CN109370361B - Graphene silicone acrylic emulsion corrosion-resistant coating material and preparation method thereof - Google Patents

Graphene silicone acrylic emulsion corrosion-resistant coating material and preparation method thereof Download PDF

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CN109370361B
CN109370361B CN201811197592.5A CN201811197592A CN109370361B CN 109370361 B CN109370361 B CN 109370361B CN 201811197592 A CN201811197592 A CN 201811197592A CN 109370361 B CN109370361 B CN 109370361B
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graphene
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李玉红
赵维
陈佑宁
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Xianyang Normal University
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Abstract

The invention belongs to the technical field of corrosion-resistant materials, and particularly relates to a graphene silicone acrylic emulsion corrosion-resistant coating material and a preparation method thereof, wherein graphene is prepared by adopting a Hummers method, and then an organic silicon prepolymer is prepared by utilizing octamethylcyclotetrasiloxane, KOH, a silane coupling agent, dimethyl sulfoxide and hexamethyldisiloxane; and finally, preparing the graphene silicone acrylic emulsion corrosion-resistant coating material by using butyl acrylate, methyl acrylate, acrylic acid, styrene, N-hydroxymethyl acrylamide, an organic silicon prepolymer solution and the like. According to the invention, the corrosion resistance of the film prepared from the silicone-acrylate emulsion added with the graphene is enhanced compared with that of a pure silicone-acrylate emulsion by measuring the acid resistance, the alkali resistance and the salt resistance, the mass loss of the film is reduced when the film is corroded by acid, alkali and salt, and the corrosion resistance of the graphene-silicone-acrylate emulsion corrosion-resistant coating material is the best when the content of the graphene is 5%.

Description

Graphene silicone acrylic emulsion corrosion-resistant coating material and preparation method thereof
Technical Field
The invention belongs to the technical field of corrosion-resistant materials, and particularly relates to a graphene silicone acrylic emulsion corrosion-resistant coating material and a preparation method thereof.
Background
The engineering material is affected by the surrounding environment to generate harmful chemical change, electrochemical change and the like, so that the original excellent performance of the material is lost, and the material becomes corroded. Common is corrosion of metallic materials and corrosion of carbon steel materials. Ferrous materials are the most widely used metallic materials, and therefore, the corrosive liquids of ferrous products are the most common. Carbon steel materials have the advantages of low price, simple manufacturing process, good plasticity, good toughness, easy processability and the like, but carbon steel materials generally have the defect of easy corrosion. To solve this problem, researchers at home and abroad have developed a number of corrosion-resistant coating materials to improve the corrosion resistance of steel materials.
The graphene is a two-dimensional honeycomb crystal formed by the thickness of a monoatomic layer formed by sp2 hybridized carbon atoms, has larger surface area and lower preparation cost, and is suitable for developing functional composite materials. Common graphene composite materials are: graphene/inorganic materials, graphene/polymers and the like, the graphene and the inorganic metal materials can be used for preparing super capacitor containers, lithium batteries and the like after being compounded, and the performance of the original polymers can be improved by compounding the graphene and the polymers. For example, the graphene/PANI nano-fiber composite material chemically repaired is prepared by in-situ polymerization of graphite oxide and aniline monomers under an acidic condition, and the specific capacitance of the PANI doped graphene composite material with the current density of 0.1A/g is up to 480F/g.
The graphene/silicone-acrylate emulsion composite material prepared by the huge Haobao et al (literature: preparation and performance of graphene and silicone-acrylate emulsion composite material) has a good dispersion state in a high polymer matrix when the dosage of graphene is 0.6-0.9%, compared with a silicone-acrylate emulsion coating film without graphene, the corrosion resistance of the composite material is improved, and when the dosage of graphene is 0.7% by mass, the acid resistance reaches 470h, the alkali resistance reaches 320h, and the salt resistance reaches 520 h. Although the corrosion resistance time is greatly improved compared with the silicone-acrylic emulsion without adding graphene, a coating material with higher corrosion resistance is still urgently needed in the practical application process, so that new materials with higher corrosion resistance need to be continuously developed.
Disclosure of Invention
The invention provides a graphene silicone acrylic emulsion corrosion-resistant coating material and a preparation method thereof, and provides a coating material with higher corrosion resistance.
