A modified multifunctional epoxy resin, its preparation method and use
By preparing modified multifunctional epoxy resins, an intermediate compound is reacted with a halogenated epoxy alkane compound in an alkaline medium to form a high-modulus three-dimensional network structure, which solves the problem of insufficient modulus of cured epoxy resins and meets the reliability requirements of semiconductor packaging.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- XIAMEN WELDTONE TECH CO LTD
- Filing Date
- 2024-07-29
- Publication Date
- 2026-06-12
Smart Images
Figure CN118955434B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic adhesives, specifically relating to a modified multifunctional epoxy resin, its preparation method, and its application. Background Technology
[0002] Epoxy resins, after curing, offer significant reliability advantages over other resins, making them a preferred choice in semiconductor packaging, adhesives, coatings, and advanced composite materials. When used in semiconductor packaging, cured epoxy resins require excellent mechanical properties to effectively protect the semiconductor materials. These mechanical properties are primarily influenced by modulus. However, most epoxy resins used in packaging are currently imported, offering richer structures and functionalities, and more precise halogen content control compared to domestically produced resins. Nevertheless, due to structural limitations, existing epoxy resins often have lower modulus after curing, failing to adequately meet packaging requirements. Summary of the Invention
[0003] The primary objective of this invention is to address the problem that existing epoxy resin-cured products have low modulus and are difficult to meet encapsulation requirements, and to provide a modified multifunctional epoxy resin.
[0004] A second objective of this invention is to provide a method for preparing the above-mentioned modified multifunctional epoxy resin.
[0005] A third objective of this invention is to provide a modified multifunctional epoxy resin prepared by the above-described preparation method.
[0006] A fourth objective of this invention is to provide the application of the above-mentioned modified multifunctional epoxy resin in semiconductor packaging.
[0007] Specifically, the modified multifunctional epoxy resin has the structure shown in formula (1);
[0008]
[0009] In formula (1), R1`` and R2`` are each independently C1 to C2 alkylene groups, R3`` and R4`` are each independently C1 to C4 alkyl groups, and R5`` and R6`` are each independently hydrogen, hydroxyl, C1 to C4 alkyl groups, or... R7`` and R8`` are each independently C1 to C4 alkylene groups, R9` and R... 10 Each is independently hydrogen, hydroxyl, C1-C4 alkyl, or R5' and R6' are each independently C1 to C4 alkylene groups.
[0010] In a preferred embodiment, the modified multifunctional epoxy resin has the structure shown in formula (2) and / or formula (3):
[0011]
[0012] In formulas (2) and (3), R1, R1', R2, and R2' are each independently a C1-C2 alkylene group, R3, R3', R4, and R4' are each independently a C1-C4 alkyl group, and R5 and R6 are each independently hydrogen, hydroxyl, C1-C4 alkyl group, or... R7, R7', R8, and R8' are each independently a C1-C4 alkylene group, and R9 and R 10 Each is independently hydrogen, hydroxyl, C1-C4 alkyl, or R5' and R6' are each independently C1 to C4 alkylene groups.
[0013] The method for preparing the modified multifunctional epoxy resin includes a substitution reaction between an intermediate compound having the structure shown in formula (4) and a halo-epoxyalkane compound having the structure shown in formula (5) in the presence of an alkaline medium, and the modified multifunctional epoxy resin is obtained after purification.
[0014]
[0015] In formulas (4) and (5), R1`` and R2`` are each independently C1 to C2 alkylene groups, R3`` and R4`` are each independently C1 to C4 alkyl groups, Q1` and Q2` are each independently hydrogen, C1 to C4 alkyl groups or hydroxyl groups, Q3` and Q4` are each independently hydrogen, C1 to C4 alkyl groups or hydroxyl groups, R is a C1 to C4 alkylene group, and X is a halogen.
[0016] In a preferred embodiment, the intermediate compound has the structure shown in formula (6) and / or formula (7);
[0017]
[0018] In formulas (6) and (7), R1, R1', R2 and R2' are each independently C1 to C2 alkylene groups, R3, R3', R4 and R4' are each independently C1 to C4 alkyl groups, Q1 and Q2 are each independently hydrogen, C1 to C4 alkyl groups or hydroxyl groups, and Q3 and Q4 are each independently hydrogen, C1 to C4 alkyl groups or hydroxyl groups.
[0019] In a preferred embodiment, the molar ratio of the intermediate compound to the halo-epoxyalkane compound is 1:(2.2 to 6.2).
