Organic fluorine-modified epoxy vinyl ester resin and preparation method and application thereof

Abstract

The present invention belongs to the technical field of polymer materials, and in particular to a kind of organic fluorine-modified epoxy vinyl ester resin and its preparation method and application. The organic fluorine-modified epoxy vinyl ester resin of the present invention comprises, by weight, 30-50 parts of epoxy resin, 0.03-0.5 parts of organic fluorine polymer modifier, 9-20 parts of unsaturated carboxylic acid, 0.01-0.1 parts of inhibitor, 0.1-1 parts of first catalyst, and 15-40 parts of active diluent. Its preparation method comprises the following steps: reacting the organic fluorine polymer modifier with epoxy resin at 60-90°C for 1-4h, adding unsaturated carboxylic acid, catalyst and inhibitor, heating to 90-120°C for 2-5h, until the acid value is less than 30mg KOH / g, then cooling to 60-80°C, adding active diluent and mixing evenly, and obtaining. The cured film obtained by the organic fluorine-modified epoxy vinyl ester resin of the present invention has excellent mechanical properties, chemical resistance and anticorrosive properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to an organic fluorine-modified epoxy vinyl ester resin and a preparation method and application thereof. Background Art

[0002] Epoxy vinyl ester resin can be used as an anti-corrosion coating to prevent the metal substrate from direct contact with corrosive substances, thereby achieving the purpose of slowing down metal corrosion. However, the barrier effect of pure epoxy vinyl ester resin anti-corrosion coating is limited and short-term, because the volume shrinkage of epoxy vinyl ester resin during the curing process is large, and micropores and defects may occur locally in the coating, which reduces the barrier performance of the coating and cannot provide long-term protection for the metal substrate.

[0003] Therefore, it is necessary to combine the structural characteristics of epoxy vinyl ester resin and introduce functional monomers or polymers to improve its anti-corrosion performance. Summary of the invention

[0004] The first object of the present invention is to provide an organic fluorine-modified epoxy vinyl ester resin, the second object of the present invention is to provide a method for preparing the organic fluorine-modified epoxy vinyl ester resin, and the third object of the present invention is to provide an application of the organic fluorine-modified epoxy vinyl ester resin.

[0005] According to the first aspect of the present invention, there is provided an organic fluorine-modified epoxy vinyl ester resin, the raw material composition of which comprises, by weight: 30-50 parts of epoxy resin, 0.03-0.5 parts of organic fluorine polymer modifier, 9-20 parts of unsaturated carboxylic acid, 0.01-0.1 parts of inhibitor, 0.1-1 parts of first catalyst, and 15-40 parts of active diluent.

[0006] In some embodiments, the method for preparing the organic fluorine polymer modifier comprises the following steps:

[0007] Take organic fluorine acrylate, organic solvent, chain transfer agent and initiator as raw materials, mix them evenly, react at 60-80°C for 8-12 hours, remove the organic solvent after the reaction is completed, then add diisocyanate and the second catalyst, react at 40-60°C for 2-3 hours to obtain an organic fluorine polymer modifier.

[0008] In some embodiments, the organic fluorine acrylate is any one of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, and 2-(perfluorohexyl)ethyl methacrylate, or a mixture of any one or more of them in any proportion.

[0009] In some embodiments, the organic solvent is any one of acetone, butanone, toluene, xylene, dioxane, dimethylformamide, and dimethyl sulfoxide, or a mixture of any one or more of them in any proportion.

[0010] In some embodiments, the chain transfer agent is any one of 2-mercaptoethanol, 3-mercaptopropanol, and 6-mercaptohexanol, or a mixture of any one or more of them in any proportion.

[0011] In some embodiments, the initiator is any one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile, and azoisobutylcyanamide, or a mixture of any one or more of them in any proportion.

[0012] In some embodiments, the diisocyanate is any one of toluene diisocyanate, p-phenylene diisocyanate, cyclohexane dimethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate, or a mixture of any one or more of them in any proportion.

[0013] In some embodiments, the second catalyst is dibutyltin dilaurate.