The invention provides a preparation method of a graphene silicone acrylic emulsion corrosion-resistant coating material, which comprises the following steps:
s1, preparing graphene by a Hummers method;
s2, preparing an organic silicon prepolymer;
mixing octamethylcyclotetrasiloxane and KOH, and reacting for 1-1.5 hours at 90-100 ℃ under the condition of stirring; adding a silane coupling agent, dimethyl sulfoxide and hexamethyldisiloxane, and reacting at a constant temperature of 85-95 ℃ for 2.5-3 hours to obtain an organic silicon prepolymer solution;
s3, preparing the graphene silicone acrylic emulsion corrosion-resistant coating material:
s31, uniformly mixing butyl acrylate, methyl acrylate, acrylic acid, styrene, N-hydroxymethyl acrylamide and the organic silicon prepolymer solution prepared by S2 to obtain a mixed monomer;
s32, uniformly mixing distilled water, sodium dodecyl benzene sulfonate, nonylphenol polyoxyethylene ether and diethanol amine to obtain a pre-reaction system;
s33, adding sodium bisulfite and a part of mixed monomer into the pre-reaction system, mixing uniformly, and adding an initiator to obtain an intermediate reaction system; adding graphene into the mixed monomer with the residual volume, and then adding the mixed monomer with the residual volume added with the graphene into the intermediate reaction system to obtain a later-stage reaction system; and finally, adding a silane coupling agent into the later-stage reaction system, and continuing the polymerization reaction to obtain the graphene silicone acrylic emulsion coating material.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, the step of S1 is as follows:
s11, preparing graphene oxide
Into a container placed in an ice-water bath according to a 23 mL: 2 g: sequentially adding 98% concentrated sulfuric acid, graphite powder and sodium nitrate in volume fraction according to the proportion of 1g, stirring for 3-5 minutes, adding potassium permanganate, controlling the temperature of the system to be less than 20 ℃, and reacting for 1.5-2 hours; heating to 35 ℃, and continuing stirring for 25-30 minutes; adding a washing solution, raising the temperature to 98 ℃, and continuously heating for 15-20 minutes; adding hydrogen peroxide with the volume fraction of 30%, uniformly mixing, filtering while hot, taking out a filter cake, and drying to obtain graphene oxide; wherein the proportion of sodium nitrate, potassium permanganate, washing liquid and hydrogen peroxide is 1 g: 6 g: 46mL of: 5 mL;
s12, preparing graphene
Mixing graphene oxide with distilled water according to a ratio of 1 mg: uniformly mixing 1mL of the solution in proportion to obtain a brown yellow suspension, ultrasonically dispersing, dropwise adding a hydrazine hydrate solution with the volume fraction of 80% at 80 ℃, reacting for 24 hours, filtering, washing a filter cake, and drying to obtain graphene, wherein the proportion of the graphene oxide to the hydrazine hydrate solution is 100 mg: 1 mL.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, in S11, the washing solution is prepared from tap water and distilled water according to a ratio of 1:1 in a volume ratio; alternatively, the washing liquid is distilled water.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, the reactions of S11 and S12 are both maintained at the respective required temperatures by means of a water bath.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, methanol, distilled water or a methanol-distilled water mixed solution is used for washing the filter cake in S12.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, in S2, the proportion of octamethylcyclotetrasiloxane, KOH, the silane coupling agent, dimethyl sulfoxide, and hexamethyldisiloxane is 20 mL: 0.10 g: 3mL of: 1mL of: 0.1 mL.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, in S31, an organic silicon prepolymer solution prepared from butyl acrylate, methyl acrylate, acrylic acid, styrene, N-methylolacrylamide and S2 is mixed according to a ratio of 15 mL: 5mL of: 1mL of: 4mL of: 0.5 g: 2mL of the mixture is mixed evenly;
in S32, distilled water, sodium dodecyl benzene sulfonate, nonylphenol polyoxyethylene ether and diethanol amine are mixed according to the proportion of 70 mL: 0.75 g: 0.25 mL: 2mL of the mixture is mixed evenly;
in S33, the dosage ratio of diethanolamine, sodium bisulfite, initiator, graphene and silane coupling agent is 2 mL: 0.1 g: 10mL of: 0.03-0.23 g: 1 mL.
Preferably, in the preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material, the dosage ratio of diethanolamine, sodium bisulfite, initiator, graphene and silane coupling agent in S3 is 2 mL: 0.1 g: 10mL of: 0.16 g: 1 mL.
In S3, the initiator is ammonium persulfate solution of 2g/100mL, and the solvent is distilled water; or the initiator is prepared according to the following method: 0.2g of zinc sulfate solution and 0.05g of zinc sulfate were dissolved in 10mL of distilled water to prepare an initiator.
