Epoxy compound and preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an epoxy compound and a preparation method and application thereof. The epoxy compound has a structure as shown in a formula (1). According to the invention, halogenated epoxypropane, a diol compound and trimethylolpropane are taken as starting raw materials, and the raw materials have active reaction types and good structural stability, so that the reaction activity can be fully exerted, the stability of the reaction process can be ensured, and the improvement of the total yield is facilitated; therefore, efficient synthesis of the epoxy compound is realized. In addition, when the epoxy compound with the specific structure is used as matrix resin of the epoxy adhesive, the toughness of the epoxy adhesive can be remarkably improved. Formula (1).

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to an epoxy compound, its preparation method, and its application. Background Technology

[0002] Epoxy compounds play a crucial role in modern industry, widely used in materials, pharmaceuticals, agriculture, and many other sectors. Trifunctional epoxy compounds, in particular, possess three reactive epoxy functional groups due to their unique molecular structure, giving them significant advantages in constructing complex polymer structures and enhancing material performance. They exhibit unique advantages in high-performance materials, adhesives, and coatings. In the field of high-performance materials, trifunctional epoxy compounds, as key monomers, can participate in the formation of highly cross-linked network structures, thereby significantly improving the mechanical strength, thermal stability, and chemical resistance of materials. For example, in the aerospace field, composite materials prepared using trifunctional epoxy compounds can be used to manufacture key components such as aircraft wings and fuselages, significantly improving load-bearing capacity and reliability while ensuring lightweight materials. In the adhesives and coatings industry, the introduction of trifunctional epoxy compounds can enhance the adhesion of adhesives to different substrates and the wear resistance and corrosion resistance of coatings, making them widely used in fields with stringent coating performance requirements, such as automotive manufacturing and shipbuilding.

[0003] Given the unique advantages of trifunctional epoxy compounds, there is a significant market demand for them. However, existing methods for synthesizing trifunctional epoxy compounds suffer from low yields, thus necessitating the development of a high-yield synthesis method.

[0004] Underfill adhesives are resin adhesives used in electronic packaging processes. They penetrate micron-level gaps through capillary action and are primarily used in semiconductor packaging. Besides filling the gaps between common PCBs and chips, they are also used between flexible printed circuit boards (FPCBs) and chips. Compared to adhesives used between chips and PCBs, those used between chips and FPCBs present greater challenges in formulation design. In addition to possessing the basic properties of conventional underfill adhesives, these adhesives also need to exhibit stronger bonding strength and toughness.

[0005] Epoxy underfillers typically contain epoxy resin, toughening agents, and curing agents. Common epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin. When trifunctional epoxy resin is chosen, the increased epoxy group content generally improves bond strength, but reduces toughness, especially at high temperatures. This is mainly because such epoxy underfillers form a three-dimensional network structure after curing, which restricts molecular chain movement. The increased number of epoxy groups in the epoxy resin leads to higher crosslinking density, further exacerbating this restriction. This makes the material brittle, and the internal stress generated by curing shrinkage cannot be released, easily leading to cracking. Summary of the Invention

[0006] The first objective of this invention is to provide a new epoxy compound that, when used as the main resin of an epoxy adhesive, can increase the toughness of the epoxy adhesive.

[0007] A second objective of this invention is to provide a method for preparing the aforementioned epoxy compound.

[0008] A third objective of the present invention is to provide the application of the above-mentioned epoxy compounds in epoxy adhesives.

[0009] The epoxy compound provided by this invention has the structure shown in formula (1): Equation (1), In equation (1), n ​​is an integer from 1 to 5.

[0010] The method for preparing epoxy compounds provided by this invention includes the following steps: S1. The halo-propylene oxide shown in formula (2) and the diol compound shown in formula (3) are subjected to a first substitution reaction in the presence of base I and a catalyst to obtain intermediate I; S2. The trimethylolpropane shown in formula (4) is subjected to a hydroxyl protection reaction, and the resulting intermediate II is subjected to a second substitution reaction with intermediate I to obtain an epoxy compound; Equation (2), Equation (3), Equation (4), In equation (1), n ​​is an integer from 1 to 5.