[0020] In a preferred embodiment, the substitution reaction is carried out at a temperature of 50–70°C for a time of 1–3 hours.
[0021] In a preferred embodiment, the haloalkylene oxide compound is selected from epichlorohydrin and / or epichlorohydrin.
[0022] In a preferred embodiment, the alkaline medium is selected from at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, sodium carbonate, and potassium carbonate.
[0023] In a preferred embodiment, the intermediate compound is prepared by a method comprising the following steps:
[0024] S1. The alkoxy-aldehyde benzene having the structure shown in formula (8) is subjected to a condensation reaction in the presence of a catalyst and then purified to obtain the first reaction product;
[0025] S2. The first reaction product is reduced in the presence of a reducing agent and then purified to obtain an intermediate compound;
[0026]
[0027] In formula (8), R1`` is a C1-C2 alkylene group, R3`` is a C1-C4 alkyl group, Q1` is hydrogen, a C1-C4 alkyl group or hydroxyl group, and Q3` is hydrogen, a C1-C4 alkyl group or hydroxyl group.
[0028] In a preferred embodiment, the alkoxy-aldehyde benzene has the structure shown in formula (9) and / or formula (10);
[0029]
[0030] In formulas (9) and (10), R1 and R1' are each independently C1 to C2 alkylene groups, R3 and R3' are each independently C1 to C4 alkyl groups, Q1 is hydrogen, C1 to C4 alkyl or hydroxyl, and Q3 is hydrogen, C1 to C4 alkyl or hydroxyl.
[0031] In a preferred embodiment, in step S1, the alkoxy-aldehyde benzene is selected from at least one of 3-methoxybenzaldehyde, 2-methyl-3-methoxybenzaldehyde, 2-ethyl-3-methoxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, and 2-methoxybenzaldehyde.
[0032] In a preferred embodiment, in step S1, the catalyst is a Laccase enzyme.
[0033] In a preferred embodiment, in step S1, the temperature of the condensation reaction is 20–30°C, and the time is 1–3 hours.
[0034] In a preferred embodiment, in step S2, the reducing agent is selected from NaBH4 and / or LiAlH4.
[0035] In a preferred embodiment, in step S2, the temperature of the reduction reaction is 20–30°C and the time is 1–5 hours.
[0036] The key to this invention is to provide a modified multifunctional epoxy resin having the structure shown in formula (1). This specific structure enables the cured product formed after curing of the modified multifunctional epoxy resin to form a dense three-dimensional network structure, thereby having a high modulus, improving the reliability of the cured product, and achieving effective protection of the substrate to which the cured product is attached. It can meet the requirements of various encapsulation applications and has good application prospects. Attached Figure Description
[0037] Figures 1-6 The figures shown are NMR spectra of the modified multifunctional epoxy resins prepared in Examples 1 to 6. Detailed Implementation
[0038] The modified multifunctional epoxy resin provided by this invention has the structure shown in formula (1). In formula (1), R1`` and R2`` are each independently C1 to C2 alkylene groups, R3`` and R4`` are each independently C1 to C4 alkyl groups, and R5`` and R6`` are each independently hydrogen, hydroxyl, C1 to C4 alkyl groups, or... R7`` and R8`` are each independently C1 to C4 alkylene groups, R9` and R... 10 Each is independently hydrogen, hydroxyl, C1-C4 alkyl, or R5' and R6' are each independently a C1-C4 alkylene group. The C1-C2 alkylene group can be methylene or ethylene. The C1-C4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. The C1-C4 alkylene group can be methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, or tert-butylene.
[0039]
[0040] In this invention, the modified multifunctional epoxy resin preferably has the structure shown in formula (2) and / or formula (3). In formula (2) and formula (3), R1, R1', R2 and R2' are each independently preferably C1-C2 alkylene groups, R3, R3', R4 and R4' are each independently preferably C1-C4 alkyl groups, and R5 and R6 are each independently preferably hydrogen, hydroxyl, C1-C4 alkyl groups, or... R7, R7', R8, and R8' are each independently preferred to be C1-C4 alkylene groups, and R9 and R 10 Each is preferably hydrogen, hydroxyl, C1-C4 alkyl, or... R5' and R9' are each preferably C1 to C4 alkylene groups. Specific examples of C1 to C2 alkylene groups, C1 to C4 alkyl groups, and C1 to C4 alkylene groups are as described above and will not be repeated here.