The invention also provides the graphene silicone acrylic emulsion corrosion-resistant coating material prepared by the method.
Compared with the prior art, the graphene silicone acrylic emulsion corrosion-resistant coating material and the preparation method thereof have the following beneficial effects:
(1) according to the invention, graphene is prepared by adopting a Hummers method, and XRD detection is carried out on graphite powder and graphene, because a strong diffraction peak exists at 26.8 degrees, the spatial arrangement of crystal layers of graphite is regular and smooth, and the peak is within the angle range in the graphite crystal lattice, so that the graphite is obtained. Graphene has a strong diffraction peak at 25.6 degrees, and compared with the XRD diffraction pattern of graphite, the 2 theta angle is shifted to the left, the peak of graphene is widened, the intensity of the peak is weakened, and thus the graphene is single-layer graphite.
(2) By performing infrared spectroscopic analysis on the silicone-acrylate emulsion prepared in the comparative example 1 and the organic silicon prepolymer prepared in the example 1, the silicone-acrylate emulsion and the prepolymer are relatively pure. At 1726cm-1Has a C ═ O stretching vibration peak at 1600cm-1～1700cm-1At this time, no characteristic peak of stretching vibration appears in the C ═ C double bond, indicating that the C ═ C double bond is absent. At 2948cm-1When is treated, appears in-CH3Peak of stretching vibration of 3000cm-1The elastic vibration peak of the C-H bond connected with the C ═ C double bond does not appear in the above, and the emulsion is pure silicone-acrylate emulsion. At 3486cm-1Here, a stretching vibration peak of-OH in the-Si-OH bond appeared at 2963cm-1Occurrence of-CH3Has a peak of stretching vibration of 3004cm-1A stretching vibration peak of C-H bond in C ═ C double bond appears at 1621cm-1The peak appears at 809cm when the expansion vibration peak of C ═ C double bond appears-1The stretching vibration peak of the organic siloxane appears at 1254cm-1The wavelength of (A) is the characteristic spectrum of the organic silicon prepolymer, and the organic silicon prepolymer is obtained.
(3) The determination of acid resistance, alkali resistance and salt resistance shows that the corrosion resistance of the film prepared from the silicone-acrylate emulsion containing the graphene is enhanced compared with the silicone-acrylate emulsion of the comparative example 1, when the film is corroded by acid, alkali and salt, the mass loss of the film is reduced, and when the content of the graphene (the mass fraction of the graphene in the silicone-acrylate emulsion) is 5%, the corrosion resistance is the best. The reason is that the graphene is single-layer compact, when the graphene is added into the silicone-acrylate emulsion, the graphene is uniformly dispersed in the silicone-acrylate emulsion, and the uniformly dispersed graphene forms a reticular physical isolation layer in a prepared membrane to play a role in shielding and protecting. The corrosion resistance of the silicone-acrylic emulsion is enhanced. Through the comparison of three graphs of acid resistance, alkali resistance and salt resistance, the mass loss is less than that of alkali and salt in the detection process of the acid resistance, and the acid resistance is stronger because hydroxide ions in the alkali are attached to the surface of the graphene/silicone-acrylate emulsion coating to enhance the surface activity, so that the graphene/silicone-acrylate emulsion coating is easier to corrode, and the hydrogen ions in the acid are attached to the surface and do not increase the surface activity, so that the acid resistance of the 5% graphene/silicone-acrylate emulsion is optimal.
(4) Through corrosion tests of different samples, the corrosion resistance to acid, alkali and salt of the graphene silicone-acrylic emulsion corrosion-resistant coating material prepared in the embodiments 1-8 is obviously superior to that of the silicone-acrylic emulsion and the prior art. The method of the invention can prepare coating materials with higher corrosion resistance.
Drawings
FIG. 1 is an acid resistance analysis of various samples;
FIG. 2 is an alkali resistance analysis of different samples;
FIG. 3 is a salt tolerance analysis of various samples;
FIG. 4 is a graph of mass loss in acid, base, salt for sample 3;
FIG. 5 is a graph of IR spectroscopy analysis of a silicone-acrylic emulsion prepared in comparative example 1;
FIG. 6 is an infrared spectrum of an organosilicon prepolymer prepared in example 1;
FIG. 7 is an XRD diffraction pattern of graphite powder raw material;
fig. 8 is an XRD diffraction spectrum of graphene prepared by the method of example 1.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the present invention should not be construed as being limited thereto. The test methods in the following examples, which are not specified in specific conditions, are generally conducted under conventional conditions, and the steps thereof will not be described in detail since they do not relate to the invention.
