A halogen-free or low-halogen anticorrosive epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid, and its preparation method and application

Abstract

The present invention relates to the field of epoxy resins and discloses a halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid, as well as its preparation method and application. The preparation method is specifically as follows: C5-C10 halogen-free monocarboxylic acid is mixed and dispersed with a liquid strong acid in a low-temperature water bath, an excess of more than 30% hydrogen peroxide aqueous solution is added dropwise, and the temperature is raised to react to prepare a crude peroxycarboxylic acid solution. The crude peroxycarboxylic acid solution is extracted with a non-water-soluble organic solvent, washed with water, and dried to obtain a weakly acidic anhydrous peroxycarboxylic acid solution. The solution is then stirred and mixed with an active olefin-based organosilicon or non-silicon compound at 15-60°C for reaction. Finally, the resin is treated with an alkali and a reducing agent, washed with water, separated and dried, and distilled under reduced pressure to obtain a highly epoxidized epoxy resin with a total halogen content of less than 10 ppm. The preparation equipment and process of the present invention are simple, no organometallic catalysis is required, and the prepared epoxy resin has high purity. It has broad application prospects in the fields of electronics, electrical engineering, and new energy.

Description

Technical Field

[0001] The present invention relates to the field of epoxy resins, and in particular to a halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid, and a preparation method and application thereof. Background Art

[0002] Epoxy resins, including silicone-modified epoxy resins, are widely used in various electronic and electrical engineering applications. With the development of new energy, ultra-large-scale integrated circuits, and microelectronic packaging, traditional epoxy resins are no longer able to meet the requirements for high-power, high-temperature resistance and corrosion resistance. The content of corrosive halogen impurities (including fluorine, chlorine, and bromine) in epoxy resins significantly affects these properties. The development of low-halogen to halogen-free anti-corrosion epoxy resins holds great promise for future applications.

[0003] The traditional method for preparing epoxy resins is to react the corresponding bisphenols with epichlorohydrin. The ionically bonded chlorides produced in the synthesis reaction can be removed to a few ppm through a water washing process, but the content of non-hydrolyzed chlorine-containing organic compounds as by-products and in the raw materials is usually not less than 5000 ppm after water washing. In US Pat. No. 3413320, recrystallization is used to purify epoxy resin to a total chlorine content of approximately 3700 ppm. Invention patent ZL201010144011.9, "Low-corrosive epoxy resin and its manufacturing method," filed by Siemens in China, extracts solid epoxy resin from a solvent to obtain an epoxy resin with a total organic and ionically bonded chlorine content of less than 100 ppm. However, solid epoxy resins are few in variety and have limited applications. Chinese invention patent application CN201110159754.8, "A method for low-temperature synthesis of ultra-high-purity o-cresol-formaldehyde epoxy resin," combines o-cresol-formaldehyde resin with epichlorohydrin. By reacting the alkane with epichlorohydrin at atmospheric pressure and low temperature under reduced pressure, recovering the epichlorohydrin, and then further dissolving it in a solvent and eluting it with alkaline catalysis, the solvent can be purified by water. This produces an epoxy resin with a total chlorine content of less than 750 ppm and a hydrolyzable chlorine content of less than 50 ppm. Chinese invention patent application CN201610657440.3, "A Synthesis Method for Ultra-High-Purity O-Cresol Epoxy Resin," uses peracetic acid oxidation to produce an epoxy resin with a hydrolyzable chlorine content of less than 20 ppm. However, peracetic acid is hazardous and unstable. Using a 20-40% aqueous peracetic acid concentration can easily hydrolyze or esterify the epoxy groups, making it difficult to obtain an epoxy resin with a high epoxy value. Public reports of high-purity, low-halogen or halogen-free epoxy resins with a total halogen content of less than 10 ppm are rare. Summary of the Invention

[0004] The primary purpose of the present invention is to provide a method for preparing a halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid.

[0005] Another object of the present invention is to provide a halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of olefin-based anhydrous peroxy acid, wherein the total halogen content of the epoxy resin is below 10 ppm and the epoxy resin has a high epoxy value.

