Naphthalene epoxy resin, preparation method thereof, naphthalene epoxy resin composition and application

Abstract

The invention relates to the technical field of materials, in particular to naphthalene-based epoxy resin, a preparation method thereof, a naphthalene-based epoxy resin composition and application. The preparation method of the naphthalene epoxy resin comprises the following steps: obtaining an active group-containing naphthalene compound # imgabs0 # and beta-substituted epichlorohydrin # imgabs1 #, wherein R1-R8 are respectively independently selected from one of H, hydroxyl, carboxyl and amino, and at least three of R1-R8 are not H; a group is one of H, alkyl, alkenyl, alkynyl and phenyl; under the action of a catalyst, a naphthalene compound containing an active group and beta-substituted epichlorohydrin are subjected to a ring-opening and ring-closing reaction to obtain polyfunctional naphthalene epoxy resin # imgabs2 # R11-R81, at least three of the polyfunctional naphthalene epoxy resin # imgabs2 # R11-R81 are # imgabs3 #, and the rest of the polyfunctional naphthalene epoxy resin # imgabs3 # is H, and R is-O-,-COO-or-NH-. The naphthalene epoxy resin disclosed by the invention has high temperature resistance, low viscosity, high purity and low chlorine, has high crosslinking density and high Tg after being cured, is excellent in heat resistance and low in chlorine content, and is suitable for the field of semiconductor packaging.

Description

Technical Field

[0001] The present application belongs to the field of material technology, and in particular relates to a naphthalene epoxy resin and a preparation method thereof, a naphthalene epoxy resin composition and an application thereof. Background Art

[0002] The structural unit, functionality and purity of epoxy resin directly determine the performance, reliability and application value of its cured material. Designing and preparing epoxy resins with high temperature resistance, low viscosity and high purity is an important development direction of synthetic resin industry and semiconductor materials. At present, the realization path of high glass transition temperature Tg epoxy resin system mainly includes: starting from the molecular design level, synthesizing and introducing rigid groups such as naphthalene rings and biphenyls or phenolic skeleton structures or designing resin structures with multi-functionality, high glass transition temperature epoxy resins can be obtained. In addition, the realization path of low viscosity epoxy resin system mainly includes: by appropriately introducing dendritic molecular structures or introducing flexible polymer skeletons, in order to reduce the viscosity of epoxy resin systems. However, by adjusting the content of rigid planar structures (benzene rings, naphthalene rings, anthracene rings, etc.), or prepolymerizing rigid structures into phenolic skeletons to improve system rigidity, or by increasing the functionality of epoxy resins, although the heat resistance of epoxy resins can be improved, the viscosity of epoxy resins will also be increased at the same time. By introducing non-polar alkyl, aliphatic ring, polysiloxane, polyether and other structures into part of the epoxy resin skeleton through molecular design / modification, the viscosity of the epoxy resin can be reduced, but it is difficult to ensure high temperature resistance. Therefore, it is usually difficult to achieve low viscosity and high glass transition temperature at the same time.

[0003] In addition, the main factor affecting the purity of epoxy resin is the chlorine content. The amount of chlorine in epoxy resin is related to the quality of epoxy resin. The adverse effect of residual chlorine content in epoxy resin on the performance of epoxy hardener is manifested in the reduction of the crosslinking density of the cured product, and the macroscopic manifestation is the reduction of its heat deformation temperature. Its adverse effect is also manifested in that when the temperature is higher than the heat deformation temperature, the electrical properties deteriorate, that is, the high-temperature dielectric loss increases and the high-temperature volume resistance decreases. In addition, the HCl produced by hydrolyzable chlorine is corrosive and will affect the insulation and high-temperature electrical properties of epoxy resin cured products. At the same time, hydrolysis will add a hydrophilic hydroxyl group (-OH) to the end group of the resin molecule. The presence of hydroxyl group affects the water resistance of the cured product, and the mechanical strength of the cured product decreases after being damp. The presence of organic chlorine will also affect the curing speed of epoxy resin. Organic chlorine also affects the further synthesis of two-step high molecular weight epoxy resin. At present, the methods for reducing the chlorine content in epoxy resins include: reducing chlorine by strictly adjusting the reactant ratio, reaction temperature, heating rate, raw material purity, etc. at the synthesis end; or starting from the purification end, reducing the total chlorine through molecular distillation, alkali refining, etc., but these methods have limited effects on reducing the chlorine content in epoxy resins. In addition, the epoxidation of double bonds with peroxy acids does not involve epichlorohydrin, so although it does not produce organic chlorine, this method is mostly used in the preparation of aliphatic epoxy resins, and the resulting epoxy resins usually have poor temperature resistance and cannot be used in heat-resistant scenarios.

[0004] Therefore, it is particularly important to develop an epoxy resin with high temperature resistance, low viscosity, high purity and low chlorine. Summary of the invention

[0005] The purpose of the present application is to provide a naphthalene epoxy resin and a preparation method thereof, a naphthalene epoxy resin composition and application, aiming to solve the problem that existing epoxy resins are difficult to have the characteristics of high temperature resistance, low viscosity and high purity and low chlorine.

[0006] In order to achieve the above application purpose, the technical solution adopted in this application is as follows:

[0007] The first aspect of the present application provides a method for preparing a naphthalene-based epoxy resin, comprising the following steps:

[0008] Obtaining naphthalene compounds containing active groups and β-substituted epichlorohydrin Wherein, R1-R8 are independently selected from one of H, hydroxyl, carboxyl, and amino, and at least three of R1-R8 are not H; the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl;

[0009] Under the action of a catalyst, the naphthalene compound containing an active group and the β-substituted epichlorohydrin undergo ring opening and ring closing reactions to obtain a multifunctional naphthalene-based epoxy resin. Among them, R11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-.

[0010] The preparation method of naphthalene epoxy resin provided by the present application uses naphthalene compounds containing active groups and β-substituted epichlorohydrin as raw materials. During the reaction, the spatial configuration or molecular dipole of the epoxy resin molecule is adjusted by the A group at the β position in the epichlorohydrin, the steric hindrance at the β position is adjusted, and the addition at the β position is inhibited, so that the active group in the naphthalene compound containing active groups attacks the carbon at the α position in the β-substituted epichlorohydrin, and the β-substituted epichlorohydrin opens along the α carbon, and the epichlorohydrin is formed, and the active group in the naphthalene compound is chemically bonded to the carbon at the α position in the substituted epichlorohydrin. As the catalytic reaction progresses, the hydroxyl group and -CH2Cl in the ring-opened epichlorohydrin are closed to form an epoxy ring again under the action of the catalyst, thereby obtaining a multifunctional naphthalene epoxy resin. The preparation method of the naphthalene epoxy resin of the present application can effectively reduce the influence of the β-position addition side reaction on the product yield, inhibit the active groups in the naphthalene compound from attacking the β-carbon in epichlorohydrin, and avoid epichlorohydrin from being connected to the naphthalene compound through the middle β-carbon after the β-carbon ring opening, and the -CH2Cl and -CH2OH after the ring opening cannot be closed again to form a four-membered ring due to the influence of the polycyclic ring steric hindrance, resulting in the inability to form an epoxy substitution on the naphthalene compound, but with isolated chloromethyl (-CH2Cl, inactive chlorine) exists, increase the chlorine content in the naphthalene epoxy resin, and consume raw material components, reduce the product yield. Therefore, the chlorine content in the naphthalene epoxy resin prepared by the present application is low and the purity is high. Moreover, the naphthalene epoxy resin includes at least a plurality of epoxy groups, which, on the one hand, is conducive to improving the crosslinking density of the resin and enhancing the rigidity of the polymer network structure, thereby obtaining high heat resistance; on the other hand, the spatial configuration or molecular dipole of the epoxy resin molecule can be adjusted by selecting the A group at the β position in the epoxy group, so that the intermolecular stacking and interaction force are weakened, and its crystallinity is destroyed, which is conducive to reducing the viscosity of the naphthalene epoxy resin, obtaining low high temperature viscosity, improving the processability of the epoxy resin, and realizing the regulation of the performance parameters such as viscosity, temperature resistance, and melting point of the naphthalene epoxy resin. Therefore, the naphthalene epoxy resin has the characteristics of high temperature resistance, low viscosity, high purity, and low chlorine. After curing, the naphthalene epoxy resin has high crosslinking density and high Tg, excellent heat resistance, and low chlorine content, and has great application value in electronic materials such as semiconductor packaging.

[0011] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the epoxy equivalent of the naphthalene epoxy resin is 110g / mol-140g / mol, the total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm. In this case, the epoxy equivalent of 110-140g / mol not only satisfies the temperature resistance of the naphthalene epoxy resin cured product, but also ensures the other properties of the naphthalene epoxy resin. The total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm, which is beneficial to the subsequent naphthalene epoxy resin and is also beneficial to reduce the corrosion of chlorine in the resin to the circuit when preparing electronic materials, ensuring the safety and stability.

[0012] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the A group is one of methyl, ethyl, vinyl, ethynyl, and phenyl. In this case, the A groups substituted at the β position in epichlorohydrin can better regulate the steric hindrance on the β carbon, inhibit the β position addition, and better regulate the spatial configuration or molecular dipole of the epoxy resin molecule, obtain low high temperature viscosity, improve the processability of the epoxy resin, and make the obtained naphthalene epoxy resin have better high temperature resistance, low viscosity, high purity, low chlorine and other characteristics.

[0013] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the β-substituted epichlorohydrin includes at least one of epichlorohydrin, methyl epichlorohydrin, and 2-(chloromethyl)-2-phenyloxirane. These β-substituted epichlorohydrins can all undergo α-carbon ring opening and ring closing reactions with naphthalene compounds containing active groups to obtain naphthalene epoxy resins.

[0014] As some possible implementations of the method for preparing the naphthalene epoxy resin of the present application, the R1 to R8 are independently selected from H or hydroxyl groups; 11 ~R 81 At least three of them are In this case, the hydroxyl group in naphthalene attacks the carbon at the α position in β-substituted epichlorohydrin, the β-substituted epichlorohydrin opens along the α carbon, and the active group in the naphthalene compound chemically bonds with the carbon at the α position in the substituted epichlorohydrin. Under the action of the catalyst, the hydroxyl group in the opened epichlorohydrin and -CH2Cl close the ring to form an epoxy ring again.

[0015] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the naphthalene compound containing active groups includes at least one of 1,2,4-trihydroxynaphthalene, 1,4,5-trihydroxynaphthalene, 1,2,3,4-tetrahydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxynaphthalene and 1,2,4,5,8-pentahydroxynaphthalene. These naphthalene compounds containing active groups are easier to carry out epoxidation reaction by replacing steric hindrance, and after epoxidation, they are all high-functionality epoxy resins with excellent temperature resistance.

[0016] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the temperature conditions of the ring opening and ring closing reactions are 25°C to 140°C, and the reaction time is 1 hour to 8 hours. Under the conditions of hot mixing treatment, the alkaline solution can better promote the further ring closing of the unclosed -OH and -Cl in the synthesis step, and timely eliminate the 1,2-chlorohydrin ether (easily hydrolyzed chlorine) generated in the synthesis step to obtain a multifunctional naphthalene epoxy resin.

[0017] As some possible implementations of the method for preparing the naphthalene epoxy resin of the present application, the ratio of the molar amount of the active group in the naphthalene compound containing the active group to the molar amount of the β-substituted epichlorohydrin is 1:(1-20). In the case of this molar ratio, the ring-opening and ring-closing reactions between the naphthalene compound containing the active group and the β-substituted epichlorohydrin can be fully ensured, so that multiple active groups on the naphthalene ring are grafted with epoxy substituents to obtain a multifunctional naphthalene epoxy resin, thereby improving the reaction efficiency.

[0018] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the catalyst includes an alkali metal hydroxide or a mixed catalyst of an alkali metal hydroxide and a quaternary ammonium salt. Among them, the alkali metal hydroxide can simultaneously catalyze the active group in the naphthalene compound containing the active group to attack the carbon ring opening at the α position in the β-substituted epichlorohydrin, and at the same time catalyze the hydroxyl group and -CH2Cl in the ring-opened epichlorohydrin to close the ring to form an epoxy ring again. In the mixed catalyst, the quaternary ammonium salt can catalyze the active group in the naphthalene compound to attack the carbon ring opening at the α position in the β-substituted epichlorohydrin to complete the ring opening reaction; in addition, the hydroxyl group and -CH2Cl in the ring-opened epichlorohydrin catalyzed by the alkali metal hydroxide close the ring to form an epoxy ring again.

