Styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, preparation method and application thereof

Abstract

The present application belongs to the technical field of anticorrosive coatings, and particularly relates to a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, a preparation method and application thereof. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is prepared by adding part of reactants, i.e. unsaturated monobasic acid and epoxy resin as a diluent, so that the anhydride groups on the styrene-maleic anhydride copolymer functionalized graphene oxide and the hydroxyl groups on the acrylic ester monomer react, the anhydride ring-opening generates carboxylic acid groups, thereby participating in the subsequent reaction of carboxylic acid and epoxy, and finally the epoxy resin is capped with carboxylic acid to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin. The cured film obtained by curing the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin has excellent barrier properties, low surface energy, good corrosion resistance and excellent mechanical properties, and the reaction is prepared by one-pot method, the preparation process is simple, and the raw material utilization rate is high.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of anticorrosive coatings, and particularly relates to a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin as well as a preparation method and application thereof. BACKGROUND

[0002] As an important part of modern materials, metals and their alloys are widely used in national defense, transportation, chemical industry and daily life. However, metals are prone to corrosion in complex working environments. According to statistics, the metal equipment and materials scrapped due to corrosion account for 20%-40% of the annual output, which brings huge losses to the economic development of the country. The corrosion problem caused by the marine environment to the metal is more severe, as seawater and sea wind contain a large amount of salt such as NaCl and MgCl2, which long-term affects the safety and long-term effectiveness of ships and marine facilities.

[0003] Generally speaking, the methods for preventing corrosion of metals mainly include improving the structure and composition of metal materials, adding corrosion inhibitors, electrochemical protection and surface coating protection. Among them, coating the metal surface with an organic coating is one of the most commonly used marine corrosion protection technologies at present, which is mature in technology, simple in operation and convenient in construction. In order to improve the corrosion resistance of the coating, it is of great significance to add an appropriate amount of inorganic nanoparticles to the epoxy vinyl ester resin to delay or shield the penetration of corrosive media. Among them, due to the unique single-layer hexagonal honeycomb lattice structure of carbon atoms of graphene, each carbon atom is sp2 hybridization, which endows it with excellent electrical conductivity, thermal conductivity, mechanical properties and anti-permeability. In the current scheme, the modified graphene oxide is usually blended with various polymers through a solvent, and then the solvent is removed to make the modified graphene oxide uniformly dispersed in the polymer. This not only causes serious waste, but also restricts the improvement of the performance of the composite material. SUMMARY

[0004] A first object of the present application is to provide a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin, a second object of the present application is to provide a preparation method of the resin, and a third object of the present application is to provide an application of the resin.

[0005] According to a first aspect of the present application, a styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is provided, and the structural formula is as follows:

[0006] In the formula, R1 is R2 is m:n = 3:1-5:1. ​

[0007] In some embodiments, the raw material composition comprises, by weight: epoxy resin 40-55 parts, unsaturated monobasic acid 10-20 parts, acrylate monomer 1-3 parts, styrene-maleic anhydride copolymer 5-10 parts, modified graphene oxide 0.01-0.1 parts, active diluent 25-33 parts, polymerization inhibitor 0.001-0.01 parts, catalyst 0.004-0.04 parts.

[0008] 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 with an epoxy equivalent weight of 230-340 g / mol; the unsaturated monobasic acid is selected from one or more of acrylic acid, methacrylic acid, crotonic acid; the acrylate monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate.

[0009] 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 hydroquinone, catechol; the active diluent is selected from one or more of styrene, α-methylstyrene, methyl acrylate.

[0010] In some embodiments, the styrene-maleic anhydride copolymer has a molecular weight of 5000-10000 and an anhydride content of 20-35%; the modified graphene oxide is obtained by functionalizing graphene oxide with 3-aminopropyl triethoxysilane.

[0011] In some embodiments, the method for preparing the modified graphene oxide comprises the following steps:

[0012] The graphene oxide and 3-aminopropyl triethoxysilane are dispersed in anhydrous ethanol to obtain a mixed solution, then the mixed solution is warmed to 79-95°C, stirred and refluxed for 3-5 hours, and water is added during stirring, after the reaction is completed, the reaction product is centrifuged, the supernatant is removed, and the obtained precipitate is washed to obtain the modified graphene oxide.

