A eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on d-a addition, and a preparation method and application thereof

Abstract

The application relates to a eugenol-based high-heat-resistance and high-flame-retardant epoxy resin composition based on D-A addition, a preparation method and application thereof, and belongs to the technical field of high-performance epoxy resins. The specific scheme is as follows: eugenol epoxy monomers and bismaleimide are added in a proper proportion, heated and uniformly mixed at 80-150 DEG C to obtain a clear and transparent solution, a proper proportion of amine curing agent is added into the solution, uniformly mixed, and then poured into a mold after vacuum bubble removal treatment, and cured into a shape in two stages of pre-curing and post-curing. Compared with a commercial epoxy resin curing system, the eugenol-based epoxy resin composition has excellent heat resistance, outstanding flame retardant performance, and meanwhile, excellent mechanical performance and processing performance are maintained. The application provides a new strategy for the application and popularization of bio-based epoxy resins, and the preparation process is simple, the cost is low, and industrial production is easy.

Description

Technical Field

[0001] This invention belongs to the field of bio-based epoxy resin preparation technology, specifically relating to a eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition, its preparation method, and its application. Background Technology

[0002] Epoxy resins possess excellent mechanical properties, thermal stability, chemical stability, and processability, leading to their wide application in aerospace, rail transportation, electronics, shipbuilding, and wind power. However, traditional epoxy resins are highly dependent on petroleum resources and cannot be recycled, posing serious resource and environmental risks. Therefore, the development of novel high-performance epoxy resins using renewable bio-based monomers as raw materials has become a global research hotspot in recent years. To date, various bio-based epoxy resins have been developed, including eugenol, vanillin, lignin, guaiacol, bisphenol A, protocatechuic aldehyde, daidzein, magnolol, resveratrol, cashew nut shell extract, vegetable oils, and tannins. However, most of these bio-based monomers still suffer from limited sourcing, high extraction costs, and high prices, hindering their widespread application. Eugenol, with its low price, wide availability, and health and environmental friendliness, has attracted significant attention and is considered one of the most promising bio-based epoxy resin monomer raw materials.

[0003] Eugenol, primarily extracted from clove flowers, is a low-viscosity liquid with low toxicity and strong antibacterial properties. It is currently mainly used in dental treatment, cosmetics, and the food industry. Its structure contains phenolic hydroxyl, methoxy, and allyl groups. Monofunctional epoxy resins can be synthesized using either the epichlorohydrin method via the phenolic hydroxyl groups or the double bond oxidation method. However, monofunctional eugenol epoxy resins are difficult to cure and can only be used as reactive diluents or additives for epoxy resins. To make eugenol epoxy resins the main resin, further modification of the active functional groups of eugenol is often necessary to prepare multifunctional epoxy resins with different functions. For example, low-dielectric silicon-containing epoxy resins can be prepared by the addition reaction of the double bond groups on the allyl group with the silanol groups in siloxanes. The flexibility of epoxy resins can be improved by the click chemistry reaction of the double bond groups on the allyl group with the mercapto groups. Flame-retardant epoxy resins can be prepared by the substitution reaction between hydroxyl groups and halides. While these methods have made some progress in flame retardant properties, they have also led to more complicated synthesis processes, lower atom utilization, higher costs, and difficulty in achieving a balance between mechanical properties, heat resistance, and flame retardant properties, thus making them difficult to apply. Summary of the Invention

[0004] To address the limitations of existing bio-based epoxy resins, such as high cost, complex synthesis processes, insufficient heat resistance, and high flammability, which hinder their application, this invention provides a strategy for efficiently utilizing eugenol-based epoxy resins. It presents a eugenol-based high-heat-resistant and high-flame-retardant epoxy resin composition based on DA addition, its preparation method, and its applications. Based on a dual curing strategy of DA addition and epoxy-amine ring-opening crosslinking, a method for synthesizing monofunctional eugenol epoxy monomers is proposed. Through the compounding of bismaleimide and amine curing agents, a ternary co-curing process is performed to achieve the goal of preparing a high-performance eugenol epoxy resin system. The cured system exhibits excellent processability, heat resistance, flame retardancy, and a highly competitive cost, showing broad prospects for commercial application.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A dacrylamide-based eugenol-based high heat-resistant and high flame-retardant epoxy resin composition comprises eugenol epoxy monomer, bismaleimide resin, and aromatic amine curing agent, wherein the chemical structural formula of the eugenol epoxy monomer is:

[0007]

[0008] As a preferred embodiment of the present invention, the ratio of the double bond of the eugenol epoxy monomer to the double bond of the bismaleimide resin is (0.7-1.3):1, and the ratio of the number of epoxy groups of the eugenol epoxy monomer to the number of active hydrogens of the aromatic amine curing agent is 1:1.

