Cyclic anhydride compound as well as preparation method and application thereof

Abstract

The invention belongs to the field of organic synthesis, and particularly relates to a cyclic anhydride compound as well as a preparation method and application thereof. The cyclic anhydride compound has a structure as shown in formula (1). According to the preparation method of the cyclic anhydride compound, provided by the invention, the cyclic anhydride compound can be constructed by three-step reaction of Michael addition, cyano hydrolysis and intramolecular condensation on the basis of a polyhydroxy aromatic compound, complicated protecting group operation is not needed, the reaction is carried out at the temperature of 70 DEG C or below, high temperature and high pressure are avoided, and the preparation method is suitable for industrial large-scale production; and meanwhile, the yield of the target product is stabilized at 60-80%. Besides, when the cyclic anhydride compound is used as a curing agent of the epoxy resin composition, the epoxy resin composition has high high-temperature-resistant bonding strength and high Tg, and the requirements of the underfill in the field of semiconductor packaging can be met. Formula (1)

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis, and particularly relates to a cyclic anhydride compound and a preparation method and application thereof. BACKGROUND

[0002] The cyclic anhydride compound is an important organic chemical intermediate, which can be subjected to ring-opening polymerization with an epoxide compound to generate a polyester, and can be widely applied in the fields of adhesives, biodegradable materials, drug carriers, coatings and the like.

[0003] However, the existing synthesis technology of the cyclic anhydride compound has significant limitations: (1) a protecting group-dependent strategy: step-by-step protection and deprotection of active groups such as hydroxyl groups are required, which leads to an increase of 3-5 steps of reaction; (2) harsh reaction conditions: some methods rely on strong corrosive reagents such as concentrated sulfuric acid and trifluoroacetic acid, or require a high-temperature and high-pressure reaction kettle above 150℃, which not only increases the equipment cost, but also easily causes side reactions, and the purity of the target product is low; (3) narrow substrate applicability: the traditional method is mostly suitable for the synthesis of simple chain anhydrides, and the construction efficiency of symmetrical cyclic structures is low, and the yield is generally low. Therefore, it has important practical value to develop a synthesis method of a cyclic anhydride compound with simple steps, mild conditions and stable yield.

[0004] An underfill adhesive (underfill adhesive, underfill adhesive) is a resin adhesive used in electronic packaging process, which penetrates micron-sized gaps through capillary action, and is mainly applied in the field of semiconductor packaging. In addition to being filled between the common PCB board and the chip, it will also be filled between the flexible soft board and the chip. Compared with filling in the chip and the PCB board, the adhesive filled between the chip and the flexible soft board has more formula design difficulty. In addition to the basic performance of the conventional underfill adhesive, the adhesive also needs to have stronger bonding strength and toughness.

[0005] Common curing agents include amine curing agents and anhydride curing agents. However, the epoxy underfill adhesive using the existing anhydride compound as a curing agent has a bonding strength of only 11 MPa after aging at 85℃, 85% for 120h, that is, the high-temperature bonding strength is low. In addition, in order to ensure the stable operation of electronic products, the glass transition temperature (Tg) of the epoxy underfill adhesive must be higher than the use temperature. If the use temperature is close to or exceeds Tg, the epoxy underfill adhesive will rapidly soften due to the increased molecular chain movement, thereby causing a decrease in strength and affecting the performance of the electronic product. SUMMARY

[0006] The first object of the present application is to provide a cyclic anhydride compound, which, when used as a curing agent of an epoxy adhesive, can improve the high-temperature bonding strength and Tg of the epoxy adhesive.

[0007] A second object of the present application is to provide a preparation method of the cyclic anhydride compound.

[0008] A third object of the present application is to provide an application of the cyclic anhydride compound in an adhesive.

[0009] The cyclic anhydride compound provided by the present application has a structure shown in formula (1'): Formula (1'), In formula (1'), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are independently H or C1-C6 alkyl.

[0010] The preparation method of the cyclic anhydride compound provided by the present application comprises the following steps: S1`. Michael addition: cyanoethylation of a polyhydroxy aromatic compound shown in formula (2') with acrylonitrile to obtain a polycyano aromatic compound; S2`. Cyano hydrolysis: hydrolysis of the polycyano aromatic compound to convert cyano groups into carboxyl groups to obtain a polycarboxyl aromatic compound; S3`. Intramolecular condensation: intramolecular anhydridization of the polycarboxyl aromatic compound to obtain a cyclic anhydride compound; Formula (2'), In formula (2'), R3, R4, R5, R 10 , R 11 and R 12 are independently H or C1-C6 alkyl.