[0019] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the ratio of the molar amount of the alkali metal hydroxide to the molar amount of the active group in the naphthalene compound containing the active group is 1: (1 to 10). Under this ratio, the alkali metal hydroxide can better catalyze the ring-opening and ring-closing reactions between the naphthalene compound containing the active group and the β-substituted epichlorohydrin, graft multiple epoxy substitutions on the naphthalene ring, and obtain a multifunctional naphthalene epoxy resin.

[0020] As some possible implementations of the method for preparing the naphthalene-based epoxy resin of the present application, the ratio of the molar amount of the quaternary ammonium salt to the molar amount of the active group in the naphthalene compound containing the active group is 1:(0.005-0.05). Under this ratio, the quaternary ammonium salt can better catalyze the active group in the naphthalene compound to attack the carbon ring opening at the α position in the β-substituted epichlorohydrin to complete the ring opening reaction.

[0021] As some possible implementations of the preparation method of the naphthalene-based epoxy resin of the present application, the alkali metal hydroxide includes: at least one of potassium hydroxide and sodium hydroxide; these alkali metal hydroxides can well catalyze the ring-opening and ring-closing reactions between the naphthalene compound containing active groups and β-substituted epichlorohydrin, and graft multiple epoxy substitutions on the naphthalene ring to obtain a multi-functional naphthalene-based epoxy resin.

[0022] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the quaternary ammonium salt includes at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride and tetrapentylammonium chloride. These quaternary ammonium salts can well catalyze the active groups in the naphthalene compound to attack the carbon ring opening at the α position in the β-substituted epichlorohydrin to complete the ring opening reaction.

[0023] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, after the ring opening and ring closing reactions, the steps of water washing and refining are also included: the crude product after the ring opening and ring closing reactions is dissolved in an organic solvent, an alkaline solution is added for hot mixing treatment, the organic phase is separated, and the naphthalene epoxy resin is obtained. Through water washing and refining, the -OH and -Cl that failed to close the ring in the synthesis step are further closed, and the 1,2-chlorohydrin ether (hydrolyzable chlorine) generated in the synthesis step is eliminated in time.

[0024] As some possible implementations of the method for preparing the naphthalene epoxy resin of the present application, the molar ratio of the crude product to the alkaline substance in the alkaline solution is (0.05-20): 1. Under this molar ratio, it can be fully ensured that the unclosed -OH and -Cl in the crude product after the alkaline substance catalyzes the ring-opening and ring-closing reactions are closed to form epoxy substitution, thereby obtaining a multifunctional naphthalene epoxy resin.

[0025] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the alkaline solution is an alkali metal hydroxide solution with a concentration of 1wt% to 10wt%. Under this concentration condition, the alkaline solution has a good ring-closing effect on the unclosed -OH and -Cl in the crude product after the ring-opening and ring-closing reactions, thereby increasing the molecular weight of the epoxy resin and the epoxy equivalent of the resin.

[0026] As some possible implementations of the preparation method of the naphthalene epoxy resin of the present application, the temperature of the heat mixing treatment is 50°C to 130°C, and the duration is 0.5 hours to 3 hours. Under the heat mixing treatment conditions, the alkaline solution can better promote the further ring closure of the un-ringed -OH and -Cl in the synthesis step, and timely eliminate the 1,2-chlorohydrin ether (easily hydrolyzed chlorine) generated in the synthesis step to obtain a multifunctional naphthalene epoxy resin.

[0027] As some possible implementations of the method for preparing the naphthalene epoxy resin of the present application, after the water washing and refining, rough treatment and recrystallization are further included. The purity of the naphthalene epoxy resin can be further purified by rough treatment and recrystallization to reduce the content of the rate.

[0028] The second aspect of the present application provides a naphthalene-based epoxy resin, the general chemical formula of which is Among them, R 11 ~R 81 At least three of them are The rest are H, R is -O-, -COO- or -NH-, and the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl.

[0029] The naphthalene epoxy resin provided by the present application comprises a naphthalene ring skeleton, on which at least three or more epoxy groups are grafted, which is conducive to improving the crosslinking density of the resin and enhancing the rigidity of the polymer network structure, thereby obtaining high heat resistance. In addition, the spatial configuration or molecular dipole of the epoxy resin molecule can be adjusted by selecting the A group at the β position in the epoxy group, so that the intermolecular stacking and interaction forces are weakened, and its crystallinity is destroyed, which is conducive to reducing the viscosity of the naphthalene epoxy resin, obtaining low high temperature viscosity, improving the processability of the epoxy resin, realizing the regulation of the performance parameters such as the viscosity, temperature resistance, and melting point of the naphthalene epoxy resin, and is conducive to reducing the viscosity of the naphthalene epoxy resin. In addition, the chlorine content in the naphthalene epoxy resin is low and the purity is high. Therefore, the naphthalene epoxy resin of the present application has the characteristics of high temperature resistance, low viscosity and high purity low chlorine, and has great application value in electronic materials such as semiconductor packaging.

[0030] As some possible implementations of the naphthalene epoxy resin of the present application, the epoxy equivalent in the naphthalene epoxy resin is 110g / mol-140g / mol, the total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm. In this case, the epoxy equivalent of 110-140g / mol not only satisfies the temperature resistance of the naphthalene epoxy resin cured product, but also ensures the other properties of the naphthalene epoxy resin. The total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm, which is conducive to reducing the corrosion of chlorine in the resin to the circuit when the subsequent naphthalene epoxy resin is matched to prepare electronic materials, which is conducive to ensuring safety and stability.

[0031] According to a third aspect of the present application, there is provided a naphthalene-based epoxy resin composition, which comprises the naphthalene-based epoxy resin prepared by the above method and / or the above naphthalene-based epoxy resin and a second epoxy resin, wherein the viscosity of the second epoxy resin is lower than that of the naphthalene-based epoxy resin.

[0032] The naphthalene epoxy resin composition provided by the present application comprises the above-mentioned naphthalene epoxy resin and the second epoxy resin, wherein the viscosity of the second epoxy resin is lower than that of the naphthalene epoxy resin, and the low-viscosity second epoxy resin is used in combination with the naphthalene epoxy resin, and the molecular spatial structure and dipole difference between the multifunctional naphthalene epoxy resin molecules and the low-viscosity second epoxy resin are utilized to reduce the stacking and interaction of molecules in the resin composition, thereby achieving the purpose of significantly reducing the viscosity of the naphthalene epoxy resin composition. In the naphthalene epoxy resin composition, the multifunctional naphthalene epoxy resin not only has high purity and low chlorine content, but also has high crosslinking density and strong rigid structure, so that the naphthalene epoxy resin composition cured product has high Tg characteristics. Therefore, the naphthalene epoxy resin composition has the characteristics of high temperature resistance, low viscosity and high purity and low chlorine.

[0033] As some possible implementations of the naphthalene epoxy resin composition of the present application, the viscosity of the second epoxy resin at a temperature of 25° C. is 100 mPa.s to 50,000 mPa.s, and the viscosity at a temperature of 150° C. is 1 mPa.s to 1,000 mPa.s. By using a low-viscosity second epoxy resin in combination with a naphthalene epoxy resin, utilizing the molecular spatial structure and dipole differences between the multifunctional naphthalene epoxy resin molecules and the low-viscosity second epoxy resin, etc., the stacking and interaction of molecules in the resin composition are reduced, and a low-viscosity naphthalene epoxy resin composition is obtained.

[0034] As some possible implementations of the naphthalene epoxy resin composition of the present application, the second epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, 1,6-dihydroxynaphthalene epoxy resin, p-aminophenol epoxy resin, and diaminodiphenylmethane epoxy resin. These second epoxy resins all have a relatively low viscosity, and when used in combination with the naphthalene epoxy resin, the stacking and interaction of molecules in the resin composition can be reduced to obtain a low-viscosity naphthalene epoxy resin composition.

[0035] As some possible implementations of the naphthalene epoxy resin composition of the present application, the naphthalene epoxy resin composition also includes an epoxy resin curing agent with a resin mass percentage of 30% to 60%. In this case, the 30% to 60% epoxy resin curing agent contained in the naphthalene epoxy resin composition can better promote the cross-linking and curing of the naphthalene epoxy resin and the second epoxy resin in the composition.

[0036] As some possible implementations of the naphthalene epoxy resin composition of the present application, the epoxy resin curing agent includes: at least one of an amine curing agent, an acid anhydride curing agent, a phenolic resin curing agent, an active ester curing agent, and a cyanate curing agent. These types of curing agents can all promote the curing of epoxy resins well. These curing agents react chemically with active hydrogen atoms in the epoxy resin to form a cross-linked structure, so that the epoxy resin molecules are cured into a solid material.

[0037] As some possible implementations of the naphthalene epoxy resin composition of the present application, the naphthalene epoxy resin composition also includes a curing accelerator with a resin mass percentage of 0.1% to 1.5%. In this case, a curing accelerator is added to the naphthalene epoxy resin composition, and the curing accelerator can affect the reaction rate and reaction mechanism between the epoxy resin and the curing agent, thereby adjusting the temperature, time and performance of the curing process. It can better promote the cross-linking and curing between the naphthalene epoxy resin and the second epoxy resin, accelerate the curing speed of the epoxy resin, improve the curing effect and increase the curing strength.

[0038] As some possible implementations of the naphthalene epoxy resin composition of the present application, the curing accelerator includes at least one of tris(dimethylaminomethyl)phenol, triethanolamine, dimethylbenzylamine, N-diglycidylaniline, diethylenediamine, triethylenediamine, tetraethylenediamine, and diisopropylamine. These curing accelerators can better promote the cross-linking and curing between the naphthalene epoxy resin and the second epoxy resin, accelerate the curing speed of the epoxy resin, improve the curing effect, and increase the curing strength.

[0039] A fourth aspect of the present application provides an application of a naphthalene-based epoxy resin composition, wherein the naphthalene-based epoxy resin composition is applied to the field of electronic materials.

[0040] The multifunctional naphthalene epoxy resin contained in the naphthalene epoxy resin composition provided by the present application is not only high in purity and low in chlorine content, but also has high cross-linking density and strong rigid structure, so that the naphthalene epoxy resin composition cured product has high Tg characteristics. Therefore, the naphthalene epoxy resin composition has the characteristics of high temperature resistance, low viscosity and high purity and low chlorine. The naphthalene epoxy resin composition has high cross-linking density and high Tg after curing, and has excellent heat resistance, and has great application value in the field of electronic materials. And the naphthalene epoxy resin composition has low chlorine content, has little corrosion to the circuit under high temperature and high humidity, has good insulation, and improves the reliability of the electronic packaging material based on the naphthalene epoxy resin.

[0041] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 1 is a schematic flow chart of a method for preparing a naphthalene-based epoxy resin provided in an embodiment of the present application;

[0043] Figure 2 is a schematic diagram of the preparation of a naphthalene-based epoxy resin composition provided in an embodiment of the present application;

[0044] Figure 3 The present application embodiment 1 provides a 1,4,5-trifunctional naphthalene epoxy resin molecule NMR hydrogen spectrum;

[0045] Figure 4 The present application embodiment 1 provides a 1,4,5-trifunctional naphthalene epoxy resin molecule NMR carbon spectrum;

[0046] Figure 5 The present application embodiment 1 provides a 1,4,5-trifunctional naphthalene epoxy resin molecule nuclear magnetic resonance mass spectrum;

[0047] Figure 6 The infrared spectrum of 1,4,5-trifunctional naphthalene epoxy resin molecule provided in Example 1 of the present application;

[0048] Figure 7 Example 2 of the present application provides a 1,4,5-trifunctional naphthylmethyl epoxy resin molecule NMR hydrogen spectrum;

[0049] Figure 8 Example 2 of the present application provides a 1,4,5-trifunctional naphthylmethyl epoxy resin molecule NMR carbon spectrum;

[0050] Fig. 9 Example 2 of the present application provides a molecular nuclear magnetic resonance mass spectrum of 1,4,5-trifunctional naphthylmethyl epoxy resin;

[0051] Fig.10 The infrared spectrum of 1,4,5-trifunctional naphthylmethyl epoxy resin molecule is provided in Example 2 of the present application. DETAILED DESCRIPTION

[0052] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0053] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0054] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0055] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0056] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0057] The term "Tg" is an abbreviation for "glass transition temperature", which means the glass transition temperature, which refers to the temperature at which a polymer changes from a glassy state to a highly elastic state. Tg is the lowest temperature at which molecular chains can move, and is a relaxation phenomenon of the amorphous part of a polymer from a frozen state to a thawed state.

