A toughened vinyl ester resin formulation, its preparation method and application

Abstract

The present invention relates to the field of environmental protection, and specifically relates to a toughened vinyl ester resin formulation, its preparation method and application. The present invention uses epoxy resin, inhibitor, catalyst, acrylic acid, and diluent as raw materials to synthesize vinyl ester resin. The present invention uses diphenylmethane diisocyanate, polypropylene glycol, 2-hydroxyethyl methacrylate, and catalyst as raw materials to synthesize polyurethane acrylate. The vinyl ester resin, polyurethane acrylate, and diaminodiphenyl sulfide, 1,1'-diaminodiferrocene undergo an amino-ene Michael addition reaction to obtain a toughened vinyl ester resin. The product has good stability, a simple operation process, and the toughness of the resin is significantly improved.

Description

Technical Field

[0001] The present invention relates to the field of environmental protection, and particularly to a toughened vinyl ester resin formulation, its preparation method and application. Background Art

[0002] Vinyl ester resin, also known as epoxy acrylate resin, is prepared by the esterification reaction of epoxy resin and acrylic acid or methacrylic acid; vinyl ester resin has high strength, good mechanical properties, and simple molding processing technology. It is an important matrix resin for glass fiber reinforced composites and is widely used in fields such as chemical industry, shipbuilding, coal power, etc.

[0003] Although vinyl ester resin has relatively high mechanical strength, it has brittleness problems, such as low impact strength and low elongation at break. The composites prepared therefrom have defects such as poor anti-bending performance and insufficient high-temperature bending performance, resulting in great limitations in its application. Therefore, toughening modification of it is of great significance for improving the performance of existing products and broadening the application fields.

[0004] Patent ZL202110374586.8 relates to a preparation method of a high-strength and high-toughness vinyl ester resin, including: first reacting diisocyanate with polyether diol to prepare a terminal isocyanate polyurethane prepolymer (PUR), then reacting the polyurethane prepolymer (PUR) with the hydroxyl group of epoxy resin to obtain a polyurethane-block modified epoxy resin (UE), and finally reacting with an unsaturated monocarboxylic acid to obtain a polyurethane-modified vinyl ester resin (VER). The preparation method of the present invention not only embeds flexible polyether chain segments into the resin structure, but also the presence of urethane bonds increases the functionality of the vinyl ester resin. Therefore, a high-strength and high-toughness vinyl ester resin cured by the present invention not only has a low shrinkage rate, high strength, but also has significantly improved impact resistance, good comprehensive performance, stable products, and a reasonable reaction route.

[0005] Patent ZL202011580204.9 discloses a high-toughness vinyl ester resin, which is obtained by mixing 86 - 64 parts by mass of a resin main body part and 14 - 36 parts by mass of an elastomer part. The present invention also provides the preparation methods of the resin main body part and the elastomer part. Through the synthetic method of vinylating the elastomer, the present invention ensures the synthesis stability, and at the same time, it is pre-dispersed in the styrene system, avoiding the problems of layering or precipitation of the elastomer due to poor compatibility with the solvent system. In addition, through the way of mixing and dispersing the resin main body and the elastomer, the present invention can control the rubber dosage in the system, enabling the performance of the final product to be flexibly matched within the selectable range. At the same time, the present invention solves the problem that partial polymerization may occur between the rubber and styrene during the preparation process, improves the content of effective elastic particles in the system, and finally ensures the performance stability of the product.

[0006] Patent ZL201911206917.6 relates to a toughened modified vinyl ester resin and its synthesis method. The method includes the following steps: (1) Add diisocyanate and flexible diol into a reaction kettle, add catalyst A, and when the isocyanate content reaches 1-9%, it is the reaction end point to obtain a terminal isocyanate group polyurethane prepolymer; (2) In another reaction kettle, put in 35-49% of epoxy resin, 10-20% of unsaturated monocarboxylic acid, 0.1-1.0% of catalyst B, 0.01-0.1% of inhibitor, and react until the acid value drops below 12mgKOH / g; (3) After cooling, add 5%-20% of polyurethane prepolymer and 0.05-0.2% of catalyst A, and react until the isocyanate group content is zero, that is, reach the reaction end point. Finally, add 30-40% of crosslinking agent to obtain a polyurethane toughened modified vinyl ester resin. Compared with the prior art, in the present invention, the polyurethane prepolymer capped with isocyanate reacts with the vinyl ester resin, introducing flexible groups on the molecular chain, optimizing the molecular structure, with complete chain extension reaction, good toughening effect, few side reactions, safe, environmentally friendly, and stable quality.

