Preparation method of epoxy resin and material for electronic and electrical appliances

Abstract

The invention discloses a preparation method of epoxy resin and a material for electronic and electrical appliances, and belongs to the technical field of epoxy resin. The preparation method of the epoxy resin comprises the following steps: 1) mixing and heating a bisphenol compound as shown in a formula 1, a Pd / COFs catalyst and allyl acetate under an alkaline condition, and reacting to obtain an allyl compound as shown in a formula 2; and 2) mixing the allyl compound as shown in the formula 2, a heteropolyacid / COFs catalyst, hydrogen peroxide and acetonitrile, and reacting to obtain the epoxy resin as shown in a formula 3. According to the preparation method, a Pd / COFs catalyst and a heteropolyacid / COFs catalyst are combined for use to sequentially catalyze and generate an allyl compound and epoxy resin, and the oxidation reaction activity under the catalysis of heteropolyacid / COFs is improved through acetonitrile peroxide generated by acetonitrile and hydrogen peroxide, so that a halogen-containing reagent does not need to be used in the preparation process of the epoxy resin; the content of halogen in epoxy resin impurities is low, and the yield of epoxy resin is high.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy resins, and in particular to a method for preparing epoxy resins and materials for electronic appliances. Background Art

[0002] Epoxy resin is an epoxy oligomer that reacts with a curing agent to form a three-dimensional network structure. It has strong adhesion, high temperature resistance, salt spray resistance, and excellent mechanical and electrical properties. In the 1930s, Dr. Pierre Castan of Switzerland first synthesized bisphenol A epoxy resin. Later, researchers found that epoxy resin was superior to phenolic and polyester in metal bonding and anti-corrosion coatings. Soon after, American companies such as Shell and Dow Chemical began to mass-produce epoxy resin through the polycondensation of bisphenol A and epichlorohydrin. In 1958, my country began to industrialize the production of independently developed epoxy resin in Shanghai; in 2009, the world produced about 3 million tons of epoxy resin, and China produced about 1.1 million tons of epoxy resin, accounting for one-third of the world's production capacity. At present, the varieties of epoxy resins are becoming increasingly abundant. In addition to the traditional alicyclic, phenolic, halogenated and polyolefin epoxy resins, new structural epoxy resins such as five-membered ring hydantoin epoxy, phenolphthalein epoxy and polyaromatic heterocyclic epoxy resins have been developed one after another. As coatings, adhesives and molding materials, they are widely used in various industrial fields such as electronics and electrical, optical machinery, aerospace, and ship transportation.

[0003] Low-chlorine epoxy resin is a solvent-free epoxy resin, which is often referred to as "low-chlorine resin" because its chlorine content is less than 80 ppm. Compared with ordinary epoxy resin, it has the following advantages: 1. Stable electrical properties: Low-chlorine resin has excellent insulation and heat resistance. The electrical properties can also be guaranteed to be stable under high temperature and high humidity. 2. Environmentally friendly and non-toxic: Low-chlorine resin does not contain carcinogenic substances such as nitrosamines, so it is widely used in food packaging, beverage bottles and other fields. 3. Strong adhesion: Low-chlorine resin has a large surface tension, high bonding strength, and is not prone to defects such as bubbles. It is very suitable for high-end electronic products and other fields. However, since the traditional raw material for the production of epoxy resin is epichlorohydrin, the chlorine content of epoxy resin is generally high, which not only faces the problem of environmental pollution, but also makes it difficult to meet the increasing requirements of large-scale integrated circuits and electronic packaging. Therefore, it is urgent to develop a method with high production efficiency, high conversion rate and low price to prepare high-purity low-halogen epoxy resin.

[0004] CN115073712B discloses a preparation method and application of a low-chlorine epoxy resin, the preparation method comprising: under a first preset reaction condition, a bisphenol A epoxy resin containing chlorine impurities undergoes an aldol condensation reaction with a polyfluoroalkyl aldehyde to obtain a reaction product; a perfluoroalkane solution is added to the reaction product for extraction, and an extraction phase and an extraction phase are separated after standing to obtain the extraction phase and the extraction phase respectively; the extraction phase includes the fluorine-containing chlorinated product, and the extraction phase includes a low-chlorine bisphenol A epoxy resin; the extraction phase and the extraction phase are separated, that is, the purpose of separating the chlorine-containing bisphenol A epoxy resin from the chlorine-free bisphenol A epoxy resin is achieved, and a low-chlorine bisphenol A epoxy resin is obtained, and the chlorine content of the low-chlorine bisphenol A epoxy resin is lower than that of the bisphenol A epoxy resin before the reaction. Although the method has low cost, high separation efficiency, and simple operation, the chlorine content of the low-chlorine bisphenol A epoxy resin prepared by the method is 32~134 ppm. It is still difficult to meet the chlorine content requirements for high-demand electronic appliances, which further affects the performance.

