An ethynylaniline type epoxy resin, a preparation method, a composition and an application thereof

Abstract

The application discloses an ethynyl aniline type epoxy resin and a preparation method, a composition and an application thereof. The preparation method of the ethynyl aniline type epoxy resin comprises the following steps: firstly, ethynyl aniline and beta-substituted epoxy chloropropane are subjected to ring-opening reaction under the action of a solvent; then, alkali metal hydroxide is added into the system, so that the intermediate is subjected to cyclization reaction, and the ethynyl aniline type epoxy resin is obtained. The epoxy group and the ethynyl group are simultaneously introduced in the application, in the curing process, not only the cross-linking reaction can be relied on the traditional epoxy group, but also the self-polymerization behavior of the ethynyl group under high-temperature conditions can be utilized, so that a more compact and stable three-dimensional network structure is formed. The "double cross-linking mechanism" significantly improves the thermal decomposition temperature and the glass transition temperature of the material, so that the material can still maintain good structural integrity in a high-temperature service environment.

Description

Technical Field

[0001] This invention belongs to the field of epoxy resin preparation technology, specifically relating to an acetylene aniline type epoxy resin and its preparation method, composition and application. Background Technology

[0002] Epoxy resin, a thermosetting resin with a highly cross-linked structure, is widely used in adhesives, electronic packaging, composite materials, aerospace, and other fields due to its excellent physical properties, electrical insulation, and flexibility in application processes. However, most existing epoxy resins are suitable for low- to medium-temperature environments, and under long-term high-temperature or thermal shock conditions, they are prone to thermal decomposition, performance degradation, and decreased mechanical strength.

[0003] As electronic components continue to evolve towards higher integration, miniaturization, and higher power density, especially in 5G communication, high-speed computing, power devices, and new energy vehicle electronic systems, these devices generate significantly more heat during operation. This places increasingly stringent demands on the heat resistance and long-term reliability of packaging materials. Simultaneously, under complex service environments, materials also require excellent dimensional stability to ensure the safe and stable operation of the system. Therefore, developing more heat-resistant epoxy resin systems has become a current research hotspot.

[0004] Currently, methods to improve the heat resistance of epoxy resins mainly focus on three dimensions: resin molecular design, curing system selection, and organic-inorganic hybridization. Among these, selecting multifunctional epoxy resins (such as tetrafunctional AG-80 and trifunctional AFG-90) to increase crosslinking density is the most direct strategy to limit high-temperature molecular chain movement and raise the glass transition temperature (Tg). Introducing rigid groups (such as benzene rings, naphthalene rings, and heterocycles) into the resin backbone can increase the rotational energy barrier of the molecular chains, delaying high-temperature softening. Post-curing processes such as stepped temperature increases help improve crosslinking integrity. However, while improving heat resistance, these methods often face problems such as excessively high system viscosity, narrow process windows, or increased costs, making it difficult to simultaneously achieve high heat resistance and good processability. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide an acetylene aniline-type epoxy resin, its preparation method, composition, and applications. This system simultaneously introduces epoxy and acetylene groups. During curing, it can undergo cross-linking reactions not only through traditional epoxy groups but also through self-polymerization reactions of the acetylene groups at high temperatures, forming a denser and more stable three-dimensional network structure. This "dual cross-linking mechanism" significantly improves the material's thermal decomposition temperature and glass transition temperature, enabling it to maintain good structural integrity even at high temperatures. Furthermore, the introduction of acetylene groups provides greater flexibility in molecular design, allowing for precise control of material properties by adjusting molecular chain rigidity, cross-linking density, and functional group distribution.

[0006] To achieve the above objectives, in a first aspect, the present invention provides an acetylene aniline type epoxy resin, with the general chemical formula:

[0007] R1 to R5 are each independently selected from one of hydrogen atom, alkyl group, and alkynyl group, and at least one of R1 to R5 is an alkynyl group.

[0008] Optionally, the epoxy equivalent of the acetylene aniline type epoxy resin is 130 g / mol to 170 g / mol.

[0009] In a second aspect, the present invention provides a method for preparing the acetylene aniline type epoxy resin as described above, comprising the following steps: firstly, acetylene aniline and β-substituted epichlorohydrin undergo a ring-opening reaction in the presence of a solvent, and then an alkali metal hydroxide is added to the system to induce a cyclization reaction in the intermediate, thereby obtaining the acetylene aniline type epoxy resin.