[0009] Furthermore, the specific preparation steps for eugenol epoxy monomers are as follows:

[0010] 1) Add eugenol, epichlorohydrin and phase transfer catalyst to a reaction vessel equipped with mechanical stirring in a molar ratio of 1:(2-10):(0.02-0.2) and heat to 50-90℃ until completely dissolved;

[0011] 2) After maintaining the temperature constant for 2-6 hours, cool the reaction vessel to room temperature using an ice-water bath, add solid NaOH to the reaction vessel, and stir at room temperature for 3-8 hours to complete the ring-closing reaction. The molar ratio of NaOH to eugenol is (2-5):1.

[0012] 3) After the reaction is complete, filter or centrifuge to remove excess alkali and generated salt. Dilute the remaining liquid with extractant and wash with deionized water 3-6 times. After pH test paper confirms neutrality, take the organic phase and perform vacuum distillation to remove the solvent. Vacuum dry to obtain eugenol epoxy monomer.

[0013] Furthermore, the phase transfer catalyst includes one or more combinations of tetramethylammonium bromide and benzyltriethylammonium chloride; the extractant includes one or more combinations of toluene, methyl isobutyl ketone, chloroform, and dichloromethane.

[0014] Furthermore, the structure of the bismaleimide resin is as follows:

[0015]

[0016] In formulas (II) and (III), R1 and R2 are both organic groups containing an aromatic ring structure, and R1 and R2 contain one or more of an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom.

[0017] Further, the aromatic amine curing agent includes one or more combinations of diethyltoluenediamine (DETDA), 4,4'-diaminodiphenyl sulfone (DDS), 4,4'-diaminobenzylmethane (DDM), 4,4'-diaminophenyl ether (DDE), 3,3'-diethyl-4,4'-diaminodiphenylmethane (H256), and p-phenylenediamine.

[0018] A method for preparing a eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition specifically includes the following steps:

[0019] 1) Add eugenol epoxy monomer and bismaleimide resin at a double bond ratio of 0.7-1.3:1, and stir at 80-150℃ for 10-30 min to obtain a uniformly mixed, clear and transparent solution;

[0020] 2) Add an equimolar amount of aromatic amine curing agent (the molar ratio of active hydrogen on the amine group of the curing agent to the epoxy functional group in the epoxy resin is 1:1) to the clear and transparent solution, and stir at 40-130℃ for 20-60 min to obtain a homogeneous and transparent solution; that is, a eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition; wherein, the stirring temperature in step 2 is lower than the stirring temperature in step 1.

[0021] The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition prepared above includes the following steps:

[0022] 3) Place the solution obtained in step 2 in a vacuum oven at 40-100℃ and degas it under vacuum for 5-30 minutes. Then pour the degassed solution into a metal mold covered with a release agent and place it in the oven. Pre-cur it at 150-200℃ for 1-5 hours. During this stage, the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds mainly occur. Then, heat it to 200-250℃ and cure it for 2-6 hours. During this stage, the DA addition curing reaction mainly occurs, and finally a cured sample with a smooth surface and uniform color is obtained.

[0023] 4) After polishing the strip obtained in step 3 to a smooth and defect-free state, perform tensile, bending, heat resistance, and flame retardant performance tests.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] 1) The eugenol-based epoxy resin of the present invention is prepared from healthy bio-based raw materials, which is in line with the concept of green and sustainable development.

[0026] 2) The preparation method of the eugenol-based epoxy resin and its composition of the present invention is simple and low in cost. It can be compounded with a variety of curing agents and bismaleimide resin, and has great potential to replace existing petroleum-based epoxy resin products. It has broad prospects for commercial application.