[0058] In the term "I / O", I stands for INPUT, which means input, and O stands for OUTPUT, which means output. I / O refers to input / output points. Both input and output are for control systems. Input refers to the measurement parameters entering the control system from the instrument, and output refers to the parameters output from the control system to the actuator. A parameter is called a point. The scale of a control system is sometimes determined by the maximum number of I / O points it can control, in this case in electronic circuits.

[0059] The terms "α" and "β" refer to the distinction between α carbon and β carbon in organic matter. They are used to mark the order of carbon atoms. The α position means "the first one". The first carbon directly connected to the functional group is called α, the second is called β, the third is called γ, and so on. Taking H2N-CH2-CH2-OH as an example, if the H2N- group is used as a reference, the carbon atom in CH2 on the left is the α carbon atom, and the one on the right is β. Addition on the β carbon is β addition, and addition on the α carbon is α addition. In epichlorohydrin, the α carbon refers to the carbon in CH2 close to the O atom (the carbon with two H atoms attached), and the β carbon is the C atom on CA (A can be a substituent such as H, methyl, etc.) (the carbon with at least one non-H atom attached). For molecules such as epichlorohydrin, the carbon close to O and with fewer non-H atoms attached is the α carbon, and the carbon with more non-H atoms attached is the β carbon, such as, Wherein A is a substituent.

[0060] The term "EMC" is the abbreviation of "Epoxy Molding Compound", which means epoxy molding material. Its full name is epoxy resin molding compound. It is a thermosetting chemical material used for semiconductor packaging. It is made of epoxy resin as the base resin, high-performance phenolic resin as the curing agent, and fillers such as silicon micropowder, as well as a variety of additives. Its main function is to protect semiconductor chips from the influence of the external environment (water vapor, temperature, pollution, etc.), and to achieve composite functions such as thermal conductivity, insulation, moisture resistance, pressure resistance, and support.

[0061] In the following chemical structure Indicates the junction site / position.

[0062] The expression forms of chlorine in epoxy resin include organic chlorine, easily saponifiable chlorine, hydrolyzable chlorine, non-hydrolyzable chlorine, active chlorine, inactive chlorine, inorganic chlorine, total chlorine, etc., among which organic chlorine = active chlorine + inactive chlorine, total chlorine = active chlorine + inactive chlorine + inorganic chlorine = organic chlorine + inorganic chlorine, easily saponifiable chlorine = hydrolyzable chlorine. Chlorine in epoxy resin usually exists in three forms, namely active chlorine, inactive chlorine and inorganic chlorine.

[0063] Saponifiable chlorine is the 1,2-chlorohydrin ether generated by α addition during the synthesis of epoxy resin. It is left behind when the dehydrochlorination ring is not fully closed. Since the chlorine on the 1,2-chlorohydrin ether is relatively active and easily hydrolyzed by trace amounts of water, it is also called hydrolyzable chlorine. Its hydrolysis produces HCl and adds a water-absorbing hydroxyl group (-OH) to the end group of the resin molecule.

[0064] Inactive chlorine mainly exists in the resin as isolated chloromethyl (-CH2Cl), which is caused by the side reaction during the resin synthesis. There is no direct method to determine inactive chlorine, and its value can only be obtained indirectly by the method of (total chlorine - easily saponifiable chlorine - inorganic chlorine = inactive chlorine). The chlorine in inactive chlorine is relatively stable and not easy to hydrolyze, so it can also be called non-hydrolyzable chlorine. Its presence will affect the linear structure of epoxy resin, but some studies have reported that its content has little effect on the performance of the cured product when it is small.

[0065] Inorganic chlorine is mainly a large amount of NaCl produced during the reaction of synthetic resin. Although it is washed with water, trace amounts of NaCl may still remain. Its presence will affect the electrical properties of epoxy resin cured products at room temperature.

[0066] At present, from the perspective of the development of the market situation, the design and preparation of epoxy resins with high temperature resistance, low viscosity and high purity is an important development direction for the synthetic resin industry and semiconductor materials. Naphthalene epoxy resin is a type of high-performance heat-resistant epoxy resin material with a rigid naphthalene ring structure. It is currently widely used in electronic component epoxy molding materials (EMC), underfill, interlayer insulation films and laminated boards. With the rapid development trend of microelectronics technology towards high functionality, high density, high I / O number and miniaturization, higher requirements are also placed on the viscosity and heat resistance of naphthalene epoxy resin materials. In theory, multi-functional naphthalene epoxy resins have better cross-linking density, and their cured products will show higher Tg and better heat resistance. In addition, the current methods for reducing the chlorine content in epoxy resins include: reducing chlorine by strictly adjusting the reactant ratio, reaction temperature, heating rate, raw material purity, etc. at the synthesis end; it is also possible to start from the purification end and reduce the total chlorine by molecular distillation, alkali refining and other methods, but these methods have limited effects on reducing the chlorine content in epoxy resins. In addition, the epoxidation of double bonds with peroxy acids does not involve epichlorohydrin, so although no organic chlorine is produced, this method is mostly used in the preparation of aliphatic epoxy resins. The resulting epoxy resins usually have poor temperature resistance or poor curing processability, and their application scenarios are limited. Therefore, it is particularly important to develop an epoxy resin that has the characteristics of high temperature resistance, low viscosity, high purity and low chlorine.

[0067] In some known technologies, naphthol and epichlorohydrin are used as raw materials to prepare naphthalene epoxy resin molecules by a two-step method, that is, firstly realize the ring opening of epichlorohydrin by a catalyst, and then realize the epoxy ring closure by adding alkali solution in the second step. A synthesis method of some naphthalene epoxy resins is provided, and some formula designs are also carried out to realize the high Tg of the resin composition, but the regulation method of chlorine content and viscosity is not involved. And the epoxy resin obtained cannot be applied to semiconductor materials due to the presence of hydrolyzable chlorine. In other known technologies, the chlorine content is reduced by optimizing the post-processing process conditions, that is, the resin prepared preliminarily is dissolved in an organic solvent, after filtering, an alkaline aqueous solution is added to the filtrate to react with a cosolvent, and the reaction is completed and washed by reduced pressure distillation to provide a low-chlorine epoxy resin, but the reduction effect on the chlorine content is not good, and the high temperature resistance and low viscosity of the epoxy resin are difficult to take into account at the same time.

[0068] By adjusting the content of rigid planar structure (benzene ring, naphthalene ring, anthracene ring, etc.), or prepolymerizing the rigid structure into a phenolic skeleton to improve the rigidity of the system, or by increasing the functionality of epoxy resin, the improvement of the heat resistance of epoxy resin is achieved. But whether it is to improve the rigid structure ratio or increase the functionality, the improvement of resin viscosity will be improved. In addition, by molecular design / modification, non-polar alkyl, aliphatic ring, polysiloxane, polyether and other structures are introduced into part of the epoxy resin skeleton to achieve, but it is difficult to ensure high temperature resistance. Realizing high Tg and low viscosity at the same time is a major problem in the molecular design of epoxy resin. At present, the preparation of naphthalene epoxy resin mostly adopts the two-step synthesis strategy of "catalyst+alkali solution", and the synthesis process is relatively complicated, and the influence of β-substitution side reaction on product yield cannot be eliminated. At the same time, the elimination effect of the organochlorine produced by the β-substitution side reaction in the later alkali solution refining process is not good, which directly affects the total chlorine content of the product.

[0069] Based on the above considerations, in order to provide an epoxy resin having high temperature resistance, low viscosity and high purity low chlorine characteristics, it is found that the selection of the group or atom at the β position in epichlorohydrin has an important influence on the generation of organochlorine by-products in epoxy resin, which also directly affects the total chlorine content of the resin, and the preparation of low-chlorine epoxy resin is also an effective means of reducing chlorine by suppressing the β substitution reaction by the screening of the group or atom at the β position in epichlorohydrin. The embodiment of the present application is based on a rigid naphthalene ring structure, and the β substitution reaction is regulated by the screening of the group or atom at the β position in epichlorohydrin, and a low-chlorine type multifunctional naphthalene epoxy resin is prepared using a "one-step method". In addition, by selecting the group or atom at the β position, the spatial configuration or molecular dipole of the epoxy resin molecule can be adjusted to realize the regulation of performance parameters such as epoxy resin viscosity, temperature resistance, and melting point.

[0070] Furthermore, in the embodiment of the present application, the multifunctional naphthalene epoxy resin prepared by design is modified by physical blending with an electronic grade low viscosity resin to reduce the viscosity of the epoxy resin composition, thereby obtaining a low viscosity epoxy resin composition. The low viscosity epoxy resin composition has high crosslinking density and high Tg after curing, excellent heat resistance, and low chlorine content, and has great application value in epoxy resin-based materials for semiconductor packaging.

[0071] For the convenience of explanation, the present application is specifically described through the following examples.

[0072] First, as Figure 1 As shown, the present application embodiment provides a method for preparing a naphthalene-based epoxy resin, comprising the following steps:

[0073] S10. Obtaining naphthalene compounds containing active groups and β-substituted epichlorohydrin Wherein, R1-R8 are independently selected from one of H, hydroxyl, carboxyl, and amino, and at least three of R1-R8 are not H; the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl;

[0074] S20. Under the action of a catalyst, a naphthalene compound containing an active group undergoes a ring-opening and ring-closing reaction with β-substituted epichlorohydrin to obtain a multifunctional naphthalene-based epoxy resin. Among them, R 11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-.

[0075] Thus, the preparation method of the naphthalene epoxy resin provided in the embodiment of the present application is to use a naphthalene compound containing an active group and β-substituted epichlorohydrin As a raw material, the A substituent group at the β position in the β-substituted epichlorohydrin increases the steric hindrance on the β carbon, thereby inhibiting the β-position addition. Under the action of a catalyst, the naphthalene compound containing an active group undergoes a ring-opening and ring-closing reaction with the β-substituted epichlorohydrin, and a multifunctional naphthalene-based epoxy resin is prepared by a "one-step method". The preparation process is simple and suitable for industrial large-scale production and application. Specifically, during the reaction process, the spatial configuration or molecular dipole of the epoxy resin molecule is adjusted by the A group at the β position in epichlorohydrin, the steric hindrance at the β position is adjusted, and the β-position addition is inhibited, so that the active group in the naphthalene compound containing an active group attacks the β-substituted epichlorohydrin. The α-carbon in the β-substituted epichlorohydrin opens the ring along the α-carbon to form The active group in the naphthalene compound chemically bonds with the carbon at the α position in the substituted epichlorohydrin. As the catalytic reaction progresses, the hydroxyl group in the ring-opened epichlorohydrin and -CH2Cl close the ring to form an epoxy ring again under the action of the catalyst. The resulting multifunctional naphthalene epoxy resin In, R 11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-. The preparation method of the naphthalene epoxy resin provided in the embodiment of the present application can effectively reduce the influence of the β-addition side reaction on the product yield, specifically, inhibiting the active groups in the naphthalene compound from attacking the β-carbon in epichlorohydrin, and preventing epichlorohydrin from passing through the β-carbon ring after opening. The middle β carbon is connected to the naphthalene compound, and the -CH2Cl after the ring opening and -CH2OH cannot be closed again to form a four-membered ring due to the influence of the polycyclic ring steric hindrance, resulting in the inability to form epoxy substitution on the naphthalene compound, but with isolated chloromethyl (-CH2Cl, inactive chlorine) exists, increases the chlorine content in the naphthalene epoxy resin, and consumes the raw material components, reducing the product yield. Therefore, the chlorine content in the naphthalene epoxy resin prepared by the embodiment of the present application is low, and the purity is high. Moreover, at least a plurality of epoxy groups are included in the naphthalene epoxy resin, on the one hand, it is conducive to improving the cross-linking density of the resin, enhancing the rigidity of the polymer network structure, so as to obtain high heat resistance; on the other hand, the spatial configuration or molecular dipole of the epoxy resin molecule can be adjusted by the selection of the A group at the β position in the epoxy group, so that the intermolecular stacking and interaction force are weakened, and its crystallinity is destroyed, it is conducive to reducing the viscosity of the naphthalene epoxy resin, obtaining low high temperature viscosity, improving the processability of the epoxy resin, and realizing the regulation of the performance parameters such as the viscosity, temperature resistance, and melting point of the naphthalene epoxy resin. Therefore, naphthalene epoxy resin has the characteristics of high temperature resistance, low viscosity, high purity and low chlorine. After curing, naphthalene epoxy resin has high crosslinking density and high Tg, excellent heat resistance and low chlorine content, and has great application value in electronic materials such as semiconductor packaging.