[0011] The preparation method of the cyclic anhydride compound provided by the present application starts from a polyhydroxy aromatic compound, and constructs the cyclic anhydride compound through three steps of Michael addition, cyano hydrolysis and intramolecular condensation, without complex protection group operation, and the reaction temperature is below 70°C, avoiding high temperature and high pressure, suitable for industrial scale production. At the same time, the yield of the target product is stable at 60%-80%, having the advantages of simple steps, mild conditions and stable yield, and being suitable for industrial production.

[0012] In addition, the cyclic anhydride compound provided by the present application has a multi-functional anhydride structure, an aromatic ring structure, and the anhydride structure is connected to the aromatic ring structure through an ether bond. The presence of the multi-functional anhydride structure can make the epoxy resin composition form a network structure. The presence of the rigid aromatic ring structure can make the formed network molecular structure more stable. The covalent bond forming the aromatic ring structure needs a higher temperature to be broken. The anhydride structure is connected to the aromatic ring structure through an ether bond, so that there is a strong intermolecular force between the two. The strong intermolecular force can make the molecular chain difficult to move and deform under high temperature conditions, avoiding excessive relaxation and separation of the molecular chain. When used as a curing agent for an epoxy resin compound, the epoxy resin composition can resist higher temperatures, and has higher high-temperature bonding strength and Tg. DETAILED DESCRIPTION

[0013] The cyclic anhydride compound provided by the present application has a structure shown in formula (1'): Formula (1'), In formula (1'), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are independently H or C1-C6 alkyl. The C1-C6 alkyl can be exemplified as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl.

[0014] In the present application, the cyclic anhydride compound preferably has a symmetrical structure, in which R1, R7, R8 and R 14 are the same, R2, R6, R9 and R 13 are the same, R3, R5, R 10 and R 12 are the same, and R4 and R 11 are the same. When the cyclic anhydride compound has a symmetrical structure, the overall structure after curing can be ensured to be in a stable state and is not easy to change due to external conditions (such as temperature change), and has higher high-temperature bonding strength and Tg. In a preferred embodiment, in formula (1'), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are all H.

[0015] The cyclic anhydride compound provided by the present application is prepared by a method comprising the following steps: S1`. Michael addition: cyanethylation of the polyhydroxy aromatic compound with acrylonitrile to obtain a polycyano aromatic compound; S2`. hydrolysis of the polycyano aromatic compound to convert the cyano group to a carboxyl group to obtain a polycarboxy aromatic compound; S3`. intramolecular condensation of the polycarboxy aromatic compound to obtain a cyclic anhydride compound.

[0016] In the preparation of the above-mentioned cyclic anhydride compound, the polyhydroxy aromatic compound has a structure represented by formula (2`): Formula (2`), In formula (2`), R3, R4, R5, R 10 , R 11 , and R 12 are each independently H or a C1-C6 alkyl group. The C1-C6 alkyl group can be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, or neopentyl.

[0017] In the preparation of the above-mentioned cyclic anhydride compound, the polyhydroxy aromatic compound preferably has a symmetrical structure, in which case R3, R5, R 10 , and R 12 are the same, and R4and R 11 are the same.

[0018] In one preferred embodiment, in formula (2`), R3, R4, R5, R 10 , R 11 , and R 12 are each H.

[0019] In the preparation process of the above-mentioned cyclic anhydride compound, in step S1`, the cyanoethylation reaction is carried out in the presence of a base and an organic solvent. The molar ratio of the base to the polyhydroxy aromatic compound is preferably 5:1-12:1, such as 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, or any value between them. The amount of acrylonitrile is preferably 5-12 times the molar amount of the polyhydroxy aromatic compound, such as 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, or any value between them. The conditions of the cyanoethylation reaction preferably include a temperature of 20-50°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or any value between them; and a time of 8-24h, such as 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, or any value between them. The base can be at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate. The organic solvent is preferably methanol and / or ethanol.

[0020] In the preparation process of the above-mentioned cyclic anhydride compound, in step S2`, the hydrolysis reaction is carried out by refluxing the polycyanophenyl compound in a concentrated hydrochloric acid / methanol system. The volume ratio of the concentrated hydrochloric acid to methanol is preferably 1:3-1:5, such as 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or any value between them. The reflux reaction time is preferably 6-24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, or any value between them.