[0007] The above patent and the prior art have carried out a series of studies on the toughening modification of vinyl ester resin. The main modification methods are: liquid rubber toughening, isocyanate (polyurethane) modification, acid or anhydride modification; rubber-like elastomer toughening is one of the most studied and maturely applied methods; the compatibility between liquid rubber and matrix resin and active diluent is poor, and phase separation is likely to occur, affecting the final stability of the product; using isocyanate monomer to modify vinyl ester resin is generally for the purpose of increasing viscosity, improving heat resistance, etc., and generally cannot improve the toughness of the resin. Summary of the Invention

[0008] The purpose of the present invention is to disclose a toughened vinyl ester resin formulation, its preparation method and application in view of the deficiencies of the prior art.

[0009] The technical solution of the present invention is: a toughened vinyl ester resin formulation and its preparation method, including the following steps:

[0010] According to mass parts, weigh 13-15 parts of vinyl ester resin, 17-21 parts of polyurethane acrylate and add them to a reactor, add 3-6 parts of diaminodiphenyl sulfide, 0.01-0.06 parts of 1,1'-diaminocferrocene, 2-4 parts of triethylamine, and 150-200 parts of DMF into the reaction kettle, mix and stir for 10-30 min and then heat up. After the reaction is completed, distill out DMF to obtain a toughened vinyl ester resin.

[0011] Preferably, the diaminodiphenyl sulfide is selected from: 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide.

[0012] Further, the reaction temperature is 80 - 120 °C, and the reaction time is 2 - 5 h.

[0013] Further, the preparation method of the vinyl ester resin is as follows:

[0014] Weigh 14 - 20 parts by mass of epoxy resin and 3 - 7 parts of inhibitor and add them to a reactor, heat, then add 2 - 5 parts of catalyst and 22 - 28 parts of acrylic acid; after the reaction ends, cool down to 65 - 85 °C, add 45 - 60 parts of diluent, and stir evenly to obtain the vinyl ester resin.

[0015] Preferably, the inhibitor is methylhydroquinone.

[0016] Preferably, the catalyst is benzyltriethylammonium chloride.

[0017] Further, the reaction temperature is 95 - 110 °C, and the reaction time is 2 - 5 h.

[0018] Further, the preparation method of the polyurethane acrylate is as follows:

[0019] Weigh 18 - 24 parts by mass of polyurethane prepolymer and add it to a reactor, heat to 100 - 120 °C, stir, and add 35 - 45 parts of 2 - hydroxyethyl methacrylate and 3 - 7 parts of catalyst under a nitrogen atmosphere. After reacting for 2 - 5 h, the polyurethane acrylate is obtained.

[0020] Preferably, the catalyst is dibutyltin dilaurate.

[0021] Further, the preparation method of the polyurethane prepolymer is as follows:

[0022] Weigh 20 - 25 parts by mass of polypropylene glycol and 13 - 17 parts of diphenylmethane diisocyanate and add them to a reactor. Under a nitrogen atmosphere, stir and heat up to 70 - 85 °C, and the reaction time is 2 - 5 h to obtain the polyurethane prepolymer.

[0023] The technical innovation point of the present invention: The vinyl ester resin, polyurethane acrylate reacts with diamino diphenyl sulfide and 1,1'-ferrocenediamine through amino-ene Michael addition reaction to obtain a toughened vinyl ester resin.

[0024] The beneficial effect of the present invention: Compared with the prior art, a toughened vinyl ester resin formulation, its preparation method and application of the present invention have the following significant advantages:

[0025] 1) The polyurethane prepolymer with polyether flexible segments prepared by the present invention is capped with 2-hydroxyethyl methacrylate to prepare polyurethane acrylate, which undergoes a free radical copolymerization cross-linking reaction with vinyl ester resin and styrene under the action of an initiator to improve the toughness of the resin; the toughening agent and the unsaturated double bonds of the resin generate chemical bonding through a free radical copolymerization reaction, improving the compatibility between the two. The product has good stability, a simple operation process, and the toughness of the resin is significantly improved.

