A modified graphene oxide, its preparation method, and its application in an icebreaking and abrasion-resistant epoxy coating for marine vessels in ice-covered areas.

Abstract

This invention discloses a modified graphene oxide, its preparation method, and an icebreaking anti-wear epoxy coating for marine vessels in ice-covered areas, as well as its application. The modified graphene oxide comprises a reaction product of an oxazolidinone compound and graphene oxide; the oxazolidinone compound is prepared from raw materials comprising: γ-(2,3-epoxypropoxy)propyltrimethoxysilane, diisocyanate, and a catalyst. The icebreaking anti-wear epoxy anti-corrosion coating for marine vessels of this invention exhibits excellent mechanical properties such as compression, bending, and tensile strength even at low temperatures, protecting the hull from the pressure and wear of ice layers, and demonstrates good adhesion and excellent anti-corrosion effect.

Description

Technical Field

[0001] This invention relates to the field of epoxy coating anti-corrosion technology, specifically to a modified graphene oxide, its preparation method, and an icebreaking and wear-resistant epoxy coating for marine ice-covered vessels and its application. Background Technology

[0002] For ships navigating in ice-covered areas, icebreaking is a constant necessity. During icebreaking, the ship's hull and lower-waterline sides are subjected to severe compression and abrasion from the ice, making the coating prone to large-scale peeling and causing significant corrosion to the hull. Currently, the most commonly used icebreaking coatings internationally are epoxy-based, such as Jotun's Marathon IQ series and Intershield 163 Inerta 160 series from international companies. While these have been used in actual shipboard applications for many years, their effectiveness has been generally limited. The domestically designed icebreaking coating for the Xue Long 2 icebreaker has used both Marathon IQ and Intershield 163 Inerta 160, but coating repairs are still required after each scientific expedition docking. Icebreaking coatings need to possess strong toughness and abrasion resistance at low temperatures to meet the demanding icebreaking requirements.

[0003] With the accelerated pace of polar development, polar shipping routes are becoming increasingly busy, and icebreakers are being built at a rapid pace. Coating manufacturers worldwide are actively developing high-performance icebreaking coatings. Domestic research on icebreaking coatings is relatively limited, starting late, lacking application cases, and yet to obtain international classification society certification. Therefore, developing internationally competitive icebreaking coatings is of great significance. Summary of the Invention

[0004] To address the problems in the prior art, this invention provides a modified graphene oxide, its preparation method, and an icebreaking anti-wear epoxy coating for marine vessels in ice-covered areas, along with its application. The icebreaking anti-wear epoxy anti-corrosion coating for marine vessels of this invention retains excellent mechanical properties such as compression, bending, and tensile strength even at low temperatures, protecting the hull from the pressure and wear of ice layers. It also exhibits good adhesion and excellent anti-corrosion effect.

[0005] One of the objectives of this invention is to provide a modified graphene oxide comprising a reaction product of an oxazolidinone compound and graphene oxide.

[0006] The oxazolidinone compound is prepared from a raw material comprising the following components:

[0007] γ-(2,3-epoxypropoxy)propyltrimethoxysilane, diisocyanate and catalyst.

[0008] In a preferred embodiment of the present invention,

[0009] The graphene oxide can be conventional graphene oxide in the prior art, preferably a single-layer or double-layer graphene oxide, more preferably the diameter of the graphene oxide is 0.5 to 5 μm; and / or the thickness of the single-layer graphene oxide is 0.8 to 1.2 nm.

[0010] The diisocyanate is a monomolecule containing a diisocyanate group, preferably selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isoflurone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate; and / or,

[0011] The catalyst is selected from at least one of tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide; preferably,

[0012] The molar ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane to diisocyanate is 2–4:1, preferably 2–2.5:1; and / or, the amount of catalyst is 0.01–1% of the total mass of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, diisocyanate, and catalyst, preferably 0.05–0.5%; and / or,

[0013] The mass ratio of the oxazolidinone compound to graphene oxide is 0.05 to 20:1, preferably 0.05 to 5:1, and more preferably 0.1 to 1:1.

[0014] In a preferred embodiment of the present invention,

[0015] The method for preparing the oxazolidinone compound includes: stirring and reacting components including γ-(2,3-epoxypropoxy)propyltrimethoxysilane, diisocyanate and catalyst at 100-150°C, preferably 110-130°C, for 4-8 h, preferably 4-6 h, to obtain the oxazolidinone compound; preferably, the reaction is carried out under N2 conditions.