[0021] In the preparation process of the above-mentioned cyclic anhydride compound, in step S3`, the intramolecular anhydride reaction is preferably carried out in the presence of dicyclohexyl carbodiimide (DCC). The molar ratio of the dicyclohexyl carbodiimide to the polycarboxylic aromatic compound is preferably 2:1-3:1, such as 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, or any value between them. The conditions of the intramolecular anhydride reaction preferably include a temperature of 0-30°C, such as 0°C, 2°C, 5°C, 8°C, 10°C, 12°C, 15°C, 18°C, 20°C, 22°C, 25°C, 30°C, or any value between them; and a time of 10-36h, such as 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, or any value between them.

[0022] The reaction mechanism of the above-mentioned preparation process of the cyclic anhydride compound is shown as follows: .

[0023] The present application also provides the use of the cyclic anhydride compound in adhesive. Specifically, the epoxy resin composition provided by the present application contains epoxy resin, toughening agent and curing agent, and optionally toner and coupling agent, wherein the curing agent contains at least the cyclic anhydride compound having the structure shown in formula (1'). The mass ratio of the epoxy resin, toughening agent, curing agent, toner and coupling agent is preferably 100:(20-300):(20-500):(0-20):(0-100). Specifically, the mass ratio of the epoxy resin and toughening agent is preferably 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 therebetween. The mass ratio of the epoxy resin and curing agent is preferably 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 therebetween. The mass ratio of the epoxy resin and toner is preferably 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 therebetween. The mass ratio of the epoxy resin and coupling agent is preferably 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 therebetween.

[0024] In a preferred embodiment, the content of the epoxy resin is 10-50 parts by weight, the content of the toughening agent is 10-30 parts by weight, the content of the curing agent is 10-50 parts by weight, the content of the toner is 0.5-2 parts by weight, and the content of the coupling agent is 1-10 parts by weight, at which point each combination can play a better synergistic role, and is more conducive to improving the high-temperature bonding strength and Tg. Specifically, the content of the epoxy resin can be 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by weight, or any value therebetween. The content of the toughening agent can be 10, 12, 15, 18, 20, 22, 25, 28, 30 parts by weight, or any value therebetween. The content of the curing agent can be 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by weight, or any value therebetween. The content of the toner can be 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2 parts by weight, or any value therebetween. The content of the coupling agent can be 1, 2, 4, 6, 8, 10 parts by weight, or any value therebetween.

[0025] In the epoxy resin composition, the curing agent contains at least a cyclic anhydride compound, which can be only a cyclic anhydride compound, or a mixture of a cyclic anhydride compound and a conventional anhydride curing agent. Among them, the cyclic anhydride compound preferably accounts for 10-100% of the total weight of the curing agent, more preferably 20-100% of the total weight of the curing agent, further preferably 30-100% of the total weight of the curing agent, further preferably 40-100% of the total weight of the curing agent, further preferably 50-100% of the total weight of the curing agent, further preferably 60-100% of the total weight of the curing agent, further preferably 70-100% of the total weight of the curing agent, further preferably 80-100% of the total weight of the curing agent, further preferably 90-100% of the total weight of the curing agent, and most preferably 100% of the total weight of the curing agent. The higher the proportion of the cyclic anhydride compound, the more conducive to improving the bonding strength. The conventional anhydride curing agent can be at least one of methyl nadic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, hexahydro-4-methylphthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride (MTHPA), methylcyclohexene-1,2-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, (2-dodecene-1-yl) succinic anhydride, glutaric anhydride, citraconic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, 2,2-dimethyl glutaric anhydride, 3-methyl glutaric anhydride, 3,3-tetramethylene glutaric anhydride, and 3,3-dimethyl glutaric anhydride.

[0026] In the epoxy resin composition, the epoxy resin composition preferably further contains a tri-functional epoxy compound having a structure represented by Formula (1), in which case the epoxy resin composition can be endowed with good toughness without affecting the high-temperature bonding strength and high Tg of the epoxy resin composition. In addition, the mass ratio of the tri-functional epoxy compound to the epoxy resin is preferably (10-300): 100, such as 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: 100, or any value therebetween.

[0027] Formula (1), In Formula (1), R 1 and R 2 are each independently H or a C1-C5 alkyl group, preferably H. The C1-C5 alkyl group can be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, or neopentyl.