[0026] 2) The tensile strength of the toughened vinyl ester resin prepared by the present invention is 55.3 MPa, the flexural strength is 91.7 MPa, the elongation at break is 23.1%, and the notched impact strength reaches 2.76 KJ / m 2 , and the comprehensive mechanical properties are the best. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The electron micrographs of the standard test specimens of the vinyl ester resins prepared in Examples 1-3 are shown in sequence: Example 1 corresponds to A, Example 2 corresponds to B, and Example 3 corresponds to C. DETAILED DESCRIPTION OF THE INVENTION

[0028] The following specific examples illustrate the implementation manners of the present invention. Those skilled in the art can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.

[0029] Example 1

[0030] A formula, preparation method and application of a toughened vinyl ester resin, and its operation steps are as follows:

[0031] Weigh 13 g of vinyl ester resin and 17 g of polyurethane acrylate and add them to a reactor. Add 3 g of diaminodiphenyl sulfide, 0.01 g of 1,1'-diaminodiferrocene, 2 g of triethylamine, and 150 g of DMF to the reaction kettle. After mixing and stirring for 10 min, heat up. After the reaction is completed, distill out DMF to obtain the toughened vinyl ester resin.

[0032] The diaminodiphenyl sulfide is selected from: 4,4'-diaminodiphenyl sulfide.

[0033] The reaction temperature is 80 °C and the reaction time is 2 h.

[0034] The preparation method of the vinyl ester resin is as follows:

[0035] Weigh 14 g of epoxy resin and 3 g of inhibitor and add them to the reactor. Heat the mixture, and then add 2 g of catalyst and 22 g of acrylic acid. After the reaction is completed, cool the temperature to 65 °C, add 45 g of diluent, and stir evenly to obtain vinyl ester resin.

[0036] The inhibitor is methylhydroquinone.

[0037] The catalyst is benzyltriethylammonium chloride.

[0038] The reaction temperature is 95 °C and the reaction time is 2 h.

[0039] The preparation method of the polyurethane acrylate is as follows:

[0040] Weigh 18 g of polyurethane prepolymer and add it to the reactor. Heat it to 100 °C, stir, and add 35 g of 2-hydroxyethyl methacrylate and 3 g of catalyst under a nitrogen atmosphere. After reacting for 2 h, polyurethane acrylate is obtained.

[0041] The catalyst is dibutyltin dilaurate.

[0042] The preparation method of the polyurethane prepolymer is as follows:

[0043] Weigh 20 g of polypropylene glycol and 13 g of diphenylmethane diisocyanate and add them to the reactor. Under a nitrogen atmosphere, stir and heat up to 70 °C. The reaction time is 2 h to obtain the polyurethane prepolymer.

[0044] Example 2

[0045] A toughened vinyl ester resin formulation, its preparation method and application, the operation steps are as follows:

[0046] Weigh 14 g of vinyl ester resin and 18 g of polyurethane acrylate and add them to the reactor. Add 4 g of diaminodiphenyl sulfide, 0.03 g of 1,1'-diaminocferrocene, 3 g of triethylamine, and 160 g of DMF to the reaction kettle. After mixing and stirring for 15 min, heat up. After the reaction is completed, distill out DMF to obtain the toughened vinyl ester resin.

[0047] The diaminodiphenyl sulfide is selected from: 3,4'-diaminodiphenyl sulfide.

[0048] The reaction temperature is 85 °C and the reaction time is 3 h.

[0049] The preparation method of the vinyl ester resin is as follows:

[0050] Weigh 16 g of epoxy resin and 4 g of inhibitor and add them to the reactor. Heat the mixture, and then add 3 g of catalyst and 24 g of acrylic acid. After the reaction is completed, cool the temperature to 70 °C, add 50 g of diluent, and stir evenly to obtain vinyl ester resin.

[0051] The inhibitor is methylhydroquinone.

[0052] The catalyst is benzyltriethylammonium chloride.

[0053] The reaction temperature is 100 °C and the reaction time is 3 h.

[0054] The preparation method of the polyurethane acrylate is as follows:

[0055] Weigh 20 g of polyurethane prepolymer and add it to the reactor. Heat it to 105 °C, stir, and add 38 g of 2-hydroxyethyl methacrylate and 4 g of catalyst under a nitrogen atmosphere. After reacting for 3 h, polyurethane acrylate is obtained.

[0056] The catalyst is dibutyltin dilaurate.

[0057] The preparation method of the polyurethane prepolymer is as follows:

[0058] Weigh 24 g of polypropylene glycol and 16 g of diphenylmethane diisocyanate and add them to the reactor. Under a nitrogen atmosphere, stir and heat up to 75 °C. The reaction time is 3 h to obtain the polyurethane prepolymer.