[0013] In some embodiments, the graphene oxide and 3-aminopropyl triethoxysilane are dispersed in anhydrous ethanol by ultrasonic treatment for 30 min.

[0014] In some embodiments, the obtained modified graphene oxide is ground to obtain a modified graphene oxide solid powder.

[0015] According to a second aspect of the present application, a method for preparing the above-mentioned styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is provided, comprising the following steps:

[0016] The styrene-maleic anhydride copolymer and modified graphene oxide are covalently grafted to obtain styrene-maleic anhydride copolymer functionalized graphene oxide, then the epoxy resin, styrene-maleic anhydride copolymer functionalized graphene oxide, polymerization inhibitor and 30%-40% of unsaturated monobasic acid are stirred uniformly at 70-90°C, then the acrylate monomer and 30%-40% of catalyst are added, and the reaction is carried out for 3-4h, then the remaining unsaturated monobasic acid and catalyst are added, stirred uniformly, then the temperature is increased to 100-120°C for reaction, until the acid value is reduced to below 10mgKOH / g, then the temperature is reduced to 70-90°C, the active diluent is added, and mixed uniformly, and the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is obtained.

[0017] The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is prepared by adding part of the reactants, unsaturated monobasic acid and epoxy resin, as a diluent, to make the anhydride groups on the styrene-maleic anhydride copolymer functionalized graphene oxide and the hydroxyl groups on the acrylate monomer react, the anhydride ring-opening generates carboxylic acid groups, thereby participating in the subsequent reaction of carboxylic acid and epoxy, and finally the carboxylic acid is used to cap the epoxy resin, to obtain the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin.

[0018] In some embodiments, the preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide comprises the following steps:

[0019] The styrene-maleic anhydride copolymer and modified graphene oxide are dissolved in a solvent to obtain a mixed solution, then the mixed solution is condensed and refluxed at 70-90°C for 10-30h, and the solvent in the reaction product is removed after the reaction is completed, and the styrene-maleic anhydride copolymer functionalized graphene oxide is obtained.

[0020] In some embodiments, the solvent is selected from one or more of acetone, butanone, dimethyl carbonate, toluene and ethylene glycol methyl ether acetate.

[0021] In some embodiments, the solvent is removed by rotary evaporation.

[0022] In some embodiments, the obtained styrene-maleic anhydride copolymer functionalized graphene oxide is ground to obtain styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.

[0023] According to a third aspect of the present application, the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin described above is used in the preparation of marine anticorrosive coatings. Specifically, it is used as heavy-duty anticorrosive coatings for the surface of steel structures or concrete, such as offshore platforms and other marine engineering facilities, ship oil pipelines, large pressure steel pipes of hydropower stations, wharf steel piles, bridges, gates, ballast water tanks, gas tanks and gas pipelines, sewage treatment tanks, buried pipelines, etc.

[0024] The beneficial effects of the present application include:

[0025] (1) The styrene-maleic anhydride copolymer is used as an intermediate in the present application, and the graphene oxide is uniformly dispersed in the vinyl ester resin through covalent reaction, which greatly improves the corrosion resistance of the resin. The styrene-maleic anhydride copolymer is grafted to modify the graphene oxide, which increases the crosslinking density of the resin and the dispersibility of the graphene oxide in the resin.

[0026] (2) The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin of the present application has excellent barrier properties, low surface energy, good corrosion resistance and excellent mechanical properties. The reaction is prepared by one-pot method, and the preparation process is simple and the raw material utilization rate is high. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The frequency-impedance modulus curve of the tinplate coated with different resins in the experiment of the present application is shown in the figure. DETAILED DESCRIPTION

[0028] The present application will be further described in detail below in conjunction with specific examples, but the embodiments of the present application are not limited thereto. The raw materials involved in the following examples can be obtained from commercial channels.

[0029] In the following examples, the molecular weight of the styrene-maleic anhydride copolymer used is 5000-10000, and the anhydride content is 20-35%.