[0041]
[0042] The method for preparing the modified multifunctional epoxy resin provided by the present invention includes a substitution reaction between an intermediate compound having the structure shown in formula (4) and a halo-epoxyalkane compound having the structure shown in formula (5) in the presence of an alkaline medium, and the modified multifunctional epoxy resin is obtained after purification.
[0043]
[0044] In formulas (4) and (5), R1`` and R2`` are each independently a C1-C2 alkylene group, R3`` and R4`` are each independently a C1-C4 alkyl group, Q1` and Q2` are each independently hydrogen, a C1-C4 alkyl group, or a hydroxyl group, Q3` and Q4` are each independently hydrogen, a C1-C4 alkyl group, or a hydroxyl group, R is a C1-C4 alkylene group, and X is a halogen. The C1-C2 alkylene group can be methylene or ethylene. The C1-C4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. The C1-C4 alkylene group can be methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, or tert-butylene. X can be fluorine, chlorine, bromine, or iodine.
[0045] In this invention, the intermediate compound preferably has the structure shown in formula (6) and / or formula (7);
[0046]
[0047] In formulas (6) and (7), R1, R1', R2, and R2' are each preferably C1-C2 alkylene groups, R3, R3', R4, and R4' are each preferably C1-C4 alkyl groups, Q1 and Q2 are each preferably hydrogen, C1-C4 alkyl groups, or hydroxyl groups, Q3 and Q4 are each preferably hydrogen, C1-C4 alkyl groups, or hydroxyl groups, R is a C1-C4 alkylene group, and X is a halogen. Specific examples of C1-C2 alkylene groups, C1-C4 alkyl groups, and C1-C4 alkylene groups are as described above and will not be repeated here.
[0048] This invention does not impose any particular limitation on the ratio of the intermediate compound to the haloepoxyalkane compound used in the substitution reaction, as long as the resulting product is mainly a modified multifunctional epoxy resin. In some specific embodiments, the molar ratio of the intermediate compound to the haloepoxyalkane compound is preferably 1:(2.2 to 6.2), such as 1:2.2, 1:2.5, 1:2.8, 1:3, 1:4, 1:5, 1:6, or any value between them.
[0049] This invention does not particularly limit the conditions for the substitution reaction, as long as the epoxy group can be modified onto the intermediate compound to obtain a modified multifunctional epoxy resin. In some specific embodiments, the temperature of the substitution reaction is preferably 50–70°C, such as 50°C, 55°C, 60°C, 65°C, 70°C, or any value between them; the time is preferably 1–3 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any value between them.
[0050] In this invention, the halocyclic epoxide compound only needs to have the structure shown in formula (5). From the perspective of the availability of raw materials, the halocyclic epoxide compound is particularly preferably epichlorohydrin and / or epichlorobutane.
[0051] In this invention, the alkaline medium can be any compound that makes the pH of the reaction system alkaline. Specific examples include at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, sodium carbonate, and potassium carbonate, more preferably sodium hydroxide and / or potassium hydroxide. This invention does not impose a specific limit on the amount of the alkaline medium used; the amount is sufficient to provide a suitable alkaline environment for the substitution reaction.
[0052] In the preparation of the modified multifunctional epoxy resin described above, the substitution reaction is preferably carried out as follows: an intermediate compound having the structure shown in formula (6) and / or formula (7) is mixed and stirred with a halo-epoxyalkane compound having the structure shown in formula (5), and simultaneously heated to 50-70°C. An alkaline medium is then added dropwise to the mixture, and the reaction is continued at 50-70°C for 1-3 hours. The mixture is then purified to obtain the modified multifunctional epoxy resin. The purification method may involve extracting the obtained product with dichloromethane as the extractant, washing the resulting extract phase with water 1-3 times, and then subjecting it to vacuum distillation.
[0053] In this invention, the intermediate compound can be obtained commercially or prepared using various methods known in the prior art. In a specific embodiment, the intermediate compound is preferably prepared by a method comprising the following steps: S1. purifying an alkoxy-aldehyde benzene having the structure shown in formula (8) after a condensation reaction in the presence of a catalyst to obtain a first reaction product; S2. purifying the first reaction product after a reduction reaction in the presence of a reducing agent to obtain the intermediate compound;
[0054]
[0055] In formula (8), R1`` is preferably a C1-C2 alkylene group, R3`` is preferably a C1-C4 alkyl group, Q1` is preferably hydrogen, a C1-C4 alkyl group, or a hydroxyl group, and Q3` is hydrogen, a C1-C4 alkyl group, or a hydroxyl group. Specific examples of C1-C2 alkylene groups and C1-C4 alkyl groups are as described above and will not be repeated here.
