CN117165116A - Large-sheet-layer-spacing modified graphene oxide composite material, acrylic coating thereof and preparation method - Google Patents
Large-sheet-layer-spacing modified graphene oxide composite material, acrylic coating thereof and preparation method Download PDFInfo
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- CN117165116A CN117165116A CN202310841182.4A CN202310841182A CN117165116A CN 117165116 A CN117165116 A CN 117165116A CN 202310841182 A CN202310841182 A CN 202310841182A CN 117165116 A CN117165116 A CN 117165116A
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- 238000000576 coating method Methods 0.000 title claims abstract description 130
- 239000011248 coating agent Substances 0.000 title claims abstract description 119
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- 238000002360 preparation method Methods 0.000 title claims description 17
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a large-sheet interlayer spacing modified graphene oxide composite material, which comprises 1 part of graphene oxide and 20 parts of KH550, wherein the graphene oxide and the 20 parts of KH550 are added into absolute ethyl alcohol to be dispersed into a uniform solution, and deionized water is added for reaction after heating, refluxing and stirring reaction; washing with absolute ethyl alcohol and deionized water respectively for multiple times, drying, adding the absolute ethyl alcohol and the deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; respectively carrying out ultrasonic treatment, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃,centrifuging to remove supernatant, washing with deionized water and absolute ethanol, and oven drying to obtain large-lamellar-spacing FTiO 2 -GO nanocomposite. The modified graphene oxide composite material has the advantages of large lamellar spacing, remarkably improved dispersion performance and capability of fully playing the role of the modified graphene oxide composite material in the coating.
Description
Technical Field
The invention relates to a modified graphene oxide composite material for a coating, in particular to a large-sheet interlayer spacing modified graphene oxide composite material, an acrylic coating thereof and a preparation method thereof.
Background
The modified graphene oxide composite material can obviously improve the corrosion resistance and weather resistance of the coating, but the application of the modified graphene oxide composite material in the coating has the common problem that the modified graphene oxide composite material is not easy to disperse, so that the effect of improving the corrosion resistance and weather resistance of the coating of the modified graphene oxide composite material can not be fully exerted. The existing graphene oxide UV curing coating with the document number of CN108384406A comprises the following components in parts by weight: 100-105 parts of acrylic modified epoxy resin, 45-75 parts of monomer, 25-50 parts of diluent, 2-8 parts of photoinitiator, 2-5 parts of co-initiator, 1-3 parts of flatting agent and 1-2.5 parts of aminosilane modified graphite oxide; the aminosilane modified graphite oxide is prepared by reacting graphene oxide with aminosilane. Further, the monomer is methacrylate substance, specifically methyl methacrylate, ethyl methacrylate or butyl methacrylate, and the leveling agent is BYK-UV3500, BYK-UV3530 or BYK-UV3570 manufactured by Pick chemical company. Further, the diluent is one or two of PEG200DMA, PEG400DMA and PEG600DMA, the acid value of the diluent is less than or equal to 0.2mgKOH/g, and the viscosity at 25 ℃ is 10-100 cps. In this way, the viscosity of the coating can be adjusted, facilitating the preparation of the coating. Further, the photoinitiator is one or two of 2, 3-butanedione, 1-phenyl-1, 2-propanedione and N-phenylglycine. Thus, the photoinitiator is liquid at room temperature, is easy to disperse, can increase the compatibility with resin, can increase the leveling property of the coating, and can improve the glossiness of the coating. Further, the co-initiator is one or two of N, N' -dimethylamino ethyl methacrylate, dimethylamino ethyl benzoate and N, N-dimethyl-p-toluidine. Thus, under the synergistic compatibility of the photoinitiator and the co-initiator, the coating can be rapidly cured into a film under the action of ultraviolet light, and the curing time is shortened. Further, the mass ratio of the graphene oxide to the aminosilane is 1:0.1-0.5, and the aminosilane is gamma-aminopropyl trimethoxy silane. In this way, the aminosilane is bonded with the graphene through the silicon oxygen group, and the amino group on the aminosilane can react with the epoxy group on the resin, so that the compatibility of the graphene and the resin is improved, the content and the dispersibility of the graphene in the resin are also improved, in addition, the amino group can react with the resin to promote the curing during the curing, the curing effect is enhanced, and the curing time is shortened. Furthermore, the addition of the aminosilane can improve the flexibility, adhesion and water resistance of the coating. However, there is a limitation in improving dispersibility only by reacting the amino group on the aminosilane with the epoxy group on the resin.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a large-sheet interlayer spacing modified graphene oxide composite material and an acrylic coating thereof, and also provides a preparation method of the coating. The modified graphene oxide composite material has remarkable large-sheet interlayer spacing characteristics, and is very beneficial to dispersion, in particular to dispersion in a coating material. The acrylic coating prepared from the large-sheet interlayer spacing modified graphene oxide composite material can fully play the role of improving the corrosion resistance and weather resistance of the coating by the modified graphene oxide composite material. The preparation method has the advantage of good reliability.