[0006] Another object of the present invention is to provide applications of the epoxy resin.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A method for preparing a halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid comprises the following preparation steps:

[0009] (1) firstly, in a water bath cooled at 5-30°C, mix and stir a C5-C10 halogen-free monocarboxylic acid and a liquid strong acid to disperse uniformly, then dropwise add a hydrogen peroxide solution under stirring, maintaining the temperature of the mixture at no more than 50°C during the addition, and after the addition is complete, maintain the mixture at 10-40°C for 3-24 hours to obtain a crude halogen-free peroxycarboxylic acid mixture;

[0010] (2) adding sulfate solid or saturated solution, stirring and dispersing uniformly, maintaining the temperature of the mixed solution below 50° C., adding a non-water-soluble organic solvent for extraction and separation or / and centrifugation, re-extracting the aqueous phase with a non-water-soluble organic solvent or / and centrifuging 1-2 times, and combining the organic phases;

[0011] (3) washing the combined organic phases 2 to 4 times with a saturated sulfate aqueous solution until the pH of the aqueous phase is 3 to 6, drying the washed organic phases, filtering, and washing the filter residue with an ester solvent and / or the organic solvent in step (2), or without washing the filter residue, to obtain an anhydrous peroxycarboxylic acid solution;

[0012] (4) stirring and mixing the olefin compound and the anhydrous peroxycarboxylic acid solution at 15-60° C. and reacting for 6-72 hours in a molar ratio of the active olefin group to the monocarboxylic acid charged in step (1) of 1:0.5-2.5, wherein the active olefin group is C=C, excluding the benzene ring;

[0013] (5) cooling, filtering, and washing the filtrate multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0014] (6) The organic phase is dried and filtered, and the filtrate is subjected to reduced pressure distillation to recover the distillate organic solvent. The residue obtained is a halogen-free or low-halogen anti-corrosion epoxy resin.

[0015] Preferably, the C5-C10 halogen-free monocarboxylic acid in step (1) is a halogen-free monocarboxylic acid containing an alicyclic, fatty or aromatic group;

[0016] The olefinic compound in step (4) is a halogen-free or low-halogen compound containing an olefinic group, wherein the olefinic group is R 1 R 2 C=CR 3 -, where R 1 ,R 2 ,R 3 =H or alkyl, including organosilicon compounds containing vinyl or allyl groups and non-silicon compounds containing vinyl, allyl or 2-propenyl groups.

[0017] Preferably, the C5-C10 halogen-free monocarboxylic acid in step (1) comprises one or more of cyclohexanecarboxylic acid, cyclohexylacetic acid, 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, benzoic acid, phenylacetic acid, and 3-phenylpropionic acid;

[0018] The vinyl or allyl organosilicon compound in step (4) is one or more of triallylphenylsilane, trivinylphenylsilane, tetraallylsilane, trivinyltrimethylcyclotrisiloxane, tetravinyltetramethylcyclotetrasiloxane, methylvinylpolysiloxane, methylvinylphenylpolysiloxane and methylallylpolysiloxane;

[0019] The non-silicon compound containing vinyl, allyl or 2-propenyl is one or more of divinylbenzene, trivinylbenzene, allylphenyl allyl ether, diallylphenyl allyl ether, di(2-propenyl)phenyl-2-propenyl ether, bisphenol A diallyl ether, 2,2'-diallylbisphenol A diallyl ether, and bis or polymaleimides.

[0020] Preferably, the preparation method of the diallylphenyl allyl ether or bisphenol A diallyl ether or 2,2'-diallylbisphenol A diallyl ether is as follows:

[0021] Diallylphenol or bisphenol A or 2,2'-diallylbisphenol A are mixed with allyl chloride in an organic solvent, an inorganic base is added under stirring, the reaction is carried out at 45-52°C for 10-24 hours, the reaction is cooled, the lower aqueous phase is separated and removed, the upper oil phase is washed with a NaOH solution, washed with water until neutral, and the solvent is removed by drying, filtering, and distillation under reduced pressure to obtain the product; the organic solvent is a water-soluble ketone or a water-insoluble ether or aromatic hydrocarbon, preferably acetone; the inorganic base is solid potassium carbonate, a 20-40wt% sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, preferably solid potassium carbonate.