[0056] In the preparation of the above intermediate compound, the alkoxy-aldehyde benzene only needs to have the structure shown in formula (8), and more preferably has the structure shown in formula (9) and / or formula (10). From the perspective of the availability of raw materials, the alkoxy-aldehyde benzene is particularly preferably selected from at least one of 3-methoxybenzaldehyde, 2-methyl-3-methoxybenzaldehyde, 2-ethyl-3-methoxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde and 2-methoxybenzaldehyde.
[0057]
[0058] In formulas (6) and (7), R1 and R1' are each independently a C1-C2 alkylene group, R3 and R3' are each independently a C1-C4 alkyl group, Q1 is hydrogen, a C1-C4 alkyl group, or a hydroxyl group, and Q3 is hydrogen, a C1-C4 alkyl group, or a hydroxyl group. Specific examples of C1-C2 alkylene groups and C1-C4 alkyl groups are as described above and will not be repeated here.
[0059] In the preparation of the above intermediate compound, the catalyst can be any existing compound capable of catalyzing the condensation reaction of the benzene ring in alkoxy-aldehyde benzene to obtain a biphenyl structure, preferably laccase. When the catalyst is laccase, the ratio of its added enzyme activity to the molar amount of alkoxy-aldehyde benzene is preferably (10-15) U:1 mmol, such as 10 U:1 mmol, 11 U:1 mmol, 12 U:1 mmol, 13 U:1 mmol, 14 U:1 mmol, 15 U:1 mmol, or any value between them.
[0060] This invention does not particularly limit the conditions for the condensation reaction, as long as the benzene ring in the alkoxy-aldehyde benzene undergoes a condensation reaction to obtain the first reaction product with a biphenyl structure. In some specific embodiments, the temperature of the condensation reaction is preferably 20-30°C, such as 20°C, 22°C, 25°C, 28°C, 30°C, or any value between them; the time is preferably 1-3 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any value between them.
[0061] In the preparation of the above intermediate compound, in step S1, the condensation reaction is preferably carried out as follows: alkoxy-aldehyde benzene having the structure shown in formula (9) and / or formula (10) is dissolved in a first organic solvent and optionally a sodium acetate buffer solution, then a catalyst is added, and the reaction is carried out at 20–30°C for 1–3 h. The reactants are then acidified and purified to obtain the first reaction product. The purification method may involve extracting the obtained product with dichloromethane as an extractant, washing the resulting extract phase with water 1–3 times, and then subjecting it to vacuum distillation.
[0062] In the preparation of the above intermediate compound, in step S1, the first reaction product may have the structure shown in formula (11), more preferably the structure shown in formula (12) and / or formula (13);
[0063]
[0064] In formula (11), R1`` and R2`` are each independently preferably C1-C2 alkylene groups, R3`` and R4`` are each independently preferably C1-C4 alkyl groups, Q1` and Q2` are each independently preferably hydrogen, C1-C4 alkyl groups or hydroxyl groups, and Q3` and Q4` are each independently preferably hydrogen, C1-C4 alkyl groups or hydroxyl groups. In formulas (12) and (13), R1 and R1` are each independently C1-C2 alkylene groups, R3 and R3` are each independently C1-C4 alkyl groups, Q1 is hydrogen, C1-C4 alkyl groups or hydroxyl groups, and Q3 is hydrogen, C1-C4 alkyl groups or hydroxyl groups. Specific examples of C1-C2 alkylene groups and C1-C4 alkyl groups are as described above and will not be repeated here.
[0065] In the preparation of the aforementioned intermediate compound, the reducing agent can be any existing compound capable of reducing the aldehyde group in the first reaction product to a hydroxyl group, such as NaBH4 and / or LiAlH4. The present invention does not impose a specific limit on the amount of reducing agent used, as long as it is sufficient to substantially completely reduce the aldehyde group in the first reaction product to a hydroxyl group. In a preferred embodiment, the molar ratio of the reducing agent to the first reaction product is (2–5):1, such as 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, or any value between them.
[0066] The present invention does not particularly limit the conditions of the reduction reaction, as long as the first reaction product can be reduced to an intermediate compound having the structure shown in formula (4). In some specific embodiments, the temperature of the reduction reaction is preferably 20-30°C, such as 20°C, 22°C, 25°C, 28°C, 30°C or any value between them; the time is preferably 1-5h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or any value between them.