[0030] Example 1

[0031] The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin of the present embodiment comprises the following steps:

[0032] (1) 0.15g of graphene oxide (GO) and 3.00g of 3-aminopropyltriethoxysilane (APTES) were dispersed in 135mL of anhydrous ethanol by ultrasonic treatment for 30min to obtain a mixed solution, then the mixed solution was heated to 80℃, and stirred and refluxed for 4 hours, and 12mL of deionized water was slowly added during continuous stirring. After the reaction was completed, the reaction product was centrifuged at a speed of 9000rpm for 10min to remove the supernatant, and the obtained precipitate was washed with anhydrous ethanol for more than 3 times, and finally the washed precipitate was dried and ground to obtain a modified graphene oxide (AGO) solid powder.

[0033] (2) 20.00 g of styrene-maleic anhydride copolymer and 0.0500 g of modified graphene oxide were dissolved in 20 g of dimethyl carbonate to obtain a mixed solution, and then the mixed solution was condensed and refluxed at 80°C for 20 h. After the reaction was completed, the reaction product was removed by rotary evaporation, and the remaining solid material was ground to obtain a styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.

[0034] (3) In a three-necked flask with mechanical stirring, 20.00 g of epoxy resin, 3.00 g of acrylic acid, 0.028% of the total mass of raw materials of polymerization inhibitor hydroquinone, and 3.12 g of styrene-maleic anhydride copolymer functionalized graphene oxide powder were added, and the reaction temperature was set to 80°C. After stirring uniformly, 0.0160 g of catalyst triphenylphosphine and 0.51 g of hydroxyethyl acrylate were added, and the reaction was continued for 4 h. Then 3.34 g of acrylic acid and 0.1500 g of catalyst benzyltriethylammonium chloride were added, and the temperature was raised to 110°C after stirring uniformly. The reaction was carried out until the acid value was reduced to below 10 mgKOH / g, and then the temperature was lowered to 80°C. Finally, 12.80 g of active diluent styrene was added until the mixture was uniform.

[0035] Example 2

[0036] The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin of this embodiment includes the following steps:

[0037] (1) 0.15 g of graphene oxide (GO) and 3.00 g of 3-aminopropyltriethoxysilane (APTES) were dispersed in 135 mL of anhydrous ethanol by ultrasonic treatment for 30 min to obtain a mixed solution. Then the mixed solution was heated to 80°C and stirred and refluxed for 4 h. During continuous stirring, 12 mL of deionized water was slowly added. After the reaction was completed, the reaction product was centrifuged at a speed of 9000 rpm for 10 min, and the supernatant was removed. The obtained precipitate was washed with anhydrous ethanol for more than 3 times, and finally the washed precipitate was dried and ground to obtain a modified graphene oxide (AGO) solid powder.

[0038] (2) 20.00 g of styrene-maleic anhydride copolymer and 0.0250 g of modified graphene oxide were dissolved in 20 g of dimethyl carbonate to obtain a mixed solution, and then the mixed solution was condensed and refluxed at 80°C for 20 h. After the reaction was completed, the reaction product was removed by rotary evaporation, and the remaining solid material was ground to obtain a styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.

[0039] (3) In a three-necked flask with mechanical stirring, 20.00 g of epoxy resin, 3.00 g of acrylic acid, 0.028% of the total mass of raw materials of polymerization inhibitor hydroquinone, and 3.12 g of styrene-maleic anhydride copolymer functionalized graphene oxide powder were added, the reaction temperature was set to 80°C, 0.016 g of catalyst triphenylphosphine and 0.51 g of hydroxyethyl acrylate were added after uniform stirring, and the reaction was continued for 4 h. Then 3.34 g of acrylic acid and 0.15 g of catalyst benzyltriethylammonium chloride were added, and the temperature was raised to 110°C after uniform stirring, and the reaction was continued until the acid value was reduced to below 10 mgKOH / g, and then the temperature was lowered to 80°C, and finally 12.80 g of active diluent styrene was added until the mixture was uniform.