[0010] Optionally, the general chemical formula of the acetylene aniline is as follows:

[0011] R1 to R5 are each independently selected from hydrogen atoms, alkyl groups, and amino groups, and at least one of them is an amino group; the chemical formula of the β-substituted epichlorohydrin is [formula missing]. In this case, the A group is one of hydrogen atom, alkyl group and phenyl group.

[0012] Optionally, the ring-opening reaction temperature can be slowly increased from room temperature to 40~110℃, with a heating rate of 1~5℃ / 10~20min, and a reaction time of 3~10h.

[0013] Optionally, the cyclization reaction temperature is 40~70℃, and the cyclization reaction time is 2~10h.

[0014] Optionally, the molar ratio of the active amino hydrogen in the acetylene aniline to the molar ratio of the β-substituted epichlorohydrin is 1:(1~20).

[0015] Optionally, the molar ratio of the active amino hydrogen in the acetylene aniline to the molar ratio of the alkali metal hydroxide is 1:(0.9-2).

[0016] Optionally, the alkali metal hydroxide is added to the system in the form of an aqueous solution, wherein the alkali metal hydroxide is sodium hydroxide or potassium hydroxide, the mass fraction of the solution is 30%~55%, and the dropping rate is 1~3 g / min.

[0017] Optionally, after the cyclization reaction is completed, the reaction system is washed with water and rotary evaporated to remove the water, excess β-substituted epichlorohydrin and solvent produced in the reaction, to obtain acetylene aniline type epoxy resin.

[0018] Optionally, the solvent includes one or a combination of water, alcohol solvents, ketone solvents, and aromatic solvents.

[0019] Optionally, the amount of solvent used is 5 to 10 times the mass of acetylene aniline.

[0020] Optionally, the alcohol solvent includes one or a combination of methanol, ethanol, isopropanol, n-butanol, n-octanol, ethylene glycol, tert-butanol, sec-butanol, isobutanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and benzyl alcohol.

[0021] Optionally, the ketone solvent includes one or a combination of acetone, methyl isobutyl ketone, butanone, cyclopentanone, methyl ethyl ketone, diisobutyl ketone, diethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, and 2-methylcyclohexanone.

[0022] Optionally, the aromatic solvent includes one or a combination of toluene and xylene.

[0023] In a third aspect, the present invention provides an acetylene aniline type epoxy resin composition comprising the acetylene aniline type epoxy resin as described above or the acetylene aniline type epoxy resin prepared by the preparation method as described above, and a curing agent.

[0024] Optionally, the curing agent includes one or a combination of amine curing agents, acid anhydride curing agents, phenolic curing agents, or imidazole curing agents.

[0025] In a fourth aspect, the present invention provides an application of the acetylene aniline type epoxy resin composition as described above, which is applied in the field of electronic packaging materials.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention introduces both epoxy groups and acetylene groups. During curing, it not only undergoes cross-linking reactions based on traditional epoxy groups but also utilizes the self-polymerization behavior of acetylene groups under high-temperature conditions to form a denser and more stable three-dimensional network structure. This "dual cross-linking mechanism" significantly increases the material's thermal decomposition temperature and glass transition temperature, enabling it to maintain good structural integrity even under high-temperature service conditions. Furthermore, the introduction of acetylene groups enhances the flexibility of molecular design; by controlling the rigidity of the molecular chains, cross-linking density, and spatial distribution of functional groups, precise control over the material's macroscopic properties can be achieved. Based on these structural advantages, this system successfully overcomes the inherent contradiction between material rigidity and processing performance, achieving an excellent combination of low viscosity and high Tg, exhibiting remarkable characteristics of balancing good processability and high heat resistance. Attached Figure Description

[0027] Figure 1 The room temperature viscosity curves of the acetylene aniline type epoxy resin and the aniline type epoxy resin prepared in Examples 1-3 and Comparative Example 1 are shown. Figure 2 The Fourier Transform Infrared (FTIR) spectra of the acetylene aniline type epoxy resin and the aniline type epoxy resin prepared in Examples 1-3 and Comparative Example 1 are shown. Figure 3 Differential scanning calorimetry (DSC) test results of the acetylene aniline type epoxy resin and aniline type epoxy resin prepared in Examples 4-6 and Comparative Example 5; Figure 4 The glass transition temperature (Tg) test results are for the acetylene aniline type epoxy resin and the cured aniline type epoxy resin prepared in Examples 4-6 and Comparative Example 5. Figure 5 The thermogravimetric analysis (TGA) results are for the acetylene aniline type epoxy resin and the cured aniline type epoxy resin prepared in Examples 4-6 and Comparative Example 5. Figure 6 The linear expansion coefficient (CTE) test results are for the acetylene aniline type epoxy resin and the cured aniline type epoxy resin prepared in Examples 4-6 and Comparative Example 5. Detailed Implementation