[0059] Example 3

[0060] A toughened vinyl ester resin formulation, its preparation method and application, and the operation steps are as follows:

[0061] Weigh 14 g of vinyl ester resin and 20 g of polyurethane acrylate and add them to the reactor. Add 5 g of diaminodiphenyl sulfide, 0.04 g of 1,1'-ferrocenediamine, 3 g of triethylamine, and 180 g of DMF to the reaction kettle. After mixing and stirring for 25 min, heat up. After the reaction is completed, distill out DMF to obtain the toughened vinyl ester resin.

[0062] The diaminodiphenyl sulfide is selected from: 3,4'-diaminodiphenyl sulfide.

[0063] The reaction temperature is 110 °C and the reaction time is 4 h.

[0064] The preparation method of the vinyl ester resin is as follows:

[0065] Weigh 18 g of epoxy resin and 6 g of inhibitor and add them to the reactor. Heat, and then add 4 g of catalyst and 26 g of acrylic acid; after the reaction is completed, cool down to 80 °C, add 55 g of diluent, and stir evenly to obtain the vinyl ester resin.

[0066] The inhibitor is methylhydroquinone.

[0067] The catalyst is benzyltriethylammonium chloride.

[0068] The reaction temperature is 105°C and the reaction time is 4 h.

[0069] The preparation method of the polyurethane acrylate is as follows:

[0070] Weigh 22 g of polyurethane prepolymer and add it to a reactor. Heat it to 115°C, stir, and add 42 g of hydroxyethyl methacrylate and 6 g of catalyst under a nitrogen atmosphere. After reacting for 4 h, polyurethane acrylate is obtained.

[0071] The catalyst is dibutyltin dilaurate.

[0072] The preparation method of the polyurethane prepolymer is as follows:

[0073] Weigh 24 g of polypropylene glycol and 16 g of diphenylmethane diisocyanate and add them to a reactor. Under a nitrogen atmosphere, stir and heat to 80°C, and the reaction time is 4 h to obtain a polyurethane prepolymer.

[0074] Example 4

[0075] A toughened vinyl ester resin formulation, its preparation method and application, and the operation steps are as follows:

[0076] Weigh 15 g of vinyl ester resin and 21 g of polyurethane acrylate and add them to a reactor. Add 6 g of diaminodiphenyl sulfide, 0.06 g of 1,1'-diaminocobaltocene, 4 g of triethylamine, and 200 g of DMF to the reaction kettle. After mixing and stirring for 30 min, heat and raise the temperature. After the reaction is completed, distill out DMF to obtain a toughened vinyl ester resin.

[0077] The diaminodiphenyl sulfide is selected from: 3,3'-diaminodiphenyl sulfide.

[0078] The reaction temperature is 120°C and the reaction time is 5 h.

[0079] The preparation method of the vinyl ester resin is as follows:

[0080] Weigh 20 g of epoxy resin and 7 g of inhibitor and add them to a reactor. Heat, and then add 5 g of catalyst and 28 g of acrylic acid; after the reaction is completed, cool down to 85°C, add 60 g of diluent, and stir evenly to obtain vinyl ester resin.

[0081] The inhibitor is methylhydroquinone.

[0082] The catalyst is benzyltriethylammonium chloride.

[0083] The reaction temperature is 110°C and the reaction time is 5 h.

[0084] The preparation method of the polyurethane acrylate is as follows:

[0085] Weigh 24 g of polyurethane prepolymer and add it to a reactor. Heat it to 120 °C, stir, and add 45 g of hydroxyethyl methacrylate and 7 g of catalyst under a nitrogen atmosphere. After reacting for 5 h, polyurethane acrylate is obtained.

[0086] The catalyst is dibutyltin dilaurate.

[0087] The preparation method of the polyurethane prepolymer is as follows:

[0088] Weigh 25 g of polypropylene glycol and 17 g of diphenylmethane diisocyanate and add them to a reactor. Under a nitrogen atmosphere, stir and heat up to 85 °C, and the reaction time is 5 h to obtain a polyurethane prepolymer.

[0089] Comparative Example 1

[0090] A toughened vinyl ester resin formulation, its preparation method and application, and the operation steps are as follows:

[0091] Weigh 13 g of vinyl ester resin and 17 g of polyurethane acrylate and add them to a reactor. Add 0.01 g of 1,1'-diaminocferrocene and 2 g of triethylamine, and add 150 g of DMF to the reaction kettle. After mixing and stirring for 10 min, heat up. After the reaction is completed, distill out DMF to obtain a toughened vinyl ester resin.