In order to achieve the aim, the large-sheet interlayer spacing modified graphene oxide composite material is characterized in that 1 part by mass of graphene oxide and 20 parts by mass of KH550 are added into absolute ethyl alcohol in a reactor to be ultrasonically dispersed to form a uniform mixed solution, and deionized water is added for continuous reaction after heating, refluxing and stirring reaction; washing with absolute ethyl alcohol and deionized water for multiple times respectively, drying the obtained substances, adding the obtained modified graphene oxide and absolute ethyl alcohol into deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part by mass of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; respectively ultrasonically treating the two solutions, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃, centrifuging to remove supernatant, washing with deionized water and absolute ethanol for multiple times respectively, and drying to obtain a product which is the FTiO with large lamellar spacing 2 -GO nanocomposite. The Chinese culture name of the kh-550 silane coupling agent is 3-aminopropyl triethoxy siliconAn alkane. The spacing between the sheets of the system can be calculated from the positions of the diffraction peaks in the XRD pattern. The invention relates to a large-sheet-spacing FTiO 2 The diffraction peak of the GO nanocomposite is 9.66 DEG, the corresponding lamellar spacing is 0.91nm; the diffraction peak of the graphene oxide used in the invention is 11.38 degrees, and the corresponding lamellar spacing is 0.78nm. Illustrating that the lamellar spacing of the system can be significantly improved, thereby being more beneficial to the FTiO in the subsequent process 2 -the dispersion of GO in the coating. The large-sheet interlayer spacing modified graphene oxide composite material has the advantages of excellent large-sheet interlayer spacing performance and being very beneficial to being dispersed in a coating.
As optimization, the heating reflux stirring reaction is carried out for 4 hours at 78 ℃, and the stable reaction temperature can be well maintained through ethanol condensation reflux; deionized water is added to continue the reaction for 1h, which is beneficial to deepening the reaction.
As optimization, the washing with absolute ethyl alcohol and deionized water respectively for multiple times is to wash with absolute ethyl alcohol and deionized water respectively for 3 times, wherein the absolute ethyl alcohol is used for high-efficiency elution, and the deionized water is used for deep elution; the washing with deionized water and absolute ethyl alcohol respectively for multiple times is to wash with deionized water and absolute ethyl alcohol respectively for 3 times, the deionized water is used for high-efficiency elution, and the absolute ethyl alcohol is used for deep elution.
Preferably, the drying is carried out in an oven at 60 ℃ for 24 hours. The drying temperature at 60 ℃ is far lower than the flash point of the 3-aminopropyl triethoxysilane at 96 ℃, which is more beneficial to industrialized safe production.
Preferably, the stirring in the water bath at 60 ℃ is magnetic stirring for 2 hours under the condition of the water bath at 60 ℃. The reaction temperature of heating reflux stirring and the drying temperature of 60 ℃ which are obviously lower than the 78 ℃ for synthesizing the modified graphene oxide can avoid the adverse effect of the reaction on the modified graphene oxide. And the magnetic stirring for 2 hours can ensure the sufficient combination of the nano titanium dioxide and the modified graphene oxide.
As an optimization, the two solutions were sonicated separately for 20min. The obtained modified graphene oxide and absolute ethyl alcohol are added into deionized water to prepare a modified graphene oxide ethanol solution, so that the stability of the solution is guaranteed; preparing a titanium dioxide aqueous solution from 0.3 part by mass of modified graphene oxide of nano titanium dioxide and deionized water, and fully utilizing the super-hydrophilicity of the nano titanium dioxide; respectively carrying out ultrasonic treatment on the two solutions for 20min, dropwise adding a titanium dioxide aqueous solution into the modified graphene oxide ethanol solution under stirring, and fully utilizing the super-hydrophilicity of nano titanium dioxide to enable the two solutions to be quickly mixed.
A certain amount of 0.1g of graphene oxide and 2gKH g of graphene oxide 550 are added into a round-bottom flask containing 100mL of absolute ethyl alcohol to be dispersed for 30min in an ultrasonic way, a uniformly dispersed mixed solution is formed, a condensing tube is connected, heating and stirring are carried out for 4h at 78 ℃, and then 20mL of deionized water is added to continue the reaction for 1h. And after the reaction is finished, washing with absolute ethyl alcohol and deionized water for 3 times respectively to wash away redundant reactants and impurities, and finally, drying the obtained sample in a 60 ℃ oven for 24 hours to obtain a modified graphene oxide sample. Then 0.1g of modified graphene oxide sample and 25mL of absolute ethyl alcohol are added into deionized water to obtain an ethanol solution of the modified graphene oxide, a certain amount of titanium dioxide (the mass ratio of the modified graphene oxide to the titanium dioxide is 10:3) and 25mL of deionized water are further taken to prepare an aqueous solution of the titanium dioxide, the two solutions are respectively subjected to ultrasonic treatment for 20min, and under the action of magnetic stirring, the aqueous solution of the titanium dioxide is dropwise added into the ethanol solution of the modified graphene oxide, and is magnetically stirred for 2h under the condition of water bath at 60 ℃. Centrifuging to remove supernatant, washing with deionized water and absolute ethanol for 3 times to remove excessive reactant and impurity, and drying the product in oven at 60deg.C for 24 hr to obtain FTiO 2 -GO nanocomposite. The Chinese culture name of the kh-550 silane coupling agent is 3-aminopropyl triethoxysilane.
The acrylic coating prepared from the large-sheet interlayer spacing modified graphene oxide composite material is prepared by adopting the FTiO 2 And (3) performing ultrasonic dispersion on the GO nanocomposite in deionized water, adding the aqueous hydroxy acrylic dispersion resin, stirring, and adding a curing agent under stirring at room temperature to obtain the acrylic coating. The obtained coating can fully play the role of the modified graphene oxide composite material, and experiments of hardness, corrosion resistance and weather resistance prove that the coating can obtain excellent comprehensive technologyThe operation effect. Wherein the FTiO is 2 The GO nanocomposite is firstly ultrasonically dispersed in deionized water and can pass through FTiO 2 The GO nanocomposite is hydrophilic in advance and is surely ensured to be fully mixed with the added aqueous hydroxyl acrylic dispersion resin.
FTiO as an optimization 2 The weight ratio of the GO nanocomposite to the aqueous hydroxy acrylic dispersion is 0.6:100. The aqueous hydroxy acrylic dispersion resin and the curing agent are aqueous hydroxy acrylic dispersion resin which consists of aqueous acrylic resin, propylene glycol butyl ether, water and a neutralizing agent, and are mixed with the curing agent aqueous polyurethane curing agent to prepare aqueous two-component acrylic paint, namely the two-component aqueous paint with the commodity mark of StebaAW2F1152 produced by Guangdong Pontai new material technology Co.
