CN116199890A - Styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin and preparation method and application thereof - Google Patents
Styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin and preparation method and application thereof Download PDFInfo
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- CN116199890A CN116199890A CN202211619911.3A CN202211619911A CN116199890A CN 116199890 A CN116199890 A CN 116199890A CN 202211619911 A CN202211619911 A CN 202211619911A CN 116199890 A CN116199890 A CN 116199890A
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- graphene oxide
- styrene
- maleic anhydride
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- functionalized graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
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- 229920000147 Styrene maleic anhydride Polymers 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
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- 239000011347 resin Substances 0.000 title claims abstract description 44
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
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- -1 acrylic ester Chemical class 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 2
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
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- 229910052751 metal Inorganic materials 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, and a preparation method and application thereof. According to the preparation method, partial unsaturated monoacid and epoxy resin serving as reactants are added to serve as diluents, so that anhydride groups on the styrene-maleic anhydride copolymer functionalized graphene oxide react with hydroxyl groups on acrylate monomers, the anhydride is opened to generate carboxylic acid groups, the subsequent reaction of carboxylic acid and epoxy is participated, and finally the epoxy resin is blocked by carboxylic acid, so that the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is obtained. The cured film obtained by curing the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin has excellent barrier property, lower surface energy, better corrosion resistance and excellent mechanical property, and the reaction adopts a one-pot method, so that the preparation process is simple, and the raw material utilization rate is high.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, and a preparation method and application thereof.
Background
As an important component of modern materials, metals and their alloys are widely used in national defense, transportation, chemical industry, daily life and the like. However, metals are also susceptible to corrosion by the corrosive medium in complex working environments. It is counted that metal equipment and materials scrapped due to corrosion account for 20% -40% of the annual production per year, which brings great losses to the economic development of the country. The corrosion problem caused by the marine environment to the metal is more serious, and seawater and sea wind contain a large amount of NaCl and MgCl 2 And the like, and affects the safety and long-term effect of ships and marine facilities for a long time.
Generally, a method for corrosion protection of metals mainly comprises: improving the structure and the components of the metal material, adding corrosion inhibitor, electrochemical protection, surface coating protection and the like. Wherein, the organic coating is coated on the metal surface, the technology is mature, the operation is simple, the construction is convenient, and the method becomes one of the most commonly used ocean anticorrosion technologies at present. In order to improve the corrosion resistance of the paint, the epoxy vinyl resin is added with a proper amount of inorganic nano particles to delay or shield the penetration of corrosive media. Wherein, because of the unique single-layer hexagonal honeycomb lattice-like carbon atom array structure of graphene, each carbon atom is sp2 hybridized, which endows the graphene with excellent performances such as electric conductivity, thermal conductivity, mechanical property, permeation resistance and the like. In the current scheme, the modified graphene oxide is blended with various polymers through a solvent, and then the solvent is removed, so that the modified graphene oxide is uniformly dispersed in the polymers. This not only results in serious waste, but also restricts the improvement of the composite material performance.
Disclosure of Invention
The first object of the invention is to provide a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, the second object of the invention is to provide a preparation method of the resin, and the third object of the invention is to provide application of the resin.
According to a first aspect of the present invention, there is provided a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin having the structural formula:
In some embodiments, the composition of the raw materials comprises, in parts by weight: 40-55 parts of epoxy resin, 10-20 parts of unsaturated monoacid, 1-3 parts of acrylate monomer, 5-10 parts of styrene-maleic anhydride copolymer, 0.01-0.1 part of modified graphene oxide, 25-33 parts of reactive diluent, 0.001-0.01 part of polymerization inhibitor and 0.004-0.04 part of catalyst.
In some embodiments, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin having an epoxy equivalent weight of 230-340 g/mol; the unsaturated monobasic acid is selected from one or more of acrylic acid, methacrylic acid and butenoic acid; the acrylate monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate.
In some embodiments, the catalyst is selected from one or more of benzyltriethylammonium chloride, triethylamine, diethylamine, triphenylphosphine; the polymerization inhibitor is selected from one or more of hydroquinone, p-tert-butyl catechol and catechol; the reactive diluent is selected from one or more of styrene, alpha-methyl styrene and methyl acrylate.