[0016] A second objective of this invention is to provide a method for preparing modified graphene oxide, which is one of the objectives of this invention, comprising reacting graphene oxide with an oxazolidinone compound under the catalysis of an acidic compound to obtain the modified graphene oxide.

[0017] In a preferred embodiment of the present invention,

[0018] The acidic compound is an acidic compound with catalytic ability, preferably at least one of hydrochloric acid, phosphoric acid, and acetic acid; and / or,

[0019] The amount of the acidic compound is 0.01-1% of the total mass of the oxazolidinone compound and graphene oxide, preferably 0.05-0.5%; and / or,

[0020] The reaction temperature is 20–80°C, preferably 60–80°C, and the reaction time is 2–8 hours, preferably 2–4 hours.

[0021] In a preferred embodiment of the present invention,

[0022] The reaction is carried out in the presence of a solvent, which is at least one of butylamine, xylene, tetrahydrofuran, dimethylformamide, and methylpyrrolidone, preferably a mixed solvent of butylamine and xylene or a mixed solvent of methylpyrrolidone and xylene. More preferably, the mass ratio of butylamine to xylene in the mixed solvent of butylamine and xylene is 1:1 to 5, and the mass ratio of butylamine to xylene in the mixed solvent of methylpyrrolidone and xylene is 1:1 to 5.

[0023] In a preferred embodiment of the present invention,

[0024] The amount of solvent used is 1 to 5 times the total mass of the oxazolidinone compound and graphene oxide.

[0025] The present invention can adopt the following specific technical solutions:

[0026] In the presence of a solvent, graphene oxide is reacted with an excess of an oxazolidinone compound under the catalysis of an acidic compound by adding the hydroxyl and carboxyl groups on the graphene oxide to form silicon-oxygen bonds. Modified graphene oxide is obtained by repeated extraction with xylene / n-butylamine and centrifugation.

[0027] A third objective of this invention is to provide an icebreaking and abrasion-resistant epoxy coating for marine ice-covered vessels, comprising modified graphene oxide as described in one objective of this invention or modified graphene oxide prepared by the method described in another objective of this invention.

[0028] In a preferred embodiment of the present invention,

[0029] The marine icebreaking anti-wear epoxy coating for ocean ice zones comprises component A and component B;

[0030] Component A includes epoxy resin, glycidyl ether, zinc phosphate, modified graphene oxide, and wetting and dispersing agents.

[0031] Each component is based on 100 parts by weight of epoxy resin.

[0032]

[0033] Component B includes an epoxy curing agent and an amino-containing organosilicon monomer;

[0034] Each component is calculated based on 100 parts by weight of epoxy curing agent.

[0035] 100 parts by weight of epoxy curing agent;

[0036] The amino-containing organosilicon monomer comprises 5-15 parts by weight; preferably 8-12 parts by weight.

[0037] The ratio of component A to component B is (3-5):1.

[0038] In a preferred embodiment of the present invention,

[0039] The epoxy resin is one or both of liquid bisphenol A type epoxy resin and bisphenol F type epoxy resin; and / or...

[0040] The glycidyl ether is phenyl glycidyl ether, benzyl glycidyl ether, C 12-14 At least one of alkyl glycidyl ethers; and / or,

[0041] The wetting and dispersing agent is a structured acrylic polymer, preferably BYK-9076 type wetting and dispersing agent; and / or,

[0042] The epoxy curing agent is at least one of phenolic amine, polyamide, and alicyclic amine; and / or

[0043] The amino-containing organosilicon monomer is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0044] In a preferred embodiment of the present invention,

[0045] The marine icebreaking anti-wear epoxy coating for ocean ice zones also contains at least one component selected from mica powder, iron oxide red, defoamer, leveling agent, and thixotropic agent.

[0046] Each component is based on 100 parts by weight of epoxy resin.

[0047]

[0048]

[0049] The defoamer is an organosilicon defoamer, preferably BYK-024 type defoamer; and / or,

[0050] The leveling agent is polyether-modified polydimethylsiloxane, preferably BYK-346 type leveling agent; and / or,

[0051] The thixotropic agent is a urea-modified polyurethane polymer, preferably a BYK-425 type thixotropic agent.