[0040] Example 3

[0041] The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin of this embodiment comprises the following steps:

[0042] (1) 0.15 g of graphene oxide (GO) and 3.00 g of 3-aminopropyltriethoxysilane (APTES) were dispersed in 135 mL of anhydrous ethanol by ultrasonic treatment for 30 min to obtain a mixed solution, and then the mixed solution was heated to 80°C and stirred under reflux for 4 h, and 12 mL of deionized water was slowly added during continuous stirring. After the reaction was completed, the reaction product was centrifuged at a speed of 9000 rpm for 10 min to remove the supernatant, and the obtained precipitate was washed with anhydrous ethanol for more than 3 times, and finally the washed precipitate was dried and ground to obtain a modified graphene oxide (AGO) solid powder.

[0043] (2) 20.00 g of styrene-maleic anhydride copolymer and 0.0250 g of modified graphene oxide were dissolved in 20 g of dimethyl carbonate to obtain a mixed solution, and then the mixed solution was condensed and refluxed at 80°C for 20 h. After the reaction was completed, the reaction product was removed by rotary evaporation, and the remaining solid material was ground to obtain a styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.

[0044] (3) In a three-necked flask with mechanical stirring, 20.00 g of epoxy resin, 3.00 g of acrylic acid, 0.028% of the total mass of raw materials of polymerization inhibitor hydroquinone, and 4.28 g of styrene-maleic anhydride copolymer functionalized graphene oxide powder were added, the reaction temperature was set to 80°C, 0.016 g of catalyst triphenylphosphine and 0.51 g of hydroxyethyl acrylate were added after uniform stirring, and the reaction was continued for 4 h. Then 3.34 g of acrylic acid and 0.15 g of catalyst benzyltriethylammonium chloride were added, the temperature was raised to 110°C after uniform stirring, and the reaction was carried out until the acid value was reduced to below 10 mgKOH / g, and then the temperature was lowered to 80°C. Finally, 12.80 g of active diluent styrene was added until the mixture was uniform, and the product was obtained.

[0045] Example 4

[0046] The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin of this embodiment includes the following steps:

[0047] (1) By ultrasonic treatment for 30 min, 0.15 g of graphene oxide (GO) and 3.00 g of 3-aminopropyltriethoxysilane (APTES) were dispersed in 135 mL of anhydrous ethanol to obtain a mixed solution, and then the mixed solution was heated to 80°C and stirred for 4 hours. During continuous stirring, 12 mL of deionized water was slowly added, and after the reaction was completed, the reaction product was centrifuged at a speed of 9000 rpm for 10 min to remove the supernatant, and the obtained precipitate was washed with anhydrous ethanol for more than 3 times, and finally the washed precipitate was dried and ground to obtain a modified graphene oxide (AGO) solid powder.

[0048] (2) 20.00 g of styrene-maleic anhydride copolymer and 0.0735 g of modified graphene oxide were dissolved in 20 g of dimethyl carbonate to obtain a mixed solution, and then the mixed solution was condensed and refluxed at 80°C for 20 h. After the reaction was completed, the reaction product was removed by rotary evaporation, and the remaining solid material was ground to obtain a styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.

[0049] (3) In a three-necked flask with mechanical stirring, 20.00 g of epoxy resin, 3.00 g of acrylic acid, 0.028% of the total mass of raw materials of polymerization inhibitor hydroquinone, and 3.12 g of styrene-maleic anhydride copolymer functionalized graphene oxide powder were added, the reaction temperature was set to 80°C, 0.016 g of catalyst triphenylphosphine and 0.51 g of hydroxyethyl acrylate were added after uniform stirring, and the reaction was continued for 4 h. Then 3.34 g of acrylic acid and 0.15 g of catalyst benzyltriethylammonium chloride were added, the temperature was raised to 110°C after uniform stirring, and the reaction was carried out until the acid value was reduced to below 10 mgKOH / g, and then the temperature was reduced to 80°C. Finally, 12.80 g of active diluent styrene was added until the mixture was uniform, and the product was obtained.