[0014] In some embodiments, the amount of each raw material used is, by weight: 5-20 parts of organic fluorine acrylate, 10-40 parts of organic solvent, 0.5-5 parts of chain transfer agent, 0.05-0.2 parts of initiator, 1-10 parts of diisocyanate, and 0.02-0.05 parts of second catalyst.

[0015] In some embodiments, the epoxy resin is any one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, or a mixture of any one or more of them in any proportion.

[0016] In some embodiments, the unsaturated carboxylic acid is any one of acrylic acid, methacrylic acid, and crotonic acid, or a mixture of any one or more of them in any proportion.

[0017] In some embodiments, the polymerization inhibitor is any one of hydroquinone, catechol, BASF 264, and polymerization inhibitor 510, or a mixture of any one or more of them in any proportion.

[0018] In some embodiments, the first catalyst is any one of triethylamine, triphenylphosphine, triethylbenzyl ammonium chloride, benzyl diethylamine, or a mixture of any one or more of them in any proportion.

[0019] In some embodiments, the active diluent is any one of styrene, isobornyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, acryloylmorpholine, and α-methylstyrene, or a mixture of any one or more of them in any proportion.

[0020] According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned organic fluorine-modified epoxy vinyl ester resin, comprising the following steps:

[0021] The organic fluorine polymer modifier is reacted with the epoxy resin at 60-90°C for 1-4h, and then the unsaturated carboxylic acid, the first catalyst and the polymerization inhibitor are added, and the temperature is raised to 90-120°C for reaction for 2-5h until the acid value is lower than 30mg KOH / g, and then the temperature is lowered to 60-80°C, and the active diluent is added and mixed evenly to obtain the product.

[0022] According to a third aspect of the present invention, there is provided a use of the above-mentioned organic fluorine-modified epoxy vinyl ester resin in the preparation of a marine anticorrosive coating.

[0023] Compared with the prior art, the beneficial effects of the present invention include:

[0024] (1) The present invention firstly undergoes a free radical polymerization reaction between an organic fluorine acrylate and a chain transfer agent, then undergoes an addition reaction between the hydroxyl group of the chain transfer agent and the isocyanate group of a diisocyanate to prepare an isocyanate-group semi-terminated organic fluorine polymer modifier, then grafts the organic fluorine polymer modifier onto the hydroxyl group of an epoxy resin through an addition reaction, and finally undergoes a ring-opening reaction between an unsaturated carboxylic acid and the epoxy resin to prepare an organic fluorine-modified epoxy vinyl ester resin. The cured film prepared from the organic fluorine-modified epoxy vinyl ester resin of the present invention has excellent mechanical properties, chemical resistance and corrosion resistance, and is suitable for use as an anticorrosive coating for metal structures in atmospheric or seawater corrosion environments.

[0025] (2) The present invention introduces an organic fluorine polymer modifier into the epoxy vinyl ester resin to prepare an organic fluorine-modified epoxy vinyl ester resin, thereby improving the crosslinking density, thermal stability, chemical corrosion resistance, photoelectric properties, hydrophobic and oleophobic properties, and mechanical properties of the epoxy vinyl ester resin.

[0026] (3) The organic fluorine polymer modifier prepared by the present invention has a low molecular weight and viscosity, and can directly participate in subsequent reactions after removing the organic solvent. No gelation will occur during the subsequent reaction. The final product does not contain an organic solvent and is safe and environmentally friendly.

[0027] (4) The present application forms a side chain structure by forming an organic fluorine polymer modifier onto the epoxy resin through an addition reaction between diisocyanate and the hydroxyl group on the side chain of the epoxy resin. This allows the organic fluorine polymer modifier to better migrate to the resin surface during the resin curing process, giving the resin lower surface energy and anti-corrosion properties, and improving the compatibility of the organic fluorine polymer with the epoxy vinyl ester resin, reducing the effect of phase separation on its performance, thereby effectively blocking corrosive substances from entering the coating.

[0028] (5) The preparation process of the organic fluorine-modified epoxy vinyl ester resin of the present invention is simple, and no organic solvent is added. The organic fluorine-modified epoxy vinyl ester resin finally obtained does not contain organic solvent and is safe and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the Fourier transform infrared spectrum of the organic fluorine polymer modifier of Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The present invention is further described in detail below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the raw materials involved in the following examples can be obtained from commercial channels.