[0022] Preferably, the liquid strong acid in step (1) is one or more of C1-C3 n-alkylsulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, nitric acid or aqueous solutions thereof with a concentration of 60 wt % or more.

[0023] Preferably, the molar ratio of the C5-C10 halogen-free monocarboxylic acid to the liquid strong acid and hydrogen peroxide in step (1) is 1:0.5-5:1-3, where the molar ratio is calculated based on pure acid and hydrogen peroxide;

[0024] The aqueous hydrogen peroxide solution in step (1) is an aqueous hydrogen peroxide solution with a content of 30 wt % or more, more preferably an aqueous hydrogen peroxide solution with a content of 50 wt % or more.

[0025] Preferably, the water-insoluble organic solvent in step (2) is cyclohexane, methylcyclohexane, ethylcyclohexane, n-hexane, n-heptane, dichloroethane, or chloroform; the ester solvent includes one or more of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, and ethyl butyrate, and the total amount of the organic solvent is 2 to 10 times the total mass of the monocarboxylic acid.

[0026] Preferably, the sulfate in step (2) is ammonium sulfate, sodium sulfate, or potassium sulfate;

[0027] The drying is carried out using an inorganic desiccant, wherein the inorganic desiccant is anhydrous sodium sulfate or anhydrous magnesium sulfate, the drying time is 1 to 12 hours, and the temperature is room temperature.

[0028] Preferably, the washing in step (5) is performed multiple times with an inorganic alkali aqueous solution and an inorganic reducing agent solution, wherein the inorganic alkali aqueous solution is an aqueous solution of potassium carbonate, sodium carbonate, potassium hydroxide, or sodium hydroxide at a concentration of less than 30 wt%, and the inorganic reducing agent solution is an aqueous solution of sulfite or thiosulfate at a concentration of 2 to 15 wt%.

[0029] The reduced pressure distillation temperature does not exceed 100° C., and the reduced pressure distillation vacuum degree is -0.06 to -0.0998 MPa.

[0030] A halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of olefin-based anhydrous peroxy acid is prepared by the above method.

[0031] The above-mentioned halogen-free or low-halogen anti-corrosion epoxy resins are used in the fields of electronics, electrical and new energy, anti-corrosion adhesives, packaging materials and protective materials.