The preparation method of the large-sheet interlayer spacing modified graphene oxide composite material is characterized by comprising the steps of 1) adding graphene oxide with a mass ratio of 1 to 20 KH550 into absolute ethyl alcohol in a reactor, performing ultrasonic dispersion to form a uniform mixed solution, heating, refluxing, stirring, reacting, and adding deionized water for continuous reaction; 2) Washing with absolute ethanol and deionized water respectively for multiple times, and drying the obtained product; 3) Adding the obtained modified graphene oxide and absolute ethyl alcohol into deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part by mass of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; 4) Respectively ultrasonically treating the two solutions, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃, centrifuging to remove supernatant, washing with deionized water and absolute ethanol for multiple times respectively, and drying to obtain a product which is the FTiO with large lamellar spacing 2 -GO nanocomposite. The Chinese culture name of the kh-550 silane coupling agent is 3-aminopropyl triethoxysilane. The method has good reliability.
As optimization, in the step 1), heating, refluxing and stirring reaction is carried out for 4 hours at 78 ℃, and deionized water is added for continuous reaction for 1 hour; washing with absolute ethyl alcohol and deionized water for multiple times respectively in the steps 2) and 4) is carried out with absolute ethyl alcohol and deionized water for 3 times respectively, and washing with deionized water and absolute ethyl alcohol for multiple times respectively is carried out with deionized water and absolute ethyl alcohol for 3 times respectively; drying is carried out by placing the dried materials in a baking oven at 60 ℃ for 24 hours; magnetically stirring in the water bath at 60 ℃ for 2 hours under the condition that the stirring in the water bath at 60 ℃ in the step 4) is the water bath at 60 ℃; the two solutions in step 4) are respectively sonicated for 20min. The method has good reliability.
The preparation method of the acrylic coating prepared from the large-sheet interlayer spacing modified graphene oxide composite material based on the preparation method comprises the steps of preparing the FTiO 2 And (3) performing ultrasonic dispersion on the GO nanocomposite in deionized water, adding the aqueous hydroxy acrylic dispersion resin, stirring, and adding a curing agent under stirring at room temperature to obtain the acrylic coating. The obtained coating can fully play the role of the modified graphene oxide composite material. The hardness, corrosion resistance and weather resistance experiments of the obtained paint prove that the paint has excellent comprehensive technical effects. The method has good reliability.
FTiO 2 The weight ratio of the GO nanocomposite to the acrylic acid is 0.6:100. The aqueous hydroxy acrylic dispersion resin and the curing agent are aqueous hydroxy acrylic dispersion resin which consists of aqueous acrylic resin, propylene glycol butyl ether, water and a neutralizing agent, and are mixed with the curing agent aqueous polyurethane curing agent to prepare aqueous two-component acrylic paint, namely the two-component aqueous paint with the commodity mark of StebaAW2F1152 produced by Guangdong Pontai new material technology Co.
After the technical scheme is adopted, the large-sheet-spacing modified graphene oxide composite material, the acrylic acid coating and the preparation method thereof have the advantages that the sheet-spacing of the modified graphene oxide composite material is large, the dispersion performance is obviously improved, the effect of the modified graphene oxide composite material can be fully exerted in the coating, the hardness, the corrosion resistance and the weather resistance of the acrylic acid coating are good, and the reliability of the preparation method is good.
Drawings
FIG. 1 is a graph showing the comparison of Raman spectra of a large-sheet interlayer spacing modified graphene oxide composite material and graphene oxide in an ethanol dispersion solvent; FIG. 2 is a comparative XRD pattern of a large-sheet spacing modified graphene oxide composite of the invention, with graphene oxide; FIG. 3 is a comparative TG pattern of a large-sheet interlayer spacing modified graphene oxide composite material of the present invention with graphene oxide; FIG. 4 is a microscopic morphology contrast chart of three enlarged scales of the large-sheet interlayer spacing modified graphene oxide composite material and graphene oxide of the present invention; FIG. 5 is a bar graph of pencil hardness values for acrylic coatings and acrylic coating bodies of varying amounts of addition for the large sheet spacing modified graphene oxide composites of the present invention; FIG. 6 is a comparative EIS graph of acrylic paint with various additions of coating of acrylic paint body immersed in 3.5wt.% NaCl solution for 150h (a, b, c, c ') and immersed for 350h (d, e, f, f') of the large sheet of interlayer spacing modified graphene oxide composite material of the present invention; FIG. 7 is a graph of macroscopic morphology of the coating of the acrylic coating and acrylic coating body of the large sheet interlayer spacing modified graphene oxide composite material of the present invention in different additive amounts compared with a salt spray test. FIG. 8 is an EIS graph of the coating ultraviolet accelerated aging test of the acrylic paint and the acrylic paint body of different addition amounts of the large sheet interlayer spacing modified graphene oxide composite material of the present invention for 150h (a, b, c, c '), 350h (d, e, f, f').