[0011] This invention uses halopropylene oxide, diol compounds, and trimethylolpropane as starting materials. These materials all possess reactive properties and good structural stability, ensuring full reactivity and stability of the reaction process, which is beneficial for improving the overall yield and thus achieving efficient synthesis of epoxy compounds. Furthermore, the epoxy compound preparation system provided by this invention is simple, easy to operate, and operates under mild reaction conditions. The entire reaction system is economical, environmentally friendly, and highly efficient.

[0012] The epoxy compound provided by this invention has a ethylene glycol segment structure with three repeating units of 3-8, a short-chain ethyl group, and three epoxy groups. The ethylene glycol segment structure and the short-chain ethyl group are both bonded to the same carbon atom, and the three epoxy groups are respectively bonded to the ends of the three ethylene glycol segment structures. When this epoxy compound with a specific structure is used as the main resin of epoxy adhesive, the toughness of the epoxy adhesive can be significantly improved. The reasons for this are speculated to be as follows: Firstly, the ethylene glycol segment structure with repeating units of 3-8 not only provides flexibility, but also allows the molecular chains to absorb energy through internal rotation and segment movement when subjected to external forces, thus improving toughness. Furthermore, it enables the formation of van der Waals forces and hydrogen bonds with a certain strength between molecules. These forces can be disrupted and reformed to some extent when subjected to external forces, thereby consuming energy and improving toughness. Secondly, the presence of polyfunctional epoxy groups allows the epoxy resin to form a three-dimensional cross-linked network structure after curing. However, excessively high cross-linking density is actually detrimental to improving toughness. The presence of ethyl groups affects the curing reaction of epoxy resin, adjusting the cross-linking density to make the cross-linked network more loose and elastic, which is more conducive to improving the toughness of epoxy adhesives. Simultaneously, the introduction of ethyl groups can break the regularity of the molecular chains, reducing the tight packing between molecular chains and lowering the rigidity of the molecular chains. This allows the molecular chains to undergo relative displacement more easily under stress, thereby improving the toughness of epoxy adhesives. Detailed Implementation

[0013] The epoxy compound provided by this invention has the structure shown in formula (1): Equation (1), In equation (1), n ​​is an integer from 1 to 5, specifically 1, 2, 3, 4, 5, etc.

[0014] The method for preparing epoxy compounds provided by this invention includes the following steps: S1. Halogenated propylene oxide is reacted with a diol compound in the presence of base I and a catalyst to carry out the first substitution reaction, yielding intermediate I; S2. Trimethylolpropane is subjected to a hydroxyl protection reaction, and then the resulting intermediate II is subjected to a second substitution reaction with intermediate I to obtain an epoxide compound.

[0015] In the preparation of the above-mentioned epoxy compound, the halo-epoxypropane has the structure shown in formula (2): Equation (2), In formula (2), X is a halogen, which can be fluorine, chlorine, bromine or iodine.

[0016] In the preparation process of the above-mentioned epoxy compounds, the diol compounds have the structure shown in formula (3): Equation (3), In equation (3), n is an integer from 1 to 5, specifically 1, 2, 3, 4, 5, etc.

[0017] In the preparation of the above-mentioned epoxy compound, the trimethylolpropane has the structure shown in formula (4): Equation (4).

[0018] The reaction equation for the preparation of the epoxy compound provided by this invention is as follows:

[0019] In a preferred embodiment, in step S1, the method for the first substitution reaction includes dissolving halopropylene oxide, base I and catalyst in organic solvent I, heating the resulting mixture to the first substitution reaction temperature under inert gas protection and stirring, adding diol compounds to carry out the first substitution reaction, removing the solvent after the reaction is complete, washing the crude product with water and drying it to obtain intermediate I.

[0020] In a preferred embodiment, step S2, the method for the hydroxyl protection reaction and the second substitution reaction includes dissolving trimethylolpropane, base II, and a protective agent in organic solvent II, placing the resulting mixture under hydroxyl protection conditions for the hydroxyl protection reaction, removing the solvent and drying after the reaction is complete to obtain intermediate II; dissolving intermediate II, base III, and a catalyst in organic solvent III, heating the resulting mixture to the second substitution reaction temperature under inert gas protection and stirring, then adding intermediate I to carry out the second substitution reaction, quenching with water, extracting, and removing the solvent after the reaction is complete to obtain an epoxy compound.