[0028] The present application will be described in detail below by way of examples. The examples are intended to explain the present application and should not be construed as limiting the present application. In the examples, unless a specific technique or condition is mentioned, the technique or condition described in the literature in the art or according to the product manual is used. In the examples, unless a manufacturer is mentioned, a conventional product available on the market is used.

[0029] In the following examples and comparative examples, the bisphenol F bisglycidyl ether was purchased from Mitsubishi Chemical Corporation under the trade designation 806, with an epoxy equivalent weight of 160 g / eq; the bisphenol A bisglycidyl ether was purchased from Mitsubishi Chemical Corporation under the trade designation 828, with an epoxy equivalent weight of 184 g / eq; and the SBS thermoplastic resin was purchased from Kortec under the trade designation D1155.

[0030] Example 1 Preparation of a cyclic anhydride compound S1`. A polyhydroxy aromatic compound having a structure represented by Formula (II), R3, R4, R5, R 10 , R 11 , and R 12The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (20 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 12 h. After the reaction was completed, the methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.

[0031] The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (20 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 12 h. After the reaction was completed, the methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.

[0032] The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (20 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 12 h. After the reaction was completed, the methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.

[0033] The nuclear magnetic resonance data and characteristic data of the cyclic anhydride compound are as follows: 1 H NMR (400 MHz, DMSO-d6) δ7.20 (p, J = 1.0 Hz, 2H), 4.57 (d, J = 1.0 Hz, 8H), 3.75 (t, J = 7.1 Hz, 8H), 2.62(t, J = 7.1 Hz, 8H). From the above results, it can be seen that the cyclic anhydride compound has a structure shown in formula (1'), and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are all H.

[0034] Example 2 Preparation of a cyclic anhydride compound S1`.The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (20 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 12 h. After the reaction was completed, the methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound. 10 , R 11 and R 12The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (15 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 24 h. After the reaction was completed, methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.

[0035] The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (15 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 24 h. After the reaction was completed, methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.

[0036] The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (15 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 24 h. After the reaction was completed, methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.

[0037] The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (15 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 24 h. After the reaction was completed, methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound. 10 11 12 13 14

[0038] Example 3 Preparation of a cyclic anhydride compound The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (15 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 24 h. After the reaction was completed, methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound. 10 11 12 The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (15 mL), concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 24 h. After the reaction was completed, methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, and the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated. The solid was filtered and dried to obtain a polycarboxyphenyl compound.​​​​​​​

[0039] S2`.The polycyanophenyl compound (0.73 g, 1.5 mmol) was dissolved in methanol (25 mL), and concentrated hydrochloric acid (5 mL) was added, and the reaction was refluxed for 6 h. After the reaction was completed, the methanol was removed by rotary evaporation, the residue was dissolved in water, extracted with dichloromethane three times, the aqueous phase was acidified with concentrated hydrochloric acid to pH 2, and a white solid was precipitated, which was filtered and dried to obtain the polycarboxyphenyl compound.

[0040] S3`.The polycarboxyphenyl compound (0.34 g, 0.7 mmol) was dissolved in dichloromethane (20 mL), and DCC (0.42 g, 2.1 mmol) was added, and the reaction was stirred at 30°C for 10 h. After the reaction was completed, the dicyclohexyl urea was removed by filtration, and the filtrate was concentrated by rotary evaporation and purified by column chromatography to obtain 0.23 g of the cyclic anhydride compound (white solid, denoted as AH-3), with a yield of 75%.

[0041] The nuclear magnetic resonance data and characteristic data of the cyclic anhydride compound are basically the same as those of Example 1, and it can be seen that the cyclic anhydride compound has the structure shown in formula (1`), and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are all H.

[0042] Preparation of a tricyclic epoxy compound S1. Epoxy chloropropane 9.2 g (0.1 mol, 1 eq) was dissolved in 200 mL of acetonitrile, followed by the addition of potassium carbonate 41.5 g (0.3 mol, 3.05 eq) and tetrabutylammonium bromide 3.2 g (0.01 mol, 0.1 eq), and the reaction was stirred at 60°C for 20 min under inert gas protection, then triethylene glycol 19.4 g (0.1 mol, 1 eq) was slowly added and the reaction was carried out for 12 h, and then the solvent was recovered by distillation under reduced pressure, and then washed with water and dried to obtain 23 g of intermediate I. 23 g (91 mmol, 1 eq) of intermediate I was dissolved in 200 mL of dichloromethane, and after nitrogen replacement, triethylamine 13.8 g (136.5 mmol, 1.5 eq) and TBSCl 15 g (0.1 mol, 1 eq) were added, and the reaction was stirred at 10°C for 6 h, and then the solvent was removed by distillation under reduced pressure, and then the crude product was washed with water and dried to obtain 27 g of intermediate II.

