CN111574857B - A kind of graphene-based nanocomposite anti-corrosion coating and preparation method - Google Patents
A kind of graphene-based nanocomposite anti-corrosion coating and preparation method Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 claims abstract 17
- 239000002114 nanocomposite Substances 0.000 claims abstract 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 16
- 238000000034 method Methods 0.000 claims abstract 7
- 239000003822 epoxy resin Substances 0.000 claims abstract 5
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims abstract 5
- 229920000647 polyepoxide Polymers 0.000 claims abstract 5
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims abstract 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 8
- 239000003973 paint Substances 0.000 claims 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 238000003756 stirring Methods 0.000 claims 3
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 claims 3
- 238000001291 vacuum drying Methods 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000002390 rotary evaporation Methods 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- -1 gamma-aminopropyltriethoxysilane modified graphene Chemical class 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000007142 ring opening reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract 4
- 238000000576 coating method Methods 0.000 abstract 4
- 238000005260 corrosion Methods 0.000 abstract 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229920006334 epoxy coating Polymers 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
本发明属于环氧涂料防腐技术领域，提供了一种石墨烯基纳米复合体防腐涂料及制备方法，主旨在于提高纳米填料在环氧树脂中的分散性。该方法主要包括：首先利用将γ‑氨丙基三乙氧基硅烷修饰氧化石墨烯表面，然后通过π‑π堆叠与苯基倍半硅氧烷修饰Fe3O4复合，所得苯基倍半硅氧烷‑石墨烯磁性纳米复合体分散液被加入到环氧树脂中并固化得到基于苯基倍半硅氧烷‑石墨烯磁性纳米复合体的防腐涂料。本发明为无溶剂型防腐涂料体系，所含纳米复合体能在涂料中稳定均匀分散；同时纳米复合体上预留的活性基团与环氧树脂交联形成互穿网状结构，有效阻止了石墨烯在使用过程中发生团聚。本发明改善了石墨烯在聚合物基质中的分散性。
The invention belongs to the technical field of epoxy coating anti-corrosion, and provides a graphene-based nano-composite anti-corrosion coating and a preparation method, which mainly aim to improve the dispersibility of nano-filler in epoxy resin. The method mainly includes: firstly using γ-aminopropyl triethoxysilane to modify the surface of graphene oxide, and then by π-π stacking and phenyl silsesquioxane to modify Fe 3 O 4 to compound, the obtained phenyl sesquioxane is obtained. The siloxane-graphene magnetic nanocomposite dispersion was added to epoxy resin and cured to obtain an anti-corrosion coating based on the phenylsilsesquioxane-graphene magnetic nanocomposite. The invention is a solvent-free anti-corrosion coating system, and the nanocomposite contained can be stably and uniformly dispersed in the coating; at the same time, the active groups reserved on the nanocomposite are cross-linked with the epoxy resin to form an interpenetrating network structure, which effectively prevents the graphite The alkene agglomerates during use. The present invention improves the dispersibility of graphene in the polymer matrix.
Description
Technical Field
The invention belongs to the technical field of epoxy coating anticorrosion, and particularly relates to a graphene-based nano composite anticorrosion coating and a preparation method thereof.
Background
Epoxy coatings have been widely used as corrosion resistant coatings for metal structures to resist corrosive substances such as oxygen, water, chloride ions, and the like. However, the micropores caused by the evaporation of the solvent during the curing of the epoxy resin become paths through which the electrolyte solution penetrates, so that the coating has poor corrosion resistance. To address this problem, nanofillers may be added to organic coatings to enhance their barrier properties and corrosion resistance. The nanofiller is capable of blocking micropores and cavities present in the coating matrix and reducing the diffusion of electrolyte to the coating/metal interface through tortuous electrolyte paths. In addition, the surface functionalization of the nano particles can increase the crosslinking density of the coating and further enhance the barrier property of the coating. In general, nanoparticles tend to agglomerate in epoxy resins, resulting in interfacial defects. Polyhedral oligomeric silsesquioxanes (POSS) have a synergistic effect of the compositional properties of organic and inorganic materials due to the nanostructured features of organic/inorganic hybrids, and can retain the original properties of modified epoxy resins to some extent. Therefore, the enhancement of the epoxy crosslinked network by the introduction of POSS is an effective means of modification. With POSS as a network crosslink, the polymer network can be reinforced by increasing crosslink density and blockiness of the rigid domains around the POSS units.