[0005] CN103275303A discloses a method for synthesizing hydrogenated bisphenol A epoxy resin using ammonium salt catalysis. The present invention is preferably based on hydrogenated bisphenol A and epihalogen such as epichlorohydrin, wherein the step 1) uses an alkyl alcohol as a raw material, adds an ammonium salt catalyst and a base at the same time, performs a ring-opening etherification reaction at 30°C to 100°C to obtain a halogen alcohol ether; then, in the same reaction system, continues to add a base, performs a ring-closing epoxidation reaction at 20°C to 80°C; and obtains a hydrogenated bisphenol A epoxy resin through post-treatment processes such as filtration, washing, separation, and decompression distillation to remove the solvent, wherein the hydrolyzable chlorine content is ≤800 ppm and the inorganic chlorine content is ≤50 ppm.

[0006] CN107022060A discloses a preparation method of a high-purity electronic-grade hydrogenated bisphenol A epoxy resin. Glycidol is used as a raw material, reacted with pyridine and methanesulfonyl chloride, washed, layered, filtered and concentrated after the reaction, and distilled to obtain a main fraction I. The main fraction I is added to a solution of hydrogenated bisphenol and sodium hydride under stirring for reaction. After the reaction is completed, the main fraction I is washed, layered and filtered, and concentrated to obtain a high-purity electronic-grade hydrogenated bisphenol A epoxy resin with a total halogen content not exceeding 1000ppm. In the preparation process of the present invention, epichlorohydrin is no longer used as a raw material during the synthesis process, but epichlorohydrin is replaced by the reaction product of glycidol and methanesulfonyl chloride, and finally a high-purity hydrogenated bisphenol A epoxy resin with a low total halogen content is obtained, but its total halogen content is still difficult to meet some industrial needs.

[0007] CN104151525B discloses a method for preparing an epoxy resin, comprising the following steps: a) etherification reaction of a polyol and a halo-epoxypropane to obtain a haloalcohol ether; the polyol is a diol, a triol or a tetraol; b) the haloalcohol ether is subjected to an elimination reaction in the presence of a dehydrohalogenation agent to obtain a crude epoxy resin product; the dehydrohalogenation agent is an alkali metal hydroxide and a quaternary ammonium salt; c) the crude epoxy resin product is refined using a mixed solution of an alkali metal hydroxide and a quaternary ammonium salt in a mass ratio of 3 to 7:1 to obtain an epoxy resin; the mass concentration of the mixed solution is 5 to 50wt%. The hydrolyzable halide content of the epoxy resin produced by the method is less than 200 ppm.

[0008] Therefore, researching and developing a new method for preparing epoxy resin is of great significance for the application of low-halogen epoxy resin. Summary of the invention

[0009] In view of this, the technical problem to be solved by the present invention is to provide a method for preparing epoxy resin and a material for electronic appliances. The preparation method does not require the use of halogen-containing reagents, and the product has the advantages of low halogen content and high yield.

[0010] In order to achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0011] The present invention provides a method for preparing an epoxy resin, comprising the following steps:

[0012] 1) mixing and heating the bisphenol compound represented by Formula 1, the Pd / COFs catalyst and allyl acetate under alkaline conditions to react and obtain the allyl compound represented by Formula 2;

[0013] 2) mixing the allyl compound represented by the above formula 2, the heteropoly acid / COFs catalyst, hydrogen peroxide and acetonitrile to react to obtain the epoxy resin represented by formula 3;

[0014] Formula 1, Formula 2: Formula 3;

[0015] Wherein, R1, R2, and R3 represent para- or meta-substitution.

[0016] R1 is selected from -(RPh) n -OH, R2 is selected from -(RPh) n -OCH2CHCH2, R3 is selected from -(RPh) n -OCH2CHOCH2;

[0017] The R is selected from -CH2-, -C(CH3)2- or ;

[0018] The n is selected from 0 or 1.

[0019] The preparation method uses the catalytic action of a Pd / COFs catalyst to react a bisphenol compound to obtain an allyl compound, and then uses the catalytic action of a heteropolyacid / COFs catalyst to further oxidize the allyl compound with hydrogen peroxide and acetonitrile to prepare an epoxy resin.