[0032] The epoxidation of olefin groups to prepare epoxy resins often uses metal-catalyzed aqueous hydrogen peroxide solutions, tert-butyl hydrogen peroxide solutions, peroxyformic acid, and peracetic acid. However, it is difficult to obtain high-purity, high-epoxy value epoxy resins from the high-epoxidation of polyolefin groups. The presence of water can cause the epoxy groups to hydrolyze after the epoxy resin is generated, particularly in a strong acidic environment. The hydrolyzate also greatly increases the difficulty of product purification and post-processing. The preparation of anhydrous peroxy acid solutions is of great value in the field of chemical synthesis. The fewer carbon atoms in a peroxy acid, the better its water solubility and the worse its stability. Short-chain peroxyformic acid and peracetic acid are extremely unstable and easily soluble in water, making it difficult to obtain pure peroxyformic acid and peracetic acid, and are easily decomposed and exploded, often existing in a certain concentration of aqueous solution. US2002177732A1 discloses a method for preparing peracetic acid aqueous solution using acetic acid, hydrogen peroxide, and sulfuric acid catalysis. Chinese invention patent CN201910601029.8, "A method for preparing anhydrous peroxybutyric acid for the synthesis of ε-caprolactone," obtains a relatively stable anhydrous peroxybutyric acid solution. ZL201810938203.3, "A method for preparing anhydrous peroxypropionic acid," obtains anhydrous peroxypropionic acid through a complex process including multiple distillation towers. CN201410642029.X uses an integrated reaction and separation device to continuously prepare and separate peracetic acid and / or peroxypropionic acid and caprolactone. CN201410645297.7, "A process for the continuous preparation of high-purity ε-caprolactone based on anhydrous peroxyisobutyric acid," uses an integrated reaction and separation device consisting of a catalytic distillation tower, a reactive distillation tower, a stirred reactor, and a distillation tower connected in sequence to continuously prepare and separate peroxyisobutyric acid and ε-caprolactone. The present invention uses a water-insoluble C5-C10 monocarboxylic acid with a relatively high organic carbon atom content and a certain concentration of hydrogen peroxide to prepare a peroxycarboxylic acid under strongly acidic catalytic conditions. The moderate organic carbon content not only improves the stability of the peroxycarboxylic acid but also provides good lipophilicity, thereby ensuring the reactivity of the epoxidized water-insoluble olefin monomer. The method is simple, employing an inactive, water-insoluble organic solvent for extraction and separation, followed by washing and drying with saturated brine, to easily obtain a weakly acidic, anhydrous peroxycarboxylic acid solution. Side reactions such as hydrolysis of epoxy groups in the epoxidized product by water are also avoided, particularly the catalytic hydrolysis of epoxy groups by a strong acid, significantly reducing the difficulty of product post-processing. The method eliminates the need for organometallic catalysis, ensures a high degree of epoxidation of the olefin groups, and avoids the introduction and residue of metal elements, thereby obtaining an epoxy resin with high purity and a high epoxy value.The experimental results of the present invention show that the use of halogen-containing m-chloroperbenzoic acid can obtain an epoxy resin with a high halogen content, while the use of the anhydrous peracid solution prepared from the halogen-free C5-C10 monocarboxylic acid of the present invention, after epoxidation of olefins, through alkali treatment and reducing agent treatment, water washing, centrifugal separation and reduced pressure distillation, can obtain a high-purity halogen-free or low-halogen epoxy resin with a high epoxy value. The halogen content mainly depends on the halogen content of the substrate olefin-based compound, and a low-halogen or halogen-free epoxy resin with a halogen content of less than 10 ppm can be obtained.

[0033] The present invention has the following significant features and beneficial effects:

[0034] (1) The anhydrous peroxycarboxylic acid solution prepared by the present invention has good stability, high activity, and a simple preparation process;

[0035] (2) When epoxidizing olefinic compounds, especially polyolefinic compounds, using the anhydrous peroxycarboxylic acid solution prepared by the present invention, no organometallic catalyst is required, and high-purity, highly epoxidized epoxy resins can be obtained;

[0036] (3) The halogen content of the prepared epoxy resin is very low, which can be as low as less than 10 ppm. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is the HNMR spectrum of the halogen-free organosilicon epoxy resin prepared in Example 1;

[0038] Figure 2 and Figure 3 They are respectively the HNMR spectrum and infrared spectrum of the low-halogen polyalkenyl compound diallylphenyl allyl ether prepared in Example 3-1;

[0039] Figure 4 and Figure 5 They are respectively the HNMR spectrum and infrared spectrum of the low-halogen high-epoxy value epoxy resin prepared in Example 3;

[0040] Figure 6 This is the infrared FTIR of the high halogen content epoxy resin prepared by using the halogen-containing peroxy acid-m-chloroperbenzoic acid CPBA epoxidized diallylphenyl allyl ether in Comparative Example 2. DETAILED DESCRIPTION

[0041] The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto. For process parameters not particularly noted, conventional techniques may be used.