[0092] The reaction temperature is 80 °C and the reaction time is 2 h.

[0093] The preparation method of the vinyl ester resin is as follows:

[0094] Weigh 14 g of epoxy resin and 3 g of inhibitor and add them to a reactor. Heat, and then add 2 g of catalyst and 22 g of acrylic acid; after the reaction is completed, cool down to 65 °C, add 45 g of diluent, and stir evenly to obtain vinyl ester resin.

[0095] The inhibitor is methylhydroquinone.

[0096] The catalyst is benzyltriethylammonium chloride.

[0097] The reaction temperature is 95 °C and the reaction time is 2 h.

[0098] The preparation method of the polyurethane acrylate is as follows:

[0099] Weigh 18 g of polyurethane prepolymer and add it to a reactor. Heat it to 100 °C, stir, and add 35 g of hydroxyethyl methacrylate and 3 g of catalyst under a nitrogen atmosphere. After reacting for 2 h, polyurethane acrylate is obtained.

[0100] The catalyst is dibutyltin dilaurate.

[0101] The preparation method of the polyurethane prepolymer is as follows:

[0102] Weigh 20 g of polypropylene glycol and 13 g of diphenylmethane diisocyanate and add them to a reactor. Under a nitrogen atmosphere, stir and heat up to 70 °C, and react for 2 h to obtain the polyurethane prepolymer.

[0103] Comparative Example 2

[0104] A toughened vinyl ester resin formulation, its preparation method and application, the operating steps are as follows:

[0105] Weigh 13 g of vinyl ester resin and 17 g of polyurethane acrylate and add them to a reactor. Add 3 g of diaminodiphenyl sulfide and 2 g of triethylamine, and add 150 g of DMF to the reaction kettle. After mixing and stirring for 10 min, heat up. After the reaction is completed, distill out DMF to obtain the toughened vinyl ester resin.

[0106] The diaminodiphenyl sulfide is selected from: 4,4'-diaminodiphenyl sulfide.

[0107] The reaction temperature is 80 °C and the reaction time is 2 h.

[0108] The preparation method of the vinyl ester resin is as follows:

[0109] Weigh 14 g of epoxy resin and 3 g of inhibitor and add them to a reactor. Heat, and then add 2 g of catalyst and 22 g of acrylic acid; after the reaction is completed, cool down to 65 °C, add 45 g of diluent, and stir evenly to obtain the vinyl ester resin.

[0110] The inhibitor is methylhydroquinone.

[0111] The catalyst is benzyltriethylammonium chloride.

[0112] The reaction temperature is 95 °C and the reaction time is 2 h.

[0113] The preparation method of the polyurethane acrylate is as follows:

[0114] Weigh 18 g of polyurethane prepolymer and add it to a reactor. Heat up to 100 °C, stir, and add 35 g of 2-hydroxyethyl methacrylate and 3 g of catalyst under a nitrogen atmosphere. After reacting for 2 h, the polyurethane acrylate is prepared.

[0115] The catalyst is dibutyltin dilaurate.

[0116] The preparation method of the polyurethane prepolymer is as follows:

[0117] Weigh 20 g of polypropylene glycol and 13 g of diphenylmethane diisocyanate and add them to a reactor. Under a nitrogen atmosphere, stir and heat up to 70 °C, and react for 2 h to obtain the polyurethane prepolymer.

[0118] Comparative Example 3

[0119] A toughened vinyl ester resin formulation, its preparation method and application, the operation steps are as follows:

[0120] Weigh 13 g of vinyl ester resin and 17 g of polyurethane acrylate and add them to a reactor, add 3 g of diaminodiphenyl sulfide, 0.01 g of 1,1'-diaminodiferrocene, and 150 g of DMF to the reaction kettle, mix and stir for 10 min, then heat up. After the reaction is completed, distill out DMF to obtain the toughened vinyl ester resin.

[0121] The diaminodiphenyl sulfide is selected from: 4,4'-diaminodiphenyl sulfide.

[0122] The reaction temperature is 80 °C and the reaction time is 2 h.