The main reagents D4 (octamethylcyclotetrasiloxane) and silane coupling agents used in the present invention are commercially available silane coupling agents KH570, DMSO (dimethyl sulfoxide), MM (hexamethyldisiloxane), OP-10 (nonylphenol polyoxyethylene ether), and the like.
Example 1
A preparation method of a graphene silicone acrylic emulsion corrosion-resistant coating material comprises the following steps:
s1, preparing graphene by a Hummers method;
s11, preparing graphene oxide
S111, 3/5 of water filled with ice blocks is filled into a 250mL beaker and is placed on a magnetic stirrer; then preparing a dry conical bottle and putting the dry conical bottle into a beaker to prepare an ice-water bath;
s112, measuring 23mL of concentrated sulfuric acid with the volume fraction of 98%, and weighing 2g of graphite powder, 1g of sodium nitrate and 6g of potassium permanganate for later use;
s113, putting the stirring magnetons into the dry conical flask prepared in the S111 by using tweezers, pouring the measured concentrated sulfuric acid into the conical flask, and fixing the conical flask by using an iron stand;
s114, adding the graphite powder and sodium nitrate weighed in the S111 into a conical flask, mixing, stirring and reacting for 3 minutes, and then adding the potassium permanganate weighed in the S111 into the conical flask; controlling the water bath temperature to be less than 20 ℃, and stirring and reacting for 2 hours in a constant-temperature water bath kettle at constant temperature; then heating the water bath to 35 ℃, continuing stirring for 30 minutes at 35 ℃, adding 46mL of washing liquid, heating the water bath to 98 ℃, continuously heating for 20 minutes at 98 ℃, wherein the liquid is brownish yellow and emits red smoke;
wherein, the tap water and the distilled water are mixed according to the volume ratio of 1:1 to prepare a washing liquid which is used after being prepared for 30 minutes;
s115, measuring 5mL of hydrogen peroxide with a volume fraction of 30% and adding the hydrogen peroxide into a brown-yellow conical flask in the S114 liquid, uniformly mixing substances in the conical flask, taking down the conical flask for filtering while the conical flask is hot, washing the conical flask with washing liquid prepared in the S114, taking out a filter cake with tweezers after the residual solid is stabilized on filter paper, lining the bottom of the filter cake with clean filter paper, and drying the filter cake in a drying oven at 60 ℃ for 12 hours to obtain graphene oxide for later use;
s12, preparing graphene
Weighing 200mg of dry graphene oxide by using an analytical balance, pouring the weighed dry graphene oxide into a 250mL beaker, adding 200mL of distilled water to obtain a brown yellow suspension, putting a probe of an ultrasonic instrument into the brown yellow suspension, and performing ultrasonic dispersion for 20 minutes at 450W; putting the solution after ultrasonic dispersion into a water bath kettle, heating the water bath to 80 ℃, then dropwise adding 2mL of 80% hydrazine hydrate solution with volume fraction, and reacting for 24 hours; and then, carrying out suction filtration by using a vacuum pump, washing the filter cake by using methanol and distilled water in sequence, and fully drying the obtained solid in a drying oven at the temperature of 60 ℃ for 12 hours to obtain graphene, and storing for later use.
S2, preparing an organic silicon prepolymer solution;
s21, preparing a dry 250mL three-neck flask, adding 20mL of D4 into the three-neck flask, weighing 0.10g of KOH by using an analytical balance, pouring the KOH into the three-neck flask by using a paper tank, and putting a dry stirring magneton into the three-neck flask; then fixing the three-neck flask on a magnetic stirrer, adjusting the temperature of the magnetic stirrer to 100 ℃, starting magnetic stirring, and reacting for 1 hour at 100 ℃ under the magnetic stirring;
s22, taking a dry 50mL small beaker, adding 3mL KH570, 1mL DMSO and 0.1mL MM, uniformly mixing, adding the mixture into a three-neck flask after S21 reaction for one hour, and reacting at a constant temperature of 90 ℃ for 3 hours to obtain an organic silicon prepolymer solution.
S3, preparing the graphene silicone acrylic emulsion corrosion-resistant coating material:
s31, uniformly mixing 15mL of butyl acrylate, 5mL of methyl acrylate, 1mL of acrylic acid, 4mL of styrene, 0.5g N-hydroxymethyl acrylamide and 2mL of the organic silicon prepolymer solution prepared by S2 to obtain a mixed monomer for later use;
0.2g of ammonium persulfate was dissolved in 10mL of distilled water to prepare an initiator for use.