[0042] Example 1:

[0043] (1) Under cooling at 25-30° C. in a water bath, 256 g (2 mol) of cyclohexanecarboxylic acid and 576 g (6 mol) of methanesulfonic acid were mixed and stirred to uniformly disperse, and 272 g (4 mol of hydrogen peroxide) of a 50% aqueous hydrogen peroxide solution was added dropwise while stirring. During the addition, the temperature of the mixture was kept below 50° C., and the addition was completed after 1 hour. The mixture was kept at 30-35° C. and reacted for 3 hours to obtain a crude halogen-free peroxycarboxylic acid mixture;

[0044] (2) Then add 300 g of saturated sodium sulfate solution, stir and disperse evenly, maintain the temperature of the mixed solution below 45°C, add 400 g of cyclohexane for extraction and separation, extract the aqueous phase again with 200 g of cyclohexane once, and combine the organic phases;

[0045] (3) The combined organic phase was washed three times with a saturated sodium sulfate aqueous solution, each time with 300 g of a desaturated sodium sulfate solution until the pH of the aqueous phase was 3-4. The washed organic phase was then dried with 100 g of anhydrous sodium sulfate at room temperature of 25°C for 2 hours, filtered, and the filter residue was washed with 60 g of ethyl acetate to obtain an anhydrous peroxycyclohexanecarboxylic acid solution, which was divided into four equal parts by mass. The first three equal parts were simultaneously subjected to the subsequent tests 1-3. The fourth equal part was sealed and stored at 5-10°C for 10 days before the subsequent test of Example 4 was performed.

[0046] (4) taking an equal portion thereof (the monocarboxylic acid, i.e., cyclohexanecarboxylic acid, is 0.5 mol according to step (1), adding 34.5 g (0.1 mol) of tetramethyltetravinylcyclotetrasiloxane ([Si(CH3)(CH=CH2)O]4) at 15-20°C, stirring and mixing, and reacting at 30-35°C for 71 hours after 1 hour;

[0047] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0048] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 25°C for 4 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 60°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 70°C and distilled under a vacuum degree of -0.096 to -0.097 MPa for 0.5 hour to remove the residual solvent. The residual liquid obtained was the silicone epoxy resin.

[0049] The epoxide value of this organosilicon epoxy resin, measured using the hydrochloric acid-acetone method, was 0.683 mol / 100 g, indicating that two or more double bonds were epoxidized, resulting in a polyepoxy compound. Although the vinyl groups in the silyl vinyl group (Si-CH=CH2) are close to the methyl-containing silicon atom, the epoxidation reaction is slow, but most of the silyl vinyl groups can still be epoxidized to form epoxy groups. Theoretical calculations show that the epoxide value of tetramethyltetravinylcyclotetrasiloxane is 0.531 mol / 100 g when two double bonds are epoxidized, 0.764 mol / 100 g when three double bonds are epoxidized, and 0.979 mol / 100 g when four double bonds are epoxidized.

[0050] The spectrum measured by HNMR is ( Figure 1 ).Depend on Figure 1 It can be seen that the H peak on the vinyl group of the unreacted Si-CH=CH2 is near the chemical shift of 5.8-6.0 ppm, and the H peak of the epoxy group of the epoxidation product Si-CH(O)CH2 is near the chemical shift of 2.0-3.0 ppm. The integrated area is large and the epoxy value is high.

[0051] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - ion chromatography method), and the total halogen content of the epoxy resin was 0 ppm, which is a halogen-free silicone epoxy resin.

[0052] Example 2:

[0053] Steps (1) to (3) are the same as in Example 1, and the subsequent reactions are carried out simultaneously with Example 1;

[0054] (4) Take one aliquot of the anhydrous peroxycyclohexanecarboxylic acid solution, add 34.5 g (0.1 mol) of tetramethyltetravinylcyclotetrasiloxane at 15-20° C., stir and mix, and then react at 30-35° C. for 47 hours;

[0055] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0056] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 25°C for 4 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 60°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 70°C and distilled under a vacuum degree of -0.096 to -0.097 MPa for 0.5 hour to remove the residual solvent. The residual liquid obtained was the silicone epoxy resin.

[0057] The epoxy value of the organosilicon epoxy resin was measured by the hydrochloric acid-acetone method and was found to be 0.596 mol / 100 g.