[0076] In some possible embodiments, the epoxy equivalent of the naphthalene epoxy resin is 110g / mol to 140g / mol, the total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm. The smaller the epoxy equivalent in the naphthalene epoxy resin of the present application, the greater the temperature resistance of the resin solidified product; the level of total chlorine and hydrolyzed chlorine also has a certain influence on the temperature resistance, such as: the higher the total chlorine and hydrolyzed chlorine, the worse the temperature resistance of the resin solidified product. In addition, the higher the total chlorine and hydrolyzed chlorine, the worse the reliability of the electronic packaging material based on the naphthalene epoxy resin, and circuit corrosion will be caused under high temperature and high humidity. The smaller the epoxy equivalent, the smaller the viscosity of the resin (molten state) in theory; the level of total chlorine and hydrolyzed chlorine also has a certain influence on the viscosity, such as: the higher the total chlorine and hydrolyzed chlorine, the greater the viscosity of the resin (molten state). In the naphthalene epoxy resin provided in the embodiment of the present application, the epoxy equivalent is 110-140 g / mol, which not only satisfies the temperature resistance of the naphthalene epoxy resin cured product, but also ensures other properties of the naphthalene epoxy resin. The total chlorine is less than 2000 ppm, and the hydrolyzed chlorine is less than 1000 ppm, which is beneficial to reduce the corrosion of chlorine in the resin to the circuit when the naphthalene epoxy resin is used to prepare electronic materials, and is beneficial to ensure safety and stability.

[0077] In some possible embodiments, in the above step S10, the naphthalene compound containing an active group The active groups in the naphthalene compound can be hydroxyl, carboxyl, and amino, and these active groups can effectively attack the carbon at the α position in the β-substituted epichlorohydrin. The number of active groups in the naphthalene compound can be three, or four, or five, or six, or seven. In this case, the position of the active group is not specifically limited and can be flexibly selected according to actual conditions. The number of active groups in the naphthalene compound can also be eight, that is, active groups are grafted on the naphthalene ring. Through subsequent reactions, 3 to 8 multiple epoxy substitutions can be formed on the naphthalene ring.

[0078] In some embodiments, the naphthalene compound containing the active group In the embodiment, R1 to R8 are independently selected from H or hydroxyl groups, and at least three of R1 to R8 are not H; in this case, the hydroxyl group in the naphthalene compound attacks the β-substituted epichlorohydrin The α-carbon of the β-substituted epichlorohydrin is ring-opened along the α-carbon, and the active group in the naphthalene compound is chemically bonded to the α-carbon of the substituted epichlorohydrin. Under the action of the catalyst, the hydroxyl group and -CH2Cl in the ring-opened epichlorohydrin are ring-closed to form an epoxy ring again. The resulting multifunctional naphthalene-based epoxy resin In, R 11 ~R 81 At least three of them are For example, the multifunctional naphthalene epoxy resin R 11 ~R 81 There are three, four, five, six, seven or eight right The specific substitution position is not specifically limited, and a naphthalene-based epoxy resin that meets the application requirements can be prepared according to actual application requirements.

[0079] In some possible embodiments, the naphthalene compound containing active groups includes at least one of 1,2,4-trihydroxynaphthalene, 1,4,5-trihydroxynaphthalene, 1,2,3,4-tetrahydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxynaphthalene and 1,2,4,5,8-pentahydroxynaphthalene. In this case, these naphthalene compounds containing active groups contain at least three hydroxyl groups. Through subsequent catalytic ring-opening and ring-closing reactions with β-substituted epichlorohydrin, at least 3 to 5 epoxy groups can be grafted on the naphthalene ring, thereby improving the functionality of the naphthalene-based epoxy resin, which is beneficial to improving the cross-linking density of the resin cured product, thereby improving the temperature resistance (glass transition temperature) of the naphthalene-based epoxy resin cured product, so that the obtained naphthalene-based epoxy resin has the characteristics of high temperature resistance, low viscosity and high purity and low chlorine.

[0080] In some specific embodiments, the naphthalene compounds containing active groups include: at least one of 1,4,5-trihydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxynaphthalene. These naphthalene compounds containing active groups replace steric hindrance and are more easily epoxidized. After epoxidation, they are all high-functionality epoxy resins with excellent temperature resistance.

[0081] In some possible embodiments, β-substituted epichlorohydrin In the embodiment of the present invention, the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl, wherein the alkyl group is a saturated hydrocarbon group, the alkenyl group is also called an olefin group, which is a hydrocarbon group formed by missing one or more hydrogen atoms in an olefin molecule containing a carbon-carbon double bond, the alkynyl group is a hydrocarbon group formed by missing one or more hydrogen atoms in a hydrocarbon molecule containing a carbon-carbon triple bond, and the phenyl group refers to a group with a benzene ring as a functional group. The embodiment of the present application can select the type, structure, and size of the A group in β-substituted epichlorohydrin, thereby regulating the spatial configuration or molecular dipole of the epoxy resin molecule, regulating the steric hindrance on the β carbon, inhibiting the β addition, and eliminating the influence of the β addition substitution side reaction on the product chlorine content, purity, yield, etc.

[0082] In some embodiments, the β-substituted epichlorohydrin In the embodiment of the present invention, the A group is one of methyl, ethyl, vinyl, ethynyl and phenyl. In this case, the A groups substituted at the β-position in epichlorohydrin can better regulate the steric hindrance on the β-carbon, inhibit the β-position addition, and better regulate the spatial configuration or molecular dipole of the epoxy resin molecule, so as to weaken the intermolecular stacking and interaction force, destroy its crystallinity, obtain low high-temperature viscosity, improve the processability of the epoxy resin, and make the obtained naphthalene epoxy resin have better high temperature resistance, low viscosity, high purity and low chlorine and other characteristics.

[0083] In some possible implementations, the β-substituted epichlorohydrin includes at least one of epichlorohydrin, methyl epichlorohydrin, and 2-(chloromethyl)-2-phenyloxirane. In some specific embodiments, the β-substituted epichlorohydrin may be methyl epichlorohydrin. All of the β-substituted epichlorohydrins used in the above embodiments of the present application can undergo α-carbon ring opening and ring closing reactions with naphthalene compounds containing active groups to obtain naphthalene-based epoxy resins.

[0084] In some possible implementations, in the above step S20, under the action of a catalyst, the naphthalene compound containing an active group and the β-substituted epichlorohydrin undergo ring-opening and ring-closing reactions to obtain a multifunctional naphthalene-based epoxy resin. Among them, R 11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-. By grafting multiple epoxy groups on the naphthalene ring, the functionality of the naphthalene epoxy resin is improved, and after subsequent curing, the crosslinking density of the resin cured product is improved, thereby improving the temperature resistance of the system (glass transition temperature), so that the prepared naphthalene epoxy resin has the characteristics of high temperature resistance, low viscosity, high purity and low chlorine.

[0085] In some possible embodiments, the catalyst includes an alkali metal hydroxide or a mixed catalyst of an alkali metal hydroxide and a quaternary ammonium salt. The catalyst of the embodiment of the present application can be either an alkali metal hydroxide or a mixed catalyst of an alkali metal hydroxide and a quaternary ammonium salt. Among them, the alkali metal hydroxide can simultaneously catalyze the active group in the naphthalene compound containing the active group to attack the carbon opening at the α position in the β-substituted epichlorohydrin, and at the same time can catalyze the hydroxyl group and -CH2Cl in the opened epichlorohydrin to close the ring to form an epoxy ring again. In the mixed catalyst, the quaternary ammonium salt can catalyze the active group in the naphthalene compound to attack the carbon opening at the α position in the β-substituted epichlorohydrin to complete the ring opening reaction; in addition, in the presence of the quaternary ammonium salt, the hydroxyl group and -CH2Cl in the opened epichlorohydrin catalyzed by the alkali metal hydroxide close the ring to form an epoxy ring again.

[0086] In some possible implementations, the ratio of the molar amount of the alkali metal hydroxide to the molar amount of the active group in the naphthalene compound containing the active group is 1:(1-10). Under this ratio, the alkali metal hydroxide can better catalyze the ring-opening and ring-closing reactions between the naphthalene compound containing the active group and the β-substituted epichlorohydrin, graft multiple epoxy substitutions on the naphthalene ring, and obtain a multifunctional naphthalene-based epoxy resin. In some embodiments, the ratio of the molar amount of the alkali metal hydroxide to the molar amount of the active group in the naphthalene compound containing the active group can be 1: (1-2), 1: (2-3), 1: (3-4), 1: (4-5), 1: (2-5), 1: (5-6), 1: (6-7), 1: (7-8), 1: (8-9), 1: (9-10), 1: (2-9), 1: (3-8), 1: (4-7), 1: (5-6), 1: (3-5), 1: (5-7), 1: (4-6), 1: (7-10), etc. Exemplarily, the ratio of the molar amount of the alkali metal hydroxide to the molar amount of the active group in the naphthalene compound containing the active group can be 1: (2-5).

[0087] In some possible implementations, the ratio of the molar amount of the quaternary ammonium salt to the molar amount of the active group in the naphthalene compound containing the active group is 1:(0.005-0.05). Under this ratio, the quaternary ammonium salt can better catalyze the active group in the naphthalene compound to attack the carbon ring opening at the α position in the β-substituted epichlorohydrin to complete the ring opening reaction. In combination with an alkali metal hydroxide to catalyze the ring closing reaction, a multifunctional naphthalene-based epoxy resin can be obtained. In some embodiments, the ratio of the molar amount of the quaternary ammonium salt to the molar amount of the active group in the naphthalene compound containing the active group can be 1: (0.005-0.008), 1: (0.008-0.01), 1: (0.01-0.015), 1: (0.015-0.02), 1: (0.02-0.025), 1: (0.025-0.03), 1: (0.03-0.035), 1: (0.035-0.04), 1: (0.04-0.045), 1: (0.045-0.05), 1: (0.005-0.01), 1: (0.01-0.02), 1: (0.02-0.03), 1: (0.01-0.03), 1: (0.03-0.04), 1: (0.04-0.05), etc. For example, the ratio of the molar amount of the quaternary ammonium salt to the molar amount of the active group in the naphthalene compound containing the active group may be 1:(0.01-0.03).

[0088] In some embodiments, in the mixed catalyst, the ratio of the molar amount of the quaternary ammonium salt to the molar amount of the active group in the naphthalene compound containing the active group is 1:(0.005-0.05), and the ratio of the molar amount of the alkali metal hydroxide to the molar amount of the active group in the naphthalene compound containing the active group is 1:(1-10). In this case, the quaternary ammonium salt in the mixed catalyst has a good catalytic effect on both the ring-opening and ring-closing reactions between the naphthalene compound containing the active group and β-substituted epichlorohydrin, and multiple epoxy substitutions are grafted on the naphthalene ring to obtain a multifunctional naphthalene epoxy resin.

[0089] In some possible embodiments, the alkali metal hydroxide includes: at least one of potassium hydroxide and sodium hydroxide; these alkali metal hydroxides can well catalyze the ring-opening and ring-closing reactions between the naphthalene compound containing active groups and β-substituted epichlorohydrin, and graft multiple epoxy substitutions on the naphthalene ring to obtain a multi-functional naphthalene-based epoxy resin.

[0090] In some possible embodiments, the quaternary ammonium salt includes at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, and tetrapentylammonium chloride. These quaternary ammonium salts can well catalyze the active groups in the naphthalene compound to attack the carbon ring opening at the α position in the β-substituted epichlorohydrin to complete the ring opening reaction.

[0091] In some possible implementations, the temperature conditions for the ring-opening and ring-closing reactions are 25° C. to 140° C., and the reaction time is 1 hour to 8 hours. Under these conditions, the ring-opening and ring-closing reactions between the naphthalene compound containing an active group and the β-substituted epichlorohydrin can be better catalyzed, and multiple epoxy substitutions are grafted onto the naphthalene ring to obtain a multifunctional naphthalene-based epoxy resin. In some embodiments, the temperature conditions for the ring-opening and ring-closing reactions can be 25°C to 30°C, 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 70°C, 70°C to 80°C, 80°C to 90°C, 90°C to 100°C, 100°C to 110°C, 110°C to 120°C, 120°C to 130°C, 130°C to 140°C, etc., and the reaction time can be 1 hour to 2 hours, 2 hours to 3 hours, 3 hours to 4 hours, 4 hours to 5 hours, 5 hours to 6 hours, 6 hours to 7 hours, 7 hours to 8 hours, etc.