[0028] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention are described in detail, clearly, and completely below. Many specific details are set forth in the following description to provide a thorough understanding of the present invention; however, the present invention may also be implemented in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0029] According to the first aspect of the present invention, the acetylene aniline type epoxy resin has the following general chemical formula:

[0030] R1 to R5 are each independently selected from one of hydrogen atom, alkyl group, and alkynyl group, and at least one of R1 to R5 is an alkynyl group.

[0031] The acetylene aniline type epoxy resin of the present invention comprises a benzene ring skeleton, on which at least one acetylene group is grafted. The acetylene group and epoxy group serve as active groups, which are beneficial to increasing the crosslinking density of the resin and enhancing the rigidity of the polymer network structure, thereby obtaining high temperature resistance.

[0032] The molecular structure of this invention contains both epoxy and acetylene groups. It can utilize epoxy groups for traditional curing to ensure processability, and utilize acetylene groups for secondary crosslinking or aromatization at high temperatures. This further improves heat resistance and thermal stability without sacrificing processability, solving the problem that traditional epoxy systems cannot simultaneously achieve both heat resistance and long-term stability. The molecular structure of this invention is suitable for more demanding high-performance electronic system operating conditions.

[0033] In the acetylene aniline type epoxy resin according to the present invention, the epoxy equivalent of the acetylene aniline type epoxy resin can be 130 g / mol to 170 g / mol.

[0034] The preparation method of acetylene aniline type epoxy resin according to the second aspect of the present invention includes the following steps: firstly, acetylene aniline and β-substituted epichlorohydrin undergo a ring-opening reaction in the presence of a solvent, and then an alkali metal hydroxide is added to the system to cause the intermediate to undergo a cyclization reaction to obtain acetylene aniline type epoxy resin.

[0035] The general chemical formula of the acetylene aniline is:

[0036] R1 to R5 are each independently selected from hydrogen atoms, alkyl groups, and amino groups, and at least one of them is an amino group. In a preferred embodiment, the acetylene aniline may be one of 2-acetylene aniline, 3-acetylene aniline, and 4-acetylene aniline.

[0037] The chemical formula of the β-substituted epichlorohydrin is: Wherein, group A is one of hydrogen atom, alkyl group, and phenyl group. Wherein, alkyl group is saturated hydrocarbon group, and phenyl group refers to group with benzene ring as functional group.

[0038] In this case, the A groups substituted at the β-position in β-substituted epichlorohydrin can better regulate the steric hindrance on the β-carbon, suppress β-addition, and better control the spatial configuration or molecular dipole of the epoxy resin molecule, thereby obtaining low high-temperature viscosity, improving the processability of the epoxy resin, and making the prepared acetylene aniline type epoxy resin have better high temperature resistance and high purity.

[0039] In one embodiment, the β-substituted epichlorohydrin includes at least one selected from epichlorohydrin, methyl epichlorohydrin, and 2-(chloromethyl)-2-phenylepoxyethylene. In a preferred embodiment, the β-substituted epichlorohydrin may be methyl epichlorohydrin.

[0040] This invention can regulate the spatial configuration or molecular dipole of epoxy resin molecules by selecting the type, structure, and size of the A group in β-substituted epichlorohydrin, thereby controlling the steric hindrance on the β carbon, suppressing β-addition, and eliminating the influence of β-addition substitution side reactions on the chlorine content, purity, and yield of the product.

[0041] In one embodiment, the molar ratio of the active amino hydrogen in the acetylene aniline to the molar ratio of the β-substituted epichlorohydrin is 1:(1~20). This molar ratio ensures sufficient ring-opening and ring-closing reactions between the active amino hydrogen of acetylene aniline and the β-substituted epichlorohydrin, allowing multiple active groups on the amino group to be grafted with epoxy substituents, resulting in a bifunctional acetylene-containing epoxy resin and improving reaction efficiency.

[0042] In one embodiment, the solvent includes one or a combination of water, alcohol solvents, ketone solvents, and aromatic solvents, and the amount used is 5 to 10 times the mass of acetylene aniline.