[0027] 3) The eugenol-based high heat-resistant and high flame-retardant epoxy resin composition of the present invention has excellent flame-retardant and heat-resistant properties, which are far superior to those of commercially available epoxy resins, and has broad application prospects in aerospace, shipbuilding, electronics, composite materials and other fields. Attached Figure Description

[0028] Figure 1 The 1H NMR spectrum of the eugenol-based epoxy monomer prepared in Example 1 ( 1 H NMR);

[0029] Figure 2 The carbon NMR spectrum of the eugenol-based epoxy monomer prepared in Example 1 ( 13 (C NMR);

[0030] Figure 3 This is a schematic diagram illustrating the curing principle of the high heat resistance and high flame retardant epoxy resin composition prepared in Example 2.

[0031] Figure 4 This is a digital photograph of the cured product after cone calorimetry testing in Example 6. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments. Obviously, the described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0033] Example 1

[0034] First, eugenol (500g), epichlorohydrin (2500g), and the phase transfer catalyst tetramethylammonium bromide (5g) were added to a 5000mL round-bottom flask equipped with a thermometer, a spherical condenser, and a stirrer. The mixture was mechanically stirred until homogeneous. The temperature was raised to 65–75℃, and the reaction was stirred for 2–2.5 hours. The mixture was then cooled to room temperature using an ice-water bath, and solid sodium hydroxide (NaOH, 292g) was added to the round-bottom flask. The mixture was stirred at room temperature for 8 hours. After the reaction was complete, the salts and excess alkali generated were removed by centrifugation, and the supernatant was collected. The supernatant was then poured into a separatory funnel, and a sufficient amount of methyl isobutyl ketone (MIBK) was added to allow the organic phase to float to the top. The mixture was washed several times with deionized water to remove residual salts and alkali. After washing until neutral, the organic phase was separated and distilled under reduced pressure using a rotary evaporator to obtain the crude product, eugenol epoxy monomer (EUEP). The epoxy equivalent was determined to be 222–226 g / mol using the hydrochloric acid-acetone method, which is close to the theoretical value.

[0035] Figure 1 , Figure 2 The eugenol-based epoxy monomers prepared in Example 1 are respectively 1 HNMR and 13 The C NMR spectrum is analyzed as follows:

[0036] The peaks with chemical shifts at 2.73 ppm and 2.89 ppm are attributed to the proton splitting peaks at position 1 of the epoxy group, the peak at 3.32 ppm corresponds to the proton splitting peaks at position 2 of the epoxy group, and the peaks at 4.01 ppm and 4.20 ppm correspond to the proton splitting peaks (3a and 3b) on the methylene group attached to the epoxy group. Therefore, the successful synthesis of the monofunctional eugenol epoxy resin can be basically confirmed. Furthermore, in Figure 2 of 13 In the C NMR spectrum, the peaks at 69.08, 50.27, and 44.57 are attributed to carbons on the epoxy groups of EUEP, further confirming the molecular structure of EUEP.

[0037] Example 2

[0038] First, eugenol epoxy monomer (EUEP, 44.0 g) and diphenylmethane-type bismaleimide resin (BDM, 35.8 g) as shown in structural formula II were added at a double bond ratio of 1:1. After stirring at 130℃ for 30 min, a clear and transparent solution was obtained. Then, DDS was added to the clear and transparent solution in an equimolar ratio (the molar ratio of the number of active hydrogens on the amine groups in DDS to the epoxy groups in EUEP was 1:1). The solution was stirred at 130℃ for 30 min to obtain a reddish-brown solution. The solution was then placed in a vacuum oven at 100℃ for vacuum degassing for 30 min. After degassing, the solution was poured into a mold covered with a release agent and cured at 180℃ for 2 h. During this stage, the main reactions were the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds. The temperature was then raised to 250℃ for 3 h, during which the main reaction was the addition curing reaction of DA. Finally, a cured sample with a smooth surface and uniform color was obtained, named EUEP-BDM-DDS.

[0039] Example 3

[0040] First, eugenol epoxy monomer (EUEP, 44.0 g) and diphenylmethane-type bismaleimide resin (BDM, 35.8 g) as shown in structural formula II were added at a double bond ratio of 1:1. The mixture was stirred at 130°C for 30 min to obtain a homogeneous, clear, and transparent solution. The solution was then cooled to 80°C, and DDM was added to the clear, transparent solution in an equimolar ratio (the molar ratio of active hydrogen on the amino groups of DDM to the epoxy groups of EUEP was 1:1). The mixture was stirred at 80°C for 20 min to obtain a reddish-brown transparent solution. This solution was then placed in an 80°C vacuum oven for vacuum degassing for 10 min. After degassing, the solution is poured into a mold covered with release agent and cured at 160℃ for 2 hours. During this stage, the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds mainly occur. Then, the temperature is raised to 230℃ and cured for 4 hours. During this stage, the DA addition curing reaction mainly occurs. Finally, a cured sample with a smooth surface and uniform color is obtained, named EUEP-BDM-DDM.