[0043] S2. 2,6-diformyl-4-hydroxypyridine 15.1 g (0.1 mol, 1 eq) was dissolved with 200 mL tetrahydrofuran, cooled to 0 °C, and then n-butyllithium 6.4 g (0.1 mol, 1 eq) and triphenylmethyl bromophosphonium 37.3 g (0.11 mol, 1.1 eq) were added under argon protection, and stirred for 1 h. After the reaction was completed, water was added for quenching, and then extracted with 200 mL dichloromethane. The organic phase was distilled under reduced pressure to remove the solvent, and 12 g of 2,6-divinyl-4-hydroxypyridine was obtained. 2,6-divinyl-4-hydroxypyridine 12 g (80 mmol, 1 eq) was dissolved with 160 mL N,N-dimethylformamide, and then potassium carbonate 33.7 g (244 mmol, 3.05 eq) and 4-dimethylaminopyridine 1 g (DMAP, 8 mmol, 0.1 eq) were added. After being warmed to 70 °C, intermediate II 40 g (0.11 mol, 1.1 eq) was slowly added, and stirred for 8 h after the addition was completed. After the reaction was completed, water was added for quenching, extracted, and distilled under reduced pressure to remove the solvent, and 40.2 g of intermediate III was obtained. 40.2 g (84 mmol, 1 eq) of intermediate III was dissolved in 160 mL dichloromethane, cooled to 0 °C, and then m-CPBA 43.5 g (252 mmol, 3 eq) was slowly added. After being warmed to 40 °C, the solution was continued to react at this temperature for 12 h. After dilution with dichloromethane, the solution was washed with saturated aqueous sodium bicarbonate solution three times, and then washed with saturated aqueous sodium thiosulfate solution twice. After the organic phase was collected and evaporated, 36.9 g of the tricyclic epoxide compound was obtained, which was recorded as EP-1.

[0044] The total yield of the reaction was 72.1 %. The nuclear magnetic resonance results were as follows: 1 H NMR (400 MHz, DMSO-d6) δ 7.05(s, 2H), 4.16 (dt, J = 12.3, 6.1 Hz, 1H), 4.02 (dt, J = 12.4, 6.2 Hz, 1H), 3.94(t, J =5.1 Hz, 2H), 3.82 (dt, J = 12.4, 6.2 Hz, 1H), 3.77 -3.71 (m, 3H), 3.74-3.55 (m, 15H), 3.42 (dd, J = 7.2, 5.5 Hz, 1H), 2.97 (dd, J = 7.2, 5.5 Hz,1H),2.89 (p, J= 5.6 Hz, 1H). From the NMR results, it can be seen that the tri-functional epoxy compound has a structure shown in Formula (1).

[0045] Test Example 1 19 parts by mass of bisphenol A bisglycidyl ether, 25 parts by mass of bisphenol F bisglycidyl ether, 20 parts by mass of SBS thermoplastic resin, 30 parts by mass of a cyclic anhydride compound (AH-1), 1 part by mass of carbon black, and 5 parts by mass of γ-glycidoxypropyltrimethoxysilane were stirred and mixed in a double planetary mixing power agitator for 30 min, with wall scraping every 15 min, and then the stirring was continued. After the micelles were mixed, vacuum defoaming was started, and the stirring was turned on at the same time. After 10 min of vacuum defoaming, the product was discharged, and an epoxy resin composition was obtained.

[0046] (1) Tg (glass transition temperature): The epoxy resin composition was cured at 150°C for 120 min, and then the Tg was measured using a differential scanning calorimeter with a test temperature increase rate of 10°C / min. The results are shown in Table 1.

[0047] (2) Bonding strength: The epoxy resin composition was coated on a silicon wafer, and then was overlaid and compressed on an FR5 substrate to make a test sample. The bonding area was 2 mm x 2.5 mm, and the glue layer thickness was 45 μm. The sample was cured at 150°C for 120 min, and then was subjected to side pushing using a Dage 4000. The bonding strength was tested at a high temperature (260°C), and the measured force value was recorded as the high-temperature bonding strength (MPa). After the cured sample was treated under heating and humidification conditions of 85°C / 85% RH for 120 h, the bonding strength was tested again at a high temperature (255°C), and the measured force value was recorded as the aged high-temperature bonding strength (MPa). The results are shown in Table 1.

