graphene.
The preparation method of the graphene water reducer comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid, ascorbic acid, tert-butyl hydroperoxide and water raw materials in parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into 30 parts by weight of water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, modified graphene, 3-mercaptopropionic acid and ascorbic acid into 50 parts by weight of water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding the tert-butyl hydroperoxide into 20 parts by weight of water, and uniformly mixing to obtain a tert-butyl hydroperoxide solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the tert-butyl hydroperoxide solution, heating to 85 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 15wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
Test example 1
The graphene water reducer prepared in the examples and the comparative examples is detected by referring to GB/T8076-2008 concrete admixture, wherein the mixing amount of the graphene water reducer is 1.5wt% of concrete;
the concrete comprises the following raw materials in proportion: 285kg/m cement (Hua Xin 42.5.5 ordinary silicon cement) 3 Fly ash (class I fly ash) 75kg/m 3 800kg/m of sand (sand with fineness modulus of 2.6) 3 1065kg/m of crushed stone (stone with particle size of 5-20 continuous graded crushed stone) 3 175kg/m of water 3 。
Table 1 concrete test results of graphene water reducer
As can be seen from Table 1, the graphene water reducer prepared by the invention can effectively improve the compressive strength of concrete, can effectively control the slump loss of concrete, prevents concrete from bleeding, is not easy to isolate, settle and delaminate, and has excellent compression resistance and bleeding performance.
The invention introduces the isopentyl tetraacrylate as the reaction monomer, so that the prepared graphene water reducer has larger steric hindrance, and has better dispersion performance in cement slurry. The introduced carboxyl has electrostatic repulsive force with negative electricity, maintains stable steric hindrance effect, plays a role in dispersion, and greatly improves the slump of concrete; the introduction of the sulfonic group improves the initial adsorption capacity of graphene water reducer molecules on the surface of cement particles, so that the fluidity retention of the graphene water reducer molecules is improved, and the graphene water reducer has good water reducing performance; the introduction of the amide group has good promotion effect on the development of concrete, and shows excellent drought strength performance; the phosphate band has negative charge and has stronger complexing ability to calcium ions, so that in a cement system, the phosphate group can be adsorbed on the surface of cement particles faster, more preferentially and more, and the polyether long side chain in the water reducing agent provides steric hindrance, so that the dispersibility is enhanced; the modified graphene contains 2 phenyl groups, and the introduction of the phenyl groups can further reduce the drying shrinkage of concrete, so that the prepared graphene water reducer has higher water reducing rate, has the function of reducing the drying shrinkage of hardened concrete, and also has obvious slump retaining performance.
Test example 2
The fluidity performance test of cement paste is carried out by referring to GB/T8077-2012 "concrete admixture homogeneity test method", wherein the mixing amount of the graphene water reducer (folding and fixing mixing amount is 0.18 wt%) and the water cement ratio (W/C) is 0.30, and the cement is Huaxin 42.5 ordinary silicon cement.
Table 2 cement test results of graphene water reducer
As shown in Table 2, the graphene water reducer prepared by the invention has good water reducing and slump retaining properties.
Graphene is introduced into the graphene water reducer prepared in the comparative example 1, and the graphene oxide cement can promote the growth of cement hydration products, so that the internal structure of the cement mortar is compact, and the compressive strength and durability of the cement mortar are improved. However, in the prior art, the compatibility of the graphene oxide and the polycarboxylate superplasticizer is poor, and the dispersibility of the graphene oxide is poor, so that the performance of cement and concrete is greatly improved.
On the basis of comparative example 1, the graphene oxide in comparative example 1 is modified by adopting a double bond-containing silane coupling agent to prepare double bond-containing graphene oxide. Preparing a core-shell modified graphene by reacting a mixed material prepared by double bond-containing graphene oxide, fumaric acid, unsaturated group-containing amide and polyvinyl alcohol under the action of an initiator and a surfactant with a sulfhydryl-containing mixed material, wherein a graphene-containing polymer is used as a core, and sulfhydryl-containing silicon dioxide is used as a shell; the preparation method comprises the steps of (1) carrying out a thiol-containing pretreatment graphene and 2, 2-diallyl bisphenol A under the action of benzoin dimethyl ether, and carrying out a alkene-thiol clicking chemical reaction under the irradiation of ultraviolet light, so that the graphene is improved to contain double bonds, and simultaneously, phenyl is introduced; preparing a graphene water reducer by reacting modified graphene with isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid and unsaturated phosphate; the modified graphene has the advantages that the core is a graphene-containing polymer, contains a large amount of hydrophilic groups, is easy to absorb water and swell, releases the graphene-containing polymer, improves the dispersion performance of graphene, and further improves the problem of poor adaptability of graphene in cement and concrete due to interaction between the released graphene-containing polymer and a water reducer.