Detailed Description
The large-sheet interlayer spacing modified graphene oxide composite material is characterized in that 1 part by mass of graphene oxide and 20 parts by mass of KH550 are added into absolute ethyl alcohol in a reactor to be ultrasonically dispersed to form a uniform mixed solution, and deionized water is added for continuous reaction after heating, refluxing and stirring reaction; washing with absolute ethyl alcohol and deionized water for multiple times respectively, drying the obtained substances, adding the obtained modified graphene oxide and absolute ethyl alcohol into deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part by mass of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; respectively ultrasonically treating the two solutions, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃, centrifuging to remove supernatant, washing with deionized water and absolute ethanol for multiple times respectively, and drying to obtain a product which is the FTiO with large lamellar spacing 2 -GO nanocomposite. Chinese cultural name of kh-550 silane coupling agentIs called 3-aminopropyl triethoxysilane. The spacing between the sheets of the system can be calculated from the positions of the diffraction peaks in the XRD pattern. The invention relates to a large-sheet-spacing FTiO 2 The diffraction peak of the GO nanocomposite is 9.66 DEG, the corresponding lamellar spacing is 0.91nm; the diffraction peak of the graphene oxide used in the invention is 11.38 degrees, and the corresponding lamellar spacing is 0.78nm. Illustrating that the lamellar spacing of the system can be significantly improved, thereby being more beneficial to the FTiO in the subsequent process 2 -the dispersion of GO in the coating. The large-sheet interlayer spacing modified graphene oxide composite material has the advantages of excellent large-sheet interlayer spacing performance and being very beneficial to being dispersed in a coating.
The heating reflux stirring reaction is carried out for 4 hours at 78 ℃, and deionized water is added for continuous reaction for 1 hour. The washing with absolute ethyl alcohol and deionized water respectively for multiple times is to wash with absolute ethyl alcohol and deionized water respectively for 3 times, and the washing with deionized water and absolute ethyl alcohol respectively for multiple times is to wash with deionized water and absolute ethyl alcohol respectively for 3 times. The drying is carried out by placing the dried materials in a 60 ℃ oven for drying for 24 hours. Stirring in a water bath at 60 ℃ is magnetic stirring for 2 hours under the condition of the water bath at 60 ℃. The two solutions were sonicated separately for 20min.
Specifically, a certain amount of 0.1g of graphene oxide and 2gKH g of graphene oxide 550 are added into a round-bottom flask containing 100mL of absolute ethyl alcohol to be dispersed for 30min in an ultrasonic manner, a uniformly dispersed mixed solution is formed, a condensing tube is connected, heating and stirring are carried out for 4h at 78 ℃, and then 20mL of deionized water is added to continue the reaction for 1h. And after the reaction is finished, washing with absolute ethyl alcohol and deionized water for 3 times respectively to wash away redundant reactants and impurities, and finally, drying the obtained sample in a 60 ℃ oven for 24 hours to obtain a modified graphene oxide sample. Then 0.1g of modified graphene oxide sample and 25mL of absolute ethyl alcohol are taken and added into deionized water to obtain an ethanol solution of the modified graphene oxide, a certain amount of titanium dioxide (the mass ratio of the modified graphene oxide to the titanium dioxide is 10:3) and 25mL of deionized water are taken to prepare an aqueous solution of the titanium dioxide, the two solutions are respectively ultrasonically treated for 20min, and under the action of magnetic stirring, the aqueous solution of the titanium dioxide is dropwise added into the ethanol solution of the modified graphene oxide, and a strip of the modified graphene oxide is subjected to water bath at 60 DEG CMagnetically stirring the mixture for 2 hours under the piece. Centrifuging to remove supernatant, washing with deionized water and absolute ethanol for 3 times to remove excessive reactant and impurity, and drying the product in oven at 60deg.C for 24 hr to obtain FTiO 2 -GO nanocomposite.
The acrylic coating prepared from the large-sheet interlayer spacing modified graphene oxide composite material is prepared by adopting the FTiO 2 And (3) performing ultrasonic dispersion on the GO nanocomposite in deionized water, adding the aqueous hydroxy acrylic dispersion resin, stirring, and adding a curing agent under stirring at room temperature to obtain the acrylic coating. The obtained coating can fully play the role of the modified graphene oxide composite material. FTiO 2 The weight ratio of the GO nanocomposite to the acrylic acid is 0.6:100. The aqueous hydroxy acrylic dispersion resin and the curing agent are aqueous hydroxy acrylic dispersion resin which consists of aqueous acrylic resin, propylene glycol butyl ether, water and a neutralizing agent, and are mixed with the curing agent aqueous polyurethane curing agent to prepare aqueous two-component acrylic paint, namely the two-component aqueous paint with the commodity mark of StebaAW2F1152 produced by Guangdong Pontai new material technology Co.
The preparation method of the large-sheet interlayer spacing modified graphene oxide composite material comprises the steps of 1) adding graphene oxide with a mass ratio of 1 to 20 KH550 into absolute ethyl alcohol in a reactor, performing ultrasonic dispersion to form a uniform mixed solution, heating, refluxing, stirring, reacting, and adding deionized water for continuous reaction; 2) Washing with absolute ethanol and deionized water respectively for multiple times, and drying the obtained product; 3) Adding the obtained modified graphene oxide and absolute ethyl alcohol into deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part by mass of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; 4) Respectively ultrasonically treating the two solutions, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃, centrifuging to remove supernatant, washing with deionized water and absolute ethanol for multiple times respectively, and drying to obtain a product which is the FTiO with large lamellar spacing 2 -GO nanocomposite. The Chinese culture name of the kh-550 silane coupling agent is 3-aminopropyl triethyleneAnd (3) an oxy silane. The spacing between the sheets of the system can be calculated from the positions of the diffraction peaks in the XRD pattern. The invention relates to a large-sheet-spacing FTiO 2 The diffraction peak of the GO nanocomposite is 9.66 DEG, the corresponding lamellar spacing is 0.91nm; the diffraction peak of the graphene oxide used in the invention is 11.38 degrees, and the corresponding lamellar spacing is 0.78nm. Illustrating that the lamellar spacing of the system can be significantly improved, thereby being more beneficial to the FTiO in the subsequent process 2 -the dispersion of GO in the coating. The large-sheet interlayer spacing modified graphene oxide composite material has the advantages of excellent large-sheet interlayer spacing performance and being very beneficial to being dispersed in a coating.