[0021] In the preparation process of the above-mentioned epoxy compound, the molar ratio of the halo-propylene oxide to the diol compound is preferably 1:(0.9~1.1), specifically it can be 1:0.9, 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1 or any value between them.

[0022] In the preparation process of the above-mentioned epoxy compound, the molar ratio of intermediate II to intermediate I is preferably 1:(3~3.3), such as 1:3, 1:3.05, 1:3.1, 1:3.15, 1:3.2, 1:3.25, 1:3.3 or any value between them.

[0023] In the preparation of the above-mentioned epoxy compound, the conditions for the first substitution reaction preferably include a temperature of 25℃ to 100℃, such as 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃ or any value between them; and a time of 2h to 18h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or any value between them.

[0024] In the preparation of the above-mentioned epoxy compound, the conditions for the hydroxyl protection reaction preferably include a temperature of 10℃~30℃, such as 10℃, 12℃, 15℃, 18℃, 20℃, 22℃, 25℃, 28℃, 30℃ or any value between them; and a time of 5h~12h, such as 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or any value between them.

[0025] In the preparation of the above-mentioned epoxy compound, the conditions for the second substitution reaction preferably include a temperature of 25℃ to 100℃, such as 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃ or any value between them; and a time of 2h to 18h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or any value between them.

[0026] In the preparation of the above-mentioned epoxy compound, the molar ratio of the protecting agent to the hydroxyl group in trimethylolpropane is preferably (0.9~1.1):1, such as 0.9:1, 0.92:1, 0.94:1, 0.96:1, 0.98:1, 1:1, 1.02:1, 1.04:1, 1.06:1, 1.08:1, 1.1:1, or any value between them. The active group protecting agent may include at least one of tert-butyldimethylchlorosilane (TBSCl), trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, dimethylphenylchlorosilane, and tert-butyldiphenylchlorosilane.

[0027] In the preparation of the above-mentioned epoxy compounds, the catalyst can be any existing substance that can improve the rate of substitution reaction, without particular limitation. Specific examples include at least one of 4-dimethylaminopyridine (DMAP), benzyltriethylammonium chloride, 18-crown ether-6, tetrabutylammonium chloride, and tetrabutylammonium bromide, with tetrabutylammonium bromide being particularly preferred. When tetrabutylammonium bromide is selected as the catalyst, it is more beneficial to improve the yield of the epoxy compounds.

[0028] In the preparation process of the above-mentioned epoxy compounds, organic solvent I, organic solvent II and organic solvent III can be any existing inert liquid substances that can be used as reaction media, and can be at least one of alcohol solvents, ester solvents, ether solvents, hydrocarbon solvents, ketone solvents, etc., without any particular limitation.

[0029] In the preparation of the above-mentioned epoxy compounds, the types of base I, base II, and base III are not particularly limited and can be conventional choices in the art, as long as they can provide an alkaline environment. For example, they can each be independently selected from at least one of cesium carbonate, sodium bicarbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium tert-butoxide, potassium tert-butoxide, triethylamine, and ammonia. In a preferred embodiment, base I is selected from at least one of cesium carbonate, potassium carbonate, and sodium carbonate; base II is selected from at least one of triethylamine, sodium hydroxide, and potassium hydroxide; and base III is selected from at least one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, and potassium hydroxide. Using the above-mentioned preferred alkaline substances in combination can more effectively promote the formation of reaction products and avoid the formation of by-products, thereby improving the product yield. Furthermore, the molar ratio of the sum of base I, base II, and base III to the halopropylene oxide is preferably (1~5):1, such as 1:1, 1.2:1, 1.5:1, 2:1, 3:1, 3.6:1, 4:1, 4.5:1, 5:1, or any value between them.

[0030] In the preparation process of the above-mentioned epoxy compounds, the terms "Ⅰ", "Ⅱ", "Ⅲ", "Ⅳ" and "Ⅴ" are merely used to distinguish the same type of substance used in different steps for ease of description, and have no other special meaning.