[0031] Example 1

[0032] The preparation method of the organic fluorine-modified epoxy vinyl ester resin of this embodiment comprises the following steps:

[0033] (1) 20 g of hexafluorobutyl methacrylate, 40 g of toluene, 3.12 g of 2-mercaptoethanol and 0.2 g of azobisisobutyronitrile were used as raw materials, mixed evenly, and reacted at 80° C. for 8 h. After the reaction was completed, toluene was removed, and then 6.95 g of toluene diisocyanate and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 45° C. for 3 h to obtain an organic fluorine polymer modifier.

[0034] (2) In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44 and 0.04g of the organic fluorine polymer modifier prepared in step (1), then place the three-necked flask in a 60°C oil bath, stir at a speed of 250r / min for 2h, until the mass percentage of isocyanate group drops below 0.5%. Then add 12.70g of acrylic acid, 0.26g of triethylbenzyl ammonium chloride and 0.01g of hydroquinone to the above three-necked flask, heat to 110°C, stir at a speed of 250r / min for 3h, until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain a light yellow transparent liquid.

[0035] The structure of the organic fluorine polymer modifier prepared in Example 1 was characterized using the Thermo Fisher Nicolet iS10 Fourier transform infrared spectrometer. The test results are as follows: Figure 1 shown.

[0036] from Figure 1 It can be seen that in the infrared absorption curve of hexafluorobutyl methacrylate, at 1638cm -1 The absorption peak at 3000cm is caused by the stretching vibration of C=C bond. -1-2800cm -1 The absorption peaks between 1638cm and 1648cm are caused by the stretching vibration of CH bonds of CH3, CH2 and CH. -1 The stretching vibration absorption peak of the C=C bond at 3317cm disappeared, indicating that the polymerization of hexafluorobutyl methacrylate was successful. After the addition reaction of 2-mercaptoethanol and toluene diisocyanate, the absorption peak at 3317cm -1 The new absorption peak at 2275cm is caused by the stretching vibration of the NH bond. -1 The vibration absorption peak of -NCO is 1528cm -1 The peak at the center is the vibration absorption peak of the carbamate group, indicating that the organic fluorine polymer modifier was successfully prepared.

[0037] Example 2

[0038] The preparation method of the organic fluorine-modified epoxy vinyl ester resin of this embodiment comprises the following steps:

[0039] (1) 20 g of hexafluorobutyl methacrylate, 40 g of toluene, 3.12 g of 2-mercaptoethanol and 0.2 g of azobisisobutyronitrile were used as raw materials, mixed evenly, and reacted at 80° C. for 8 h. After the reaction was completed, toluene was removed, and then 6.95 g of toluene diisocyanate and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 45° C. for 3 h to obtain an organic fluorine polymer modifier.

[0040] (2) In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44 and 0.08g of the organic fluorine polymer modifier prepared in step (1), then place the three-necked flask in a 70°C oil bath, stir at a speed of 250r / min for 1h, until the mass percentage of isocyanate groups drops below 0.5%. Then add 12.70g of acrylic acid, 0.26g of triethylbenzyl ammonium chloride and 0.01g of hydroquinone to the above three-necked flask, heat to 110°C, stir at a speed of 250r / min for 3h, until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain a light yellow transparent liquid.

[0041] Example 3

[0042] The preparation method of the organic fluorine-modified epoxy vinyl ester resin of this embodiment comprises the following steps:

[0043] (1) 20 g of hexafluorobutyl methacrylate, 40 g of toluene, 3.12 g of 2-mercaptoethanol and 0.2 g of azobisisobutyronitrile were used as raw materials, mixed evenly, and reacted at 80° C. for 8 h. After the reaction was completed, toluene was removed, and then 6.95 g of toluene diisocyanate and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 45° C. for 3 h to obtain an organic fluorine polymer modifier.