[0020] The preparation method uses a Pd / COFs catalyst and a heteropolyacid / COFs catalyst in combination, so that the overall amount of the catalyst used in the method is small and the cost is low.

[0021] In the above method, the acetonitrile in step 2) reacts with hydrogen peroxide to obtain acetonitrile peroxide, which has excellent oxidation effect on the oxidation reaction of the allyl compound shown in Formula 2 catalyzed by the heteropolyacid / COFs catalyst, thereby significantly improving the yield of the epoxy resin shown in Formula 3. The method of the present invention enables the prepared epoxy resin to have a high yield, and no halogen reagent is added during the reaction process, so that the total halogen content in the impurities of the epoxy resin is low.

[0022] By comparing the addition of hydrogen peroxide without acetonitrile, it is proved that hydrogen peroxide and acetonitrile can improve the reaction activity and promote the reaction. This may be because part of the acetonitrile is oxidized by hydrogen peroxide to peroxyacetonitrile. As an active intermediate, peroxyacetonitrile promotes the preparation of epoxy resin due to its instability and high activity. The unoxidized acetonitrile also acts as a solvent. The mixed use of hydrogen peroxide and acetonitrile enhances the activity of the reaction and significantly improves the yield of epoxy resin.

[0023] Preferably, the epoxy resin represented by Formula 3 is selected from any of the following structures:

[0024] .

[0025] Preferably, in the step 2), the molar ratio of hydrogen peroxide to acetonitrile is 1:(10-50); more preferably 1:50.

[0026] Preferably, in the present invention, the loading amount of Pd in ​​the Pd / COFs catalyst in step 1) is 1.0 wt% to 3.0 wt%; more preferably 2.0 wt% to 3.0 wt%; and in some specific embodiments of the present invention, it is preferably 3.0 %wt.

[0027] Preferably, the COFs in the Pd / COFs catalyst is selected from one or more of trimesaldehyde-p-phenylenediamine-COF (TFB-DBCOF), trimesaldehyde-benzidine-COF (TFB-BD COF), trimesaldehyde-4,4'-diamino-p-terphenyl-COF (TFB-Td COF); more preferably trimesaldehyde-4,4'-diamino-p-terphenyl-COF (TFB-TdCOF), because the TFB-Td COF has a larger specific surface area and porosity.

[0028] The Pd / COFs catalyst is represented as Pd / TFB-DB COF or Pd / TFB-BD COF or Pd / TFB-Td COF.

[0029] The Pd / COFs catalyst enables the yield of step 1) of the above method to be as high as 90%, and the catalyst recovery rate is high, which significantly reduces the cost.

[0030] Preferably, in the present invention, the mass ratio of heteropoly acid to COFs material in the heteropoly acid / COFs catalyst in step 2) is 1:(1-4); more preferably 1:(1-2); and in some specific embodiments of the present invention, preferably 1:1.

[0031] Preferably, the heteropoly acid is selected from phosphotungstic acid (H3PW 12 O 40 ), phosphomolybdic acid (H5Mo 12 O 41 P), silicophosphate (H 12 K3O4PSi3) or more;

[0032] Preferably, the COFs in the heteropolyacid / COFs catalyst are selected from one or more of TFB-DB COF, TFB-BD COF and TFB-TdCOF.

[0033] The heteropolyacid / COFs catalyst is represented by H3PW 12 O 40 / TFB-DB COF or H3PW 12 O 40 / TFB-BD COF or H3PW 12 O 40 / TFB-Td COF or H5Mo 12 O 41 P / TFB-DB COF or H5Mo 12 O 41 P / TFB-BD COF or H5Mo 12 O 41 P / TFB-Td COF or H12 K3O4PSi3 / TFB-DB COF or H 12 K3O4PSi3 / TFB-BD COF or H 12 K3O4PSi3 / TFB-Td COF.

[0034] Preferably, the mixed solvent in step 2) of the present invention further comprises an alcohol solvent;

[0035] Preferably, the mixed solvent in step 2) further includes methanol or ethanol.

[0036] The alcohol solvent can increase the solubility of the allyl compound shown in Formula 2, so the mixed solvent of acetonitrile and methanol is more conducive to the reaction.

[0037] The volume ratio of the acetonitrile to the alcohol solvent is (1-5):1.

[0038] Preferably, in the step 1), the mass percentage of the Pd / COFs catalyst is 1.0% to 5.0% of the bisphenol compound; more preferably, it is 3.2%.

[0039] Preferably, the mass ratio of allyl acetate to bisphenol compound is (1-2):1; further

[0040] The preferred ratio is 1.2:1.