In some embodiments, the styrene-maleic anhydride copolymer has a molecular weight of 5000 to 10000 and an anhydride content of 20 to 35%; the modified graphene oxide is obtained by functionalizing graphene oxide with 3-aminopropyl triethoxysilane.
In some embodiments, the method of preparing the modified graphene oxide comprises the steps of:
dispersing graphene oxide and 3-aminopropyl triethoxysilane in absolute ethyl alcohol to obtain a mixed solution, heating the mixed solution to 79-95 ℃, stirring and refluxing for 3-5 hours, adding water in the stirring process, centrifuging a reaction product after the reaction is finished, removing supernatant, and washing the obtained precipitate to obtain the graphene oxide-3-aminopropyl triethoxysilane.
In some embodiments, graphene oxide and 3-aminopropyl triethoxysilane are dispersed in absolute ethanol by sonication for 30 min.
In some embodiments, the resulting modified graphene oxide is milled to yield a modified graphene oxide solid powder.
According to a second aspect of the present invention, there is provided a method for preparing the above styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, comprising the steps of:
the preparation method comprises the steps of firstly, carrying out covalent grafting on a styrene-maleic anhydride copolymer and modified graphene oxide to obtain styrene-maleic anhydride copolymer functionalized graphene oxide, then uniformly stirring epoxy resin, the styrene-maleic anhydride copolymer functionalized graphene oxide, a polymerization inhibitor and 30% -40% of unsaturated monoacid at 70-90 ℃, then adding an acrylic ester monomer and 30% -40% of catalyst, reacting for 3-4h, then adding the rest unsaturated monoacid and the catalyst, uniformly stirring, then heating to 100-120 ℃ for reacting until the acid value is reduced to below 10mgKOH/g, then cooling to 70-90 ℃, adding an active diluent, and uniformly mixing to obtain the modified graphene oxide.
According to the invention, partial reactant unsaturated monobasic acid and epoxy resin are added to serve as diluents, so that an anhydride group on the styrene-maleic anhydride copolymer functionalized graphene oxide reacts with a hydroxyl group on an acrylic ester monomer, and the anhydride is opened to generate a carboxylic acid group, thereby participating in the subsequent reaction of carboxylic acid and epoxy. And finally, capping the epoxy resin with carboxylic acid to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin.
In some embodiments, the method of preparing styrene-maleic anhydride copolymer functionalized graphene oxide comprises the steps of:
and (3) dissolving the styrene-maleic anhydride copolymer and the modified graphene oxide in a solvent to obtain a mixed solution, condensing and refluxing the mixed solution at 70-90 ℃ for 10-30 hours, and removing the solvent in a reaction product after the reaction is finished to obtain the modified graphene oxide.
In some embodiments, the solvent is selected from one or more of acetone, butanone, dimethyl carbonate, toluene, ethylene glycol methyl ether acetate.
In some embodiments, the solvent is removed by rotary evaporation.
In some embodiments, the resulting styrene-maleic anhydride copolymer functionalized graphene oxide is milled to yield a styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.
According to a third aspect of the invention, there is provided the use of the above styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin in the preparation of marine anti-corrosion coating. The heavy anti-corrosion coating is particularly used as heavy anti-corrosion coating for the surfaces of steel structures or concrete of marine engineering facilities such as offshore platforms, ship oil pipelines, large-scale pressure steel pipes of hydropower stations, wharf steel piles, bridges, gates, ballast water tanks, gas pipes, sewage treatment tanks, buried pipelines and the like.
The beneficial effects of the invention include:
(1) According to the invention, the styrene-maleic anhydride copolymer is used as an intermediate, and graphene oxide is uniformly dispersed in vinyl ester resin through covalent reaction, so that the corrosion resistance of the resin is greatly improved. According to the invention, the graphene oxide is grafted and modified by the styrene-maleic anhydride copolymer, so that the crosslinking density of the resin and the dispersibility of the graphene oxide in the resin are increased.