[0067] In the preparation of the above intermediate compound, in step S2, the reduction reaction is preferably carried out in the following manner: the first reaction product obtained in step S1 is dissolved in a second organic solvent, a reducing agent is added, and the reaction is carried out at 20-30°C for 1-5 hours. Then, the second organic solvent is added to stop the reaction. The reaction solution is rotary evaporated, and then extracted with dichloromethane as an extractant. The resulting extract phase is washed with water 1-3 times and then subjected to vacuum distillation to obtain the intermediate compound.
[0068] In the preparation of the above intermediate compound, the first organic solvent and the second organic solvent are each independently preferably selected from at least one of methanol, acetone, ethanol, benzene, toluene and N,N-dimethylformamide.
[0069] Furthermore, the terms "first" and "second" are used merely for ease of distinction and description, and have no other special meaning.
[0070] The present invention will be described in detail below through specific embodiments.
[0071] The raw materials used in the following preparation examples and their sources are as follows: Bisphenol A type epoxy resin, purchased from Mitsubishi Chemical, grade 828; Laccase enzyme, purchased from Sigma-Aldrich, grade 38429.
[0072] Preparation Example 1: Preparation of Modified Multifunctional Epoxy Resin
[0073] The preparation method of the modified multifunctional epoxy resin provided by this invention includes the following specific steps and reaction process:
[0074] S1. Dissolve 3-methoxybenzaldehyde (353.7 mg, 2.6 mmol) in 9 mL of acetone, then add 430 mL of sodium acetate buffer solution and Laccase enzyme (2.5 mg, 27 U). After reacting at room temperature for 2 h, acidify the mixture with HCl (5 M, 25 mL), stir at room temperature for 5 min, then extract with dichloromethane, wash with water, and dry by vacuum distillation to obtain the first reaction product.
[0075] S2. The first reaction product (270 mg, 1 mmol) from step S1 was dissolved in 20 mL of methanol solution. NaBH4 (95 mg, 2.5 mmol) was added and the mixture was reacted at room temperature for 3 h. When the reaction time was up, the reaction was stopped by adding a large amount of methanol. The mixture after the reaction was rotary evaporated, then extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the intermediate compound.
[0076] S3. The intermediate compound (274 mg, 1 mmol) from step S1 and epichlorohydrin (230 mg, 2.5 mmol) were mixed and stirred while being heated. When the temperature reached 50 °C, 35 mL of 30% NaOH solution was added dropwise to the mixture. After the addition was complete, the temperature was raised to 70 °C and the reaction continued for 1 h. Then, the mixture was extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the modified multifunctional epoxy resin. Its synthesis process and structure are shown below.
[0077] Depend on Figure 1 As can be seen, the successful synthesis of the modified multifunctional epoxy resin with the structure shown below was confirmed by nuclear magnetic resonance (NMR) testing.
[0078]
[0079] Preparation Example 2: Preparation of Modified Multifunctional Epoxy Resin
[0080] S1. Dissolve 2-methyl-3-methoxybenzaldehyde (390.4 mg, 2.6 mmol) in 9 mL of acetone, then add 430 mL of sodium acetate buffer solution and Laccase enzyme (2.5 mg, 27 U). After reacting at room temperature for 2 h, acidify the mixture with HCl (5 M, 25 mL), stir at room temperature for 5 min, extract with dichloromethane, wash with water, and dry by vacuum distillation to obtain the first reaction product.
[0081] S2. The first reaction product (298 mg, 1 mmol) from step S1 was dissolved in 20 mL of methanol solution. NaBH4 (95 mg, 2.5 mmol) was added and the mixture was reacted at room temperature for 3 h. When the reaction time was up, the reaction was stopped by adding a large amount of methanol. The mixture after reaction was rotary evaporated, then extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the intermediate compound.
[0082] S3. The intermediate compound (302 mg, 1 mmol) from step S1 and epichlorohydrin (230 mg, 2.5 mmol) were mixed and stirred while being heated. When the temperature reached 50 °C, 35 mL of 30% NaOH solution was added dropwise to the mixture. After the addition was complete, the temperature was raised to 70 °C and the reaction continued for 1 h. Then, the mixture was extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the modified multifunctional epoxy resin.
[0083] Depend on Figure 2 As can be seen, the successful synthesis of the modified multifunctional epoxy resin with the structure shown below was confirmed by nuclear magnetic resonance (NMR) testing.