[0031] The present invention also provides the application of the epoxy compound in epoxy adhesives. Specifically, the epoxy adhesive contains an epoxy resin, a trifunctional epoxy compound, a toughening agent, a curing agent, and optionally colorants and coupling agents. The mass ratio of the epoxy resin to the trifunctional epoxy compound is preferably 100:(10~300), such as 100:10, 100:20, 100:50, 100:80, 100:100, 100:120, 100:150, 100:180, 100:200, 100:220, 100:250, 100:280, 100:300, or any value between them. The preferred mass ratio of epoxy resin to toughening agent is 100:(20~300), such as 100:20, 100:50, 100:80, 100:100, 100:120, 100:150, 100:180, 100:200, 100:220, 100:250, 100:280, 100:300 or any value between them. The preferred mass ratio of epoxy resin to curing agent is 100:(20~500), such as 100:20, 100:50, 100:80, 100:100, 100:120, 100:150, 100:180, 100:200, 100:220, 100:250, 100:280, 100:300, 100:320, 100:350, 100:380, 100:400, 100:420, 100:450, 100:480, 100:500 or any value between them. The preferred mass ratio of epoxy resin to colorant is 100:(0~20), such as 0, 100:1, 100:2, 100:4, 100:6, 100:8, 100:10, 100:12, 100:14, 100:16, 100:18, 100:20, or any value between them. The preferred mass ratio of epoxy resin to coupling agent is 100:(0~100), such as 0, 100:2, 100:5, 100:10, 100:13, 100:15, 100:18, 100:20, 100:50, 100:80, 100:100, or any value between them.

[0032] The present invention will be further described below with reference to the embodiments.

[0033] In the following examples and comparative examples, the bisphenol A type epoxy resin was purchased from KUKDO Corporation of South Korea, with the grade YD-128; the bisphenol F type epoxy resin was purchased from Mitsubishi Chemical Corporation, with the grade 806; and the SBS thermoelastic resin was purchased from Kronen, with the grade D1155.

[0034] Preparation Example 1: Epoxy Compounds and Their Preparation Methods S1. 9.2 g (0.1 mol, 1 eq) of epichlorohydrin was dissolved in 200 mL of acetonitrile, followed by the addition of 41.5 g (0.3 mol, 3.05 eq) of potassium carbonate and 3.2 g (0.01 mol, 0.1 eq) of tetrabutylammonium bromide. The mixture was heated to 60 °C and stirred for 20 min under inert gas protection. Then, 10.6 g (0.1 mol, 1 eq, having the structure shown in formula (3), n is 1) of ethylene glycol ether was slowly added and the mixture was reacted for 12 h. After the reaction was completed, the solvent was recovered by vacuum distillation, washed with water, and dried to obtain 15 g of intermediate I.

[0035] S2. Dissolve 13.4 g (0.1 mol, 1 eq) of trimethylolpropane in 1 L of dichloromethane, purge with nitrogen, add 15.18 g (150 mmol, 1.5 eq) of triethylamine and 15 g (0.1 mol, 1 eq) of TBSCl, stir at 10 °C for 6 h, remove the solvent by vacuum distillation after the reaction is complete, wash the crude product with water and dry to obtain 43.4 g of intermediate II. 47.6 g (0.1 mol, 1 eq) of intermediate II was dissolved in 180 mL of N,N-dimethylformamide, followed by the addition of 37.9 g (277 mmol, 3.05 eq) of potassium carbonate and 1 g (9 mmol, 0.1 eq) of DMAP. After heating to 60 °C, 71.3 g (330 mmol, 3.3 eq) of intermediate I was slowly added. The reaction was stirred for 10 h after the addition was complete. After the reaction was completed, water was added to quench the reaction, followed by extraction with 200 mL of dichloromethane. The organic phase was then distilled under reduced pressure to remove the solvent, yielding 46.4 g of the epoxy compound, designated EPD-01.