[0052] In the marine ice-breaking anti-wear epoxy coating for ships of the present invention, epoxy resin serves as a film-forming agent, glycidyl ether plays a role in dilution and viscosity reduction, zinc phosphate mainly plays a role in corrosion prevention, modified graphene oxide can improve corrosion resistance and mechanical strength, wetting and dispersing agents can improve the compatibility between various substances, and amino-containing organosilicon monomers can improve adhesion.

[0053] The fourth objective of this invention is to provide a method for preparing an icebreaking and abrasion-resistant epoxy coating for marine ice-covered vessels, which is also the objective of this invention (as described in the third objective of this invention). The method includes: first, mixing component A and component B according to their respective dosages; and then mixing component A and component B according to the stated dosage ratio to obtain the icebreaking and abrasion-resistant epoxy coating for marine ice-covered vessels.

[0054] The present invention can adopt the following specific technical solutions:

[0055] Under stirring, the wetting and dispersing agent, thixotropic agent, defoamer, and leveling agent are first mixed evenly with epoxy resin and glycidyl ether according to the weight parts. Then, zinc phosphate, mica powder, and iron oxide are added according to the weight parts, and the mixture is ground in a sand mill until the fineness reaches 80 mesh. Modified graphene oxide is then added to obtain component A. Under stirring, epoxy curing agent and amino-containing organosilicon monomer are added according to the weight parts to obtain component B. Then, components A and B are mixed according to the above dosage ratio to obtain the marine ice-breaking anti-wear epoxy coating for ships.

[0056] The fifth objective of this invention is to provide an application of the marine ice-breaking anti-wear epoxy coating for ships navigating in marine ice areas, as described in the third objective of this invention, or the marine ice-breaking anti-wear epoxy coating for ships prepared by the method described in the fourth objective of this invention.

[0057] The marine icebreaking anti-wear epoxy coating of this invention contains modified graphene oxide functional filler. It utilizes the reaction of the alkoxy groups of the oxazolidinone compound with the hydroxyl and carboxyl groups on the graphene oxide to form chemical bonds, so that the dispersed graphene oxide is bonded together by the oxazolidinone compound. The epoxy groups on the graphene oxide then react with the amino groups, and also form chemical bonds with the resin. Finally, the resin / graphene oxide / oxazolidinone compound are chemically bonded together to jointly provide the icebreaking coating with high toughness and super wear resistance in low temperature environments.

[0058] Compared to untreated graphene oxide fillers, this invention effectively chemically modifies and composites graphene oxide. The conjugation effect between graphene oxides is reduced, hydrophilicity is decreased, and they are more uniformly dispersed in the coating system, thus ensuring improved mechanical properties.

[0059] Compared to other methods for treating graphene oxide, this invention has the following unique features: First, by modifying graphene oxide with oxazolidinone compounds, the hydrophilic groups of graphene oxide are reduced while the lipophilic epoxy groups are retained. This allows graphene oxide to form a network structure under the influence of the oxazolidinone compounds. After the final coating is cured, the graphene oxide / oxazolidinone compound is completely chemically bonded to the resin, forming an integral structure with the resin. This results in superior mechanical properties compared to curing the coating as a filler. Second, the modified oxazolidinone compound is insensitive to temperature changes and maintains good toughness and strength even at low temperatures, improving the low-temperature brittleness of epoxy resin. Simultaneously, the grid-layered structure of graphene oxide can withstand strong structural stresses, complementing the toughness and strength of the oxazolidinone compound. Detailed Implementation

[0060] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0061] All raw materials used in the examples are conventional commercially available raw materials.

[0062] Example 1

[0063] The preparation method of the oxazolidinone compound is as follows: Under the condition of N2 introduction, the molar ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane to toluene diisocyanate is 2:1, and 0.1% of tetraethylammonium bromide by total mass is added. The mixture is stirred at 120°C for 4 h to obtain the oxazolidinone compound.

[0064] The modified graphene oxide preparation method is as follows: 1g of the above-mentioned oxazolidinone compound and 10g of graphene oxide (Nanjing Xianfeng Nanotechnology XF002-2) are mixed by ultrasonic vibration in 220g of a mixed solvent of butylamine and xylene (mass ratio of butylamine to xylene is 1:1). Then, 0.1% hydrochloric acid (mass fraction 37%) of the total mass of the oxazolidinone compound and graphene oxide is added dropwise under stirring, and the reaction is carried out at 80℃ for 2h. The mixture is extracted with a mixed solvent of xylene and n-butylamine (mass ratio 1:1) until the pH is neutral, and centrifuged to obtain TDI oxazolidinone compound modified graphene oxide.