[0041] Example 4

[0042] First, eugenol epoxy monomer (EUEP, 44.0 g) and diphenylmethane-type bismaleimide resin (BDM, 35.8 g) as shown in structural formula II were added at a double bond ratio of 1:1. The mixture was stirred at 130°C for 30 min to obtain a homogeneous, clear, and transparent solution. The temperature was then lowered to 60°C, and DETDA was added to the clear, transparent solution in an equimolar ratio (the molar ratio of active hydrogen on the amino groups of DETDA to the epoxy groups of EUEP was 1:1). The mixture was stirred at 60°C for 10 min to obtain a reddish-brown transparent solution. This solution was then placed in a 60°C vacuum oven for vacuum degassing for 10 min. After degassing, the solution is poured into a mold covered with release agent and cured at 150℃ for 2 hours. During this stage, the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds mainly occur. Then, the temperature is raised to 230℃ and cured for 4 hours. During this stage, the DA addition curing reaction mainly occurs. Finally, a cured sample with a smooth surface and uniform color is obtained, named EUEP-BDM-DETDA.

[0043] Example 5

[0044] First, eugenol epoxy monomer (EUEP, 44.0 g) and diphenylmethane-type bismaleimide resin (BDM, 35.8 g) as shown in structural formula II were added at a double bond ratio of 1:1. After stirring at 130℃ for 30 min, a clear and transparent solution with uniform mixing was obtained. Then, DDE was added to the clear and transparent solution in an equimolar ratio (the molar ratio of the number of active hydrogens on the amine groups in DDE to the epoxy groups in EUEP was 1:1). After stirring at 130℃ for 30 min, a reddish-brown solution was obtained. The solution was then placed in a vacuum oven at 100℃ for vacuum degassing for 20 min. After degassing, the solution was poured into a mold covered with a release agent and cured at 180℃ for 2 h. During this stage, the main reactions were the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds. The temperature was then raised to 250℃ for 3 h, during which the main reaction was the addition curing reaction of DA. Finally, a cured sample with a smooth surface and uniform color was obtained, named EUEP-BDM-DDE.

[0045] Example 6

[0046] First, eugenol epoxy monomer (EUEP, 46.2 g) and T-type bismaleimide resin (TMI, 36.9 g) as shown in structural formula III were added at a double bond ratio of 0.7:1. After heating and stirring at 130℃ for 30 min, a clear and transparent solution with uniform mixing was obtained. Then, DDS was added to the clear and transparent solution in an equimolar ratio (the molar ratio of the number of active hydrogens on the amine groups in DDS to the epoxy groups in EUEP was 1:1). The solution was stirred at 130℃ for 30 min to obtain a reddish-brown solution. The solution was placed in a vacuum oven at 100℃ for vacuum degassing for 30 min. After degassing, the solution was poured into a mold covered with a release agent and cured at 180℃ for 2 h. During this stage, the main reactions were the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds. The temperature was then raised to 250℃ for 3 h, during which the main reaction was the DA addition curing reaction. Finally, a cured sample with a smooth surface and uniform color was obtained, named EUEP-TMI-DDS.

[0047] Example 7

[0048] First, eugenol epoxy monomer (EUEP, 46.2 g) and T-type bismaleimide resin (TMI, 36.9 g) as shown in structural formula III were added at a double bond ratio of 0.7:1. The mixture was stirred at 130°C for 30 min to obtain a homogeneous, clear, and transparent solution. The solution was then cooled to 80°C, and DDM was added to the clear, transparent solution in an equimolar ratio (the molar ratio of active hydrogen on the amino groups of DDM to the epoxy groups of EUEP was 1:1). The mixture was stirred at 80°C for 20 min to obtain a reddish-brown solution. This solution was then placed in an 80°C vacuum oven for vacuum degassing for 10 min. After degassing, the solution is poured into a mold covered with release agent and cured at 160℃ for 2 hours. During this stage, the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds mainly occur. Then, the temperature is raised to 230℃ and cured for 4 hours. During this stage, the DA addition curing reaction mainly occurs. Finally, a cured sample with a smooth surface and uniform color is obtained, named EUEP-TMI-DDM.