S32, adding 70mL of distilled water, 0.75g of sodium dodecyl benzene sulfonate, 0.25mL of OP-10 and 2mL of diethanolamine into a clean three-neck flask, uniformly mixing, putting a clean stirring magneton into the three-neck flask, fixing the three-neck flask on a magnetic stirrer, and heating to 60 ℃ under magnetic stirring to obtain a pre-reaction system;
s33, adding 0.1g of sodium bisulfite and a mixed monomer with a half volume (36mL) into the pre-reaction system, uniformly stirring, dropwise adding 10mL of prepared initiator, and observing that a reagent in the three-necked bottle is milky white to obtain an intermediate reaction system; adding 0.03g of graphene into the mixed monomer with the residual volume (36mL), copolymerizing the graphene and the silicone-acrylic emulsion, and then adding the mixed monomer with the residual volume and added with the graphene into the intermediate reaction system to obtain a later-stage reaction system; the mixed monomer added with the residual volume of the graphene is dripped for four times in 20 minutes, and the initiator is dripped for six times in 30 minutes; and finally, adding 1mL of KH-570 into the later-stage reaction system, automatically raising the temperature of the later-stage reaction system to 80-85 ℃, adjusting the temperature of a magnetic stirrer to 85 ℃, keeping the temperature, continuously polymerizing for one and a half hours at a constant temperature, and after the copolymerization is finished, uniformly dispersing the graphene in the silicone-acrylate emulsion to obtain the graphene silicone-acrylate emulsion coating material, wherein the mass fraction of the graphene in the graphene silicone-acrylate emulsion coating material is 1%.
Example 2
A preparation method of a graphene silicone acrylic emulsion corrosion-resistant coating material is disclosed, wherein the mass of graphene added in S33 is 0.1g, and the rest operations are the same as those in example 1; the mass fraction of graphene in the graphene silicone acrylic emulsion coating material prepared in example 2 is 3%.
Example 3
A preparation method of a graphene silicone acrylic emulsion corrosion-resistant coating material is disclosed, wherein the mass of graphene added in S33 is 0.16g, and the rest operations are the same as those in example 1; the mass fraction of graphene in the graphene silicone acrylic emulsion coating material prepared in example 2 is 5%.
Example 4
The preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material is that the mass of graphene added in S33 is 0.23g, and the rest of the operations are the same as those in example 1; the mass fraction of graphene in the graphene silicone acrylic emulsion coating material prepared in example 2 is 7%.
Example 5
A preparation method of a graphene silicone acrylic emulsion corrosion-resistant coating material is disclosed, wherein in S11, the washing liquid is distilled water; in S21, the reaction is carried out for 1.5 hours at 100 ℃ under the magnetic stirring; in S22, reacting at a constant temperature of 90 ℃ for 2.5 hours; the dosage of all reagents is halved; the rest of the procedure was the same as in example 3.
Example 6
The operation of a preparation method of a graphene silicone acrylic emulsion corrosion-resistant coating material is the same as that of example 3, except that the step of S1 is changed to:
s11, preparing graphene oxide
Adding 23mL of 98 volume percent concentrated sulfuric acid, 2g of graphite powder and 1g of sodium nitrate into a triangular conical flask placed in an ice-water bath, stirring for 5 minutes, adding 6g of potassium permanganate, controlling the temperature of the system to be less than 20 ℃, and reacting for 1.5 hours; heating to 35 ℃, and continuing stirring for 25 minutes at 35 ℃; adding 46mL of washing solution, then raising the temperature to 98 ℃, and continuously heating for 15 minutes at 98 ℃; adding 5mL of 30% hydrogen peroxide by volume, uniformly mixing, filtering while hot, taking out a filter cake, and drying in a drying oven at 60 ℃ for 10 hours to obtain graphene oxide;
s12, preparing graphene
Uniformly mixing 200mg of graphene oxide with 200mL of distilled water to obtain a brownish yellow suspension, ultrasonically dispersing for 20 minutes at 400W, dropwise adding 2mL of 80% hydrazine hydrate solution with volume fraction at 80 ℃, reacting for 24 hours, carrying out suction filtration by using a vacuum pump, washing a filter cake by using a methanol-distilled water mixed solution, wherein the volume fraction of methanol in the methanol-distilled water mixed solution is 15%, and drying to obtain the graphene.
Example 7
The operation of a preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material is the same as that of example 6, except that distilled water is used for washing a filter cake in S12.