[0050] Example 5

[0051] The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin of this embodiment includes the following steps:

[0052] (1) By ultrasonic treatment for 30 min, 0.15 g of graphene oxide (GO) and 3.00 g of 3-aminopropyltriethoxysilane (APTES) were dispersed in 135 mL of anhydrous ethanol to obtain a mixed solution, and then the mixed solution was heated to 80°C and stirred for 4 hours. During continuous stirring, 12 mL of deionized water was slowly added, and after the reaction was completed, the reaction product was centrifuged at a speed of 9000 rpm for 10 min to remove the supernatant, and the obtained precipitate was washed with anhydrous ethanol for more than 3 times, and finally the washed precipitate was dried and ground to obtain a modified graphene oxide (AGO) solid powder.

[0053] (2) 20.00 g of styrene-maleic anhydride copolymer and 0.0735 g of modified graphene oxide were dissolved in 20 g of dimethyl carbonate to obtain a mixed solution, and then the mixed solution was condensed and refluxed at 80°C for 20 h. After the reaction was completed, the reaction product was removed by rotary evaporation, and the remaining solid material was ground to obtain a styrene-maleic anhydride copolymer functionalized graphene oxide solid powder.

[0054] (3) In a three-necked flask with mechanical stirring, 20.00 g of epoxy resin, 3.00 g of acrylic acid, 0.028% of the total mass of raw materials of polymerization inhibitor hydroquinone and 4.28 g of styrene-maleic anhydride copolymer functionalized graphene oxide powder were put in, the reaction temperature was set to 80°C, 0.016 g of catalyst triphenylphosphine and 0.51 g of hydroxyethyl acrylate were added after stirring uniformly, and the reaction was continued for 4 h. Then 3.34 g of acrylic acid and 0.15 g of catalyst benzyltriethylammonium chloride were added, and the temperature was raised to 110°C after stirring uniformly, and the reaction was continued until the acid value was reduced to below 10 mgKOH / g, and then the temperature was reduced to 80°C, and finally 12.80 g of active diluent styrene was added until it was uniformly mixed.

[0055] Comparative Example 1

[0056] Epoxy glass flake paint (IPN8710 type, produced by Cangzhou Jiasheng Paint Co., Ltd., with epoxy resin as the main binder and glass flake as the filler).

[0057] In the following, the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin prepared in Examples 1-5 and the epoxy glass flake paint of Comparative Example 1 were respectively coated on the polished tinplate, and after curing, the cured film was obtained, and the corrosion resistance and mechanical properties of the cured film were tested, and the test methods were as follows:

[0058] 1. Chemical corrosion resistance test: the cured film coated on the polished tinplate was immersed in 10wt% NaOH solution, 10wt% HCl solution and 3.5wt% NaCl solution respectively for 15 days, and then taken out, and the phenomena such as blistering, rusting and peeling of the cured film were observed.

[0059] 2. Salt spray resistance test: the salt spray resistance of the cured film coated on the polished tinplate was tested using a salt spray corrosion test chamber with a scale of BGD 880 / S.

[0060] 3. Tensile strength and fracture growth rate: the mechanical properties of the cast body of the cured film coated on the polished tinplate were tested according to the national standard GB / T1040.3-2006.

[0061] The test results are shown in Table 1.

[0062] Table 1 Performance test results of cured film

[0063]

[0064] Note: "none" in Table 1 represents no blistering, rusting, peeling and other phenomena.

[0065] As shown in Table 1, compared to 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 of the present invention exhibits superior corrosion resistance to corrosive media such as acids, alkalis, water, air, and chloride ions, and also demonstrates better mechanical properties. The tensile strength of the cured film obtained by curing the resin in Example 5 is relatively lower than that of the other examples, while the elongation at break is relatively higher. This is because the excessive addition of graphene oxide to the resin in Example 5 increases the toughness of the cured film; however, the excess graphene oxide does not participate in the reaction and agglomerates in the resin, reducing the tensile properties of the cured film.

[0066] Then, in order to further test the anti-corrosion performance of the resin of the present invention, the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin prepared in Examples 2-5 and the epoxy glass flake coating of Comparative Example 1 were coated on the polished tinplate with a coating thickness of 25 μm, and the corrosion rate of the tinplate was measured by impedance line.