[0036] The overall yield of the reaction was 82%. The NMR results are as follows: ¹H NMR (400 MHz, DMSO-do) δ 7.08 (s, 6H), 4.19 (dt, J=12.3, 6.1 Hz, 6H), 4.04 (dt, J= 12.4, 6.2 Hz, 6H), 3.96 (t, J=5.1 Hz, 6H), 3.85 (dt, J= 12.4, 6.2 Hz, 6H), 3.79 -3.72 (m, 3H), 3.72-3.53 (m, 6H), 3.39 (dd, J= 7.2, 5.5 Hz, 6H), 2.94 (dd, J= 7.2, 5.5 Hz, 2H), 2.85 (p, J=5.6 Hz, 3H). The NMR results show that the epoxy compound has the structure shown in formula (1).

[0037] Preparation Example 2: Epoxide Compounds and Their Preparation Methods S1. 92 g of epichlorohydrin (1 mol, 1 eq) was dissolved in 2 L of acetonitrile, followed by the addition of 415 g of potassium carbonate (3 mol, 3.05 eq) and 32 g of tetrabutylammonium bromide (0.1 mol, 0.1 eq). The mixture was heated to 50 °C and stirred for 20 min under inert gas protection. Then, 106 g of ethylene glycol ether (1 mol, 1 eq, with the structure shown in formula (3), n=1) was slowly added and the mixture was reacted for 18 h. After the reaction was completed, the solvent was recovered by vacuum distillation, washed with water, and dried to obtain 161 g of intermediate I.

[0038] S2. Dissolve 134 g (1 mol, 1 eq) of trimethylolpropane in 1 L of dichloromethane, replace with nitrogen, add 151.8 g (1.5 mol, 1.5 eq) of triethylamine and 150 g (1 mol, 1 eq) of TBSCl, stir at 30 °C for 5 h, remove the solvent by vacuum distillation after the reaction is complete, wash the crude product with water and dry to obtain 430 g of intermediate II. 476.8 g (1 mol, 1 eq) of intermediate II was dissolved in 2 L of N,N-dimethylformamide, followed by the addition of 379 g (2.7 mol, 3.05 eq) of potassium carbonate and 10 g (90 mmol, 0.1 eq) of DMAP. After heating to 50 °C, 712.8 g (3.3 mol, 3.3 eq) of intermediate I was slowly added. The reaction was stirred for 18 h after the addition was complete. After the reaction was completed, water was added to quench the reaction, followed by extraction with 2 L of dichloromethane. The organic phase was then distilled under reduced pressure to remove the solvent, yielding 474 g of epoxide, designated EPD-02.

[0039] The overall yield of the reaction was 83.8%. The NMR results are as follows: ¹H NMR (400 MHz, DMSO-do) δ 7.10 (s, 6H), 4.21 (dt, J=12.3, 6.1 Hz, 6H), 4.06 (dt, J= 12.4, 6.2 Hz, 6H), 3.98 (t, J=5.1 Hz, 6H), 3.87 (dt, J= 12.4, 6.2 Hz, 6H), 3.79 -3.72 (m, 3H), 3.72-3.53 (m, 6H), 3.41 (dd, J= 7.2, 5.5 Hz, 6H), 2.96 (dd, J= 7.2, 5.5 Hz, 2H), 2.87 (p, J=5.6 Hz, 3H). The NMR results show that the epoxy compound has the structure shown in formula (1).

[0040] Preparation Example 3: Epoxy Compounds and Their Preparation Methods S1. 138 g (1.5 mol, 1 eq) of epichlorohydrin was dissolved in 3 L of acetonitrile, followed by the addition of 622 g (4.6 mol, 3.05 eq) of potassium carbonate and 96 g (0.15 mol, 0.1 eq) of tetrabutylammonium bromide. The mixture was heated to 55 °C and stirred for 20 min under inert gas protection. Then, 159 g (1.5 mol, 1 eq, with the structure shown in formula (3), n = 2) of ethylene glycol ether was slowly added and the mixture was reacted for 5 h. After the reaction was completed, the solvent was recovered by vacuum distillation, washed with water, and dried to obtain 236 g of intermediate I.