[0084]
[0085] Preparation Example 3: Preparation of Modified Multifunctional Epoxy Resin
[0086] S1. 2-Ethyl-3-methoxybenzaldehyde (426.9 mg, 2.6 mmol) was dissolved in 9 mL of acetone, and then 430 mL of sodium acetate buffer solution and Laccase enzyme (2.5 mg, 27 U) were added. After reacting at room temperature for 2 h, the mixture was acidified with HCl (5 M, 25 mL), stirred at room temperature for 5 min, extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the first reaction product.
[0087] S2. The first reaction product (326 mg, 1 mmol) from step S1 was dissolved in 20 mL of methanol solution. NaBH4 (95 mg, 2.5 mmol) was added and the mixture was reacted at room temperature for 3 h. When the reaction time was up, the reaction was stopped by adding a large amount of methanol. The mixture after the reaction was rotary evaporated, then extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the intermediate compound.
[0088] S3. The intermediate compound (330 mg, 1 mmol) from step S1 and epichlorohydrin (230 mg, 2.5 mmol) were mixed and stirred while being heated. When the temperature reached 50 °C, 35 mL of 30% NaOH solution was added dropwise to the mixture. After the addition was complete, the temperature was raised to 70 °C and the reaction continued for 1 h. Then, the mixture was extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the modified multifunctional epoxy resin.
[0089] Depend on Figure 3 As can be seen, the successful synthesis of the modified multifunctional epoxy resin with the structure shown below was confirmed by nuclear magnetic resonance (NMR) testing.
[0090]
[0091] Preparation Example 4: Preparation of Modified Multifunctional Epoxy Resin
[0092] S1. 2-Hydroxy-3-methoxybenzaldehyde (395.6 mg, 2.6 mmol) was dissolved in 9 mL of acetone, and then 430 mL of sodium acetate buffer solution and Laccase enzyme (2.5 mg, 27 U) were added. After reacting at room temperature for 2 h, the mixture was acidified with HCl (5 M, 25 mL), stirred at room temperature for 5 min, extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the first reaction product.
[0093] S2. The first reaction product (302 mg, 1 mmol) from step S1 was dissolved in 20 mL of methanol solution. NaBH4 (95 mg, 2.5 mmol) was added and the mixture was reacted at room temperature for 3 h. When the reaction time was up, the reaction was stopped by adding a large amount of methanol. The mixture after the reaction was rotary evaporated, then extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the intermediate compound.
[0094] S3. The intermediate compound (306 mg, 1 mmol) from step S1 and epichlorohydrin (462.5 mg, 5 mmol) were mixed and stirred while being heated. When the temperature reached 50 °C, 35 mL of 30% NaOH solution was added dropwise to the mixture. After the addition was complete, the temperature was raised to 70 °C and the reaction continued for 1 h. Then, the mixture was extracted with dichloromethane, washed with water, and dried by vacuum distillation to obtain the modified multifunctional epoxy resin.
[0095] Depend on Figure 4 As can be seen, the successful synthesis of the modified multifunctional epoxy resin with the structure shown below was confirmed by nuclear magnetic resonance (NMR) testing.
[0096]
[0097] Preparation Example 5: Preparation of Modified Multifunctional Epoxy Resin
[0098] The modified multifunctional epoxy resin was prepared according to the method of Preparation Example 4, except that 3-methoxy-4-hydroxybenzaldehyde was used instead of 2-hydroxy-3-methoxybenzaldehyde in the same molar amount, and all other conditions were the same as in Preparation Example 4, to obtain the modified multifunctional epoxy resin.
[0099] Depend on Figure 5 As can be seen, the successful synthesis of the modified multifunctional epoxy resin with the structure shown below was confirmed by nuclear magnetic resonance (NMR) testing.
[0100]
[0101] Preparation Example 6: Preparation of Modified Multifunctional Epoxy Resin
[0102] The modified multifunctional epoxy resin was prepared according to the method of Preparation Example 1, except that the same molar amount of 2-methoxybenzaldehyde was used instead of 3-methoxybenzaldehyde, and all other conditions were the same as in Preparation Example 1, to obtain the modified multifunctional epoxy resin.
[0103] Depend on Figure 6 As can be seen, the successful synthesis of the modified multifunctional epoxy resin with the structure shown below was confirmed by nuclear magnetic resonance (NMR) testing.
[0104]
[0105] Example 1: Preparation of epoxy resin adhesive
[0106] The components and their weight parts of the epoxy resin adhesive are as follows: 15 parts of the modified multifunctional epoxy resin provided in Preparation Example 1, 25 parts of bisphenol A type epoxy resin, 10 parts of m-phenylenediamine, and 50 parts of silica micro powder.