Example 8
The preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material comprises the following steps: dissolving 0.2g of zinc sulfate solution and 0.05g of zinc sulfate in 10mL of distilled water to prepare an initiator; the rest of the procedure was the same as in example 3.
Comparative example 1
A preparation method of silicone-acrylate emulsion comprises the following steps:
the steps of S1 and S2 are the same as those of example 1, and the step of S3 is as follows:
s31, taking a clean 100mL beaker, adding 15mL of butyl acrylate, 5mL of methyl acrylate, 1mL of acrylic acid, 4mL of styrene, 0.5g N-hydroxymethyl acrylamide and 2mL of the prepared organic silicon prepolymer solution, and uniformly stirring and mixing reagents in the beaker to obtain a mixed monomer for later use;
a new clean small beaker is prepared, 0.2g of ammonium persulfate and 10mL of distilled water are added, stirred to dissolve the ammonium persulfate, and an initiator is prepared for later use.
S32, preparing a 250mL clean three-neck flask, adding 70mL distilled water, 0.75g sodium dodecyl benzene sulfonate, 0.25mL OP-10 and 2mL diethanolamine into the three-neck flask; putting a clean stirring magneton into a three-neck flask, fixing the three-neck flask on a magnetic stirrer, and heating to 60 ℃ under the magnetic stirring;
s33, adding 0.1g of sodium bisulfite and half volume (36mL) of mixed monomers; after stirring and mixing, the initiator prepared in S31 and the residual volume of the mixed monomer (36mL) are added dropwise, the residual volume of the mixed monomer is added dropwise four times in 20 minutes, and the initiator is added dropwise six times in 30 minutes. And after the initiator and the rest of the mixed monomers are dripped, automatically raising the temperature of the system to 80-85 ℃, enabling the reagent in the three-neck flask to be milk white, adjusting the temperature of the magnetic stirrer to 85 ℃, keeping the temperature, and continuously polymerizing for one and a half hours at constant temperature to obtain the silicone-acrylate emulsion.
To verify the effect of the invention, we performed the following series of experiments:
firstly, preparing a film sample
Preparing a clean glass slide, respectively and uniformly coating the silicone-acrylate emulsion prepared by the method in the comparative example 1-2 and the graphene silicone-acrylate emulsion prepared by the method in the embodiment 1-8 on the glass slide, adjusting the temperature of a drying box to 90 ℃, putting the glass slide into the drying box, and drying. Film samples are respectively prepared, and the film samples corresponding to the methods of comparative example 1 and examples 1-8 are respectively named as sample C, sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7 and sample 8. Three parallel experiments were performed for each sample.
Secondly, corrosion resistance detection
(1) Preparing 5mL/100mL hydrochloric acid solution, 5g/100mL sodium hydroxide solution and 3g/100mL sodium chloride solution respectively, soaking the sample C, the sample 1, the sample 2, the sample 3, the sample 4, the sample 5, the sample 6, the sample 7 and the sample 8 in the 5mL/100mL hydrochloric acid solution, the 5g/100mL sodium hydroxide solution or the 3g/100mL sodium chloride solution respectively, and observing the corrosion resistance (the membrane surface is completely corroded) time of different samples in different solutions.
A graphene/silicone-acrylate emulsion composite material prepared by Haobao et al (literature: preparation and performance of graphene and silicone-acrylate emulsion composite material) is subjected to a corrosivity control experiment, and a film sample is formed on the graphene/silicone-acrylate emulsion composite material prepared by the method according to the method in 'I and preparation of film sample', and the method is called as a control group. The results are shown in Table 1.
TABLE 1 Corrosion resistance time of different samples in different solutions
Figure BDA0001829191190000131
Figure BDA0001829191190000141
(2) Respectively preparing 0.5mol/L hydrochloric acid solution, 0.5mol/L sodium hydroxide solution and 0.5mol/L sodium chloride solution, respectively soaking the sample C, the sample 1, the sample 2, the sample 3 and the sample 4 in the 0.5mol/L hydrochloric acid solution, the 0.5mol/L sodium hydroxide solution or the 0.5mol/L sodium chloride solution for 48 hours, taking out the membrane every eight hours, drying and weighing the mass of the membrane, and recording data.
Fig. 1 is an acid resistance analysis of different samples, and it can be observed from the curve trend in fig. 1 that when graphene is added to the silicone-acrylic emulsion, the acid resistance is enhanced, as can be seen from the mass change of the ordinate, and can also be derived from the curve gradient change trend, and it can be found that the silicone-acrylic emulsion containing 5% by mass of graphene (sample 3) has the best acid resistance, because the copolymerization effect of the graphene containing 5% by mass with the silicone-acrylic emulsion is the best, and the network structure uniformly distributed in the film is better, and plays a greater protection role.