[0058] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - ion chromatography method), and the total halogen content of the epoxy resin was 0 ppm, which is a halogen-free silicone epoxy resin.

[0059] Example 3:

[0060] Example 3-1: Low halogen polyalkenyl compound diallylphenyl allyl ether (CH2=CHCH2O-Ph(CH2CH=CH2)2)

[0061] (1) In a 1000 ml four-necked flask equipped with a reflux cooler, 174 g (1 mol) of diallylphenol, 200 ml of acetone, and 91.8 g (1.2 mol) of allyl chloride were added at room temperature, and 165.6 g (1.2 mol) of solid potassium carbonate was added under stirring. The mixture was then heated to 50° C. and reacted for 10 hours, followed by cooling.

[0062] (2) Add 1000 ml of deionized water and 200 ml of petroleum ether, stir and separate to remove the lower aqueous phase, wash the upper oil phase with 10% NaOH and centrifuge for separation twice, using 100 g of 10% NaOH each time, and finally wash with 150 g of deionized water three times until neutral, then add 20 g of anhydrous magnesium sulfate and dry at room temperature at 25°C for 8 hours, and filter;

[0063] (3) The obtained filtrate is subjected to reduced pressure distillation to remove the solvent first, and then subjected to reduced pressure distillation to evaporate the etherified liquid, which is diallylphenyl allyl ether (CH2=CHCH2O-Ph(CH2CH=CH2)2), which is set aside.

[0064] By HNMR ( Figure 2 ) and infrared spectroscopy ( Figure 3 ) were tested respectively for this low-halogen diallylphenyl allyl ether, and the spectra all showed that they were consistent with the corresponding molecular structures.

[0065] The halogen content of this compound was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products-ion chromatography), and the total halogen content was 0.50 ppm, indicating a low-halogen polyene compound.

[0066] 3-2: Epoxidation reaction

[0067] Steps (1) to (3) are the same as in Example 1, and the subsequent reactions are carried out simultaneously with Example 1;

[0068] (4) Take one aliquot of the anhydrous peroxycyclohexanecarboxylic acid solution; add 28.5 g (0.133 mol) of low-halogen diallylphenyl allyl ether (CH2=CHCH2O-Ph(CH2CH=CH2)2, total halogen content of 0.50 ppm) prepared in Example 3-1 at 15-20°C, stir and mix, and react at 30-35°C for 24 hours after 1 hour;

[0069] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0070] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 25°C for 4 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 60°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 80°C and distilled under a vacuum degree of -0.096 to -0.097 MPa for 0.5 hour to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0071] The epoxy value of this epoxy resin, measured using the hydrochloric acid-acetone method, was 0.998 mol / 100 g, indicating that two or more reactive double bonds were epoxidized to form a polyepoxy compound. The epoxidation product of diallylphenyl allyl ether with two double bonds had an epoxy value of 0.813 mol / 100 g, while the epoxidation product with three double bonds had an epoxy value of 1.145 mol / 100 g.

[0072] It can be seen that most of the allyl groups can be epoxidized, and compared with the vinyl groups on the silyl vinyl group, the allyl group is more active.

[0073] The epoxy product was tested by HNMR and IR spectroscopy. Figure 4 and Figure 5 .Depend on Figure 4 It can be seen that the chemical shift of the epoxy product is around 2.0-3.0 ppm, which is the H peak of the epoxy group of the epoxidation product -CH(O)CH2, and the integrated area is large, and the epoxy value is high. Figure 5 It can be seen that the epoxidation product is at 912 and 773 cm -1 The characteristic absorption peak of epoxy group is very obvious, with a high epoxy value.

[0074] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products-ion chromatography), and the total halogen content of the epoxy product was 0.45 ppm, which is a low-halogen polyepoxy epoxy resin.