[0048] (3) Modulus: After the epoxy resin composition was cured at 160°C / 100 min, a sample bar with a size of 55 mm x 5 mm x 2 mm was made, and was tested on a DMA. The measurement mode was dual cantilever mode, the vibration frequency was 1 Hz, the amplitude was 10 μm, the temperature increase rate was 10°C / min, the temperature range was -65°C to 300°C, and the modulus data at 200°C were selected for comparison. The results are shown in Table 1.

[0049] (4) Elongation at break: After the epoxy resin composition was cured, a dog bone sample bar was made, and was tested on a DMA instrument using a tensile mode. The sample was heated from room temperature to 250°C, and was kept at the high temperature for 1.2 min. The sample was loaded at a rate of 6 N / min to 18 N. The results are shown in Table 1.

[0050] Test Example 2 An epoxy resin composition was obtained by stirring and mixing 19 parts by mass of bisphenol A bisglycidyl ether, 25 parts by mass of bisphenol F bisglycidyl ether, 20 parts by mass of SBS thermoplastic resin, 15 parts by mass of cyclic anhydride compound (AH-2), 15 parts by mass of methyl nadic anhydride, 1 part by mass of carbon black, and 5 parts by mass of γ-glycidoxypropyltrimethoxysilane in a double planetary mixing power stirred tank for 30 min, scraping the wall every 15 min of stirring, and then continuing to stir, and then opening the vacuum degassing after the micelles were stirred and mixed, and opening the stirring at the same time of the vacuum degassing, and discharging after 10 min of vacuum degassing.

[0051] The Tg, adhesive strength, modulus, and elongation at break of the epoxy resin composition were tested according to the method of Test Example 1, and the results are shown in Table 1.

[0052] Test Example 3 An epoxy resin composition was obtained by stirring and mixing 19 parts by mass of bisphenol A bisglycidyl ether, 25 parts by mass of bisphenol F bisglycidyl ether, 20 parts by mass of SBS thermoplastic resin, 5 parts by mass of cyclic anhydride compound (AH-3), 25 parts by mass of methyl nadic anhydride, 1 part by mass of carbon black, and 5 parts by mass of γ-glycidoxypropyltrimethoxysilane in a double planetary mixing power stirred tank for 30 min, scraping the wall every 15 min of stirring, and then continuing to stir, and then opening the vacuum degassing after the micelles were stirred and mixed, and opening the stirring at the same time of the vacuum degassing, and discharging after 10 min of vacuum degassing.

[0053] The Tg, adhesive strength, modulus, and elongation at break of the epoxy resin composition were tested according to the method of Test Example 1, and the results are shown in Table 1.

[0054] Test Example 4 An epoxy resin composition was prepared according to the method of Test Example 1, except that 30 parts by mass of cyclic anhydride compound (AH-1) was replaced with a mixture of 25 parts by mass of cyclic anhydride compound (AH-1) and 5 parts by mass of methyl nadic anhydride, and the other conditions were the same as those of Test Example 1, to obtain the epoxy resin composition.

[0055] The Tg, adhesive strength, modulus, and elongation at break of the epoxy resin composition were tested according to the method of Test Example 1, and the results are shown in Table 1.

[0056] Test Example 5 An epoxy resin composition was prepared according to the method of Test Example 1, except that 19 parts by mass of bisphenol A bisglycidyl ether was replaced with a mixture of 10 parts by mass of bisphenol A bisglycidyl ether and 9 parts by mass of tri-functional epoxy compound (EP-1), and the other conditions were the same as those of Test Example 1, to obtain the epoxy resin composition.

[0057] The Tg, adhesive strength, modulus and elongation at break of the epoxy resin composition were tested according to the method of Test Example 1, and the results are shown in Table 1.

[0058] Comparative Test Example 1 An epoxy resin composition was prepared according to the method of Test Example 2, except that the cyclic anhydride compound (AH-2) was replaced with methyl nadic anhydride in the same weight parts, and the other conditions were the same as those of Test Example 2, to obtain a reference epoxy resin composition.

[0059] The Tg, adhesive strength, modulus and elongation at break of the reference epoxy resin composition were tested according to the method of Test Example 1, and the results are shown in Table 1.