[0067] The specific testing method is as follows: The corrosion resistance of the metal coating was characterized using a CHI660E electrochemical workstation via potentiodynamic polarization curve testing. A three-electrode electrolytic cell system was used, with tinplate as the working electrode, a platinum electrode as the counter electrode, and an Ag / AgCl system as the reference electrode. A 3.5 wt% sodium chloride aqueous solution was used as the electrolyte medium. Resin was coated onto the working electrode in 1 cm × 1 cm increments, and testing was conducted at open-circuit potential.

[0068] Test results as follows Figure 1 As shown. From Figure 1 It can be seen that the tinplate coated with the resin of the present invention exhibits low-frequency (10) [higher frequency (10)]. -2 The impedance modulus at Hz is significantly higher than that of the tinplate coated with the coating of Comparative Example 1, and the impedance modulus at low frequencies is relatively large, which indicates that the resin of the present invention has better corrosion resistance.

[0069] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin characterized in that, The structural formula is: wherein, denotes graphene oxide, R1is , R1in denotes a residue of an unsaturated monobasic acid selected from one or more of acrylic acid, methacrylic acid, butenoic acid, R2is or or m:n = 3:1 - 5:1 ; The preparation method comprises the following steps: The styrene-maleic anhydride copolymer and the modified graphene oxide are covalently grafted to obtain styrene-maleic anhydride copolymer functionalized graphene oxide, then the epoxy resin, the styrene-maleic anhydride copolymer functionalized graphene oxide, the polymerization inhibitor and 30%-40% of the unsaturated monobasic acid are uniformly stirred at 70-90 DEG C, then the acrylic ester monomer and 30%-40% of the catalyst are added, the reaction is carried out for 3-4 h, then the remaining unsaturated monobasic acid and the catalyst are added and uniformly stirred, then the temperature is increased to 100-120 DEG C for reaction until the acid value is reduced to below 10 mgKOH / g, then the temperature is reduced to 70-90 DEG C, the active diluent is added and uniformly mixed, and the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin is obtained.

2. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 1, characterized in that, The raw material composition comprises, in parts by weight, the epoxy resin 40-55 parts, the unsaturated monobasic acid 10-20 parts, the acrylic ester monomer 1-3 parts, the styrene-maleic anhydride copolymer 5-10 parts, the modified graphene oxide 0.01-0.1 parts, the active diluent 25-33 parts, the polymerization inhibitor 0.001-0.01 parts and the catalyst 0.004-0.04 parts.

3. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 2, characterized in that, The epoxy resin is selected from bisphenol A type epoxy resins with an epoxy equivalent weight of 230-340 g / mol; the acrylic ester monomer is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate.

4. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 2 or 3, characterized in that, The catalyst is selected from one or more of benzyltriethylammonium chloride, triethylamine, diethylamine and triphenylphosphine; the polymerization inhibitor is selected from one or more of hydroquinone, p-tert-butyl hydroquinone and catechol; and the active diluent is selected from one or more of styrene, alpha-methylstyrene and methyl acrylate.

5. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 2 or 3, characterized in that, The molecular weight of the styrene-maleic anhydride copolymer is 5000-10000, and the anhydride content is 20-35%.

6. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 5, characterized in that, The preparation method of the modified graphene oxide comprises the following steps: The graphene oxide and 3-aminopropyl triethoxysilane are dispersed in anhydrous ethanol to obtain a mixed solution, then the mixed solution is heated to 79-95 DEG C, stirred and refluxed for 3-5 hours, water is added during stirring, the reaction product is centrifuged after the reaction is completed, the supernatant is removed, and the obtained precipitate is washed to obtain the modified graphene oxide.

7. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 1, characterized in that, The preparation method of the styrene-maleic anhydride copolymer functionalized graphene oxide comprises the following steps: The styrene-maleic anhydride copolymer and the modified graphene oxide are dissolved in a solvent to obtain a mixed solution, then the mixed solution is condensed and refluxed at 70-90 DEG C for 10-30 h, and the solvent in the reaction product is removed after the reaction is completed.

8. The styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin according to claim 7, characterized in that, The solvent is selected from one or more of acetone, butanone, dimethyl carbonate, toluene and ethylene glycol methyl ether acetate.

9. Use of the styrene-maleic anhydride copolymer functionalized graphene oxide modified vinyl ester resin in any one of claims 1-8 in the preparation of marine anticorrosive paint.

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