[0049] Example 8

[0050] First, eugenol epoxy monomer (EUEP, 46.2 g) and T-type bismaleimide resin (TMI, 36.9 g) as shown in structural formula III were added at a double bond ratio of 0.7:1. The mixture was stirred at 130°C for 30 min to obtain a homogeneous, clear, and transparent solution. The solution was then cooled to 60°C, and DETDA was added to the clear, transparent solution in an equimolar ratio (the molar ratio of active hydrogen on the amino groups of DETDA to the epoxy groups of EUEP was 1:1). The mixture was stirred at 60°C for 10 min to obtain a reddish-brown solution. This solution was then placed in a 60°C vacuum oven for vacuum degassing for 10 min. After degassing, the solution is poured into a mold covered with release agent and cured at 150℃ for 2 hours. During this stage, the ring-opening crosslinking of epoxy-amine and the addition reaction of double bonds mainly occur. Then, the temperature is raised to 230℃ and cured for 4 hours. During this stage, the DA addition curing reaction mainly occurs. Finally, a cured sample with a smooth surface and uniform color is obtained, named EUEP-TMI-DETDA.

[0051] Example 9

[0052] First, eugenol epoxy monomer (EUEP, 46.2 g) and T-type bismaleimide resin (TMI, 26.9 g) as shown in structural formula III were added at a double bond ratio of 0.7:1. After stirring at 130℃ for 30 min, a clear and transparent solution was obtained. Then, DDE was added to the clear and transparent solution in an equimolar ratio (the molar ratio of the number of active hydrogens on the amine groups in DDE to the epoxy groups in EUEP was 1:1). The solution was stirred at 130℃ for 30 min to obtain a reddish-brown solution. The solution was placed in a vacuum oven at 100℃ for vacuum degassing for 20 min. After degassing, the solution was poured into a mold covered with a release agent and cured at 180℃ for 2 h. During this stage, the main reactions were ring-opening crosslinking of epoxy-amine and double bond addition. The temperature was then raised to 250℃ for 3 h, during which the main reaction was DA addition curing. Finally, a cured sample with a smooth surface and uniform color was obtained, named EUEP-TMI-DDE.

[0053] Comparative Example 1

[0054] Commercially available bisphenol A type epoxy resin E54 (epoxy equivalent of 184 g / mol) and DDS (the molar ratio of active hydrogen on the amine group of the curing agent to the epoxy group of the epoxy resin is 1:1) were completely melted at 130℃ to form a homogeneous and transparent solution. This solution was then placed in a 100℃ vacuum oven for vacuum degassing for 30 minutes, and cured according to a process of pre-curing at 180℃ for 2 hours and then curing at 250℃ for 3 hours.

[0055] Comparative Example 2

[0056] Commercially available bisphenol A type epoxy resin E54 (epoxy equivalent of 184 g / mol) and DDM (the molar ratio of active hydrogen on the amine group of the curing agent to the epoxy group of the epoxy resin is 1:1) were completely melted at 80℃ to completely dissolve the DDM and form a homogeneous and transparent solution. This solution was then placed in an 80℃ vacuum oven for vacuum degassing for 10 minutes, and cured according to a process of pre-curing at 160℃ for 2 hours and then curing at 230℃ for 4 hours.

[0057] Comparative Example 3

[0058] Commercially available bisphenol A type epoxy resin E54 (epoxy equivalent of 184 g / mol) was mixed evenly with DETDA (the molar ratio of active hydrogen on the amine group in the curing agent to the epoxy group in the epoxy resin was 1:1) at 60℃. The solution was then placed in a vacuum oven at 60℃ for vacuum degassing for 10 min. After that, it was placed in the oven and cured according to the process of pre-curing at 150℃ for 2 h and then curing at 230℃ for 4 h.

[0059] Comparative Example 4

[0060] Commercially available bisphenol A type epoxy resin E54 (epoxy equivalent of 184 g / mol) and DDE (the molar ratio of active hydrogen on the amine group of the curing agent to the epoxy group of the epoxy resin is 1:1) were completely melted at 130℃ to completely dissolve the DDE and form a homogeneous and transparent solution. This solution was then placed in a 100℃ vacuum oven for vacuum degassing for 20 minutes, and cured according to a process of pre-curing at 180℃ for 2 hours and then curing at 250℃ for 3 hours.