Wherein in the step 1), heating, refluxing and stirring are carried out for 4 hours at 78 ℃, and deionized water is added for continuous reaction for 1 hour; washing with absolute ethyl alcohol and deionized water for multiple times respectively in the steps 2) and 4) is carried out with absolute ethyl alcohol and deionized water for 3 times respectively, and washing with deionized water and absolute ethyl alcohol for multiple times respectively is carried out with deionized water and absolute ethyl alcohol for 3 times respectively; drying is carried out by placing the dried materials in a baking oven at 60 ℃ for 24 hours; magnetically stirring in the water bath at 60 ℃ for 2 hours under the condition that the stirring in the water bath at 60 ℃ in the step 4) is the water bath at 60 ℃; the two solutions in step 4) are respectively sonicated for 20min.
Wherein, FTiO 2 -preparation of GO nanocomposite: 0.1g of graphene oxide and 2gKH g of graphene oxide 550 are added into a round-bottomed flask containing 100mL of absolute ethyl alcohol to be dispersed for 30min by ultrasonic, a uniformly dispersed mixed solution is formed, a condenser tube is connected, heating and stirring are carried out at 78 ℃ for 4h, and then 20mL of deionized water is added to continue the reaction for 1h. And after the reaction is finished, washing with absolute ethyl alcohol and deionized water for 3 times respectively to wash away redundant reactants and impurities, and finally, drying the obtained sample in a 60 ℃ oven for 24 hours to obtain a modified graphene oxide sample. Then 0.1g of modified graphene oxide sample and 25mL of absolute ethyl alcohol are taken and added into deionized water to obtain an ethanol solution of the modified graphene oxide, a certain amount of titanium dioxide (the mass ratio of the modified graphene oxide to the titanium dioxide is 10:3) and 25mL of deionized water are taken to prepare an aqueous solution of the titanium dioxide, the two solutions are respectively ultrasonically treated for 20min, and under the action of magnetic stirring, the aqueous solution of the titanium dioxide is dripped into the modified graphene oxideAnd (3) magnetically stirring the graphene oxide in an ethanol solution for 2 hours under the condition of water bath at 60 ℃. Centrifuging to remove supernatant, washing with deionized water and absolute ethanol for 3 times to remove excessive reactant and impurity, and drying the product in oven at 60deg.C for 24 hr to obtain FTiO 2 -GO nanocomposite. The Chinese culture name of the kh-550 silane coupling agent is 3-aminopropyl triethoxysilane.
FTiO 2 -GO structural analysis: referring to FIG. 1, in the Raman spectrum, D wave Duan Chang represents sp within the graphene material 2 Defects in the hybrid structure, including sp due to the introduction of oxygen-containing groups 3 Defects caused by hybridization and carbon atom deletion, and defects caused by hetero atoms entering a graphite carbon skeleton. The G peak represents sp in graphene skeleton 2 A hybrid structure. The peak intensity ratio I can be used in general D /I G The value characterizes how much the defect is in the system. Fitting calculation analysis of GO-capable I by Origin software D /I G 2.11, FTiO 2 I of GO D /I G 2.28, showing that after KH550 modification treatment, FTiO 2 The degree of disorder and the degree of disorder of the GO system are significantly improved.
Referring to fig. 2, the sheet spacing of the system can be calculated from the position of the diffraction peak in the XRD pattern. FTiO modified by KH550 as shown 2 The diffraction peak of GO is at 9.66 DEG, the corresponding lamellar spacing is 0.91nm. The modification of KH550 can obviously improve the lamellar spacing of the system, thereby being more beneficial to FTiO in the subsequent process 2 -the dispersion of GO in the coating.
Referring to FIG. 3, a diagram is shown of GO, FTiO 2 TG curve of GO. As can be seen from the figure, the mass change of graphene oxide is small when the temperature is lower than 200 ℃, and the mass loss rapidly changes in the temperature range of 200 ℃ to 250 ℃ when the temperature is higher than 200 ℃. Wherein the graphene oxide has a heat loss of about 30%, which means that in this temperature range, a large amount of oxygen-containing groups in the graphene oxide undergo thermal decomposition, resulting in a large amount of heat loss. And FTiO 2 -GO nanocomposite appearance of the first phase in a temperature range of less than 200 °cThere was a rapid mass loss change of about 15% of the mass loss, probably due to degradation of KH550 grafted onto the graphene oxide surface. A second, more rapid mass loss occurs in the range of temperatures above 200 ℃ and below 600 ℃, possibly due to thermal decomposition of the oxygen-containing functional groups on the graphene oxide surface. As the temperature continues to rise, the mass loss changes relatively slowly as the temperature goes above 600℃and from FTiO 2 The final residual mass of GO can be seen, FTiO 2 The residual mass of GO is obviously higher than that of graphene oxide, which proves that FTiO obtained after further modification of KH550 2 The stability of GO is significantly higher than that of graphene oxide.