The presence of Graphene Oxide (GO) hydrophilic groups gives it excellent affinity for epoxy resins. The incorporation of GO into the epoxy matrix can enhance the mechanical properties, thermal stability and corrosion resistance of the epoxy resin, however, GO nanoplates have a tendency to self-polymerize in the polymer matrix due to high surface area and strong van der waals forces. To improve the interaction between the nanofiller interfaces in the polymer matrix, covalent and non-covalent modification of the GO nanoplates is required.
Therefore, the introduction of novel nanocomposites to improve nanofiller dispersibility in epoxy resins remains a challenge of current research value.
Disclosure of Invention
The invention provides a graphene-based nano-composite anticorrosive paint and a preparation method thereof, the prepared phenyl silsesquioxane-graphene magnetic nano-composite has good dispersibility in epoxy resin, can effectively improve crosslinking density and increase barrier property, thereby enhancing the anticorrosive property of the paint, and the composite paint has no solvent, is environment-friendly and is convenient to store, sell and use.
In order to achieve the purpose, the detailed process of the technical scheme of the invention comprises the following steps:
(1) introducing argon into a 500ml two-neck round-bottom flask for 10min, adding 12ml (0.05mol) phenyl triethoxy silicon, dropwise adding an acetic acid aqueous solution (0.1-5 wt%) by using a dropping funnel under an ice bath condition, reacting for 2-12h, placing the obtained transparent solution at-5-22 ℃ to obtain white precipitate, performing suction filtration and vacuum drying to obtain phenyl silanetriol;
(2) heating the phenyl silanetriol prepared in the step (1) and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane (the mass fraction of the phenyl silanetriol is 20% -70%) in ethanol to 40-100 ℃, hydrolyzing for 1-6h, performing rotary evaporation to dryness, adding acetone to dissolve, performing rotary evaporation again to dryness, and performing vacuum drying to obtain phenyl silsesquioxane;
(3) the phenyl silsesquioxane prepared in the step (2) and the gamma-aminopropyltriethoxysilane modified Fe3O4(the weight percentage of the phenyl silsesquioxane is 10-90%) is heated to 40-100 ℃ in 100ml acetone and mechanically stirred for 2-24h, magnetically separated and washed with acetone for three times, and dried in vacuum to obtain Fe3O4@POSS；
(4) Using 10ml acetone as solvent, preparing Fe by the step (3)3O4@ POSS and gamma-aminopropyltriethoxysilane modified graphene oxide (Fe)3O4The mass fraction of @ POSS is 10% -90%), and then the mixture is subjected to ultrasonic treatment for 1-12h to obtain the phenyl silsesquioxane-graphene magnetic nano complex (Fe)3O4@POSS/GO）；
(5) Fe prepared in the step (4) is added3O4@ POSS/GO (with the mass fraction of 0.1wt% -2wt%) is added with a small amount of acetone for ultrasonic dispersion for 1-2h, and then added into 25g of epoxy resin, and mechanically stirred for dispersion for 20-30 min. Vacuumizing for 15-30min to remove acetone, taking out, adding a curing agent (the mass fraction is 10-35 wt%) under mechanical stirring, stirring for 5-15min, placing in a vacuum oven to remove bubbles, coating on a tin plate, and finally curing at 40-60 ℃ for 1-2h, 70-85 ℃ for 1-2h and 90-110 ℃ for 1-3 h;
preferably, the Fe3O4@ POSS/GO is 0.3wt% in the epoxy resin.
Preferably, the mass fraction of the curing agent D230 in the epoxy resin is 28 wt%.
The graphene-based nano complex anticorrosive paint preferably prepared by the invention is a solvent-free paint system, the paint fineness is less than 30 micrometers, and the water content of a paint film is less than 1%.