[0041] S2. Dissolve 201 g (1.5 mol, 1 eq) of trimethylolpropane in 1.5 L of dichloromethane, purge with nitrogen, add 228 g (2.2 mol, 1.5 eq) of triethylamine and 225 g (1.5 mol, 1 eq) of TBSCl, stir at 20 °C for 8 h, remove the solvent by vacuum distillation after the reaction is complete, wash the crude product with water and dry to obtain 640 g of intermediate II. 715 g (1.5 mol, 1 eq) of intermediate II was dissolved in 3 L of N,N-dimethylformamide, followed by the addition of 565 g (2.7 mol, 3.05 eq) of potassium carbonate and 16.6 g (136 mmol, 0.1 eq) of DMAP. After heating to 70 °C, 1.07 kg (4.95 mol, 3.3 eq) of intermediate I was slowly added. The reaction was stirred for 8 h after the addition was complete. After the reaction was completed, water was added to quench the reaction, followed by extraction with 3 L of dichloromethane. The organic phase was then distilled under reduced pressure to remove the solvent, yielding 687.6 g of epoxide, designated EPD-03.

[0042] The overall yield of the reaction was 81%. The NMR results are as follows: ¹H NMR (400 MHz, DMSO-do) δ 7.06 (s, 6H), 4.17 (dt, J=12.3, 6.1 Hz, 6H), 4.02 (dt, J= 12.4, 6.2 Hz, 6H), 3.94 (t, J=5.1 Hz, 6H), 3.83 (dt, J= 12.4, 6.2 Hz, 6H), 3.79 -3.72 (m, 3H), 3.72-3.53 (m, 6H), 3.37 (dd, J= 7.2, 5.5 Hz, 6H), 2.92 (dd, J= 7.2, 5.5 Hz, 2H), 2.83 (p, J=5.6 Hz, 3H). The NMR results show that the epoxy compound has the structure shown in formula (1).

[0043] Preparation Example 4: Epoxides and their Preparation Methods The epoxy compound was prepared according to the method of Preparation Example 1, except that epichlorohydrin was replaced by the same molar amount of epibromopropane, and ethylene glycol ether (having the structure shown in Formula (3), n is 1) was replaced by the same molar amount of ethylene glycol ether (having the structure shown in Formula (3), n is 5). The other conditions were the same as in Preparation Example 1, and the epoxy compound was obtained, which was denoted as EPD-04.

[0044] The overall yield of the reaction was 66%. The NMR results are as follows: ¹H NMR (400 MHz, DMSO-do) δ 7.09 (s, 6H), 4.20 (dt, J=12.3, 6.1 Hz, 6H), 4.05 (dt, J= 12.4, 6.2 Hz, 6H), 3.97 (t, J=5.1 Hz, 6H), 3.86 (dt, J= 12.4, 6.2 Hz, 6H), 3.79 -3.72 (m, 3H), 3.72-3.53 (m, 6H), 3.40 (dd, J= 7.2, 5.5 Hz, 6H), 2.95 (dd, J= 7.2, 5.5 Hz, 2H), 2.86 (p, J=5.6 Hz, 3H). The NMR results show that the epoxy compound has the structure shown in formula (1).

[0045] Comparative Preparation Example 1: Reference Epoxide and its Preparation Method S1. 9.2 g (0.1 mol, 1 eq) of epichlorohydrin was dissolved in 200 mL of acetonitrile, followed by the addition of 41.5 g (0.3 mol, 3.05 eq) of potassium carbonate and 3.2 g (0.01 mol, 0.1 eq) of tetrabutylammonium bromide. The mixture was heated to 60 °C and stirred for 20 min under inert gas protection. Then, 10.6 g (0.1 mol, 1 eq, with the structure shown in formula (3), n is 1) of ethylene glycol ether was slowly added and the mixture was reacted for 12 h. After the reaction was completed, the solvent was recovered by vacuum distillation, washed with water, and dried to obtain 15 g of intermediate I. S2. 13.6 g (0.1 mol, 1 eq) of pentaerythritol was dissolved in 1 L of dichloromethane, purged with nitrogen, and 40.5 g (0.4 mol, 4 eq) of triethylamine and 78.2 g (0.41 mol, 4.1 eq) of p-toluenesulfonyl chloride were added. The mixture was stirred at 10 °C for 6 h. After the reaction was completed, the solvent was removed by vacuum distillation. The crude product was washed with water and dried to obtain 75.3 g of intermediate II. 75.3 g (0.1 mol, 1 eq) of intermediate II was dissolved in 180 mL of N,N-dimethylformamide, followed by the addition of 51.1 g (0.41 mol, 4.1 eq) of potassium carbonate and 1 g (10 mmol, 0.1 eq) of DMAP. The mixture was heated to 60 °C and then 95 g (0.44 mol, 4.4 eq) of intermediate I was slowly added. After the addition was complete, the mixture was stirred for 10 h. After the reaction was completed, the mixture was quenched with water and then extracted with 200 mL of dichloromethane. The organic phase was then distilled under reduced pressure to remove the solvent, yielding the reference epoxy compound, denoted as DEPD-01.