[0065] The formulation of the marine icebreaking and abrasion-resistant epoxy coating for ships in ice-covered areas is as follows:

[0066] Component A:

[0067]

[0068] Component B:

[0069] Epoxy curing agent (3985L type alicyclic amine, Aidi Ke) 100 parts by weight;

[0070] 5 parts by weight of 3-aminopropyltrimethoxysilane;

[0071] By mixing component A and component B in a mass ratio of 3:1, an icebreaking and abrasion-resistant epoxy coating for marine ice-covered areas is prepared.

[0072] The specific preparation process of the icebreaking and abrasion-resistant epoxy coating for marine ice-covered areas is as follows:

[0073] Under stirring, the wetting and dispersing agent, thixotropic agent, defoamer, and leveling agent are first mixed evenly with epoxy resin and phenyl glycidyl ether according to their weight parts. Then, zinc phosphate, mica powder, and iron oxide are added according to their weight parts, and the mixture is ground in a sand mill until the fineness reaches 80 mesh. Then, the modified graphene oxide mentioned above is added to obtain component A. Under stirring, epoxy curing agent and amino-containing organosilicon monomers are added according to their weight parts to obtain component B. Component A and component B are mixed in a mass ratio of 3:1 to obtain an icebreaking and wear-resistant epoxy coating for marine ice areas.

[0074] Example 2

[0075] The preparation process of the oxazolidinone compound in this embodiment is the same as that in Example 1, except that the diisocyanate is different (diphenylmethane diisocyanate is used in this embodiment).

[0076] The preparation process of the modified graphene oxide in this embodiment is the same as in Example 1.

[0077] The preparation process of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is the same as that in Example 1, except for the components and dosages:

[0078] The formulation of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is as follows:

[0079] Component A:

[0080]

[0081] Component B:

[0082] Epoxy curing agent (NC541 type phenolic amine, Cardelli) 100 parts by weight;

[0083] 15 parts by weight of 3-aminopropyltriethoxysilane;

[0084] A component A and component B are mixed in a mass ratio of 5:1 to obtain an icebreaking and abrasion-resistant epoxy coating for marine ice-covered areas.

[0085] Example 3

[0086] The preparation process of the oxazolidinone compound in this embodiment is the same as that in Example 1, except that the diisocyanate is different (isoflurone diisocyanate is used in this embodiment).

[0087] The preparation process of the modified graphene oxide in this embodiment is the same as in Example 1.

[0088] The preparation process of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is the same as that in Example 1, except for the components and dosages:

[0089] The formulation of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is as follows:

[0090] Component A:

[0091]

[0092] Component B:

[0093] Epoxy curing agent (PRO534 type polyamide, Shanghai Dekun) 100 parts by weight;

[0094] 15 parts by weight of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane;

[0095] A component A and component B are mixed in a mass ratio of 4:1 to obtain an icebreaking and abrasion-resistant epoxy coating for marine ice-covered areas.

[0096] Example 4

[0097] The preparation method of the oxazolidinone compound is as follows: Under the condition of N2 introduction, the molar ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane to toluene diisocyanate is 2:1, and 0.1% of tetraethylammonium bromide by total mass is added. The mixture is stirred at 120°C for 4 h to obtain the oxazolidinone compound.

[0098] The modified graphene oxide preparation method is as follows: 10g of the above-mentioned oxazolidinone compound and 10g of graphene oxide (Nanjing Xianfeng Nanotechnology XF002-2) were mixed by ultrasonic vibration in 420g of a mixed solvent of methylpyrrolidone and xylene (mass ratio of methylpyrrolidone and xylene is 1:1). Then, 0.1% hydrochloric acid (mass fraction 37%) of the total mass of the oxazolidinone compound and graphene oxide was added dropwise under stirring, and the reaction was carried out at 80℃ for 2h. The mixture was extracted with a mixed solvent of xylene and methylpyrrolidone (mass ratio 1:1) until the pH was neutral, and centrifuged to obtain TDI oxazolidinone compound modified graphene oxide 2#.