FTiO 2 -GO morphology analysis: as shown in FIG. 4, is graphene oxide and FTiO 2 -TEM microtomography of different magnifications of GO. From figures (a) - (c) it can be seen that graphene oxide is in the form of a thin layer, the surface of the layer is smooth and has semitransparent folds, and these folds can provide a large number of active sites for the subsequent modification of the nano-oxide. Also as can be seen from figures (a) - (c), there are darker and lighter areas on the graphene oxide surface, which may indicate that there is a greater stacking of graphene oxide sheets in the areas, because the oxygen-containing functional groups on the graphene oxide surface cause stronger van der waals forces between the sheets, thereby forming stacked sheets. Conversely, lighter areas indicate fewer stacks of graphene oxide sheets. From figures (d) - (f), it can be seen that when graphene oxide is modified by KH550, darker areas are relatively increased, which indicates that graphene oxide sheets are stacked, and the thickness of the graphene oxide sheets is increased. Also, as can be seen from the figure, the presence of the dot-like substance on the graphene oxide sheets indicates that the titanium oxide was successfully decorated at the folds of the graphene oxide sheets. Bonding graphene oxide and FTiO 2 The image of GO after being ultrasonically dispersed in deionized water for 72 hours shows that the sample in the graphene oxide is subjected to ultrasonic standing for 72 hours, and obvious layering and precipitation of the sample in the bottle occur, which indicates that the dispersibility of the graphene oxide in the deionized water is poor. When graphene oxide is modified by KH550,and further modified with titanium dioxide to give FTiO 2 The GO nanocomposite can form a solution which is uniformly dispersed in deionized water, and obvious layering and precipitation phenomena do not occur in a bottle after ultrasonic standing for 72 hours, which indicates that FTiO 2 The GO nanocomposite has good dispersibility in deionized water.
Wherein, FTiO 2 -preparation of GO/acrylic paint: will be 0.005g FTiO 2 The GO nanocomposite is ultrasonically dispersed in deionized water for 1h, then 5g of acrylic acid is poured, stirred at room temperature for 30min, and a curing agent (the mass ratio of the curing agent to the acrylic acid is 20:1) is added, so that 0.1wt.% of the acrylic acid coating is obtained. Composite acrylic paints with addition amounts of 0.3wt.%, 0.6wt.%, 1.0wt.%, 1.5wt.% were prepared in this way, respectively, denoted 0.1F, 0.3F, 0.6F, 1.0F and 1.5F. Before using, the carbon steel sample plate is polished by 400# sand paper, 800# sand paper and 1200# sand paper, and absolute ethyl alcohol is used for removing greasy dirt and scraps on the surface of the steel plate. And then uniformly spraying the coating on the surface of the steel plate, controlling the thickness of the coating within the range of 50+/-10 mu m, and drying and curing for 24 hours at room temperature to obtain the composite acrylic acid coating sample. The aqueous hydroxy acrylic dispersion resin and the curing agent are aqueous hydroxy acrylic dispersion resin which consists of aqueous acrylic resin, propylene glycol butyl ether, water and a neutralizing agent, and are mixed with the curing agent aqueous polyurethane curing agent to prepare aqueous two-component acrylic paint, namely the two-component aqueous paint with the commodity mark of StebaAW2F1152 produced by Guangdong Pontai new material technology Co.
FTiO 2 Basic Properties of GO/acrylic coating, different FTiO 2 The thickness of the acrylic composite coating with the addition of GO is shown in Table 1 below, and the thickness of all composite coatings is controlled at 40.+ -.10. Mu.m.
TABLE 1FTiO 2 -thickness (μm) of GO/acrylic composite coating.
FIG. 5 is a different FTiO 2 -pencil hardness value comparison of acrylic composite coating with GO addition. From the graphIt is known that the hardness of the pure acrylic coating is 2H, when FTiO 2 At an addition level of 0.6wt.% GO, the hardness of the acrylic composite coating increases to 3H; FTiO 2 At addition levels of 0.1wt.% and 1.5wt.% GO, the hardness of the acrylic composite coating decreases to H. This indicates FTiO 2 FTiO when the addition amount of GO is moderate 2 GO can promote the compactness of the coating, so that the hardness of the coating can be improved.
FTiO 2 Corrosion resistance of GO/acrylic coating: evaluation of FTiO addition Using electrochemical impedance test and salt spray Corrosion test 2 Anti-corrosion properties of the acrylic coating of GO. FIG. 6 is a schematic diagram of different proportions of FTiO 2 EIS profile of GO/acrylic composite coating and pure acrylic coating immersed in 3.5wt.% NaCl solution for different times. Referring to the electrochemical Bode diagrams of fig. 6 (a, d) and table 2 below, the low frequency impedance modulus value of the acrylic composite coating was 10 when the soaking time was 150h 9 -10 11 . When the soaking time reaches 350h, the low-frequency impedance modulus value of the 0.6F/acrylic composite coating is still kept at 10 11 The low-frequency impedance modulus values of other composite coatings are reduced by 1-5 orders of magnitude, which indicates that FTiO permeates with corrosive electrolyte 2 The addition of the GO can effectively improve the barrier property and the corrosion resistance of the acrylic coating. But the low-frequency impedance modulus of the 1.5F/acrylic composite coating is obviously reduced by about 6 orders of magnitude; the low frequency impedance modulus of the 0.1F/acrylic composite coating was reduced by about 4 orders of magnitude, while the low frequency impedance modulus of the pure acrylic coating was reduced by only about two orders of magnitude, indicating FTiO 2 Either too low or too high a content of GO does not allow a good corrosion protection of the composite coating. In the electrochemical Phase diagram of FIG. 6 (b, e), the 0.1F/acrylic composite coating has two relaxation times when the soak time reaches 350h, illustrating FTiO 2 When the addition amount of GO is too low, the barrier capability of the coating cannot be improved, so that the protective capability of the coating is weakened. Although the phase angle of the other coating decreases with increasing soak time, there is still only one relaxation time, indicating FTiO 2 The addition of GO enables a certain protection of the coating against penetration by corrosive media. Electrochemical Nyquist diagram as in FIG. 6 (c, c ', f, f')As can be seen, the impedance spectra of all coatings exhibit a semicircular shape, and the corresponding Bode plot has only one time constant. Meanwhile, the capacitive arc radius of the impedance reflects the shielding performance of the coating, and the larger the radius is, the lower the porosity of the coating is, the better the physical shielding performance of the coating is, and the stronger the corrosion resistance is. Different FTiO in the figure 2 FTiO with GO content 2 The arc resistance of the GO/acrylic composite coating is semicircular, but the arc resistance radius of the composite coating is greatly changed with the increase of the soaking time of the template in the 3.5wt.% NaCl salt solution. When the sample plate soaking time reaches 350h, the arc-tolerant radius of the 0.6F/acrylic composite coating is still large and is larger than that of the pure acrylic coating, which shows that with penetration of corrosive electrolyte, FTiO 2 The GO reduces the porosity of the acrylic coating, delays the penetration of the corrosive electrolyte from the micropores to the matrix, and effectively prevents the penetration of the corrosive electrolyte into the coating through the micropores left during curing, thereby improving the physical barrier property of the coating. In summary, when the soaking time reaches 350h, the corrosion resistance of different coatings is as follows: 0.6F>0.3F>1.0F>0.1F>Acrylic acid>1.5F. Thus FTiO 2 The anticorrosion properties of the composite coating are best at a GO content of 0.6 wt.%.