Fig. 2 is an analysis of alkali resistance of different samples, and it can be observed from the curve trend in fig. 2 that when graphene is added to silicone-acrylic emulsion, alkali resistance is enhanced because single-layer graphene is uniformly dispersed in the emulsion to play a role of isolation. From the magnitude of the change in mass on the ordinate and from the trend of the change in the slope of the curve, the alkali resistance was the best when the graphene mass fraction was 5% (sample 3).
Fig. 3 is a salt tolerance analysis of different samples, and it can be observed from the trend of the curves in fig. 3 that when graphene is added to the silicone-acrylic emulsion, the salt tolerance is enhanced because the addition of graphene acts as a shield. The best salt tolerance can be obtained from the mass change of the ordinate and the curve gradient change trend, and the graphene content is 5%.
FIG. 4 is a graph of mass loss in acid, base, salt for sample 3. From fig. 4, it can be seen that the acid resistance is the best, and the acid resistance is the most stable in the time period of 16h to 24h, because the hydroxyl ions in the alkali are attached to the surface of the graphene/silicone-acrylate emulsion coating, so that the surface activity is enhanced, and the corrosion is easy, and the hydrogen ions in the acid are attached to the surface without increasing the surface activity, so that the acid resistance of the graphene/silicone-acrylate emulsion is the best.
Infrared spectroscopic analysis of silicone-acrylate emulsion
FIG. 5 is an infrared spectrum analysis chart of the silicone-acrylic emulsion prepared in comparative example 1, and it can be seen from FIG. 5 that the infrared wavelength is 1726cm-1Has a C ═ O stretching vibration peak at 1500cm-1～1600cm-1At this time, no characteristic peak of stretching vibration appears in the C ═ C double bond, indicating that the C ═ C double bond is absent. At 2948cm-1When is treated, appears in-CH3Peak of stretching vibration of 3000cm-1The absence of a stretching vibration peak of the C — H bond linked to the C ═ C double bond in the above indicates that no double bond is present in the silicone-acrylic emulsion,indicating that the polymerization reaction of the organic silicon prepolymer and the acrylic resin is complete. Therefore, the above can be described as a silicone-acrylic emulsion.
Infrared spectroscopic analysis of organosilicon prepolymer
FIG. 6 is an infrared spectrum of the organosilicon prepolymer prepared in example 1. From the observation of FIG. 6, the wavelength was 3486cm-1Here, a stretching vibration peak of-OH in the-Si-OH bond appeared at 2963cm-1Occurrence of-CH3Has a peak of stretching vibration of 3004cm-1A stretching vibration peak of C-H bond in C ═ C double bond appears at 1621cm-1The peak appears at 809cm when the expansion vibration peak of C ═ C double bond appears-1The stretching vibration peak of the organic siloxane appears at 1254cm-1The wavelength of (A) is the characteristic spectrum of the organic silicon prepolymer. The polymer can be obtained by analyzing the infrared spectrum of the organic silicon prepolymer.
XRD diffraction analysis of graphite powder
FIG. 7 is XRD diffraction pattern of graphite powder material, which has strong diffraction peak at 26.8 deg. and regular and smooth spatial arrangement of graphite crystal layer, and the peak is in the angle range of graphite crystal lattice.
Sixthly, XRD diffraction analysis of graphene
Fig. 8 is an XRD diffraction spectrum of the graphene prepared by the method of example 1, in fig. 4, the graphene has a strong diffraction peak at 25.6 °, and compared with the XRD diffraction pattern of graphite, the 2 θ angle is shifted to the left, the peak of the graphene is broadened, and the intensity of the peak is weakened, so that the graphene is a single-layer graphite.