[0043] The alcohol solvents include one or a combination of methanol, ethanol, isopropanol, n-butanol, n-octanol, ethylene glycol, tert-butanol, sec-butanol, isobutanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and benzyl alcohol; the ketone solvents include one or a combination of acetone, methyl isobutyl ketone, butanone, cyclopentanone, methyl ethyl ketone, diisobutyl ketone, diethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, and 2-methylcyclohexanone; the aromatic solvents include one or a combination of toluene and xylene.

[0044] In a preferred embodiment of the present invention, the solvent is a mixed solvent. The mixed solvent is preferably a water and an alcohol-based solvent. The water and alcohol-based solvent is preferably a water and isopropanol. The mixed solvent works together during the synthesis process to form a homogeneous or microemulsion system, allowing the acetylene aniline ring-opening intermediate to fully contact the β-substituted epichlorohydrin molecules, avoiding the problem of a small reaction interface and limited mass transfer due to phase insolubility, thus significantly improving the reaction rate and raw material conversion rate. This ring-opening reaction is exothermic; if there is no solvent or only an excess of β-substituted epichlorohydrin is used, local heat accumulation may occur, leading to temperature runaway and triggering side reactions such as epichlorohydrin self-polymerization and amino oxidation. The presence of the mixed solvent can effectively inhibit rapid polymerization.

[0045] In one embodiment, after uniformly mixing β-substituted epichlorohydrin and a solvent, acetylene aniline is added dropwise using a constant-pressure funnel. The mixture is heated to 40-110°C, and the reaction temperature is slowly increased from room temperature to the required temperature. The heating rate can be 1-5°C / 10-20 min, and the ring-opening reaction time can be 2-10 h. This temperature control method effectively suppresses the thermal accumulation of the strongly exothermic epoxy ring-opening reaction by slowly increasing the temperature, avoiding phenomena such as explosive polymerization and runaway temperatures caused by local overheating. The mild heating conditions significantly reduce side reactions such as epoxy hydrolysis, hydroxyl etherification, and ammonia oxidation, improving the epoxy group retention rate and ensuring the reaction proceeds along the expected path. Uniform and slow heating ensures a consistent temperature within the reaction vessel, resulting in a product with a narrow molecular weight distribution and uniform cross-linking structure, preventing localized gelation caused by uneven temperature. This method is a key technical measure for achieving controllable, efficient, and safe epoxy ring-opening reactions. In some embodiments, the reaction temperature can be 40℃~50℃, 50℃~60℃, 60℃~70℃, 70℃~80℃, 80℃~90℃, 90℃~100℃, 100℃~110℃, etc., and the reaction time can be 2 hours~3 hours, 3 hours~4 hours, 4 hours~5 hours, 5 hours~6 hours, 6 hours~7 hours, 7 hours~8 hours, 8 hours~9 hours, 9 hours~10 hours, etc.

[0046] In this ring-opening reaction, quaternary ammonium salts such as tetramethylammonium bromide and benzyltriethylammonium bromide; tertiary amines such as benzyldimethylamine or 2,4,6-tris(dimethylaminomethyl)phenol; and imidazole catalysts such as 1-methylimidazole and 2-ethyl-4-methylimidazole can be used. The molar ratio of the active amino hydrogen in acetylene aniline to the molar ratio of the catalyst is 1:(0.005~0.5). The compounds are not limited to those shown above, as long as they are compounds that can promote the attack of the active amino hydrogen in acetylene aniline on the α-carbon in β-substituted epichlorohydrin to complete the ring-opening reaction.

[0047] In one embodiment, the molar ratio of the active amino hydrogen in the acetylene aniline to the molar ratio of the alkali metal hydroxide is 1:(0.9-2). The alkali metal hydroxide is typically added to the system in the form of an aqueous solution, such as sodium hydroxide or potassium hydroxide, with a mass fraction of 30%-55% and a dropping rate of 1-3 g / min. The alkali metal hydroxide catalyzes the ring-closure of the hydroxyl group and -CH₂Cl in the ring-opened epichlorohydrin, re-forming an epoxy ring. Under this ratio, the alkali metal hydroxide effectively catalyzes the ring-opening and ring-closing reactions between the active hydrogen of acetylene aniline and β-substituted epichlorohydrin, grafting multiple epoxy substitutions onto the benzene ring to obtain a bifunctional acetylene epoxy resin.