[0099] The preparation process of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is the same as that in Example 1, except for the components and dosages:

[0100] The formulation of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is as follows:

[0101] Component A:

[0102]

[0103]

[0104] Component B:

[0105] Epoxy curing agent (3985L type alicyclic amine, Aidi Ke) 100 parts by weight;

[0106] 5 parts by weight of 3-aminopropyltrimethoxysilane;

[0107] By mixing component A and component B in a mass ratio of 3:1, an icebreaking and abrasion-resistant epoxy coating for marine ice-covered areas is prepared.

[0108] Example 5

[0109] The preparation process of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is the same as that in Example 1, except for the components and dosages:

[0110] The formulation of the marine icebreaking anti-wear epoxy coating for ocean ice areas in this embodiment is as follows:

[0111] Component A:

[0112]

[0113] Component B:

[0114] Epoxy curing agent (NC541 type phenolic amine, Cardelli) 100 parts by weight;

[0115] 5 parts by weight of 3-aminopropyltrimethoxysilane;

[0116] A component A and component B are mixed in a mass ratio of 5:1 to obtain an icebreaking and abrasion-resistant epoxy coating for marine ice-covered areas.

[0117] Comparative Example 1

[0118] The preparation process of the epoxy coating in Comparative Example 1 was the same as that in Example 5, except for the components and dosages.

[0119] The formulation of the epoxy coating in Comparative Example 1 is as follows:

[0120] Component A:

[0121]

[0122] Component B:

[0123] Epoxy curing agent (NC541 type phenolic amine, Cardelli) 100 parts by weight;

[0124] 5 parts by weight of 3-aminopropyltrimethoxysilane;

[0125] An epoxy coating is prepared by mixing component A and component B in a mass ratio of 5:1.

[0126] Comparative Example 2

[0127] The preparation process of the epoxy coating in Comparative Example 2 was the same as that in Example 5, except for the components and dosages.

[0128] The formulation of the epoxy coating in Comparative Example 2 is as follows:

[0129] Component A:

[0130]

[0131] Component B:

[0132] Epoxy curing agent (NC541 type phenolic amine, Cardelli) 100 parts by weight;

[0133] 5 parts by weight of 3-aminopropyltrimethoxysilane;

[0134] An epoxy coating is prepared by mixing component A and component B in a mass ratio of 5:1.

[0135] The epoxy coatings prepared in Examples 1-5 and Comparative Examples 1-2 were used to prepare salt spray resistance, cathodic disbondment resistance, and seawater resistance samples, as well as compression, bending, and tensile samples. Salt spray resistance was determined using a Q-FOG-CCT1100 salt spray test chamber according to GB / T 1771. Compression, bending, and tensile strength tests, as well as seawater immersion resistance tests, were conducted using an E43.504 microcomputer-controlled electronic universal testing machine / GDX-70-350G high and low temperature test chamber according to ASTM D695, ASTM D790, ASTM D638, and GB / T 9274. Abrasion resistance tests were conducted according to ISO 7784-2, and adhesion tests were conducted according to ISO 4624. The test results are compared below:

[0136] Table 1 Coating Performance

[0137]

[0138] As can be seen from Examples 1-5, Comparative Examples 1-2 and Table 1, by adding the modified graphene oxide of the present invention, the coatings formed by the marine ice-breaking anti-wear epoxy coatings prepared in Examples 1-5 have significantly better salt spray resistance, seawater immersion resistance, wear resistance and mechanical properties than the coatings formed by the epoxy ice-breaking coatings prepared in Comparative Examples 1 and 2.

[0139] The content described in this invention is not limited to the embodiments described herein.

[0140] This article uses specific examples to illustrate the structure and implementation of the present invention. The description of the above embodiments is only for the purpose of helping to understand the core idea of ​​the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A modified graphene oxide, comprising a reaction product of an oxazolidone compound and graphene oxide. The oxazolidone compound is prepared from raw materials comprising: γ-(2,3-epoxypropoxy)propyl trimethoxysilane, diisocyanate and catalyst; The components comprising γ-(2,3-epoxypropoxy)propyl trimethoxysilane, diisocyanate and catalyst are stirred and reacted at 100-150℃ for 4-8h to obtain the oxazolidone compound; The method for preparing the oxazolidinone compound comprises: A method for preparing the modified graphene oxide, comprising reacting graphene oxide with the oxazolidone compound under catalysis of an acidic compound to obtain the modified graphene oxide.