[0060] Table 1

[0061] As can be seen from the results of the examples, the total yield of the cyclic anhydride compound prepared by the method provided by the present application can be stabilized at more than 75%, and the efficient synthesis of the cyclic anhydride compound can be achieved.

[0062] As can be seen from the results of Table 1, the epoxy resin composition provided by Test Examples 1-5 contains the cyclic anhydride compound having the structure shown in formula (1') and the results show that the high-temperature adhesive strength of the obtained epoxy resin composition can be more than 20.88 MPa, the high-temperature adhesive strength after aging can be more than 12.95 MPa, and the Tg can be more than 118°C, that is, the epoxy resin composition has high high-temperature adhesive strength and high Tg, and can meet the needs of the underfill adhesive in the field of semiconductor packaging. Compared with Test Example 2, the only difference of Comparative Test Example 1 is that the cyclic anhydride compound is replaced with methyl nadic anhydride in the same weight parts, and the results show that the high-temperature adhesive strength of Comparative Test Example 1 is reduced to 15.23 MPa, the high-temperature adhesive strength after aging is reduced to 10.44 MPa, and the Tg is reduced to 109°C. As can be seen from the comparison between Test Example 1 and Test Example 5, when the epoxy resin composition also contains the tricyclic epoxy compound having the structure shown in formula (1), the epoxy resin composition can be endowed with better toughness.

[0063] Although the embodiments of the present application have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present application, and those of ordinary skill in the art can make changes, modifications, replacements and variations to the above embodiments without departing from the principles and spirit of the present application within the scope of the present application.

Claims

1. A cyclic anhydride compound, characterized by, The cyclic anhydride compound has a structure shown in formula (1`): Formula (1'), In formula (1'), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are independently of each other H or C1-C6 alkyl.

2. The cyclic anhydride compound according to claim 1, wherein The cyclic anhydride compound has a symmetrical structure.

3. The cyclic anhydride compound according to claim 1, wherein In formula (1), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , and R 14 are each H.

4. The method for producing the cyclic anhydride compound according to any one of claims 1 to 3, characterized by, The method comprises the following steps: S1`. Michael addition: cyanoethylation of a polyhydroxy aromatic compound shown in formula (2`) with acrylonitrile to obtain a polycyano aromatic compound; S2`. Cyano hydrolysis: hydrolysis of the polycyano aromatic compound to convert cyano groups into carboxyl groups to obtain a polycarboxy aromatic compound; S3`. Intramolecular condensation: intramolecular anhydride reaction of the polycarboxy aromatic compound to obtain a cyclic anhydride compound; Equation (2'), In formula (2'), R3, R4, R5, R 10 , R 11 and R 12 are each independently H or C1-C6 alkyl.

5. The method of claim 4, wherein the cyclic anhydride compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. The polyhydroxy aromatic compound has a symmetrical structure.

6. The method of claim 4, wherein the cyclic anhydride compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. In formula (2), R3, R4, R5, R 10 , R 11 , and R 12 are each H.

7. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein In step S1`, the cyanoethylation reaction is carried out in the presence of a base and an organic solvent; Preferably, the molar ratio of the base to the polyhydroxy aromatic compound is 5:1 to 12:1; Preferably, the amount of acrylonitrile is 5 to 12 times the molar amount of the polyhydroxy aromatic compound; Preferably, the cyanoethylation reaction conditions include a temperature of 20 to 50°C and a time of 8 to 24h; Preferably, the base is selected from at least one of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate; Preferably, the organic solvent is methanol and / or ethanol.

8. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein In step S2`, the hydrolysis reaction mode includes refluxing the polycyano aromatic compound in a concentrated hydrochloric acid / methanol system; Preferably, the volume ratio of the concentrated hydrochloric acid to methanol is 1:3 to 1:5; Preferably, the refluxing reaction time is 6h to 24h.

9. The method for producing a cyclic anhydride compound according to any one of claims 4 to 6, wherein In step S3`, the intramolecular anhydride reaction is carried out in the presence of dicyclohexyl carbodiimide; Preferably, the molar ratio of the dicyclohexyl carbodiimide to the polycarboxy aromatic compound is 2:1 to 3:1; Preferably, the intramolecular anhydride reaction conditions include a temperature of 0 to 30°C and a time of 10 to 36h.

10. Use of the cyclic anhydride compound of any one of claims 1 to 3 in an adhesive.

Images