[0048] In the reaction, a suitable amount of a mixed catalyst of alkali metal hydroxide and quaternary ammonium salt can also be added. The alkali metal hydroxide catalyzes the ring-closure of the hydroxyl group and -CH2Cl in the ring-opened epichlorohydrin, re-forming an epoxy ring. In the mixed catalyst, the quaternary ammonium salt catalyzes the attack of the active hydrogen of the amino group in acetylene aniline on the α-position carbon atom in the β-substituted epichlorohydrin, completing the ring-opening reaction; additionally, in the presence of the quaternary ammonium salt, the alkali metal hydroxide catalyzes the ring-closure of the hydroxyl group and -CH2Cl in the ring-opened epichlorohydrin, re-forming an epoxy ring. In one specific embodiment, the mixed catalyst can be sodium hydroxide and a quaternary ammonium salt.

[0049] In one embodiment, the addition of an alkali metal hydroxide to perform a ring-closing reaction can be carried out at a temperature of 40-70°C for 2-10 hours. In some embodiments, the reaction temperature can be 40-50°C, 50-60°C, 60-70°C, etc., and the reaction time can be 2-3 hours, 3-4 hours, 4-5 hours, 5-6 hours, 6-7 hours, 7-8 hours, 8-9 hours, 9-10 hours, etc.

[0050] After the cyclization reaction is completed, the reaction system is washed with water and rotary evaporated to remove the water, excess β-substituted epichlorohydrin, and organic solvent produced in the reaction, yielding an acetylene aniline type epoxy resin. Alternatively, purification can be achieved by adding an alkaline solution, wherein the alkaline solution is an alkali metal hydroxide solution with a concentration of 1wt% to 10wt%. Under these concentration conditions, the alkaline solution has a good ring-closing effect on the unclosed -OH and -Cl groups in the crude product after both ring-opening and ring-closing reactions, increasing the molecular weight of the epoxy resin and its epoxy value.

[0051] The acetylene aniline type epoxy resin composition according to a third aspect of the present invention comprises the acetylene aniline type epoxy resin as described above.

[0052] In one embodiment, the acetylene aniline-type epoxy resin composition further includes a curing agent in an amount of 30% to 90% by weight relative to the acetylene aniline-type epoxy resin. In this case, the inclusion of the above-mentioned amount of curing agent in the acetylene aniline-type epoxy resin composition can effectively promote the cross-linking and curing of the acetylene aniline-type epoxy resin in the composition. The curing agent may include one or a combination of amine curing agents, acid anhydride curing agents, phenolic curing agents, or imidazole curing agents, without particular limitation. These types of curing agents can all effectively promote the curing of the epoxy resin by chemically reacting their active hydrogen atoms with the epoxy groups in the acetylene aniline epoxy resin to form a cross-linked structure, thereby curing the epoxy resin molecules into a robust material. In one embodiment, the curing agent may be 4,4'-diaminodiphenylmethane (DDM). In some embodiments, the mass percentage of the curing agent in the epoxy resin composition may be 30%–35%, 35%–40%, 40%–50%, 50%–60%, 60%–70%, 70%–80%, 80%–90%, etc.

[0053] In one embodiment, the acetylene aniline-type epoxy resin composition further includes a curing accelerator at a mass percentage of 0.1% to 1.5% relative to the acetylene aniline-type epoxy resin. In this case, the addition of a curing accelerator to the acetylene aniline-type epoxy resin composition can influence the reaction rate and mechanism between the acetylene aniline-type epoxy resin and the curing agent, thereby adjusting the temperature, time, and performance of the curing process, accelerating the curing speed of the acetylene aniline-type epoxy resin, improving the curing effect, and increasing the cured strength. In some embodiments, the mass percentage of the curing accelerator in the epoxy resin composition may be 0.1%–0.3%, 0.3%–0.5%, 0.5%–0.8%, 0.8%–1.0%, 1.0%–1.2%, 1.2%–1.5%, 0.2%–1.4%, 0.3%–1.3%, 0.4%–1.2%, 0.5%–1.1%, 0.6%–1.0%, 0.7%–0.9%, 0.8%–1.2%, etc.