Compared with the prior art, the Fe prepared by the invention3O4The @ POSS/GO nano complex contains epoxy and amino active groups, can be used as a crosslinking point of epoxy resin to reinforce a crosslinking network and changeThe dispersibility of the nano filler is improved, and meanwhile, the composite is in a hydrophobic three-dimensional structure, so that the barrier property of the coating can be improved. The obtained anticorrosive paint based on the phenyl silsesquioxane-graphene magnetic nano complex does not contain an organic solvent, the fineness of the nano filler in the paint is 12 microns, the water content of a paint film after curing is lower than 1%, and the anticorrosive paint is convenient to spray and use, and is green and environment-friendly.
Drawings
FIG. 1 is a schematic representation of the preparation of a phenylsilsesquioxane of the present invention;
FIG. 2 shows Fe of the present invention3O4@ POSS preparation scheme;
FIG. 3 shows Fe of the present invention3O4The structure schematic diagram of @ POSS/GO;
FIG. 4 is a schematic view of the appearance of the composite coating and coating prepared according to the present invention;
FIG. 5 is a TGA profile of a composite coating paint film prepared according to example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
(1) Preparation of phenyl silsesquioxane
Argon is introduced into a 500ml two-neck round-bottom flask for 10min, 12ml (0.05mol) of phenyl triethoxy silicon is added, 5.4g of acetic acid aqueous solution (1.8 wt%) is dropwise added by a dropping funnel under an ice bath condition, then the reaction is carried out for 4h, the obtained transparent solution is refrigerated at 4 ℃, white precipitate appears after overnight, and phenyl silanetriol is obtained by vacuum filtration and drying. Heating 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and phenyl silanetriol according to the molar ratio of 1:2 in ethanol to 80 ℃, hydrolyzing for 2h, carrying out rotary evaporation to dryness, adding acetone to dissolve, carrying out rotary evaporation again to dryness, and carrying out vacuum drying to obtain white solid phenyl silsesquioxane. The preparation process is shown in figure 1.
（2）Fe3O4Preparation of @ POSS
0.2g of phenyl silsesquioxane and 0.2g of gamma-aminopropyltriethoxysilane modified Fe are taken3O4Dissolving with 100ml acetone, reacting at 80 deg.C under the protection of argon gas with mechanical stirring for 12h, and magnetically separatingWashing with acetone for three times, and vacuum drying to obtain Fe3O4@ POSS. The preparation process is shown in figure 2.
（3）Fe3O4Preparation of @ POSS/GO
0.3g Fe in 10ml acetone solvent3O4Mixing @ POSS with 0.3g of gamma-aminopropyltriethoxysilane modified GO (graphene oxide colloid), and carrying out ultrasonic treatment for 6h to obtain Fe3O4@ POSS/GO, whose structure is shown in FIG. 3.
(4) Preparation of anticorrosive paint based on phenyl silsesquioxane-graphene magnetic nano complex
And (3) ultrasonically treating the tinplate with ethanol and acetone in sequence, and then drying the tinplate in an oven for later use. Subsequently, 0.025gFe3O4@ POSS/GO is added into 5ml of acetone for ultrasonic dispersion for 1 hour, then added into 25g of epoxy resin, and mechanically stirred and dispersed for 30 min. Vacuumizing for 15min to remove acetone, taking out, adding 7g of curing agent D230 under mechanical stirring, stirring for reacting for 5min, placing in a vacuum oven to remove bubbles, coating on a tin plate, and finally curing at 50 ℃ for 1h, at 80 ℃ for 2h and at 100 ℃ for 1 h. The composite coating and paint film are shown in FIG. 4.
Example 2
Example 2 was the same as example 1, except that Fe3O4@ POSS/GO is 0.075 g.
Example 3
Example 3 operates the same as example 1, the only difference being Fe3O4@ POSS/GO is 0.125 g.
The anti-corrosive paint films of graphene-based nanocomposite prepared in examples 1-3 were subjected to salt spray resistance evaluation, and the test was performed according to GB/T1771 for an experimental period of 10 days using a 5wt% aqueous solution of sodium chloride as a salt spray reagent. The results are shown in Table 1.