[0123] The preparation method of the vinyl ester resin is as follows:

[0124] Weigh 14 g of epoxy resin and 3 g of inhibitor and add them to a reactor, heat, then add 2 g of catalyst and 22 g of acrylic acid; after the reaction is completed, cool down to 65 °C, add 45 g of diluent, and stir evenly to obtain the vinyl ester resin.

[0125] The inhibitor is methylhydroquinone.

[0126] The catalyst is benzyltriethylammonium chloride.

[0127] The reaction temperature is 95 °C and the reaction time is 2 h.

[0128] The preparation method of the polyurethane acrylate is as follows:

[0129] Weigh 18 g of polyurethane prepolymer and add it to a reactor, heat to 100 °C, stir, and add 35 g of 2-hydroxyethyl methacrylate and 3 g of catalyst under a nitrogen atmosphere. After reacting for 2 h, the polyurethane acrylate is prepared.

[0130] The catalyst is dibutyltin dilaurate.

[0131] The preparation method of the polyurethane prepolymer is as follows:

[0132] Weigh 20 g of polypropylene glycol and 13 g of diphenylmethane diisocyanate and add them to a reactor. Under a nitrogen atmosphere, stir and heat up to 70 °C. The reaction time is 2 h to obtain the polyurethane prepolymer.

[0133] Mechanical property test: The resin casting plate was cut into standard test specimens required by the national standard (GB / T 2567—2008), and a universal material testing machine was used to test the mechanical properties; Impact strength test: A cantilever beam impact testing machine was used to test the notched impact strength of the material.

[0134] The test results of the above examples and comparative examples are shown in the following table:

[0135]

Claims

1. A preparation method of a toughened vinyl ester resin, the operation steps of which are as follows: According to mass parts, weigh 13 - 15 parts of vinyl ester resin, 17 - 21 parts of polyurethane acrylate and add them into a reactor, add 3 - 6 parts of diaminodiphenyl sulfide, 0.01 - 0.06 parts of 1,1”-diaminodiferrocene, 2 - 4 parts of triethylamine, and 150 - 200 parts of DMF into the reaction kettle, mix and stir for 10 - 30 min and then heat up. After the reaction is completed, distill out DMF to obtain the toughened vinyl ester resin; The preparation method of the vinyl ester resin is as follows: According to mass parts, weigh 14 - 20 parts of epoxy resin, 3 - 7 parts of inhibitor and add them into a reactor, heat, and then add 2 - 5 parts of catalyst, 22 - 28 parts of acrylic acid; after the reaction is completed, cool down to 65 - 85 °C, add 45 - 60 parts of diluent, and stir evenly to obtain the vinyl ester resin; The preparation method of the polyurethane acrylate is as follows: According to mass parts, weigh 18 - 24 parts of polyurethane prepolymer and add it into a reactor, heat to 100 - 120 °C, stir, and add 35 - 45 parts of 2-hydroxyethyl methacrylate and 3 - 7 parts of catalyst under a nitrogen atmosphere, and react for 2 - 5 h to obtain the polyurethane acrylate; The preparation method of the polyurethane prepolymer is as follows: According to mass parts, weigh 20 - 25 parts of polypropylene glycol, 13 - 17 parts of diphenylmethane diisocyanate and add them into a reactor, stir and heat up to 70 - 85 °C under a nitrogen atmosphere, and the reaction time is 2 - 5 h to obtain the polyurethane prepolymer.

2. The preparation method of a toughened vinyl ester resin according to claim 1, wherein: The diaminodiphenyl sulfide is selected from 4,4”-diaminodiphenyl sulfide, 3,4”-diaminodiphenyl sulfide, 3,3”-diaminodiphenyl sulfide.

3. The preparation method of a toughened vinyl ester resin according to claim 1, wherein: The heating temperature in the preparation of the toughened vinyl ester resin is 80 - 120 °C, and the reaction time is 2 - 5 h.

4. The preparation method of a toughened vinyl ester resin according to claim 1, characterized in that: The inhibitor is methylhydroquinone.

5. The preparation method of a toughened vinyl ester resin according to claim 1, characterized in that: The catalyst used in the preparation of the polyurethane acrylate is benzyltriethylammonium chloride.

6. The preparation method of a toughened vinyl ester resin according to claim 1, characterized in that: The heating temperature in the preparation of the vinyl ester resin is 95 - 110 °C, and the reaction time is 2 - 5 h.

7. The preparation method of a toughened vinyl ester resin according to claim 1, characterized in that: The catalyst used in the preparation of the polyurethane acrylate is dibutyltin dilaurate.

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