2. The modified graphene oxide of claim 1, wherein: The diisocyanate is a monomolecular substance containing diisocyanate groups; and / or, The catalyst is at least one selected from the group consisting of tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide; and / or, The molar ratio of γ-(2,3-epoxypropoxy)propyl trimethoxysilane to diisocyanate is 2-4:1; and / or, The amount of the catalyst is 0.01-1% of the total mass of γ-(2,3-epoxypropoxy)propyl trimethoxysilane, diisocyanate and catalyst; and / or, The mass ratio of the oxazolidone compound to graphene oxide is 0.05-20:

1.

3. The modified graphene oxide of claim 1, wherein: The diisocyanate is at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate; and / or, The molar ratio of γ-(2,3-epoxypropoxy)propyl trimethoxysilane to diisocyanate is 2-2.5:1; and / or, The amount of the catalyst is 0.05-0.5% of the total mass of γ-(2,3-epoxypropoxy)propyl trimethoxysilane, diisocyanate and catalyst; and / or, The mass ratio of the oxazolidone compound to graphene oxide is 0.05-5:

1.

4. A method for preparing the modified graphene oxide of any one of claims 1-3, comprising reacting graphene oxide with the oxazolidone compound under catalysis of an acidic compound to obtain the modified graphene oxide.

5. The method of claim 4, wherein: The acidic compound is an acidic compound having catalytic ability; and / or, The amount of the acidic compound is 0.01-1% of the total mass of the oxazolidone compound and graphene oxide; and / or, The reaction temperature is 20-80℃, and the reaction time is 2-8h.

6. The method of claim 4, wherein: The acidic compound is at least one selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid; and / or, The amount of the acidic compound is 0.05-0.5% of the total mass of the oxazolidone compound and graphene oxide.

7. An ice-breaking and anti-wear epoxy coating for marine ice-class ships, comprising the modified graphene oxide of any one of claims 1-3 or the modified graphene oxide prepared by the method of any one of claims 4-6. ​ 8.The ice-class marine ship ice-breaking and anti-abrasion epoxy coating of claim 7, wherein: the ice-class marine ship ice-breaking and anti-abrasion epoxy coating comprises an A component and a B component; the A component comprises an epoxy resin, a glycidyl ether, a zinc phosphate, a modified graphene oxide, and a wetting dispersant; each component is based on 100 parts by weight of the epoxy resin, wherein: the epoxy resin is 100 parts by weight; the glycidyl ether is 5 to 15 parts by weight; the zinc phosphate is 25 to 40 parts by weight; the modified graphene oxide is 10 to 25 parts by weight; and the wetting dispersant is 3 to 6 parts by weight; the B component comprises an epoxy curing agent and an amino-containing organosilicon monomer; each component is based on 100 parts by weight of the epoxy curing agent, wherein: the epoxy curing agent is 100 parts by weight; and the amino-containing organosilicon monomer is 5 to 15 parts by weight; and a ratio of the A component to the B component is 3 to 5:

1. 9.The ice-class marine ship ice-breaking and anti-abrasion epoxy coating of claim 8, wherein: the A component comprises: the epoxy resin is 100 parts by weight; the glycidyl ether is 8 to 10 parts by weight; the zinc phosphate is 30 to 40 parts by weight; the modified graphene oxide is 15 to 20 parts by weight; and the wetting dispersant is 4 to 6 parts by weight; and the B component comprises: the epoxy curing agent is 100 parts by weight; and the amino-containing organosilicon monomer is 8 to 12 parts by weight. 10.The ice-class marine ship ice-breaking and anti-abrasion epoxy coating of claim 8, wherein: the epoxy resin is one or both of a liquid bisphenol A type epoxy resin and a bisphenol F type epoxy resin; and / or the glycidyl ether is at least one of a phenyl glycidyl ether, a benzyl glycidyl ether, and a C12-14 alkyl glycidyl ether; and / or the epoxy curing agent is at least one of a phenolic amine, a polyamide, and an alicyclic amine; and / or the amino-containing organosilicon monomer is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. The A component and the B component are mixed according to the respective component amounts, and then the A component and the B component are mixed according to the ratio to obtain the ice-class marine ship ice-breaking and anti-abrasion epoxy coating. 12.Use of the ice-class marine ship ice-breaking and anti-abrasion epoxy coating of any one of claims 7 to 10 or prepared by the method of claim 11 in a ship sailing in an ice area. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 11. A process for the preparation of an ice-class marine anti-wear epoxy coating for ships as claimed in any one of claims 7 to 10, comprising: ​ ​

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