TABLE 2FTiO 2 Low frequency impedance modulus value |z| of the GO/acrylic composite coating 0.01 (ohmscm 2 )。
The salt spray test shows that different addition amounts of FTiO 2 Effect of GO nanocomposite on corrosion protection properties of acrylic coatings. The macroscopic morphology of the samples after exposure to 5wt.% NaCl salt solution for 350 hours is shown in fig. 7. As is clear from FIG. 7 (b, F), there is a significant corrosion product formation at the scratches of the 0.1F, 1.5F/acrylic composite coating, and the corrosion spread is relatively severe, indicating that FTiO 2 Too low and too high an addition of GO may not be able to exert a barrier effect. As can be seen from FIGS. 7 (c-e), however, the coating is scratched by corrosionThe corrosion products are obviously reduced, which means that a certain addition amount of FTiO 2 The addition of GO can have a certain barrier effect on the penetration of corrosive media, in particular FTiO 2 The addition of GO at 0.6wt.% minimizes corrosion products of the acrylic coating and the corrosion resistance of the coating is best, which is also consistent with the data results of EIS testing.
FTiO 2 Weather resistance of GO/acrylic coating: to further verify the weather resistance of the coating, FTiO was characterized by uv aging test and electrochemical impedance test 2 Impact of addition of GO on the weather resistance of the acrylic coating. As can be seen from a combination of the electrochemical Bode diagrams of FIG. 8 (a, d) and the low frequency impedance modulus values of Table 3 below, the low frequency impedance modulus values of the acrylic composite coatings of 0.1F, 0.3F, 0.6F, 1.0F and 1.5F reached 10 after 150h of UV irradiation 10 -10 11 Within the range where the low frequency impedance modulus of the 0.1F/acrylic composite coating is slightly higher than the other coatings. After 350 hours of ultraviolet irradiation, the low frequency impedance modulus value of the 0.6F/acrylic composite coating is maximum, the low frequency impedance modulus value of the 0.1F/acrylic composite coating is reduced by about one order of magnitude, and the low frequency impedance modulus value of the 1.5F/acrylic composite coating is reduced by about two orders of magnitude. In the electrochemical Phase diagram of fig. 8 (b, e), the Phase angle is somewhat reduced when the different coatings are immersed for different times, but all coatings have only one relaxation time, indicating the addition of FTiO 2 The coating of GO has certain weather resistance. Referring to the electrochemical Nyquist plot of fig. 8 (c, c ', F, F'), when the template is irradiated under uv light for 150 hours, the capacitive arc radius of the 0.1F/acrylic composite coating is maximum and greater than that of the pure acrylic coating; when the template is irradiated under ultraviolet light for 350 hours, the arc-tolerant radius of the 0.6F/acrylic composite coating is maximum and is obviously larger than that of the 0.1F/acrylic composite coating. In summary, when the irradiation time of the sample plate reaches 350h, the weather resistance rules of different coatings are as follows: 0.6F>0.1F>0.3F>1.0F>Acrylic acid>1.5F. Thus FTiO 2 The weather resistance of the composite coating is best at an addition of 0.6 wt.%.
TABLE 3FTiO 2 -GO/propyleneLow frequency impedance modulus value of acid composite coating 0.01 (ohmscm 2 )。
In conclusion, the graphene oxide surface prepared by improving the Hummers method presents an obvious semitransparent fold lamellar structure, and the surface of the graphene oxide contains rich oxygen-containing groups and is TiO 2 Provides a large number of active sites. By FTiO 2 The infrared spectrum of GO can be seen that graphene oxide is modified by KH550 and then is at 1737cm -1 The stretching vibration peak representing the carboxyl group C ═ O disappeared at 2971cm -1 A new absorption peak appears at the position of-CH 2 Is a stretching vibration peak of (2). At 882cm -1 The characteristic absorption peak of Si-OH is 1049cm -1 And 1096cm -1 Stretching vibration peaks of Si-O-C and Si-O-Si occur, respectively, because KH550 is hydrolyzed to generate Si-OH, thereby proving that KH550 is successfully modified on graphene oxide sheets. FTiO 2 I of GO D /I G The disorder degree of the system is proved to be increased from 2.11 to 2.28 of graphene oxide. FTiO modified graphene oxide by KH550 2 The increase of the lamellar spacing corresponding to GO from 0.78nm to 0.91nm suggests that the modification of KH550 achieves exfoliation of graphene oxide lamellae to some extent, thereby reducing the van der waals forces between lamellae. FTiO was found by thermogravimetric analysis in the room temperature-250℃range 2 The mass loss of GO is 15% and higher than that of graphene oxide, proving FTiO 2 -GO has excellent thermal stability.