[0075] Example 4:

[0076] (4) Anhydrous peroxycyclohexanecarboxylic acid solution stored at 5-10°C for 10 days was taken out (observed to be no significant change compared to the freshly prepared anhydrous peroxy acid solution); 28.5 g (0.133 mol) of the low-halogen diallylphenyl allyl ether prepared in Example 3-1 was added at 15-20°C, stirred and mixed, and reacted at 30-35°C for 24 hours after 1 hour;

[0077] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0078] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 25°C for 4 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 60°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 80°C and distilled under a vacuum degree of -0.096 to -0.097 MPa for 0.5 hour to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0079] The epoxy value of this epoxy resin was measured by the hydrochloric acid-acetone method to be 0.992 mol / 100 g, indicating that it is a polyepoxy compound.

[0080] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products-ion chromatography), and the total halogen content of the epoxidized polyene compound was 0.47 ppm, which is a low-halogen polyepoxy epoxy resin.

[0081] As can be seen from Example 4 above, after the peracid solution was stored for 10 days, it was observed that there was no significant change compared with the freshly prepared anhydrous peracid solution. The epoxy value of the epoxy product obtained by epoxidizing the polyene compound under the same conditions remained almost unchanged, and the peracid solution had a certain stability.

[0082] Examples 1 and 2 show that when the anhydrous peroxyacid prepared by the present invention epoxidizes the halogen-free olefin-based compound, a halogen-free, highly epoxidized epoxy resin can be obtained. During post-treatment, the epoxy group is subjected to minimal ring-opening side reactions, thereby maintaining a high epoxy value. Examples 3 and 4 show that when the anhydrous peroxyacid prepared by the present invention epoxidizes the low-halogen olefin-based compound, a low-halogen, highly epoxidized epoxy resin can be obtained. The halogen content in the product epoxy resin is slightly lower than that of the starting low-halogen olefin-based compound. At the same time, during post-treatment, the epoxy group is subjected to minimal ring-opening side reactions, thereby maintaining a high epoxy value.

[0083] Comparative Example 1: Stability of organic solvents in peroxyacids.

[0084] (1) Take 10 g of powdered meta-chloroperbenzoic acid (CPBA, concentration 80 wt%) at room temperature, add 20 g of toluene, stir evenly, and leave at room temperature for 1 day to obtain a light yellow solid.

[0085] It can be seen that the traditional use of CPBA and reactive toluene (the methyl group on the benzene ring in toluene is oxidized by peroxyacid) as organic solvents will inevitably consume peroxides and form a large amount of by-products.

[0086] (2) Take 10 g of powdered meta-chloroperbenzoic acid (CPBA, concentration 80 wt%) at room temperature, add 20 g of ethyl acetate, stir to dissolve, then add 5 g of cyclohexane. After standing at room temperature for 3 days, there is no obvious change.

[0087] This shows that ester solvents and cyclohexane also have a certain stability to the halogen-containing peroxy acid CPBA.

[0088] Comparative Example 2: Epoxidation of high halogen content by CPBA method.

[0089] (1) Take 71.2 g of 80 wt% CPBA, add 150 g of ethyl acetate, stir at room temperature to dissolve, then add 50 g of cyclohexane, add 50 g of anhydrous magnesium sulfate to dry, filter after 2 hours, and the filtrate is an anhydrous m-chloroperbenzoic acid solution;

[0090] (2) Add 21.4 g (0.1 mol) of low-halogen diallylphenyl allyl ether prepared in Example 3-1 at 15-20° C., stir and mix, and react at 30-35° C. for 24 hours after 1 hour;

[0091] (3) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0092] (4) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 25°C for 4 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 60°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent. The temperature was then raised to 80°C and the organic solvent was distilled under a vacuum degree of -0.098 to -0.099 MPa for 0.5 hour to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0093] The epoxy value of the epoxy resin measured by the hydrochloric acid-acetone method was 0.903 mol / 100 g, indicating that the epoxy resin is a polyepoxy compound.

[0094] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products-ion chromatography), and the total halogen content of this epoxy resin was 18751 ppm, which is a high-halogen epoxy resin.