[0044] (2) In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44 and 0.16g of the organic fluorine polymer modifier prepared in step (1), then place the three-necked flask in an 80°C oil bath, stir at a speed of 250r / min for 1h, until the mass percentage of isocyanate groups drops below 0.5%. Then add 12.70g of acrylic acid, 0.26g of triethylbenzyl ammonium chloride and 0.01g of hydroquinone to the above three-necked flask, heat to 110°C, stir at a speed of 250r / min for 3h, until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain a light yellow transparent liquid.

[0045] Example 4

[0046] The preparation method of the organic fluorine-modified epoxy vinyl ester resin of this embodiment comprises the following steps:

[0047] (1) 20 g of hexafluorobutyl methacrylate, 40 g of toluene, 3.12 g of 2-mercaptoethanol and 0.2 g of azobisisobutyronitrile were used as raw materials, mixed evenly, and reacted at 70° C. for 12 h. After the reaction was completed, toluene was removed, and then 6.72 g of hexamethylene diisocyanate and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 50° C. for 3 h to obtain an organic fluorine polymer modifier.

[0048] (2) In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44 and 0.04g of the organic fluorine polymer modifier prepared in step (1), then place the three-necked flask in an 80°C oil bath, stir at a speed of 250r / min for 1h, until the mass percentage of isocyanate groups drops below 0.5%. Then add 12.70g of acrylic acid, 0.26g of triethylbenzyl ammonium chloride and 0.01g of hydroquinone to the above three-necked flask, heat to 110°C, stir at a speed of 250r / min for 3h, until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain a light yellow transparent liquid.

[0049] Example 5

[0050] The preparation method of the organic fluorine-modified epoxy vinyl ester resin of this embodiment comprises the following steps:

[0051] (1) 20 g of hexafluorobutyl methacrylate, 40 g of toluene, 3.12 g of 2-mercaptoethanol and 0.2 g of azobisisobutyronitrile were used as raw materials, mixed evenly, and reacted at 80° C. for 12 h. After the reaction was completed, toluene was removed, and then 6.72 g of hexamethylene diisocyanate and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 60° C. for 3 h to obtain an organic fluorine polymer modifier.

[0052] (2) In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44 and 0.08g of the organic fluorine polymer modifier prepared in step (1), then place the three-necked flask in an 80°C oil bath, stir at a speed of 250r / min for 1h, until the mass percentage of isocyanate groups drops below 0.5%. Then add 12.70g of acrylic acid, 0.26g of triethylbenzyl ammonium chloride and 0.01g of hydroquinone to the above three-necked flask, heat to 110°C, stir at a speed of 250r / min for 3h, until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain a light yellow transparent liquid.

[0053] Example 6

[0054] The preparation method of the organic fluorine-modified epoxy vinyl ester resin of this embodiment comprises the following steps:

[0055] (1) 20 g of hexafluorobutyl methacrylate, 40 g of toluene, 3.12 g of 2-mercaptoethanol and 0.2 g of azobisisobutyronitrile were used as raw materials, mixed evenly, and reacted at 80° C. for 12 h. After the reaction was completed, toluene was removed, and then 6.72 g of hexamethylene diisocyanate and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 60° C. for 3 h to obtain an organic fluorine polymer modifier.

[0056] (2) In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44 and 0.16g of the organic fluorine polymer modifier prepared in step (1), then place the three-necked flask in an 80°C oil bath, stir at a speed of 250r / min for 1h, until the mass percentage of isocyanate groups drops below 0.5%. Then add 12.70g of acrylic acid, 0.26g of triethylbenzyl ammonium chloride and 0.01g of hydroquinone to the above three-necked flask, heat to 110°C, stir at a speed of 250r / min for 3h, until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain a light yellow transparent liquid.

[0057] Comparative Example 1

[0058] The preparation method of the epoxy vinyl ester resin of this comparative example comprises the following steps:

[0059] In a three-necked flask, add 40.00g of bisphenol A epoxy resin E-44, 12.70g of acrylic acid, 0.26g of triethylbenzylammonium chloride and 0.01g of hydroquinone, place the three-necked flask in a 110°C oil bath, stir at 250r / min for 3h until the acid value is lower than 30mg KOH / g, cool to 80°C, add 22.58g of active diluent styrene, until mixed evenly, to obtain epoxy vinyl ester resin.