[0054] The curing accelerator may include: 2-methylimidazoline (2MZL), 2-heptadecylimidazolium (C17Z), 2-ethyl-4-methylimidazolium (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazolium (2E4MZ-CN), wherein the imidazolium accelerator is selected from 2-methylimidazolium (2MZ), 1-dodecyl-2-methyl-3-benzylimidazolium chloride (SFZ), 1-cyanoethyl-2-undecylimidazolium (C11Z-CN), 1-cyanoethyl-2-phenylimidazolium (2PZ-CN), 1,3-dibenzyl-2-methylimidazolium chloride (FFZ), 2-ethyl-4-methylimidazolium (2E4MZ), 1-cyanoethyl-2-methylimidazolium (2MZ-CN), etc. At least one of the following curing accelerators: Z-CN), 2-undecylimidazolium (C11Z), 1-cyanoethyl-2-phenylimidazolium trimellitate (2PZ-CNS), 1-benzyl-2-methylimidazolium (1B2MZ), 2-phenyl-4-methylimidazolium (2P4MZ), 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate (C11Z-CNS), 2-phenylimidazolium (2PZ), 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate (2E4MZ-CNS), trimellitate (2MZ-CNS), and 2,4-diamino-6-[2'-methylimidazolium-(1')]ethyl-S-triazine (2MZ-A). These curing accelerators can all better promote the cross-linking and curing between the acetylene aniline-type epoxy resin and the curing agent, accelerating the curing speed of the epoxy resin, improving the curing effect, and increasing the cured strength.

[0055] The acetylene aniline type epoxy resin composition according to the fourth aspect of the present invention can be applied in the field of electronic packaging materials.

[0056] The following specific embodiments illustrate the acetylene aniline type epoxy resin, its preparation method, composition, and application of the present invention.

[0057] Main raw materials and equipment used: Unless otherwise specified, the raw materials and equipment used in each embodiment and comparative example are the same. The sources of the main raw materials used are shown in Table 1: Table 1 Sources of Raw Materials

[0058] Example 1

[0059] This embodiment provides a method for preparing acetylene aniline-type epoxy resin. The specific steps are as follows: At room temperature, 92.52g of epichlorohydrin, 27.33g of isopropanol, and 42.67g of water are added to a 250ml four-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser, and nitrogen introduction device. After stirring evenly, 11.71g of 3-acetylene aniline is added dropwise to the four-necked flask using a constant pressure funnel (the addition is controlled to be completed within 1 hour). Simultaneously, the temperature is slowly raised to 70℃ under a nitrogen atmosphere (heating rate 5℃ / 15min). After the temperature stabilizes, the reaction is continued with stirring for 3 hours to complete the ring-opening reaction. After the reaction was completed, the temperature was lowered to 55°C, and then 19.8 g of a 50% sodium hydroxide solution (the molar ratio of the active amino hydrogen in 3-acetyleneaniline to the molar ratio of the alkali metal hydroxide was 1:1.2) was added dropwise to a four-necked flask (the sodium hydroxide dropping rate was 1 g / min). After the addition was completed, the reaction was continued at this temperature for 3 hours. After the reaction was completed, the system temperature was cooled to room temperature, and the system was washed with hot water at 70°C until the pH was neutral. The solvent was removed by rotary evaporation, and the product was placed in a vacuum drying oven to remove excess solvent, thus obtaining acetyleneaniline type epoxy resin.

[0060] Example 2

[0061] Except for replacing 3-acetyleneaniline with 4-acetyleneaniline, everything else is the same as in Example 1.

[0062] Example 3

[0063] Except for replacing 3-acetyleneaniline with 2-acetyleneaniline, everything else is the same as in Example 1.

[0064] Example 4

[0065] An acetylene aniline type epoxy resin composition comprises the following components: 100 parts of 3-acetylene aniline epoxy resin prepared in Example 1 and 34 parts of 4,4'-diaminodiphenylmethane (DDM), which are dissolved at 90°C and cured under a curing process of 100°C / 2h + 140°C / 2h + 160°C / 2h + 200°C / 2h + 240°C / 2h + 260°C / 2h to obtain an epoxy / DDM cured system.

[0066] Example 5

[0067] An acetylene aniline type epoxy resin composition comprises the following components: 100 parts of 4-acetylene aniline epoxy resin prepared in Example 2 and 34 parts of 4,4'-diaminodiphenylmethane (DDM), which are dissolved at 90°C and cured under a curing process of 100°C / 2h+140°C / 2h+160°C / 2h+200°C / 2h+240°C / 2h+260°C / 2h to obtain an epoxy / DDM cured system.

[0068] Example 6

[0069] An acetylene aniline type epoxy resin composition comprises the following components: 100 parts of 2-acetylene aniline epoxy resin prepared in Example 3 and 34 parts of 4,4'-diaminodiphenylmethane (DDM), which are dissolved at 90°C and cured under a curing process of 100°C / 2h+140°C / 2h+160°C / 2h+200°C / 2h+240°C / 2h+260°C / 2h to obtain an epoxy / DDM cured system.