(2) The cured film obtained by curing the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin has excellent barrier property, lower surface energy, better corrosion resistance and excellent mechanical property, and the reaction adopts a one-pot method, so that the preparation process is simple, and the raw material utilization rate is high.
Drawings
FIG. 1 is a graph showing the frequency-impedance modulus at 25 μm film thickness of tinplate coated with different resins, respectively, in the experiments of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto. The starting materials referred to in the examples below are all available from commercial sources.
In the examples below, styrene-maleic anhydride copolymers having a molecular weight of 5000-10000 and an anhydride content of 20-35% were used.
Example 1
The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin comprises the following steps:
(1) Dispersing 0.15g of Graphene Oxide (GO) and 3.00g of 3-aminopropyl triethoxysilane (APTES) in 135mL of absolute ethyl alcohol by ultrasonic treatment for 30min to obtain a mixed solution, heating the mixed solution to 80 ℃, stirring and refluxing for 4 hours, slowly adding 12mL of deionized water in the continuous stirring process, centrifuging a reaction product at 9000rpm for 10min after the reaction is finished, removing supernatant, washing the obtained precipitate with the absolute ethyl alcohol for more than 3 times, and finally drying and grinding the washed precipitate to obtain the modified graphene oxide (AGO) solid powder.
(2) And dissolving 20.00g of styrene-maleic anhydride copolymer and 0.0500g of modified graphene oxide in 20g of dimethyl carbonate to obtain a mixed solution, condensing and refluxing the mixed solution at 80 ℃ for 20 hours, removing a solvent from a reaction product through rotary evaporation after the reaction is finished, and grinding the rest solid matters to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.
(3) Into a three-neck flask with mechanical stirring, 20.00g of epoxy resin, 3.00g of acrylic acid, a polymerization inhibitor hydroquinone accounting for 0.028% of the total mass of raw materials and 3.12g of styrene-maleic anhydride copolymer functionalized graphene oxide powder are put into the three-neck flask, the reaction temperature is set to 80 ℃, after stirring uniformly, 0.0160g of catalyst triphenylphosphine and 0.51g of hydroxyethyl acrylate are added, and the reaction is continued for 4 hours. Then adding 3.34g of acrylic acid and 0.1500g of catalyst benzyl triethyl ammonium chloride, stirring uniformly, heating to 110 ℃ for reaction until the acid value is reduced to below 10mgKOH/g, cooling to 80 ℃, and finally adding 12.80g of active diluent styrene until the mixture is uniformly mixed, thus obtaining the catalyst.
Example 2
The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin comprises the following steps:
(1) Dispersing 0.15g of Graphene Oxide (GO) and 3.00g of 3-aminopropyl triethoxysilane (APTES) in 135mL of absolute ethyl alcohol by ultrasonic treatment for 30min to obtain a mixed solution, heating the mixed solution to 80 ℃, stirring and refluxing for 4 hours, slowly adding 12mL of deionized water in the continuous stirring process, centrifuging a reaction product at 9000rpm for 10min after the reaction is finished, removing supernatant, washing the obtained precipitate with the absolute ethyl alcohol for more than 3 times, and finally drying and grinding the washed precipitate to obtain the modified graphene oxide (AGO) solid powder.
(2) And dissolving 20.00g of styrene-maleic anhydride copolymer and 0.0250g of modified graphene oxide in 20g of dimethyl carbonate to obtain a mixed solution, condensing and refluxing the mixed solution at 80 ℃ for 20 hours, removing a solvent from a reaction product through rotary evaporation after the reaction is finished, and grinding the rest solid matters to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.
(3) Into a three-neck flask with mechanical stirring, 20.00g of epoxy resin, 3.00g of acrylic acid, a polymerization inhibitor hydroquinone accounting for 0.028% of the total mass of raw materials and 3.12g of styrene-maleic anhydride copolymer functionalized graphene oxide powder are put into the three-neck flask, the reaction temperature is set to 80 ℃, after stirring uniformly, 0.016g of catalyst triphenylphosphine and 0.51g of hydroxyethyl acrylate are added, and the reaction is continued for 4 hours. Then adding 3.34g of acrylic acid and 0.15g of catalyst benzyl triethyl ammonium chloride, stirring uniformly, heating to 110 ℃ for reaction until the acid value is reduced to below 10mgKOH/g, cooling to 80 ℃, and finally adding 12.80g of active diluent styrene until the mixture is uniformly mixed, thus obtaining the catalyst.