[0107] The preparation method of this epoxy resin adhesive is as follows: Modified multifunctional epoxy resin, bisphenol A type epoxy resin and m-phenylenediamine are mixed evenly in a container to obtain a premix. Silica micro powder is added to the above premix and mixed evenly. Then the resulting mixture is passed through three rollers twice, and then transferred to a double planetary hybrid stirring tank and stirred for 30 minutes. The wall is scraped when the stirring time is 15 minutes. After the mixing is completed, the above mixture is subjected to vacuum degassing treatment, and then discharged to obtain epoxy resin adhesive.
[0108] Example 2: Preparation of epoxy resin adhesive
[0109] The components and their weight parts of the epoxy resin adhesive are as follows: 35 parts of the modified multifunctional epoxy resin provided in Preparation Example 1, 5 parts of bisphenol A type epoxy resin, 10 parts of m-phenylenediamine, and 50 parts of silica micro powder.
[0110] The preparation method of this epoxy resin adhesive is as follows: Modified multifunctional epoxy resin, bisphenol A type epoxy resin and m-phenylenediamine are mixed evenly in a container to obtain a premix. Silica micro powder is added to the above premix and mixed evenly. Then the resulting mixture is passed through three rollers twice, and then transferred to a double planetary hybrid stirring tank and stirred for 30 minutes. The wall is scraped when the stirring time is 15 minutes. After the mixing is completed, the above mixture is subjected to vacuum degassing treatment, and then discharged to obtain epoxy resin adhesive.
[0111] Example 3: Preparation of epoxy resin adhesive
[0112] The components and their weight parts of the epoxy resin adhesive are as follows: 5 parts of the modified multifunctional epoxy resin provided in Preparation Example 1, 35 parts of bisphenol A type epoxy resin, 10 parts of m-phenylenediamine, and 50 parts of silica micro powder.
[0113] The preparation method of this epoxy resin adhesive is as follows: Modified multifunctional epoxy resin, bisphenol A type epoxy resin and m-phenylenediamine are mixed evenly in a container to obtain a premix. Silica micro powder is added to the above premix and mixed evenly. Then the resulting mixture is passed through three rollers twice, and then transferred to a double planetary hybrid stirring tank and stirred for 30 minutes. The wall is scraped when the stirring time is 15 minutes. After the mixing is completed, the above mixture is subjected to vacuum degassing treatment, and then discharged to obtain epoxy resin adhesive.
[0114] Example 4: Preparation of epoxy resin adhesive
[0115] An epoxy resin adhesive was prepared according to the method of Example 1, except that the modified multifunctional epoxy resin provided in Preparation Example 2 was used instead of the modified multifunctional epoxy resin provided in Preparation Example 1 in the same weight proportions, and all other conditions were the same, to obtain the epoxy resin adhesive.
[0116] Example 5: Preparation of epoxy resin adhesive
[0117] An epoxy resin adhesive was prepared according to the method of Example 1, except that the modified multifunctional epoxy resin provided in Preparation Example 3 was used instead of the modified multifunctional epoxy resin provided in Preparation Example 1 in the same weight parts, and all other conditions were the same, to obtain the epoxy resin adhesive.
[0118] Example 6: Preparation of epoxy resin adhesive
[0119] An epoxy resin adhesive was prepared according to the method of Example 1, except that the modified multifunctional epoxy resin provided in Preparation Example 4 was used instead of the modified multifunctional epoxy resin provided in Preparation Example 1 in the same weight parts, and all other conditions were the same, to obtain the epoxy resin adhesive.
[0120] Example 7: Preparation of epoxy resin adhesive
[0121] An epoxy resin adhesive was prepared according to the method of Example 1, except that the modified multifunctional epoxy resin provided in Preparation Example 5 was used instead of the modified multifunctional epoxy resin provided in Preparation Example 1 in the same weight parts, and all other conditions were the same, to obtain the epoxy resin adhesive.
[0122] Example 8: Preparation of epoxy resin adhesive
[0123] An epoxy resin adhesive was prepared according to the method of Example 1, except that the modified multifunctional epoxy resin provided in Preparation Example 6 was used instead of the modified multifunctional epoxy resin provided in Preparation Example 1 in the same weight parts, and all other conditions were the same, to obtain the epoxy resin adhesive.
[0124] Comparative Example 1: Preparation of Reference Epoxy Resin Adhesive
[0125] A reference epoxy resin adhesive was prepared according to the method of the embodiment, except that the same parts by weight of bisphenol A type epoxy resin was used instead of the modified multifunctional epoxy resin provided in Preparation Example 1, and all other conditions were the same, to obtain the reference epoxy resin adhesive.