[0070] Comparative Example 1 Except for replacing 3-acetyleneaniline with aniline, everything else is the same as in Example 1.

[0071] Comparative Example 2 Except for replacing the amount of epichlorohydrin with 185g, everything else is the same as in Example 1.

[0072] Comparative Example 3 Except for replacing the amount of epichlorohydrin with 46.25g, everything else is the same as in Example 1.

[0073] Comparative Example 4 Except for replacing the amount of epichlorohydrin with 138.75g, everything else is the same as in Example 1.

[0074] Comparative Example 5 An aniline-type epoxy resin composition comprises the following components: 100 parts of 3-acetylene aniline epoxy resin prepared in Example 1 and 38 parts of 4,4'-diaminodiphenylmethane (DDM), which are dissolved at 80°C and cured under a curing process of 100°C / 2h + 140°C / 2h + 160°C / 2h to obtain an epoxy / DDM cured system.

[0075] Performance testing To investigate the efficiency of the preparation methods for acetylene aniline / aniline epoxy resins in Examples 1-3 and Comparative Examples 1-4, and the basic properties of the successfully prepared epoxy resin products, the yield of the preparation methods was calculated based on the mass of the raw materials used to synthesize the resins and the mass of the synthesized resin products. The epoxy equivalent of the resins was also tested, and the results are shown in Table 2. The viscosity of the acetylene aniline epoxy resins in Examples 1-3 and the aniline epoxy resin in Comparative Example 1 was tested using a rheometer, and the products were characterized using Fourier transform infrared spectroscopy. The test results are attached. Figures 1-2 As shown.

[0076] To verify the temperature resistance and dimensional stability of the acetylene aniline type epoxy resin compositions of Examples 4-6 of this invention, the Tg of the cured product was measured using a dynamic thermomechanical analyzer (DMA), and the thermogravimetric analysis (TGA) was used to measure the 5% thermogravimetric temperature T of the cured product under a nitrogen atmosphere. dThe char residue at 800℃ was used to determine the coefficient of linear expansion (CTE) of the cured product at high temperature using a static thermomechanical analyzer (TMA). The test results are attached. Figures 4-6 .

[0077] Table 2 shows that the yields of the products in Examples 1-3 were 83%-85.3%, while the yields in Comparative Examples 1-4 were 77.6%-88.5%, indicating that the synthesis results of the products in the Examples were relatively more stable. The epoxy equivalents of the acetylene aniline type epoxy resins in Examples 1-3 were all slightly lower than those in Comparative Examples 2-4, indicating that the epoxy values ​​of the products in the Examples were higher. According to... Figure 1 Test results show that at room temperature (25℃), the viscosities of Examples 1-3 are 209 mPa·s, 1853 mPa·s, and 570 mPa·s, respectively. Due to structural differences, these viscosities are greater than the viscosity of Comparative Example 1 (189 mPa·s). However, all are liquid at room temperature and exhibit good processing performance. The increased viscosity of 4-acetylene aniline epoxy resin is mainly due to the combined effects of differences in molecular structure, intermolecular interactions, and reactivity. Figure 2 The test results showed that the products of Examples 1-3 and Comparative Example 1 of the present invention were within 910 cm. -1 An epoxy peak (-COC) appears at 2100 cm⁻¹, as seen in Examples 1-3. -1 and 3300cm -1 The retention of the alkynyl peak at the position proves the successful preparation of the acetylene aniline / aniline epoxy resin; according to Figure 3 Test results show that Comparative Example 5 only exhibited one curing exothermic peak, with a peak temperature of 160℃ (epoxy curing peak). Examples 4-6 all showed two exothermic peaks, with peak temperatures of 158℃ and 250℃, respectively. 158℃ corresponds to epoxy curing, and 250℃ corresponds to alkynyl cyclotrimerization. This dual-curing mechanism improves the temperature resistance of the material. Figures 4-6 The test results show that the acetylene aniline type epoxy resins prepared in Examples 4 to 6 of this invention all have good temperature resistance and dimensional stability, and the tests show that they have high Tg and low CTE. Figure 4 Test results show that the Tg of Comparative Example 5 is 152℃, while the Tg of Examples 4 to 6 are much higher than that of Comparative Example 5, with the highest Tg reaching 293℃, indicating good heat resistance. Figure 5 Test results show that Comparative Example 5 exhibits a 5% thermogravimetric loss temperature T under a nitrogen atmosphere. d The residual carbon content was 18% at 285°C and 800°C, while in Examples 4-5, the thermal weight loss was 5% under a nitrogen atmosphere. d Above 348℃ and 800℃, the residual carbon rate is above 38%. A high residual carbon rate means that the material retains a significant amount of carbon residue after high-temperature decomposition, forming a stable carbonized layer, effectively maintaining the integrity of the encapsulation structure and slowing down thermal degradation. According to... Figure 6 The test results show that in Examples 4-5, the CTE of the acetylene aniline-type epoxy resin composition at -50℃ to 80℃ is ≤50ppm / K, indicating good dimensional stability. This is crucial for applications in high-temperature environments such as high-power electronic packaging materials. The above test data demonstrates that the curing system based on acetylene aniline-type epoxy resin of this invention has good heat resistance, dimensional stability, and high-temperature stability.