[0060] Next, the organic fluorine-modified epoxy vinyl ester resins prepared in Examples 1-6 and the epoxy vinyl ester resin prepared in Comparative Example 1 were coated on polished tinplate to obtain heat-cured films, and then the heat-cured films were tested for anti-corrosion properties and mechanical properties.

[0061] 1. Preparation of thermal curing film

[0062] The tinplate purchased on the market was polished with 400 mesh and 1500 mesh sandpaper, scrubbed with deionized water and anhydrous ethanol, and dried in an oven for use. The resins obtained in Examples 1-6 and Comparative Example 1 were added with 0.3wt% of the resin mass as the accelerator cobalt cyclohexane acid and mixed evenly, and then 1wt% of the resin mass as the curing agent methyl ethyl ketone peroxide was added, mixed evenly, and the bubbles were removed by vacuum. Then a 250um wet film preparation device was used to prepare a film on the tinplate plate, first cured at room temperature for 24 hours, then placed in an 80°C oven for curing for about 3 hours, and then placed in a 130°C oven for curing for about 2 hours to obtain a heat-cured film.

[0063] 2. Anti-corrosion and mechanical properties test

[0064] (1) Chemical corrosion resistance test: The cured films coated on the polished tinplate were immersed in 10 wt % NaOH solution for 7 days, then taken out and the cured films were observed for blistering, rusting, shedding, etc.

[0065] (2) Tensile strength and elongation at break: The mechanical properties of the cast body of the cured film coated on the polished tinplate were tested in accordance with the national standard GB / T1040.3-2006.

[0066] The test results are shown in Table 1.

[0067] Table 1 Performance test results of cured films made from the resins of Examples 1-6 and Comparative Example 1

[0068] Test items Tensile strength / MPa Elongation at break / % Resistant to 10% NaOH solution / 7d Comparative Example 1 44.56 8.28 Foaming Example 1 70.56 10.50 none Example 2 73.19 11.21 none Example 3 74.63 12.94 none Example 4 71.12 10.79 none Example 5 77.01 13.61 none Example 6 80.94 12.23 none

[0069] Note: "None" in Table 1 means no blistering, rusting, falling off, etc.

[0070] It can be seen from the test results in Table 1 that, relative to the cured film made from the epoxy vinyl ester resin of Comparative Example 1, the cured films made from the organic fluorine-modified epoxy vinyl ester resins of Examples 1-6 have better chemical resistance, and the mechanical properties are also significantly improved.

[0071] Then, in order to further evaluate the anti-corrosion performance of the organic fluorine-modified epoxy vinyl ester resin of the present invention, the resins prepared in Examples 4-6 and Comparative Example 1 were coated on tinplate, respectively, with a thickness of 80±5 μm. The anti-corrosion performance of the samples was evaluated by electrochemical impedance spectroscopy, using a three-electrode system, with a platinum electrode as the auxiliary electrode, a saturated calomel electrode as the reference electrode, a coated tinplate as the working electrode, and a 3.5 wt% NaCl aqueous solution as the corrosion medium. The frequency range of the electrochemical impedance spectroscopy (EIS) was 10 5 Hz to 10 -2 Hz, using a sine perturbation with an amplitude of 20 mV at open circuit potential (OCP). The low-frequency impedance modulus is used as a quantitative indicator of anti-corrosion performance. The test results of different samples immersed in 3.5wt% NaCl aqueous solution for 80 days are shown in Table 2.

[0072] Table 2 Low frequency impedance modulus of different samples immersed in 3.5wt% NaCl aqueous solution for 80 days

[0073] Testing days Day 0 80 days Comparative Example 1 <![CDATA[2.98×10 10 ]]> <![CDATA[2.51×10 4 ]]> Example 4 <![CDATA[9.44×10 10 ]]> <![CDATA[4.20×10 10 ]]> Example 5 <![CDATA[9.17×10 10 ]]> <![CDATA[4.46×10 10 ]]> Example 6 <![CDATA[1.03×10 11 ]]> <![CDATA[4.87×10 10 ]]>