Example 3
The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin comprises the following steps:
(1) Dispersing 0.15g of Graphene Oxide (GO) and 3.00g of 3-aminopropyl triethoxysilane (APTES) in 135mL of absolute ethyl alcohol by ultrasonic treatment for 30min to obtain a mixed solution, heating the mixed solution to 80 ℃, stirring and refluxing for 4 hours, slowly adding 12mL of deionized water in the continuous stirring process, centrifuging a reaction product at 9000rpm for 10min after the reaction is finished, removing supernatant, washing the obtained precipitate with the absolute ethyl alcohol for more than 3 times, and finally drying and grinding the washed precipitate to obtain the modified graphene oxide (AGO) solid powder.
(2) And dissolving 20.00g of styrene-maleic anhydride copolymer and 0.0250g of modified graphene oxide in 20g of dimethyl carbonate to obtain a mixed solution, condensing and refluxing the mixed solution at 80 ℃ for 20 hours, removing a solvent from a reaction product through rotary evaporation after the reaction is finished, and grinding the rest solid matters to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.
(3) Into a three-neck flask with mechanical stirring, 20.00g of epoxy resin, 3.00g of acrylic acid, a polymerization inhibitor hydroquinone accounting for 0.028% of the total mass of raw materials and 4.28g of styrene-maleic anhydride copolymer functionalized graphene oxide powder are put into the three-neck flask, the reaction temperature is set to 80 ℃, after stirring uniformly, 0.016g of catalyst triphenylphosphine and 0.51g of hydroxyethyl acrylate are added, and the reaction is continued for 4 hours. Then adding 3.34g of acrylic acid and 0.15g of catalyst benzyl triethyl ammonium chloride, stirring uniformly, heating to 110 ℃ for reaction until the acid value is reduced to below 10mgKOH/g, cooling to 80 ℃, and finally adding 12.80g of active diluent styrene until the mixture is uniformly mixed, thus obtaining the catalyst.
Example 4
The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin comprises the following steps:
(1) Dispersing 0.15g of Graphene Oxide (GO) and 3.00g of 3-aminopropyl triethoxysilane (APTES) in 135mL of absolute ethyl alcohol by ultrasonic treatment for 30min to obtain a mixed solution, heating the mixed solution to 80 ℃, stirring and refluxing for 4 hours, slowly adding 12mL of deionized water in the continuous stirring process, centrifuging a reaction product at 9000rpm for 10min after the reaction is finished, removing supernatant, washing the obtained precipitate with the absolute ethyl alcohol for more than 3 times, and finally drying and grinding the washed precipitate to obtain the modified graphene oxide (AGO) solid powder.
(2) 20.00g of styrene-maleic anhydride copolymer and 0.0735g of modified graphene oxide are dissolved in 20g of dimethyl carbonate to obtain a mixed solution, the mixed solution is condensed and refluxed for 20h at 80 ℃, after the reaction, the solvent is removed from the reaction product by rotary evaporation, and the rest solid matters are ground to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.
(3) Into a three-neck flask with mechanical stirring, 20.00g of epoxy resin, 3.00g of acrylic acid, a polymerization inhibitor hydroquinone accounting for 0.028% of the total mass of raw materials and 3.12g of styrene-maleic anhydride copolymer functionalized graphene oxide powder are put into the three-neck flask, the reaction temperature is set to 80 ℃, after stirring uniformly, 0.016g of catalyst triphenylphosphine and 0.51g of hydroxyethyl acrylate are added, and the reaction is continued for 4 hours. Then adding 3.34g of acrylic acid and 0.15g of catalyst benzyl triethyl ammonium chloride, stirring uniformly, heating to 110 ℃ for reaction until the acid value is reduced to below 10mgKOH/g, cooling to 80 ℃, and finally adding 12.80g of active diluent styrene until the mixture is uniformly mixed, thus obtaining the catalyst.