FTiO of 2 After the GO nanocomposite is added to the acrylic coating, the coating is subjected to FTiO 2 Testing of basic Properties of GO/acrylic coating, FTiO 2 The addition of GO increases the hardness of the coating from 2H to 3H and the adhesion value from 2.54MPa to 2.72MPa. As can be seen from the Nyquist diagram and the Bode diagram, when the soaking time of the template reaches 350h, the arc radius of the capacitive reactance of the 0.6F composite coating is maximum, and the low-frequency impedance modulus value is |Z| 0.01 Also maximum, up to 6.060 ×10 10 Description of TiO 2 The addition of the GO nanocomposite at 0.6wt.% can improve the corrosion resistance of the composite acrylic coating. And the salt spray test results are also consistent with the EIS data results of the composite acrylic coating. In the 350h ultraviolet aging test, the arc radius of the capacitive reactance of the 0.6F composite coating is maximum, and the low-frequency impedance modulus value is also maximum, reaching 3.387 multiplied by 10 10 Description of FTiO 2 The weather resistance of the composite acrylic coating is best at an addition of 0.6wt.% GO nanocomposite. Taken together, FTiO 2 The optimal addition amount of the GO nanocomposite is 0.6wt.%, and the prepared coating can fully play the role of the modified graphene oxide composite.
In a word, the large-sheet-spacing modified graphene oxide composite material, the acrylic acid coating and the preparation method thereof have the advantages that the sheet-spacing of the modified graphene oxide composite material is large, the dispersion performance is obviously improved, the effect of the modified graphene oxide composite material can be fully exerted in the coating, the hardness, the corrosion resistance and the weather resistance of the acrylic acid coating are excellent, and the reliability of the preparation method is good.
Claims (10)
1. A large-sheet interlayer spacing modified graphene oxide composite material is characterized in that 1 part by mass of graphene oxide and 20 parts by mass of KH550 are added into absolute ethyl alcohol in a reactor to be ultrasonically dispersed to form a uniform mixed solution, and deionized water is added for continuous reaction after heating, refluxing and stirring reaction; washing with absolute ethyl alcohol and deionized water for multiple times respectively, drying the obtained substances, adding the obtained modified graphene oxide and absolute ethyl alcohol into deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part by mass of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; respectively ultrasonically treating the two solutions, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃, centrifuging to remove supernatant, washing with deionized water and absolute ethanol for multiple times respectively, and drying to obtain a product which is the FTiO with large lamellar spacing 2 -GO nanocomposite.
2. The large-sheet interlayer spacing modified graphene oxide composite material according to claim 1, wherein the heating reflux stirring reaction is heating stirring reaction 4h at 78 ℃, and deionized water is added to continue reaction 1h.
3. The large-sheet interlayer spacing modified graphene oxide composite material according to claim 1, wherein the washing with absolute ethanol and deionized water respectively is performed 3 times each with absolute ethanol and deionized water, and the washing with deionized water and absolute ethanol respectively is performed 3 times each with deionized water and absolute ethanol.
4. The large sheet spacing modified graphene oxide composite material according to claim 1, wherein said drying is carried out by drying in an oven at 60 ℃ for 24h.
5. The large sheet spacing modified graphene oxide composite of claim 1, wherein the stirring in the 60 ℃ water bath is magnetic stirring under conditions of 60 ℃ water bath 2h.
6. The large-sheet interlayer spacing modified graphene oxide composite material according to claim 1, wherein the respective ultrasonic treatment of the two solutions is respective ultrasonic treatment of the two solutions for 20 minutes.
7. The acrylic paint of claim 1, wherein said FTiO is prepared from a composite of a large-sheet-spacing modified graphene oxide 2 And (3) performing ultrasonic dispersion on the GO nanocomposite in deionized water, adding the aqueous hydroxy acrylic dispersion resin, stirring, and adding a curing agent under stirring at room temperature to obtain the primer-topcoat composite coating.
8. The acrylic paint of claim 1, wherein FTiO 2 The weight ratio of the GO nanocomposite to the aqueous hydroxy acrylic dispersion resin is 0.6:100.
9. Claim and claimThe preparation method of the large-sheet interlayer spacing modified graphene oxide composite material is characterized by comprising the steps of 1) adding KH550 with mass ratio of 1 graphene oxide to 20 into absolute ethyl alcohol in a reactor, performing ultrasonic dispersion to form a uniform mixed solution, heating, refluxing, stirring, reacting, and adding deionized water for continuous reaction; 2) Washing with absolute ethanol and deionized water respectively for multiple times, and drying the obtained product; 3) Adding the obtained modified graphene oxide and absolute ethyl alcohol into deionized water to prepare a modified graphene oxide ethanol solution, and preparing 0.3 part by mass of nano titanium dioxide and deionized water into a titanium dioxide aqueous solution; 4) Respectively ultrasonically treating the two solutions, dropwise adding a titanium dioxide aqueous solution into a modified graphene oxide ethanol solution under stirring, stirring in a water bath at 60 ℃, centrifuging to remove supernatant, washing with deionized water and absolute ethanol for multiple times respectively, and drying to obtain a product which is the FTiO with large lamellar spacing 2 -GO nanocomposite.
10. The process of claim 9 wherein in step 1) the heating reflux stirring reaction is heating stirring reaction 4h at 78 ℃ and the continuing reaction with deionized water is continuing reaction 1h; washing with absolute ethyl alcohol and deionized water for multiple times respectively in the steps 2) and 4) is carried out with absolute ethyl alcohol and deionized water for 3 times respectively, and washing with deionized water and absolute ethyl alcohol for multiple times respectively is carried out with deionized water and absolute ethyl alcohol for 3 times respectively; drying is carried out by placing the dried product in a 60 ℃ oven for drying 24h; 2h under the condition that the stirring in the water bath at 60 ℃ in the step 4) is the magnetic stirring in the water bath at 60 ℃; the two solutions in step 4) are respectively sonicated for 20min.
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