In summary, the graphene water reducer prepared by the method comprises isopentenyl alcohol polyoxyethylene ether, isovaleryltetraester tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate and modified graphene raw materials, the prepared graphene water reducer is a star-shaped macromolecular substance, and simultaneously contains phosphate groups, sulfonic acid groups, phenyl groups and amide groups, meanwhile, the core of the modified graphene is a polymer containing graphene, a large amount of hydrophilic groups contained in the graphene-containing polymer are easy to absorb water and swell, and break shells to release interaction between the graphene-containing polymer and the graphene water reducer, so that the water reducer has excellent adaptability to cement and concrete, slump retention, early strength and slow release performance, effectively disperses graphene oxide, improves the appearance of cement, stores the growth of a water-soluble product of the cement, enables the internal structure of the cement mortar to be compact, further improves the compression resistance and bending strength of the cement mortar, and enables the star-shaped graphene water reducer prepared by the method to be separated from a hydrolysis center so as to keep good slurry fluidity.
The preparation method is simple, has low raw material cost, and has good performances of water reduction, slump loss protection, early strength, slow release and the like.
Claims (7)
1. The utility model provides a graphene water reducer which characterized in that: the preparation method comprises the following raw materials: isopentenyl alcohol polyoxyethylene ether, isovaleryltetra tetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate, modified graphene, 3-mercaptopropionic acid, ascorbic acid and an initiator;
the preparation method of the modified graphene comprises the following steps: uniformly mixing double bond-containing graphene oxide, fumaric acid, unsaturated group-containing amide, water and polyvinyl alcohol, heating for reaction under the action of an initiator and a surfactant, and finally obtaining mercapto-containing pretreated graphene under the action of a mercapto-containing silane coupling agent and tetraethoxysilane; finally preparing modified graphene by thiol-pretreated graphene and 2, 2-diallyl bisphenol A under ultraviolet irradiation.
2. The graphene water reducer of claim 1, wherein: the unsaturated phosphate is one or a mixture of 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, 9-octadecen-1-ol phosphate, dimethyl vinyl phosphate, allyl diethyl phosphate and triallyl phosphate.
3. The graphene water reducer of claim 1, wherein: the initiator is one or a mixture of more of potassium persulfate, ammonium persulfate, benzoyl peroxide and tert-butyl hydroperoxide.
4. The graphene water reducer of claim 1, wherein: the sulfhydryl-containing silane coupling agent is mercaptopropyl triethoxysilane;
the amide containing unsaturated groups is one or a mixture of more of N, N-methylene bisacrylamide, N-vinyl caprolactam, N-vinyl formamide, 2-methacrylamide and N- (3-dimethylaminopropyl) methacrylamide.
5. The graphene water reducer of claim 1, wherein: the surfactant is one or a mixture of more of sodium alcohol ether sulfate, secondary alkyl sodium sulfonate and fatty acid methyl ester ethoxylate sodium sulfonate.
6. A method for preparing the graphene water reducer according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
step 1, weighing isopentenyl alcohol polyoxyethylene ether, isotetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate and modified graphene raw materials according to parts by weight;
step 2, adding the isopentenyl alcohol polyoxyethylene ether into water, and uniformly mixing to obtain an isopentenyl alcohol polyoxyethylene ether solution;
step 3, adding isovaleryltetraacrylate, 2-acrylamide-1-methylpropanesulfonic acid, unsaturated phosphate, modified graphene, 3-mercaptopropionic acid and ascorbic acid into water, and uniformly mixing to obtain a graphene-containing mixed material;
step 4, adding an initiator into water, and uniformly mixing to obtain an initiator solution;
and 5, uniformly mixing the isopentenol polyoxyethylene ether solution, the graphene-containing mixed material and the initiator solution, heating to 80-90 ℃ for reaction for 1-5h, cooling to room temperature after the reaction is finished, regulating the pH to be neutral by adopting a 10-20wt% sodium hydroxide aqueous solution, and finally centrifuging to obtain precipitate, washing and drying to obtain the graphene water reducer.
7. Use of a graphene water reducer according to any one of claims 1-5 as a cement, concrete dispersant.
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