[0046] The overall yield of the reaction was 73%. The NMR results are as follows: ¹H NMR (400 MHz, DMSO-do) δ 7.08 (s, 8H), 4.19 (dt, J=12.3, 6.1 Hz, 8H), 4.04 (dt, J= 12.4, 6.2 Hz, 8H), 3.96 (t, J=5.1 Hz, 8H), 3.85 (dt, J= 12.4, 6.2 Hz, 8H), 3.79 -3.72 (m, 4H), 3.72-3.53 (m, 8H), 3.39 (dd, J= 7.2, 5.5 Hz, 8H). Example 1: Epoxy Resin Composition and its Preparation Method (1) The raw material composition is as follows: 26 parts by weight of bisphenol A type epoxy resin; 12 parts by weight of bisphenol F type epoxy resin; 20 parts by weight of epoxy compound (EPD-01); 20 parts by weight of SBS thermoelastic resin; 20 parts by weight of methylnadic anhydride; 1 part by weight of carbon black; 1 part by mass of γ-epoxypropoxypropyltrimethoxysiloxane.

[0047] (2) Preparation method of epoxy resin composition: Bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy compound, SBS thermoelastic resin, methyl nadic anhydride, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirring vessel for 30 minutes. The vessel walls were scraped every 10 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0048] Example 2: Epoxy Resin Composition and its Preparation Method An epoxy resin composition was prepared according to the method of Example 1, except that epoxy compound (EPD-01) was replaced with epoxy compound (EPD-02) in the same weight proportions, and the other conditions were the same as in Example 1, to obtain the epoxy resin composition.

[0049] Example 3: Epoxy Resin Composition and its Preparation Method An epoxy resin composition was prepared according to the method of Example 1, except that epoxy compound (EPD-01) was replaced with epoxy compound (EPD-03) in the same weight proportions, and the other conditions were the same as in Example 1, to obtain the epoxy resin composition.

[0050] Example 4: Epoxy Resin Composition and its Preparation Method An epoxy resin composition was prepared according to the method of Example 1, except that epoxy compound (EPD-01) was replaced with epoxy compound (EPD-04) in the same weight proportions, and the other conditions were the same as in Example 1, to obtain the epoxy resin composition.

[0051] Comparative Example 1: Reference epoxy resin composition and its preparation method An epoxy resin composition was prepared according to the method of Example 1, except that the epoxy compound (EPD-01) was replaced with the same part by weight of the reference epoxy compound (DEPD-01), and the other conditions were the same as in Example 1, to obtain the reference epoxy resin composition.

[0052] Comparative Example 2: Reference epoxy resin composition and its preparation method An epoxy resin composition was prepared according to the method of Example 1, except that the epoxy compound (EPD-01) was replaced with the same amount of bisphenol A type epoxy resin, and the other conditions were the same as in Example 1, to obtain a reference epoxy resin composition.

[0053] Test case The epoxy resin compositions obtained in the above embodiments and the reference epoxy resin composition obtained in the comparative example were heat-cured in an oven at 80°C for 50 min. After the cured products were made into standard samples, the elongation at break was tested using a tensile testing machine according to the method disclosed in GB / T 1040.3-2006, with the tensile speed controlled at 50 mm / min. The results are shown in Table 1.