[0092] In some possible implementations, the ratio of the molar amount of the active group in the naphthalene compound containing an active group to the molar amount of the β-substituted epichlorohydrin is 1:(1-20). In the case of such a molar ratio, the ring-opening and ring-closing reactions between the naphthalene compound containing an active group and the β-substituted epichlorohydrin can be fully ensured, so that multiple active groups on the naphthalene ring are grafted with epoxy substituents to obtain a multifunctional naphthalene-based epoxy resin, thereby improving the reaction efficiency. In some embodiments, the ratio of the molar amount of the active group in the naphthalene compound containing the active group to the molar amount of β-substituted epichlorohydrin can be 1: (2-10), 1: (3-10), 1: (4-10), 1: (5-10), 1: (6-10), 1: (7-10), 1: (8-10), 1: (9-10), 1: (1-9), 1: (1-8), 1: (1-7), 1: (1-6), 1: (1-5), 1: (1-4), 1: (1-3), 1: (1-2), 1: (2-9), 1: (3-8), 1: (4-7), 1: (5-6), 1: (3-5), 1: (5-7), 1: (4-6), 1: (8-10), etc.

[0093] In some possible embodiments, after the ring-opening and ring-closing reactions, a washing and refining step is further included: the crude product after the ring-opening and ring-closing reactions is dissolved in an organic solvent, an alkaline solution is added for hot mixing, the organic phase is separated, and the washing is performed to obtain a naphthalene-based epoxy resin. In the embodiment of the present application, the crude product after the ring-opening and ring-closing reactions is washed and refined with an alkaline solution under heating conditions, and the -OH and -Cl that are not ring-closed in the synthesis step are further ring-closed by high temperature and alkaline water, and the 1,2-chlorohydrin ether (hydrolyzed chlorine) generated in the synthesis step is promptly eliminated.

[0094] In some embodiments, when β-substituted epichlorohydrin uses epichlorohydrin as the starting reaction substrate, due to the small steric hindrance of the β-substituent, unclosed -OH and -Cl may appear on the naphthalene ring after the ring-opening and ring-closing reactions. By using an alkaline solution to purify under heating conditions, -OH and -Cl are promoted to close the ring and form an epoxy substitution on the naphthalene ring.

[0095] In other embodiments, when the A group in the β-substituted epichlorohydrin is one of an alkyl, alkenyl, alkynyl, or phenyl group, due to the large steric hindrance of the A group in the substituted epichlorohydrin, there will be no β addition in the system to produce chlorine that is not easily hydrolyzed, and the total chlorine has reached a relatively low level. In this case, even without hydrolysis and refining, the total chlorine in the naphthalene-based epoxy resin is already sufficiently low. It is also possible to further reduce the content of easily hydrolyzed chlorine in the naphthalene-based epoxy resin by washing and refining.

[0096] In some possible embodiments, the organic solvent includes: at least one of toluene, dichloromethane, chloroform, and dimethyl sulfoxide; these organic solvents have good solubility for the crude products after the ring-opening and ring-closing reactions, which is beneficial for the subsequent washing and refining of the crude products.

[0097] In some possible embodiments, the molar ratio of the crude product to the alkaline substance in the alkaline solution is (0.05-20):1. Under this molar ratio, it can be fully ensured that the unclosed-OH and -Cl in the crude product after the alkaline substance catalyzes the ring-opening and ring-closing reactions are closed to form epoxy substitution to obtain a multifunctional naphthalene epoxy resin. In some embodiments, the molar ratio of the crude product to the alkaline substance in the alkaline solution can be 1: (0.05-0.1), 1: (0.1-0.5), 1: (0.5-1), 1: (1-2), 1: (2-5), 1: (5-8), 1: (8-10), 1: (10-12), 1: (12-15), 1: (15-18), 1: (18-20), etc. Exemplarily, the molar ratio of the crude product to the alkaline substance in the alkaline solution can be 1: (0.1-5).

[0098] In some possible embodiments, the alkaline solution is an alkali metal hydroxide solution with a concentration of 1wt% to 10wt%. Under this concentration condition, the alkaline solution has a good ring-closing effect on the -OH and -Cl in the crude product after the ring-opening and ring-closing reactions, improves the molecular weight of the epoxy resin, and increases the epoxy equivalent of the resin. Wherein, the alkali metal hydroxide includes: at least one of potassium hydroxide and sodium hydroxide. Exemplarily, the alkaline solution can be 1wt% to 2wt%, 2wt% to 3wt%, 3wt% to 4wt%, 4wt% to 5wt%, 5wt% to 6wt%, 6wt% to 7wt%, 7wt% to 8wt%, 8wt% to 9wt%, 9wt% to 10wt%, 2wt% to 8wt%, 3wt% to 7wt%, 4wt% to 6wt%, 5wt% to 9wt%, etc.

[0099] In some possible embodiments, the temperature of the hot mixing treatment is 50°C to 130°C, and the duration is 0.5 hours to 3 hours. Under the conditions of the hot mixing treatment, the alkaline solution can better promote the further ring closure of the unclosed-OH and -Cl in the synthesis step, and promptly eliminate the 1,2-chlorohydrin ether (hydrolyzed chlorine) produced in the synthesis step to obtain a multifunctional naphthalene epoxy resin. In some embodiments, the temperature conditions of the hot mixing treatment can be 50°C to 60°C, 60°C to 70°C, 70°C to 80°C, 80°C to 90°C, 90°C to 100°C, 100°C to 110°C, 110°C to 120°C, 120°C to 130°C, etc., and the treatment time can be 0.5 hours to 1 hour, 1 hour to 1.5 hours, 1.5 hours to 2 hours, 2 hours to 2.5 hours, 2.5 hours to 3 hours, etc.

[0100] In some possible embodiments, after washing and refining, rough treatment and recrystallization are also included. By rough treatment and recrystallization of the washed and refined product, the resin can be purified and the quality and purity of the naphthalene epoxy resin can be improved so as to obtain better performance and quality in subsequent processing or preparation processes. Wherein, the rough treatment includes washing the naphthalene epoxy resin with an appropriate solvent to remove pollutants, grease or other organic matter attached to the surface of the resin. Solvent washing can help improve the cleanliness and quality of the resin. The selected solvent can be a water-soluble organic system, such as methanol aqueous solution, ethanol aqueous solution, acetic acid aqueous solution, etc., specifically ethanol aqueous solution. Wherein, the recrystallization operation is conducive to improving the purity and physical properties of the resin, and removing impurities and insolubles therein. Recrystallization can improve the transparency, solubility, melting point and other characteristics of the naphthalene epoxy resin, making it more suitable for specific application requirements. The processing method of recrystallization generally includes the steps of: 1. dissolving: adding the naphthalene epoxy resin to an appropriate solvent, heating and stirring under appropriate temperature conditions, so that the resin is completely dissolved in the solvent. ②Crystallization: Slowly cool the dissolved resin solution, or induce resin crystallization by adding an anti-solvent or adjusting the concentration of the solvent. The resin molecules will gradually precipitate out of the solution to form crystals. ③Separation and washing: The formed resin crystals are separated from the solvent, usually by filtration or centrifugation. Subsequently, the resin crystals can be washed with an appropriate detergent or solvent to remove residual solvent and other impurities. ④Drying: Dry the washed resin crystals, usually at low temperature. The purity, physical properties and appearance characteristics of naphthalene epoxy resins are improved through recrystallization treatment, making them more suitable for specific application fields, such as high-purity materials, optical materials, electronic materials, etc.

[0101] In some embodiments, the recrystallization solvent system can be an ethanol / water system, and the volume ratio can be (1-20):1. Further, an ethanol / water system with a volume ratio of (5-12):1 is used.

[0102] In some embodiments, the preparation method of naphthalene epoxy resin comprises the following steps:

[0103] S11. Obtaining naphthalene compounds containing active groups and β-substituted epichlorohydrin Wherein, R1-R8 are independently selected from one of H, hydroxyl, carboxyl, and amino, and at least three of R1-R8 are not H; the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl;

[0104] S21. Under the action of a catalyst, a naphthalene compound containing an active group undergoes a ring-opening and ring-closing reaction with a β-substituted epichlorohydrin to obtain a crude product;

[0105] S30. The crude product after the ring-opening and ring-closing reactions is dissolved in an organic solvent, an alkaline solution is added for heat mixing, the organic phase is separated, and washed with water to obtain a washed refined product;

[0106] S40. The washed refined product is subjected to rough treatment and recrystallization to obtain a multifunctional naphthalene epoxy resin. Among them, R 11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-.

[0107] In a second aspect, the present application also provides a naphthalene epoxy resin, the general chemical formula of the naphthalene epoxy resin is Among them, R 11 ~R 81 At least three of them are The rest are H, R is -O-, -COO- or -NH-, and the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl.

[0108] The naphthalene epoxy resin provided in the embodiment of the present application comprises a naphthalene ring skeleton, on which at least three or more Epoxy group, is conducive to improving the cross-linking density of resin, enhancing the rigidity of polymer network structure, so as to obtain high heat resistance. In addition, by the selection of the A group in the β position in the epoxy group, the spatial configuration or molecular dipole of the epoxy resin molecule can be adjusted, so that the intermolecular stacking and interaction force are weakened, and its crystallinity is destroyed, which is conducive to reducing the viscosity of naphthalene epoxy resin, and low high temperature viscosity is obtained, and the processability of epoxy resin is improved, and the regulation of the performance parameters such as the viscosity, temperature resistance, and melting point of naphthalene epoxy resin is realized, which is conducive to reducing the viscosity of naphthalene epoxy resin. And, naphthalene epoxy resin has low chlorine content and high purity. Therefore, the naphthalene epoxy resin of the present application embodiment has the characteristics of high temperature resistance, low viscosity and high purity low chlorine, and has huge application value in electronic materials such as semiconductor packaging.

[0109] In some possible embodiments, the epoxy equivalent in the naphthalene epoxy resin is 110g / mol to 140g / mol, the total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm. In the naphthalene epoxy resin provided in the embodiment of the present application, the epoxy equivalent is 110 to 140g / mol, which not only meets the temperature resistance of the naphthalene epoxy resin cured product, but also ensures the other properties of the naphthalene epoxy resin. The total chlorine is less than 2000ppm, and the hydrolyzed chlorine is less than 1000ppm, which is beneficial to reduce the corrosion of chlorine in the resin to the circuit when the subsequent naphthalene epoxy resin is matched to prepare electronic materials, which is beneficial to ensure safety and stability.

[0110] In some possible embodiments, the naphthalene-based epoxy resin can be typically but not limited to 1,4,5-trifunctional naphthalene epoxy resin, 1,4,5-trifunctional naphthylmethyl epoxy resin, 1,2,4-trifunctional naphthylmethyl epoxy resin, 1,2,3,4-tetrafunctional naphthylmethyl epoxy resin, 1,3,6,8-tetrafunctional naphthylmethyl epoxy resin, 1,4,5,8-tetrafunctional naphthylmethyl epoxy resin, 1,2,4,5,8-pentafunctional naphthylmethyl epoxy resin, 1,4,5-trifunctional naphthalene 2-(chloromethyl)-2-phenyl epoxy resin, and the like.

[0111] The naphthalene-based epoxy resin provided in the embodiments of the present application can be prepared by the method of the embodiments described above.

[0112] In a third aspect, an embodiment of the present application provides a naphthalene-based epoxy resin composition, which includes a naphthalene-based epoxy resin prepared by the above method and / or the above-mentioned naphthalene-based epoxy resin and a second epoxy resin; wherein the viscosity of the second epoxy resin is lower than that of the naphthalene-based epoxy resin.

[0113] The naphthalene epoxy resin composition provided by the embodiment of the present application includes the above-mentioned naphthalene epoxy resin and the second epoxy resin, the viscosity of the second epoxy resin is lower than that of the naphthalene epoxy resin, and the low-viscosity second epoxy resin is used in combination with the naphthalene epoxy resin, and the molecular spatial structure and dipole difference between the multifunctional naphthalene epoxy resin molecule and the low-viscosity second epoxy resin are utilized to reduce the accumulation and interaction of molecules in the resin composition, so as to achieve the purpose of significantly reducing the viscosity of the naphthalene epoxy resin composition. In the naphthalene epoxy resin composition, the multifunctional naphthalene epoxy resin not only has high purity and low chlorine content, but also has high crosslinking density and strong rigid structure so that the naphthalene epoxy resin composition cured product has high Tg characteristics. Therefore, the naphthalene epoxy resin composition has the characteristics of high temperature resistance, low viscosity and high purity and low chlorine.