[0074] The larger the low-frequency impedance modulus, the better the anti-corrosion performance. As can be seen from Table 2, after being immersed in a 3.5wt% NaCl aqueous solution for 80 days, the low-frequency impedance modulus value of the heat-cured film prepared from the organic fluorine-modified epoxy vinyl ester resin of Examples 4-6 was increased by six orders of magnitude compared to the heat-cured film prepared from the epoxy vinyl ester resin of Comparative Example 1, indicating that after the organic fluorine polymer modifier is introduced into the epoxy vinyl ester resin of the present invention, the anti-corrosion performance of the resin is greatly improved, and also indicating that the organic fluorine-modified epoxy vinyl ester resin of the present invention has excellent anti-corrosion performance.

[0075] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An organic fluorine-modified epoxy vinyl ester resin, characterized in that: The raw material composition is as follows: 30-50 parts of epoxy resin, 0.03-0.5 parts of organic fluorine polymer modifier, 9-20 parts of unsaturated carboxylic acid, 0.01-0.1 parts of polymerization inhibitor, 0.1-1 parts of first catalyst, and 15-40 parts of active diluent, in parts by weight; The preparation method of the organic fluorine polymer modifier comprises the following steps: Take organic fluorine acrylate, organic solvent, chain transfer agent and initiator as raw materials, mix them evenly, react at 60-80°C for 8-12 hours, remove the organic solvent after the reaction is completed, then add diisocyanate and the second catalyst, react at 40-60°C for 2-3 hours to obtain an organic fluorine polymer modifier.

2. The organic fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that: The organic fluorine acrylate is any one of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, and 2-(perfluorohexyl)ethyl methacrylate, or a mixture of any one or more of them in any proportion; The organic solvent is any one of acetone, butanone, toluene, xylene, dioxane, dimethylformamide, and dimethyl sulfoxide, or a mixture of any one or more of them in any proportion; The chain transfer agent is any one of 2-mercaptoethanol, 3-mercaptopropanol, and 6-mercaptohexanol, or a mixture of any proportion of the above; The initiator is any one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile and azoisobutylcyanoformamide, or a mixture of any proportion of the above.

3. The organic fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that: The diisocyanate is any one of toluene diisocyanate, p-phenylene diisocyanate, cyclohexane dimethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate, or a mixture of any one or more of them in any proportion; The second catalyst is dibutyltin dilaurate.

4. The organic fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that: In parts by weight, the usage of each raw material is: 5-20 parts of organic fluorine acrylate, 10-40 parts of organic solvent, 0.5-5 parts of chain transfer agent, 0.05-0.2 parts of initiator, 1-10 parts of diisocyanate, and 0.02-0.05 parts of the second catalyst.

5. The organic fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that: The epoxy resin is any one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin or a mixture of any one or more of them in any proportion; The unsaturated carboxylic acid is any one of acrylic acid, methacrylic acid and crotonic acid, or a mixture of any proportion of the unsaturated carboxylic acid.

6. The organic fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that: The inhibitor is any one of hydroquinone, catechol, BASF 264, inhibitor 510, or a mixture of any proportion of more than one of them; The first catalyst is any one of triethylamine, triphenylphosphine, triethylbenzylammonium chloride and benzyldiethylamine or a mixture of any one or more of them in any proportion.

7. The organic fluorine-modified epoxy vinyl ester resin according to claim 1, characterized in that: The active diluent is any one of styrene, isobornyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, acryloylmorpholine, and α-methylstyrene, or a mixture of any one or more of the above in any proportion.

8. The method for preparing the organic fluorine-modified epoxy vinyl ester resin according to any one of claims 1 to 7, characterized in that: The following steps are involved: The organic fluorine polymer modifier is reacted with the epoxy resin at 60-90°C for 1-4h, and then the unsaturated carboxylic acid, the first catalyst and the polymerization inhibitor are added, and the temperature is raised to 90-120°C for reaction for 2-5h until the acid value is lower than 30 mg KOH / g, and then the temperature is lowered to 60-80°C, and the active diluent is added and mixed evenly to obtain the product.

9. Use of the organic fluorine-modified epoxy vinyl ester resin according to any one of claims 1 to 7 in the preparation of marine anticorrosive coatings.

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