[0054] Table 1

[0055] As can be seen from the results of the examples, the method provided by the present invention can achieve an overall yield of over 81% in preparing epoxy compounds, thus enabling efficient synthesis of epoxy compounds.

[0056] As can be seen from the results in Table 1, the epoxy resin composition provided by the present invention, with the addition of the epoxy compound with the structure shown in Formula (1), shows that the elongation at break can reach more than 5.5%. The only difference between Comparative Examples 1 and 2 and Example 1 is that they do not contain the epoxy compound with the structure shown in Formula (1), and the elongation at break is reduced to 3.2% and 2.1%, respectively. It can be seen that the epoxy compound with the structure shown in Formula (1) can impart good toughness to the epoxy resin composition.

[0057] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. An epoxy compound, characterized in that, The epoxy compound has the structure shown in formula (1): Equation (1), In equation (1), n ​​is an integer from 1 to 5.

2. The method for preparing the epoxy compound according to claim 1, characterized in that, The method includes the following steps: S1. The halo-propylene oxide shown in formula (2) and the diol compound shown in formula (3) are subjected to a first substitution reaction in the presence of base I and a catalyst to obtain intermediate I; S2. The trimethylolpropane shown in formula (4) is subjected to a hydroxyl protection reaction, and the resulting intermediate II is subjected to a second substitution reaction with intermediate I to obtain an epoxy compound; Equation (2), Equation (3), Equation (4), In equation (2), X is a halogen; In equation (3), n is an integer from 1 to 5.

3. The method for preparing the epoxy compound according to claim 2, characterized in that, In step S1, the method for the first substitution reaction includes dissolving halopropylene oxide, base I and catalyst in organic solvent I, heating the resulting mixture to the first substitution reaction temperature under inert gas protection and stirring, then adding diol compounds to carry out the first substitution reaction, removing the solvent after the reaction is complete, washing the crude product with water and drying it to obtain intermediate I.

4. The method for preparing the epoxy compound according to claim 2 or 3, characterized in that, In step S2, the method for the hydroxyl protection reaction and the second substitution reaction includes dissolving trimethylolpropane, base II, and a protective agent in organic solvent II, placing the resulting mixture under hydroxyl protection conditions for the hydroxyl protection reaction, removing the solvent and drying after the reaction is complete to obtain intermediate II; dissolving intermediate II, base III, and a catalyst in organic solvent III, heating the resulting mixture to the second substitution reaction temperature under inert gas protection and stirring, then adding intermediate I to carry out the second substitution reaction, quenching with water, extracting, and removing the solvent after the reaction is complete to obtain an epoxy compound.

5. The method for preparing the epoxy compound according to claim 4, characterized in that, The protective agent is selected from at least one of tert-butyldimethylchlorosilane, trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, dimethylphenylchlorosilane, and tert-butyldiphenylchlorosilane.

6. The method for preparing the epoxy compound according to claim 4, characterized in that, The catalyst is selected from at least one of 4-dimethylaminopyridine, benzyltriethylammonium chloride, 18-crown ether-6, tetrabutylammonium chloride, and tetrabutylammonium bromide.

7. The method for preparing the epoxy compound according to claim 4, characterized in that, The base I is selected from at least one of cesium carbonate, potassium carbonate, and sodium carbonate; the base II is selected from at least one of triethylamine, sodium hydroxide, and potassium hydroxide; and the base III is selected from at least one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, and potassium hydroxide.

8. The method for preparing the epoxy compound according to claim 2, characterized in that, The molar ratio of the halo-propylene oxide to the diol compound is 1:(0.9~1.1); the molar ratio of intermediate II to intermediate I is 1:(3~3.3).

9. The method for preparing the epoxy compound according to claim 2, characterized in that, The conditions for the first substitution reaction include a temperature of 25℃~100℃ and a time of 2h~18h; The conditions for the hydroxyl protection reaction include a temperature of 10℃~30℃ and a time of 5h~12h; The conditions for the second substitution reaction include a temperature of 25℃ to 100℃ and a time of 2h to 18h.

10. The use of the epoxy compound of claim 1 in epoxy adhesives.

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