[0126] Test case
[0127] The epoxy resin adhesives prepared in the above examples and comparative examples were subjected to performance tests on viscosity, glass ring transition temperature and modulus according to the following methods. The results are shown in Table 1.
[0128] (1) Viscosity: The initial viscosity of the epoxy resin adhesive when it was freshly prepared and the viscosity after standing for 24 hours were tested using a BROOKFIELD viscometer. Specifically, at room temperature, the epoxy adhesive was rotated and stirred for 30 minutes using a 29# rotor, and the viscosity data was measured at a speed of 5 rpm.
[0129] (2) Glass transition temperature (Tg): The epoxy resin adhesive was cured at 150℃ / 120min and the glass transition temperature was determined using a differential calorimeter. The heating rate during the test was 10℃ / min.
[0130] (3) Modulus: After curing the epoxy resin adhesive at 150℃ / 120min, a sample with a size of 55mm*5mm*2mm was made and tested on DMA. The measurement mode was dual cantilever mode, the vibration frequency was 1Hz, the amplitude was 10μm, the heating rate was 10℃ / min, and the test temperature range was -65℃~300℃. The modulus data at 200℃ was selected for comparison.
[0131] Table 1
[0132]
[0133] 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. The application of a modified multifunctional epoxy resin in semiconductor packaging, characterized in that, The modified multifunctional epoxy resin has the structure shown in formula (2) and / or formula (3): Equation (2), Equation (3), In formulas (2) and (3), R1, R1', R2, and R2' are each independently C1-C2 alkylene groups, R3, R3', R4, and R4' are each independently C1-C4 alkyl groups, R5 and R6 are each independently hydrogen or C1-C4 alkyl groups, R7, R7', R8, and R8' are each independently C1-C4 alkylene groups, and R9 and R 10 Each is independently hydrogen or a C1-C4 alkyl group; The method for preparing the modified multifunctional epoxy resin includes a substitution reaction between an intermediate compound having the structure shown in formula (6) and / or formula (7) and a halo-epoxyalkane compound having the structure shown in formula (5) in the presence of an alkaline medium, and the modified multifunctional epoxy resin is obtained after purification. Equation (6), Equation (7), Equation (5), In formulas (6) and (7), R1, R1', R2 and R2' are each independently C1~C2 alkylene groups, R3, R3', R4 and R4' are each independently C1~C4 alkyl groups, Q1 and Q2 are each independently hydrogen or C1~C4 alkyl groups, and Q3 and Q4 are each independently hydrogen or C1~C4 alkyl groups; in formula (5), R is a C1~C4 alkylene group, and X is a halogen. The intermediate compound was prepared using a method comprising the following steps: S1. Alkoxy-aldehyde benzene having the structure shown in formula (9) and / or formula (10) is purified by condensation reaction in the presence of a catalyst to obtain the first reaction product; S2. The product of the first reaction is reduced in the presence of a reducing agent and then purified to obtain an intermediate compound; Equation (9), Equation (10), In formulas (9) and (10), R1 and R1' are each independently C1~C2 alkylene groups, R3 and R3' are each independently C1~C4 alkyl groups, Q1 is hydrogen or C1~C4 alkyl group, and Q3 is C1~C4 alkyl group.
2. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, The molar ratio of the intermediate compound to the halo-oxidized alkylene compound is 1:(2.2~6.2).
3. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, The substitution reaction is carried out at a temperature of 50-70°C for 1-3 hours.
4. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, The haloalkylene oxide compound is selected from epichlorohydrin and / or epichlorobutane.
5. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, The alkaline medium is selected from at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, sodium carbonate, and potassium carbonate.
6. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, In step S1, the alkoxy-aldehyde benzene is selected from at least one of 3-methoxybenzaldehyde, 2-methyl-3-methoxybenzaldehyde, 2-ethyl-3-methoxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, and 2-methoxybenzaldehyde.
7. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, In step S1, the catalyst is Laccase enzyme.
8. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, In step S1, the condensation reaction is carried out at a temperature of 20-30°C for 1-3 hours.
9. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, In step S2, the reducing agent is selected from NaBH4 and / or LiAlH4.
10. The application of the modified multifunctional epoxy resin according to claim 1 in semiconductor packaging, characterized in that, In step S2, the reduction reaction is carried out at a temperature of 20-30°C for 1-5 hours.