Example 5
The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin comprises the following steps:
(1) Dispersing 0.15g of Graphene Oxide (GO) and 3.00g of 3-aminopropyl triethoxysilane (APTES) in 135mL of absolute ethyl alcohol by ultrasonic treatment for 30min to obtain a mixed solution, heating the mixed solution to 80 ℃, stirring and refluxing for 4 hours, slowly adding 12mL of deionized water in the continuous stirring process, centrifuging a reaction product at 9000rpm for 10min after the reaction is finished, removing supernatant, washing the obtained precipitate with the absolute ethyl alcohol for more than 3 times, and finally drying and grinding the washed precipitate to obtain the modified graphene oxide (AGO) solid powder.
(2) 20.00g of styrene-maleic anhydride copolymer and 0.0735g of modified graphene oxide are dissolved in 20g of dimethyl carbonate to obtain a mixed solution, the mixed solution is condensed and refluxed for 20h at 80 ℃, after the reaction, the solvent is removed from the reaction product by rotary evaporation, and the rest solid matters are ground to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.
(3) Into a three-neck flask with mechanical stirring, 20.00g of epoxy resin, 3.00g of acrylic acid, a polymerization inhibitor hydroquinone accounting for 0.028% of the total mass of raw materials and 4.28g of styrene-maleic anhydride copolymer functionalized graphene oxide powder are put into the three-neck flask, the reaction temperature is set to 80 ℃, after stirring uniformly, 0.016g of catalyst triphenylphosphine and 0.51g of hydroxyethyl acrylate are added, and the reaction is continued for 4 hours. Then adding 3.34g of acrylic acid and 0.15g of catalyst benzyl triethyl ammonium chloride, stirring uniformly, heating to 110 ℃ for reaction until the acid value is reduced to below 10mgKOH/g, cooling to 80 ℃, and finally adding 12.80g of active diluent styrene until the mixture is uniformly mixed, thus obtaining the catalyst.
Comparative example 1
Epoxy glass flake paint (IPN 8710 type, manufactured by Cangzhou Jiasheng paint Co., ltd.) using epoxy resin as a main base material and glass flakes as a filler.
The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin prepared in examples 1 to 5 and the epoxy glass flake coating prepared in comparative example 1 are respectively coated on polished tinplate, cured to obtain a cured film, and the cured film is subjected to corrosion resistance and mechanical property test by the following test method:
1. chemical resistance test: the cured film coated on the polished tinplate was immersed in 10wt% naoh solution, 10wt% hcl solution, and 3.5wt% nacl solution for 15 days, respectively, and then taken out, and the presence or absence of foaming, rust, falling off, and the like of the cured film was observed.
2. Salt spray resistance test: salt spray resistance test was performed on cured films coated on the polished tinplate using a BGD 880/S salt spray corrosion test box.
3. Tensile strength and fracture growth rate: the casting physical property test is carried out on the solidified film coated on the polishing tinplate according to the national standard GB/T1040.3-2006.
The test results are shown in Table 1.
TABLE 1 results of Performance test of cured films
Note that: in Table 1, "none" means no foaming, rust, falling off, etc.
As can be seen from Table 1, compared with the epoxy glass flake coating of comparative example 1, the cured film obtained by curing the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin has better corrosion resistance to corrosive media such as acid, alkali, water, air, chloride ions and the like and better mechanical property. The tensile strength of the cured film obtained by curing the resin of example 5 is lower than that of the other examples, and the elongation at break is higher than that of the other examples, because the graphene oxide in the resin of example 5 is excessively added to increase the toughness of the cured film, but the excessive graphene oxide does not participate in the reaction, is agglomerated in the resin, and reduces the tensile properties of the cured film.
Then, in order to further examine the corrosion resistance of the resin of the present invention, the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin prepared in examples 2 to 5 and the epoxy glass flake coating of comparative example 1 were coated on polished tinplate to a thickness of 25 μm, and the corrosion rate of the tinplate was measured by resistance wire.