[0041] Preferably, in the step 2), the mass ratio of the allyl compound to the heteropolyacid / COFs catalyst is 100:(0.5-1), and more preferably 100:0.5.

[0042] Preferably, the mass ratio of the allyl compound to hydrogen peroxide is 1:(1-3), and more preferably 1:1.

[0043] Preferably, the alkaline condition in step 1) is provided by one or more of LiOH, NaOH, KOH, Na2CO3, K2CO3.

[0044] The method of the invention is green and environmentally friendly, the reaction raw materials are low in price and safe to use, the catalyst dosage of the entire route is low, the reaction activity is high, the yield of the target product epoxy resin is high, and it is suitable for large-scale industrial production.

[0045] The present invention also provides a material for electronic appliances, including an epoxy resin material;

[0046] The epoxy resin material is obtained by polymerizing the epoxy resin prepared by the above-mentioned preparation method;

[0047] The total chlorine content of impurities in the epoxy resin is less than 50 ppm.

[0048] Epoxy resin with low chlorine content reduces the chlorine content in epoxy resin materials, making the electrical properties of epoxy resin materials stable, environmentally friendly and non-toxic, with strong adhesion, and not prone to defects such as bubbles, and then it can be used to prepare materials for electronic appliances.

[0049] The electronic and electrical material can be widely used in semiconductor packaging, electronic components, optical devices, etc.

[0050] Compared with the prior art, the preparation method of the epoxy resin provided by the present invention comprises the following steps: 1) mixing and heating the bisphenol compound shown in Formula 1, Pd / COFs catalyst and allyl acetate under alkaline conditions to react and obtain the allyl compound shown in Formula 2; 2) mixing the allyl compound shown in Formula 2, heteropolyacid / COFs catalyst, hydrogen peroxide and acetonitrile to react and obtain the epoxy resin shown in Formula 3; wherein R1, R2 and R3 represent para- or meta-substitution, and R1 is selected from -(RPh) n -OH, R2 is selected from -(RPh) n -OCH2CHCH2, R3 is selected from -(RPh) n -OCH2CHOCH2; wherein R is selected from -CH2-, -C(CH3)2- or ; The n is selected from 0 or 1. The preparation method adopts a Pd / COFs catalyst and a heteropoly acid / COFs catalyst to catalyze the generation of an allyl compound and an epoxy resin in sequence, and uses acetonitrile peroxide generated by acetonitrile and hydrogen peroxide as an oxidant to increase the oxidation reaction activity under the catalysis of the heteropoly acid / COFs, so that no halogen-containing reagent is required in the preparation process of the epoxy resin, the halogen content in the impurities of the epoxy resin is low, and the yield is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 The bisphenol F allyl ether prepared in Example 1 1 H NMR spectrum;

[0052] Figure 2 The bisphenol F epoxy resin prepared in Example 1 1 H NMR spectrum;

[0053] Figure 3 The ESI mass spectrum of the bisphenol F epoxy resin prepared in Example 1 (Exact Mass=312.14, [M+23]);

[0054] Figure 4 The bisphenol A allyl ether prepared in Example 2 1 H NMR spectrum;

[0055] Figure 5 The bisphenol A epoxy resin prepared in Example 2 1 H NMR spectrum;

[0056] Figure 6 The ESI mass spectrum of the bisphenol A epoxy resin prepared in Example 2 (Exact Mass=340.17, [M+23]);

[0057] Figure 7 The resorcinol allyl ether prepared in Example 3 1 H NMR spectrum;

[0058] Figure 8 The resorcinol epoxy resin prepared in Example 3 1 H NMR spectrum;

[0059] Fig. 9 This is a test chart of the total chlorine content in the bisphenol F epoxy resin prepared in Example 1;

[0060] Fig.10 This is a test chart of the total chlorine content in the bisphenol A epoxy resin prepared in Example 2;

[0061] Fig.11 This is a test chart of the total chlorine content in the resorcinol-type epoxy resin prepared in Example 3. DETAILED DESCRIPTION

[0062] To further illustrate the present invention, the preparation method of the epoxy resin provided by the present invention and the materials for electronic appliances are described in detail below in combination with the embodiments. The following COFs can be prepared in large quantities at room temperature and pressure, and are suitable for scale-up production. The preparation method thereof refers to ACS Appl. Mater. Interfaces 2021, 13, 8, 10513~10523. The preparation of the following TFB-DBCOF, TFB-BD COF and TFB-Td COF refers to Song Sannan. Preparation of polymer skeleton materials and study of their iodine adsorption properties [D]. Jilin University).