The moisture content of the composite coating paint film prepared in example 3 was measured by TGA as shown in figure 5. The loss of mass at 150 ℃ is due to the water content of the paint film itself, which means that the moisture content of the paint film is less than 1%, and the epoxy resin is decomposed into carbon dioxide and moisture at a temperature of 335 ℃ and 440 ℃ resulting in a rapid loss of paint film mass and finally a carbon chain skeleton remains.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Table-composite coating salt spray resistance evaluation
| Sample (I) | Resistance to salt spray (10) |
| Example 1 | The paint film has smooth surface and rust lines only appear at the scratched part |
| Example 2 | The paint film has smooth surface and rust lines only appear at the scratched part |
| Example 3 | The paint film has smooth surface and rust lines only appear at the scratched part |
Claims (10)
1. A preparation method of a graphene-based nanocomposite is characterized by comprising the following steps:
dropwise adding an acetic acid aqueous solution with the mass fraction of 0.1-5wt% into phenyl triethoxy silicon under the ice bath condition in the step (1), stirring for reacting for 2-12h, then placing at-5-22 ℃ to obtain white precipitate, performing suction filtration and vacuum drying to obtain phenyl silanetriol;
step (2) heating the phenyl silanetriol prepared in the step (1) and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane in ethanol to 40-100 ℃, hydrolyzing for 1-6h, performing rotary evaporation to dryness, adding acetone to dissolve, performing rotary evaporation again to dryness, and performing vacuum drying to obtain phenyl silsesquioxane;
step (3) the phenyl silsesquioxane prepared in the step (2) is preparedFe modified by alkyl and gamma-aminopropyltriethoxysilane3O4Heating to 40-100 deg.C in acetone, mechanically stirring for 2-24h, magnetically separating, washing with acetone for three times, and vacuum drying to obtain Fe3O4@POSS；
Step (4) taking acetone as a solvent, and mixing the Fe prepared in the step (3)3O4Mixing the @ POSS and gamma-aminopropyltriethoxysilane modified graphene oxide, and performing ultrasonic treatment for 1-12h to obtain phenyl silsesquioxane-graphene magnetic nano complex Fe3O4@POSS/GO。
2. The method of claim 1, wherein the graphene-based nanocomposite comprises: the phenyl silsesquioxane is a double-epoxy double-layer cage-shaped silsesquioxane derivative.
3. The method of claim 1, wherein the graphene-based nanocomposite comprises: said Fe3O4@ POSS is Fe3O4The surface amino and the phenyl silsesquioxane epoxy group are in ring-opening coupling to form a three-dimensional structure.
4. The method of claim 1, wherein the graphene-based nanocomposite comprises: said Fe3O4The @ POSS/GO is the compound Fe of gamma-aminopropyltriethoxysilane-modified graphene oxide through pi-pi stacking effect3O4The spatial three-dimensional structure formed by the @ POSS.
5. The method of claim 1, wherein the graphene-based nanocomposite comprises: in the step (2), the mass fraction of the phenyl silanetriol is 20-70%.
6. The method of claim 1, wherein the graphene-based nanocomposite comprises: in the step (3), the mass fraction of the phenyl silsesquioxane is 10-90%.
7. The method of claim 1, wherein the graphene-based nanocomposite comprises: fe in step (4)3O4The mass fraction of @ POSS is 10-90%.
8. A graphene-based nanocomposite anticorrosive paint prepared by using the graphene-based nanocomposite according to any one of claims 1 to 7, wherein: fe prepared in the step (4) is added3O4Adding a small amount of acetone into the @ POSS/GO to perform ultrasonic dispersion for 1-2h, then adding the mixture into epoxy resin, and mechanically stirring and dispersing for 20-30 min; vacuumizing for 15-30min to remove acetone, and obtaining the anticorrosive paint.
9. The graphene-based nanocomposite anticorrosive paint according to claim 8, wherein: the anticorrosive paint is a solvent-free system, the fineness of the paint is less than 30 micrometers, and the moisture content of a paint film is less than 1%.
10. The graphene-based nanocomposite anticorrosive paint according to claim 8, wherein: said Fe3O4The @ POSS/GO nano composite accounts for 0.1-2% of the mass of the epoxy resin, and the curing agent accounts for 10-35%.
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