[0114] The embodiment of the present application does not specifically limit the ratio of the naphthalene epoxy resin and the second epoxy resin in the naphthalene epoxy resin composition. The mixture of the naphthalene epoxy resin and the low-viscosity resin can be any ratio; for example, the mass ratio of the naphthalene epoxy resin and the second epoxy resin can be any ratio of 1:99 to 99:1. If the multifunctional naphthalene epoxy resin accounts for a larger proportion, the temperature resistance of the naphthalene epoxy resin composition system is higher, and if the second epoxy resin accounts for a larger proportion, the viscosity of the naphthalene epoxy resin composition is lower. In practical applications, the proportion can be made according to specific application requirements such as viscosity and temperature resistance. In addition, the mixing conditions of the naphthalene epoxy resin and the second epoxy resin are not limited, and can be mixed in the range of 80 to 150°C to ensure that the two resins are mixed evenly at a temperature where they melt into a liquid to obtain a naphthalene epoxy resin composition.

[0115] In some possible embodiments, the viscosity of the second epoxy resin at a temperature of 25°C is 100mPa.s to 50000mPa.s, and the viscosity at a temperature of 150°C is 1mPa.s to 1000mPa.s. The second epoxy resin used in the embodiment of the present application has a relatively low viscosity at both room temperature and high temperature. By using a low-viscosity second epoxy resin in combination with a naphthalene epoxy resin, the molecular spatial structure and dipole differences between the multifunctional naphthalene epoxy resin molecules and the low-viscosity second epoxy resin are utilized to reduce the stacking and interaction of molecules in the resin composition, and obtain a low-viscosity naphthalene epoxy resin composition. In actual application, the second epoxy resin of suitable viscosity can be selected and combined with the naphthalene epoxy resin according to specific application requirements to obtain a naphthalene epoxy resin composition whose viscosity meets the specific application requirements. In some embodiments, the viscosity of the second epoxy resin at a temperature of 25° C. may be 100 mPa.s to 500 mPa.s, 500 mPa.s to 1000 mPa.s, 1000 mPa.s to 2000 mPa.s, 2000 mPa.s to 5000 mPa.s, 5000 mPa.s to 10000 mPa.s, 10000 mPa.s to 20000 mPa.s, 20000 mPa.s to 30000 mPa. The viscosity of the liquid can be 1mPa.s to 10mPa.s, 10mPa.s to 100mPa.s, 100mPa.s to 300mPa.s, 300mPa.s to 500mPa.s, 500mPa.s to 800mPa.s, 800mPa.s to 1000mPa.s, etc. The viscosity at 150°C can be 1mPa.s to 10mPa.s, 100mPa.s to 100mPa.s, 100mPa.s to 300mPa.s, 300mPa.s to 500mPa.s, 500mPa.s to 800mPa.s, 800mPa.s to 1000mPa.s, etc.

[0116] In some possible embodiments, the second epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, 1,6-dihydroxynaphthalene epoxy resin, para-aminophenol epoxy resin, and diaminodiphenylmethane epoxy resin. These second epoxy resins all have a relatively low viscosity, and when used in combination with naphthalene epoxy resins, the stacking and interaction of molecules in the resin composition can be reduced to obtain a low-viscosity naphthalene epoxy resin composition. Among them, bisphenol A epoxy resin is a commonly used epoxy resin with good insulation, chemical resistance and mechanical properties. It can be used to prepare electronic components, coatings, adhesives, etc. Its viscosity is generally between 1000-2000mPa·s. Bisphenol F epoxy resin is a high-performance epoxy resin with excellent heat resistance, electrical properties and chemical resistance. Its viscosity is generally between 500-3000mPa·s. 1,6-dihydroxynaphthalene epoxy resin is an epoxy resin with a high glass transition temperature and excellent mechanical properties. Its viscosity is generally between 1000-5000mPa·s. Para-aminophenol epoxy resin is an epoxy resin with excellent electrical properties and chemical resistance. Its viscosity is generally between 200-1000mPa·s. Diaminodiphenylmethane epoxy resin is an epoxy resin with good mechanical properties and excellent heat resistance. Its viscosity is generally between 500-3000mPa·s.

[0117] In some possible embodiments, the schematic diagram of the preparation process of the naphthalene epoxy resin composition is shown in the attached Figure 2 As shown: Under the action of the catalyst, the naphthalene compound containing active groups With β-substituted epichlorohydrin Ring-opening and ring-closing reactions occur, and after washing, refining, rough treatment, and recrystallization, a multifunctional naphthalene epoxy resin is obtained. Wherein, R1-R8 are independently selected from one of H, hydroxyl, carboxyl, and amino, and at least three of R1-R8 are not H; the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl; R 11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-. A multifunctional naphthalene epoxy resin is mixed with a low-viscosity second epoxy resin such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a 1,6-dihydroxynaphthalene epoxy resin, a p-aminophenol epoxy resin, a diaminodiphenylmethane epoxy resin, etc. to obtain a naphthalene epoxy resin composition.

[0118] In some possible embodiments, the naphthalene epoxy resin composition also includes an epoxy resin curing agent with a resin mass percentage of 30% to 60%. In this case, the 30% to 60% epoxy resin curing agent contained in the naphthalene epoxy resin composition can better promote the cross-linking and curing of the naphthalene epoxy resin and the second epoxy resin in the composition. In some embodiments, the mass percentage of the epoxy resin curing agent in the naphthalene epoxy resin composition can be 30% to 35%, 35% to 40%, 40% to 45%, 45% to 50%, 50% to 55%, 55% to 60%, 30% to 50%, 30% to 40%, 40% to 60%, 50% to 60%, etc.

[0119] In some possible embodiments, the epoxy resin curing agent includes at least one of an amine curing agent, an anhydride curing agent, a phenolic resin curing agent, an active ester curing agent, and a cyanate curing agent. These types of curing agents can all promote the curing of epoxy resins well. These curing agents react chemically with the active hydrogen atoms in the epoxy resin to form a cross-linked structure, so that the epoxy resin molecules are cured into a solid material. The specific selection of curing agent depends on the required performance and application requirements. Specifically, an amine curing agent refers to a Lewis base containing nitrogen atoms in the molecule, and the nitrogen atoms can participate in the cross-linking reaction of the epoxy resin, and finally form a highly cross-linked thermosetting epoxy plastic. Amine curing agents have the characteristics of being cheap and easy to obtain, highly reactive, and having variable performance. They account for about a share of the entire curing agent market, among which aliphatic amines, alicyclic amines, and aromatic amine curing agents have the widest range of use. Anhydride curing agents are generally a compound containing anhydride functional groups, such as maleic anhydride. After anhydride curing agents are added to epoxy resins, when subjected to heat or other triggering conditions, the anhydride curing agents react with the active hydrogen atoms in the epoxy resin to form ester bonds. This reaction process is called anhydride ring-opening reaction, through which a cross-linked structure is formed between epoxy resin molecules, thereby achieving curing. Phenolic resin curing agents are a class of compounds containing phenolic functional groups, such as condensation products of formaldehyde and phenol. After adding phenolic resin curing agents to epoxy resins, through heat treatment, the phenolic resin curing agents will undergo a condensation reaction with the active hydrogen atoms in the epoxy resin to form a three-dimensional network structure. This reaction process is called phenolic polycondensation reaction, through which a cross-linked structure is formed between epoxy resin molecules, thereby achieving curing. Active ester curing agents are generally compounds containing ester functional groups, such as polyol esters. After adding active ester curing agents to epoxy resins, when subjected to heat or other triggering conditions, the active ester curing agents will react with the active hydrogen atoms in the epoxy resin to form ester bonds. This reaction process is called esterification reaction, through which a cross-linked structure is formed between epoxy resin molecules, thereby achieving curing. Cyanate curing agent is a commonly used room temperature curing agent with the characteristics of fast curing, which can complete the curing reaction at room temperature; excellent physical properties, such as high hardness, high strength and wear resistance; wide range of applications, can react and cure with a variety of resin systems such as epoxy resin, polyester resin and polyurethane.

[0120] In some embodiments, the amine curing agent includes: m-phenylenediamine (MPD), diaminodiphenylmethane (DDM), diaminodiphenyl sulfone (DDS), diethylenetriamine (DETA), triethylenetetramine (TETA), 4,4'-methylenebis(2-methyl-6-ethylaniline), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-diethylaniline) (ME-DDM), polyetheramine curing agent (D230, D400, D2000), etc. These amine curing agents are Lewis bases containing nitrogen atoms, and the nitrogen atoms can participate in the cross-linking reaction of naphthalene epoxy resins to form highly cross-linked thermosetting epoxy plastics.

[0121] In some embodiments, anhydride curing agents include: phthalic anhydride (PA), maleic anhydride (MA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride (MeHHPA), nadic anhydride, methylnadic anhydride (MNA), glutaric anhydride, terpene anhydride, methylcyclohexene tetracarboxylic dianhydride, dodecenyl succinic anhydride, etc. These anhydride curing agents all contain anhydride functional groups, which can react with active hydrogen atoms in naphthalene epoxy resins to form cross-linked structures between epoxy resin molecules to obtain a cured product of naphthalene epoxy resins.

[0122] In some embodiments, phenolic resin curing agents include: phenolic resin, cresol resin, phenolic aralkyl resin containing biphenylene skeleton, phenolic aralkyl resin containing phenylene skeleton, phenolic resin containing biphenylene skeleton, phenolic resin containing naphthalene ring skeleton, phenolic resin with triphenylmethane skeleton, etc. These phenolic resin curing agents all contain phenolic functional groups, which can react with active hydrogen atoms in naphthalene epoxy resin to form cross-linked structures between epoxy resin molecules to obtain a cured product of naphthalene epoxy resin.

[0123] In some embodiments, active ester curing agents include: active ester compounds of dicyclopentadiene-type biphenol structure, naphthalene-type active ester compounds, active ester compounds of acetylated linear phenolic resins, active ester compounds of benzoylated linear phenolic resins, etc. These active ester curing agents all contain ester functional groups, which can react with active hydrogen atoms in naphthalene-based epoxy resins to form cross-linked structures between epoxy resin molecules to obtain a cured product of naphthalene-based epoxy resins.

[0124] In some embodiments, the cyanate curing agent includes: phenoxypropane cyanate (PAC), which is a commonly used cyanate curing agent that can react with epoxy resin to form a cured product with excellent performance; isopropyl cyanate (IPC), which has a faster curing speed and is widely used in coatings and adhesives and other fields; triphenyl cyanate (TPC), which has a higher reactivity and curing speed, and can react with a variety of resin materials to obtain high-performance cured products.

[0125] In some possible embodiments, the naphthalene epoxy resin composition also includes a curing accelerator with a mass percentage of 0.1% to 1.5%. In this case, a curing accelerator is added to the naphthalene epoxy resin composition, and the curing accelerator can affect the reaction rate and reaction mechanism between the epoxy resin and the curing agent, thereby adjusting the temperature, time and performance of the curing process. It can better promote the cross-linking and curing between the naphthalene epoxy resin and the second epoxy resin, accelerate the curing speed of the epoxy resin, improve the curing effect and increase the curing strength. Common types of curing accelerators include: tertiary amine curing accelerators, which are a class of compounds that promote curing by reacting with active hydrogen atoms in epoxy resins. Exemplary ones include diethylenediamine (DEDA), triethylenediamine (TEPA), tetraethylenediamine (TETA), etc. Anhydride curing accelerators are a class of compounds that promote curing by ring-opening reactions with epoxy groups in epoxy resins. Exemplary ones include maleic anhydride, phthalic anhydride, etc. Thiol curing accelerators are a class of compounds that promote curing by ring-opening reactions with epoxy groups in epoxy resins. Exemplary ones include mercaptoethanol, mercaptopropanol, etc. Organic acid curing accelerators are a class of compounds that promote curing by ring-opening reaction with epoxy groups in epoxy resins. Exemplary ones include fatty acids, aromatic acids, etc. In some embodiments, the mass percentage of the curing accelerator in the naphthalene epoxy resin composition can be 0.1% to 0.3%, 0.3% to 0.5%, 0.5% to 0.8%, 0.8% to 1.0%, 1.0% to 1.2%, 1.2% to 1.5%, 0.2% to 1.4%, 0.3% to 1.3%, 0.4% to 1.2%, 0.5% to 1.1%, 0.6% to 1.0%, 0.7% to 0.9%, 0.8% to 1.2%, etc.

[0126] In some possible embodiments, the curing accelerator includes at least one of tris(dimethylaminomethyl)phenol, triethanolamine, dimethylbenzylamine, N-diglycidylaniline, diethylenediamine (DEDA), triethylenediamine (TEPA), tetraethylenediamine (TETA), and diisopropylamine (DIPA). These curing accelerators can better promote the cross-linking and curing between the naphthalene epoxy resin and the second epoxy resin, accelerate the curing speed of the epoxy resin, improve the curing effect, and increase the curing strength.