[0078] Table 2 Yield and epoxy equivalent of acetylene aniline type epoxy resin

[0079] While specific embodiments of the invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art should understand that modifications can be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.

Claims

1. An acetylene aniline type epoxy resin, characterized in that, The general chemical formula is R1 to R5 are each independently selected from one of hydrogen atom, alkyl group, and alkynyl group, and at least one of R1 to R5 is an alkynyl group.

2. The acetylene aniline type epoxy resin according to claim 1, characterized in that, The epoxy equivalent of the acetylene aniline type epoxy resin is 130 g / mol to 170 g / mol.

3. A method for preparing an acetylene aniline-type epoxy resin according to any one of claims 1-2, characterized in that, Includes the following steps: First, acetylene aniline and β-substituted epichlorohydrin undergo a ring-opening reaction in the presence of a solvent. Then, an alkali metal hydroxide is added to the system to induce a cyclization reaction in the intermediate, thereby obtaining an acetylene aniline-type epoxy resin.

4. The method for preparing acetylene aniline type epoxy resin according to claim 3, characterized in that, The general chemical formula of the acetylene aniline is: R1 to R5 are each independently selected from hydrogen atoms, alkyl groups, and amino groups, and at least one of them is an amino group; the chemical formula of the β-substituted epichlorohydrin is [formula missing]. In this case, the A group is one of hydrogen atom, alkyl group and phenyl group.

5. The method for preparing acetylene aniline type epoxy resin according to claim 3, characterized in that, The ring-opening reaction temperature is controlled to be slowly increased from room temperature to 40~110℃, with a heating rate of 1~5℃ / 10~20min, and the reaction time is 3~10h; the cyclization reaction temperature is controlled to be 40~70℃, and the cyclization reaction time is 2~10h.

6. The method for preparing acetylene aniline type epoxy resin according to claim 3, characterized in that, The molar ratio of the active amino hydrogen in the acetylene aniline to the molar ratio of the β-substituted epichlorohydrin is 1:(1~20); the molar ratio of the active amino hydrogen in the acetylene aniline to the molar ratio of the alkali metal hydroxide is 1:(0.9~2).

7. The method for preparing acetylene aniline type epoxy resin according to claim 3, characterized in that, The alkali metal hydroxide is added to the system in the form of an aqueous solution, wherein the alkali metal hydroxide is sodium hydroxide or potassium hydroxide, the mass fraction of the solution is 30%~55%, and the dropping rate is 1~3 g / min.

8. The method for preparing acetylene aniline type epoxy resin according to claim 3, characterized in that, The solvent includes one or a combination of water, alcohol-based solvents, ketone-based solvents, and aromatic solvents; the amount used is 5 to 10 times the mass of acetylene aniline; The alcohol solvents include one or a combination of methanol, ethanol, isopropanol, n-butanol, n-octanol, ethylene glycol, tert-butanol, sec-butanol, isobutanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and benzyl alcohol. The ketone solvents include one or a combination of acetone, methyl isobutyl ketone, butanone, cyclopentanone, methyl ethyl ketone, diisobutyl ketone, diethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, and 2-methylcyclohexanone. The aromatic solvent includes one or a combination of toluene and xylene.

9. An acetylene aniline type epoxy resin composition, characterized in that, The epoxy resin comprises the acetylene aniline type epoxy resin according to any one of claims 1-2 or the acetylene aniline type epoxy resin prepared by the preparation method according to any one of claims 3-8 and a curing agent.

10. The application of the acetylene aniline type epoxy resin composition according to any one of claims 9, characterized in that, It is used in the field of electronic packaging materials.

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