[0063] The following Pd / TFB-DB COF catalyst, Pd / TFB-BD COF catalyst and Pd / TFB-Td COF catalyst are all Pd / COFs catalysts, and their preparation methods are as follows:

[0064] The divalent palladium compound and COFs material (TFB-DB COF or TFB-BD COF or TFB-Td COF) are mixed and dissolved in an organic solvent, stirred thoroughly and evaporated to obtain a Pd / COFs catalyst, and the content of Pd in ​​COFs is quantified by ICP (inductively coupled plasma emission spectroscopy).

[0065] The following H3PW 12 O 40 / TFB-Td COF or H5Mo 12 O 41 P / TFB-Td COF are heteropolyacid / COFs catalysts. The preparation method thereof comprises the following steps:

[0066] Heteropolyacid H3PW 12 O 40 or H5Mo 12 O 41 P and the COFs material are mixed and dissolved in an organic solvent, and after being fully stirred, the solvent is evaporated to obtain the heteropoly acid / COFs catalyst.

[0067] Example 1

[0068] Bisphenol F (scientific name: 4,4-dihydroxydiphenylmethane) (200.08 g, 1.0 mol), allyl acetate (150.75 g, 1.5 mol), and potassium carbonate (13.80 g, 0.1 mol) were dissolved in 1.0 L of anhydrous methanol solution, and Pd / TFB-Td COF catalyst (i.e., the carrier is TFB-Td COF, the active ingredient is Pd, wherein Pd accounts for 3.0 wt% of the COF material, Pd is 0.001 mol, and TFB-Td COF is 3.53 g) was added, heated to reflux, and after the reaction was stopped by nuclear magnetic resonance detection, the reaction solution was filtered, the catalyst Pd / TFB-Td COF was recovered, and the solvent was evaporated to obtain an oily product, namely bisphenol F allyl ether (254.94 g, yield 91%). 1 H NMR(300 MHz, Chloroform-d) δ 7.11 (s, 4H), 6.90 (s, 4H), 6.10 (s, 2H), 5.47 (s,2H), 5.30 (s, 2H), 4.56 (s, 4H), 3.99 (s, 1H), 3.90 (s, 1H). (such as Figure 1 as shown).

[0069]

[0070] Bisphenol F allyl ether (254.94 g, 0.91 mol), H3PW 12 O 40 / TFB-Td COF (2.55 g, the catalyst was added at 1% wt of the substrate, of which H3PW 12 O 40The mass ratio of H3PW to COF was 1:1), and H3PW was dispersed and dissolved in a mixed solvent of acetonitrile and methanol (1.6 L acetonitrile and 0.4 L methanol). H2O2 (61.89 g, 1.82 mol) was slowly added dropwise. After the reaction was completed by TCL monitoring, the solid was filtered and H3PW was recovered. 12 O 40 / TFB-Td COF, the remaining liquid was rotary evaporated, extracted with ethyl acetate / water, the organic phases were combined, dehydrated with anhydrous magnesium sulfate, and dried in vacuo to obtain a viscous orange product, which was purified by column chromatography with ethyl acetate and petroleum ether (1:50 to 1:20) as the eluent to obtain a light yellow liquid, namely bisphenol F type epoxy resin (156.79 g, yield 55.2%), with a total yield of 50.23%. The total chlorine content was 0.01 ppm as determined by ICP-MS (inductively coupled plasma mass spectrometry). 1 H NMR (300 MHz, Chloroform-d) δ 7.10 (s, 4H), 6.84 (s, 4H), 4.12 (s, 4H), 3.91 (d, J = 23.2Hz, 4H), 3.34 (s, 2H), 2.91 (s, 2H), 2.76 (s, 2H).(such as Figure 2 as shown).

[0071] Figure 3 This is the ESI mass spectrum of the bisphenol F epoxy resin prepared in Example 1 (Exact Mass=312.14, [M+23]).