[0127] In some specific embodiments, when an active ester curing agent or an acid anhydride curing agent is used, a tertiary amine curing accelerator can be used to better promote the curing of the epoxy resin.

[0128] In a fourth aspect, an embodiment of the present application provides an application of a naphthalene-based epoxy resin composition, wherein the naphthalene-based epoxy resin composition is applied to the field of electronic materials.

[0129] The multifunctional naphthalene epoxy resin contained in the naphthalene epoxy resin composition provided by the embodiment of the present application is not only high in purity and low in chlorine content, but also has high cross-linking density and strong rigid structure so that the naphthalene epoxy resin composition cured product has high Tg characteristics. Therefore, the naphthalene epoxy resin composition has the characteristics of high temperature resistance, low viscosity and high purity and low chlorine. The naphthalene epoxy resin composition has high cross-linking density and high Tg after curing, and has excellent heat resistance, and has great application value in the field of electronic materials. And the naphthalene epoxy resin composition has low chlorine content, has little corrosion to the circuit under high temperature and high humidity, has good insulation, and improves the reliability of the electronic packaging material based on the naphthalene epoxy resin.

[0130] The naphthalene epoxy resin composition of the present application is not only suitable for the preparation of high heat-resistant, low viscosity, high-purity epoxy resin, but also suitable for the field of electronic materials such as semiconductor devices. In some possible embodiments, the electronic material includes: at least one of semiconductor packaging materials, filling materials, interlayer insulating materials, and laminated boards. Exemplary, the naphthalene epoxy resin composition is applied to the matrix resin in epoxy molding materials (EMC), bottom filling glue (Underfill), interlayer insulating films, and laminated boards in semiconductor devices.

[0131] In some possible implementations, the naphthalene-based epoxy resin in the embodiment of the present application can be configured with a cross-linking agent, a filler, an additive, etc. to form a slurry due to its high melting point, and then coated. The coated film material will not have a sticky surface, and is easy to operate in the subsequent process of the semi-cured sheet.

[0132] Example

[0133] The following is explained in conjunction with specific embodiments. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If no specific techniques or conditions are indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer of the reagents or instruments is not indicated, they are all conventional products that can be obtained commercially.

[0134] Example 1

[0135] The present application provides a 1,4,5-trifunctional naphthalene epoxy resin, the preparation of which comprises the following steps:

[0136] 1. Take 1,5-naphthalenediol as raw material, and obtain 1,4,5-trihydroxynaphthalene through oxidation and reduction treatment. The specific steps are:

[0137] ① At room temperature, add 1.5L hydrogen peroxide to a 10L reactor, and slowly add 840mL acetic anhydride from a constant pressure dropping funnel. Keep the temperature in the reactor below 40°C during the addition process and stir for 4h. Under vigorous stirring, slowly add 2L of a methanol / dichloromethane mixed solution containing 300g 1,5-naphthalene diol to the reactor. Keep the temperature in the reactor below 50°C during the addition process and stir for 1h after the addition. After the reactor cools to room temperature, dichloromethane is removed by vacuum distillation. Slowly pour the reaction solution into 6L of rapidly stirred ice water and filter with suction. The filter cake is slurried with water and filtered again with suction. After dissolving the filter cake with dichloromethane, it is eluted with a silica gel column and the intermediate quinone is obtained by rotary evaporation to remove dichloromethane.

[0138] ② At room temperature, add 66g of intermediate quinone and 1.5L of ethyl acetate to a 10L reactor and dissolve by ultrasonication. Then pour in 1.5L of an aqueous solution containing 270g of sodium dithionite and stir at room temperature for half an hour. Separate the organic layer, wash the organic layer with saturated brine, and remove the solvent by rotary evaporation to obtain 1,4,5-trihydroxynaphthalene solid.

[0139] 2. Pour the 1,4,5-trihydroxynaphthalene solid obtained in step 1 into a 2L three-necked flask, add 870mL of epichlorohydrin and 90g of an aqueous solution of sodium hydroxide (mass fraction of 30%), and react at 80°C for 5h. After the reaction solution is cooled to room temperature, separate the liquids, wash the organic layer with saturated brine and concentrate to obtain a crude product.

[0140] 3. Dissolve the crude product obtained in step 2 in toluene, add 800 mL of 5% sodium hydroxide solution, heat to 120°C, stir vigorously for 1 hour, and then let stand to room temperature. Separate the organic phase, wash with water, and concentrate to obtain a yellow solid.

[0141] 4. Pour the yellow solid obtained in step 3 into a 50% ethanol aqueous solution, and filter it. Rinse the filter cake with water and ethanol and dry it. Recrystallize it with ethanol / water and ethyl acetate / petroleum ether systems respectively, and filter it to obtain the target product 1,4,5-trifunctional naphthalene epoxy resin.

[0142] Example 2

[0143] The present application provides a 1,4,5-trifunctional naphthylmethyl epoxy resin, the preparation of which comprises the following steps:

[0144] 1. Using 1,5-naphthalenediol as a raw material, 1,4,5-trihydroxynaphthalene is obtained through oxidation and reduction. The specific preparation steps are the same as those in Example 1.

[0145] 2. Pour the 1,4,5-trihydroxynaphthalene solid obtained in step 1 into a 2L three-necked flask, add 950mL of β-methyl epichlorohydrin and 90g of an aqueous solution of sodium hydroxide (mass fraction of 30%), and react at 80°C for 5h. After the reaction solution is cooled to room temperature, separate the liquids, wash the organic layer with saturated brine and concentrate to obtain a crude product.

[0146] 3. Pour the crude product obtained in step 2 into a 50% ethanol aqueous solution for slurrying and suction filtering. The filter cake is rinsed with water and ethanol and dried. Recrystallization is performed using ethanol / water and ethyl acetate / petroleum ether systems respectively, and suction filtering is performed to obtain the target product 1,4,5-trifunctional naphthylmethyl epoxy resin.

[0147] Example 3

[0148] A naphthalene epoxy resin composition comprises the 1,4,5-trifunctional naphthalene epoxy resin and 1,6-dihydroxynaphthalene epoxy resin prepared in Example 1, wherein the mass ratio of the 1,4,5-trifunctional naphthalene epoxy resin to the 1,6-dihydroxynaphthalene epoxy resin is 0.4g:1.6g.

[0149] Example 4

[0150] A naphthalene-based epoxy resin composition comprises the 1,4,5-trifunctional naphthylmethyl epoxy resin and 1,6-dihydroxynaphthalene epoxy resin prepared in Example 2, wherein the mass ratio of the 1,4,5-trifunctional naphthylmethyl epoxy resin to the 1,6-dihydroxynaphthalene epoxy resin is 0.4g:1.6g.

[0151] Example 5

[0152] A naphthalene epoxy resin composition comprises 20 parts of 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1, 80 parts of 1,6-dihydroxynaphthalene epoxy resin and 44 parts of polyetheramine curing agent.

[0153] Example 6

[0154] A naphthalene epoxy resin composition comprises 5 parts of 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1, 95 parts of 1,6-dihydroxynaphthalene epoxy resin, 124 parts of methylhexahydrophthalic anhydride curing agent and 1 part of tris(dimethylaminomethyl)phenol curing accelerator.

[0155] Example 7

[0156] A naphthalene epoxy resin composition comprises 20 parts of 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1, 80 parts of 1,6-dihydroxynaphthalene epoxy resin, 127 parts of methylhexahydrophthalic anhydride curing agent and 1 part of tris(dimethylaminomethyl)phenol curing accelerator.

[0157] Example 8

[0158] A naphthalene epoxy resin composition comprises 20 parts of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1, 80 parts of 1,6-dihydroxynaphthalene epoxy resin and 37.4 parts of diaminodiphenylmethane curing agent.

[0159] Example 9

[0160] A naphthalene epoxy resin composition comprises 20 parts of 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2, 80 parts of 1,6-dihydroxynaphthalene epoxy resin and 44 parts of polyetheramine curing agent.

[0161] Example 10

[0162] A naphthalene epoxy resin composition comprises 5 parts of 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2, 95 parts of 1,6-dihydroxynaphthalene epoxy resin, 124 parts of methylhexahydrophthalic anhydride curing agent and 1 part of tris(dimethylaminomethyl)phenol curing accelerator.

[0163] Embodiment 11

[0164] A naphthalene epoxy resin composition comprises 20 parts of 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2, 80 parts of 1,6-dihydroxynaphthalene epoxy resin, 127 parts of methylhexahydrophthalic anhydride curing agent and 1 part of tris(dimethylaminomethyl)phenol curing accelerator.

[0165] Example 12

[0166] A naphthalene epoxy resin composition comprises 20 parts of 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2, 80 parts of 1,6-dihydroxynaphthalene epoxy resin and 37.4 parts of diaminodiphenylmethane curing agent.

[0167] Embodiment 13

[0168] The embodiment of the present application provides a 1,2,4-trifunctional naphthylmethyl epoxy resin, and the preparation method thereof is different from that of Example 2 in that 1,2,4-trihydroxynaphthalene is used as the naphthalene raw material in step 1.

[0169] Embodiment 14

[0170] The embodiment of the present application provides a 1,2,3,4-tetrafunctional naphthylmethyl epoxy resin, and the preparation thereof is different from that of Example 2 in that: in step 1, 1,2,3,4-tetrahydroxynaphthalene is used as the naphthalene raw material.

[0171] Embodiment 15

[0172] The embodiment of the present application provides a 1,3,6,8-tetrafunctional naphthylmethyl epoxy resin, and the preparation thereof is different from that of Example 2 in that: in step 1, 1,3,6,8-tetrahydroxynaphthalene is used as the naphthalene raw material.

[0173] Example 16

[0174] The embodiment of the present application provides a 1,4,5,8-tetrafunctional naphthylmethyl epoxy resin, and the preparation thereof is different from that of Example 2 in that: in step 1, 1,4,5,8-tetrahydroxynaphthalene is used as the naphthalene raw material.

[0175] Embodiment 17

[0176] The embodiment of the present application provides a 1,2,4,5,8-pentafunctional naphthylmethyl epoxy resin, and the preparation thereof is different from that of Example 2 in that: in step 1, 1,2,4,5,8-pentahydroxynaphthalene is used as the naphthalene raw material.

[0177] Comparative Example 1

[0178] A commercially available 1,6-dihydroxynaphthalene epoxy resin was used as Comparative Example 1.

[0179] In order to verify the advancement of the naphthalene epoxy resin and its preparation method, naphthalene epoxy resin composition, etc. in the examples of the present application, the following performance tests were conducted on the above examples:

[0180] A. Qualitative tests were performed on the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 and the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2. The test results are shown in the attached table. Figure 3 ~Attached Fig.10 As shown. Figure 3 The H NMR spectrum of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is attached. Figure 4 The NMR carbon spectrum of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is attached. Figure 5 The NMR mass spectrum of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is shown in the attached figure. Figure 6 This is the infrared spectrum of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1.

[0181] Attached Figure 7 The H NMR spectrum of the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 is shown in the attached figure. Figure 8 The NMR carbon spectrum of the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 is attached. Fig. 9 The NMR mass spectrum of the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 is shown in the attached figure. Fig.10 This is the infrared spectrum of the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2.

[0182] B. The total chlorine, hydrolyzed chlorine, inorganic chlorine, sodium ion, epoxy equivalent, viscosity, melting point and other parameters of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1, the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2, and the multifunctional naphthylmethyl epoxy resins with different substitution sites prepared in Examples 13 to 17 were tested respectively. The test standards and test results are as follows:

[0183] ①Total chlorine test standard: refer to ISO 21627-32009 (E) Determination of chlorine content of plastic epoxy resin Part 3: Determination method of total chlorine.

[0184] ②Inorganic chlorine test standard: refer to GB / T 4618.1-2008 Determination of chlorine content of plastic epoxy resin Part 1: Determination method of inorganic chlorine.

[0185] ③Sodium ion concentration test standard: Refer to the national standard GB12007.2-89 for the method of determining the sodium ion content in epoxy resin water extract.

[0186] ④Epoxy equivalent test standard: refer to the national standard GB / T 4612-2008 "Determination of epoxy equivalent of plastic epoxy compounds".

[0187] ⑤Viscosity test standard: refer to the national standard GB / T 22314-2008 "Method for Determination of Viscosity of Plastic Epoxy Resins".

[0188] ⑥ Melting point test standard: Using a differential scanning calorimeter (DSC), at a heating rate of 10°C / min, the peak temperature of the endothermic peak of the obtained curve is determined as the melting point.