It should be noted that when numerical ranges are given herein, it is understood that both endpoints of each of the numerical ranges and any number between the endpoints are optional unless the invention otherwise specifically states. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material is characterized by comprising the following steps:
s1, preparing graphene by a Hummers method;
s2, preparing an organic silicon prepolymer;
mixing octamethylcyclotetrasiloxane and KOH, and reacting for 1-1.5 hours at 90-100 ℃ under the condition of stirring; adding a silane coupling agent, dimethyl sulfoxide and hexamethyldisiloxane, and reacting at a constant temperature of 85-95 ℃ for 2.5-3 hours to obtain an organic silicon prepolymer solution;
s3, preparing the graphene silicone acrylic emulsion corrosion-resistant coating material:
s31, uniformly mixing butyl acrylate, methyl acrylate, acrylic acid, styrene, N-hydroxymethyl acrylamide and the organic silicon prepolymer solution prepared by S2 to obtain a mixed monomer;
s32, uniformly mixing distilled water, sodium dodecyl benzene sulfonate, nonylphenol polyoxyethylene ether and diethanol amine to obtain a pre-reaction system;
s33, adding sodium bisulfite and a part of mixed monomer into the pre-reaction system, mixing uniformly, and adding an initiator to obtain an intermediate reaction system; adding graphene into the mixed monomer with the residual volume, and then adding the mixed monomer with the residual volume added with the graphene into the intermediate reaction system to obtain a later-stage reaction system; and finally, adding a silane coupling agent into the later-stage reaction system, and continuing the polymerization reaction to obtain the graphene silicone acrylic emulsion coating material.
2. The preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 1, wherein the step of S1 is as follows:
s11, preparing graphene oxide
Into a container placed in an ice-water bath according to a 23 mL: 2 g: sequentially adding 98% concentrated sulfuric acid, graphite powder and sodium nitrate in volume fraction according to the proportion of 1g, stirring for 3-5 minutes, adding potassium permanganate, controlling the temperature of the system to be less than 20 ℃, and reacting for 1.5-2 hours; heating to 35 ℃, and continuing stirring for 25-30 minutes; adding a washing solution, raising the temperature to 98 ℃, and continuously heating for 15-20 minutes; adding hydrogen peroxide with the volume fraction of 30%, uniformly mixing, filtering while hot, taking out a filter cake, and drying to obtain graphene oxide; wherein the proportion of sodium nitrate, potassium permanganate, washing liquid and hydrogen peroxide is 1 g: 6 g: 46mL of: 5 mL;
s12, preparing graphene
Mixing graphene oxide with distilled water according to a ratio of 1 mg: uniformly mixing 1mL of the solution in proportion to obtain a brown yellow suspension, ultrasonically dispersing, dropwise adding a hydrazine hydrate solution with the volume fraction of 80% at 80 ℃, reacting for 24 hours, filtering, washing a filter cake, and drying to obtain graphene, wherein the proportion of the graphene oxide to the hydrazine hydrate solution is 100 mg: 1 mL.
3. The method for preparing the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 2, wherein in S11, the washing solution is prepared from tap water and distilled water according to a ratio of 1:1 in a volume ratio; alternatively, the washing liquid is distilled water.
4. The method for preparing the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 2, wherein the reactions of S11 and S12 are performed by means of water bath to maintain the respective required temperatures.
5. The method for preparing the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 2, wherein the filter cake is washed with methanol, distilled water or methanol-distilled water mixture in S12.
6. The preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 1, wherein in S2, the proportion of octamethylcyclotetrasiloxane, KOH, silane coupling agent, dimethyl sulfoxide and hexamethyldisiloxane is 20 mL: 0.10 g: 3mL of: 1mL of: 0.1 mL. .
7. The method for preparing the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 1, wherein in S31, a solution of a silicone prepolymer prepared from butyl acrylate, methyl acrylate, acrylic acid, styrene, N-methylol acrylamide and S2 is prepared in a ratio of 15 mL: 5mL of: 1mL of: 4mL of: 0.5 g: 2mL of the mixture is mixed evenly;
in S32, distilled water, sodium dodecyl benzene sulfonate, nonylphenol polyoxyethylene ether and diethanol amine are mixed according to the proportion of 70 mL: 0.75 g: 0.25 mL: 2mL of the mixture is mixed evenly;
in S33, the dosage ratio of diethanolamine, sodium bisulfite, initiator, graphene and silane coupling agent is 2 mL: 0.1 g: 10mL of: 0.03-0.23 g: 1 mL.
8. The preparation method of the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 7, wherein the dosage ratio of diethanolamine, sodium bisulfite, initiator, graphene and silane coupling agent in S3 is 2 mL: 0.1 g: 10mL of: 0.16 g: 1 mL.
9. The method for preparing the graphene silicone acrylic emulsion corrosion-resistant coating material according to claim 6, wherein the initiator in S3 is a 2g/100mL ammonium persulfate solution, and the solvent is distilled water.
10. The graphene silicone acrylic emulsion corrosion-resistant coating material prepared by the method according to any one of claims 1-9.
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