[0072]

[0073] Example 2

[0074] Bisphenol A (scientific name: 2,2-bis(4′-hydroxyphenyl)propane) (228.12 g, 1.0 mol), allyl acetate (120.6 g, 1.2 mol), and potassium hydroxide (5.60 g, 0.1 mol) were dissolved in 1.0 L of anhydrous ethanol solution, and Pd / TFB-Td COF catalyst (i.e., the carrier is TFB-Td COF, the active ingredient is Pd, wherein Pd accounts for 3.0%wt of COF material, Pd is 0.001 mol, and TFB-Td COF is 3.3 g) was added, heated to reflux, and after the reaction stopped by nuclear magnetic resonance monitoring, the reaction solution was filtered, the catalyst Pd / TFB-Td COF was recovered, and the solvent was evaporated to obtain an oily product, which is bisphenol A allyl ether (277.98 g, yield 90.2%). 1H NMR(400 MHz, Chloroform-d) δ 7.14 (s, 4H), 6.83 (s, 4H), 6.03 (s, 2H), 5.43 (s,2H), 5.28 (d, J = 12.0 Hz, 2H), 4.51 (d, J = 8.4 Hz, 4H), 1.64 (s, 6H). (e.g. Figure 4 as shown).

[0075]

[0076] Bisphenol A allyl ether (277.98 g, 0.90 mol), H3PW 12 O 40 / TFB-Td COF (2.78 g, added according to 1% wt of substrate, H3PW 12 O 40 The mass ratio of 1:1 with COF was dispersed and dissolved in a mixed solvent of acetonitrile and methanol (1.8 L acetonitrile, 0.2 L methanol), and H2O2 (61.22 g, 1.80 mol) was slowly added dropwise. After the reaction was completed under TCL monitoring, the solid was filtered and the COF material was recovered. The remaining liquid was rotary evaporated and extracted with ethyl acetate / water. The organic phases were combined and dehydrated with anhydrous magnesium sulfate. The crude product was obtained after vacuum drying and purified by column chromatography. The eluent was ethyl acetate and petroleum ether (1:50 to 1:20) to obtain a yellow oily liquid, which was bisphenol A type epoxy resin (216.76 g, yield 70.8%). The total chlorine content was 14.64 ppm as determined by ICP-MS. 1 H NMR (300 MHz, Chloroform-d) δ 7.15 (s, 4H), 6.82 (d, J = 8.8 Hz, 4H), 4.21 (s, 2H), 3.93 (d, J = 11.0 Hz, 2H), 3.34 (s, 2H), 2.92 (s, 2H), 2.75 (s, 2H), 1.63 (s, 6H). (e.g. Figure 5 as shown).

[0077] Figure 6 This is the ESI mass spectrum of the bisphenol A epoxy resin prepared in Example 2 (Exact Mass=340.17, [M+23]).

[0078]

[0079] Example 3

[0080] Resorcinol (110.04 g, 1.0 mol), allyl acetate (120.60 g, 1.2 mol), and sodium hydroxide (3.40 g, 0.1 mol) were dissolved in 1.0 L of anhydrous ethanol solution, and Pd / TFB-Td COF catalyst (i.e., the carrier is TFB-Td COF, the active ingredient is Pd, wherein Pd accounts for 3.0%wt of COF material, Pd is 0.001 mol, and TFB-Td COF is 3.53 g) was added, heated to reflux, and after the reaction stopped by nuclear magnetic resonance monitoring, the reaction solution was filtered, the TFB-Td COF loaded with palladium catalyst was recovered, and the solvent was evaporated to obtain an oily product, which was resorcinol allyl ether (100.91 g, yield 91.7%). 1 H NMR (300 MHz, Chloroform-d) δ 7.17 (s, 1H), 6.54 (s, 3H), 6.04 (s, 2H), 5.48 (s, 2H), 5.34(s, 2H), 4.51 (s, 4H). (e.g. Figure 7 as shown).

[0081]

[0082] Resorcinol allyl ether (100.91 g, 0.53 mol), H3PW 12 O 40 / TFB-Td COF (1.00 g, added according to 1%wt of substrate, H3PW 12 O 40 The mass ratio of 1:1 with COF was dispersed and dissolved in a mixed solvent of acetonitrile and methanol (1.8 L acetonitrile, 0.2 L methanol), and H2O2 (36.05 g, 1.06 mol) was slowly added dropwise. After the reaction was completed under TCL monitoring, the solid was filtered and the COF material was recovered. The remaining liquid was rotary evaporated and extracted with ethyl acetate / water. The organic phases were combined and dehydrated with anhydrous magnesium sulfate. The crude product was obtained after vacuum drying and purified by column chromatography. The eluent was ethyl acetate and petroleum ether (1:50 to 1:20). The product was collected and the solvent was dried to obtain the product resorcinol-type epoxy resin (128.55 g, yield 73.5%). The total chlorine content was 21.55 ppm as determined by ICP. 1 H NMR(300 MHz, Chloroform-d) δ 7.18 (s, 1H), 6.50 (s, 3H), 4.22 (s, 2H), 3.95 (s,2H), 3.36 (s, 2H), 2.92 (s, 2H), 2.76 (s, 2H). (e.g. Figure 8 as shown).