[0189] ⑦ Hydrolyzed chlorine test standard: refer to the national standard plan "Determination of chlorine content of plastic epoxy resin Part 2: easily saponifiable chlorine".

[0190] The test results of the above parameters are shown in Table 1 below:

[0191] Table 1

[0192]

[0193] It can be seen from the test results in Table 1 above that the epoxy equivalent of the naphthalene epoxy resin prepared in Examples 1 to 2 and Examples 13 to 17 of the present application is 110 g / mol to 140 g / mol, the total chlorine is less than 2000 ppm, the hydrolyzed chlorine is less than 1000 ppm, and the sodium ion concentration is less than 0.054 ppm. Among them, the epoxy equivalents of the naphthalene epoxy resins prepared in Examples 1 and 2 are specifically 119 g / mol and 135 g / mol, respectively, and the epoxy equivalent of the 1,2,4-trifunctional naphthylmethyl epoxy resin prepared in Example 13 is as high as 138 g / mol. In addition, the total chlorine of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is only 823 ppm, the hydrolyzed chlorine is only 346 ppm, and the sodium ion concentration is 0.0 47 ppm. The sodium ion concentration of the 1,2,4-trifunctional naphthylmethyl epoxy resin prepared in Example 13 is only 0.044 ppm. Sodium ions as metal ions are also not allowed in packaging materials, which will affect the failure of the electrical properties of packaging materials. Epoxy resins with low sodium ion concentrations have better application prospects in the fields of electronic packaging materials. In addition, the naphthalene epoxy resins prepared in Examples 1 to 2 and Examples 13 to 17 have low viscosities, among which the viscosity of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is only 1.24 (mPa.s) at 170°C. In addition, the melting point of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is 134°C and the melting point of the 1,4,5-trifunctional naphthyl methyl epoxy resin prepared in Example 2 is 95°C, and the melting point of the multifunctional naphthyl methyl epoxy resins with different substitution sites prepared in Examples 13 to 17 is 65 to 91°C, all of which have relatively low melting points.

[0194] C. In order to verify the improvement effect of low viscosity 1,6-dihydroxynaphthalene epoxy resin on the viscosity of naphthalene epoxy resin in the naphthalene epoxy resin compositions of Examples 3 and 4, the room temperature viscosity and high temperature viscosity of 1,4,5-trifunctional naphthalene epoxy resin, 1,4,5-trifunctional naphthylmethyl epoxy resin and 1,6-dihydroxynaphthalene epoxy resin were tested respectively with uncombined 1,4,5-trifunctional naphthalene epoxy resin, 1,4,5-trifunctional naphthylmethyl epoxy resin, 1,6-dihydroxynaphthalene epoxy resin, naphthalene epoxy resin composition of Example 3 and naphthalene epoxy resin composition of Example 4 as references. The test results are shown in Table 2 below:

[0195] Table 2

[0196]

[0197] It can be seen from the test results in Table 2 above that the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 of the present application and the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 can be combined with the low-viscosity epoxy resin 1,6-dihydroxynaphthalene epoxy resin to significantly reduce the viscosity of the naphthalene epoxy resin composition. Under high temperature conditions of 170°C, the viscosity of the naphthalene epoxy resin composition of Example 3 is only 0.56 mPa.s, and the viscosity of the naphthalene epoxy resin composition of Example 4 is only 0.97 mPa.s.

[0198] D. In order to verify the Tg of the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 of the present application and the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 after curing, 1,6-dihydroxynaphthalene epoxy resin was used as a reference, and the 1,6-dihydroxynaphthalene epoxy resin provided in Comparative Example 1, the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 and the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 were respectively stirred evenly with different curing agents and curing accelerators and then cured at high temperature. Among them, the types and amounts of curing agents and curing accelerators are shown in Table 3 below. Then, the Tg values ​​of the cured products were determined by differential scanning calorimetry (DSC). The test results are shown in Table 3 below:

[0199] Table 3

[0200]

[0201] It can be seen from the test results in Table 3 above that, in the case of the same curing agent, the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 of the present application and the 1,4,5-trifunctional naphthyl methyl epoxy resin prepared in Example 2 can better crosslink with the curing agent, and the Tg after curing is significantly higher than the Tg after curing of the 1,6-dihydroxynaphthalene type epoxy resin in Comparative Example 1. In particular, the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 is stirred evenly with diaminodiphenylmethane and then subjected to high temperature curing, and the Tg after curing reaches 226°C; the 1,4,5-trifunctional naphthyl methyl epoxy resin prepared in Example 2 is stirred evenly with diaminodiphenylmethane and then subjected to high temperature curing, and the Tg after curing reaches 210°C.

[0202] E. The naphthalene epoxy resin compositions of Examples 5 to 8, which include the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 or the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2, 1,6-dihydroxynaphthalene type epoxy resin low viscosity epoxy resin, curing agent, curing accelerator and other components, were respectively subjected to high temperature curing, and the Tg value of the cured product was measured by differential scanning calorimetry (DSC). The test results are shown in Table 4 below:

[0203] Table 4

[0204]

[0205] From the test results in Table 4 above, it can be seen that the 1,4,5-trifunctional naphthalene epoxy resin prepared in Example 1 of the present application or the 1,4,5-trifunctional naphthylmethyl epoxy resin prepared in Example 2 are respectively matched with 1,6-dihydroxynaphthalene type epoxy resin low viscosity epoxy resin, and different curing agents, curing accelerators and other components to form the naphthalene epoxy resin compositions of Examples 5 to 12, all of which have good curing effects and show high Tg after curing. This shows that the naphthalene epoxy resin compositions of Examples 1 to 12 all have good heat resistance.

[0206] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the aforementioned embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in each embodiment can be combined in any way. The scope of protection of the present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims. Therefore, the scope of protection of the present application shall be based on the scope of protection of the claims.

Claims

1. A method for preparing a naphthalene-based epoxy resin, characterized in that: The following steps are involved: Obtaining naphthalene compounds containing active groups and β-substituted epichlorohydrin Wherein, R1-R8 are independently selected from one of H, hydroxyl, carboxyl, and amino, and at least three of R1-R8 are not H; the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl; Under the action of a catalyst, the naphthalene compound containing an active group and the β-substituted epichlorohydrin undergo ring opening and ring closing reactions to obtain a multifunctional naphthalene-based epoxy resin. Among them, R 11 ~R 81 At least three of them are The rest are H, and R is -O-, -COO- or -NH-.

2. The method for preparing a naphthalene-based epoxy resin according to claim 1, wherein The epoxy equivalent of the naphthalene epoxy resin is 110 g / mol to 140 g / mol, the total chlorine content is less than 2000 ppm, and the hydrolyzed chlorine content is less than 1000 ppm.

3. The method for preparing a naphthalene-based epoxy resin according to claim 1, wherein The A group is one of methyl, ethyl, vinyl, ethynyl and phenyl.

4. The method for preparing a naphthalene-based epoxy resin according to claim 1, wherein The R1 to R8 are independently selected from H or hydroxyl; 11 ~R 81 At least three of them are 5. The method for preparing a naphthalene-based epoxy resin according to any one of claims 1 to 4, characterized in that: The temperature condition of the ring-opening and ring-closing reactions is 25° C. to 140° C., and the reaction time is 1 hour to 8 hours.

6. The method for preparing a naphthalene-based epoxy resin according to claim 5, wherein: The ratio of the molar amount of the active group in the naphthalene compound containing the active group to the molar amount of the β-substituted epichlorohydrin is 1:(1-20).

7. The method for preparing a naphthalene-based epoxy resin according to any one of claims 1 to 4 or 6, characterized in that: The naphthalene compound containing active groups includes at least one of 1,2,4-trihydroxynaphthalene, 1,4,5-trihydroxynaphthalene, 1,2,3,4-tetrahydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxynaphthalene and 1,2,4,5,8-pentahydroxynaphthalene.

8. The method for preparing a naphthalene-based epoxy resin according to any one of claims 1 to 4 or 6, characterized in that: The β-substituted epichlorohydrin includes at least one of epichlorohydrin, methyl epichlorohydrin and 2-(chloromethyl)-2-phenyloxirane.

9. The method for preparing a naphthalene-based epoxy resin according to any one of claims 1 to 4 or 6, characterized in that: The catalyst includes an alkali metal hydroxide or a mixed catalyst of an alkali metal hydroxide and a quaternary ammonium salt.

10. The method for preparing a naphthalene-based epoxy resin according to claim 9, wherein: The ratio of the molar amount of the alkali metal hydroxide to the molar amount of the active group in the naphthalene compound containing the active group is 1:(1-10); And / or, the ratio of the molar amount of the quaternary ammonium salt to the molar amount of the active group in the naphthalene compound containing the active group is 1:(0.005-0.05).

11. The method for preparing a naphthalene-based epoxy resin according to claim 9, wherein: The alkali metal hydroxide includes: at least one of potassium hydroxide and sodium hydroxide; And / or, the quaternary ammonium salt includes at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride and tetrapentylammonium chloride.

12. The method for preparing a naphthalene-based epoxy resin according to any one of claims 1 to 4, 6, 10 to 11, characterized in that: After the ring-opening and ring-closing reactions, the process further includes washing and refining steps: dissolving the crude product after the ring-opening and ring-closing reactions in an organic solvent, adding an alkaline solution for heat mixing, separating the organic phase, and washing with water to obtain the naphthalene epoxy resin.

13. The method for preparing a naphthalene-based epoxy resin according to claim 12, wherein: The molar ratio of the crude product to the alkaline substance in the alkaline solution is (0.05-20):

1.

14. The method for preparing a naphthalene-based epoxy resin according to claim 12, wherein: The alkaline solution is an alkali metal hydroxide solution with a concentration of 1wt% to 10wt%.

15. The method for preparing a naphthalene-based epoxy resin according to claim 12, wherein: The temperature of the heat mixing treatment is 50° C. to 130° C., and the duration is 0.5 hour to 3 hours.

16. The method for preparing a naphthalene-based epoxy resin according to claim 12, wherein: After the water washing and refining, rough treatment and recrystallization are also included.

17. A naphthalene-based epoxy resin, characterized in that: The general chemical formula of the naphthalene epoxy resin is Among them, R 11 ~R 81 At least three of them are The rest are H, R is -O-, -COO- or -NH-, and the A group is one of H, alkyl, alkenyl, alkynyl, and phenyl.

18. The naphthalene-based epoxy resin according to claim 17, wherein The epoxy equivalent of the naphthalene epoxy resin is 110 g / mol to 140 g / mol, the total chlorine content is less than 2000 ppm, and the hydrolyzed chlorine content is less than 1000 ppm.

19. A naphthalene-based epoxy resin composition, characterized in that: The naphthalene-based epoxy resin composition comprises a naphthalene-based epoxy resin prepared by the method according to any one of claims 1 to 16 and / or a naphthalene-based epoxy resin according to any one of claims 17 to 18 and a second epoxy resin, wherein the viscosity of the second epoxy resin is lower than that of the naphthalene-based epoxy resin.

20. The naphthalene-based epoxy resin composition according to claim 19, wherein The viscosity of the second epoxy resin at a temperature of 25° C. is 100 mPa.s to 50,000 mPa.s, and the viscosity at a temperature of 150° C. is 1 mPa.s to 1,000 mPa.s.

21. The naphthalene-based epoxy resin composition according to claim 20, wherein The second epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, 1,6-dihydroxynaphthalene epoxy resin, p-aminophenol epoxy resin, and diaminodiphenylmethane epoxy resin.

22. The naphthalene-based epoxy resin composition according to any one of claims 19 to 21, characterized in that: The naphthalene epoxy resin composition also includes an epoxy resin curing agent with a resin mass percentage of 30% to 60%.

23. The naphthalene-based epoxy resin composition according to claim 22, wherein The epoxy resin curing agent includes at least one of an amine curing agent, an acid anhydride curing agent, a phenolic resin curing agent, an active ester curing agent, and a cyanate curing agent.

24. The naphthalene-based epoxy resin composition according to claim 22, wherein The naphthalene epoxy resin composition also includes a curing accelerator with a resin mass percentage of 0.1% to 1.5%.

25. The naphthalene-based epoxy resin composition according to claim 24, wherein The curing accelerator comprises at least one of tris(dimethylaminomethyl)phenol, triethanolamine, dimethylbenzylamine, N-diglycidylaniline, diethylenediamine, triethylenediamine, tetraethylenediamine and diisopropylamine.

26. An application of a naphthalene-based epoxy resin composition, characterized in that: The naphthalene-based epoxy resin composition according to any one of claims 19 to 25 is applied to the field of electronic materials.

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