[0061] Table 1 shows the mechanical properties, dynamic thermomechanical analysis, thermogravimetric analysis, and flame retardant properties of the cured resins obtained in Examples 2-9 and Comparative Examples 1-4.

[0062] Table 1. Performance comparison of the cured resins obtained in Examples 2-9 and Comparative Examples 1-4

[0063]

[0064]

[0065] The above results fully demonstrate that the eugenol-based epoxy resin composition of the present invention has excellent heat resistance, outstanding flame retardancy and high mechanical properties. Moreover, the preparation process is simple and low-cost, making it suitable for large-scale industrial production. It has extremely high market competitiveness in replacing traditional petroleum-based epoxy resins in high-tech fields such as rail transportation, electronics, and aerospace.

[0066] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. The application of a eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition, characterized in that: The composition comprises eugenol epoxy monomer, bismaleimide resin and aromatic amine curing agent, wherein the ratio of double bonds in eugenol epoxy monomer to double bonds in bismaleimide resin is (0.7~1.3):1, and the ratio of epoxy groups in eugenol epoxy monomer to active hydrogens in aromatic amine curing agent is 1:

1. The method for preparing the composition includes the following steps: Step 1: Mix eugenol epoxy monomer and bismaleimide resin, and stir at 80-150℃ for 10-30 min to obtain a uniform, clear and transparent solution. Step 2: Add aromatic amine curing agent to the solution obtained in Step 1, and stir at 40-130℃ for 10-60 min to obtain a homogeneous and transparent solution, namely the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition; wherein, the stirring temperature in Step 2 is lower than the stirring temperature in Step 1. The composition forms a dual-cured network through a DA addition reaction and an epoxy-amine ring-opening crosslinking reaction. The specific steps are as follows: The DA-based eugenol-based high heat-resistant and high flame-retardant epoxy resin composition was placed in a vacuum oven at 40-100℃. After vacuum degassing, the solution was poured into a metal mold covered with a release agent. It was pre-cured at 150-200℃ for 1-5 h, and then heated to 200-250℃ for 2-6 h to obtain the cured product of the DA-based eugenol-based high heat-resistant and high flame-retardant epoxy resin composition.

2. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition according to claim 1, characterized in that: The structural formula of the eugenol epoxy monomer is shown in Formula I: （Ⅰ）。 3. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition according to claim 1, characterized in that, The preparation method of the eugenol epoxy monomer is as follows: eugenol, epichlorohydrin, and phase transfer catalyst are added to a reaction system with mechanical stirring, the temperature is raised to 50-90℃, and the reaction is maintained at a constant temperature for 2-6 h. After the reaction is completed, the system is cooled to room temperature using an ice-water bath, and solid sodium hydroxide is added to the reaction system. The system is stirred at room temperature for 3-8 h to complete the ring-closing reaction. The supernatant is obtained by filtration or centrifugation, the organic phase is extracted and washed with water, the solvent is removed by vacuum distillation, and the eugenol epoxy monomer is obtained after vacuum drying.

4. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition according to claim 3, characterized in that: The molar ratio of eugenol, epichlorohydrin and phase transfer catalyst is 1:(2~10):(0.02~0.2), and the molar ratio of sodium hydroxide to eugenol is (2~5):

1.

5. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition according to claim 3, characterized in that: The phase transfer catalyst includes one or more combinations of tetramethylammonium bromide and benzyltriethylammonium chloride.

6. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition according to claim 3, characterized in that: The extractant used in the extraction includes one or more combinations of toluene, methyl isobutyl ketone, chloroform, and dichloromethane.

7. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition based on DA addition according to claim 1, characterized in that, The structure of the bismaleimide resin is shown in structural formula II or structural formula III: （Ⅱ）， （Ⅲ）； R1 and R2 are both organic groups containing an aromatic ring structure, and R1 and R2 contain one or more of an oxygen atom, a nitrogen atom, a phosphorus atom or a halogen atom.

8. The application of the eugenol-based high heat-resistant and high flame-retardant epoxy resin composition according to claim 1, characterized in that: The aromatic amine curing agent includes one or more combinations of diethyltoluenediamine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzylmethane, 4,4'-diaminophenyl ether, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and p-phenylenediamine.

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