[0083]

[0084] Example 4

[0085] Resorcinol (110.04 g, 1.0 mol), allyl acetate (120.60 g, 1.2 mol), and sodium hydroxide (3.40 g, 0.1 mol) were dissolved in 1.0 L of anhydrous ethanol solution, and Pd / TFB-Td COF catalyst (i.e., the carrier is TFB-Td COF, the active ingredient is Pd, wherein Pd accounts for 3%wt of COF material, Pd is 0.001 mol, and TFB-Td COF is 3.53 g) was added, heated to reflux, and after the reaction stopped by nuclear magnetic resonance monitoring, the reaction liquid was filtered, the catalyst Pd / TFB-Td COF was recovered, and the solvent was evaporated to obtain an oily product, which was resorcinol allyl ether (93.54 g, yield 85.0%). 1 H NMR (300 MHz, Chloroform-d) δ7.17 (s, 1H), 6.54 (s, 3H), 6.04 (s, 2H), 5.48 (s, 2H), 5.34 (s, 2H), 4.51 (s, 4H).

[0086]

[0087] Resorcinol allyl ether (93.54 g, 0.49 mol), H5Mo 12 O 41 P / TFB-Td COF catalyst (0.50 g, added according to 1% wt of substrate, H5Mo 12 O 41 The mass ratio of P to COF was 1:1) and dispersed in a mixed solvent of methanol and acetonitrile (methanol 0.5 L, acetonitrile 0.5 L), and H2O2 (50.00 g, 1.47 mol) was slowly added dropwise. After the reaction was completed under TCL monitoring, the solid was filtered and the COF material was recovered. The remaining liquid was rotary evaporated and extracted with ethyl acetate / water. The organic phases were combined and dehydrated with anhydrous magnesium sulfate. The crude product was obtained after vacuum drying and purified by column chromatography. The eluent was ethyl acetate and petroleum ether (1:50 to 1:20). The product was collected and the solvent was rotary dried to obtain the product hydroquinone-type epoxy resin (41.14 g, yield 71.2%).

[0088]

[0089] Fig. 9 This is a test chart of the total chlorine content in the bisphenol F epoxy resin prepared in Example 1, indicating that the total chlorine content in the bisphenol F epoxy resin is 0.01 ppm.

[0090] Fig.10 This is a test chart of the total chlorine content in the bisphenol A type epoxy resin prepared in Example 2, indicating that the total chlorine content in the bisphenol F type epoxy resin is 21.55 ppm.

[0091] Fig.11 This is a test chart of the total chlorine content in the resorcinol-type epoxy resin prepared in Example 3, indicating that the total chlorine content in the bisphenol F-type epoxy resin is 14.64 ppm.

[0092] Comparative Example 1

[0093] Dissolve bisphenol F (scientific name: 4,4-dihydroxydiphenylmethane) (200.08 g, 1.0 mol), allyl acetate (150.75 g, 1.5 mol) and potassium carbonate (13.80 g, 0.1 mol) in 1.0 L of anhydrous methanol solution, add PdAcO2 (0.11 g, 0.001 mol) and triphenylphosphine (2.62 g, 0.01 mol), heat to reflux, monitor the reaction by NMR, filter, rotary evaporate and vacuum dry to obtain 152.12 g of oil with a yield of 54.3%.

[0094]

[0095] Comparative Example 2

[0096] Resorcinol (110.04 g, 1.0 mol), allyl acetate (120.60 g, 1.2 mol) and NaOH (3.40 g, 0.1 mol) were dissolved in 1.0 L of anhydrous methanol solution, and Pd / TFB-Td COF catalyst (Pd accounted for 3.0%wt of COF material, Pd was 0.001 mol, and TFB-Td COF was 3.53 g) was added. The mixture was heated to reflux. After the reaction stopped under nuclear magnetic resonance monitoring, the mixture was filtered, rotary evaporated, and vacuum dried to obtain 152.31 g of an oily substance with a yield of 80.12%.

[0097]

[0098] Comparative Example 3

[0099] Bisphenol A allyl ether (200.00 g, 0.64 mol), H3PW 12 O 40 / TFB-Td COF catalyst (1.96 g, added according to 1%wt of substrate, H3PW 12 O 40The ratio of 1:1 to COF was dispersed and dissolved in 8 L of methanol solvent, H2O2 was slowly added dropwise, and after the reaction was completed under TCL monitoring, the solid was filtered to recover the COF material, and the remaining liquid was rotary evaporated and extracted with ethyl acetate / water. The organic phases were combined, dehydrated with anhydrous magnesium sulfate, and the crude product was obtained after vacuum drying. It was purified by column chromatography to obtain bisphenol A epoxy resin (28.32 g, yield 13.0%).