The test method specifically comprises the following steps: the corrosion resistance of the metal coating is characterized by adopting a CHI660E electrochemical workstation through a potentiodynamic polarization curve test method, wherein a three-electrode electrolytic cell system is used in the test, a tinplate is used as a working electrode, a platinum electrode is used as a counter electrode, an Ag/AgCl system is used as a reference electrode, and a 3.5wt% sodium chloride aqueous solution is used as an electrolyte medium. The resin was coated on the working electrode in a 1cm by 1cm format and tested at open circuit potential.
The detection results are shown in FIG. 1. As can be seen from fig. 1, the low frequency (10 -2 Hz) is significantly higher than the tinplate coated with the coating of comparative example 1, and the resistance modulus at low frequencies is greater, thus indicating that the resin of the present invention has better corrosion resistance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is characterized by having the structural formula:
2. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 1, wherein the raw material composition comprises, in parts by weight: 40-55 parts of epoxy resin, 10-20 parts of unsaturated monoacid, 1-3 parts of acrylate monomer, 5-10 parts of styrene-maleic anhydride copolymer, 0.01-0.1 part of modified graphene oxide, 25-33 parts of reactive diluent, 0.001-0.01 part of polymerization inhibitor and 0.004-0.04 part of catalyst.
3. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 2, wherein the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin with an epoxy equivalent of 230-340 g/mol; the unsaturated monoacid is selected from one or more of acrylic acid, methacrylic acid and butenoic acid; the acrylic ester monomer is one or more selected from hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate.
4. A styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 2 or 3, wherein the catalyst is selected from one or more of benzyltriethylammonium chloride, triethylamine, diethylamine, triphenylphosphine; the polymerization inhibitor is selected from one or more of hydroquinone, p-tert-butyl catechol and catechol; the reactive diluent is selected from one or more of styrene, alpha-methyl styrene and methyl acrylate.
5. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 2 or 3, wherein the molecular weight of the styrene-maleic anhydride copolymer is 5000-10000 and the anhydride content is 20-35%; the modified graphene oxide is obtained by functionalizing graphene oxide with 3-aminopropyl triethoxysilane.
6. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 5, wherein the preparation method of the modified graphene oxide comprises the following steps:
dispersing graphene oxide and 3-aminopropyl triethoxysilane in absolute ethyl alcohol to obtain a mixed solution, heating the mixed solution to 79-95 ℃, stirring and refluxing for 3-5 hours, adding water in the stirring process, centrifuging a reaction product after the reaction is finished, removing supernatant, and washing the obtained precipitate to obtain the graphene oxide-3-aminopropyl triethoxysilane.
7. The method for preparing a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to any one of claims 1 to 6, comprising the steps of:
the preparation method comprises the steps of firstly, carrying out covalent grafting on a styrene-maleic anhydride copolymer and modified graphene oxide to obtain styrene-maleic anhydride copolymer functionalized graphene oxide, then uniformly stirring epoxy resin, the styrene-maleic anhydride copolymer functionalized graphene oxide, a polymerization inhibitor and 30% -40% of unsaturated monoacid at 70-90 ℃, then adding an acrylic ester monomer and 30% -40% of catalyst, reacting for 3-4h, then adding the rest unsaturated monoacid and the catalyst, uniformly stirring, then heating to 100-120 ℃ for reacting until the acid value is reduced to below 10mgKOH/g, then cooling to 70-90 ℃, adding an active diluent, and uniformly mixing to obtain the modified graphene oxide.
8. The method for preparing the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 7, wherein the method for preparing the styrene-maleic anhydride copolymer functionalized graphene oxide comprises the following steps:
and (3) dissolving the styrene-maleic anhydride copolymer and the modified graphene oxide in a solvent to obtain a mixed solution, condensing and refluxing the mixed solution at 70-90 ℃ for 10-30 hours, and removing the solvent in a reaction product after the reaction is finished to obtain the modified graphene oxide.
9. The method for preparing a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 8, wherein the solvent is one or more selected from acetone, butanone, dimethyl carbonate, toluene, and ethylene glycol methyl ether acetate.
10. Use of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to any one of claims 1-6 in the preparation of marine anti-corrosion coating.
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