[0100]

[0101] Comparative Example 4

[0102] Resorcinol allyl ether (50.00 g, 0.26 mol), H3PW 12 O 40 / TFB-Td COF (0.50 g, added according to 1%wt of substrate, H3PW 12 O 40 The mass ratio of 1:1 to COF was dispersed and dissolved in methanol solvent (0.5 L), H2O2 was slowly added dropwise, and after the reaction was completed under TCL monitoring, the solid was filtered to recover the COF material, the remaining liquid was rotary evaporated, extracted with ethyl acetate / water, the organic phases were combined, and water was removed by anhydrous magnesium sulfate. The crude product was obtained after vacuum drying and purified by column chromatography. The eluent was ethyl acetate and petroleum ether (1:50 to 1:20). The product was collected and the solvent was rotary dried to obtain 7.80 g of the product hydroquinone-type epoxy resin with a yield of 13.5%.

[0103]

[0104] The above embodiments of epoxy resin are only used to help understand the method of the present invention and its core concept. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing an epoxy resin, characterized in that: The following steps are involved: 1) mixing and heating the bisphenol compound represented by Formula 1, the Pd / COFs catalyst and allyl acetate under alkaline conditions to react and obtain the allyl compound represented by Formula 2; 2) mixing the allyl compound represented by the above formula 2, the heteropoly acid / COFs catalyst, hydrogen peroxide and acetonitrile to react to obtain the epoxy resin represented by formula 3; Formula 1, Formula 2: Formula 3; Wherein, R1, R2, and R3 represent para- or meta-substitution; R1 is selected from -(RPh) n -OH, R2 is selected from -(RPh) n -OCH2CHCH2, R3 is selected from -(RPh) n -OCH2CHOCH2; The R is selected from -CH2-, -C(CH3)2- or ; The n is selected from 0 or 1.

2. The preparation method according to claim 1, characterized in that: The epoxy resin shown in Formula 3 is selected from any of the following structures: 。 3. The preparation method according to claim 1 or 2, characterized in that: In the step 2), the molar ratio of hydrogen peroxide to acetonitrile is 1:(10-50).

4. The preparation method according to claim 1, characterized in that: In the step 1), the loading amount of Pd in ​​the Pd / COFs catalyst is 1.0 wt% to 3.0 wt%; The COFs in the Pd / COFs catalyst is selected from one or more of trimesaldehyde-p-phenylenediamine-COF, trimesaldehyde-benzidine-COF, trimesaldehyde-4,4'-diamino-p-terphenyl-COF.

5. The preparation method according to claim 1, characterized in that: The mass ratio of heteropoly acid to COFs material in the heteropoly acid / COFs catalyst in step 2) is 1:(1-4); The COFs in the heteropolyacid / COFs catalyst is selected from one or more of trimesaldehyde-p-phenylenediamine-COF, trimesaldehyde-benzidine-COF, trimesaldehyde-4,4'-diamino-p-terphenyl-COF; The heteropoly acid in the heteropoly acid / COFs catalyst is selected from one or more of phosphotungstic acid, phosphomolybdic acid and silicophosphoric acid.

6. The preparation method according to claim 1, characterized in that: The mixed solvent in step 2) further includes methanol or ethanol.

7. The preparation method according to claim 1 or 4, characterized in that: In the step 1), the mass percentage of the Pd / COFs catalyst is 1.0% to 5.0% of the bisphenol compound shown in Formula 1; The mass ratio of the allyl acetate to the bisphenol compound represented by Formula 1 is (1-2):

1.

8. The preparation method according to claim 1 or 5, characterized in that: In the step 2), the mass ratio of the allyl compound to the heteropolyacid / COFs catalyst is 100:(0.5-1); The mass ratio of the allyl compound to hydrogen peroxide is 1:(1-3).

9. The preparation method according to claim 1, characterized in that: The alkaline condition in step 1) is provided by one or more of LiOH, NaOH, KOH, Na2CO3, K2CO3.

10. A material for electronic appliances, characterized in that: including epoxy resin materials; The epoxy resin material is obtained by polymerizing the epoxy resin prepared by the preparation method according to any one of claims 1 to 9; The total chlorine content of impurities in the epoxy resin is less than 50 ppm.

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