[0095] The infrared spectrum of this epoxy resin is shown below Figure 6 As shown in the figure, the halogen-containing peroxy acid forms an ester group with the epoxy group of some epoxy resins after epoxidation ( Figure 6 Medium 1726cm -1 absorption peak), making it difficult to remove the halogen and the halogen content in the resin is very high.

[0096] Example 5:

[0097] (1) Under cooling at 10-20° C. in a water bath, 116 g (1 mol) of n-hexanoic acid, 330 g (3 mol) of ethylsulfonic acid, and 140 g of 70% sulfuric acid (1 mol) were mixed and stirred to uniformly disperse, and 88.4 g (1.3 mol of hydrogen peroxide) of 50% aqueous solution was added dropwise under stirring. During the addition, the temperature of the mixed solution was kept below 40° C., and the addition was completed after 1 hour. The mixed solution was kept at 20-25° C. and reacted for 20 hours to obtain a crude halogen-free peroxycarboxylic acid mixed solution;

[0098] (2) Then, 150 g of saturated ammonium sulfate solution was added, stirred and dispersed uniformly, and the temperature of the mixed solution was maintained below 45°C. 100 g of cyclohexane and 100 g of dichloroethane were added for extraction and centrifugal separation. The aqueous phase was extracted once again with 50 g of cyclohexane and 50 g of dichloroethane, and the organic phases were combined;

[0099] (3) The combined organic phases were washed three times with a saturated aqueous ammonium sulfate solution, each time with 150 g of a desaturated ammonium sulfate solution until the pH of the aqueous phase was 3-4. The washed organic phases were then dried over 30 g of anhydrous magnesium sulfate at room temperature of 30° C. for 2 hours and filtered to obtain an anhydrous peroxyhexanoic acid solution, which was divided into two equal portions, one of which was used in Example 6.

[0100] (4) Take one aliquot, add 34.5 g (0.1 mol) of tetramethyltetravinylcyclotetrasiloxane at 15-20°C, stir and mix, and after 1 hour, react at 50-55°C for 23 hours;

[0101] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0102] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 30°C for 2 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 50°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 70°C and distilled under a vacuum degree of -0.098 to -0.099 MPa for 0.5 hour to remove the residual solvent. The residual liquid obtained was the silicone epoxy resin.

[0103] The epoxy value was measured by the hydrochloric acid-acetone method and was 0.612 mol / 100 g.

[0104] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - ion chromatography method), and the total halogen content of this silicone epoxy resin was 0.85 ppm, which is a low-halogen silicone epoxy resin.

[0105] Example 6:

[0106] Steps (1) to (3) are the same as in Example 5, and the subsequent steps are carried out simultaneously with Example 5;

[0107] (4) Take another equal portion of anhydrous n-peroxyhexanoic acid prepared in Example 5, add 28.5 g (0.133 mol) of low-halogen diallylphenyl allyl ether prepared in Example 3-1 at 15-20° C., stir and mix, and react at 50-55° C. for 6 hours after 1 hour;

[0108] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0109] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 30°C for 2 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 50°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 80°C and distilled under a vacuum degree of -0.098 to -0.099 MPa for 1 hour to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0110] The epoxy value was measured by the hydrochloric acid-acetone method and was 0.908 mol / 100 g.

[0111] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - ion chromatography), and the total halogen content of this epoxy resin was 1.96 ppm, which is a low-halogen epoxy resin.

[0112] Example 7:

[0113] (1) Under cooling at 10-20° C. in a water bath, 116 g (1 mol) of hexanoic acid, 122 g (1 mol) of benzoic acid, 76.8 g (0.8 mol) of methanesulfonic acid, and 21 g (0.2 mol) of 60% nitric acid were mixed and stirred to uniformly disperse, and 340 g (5 mol of hydrogen peroxide) of 50% aqueous hydrogen peroxide solution was added dropwise under stirring. During the addition, the temperature of the mixed solution was kept below 50° C., and the addition was completed after 1 hour. The mixed solution was kept at 25-30° C. to react for 4 hours to obtain a crude halogen-free peroxycarboxylic acid mixed solution;

[0114] (2) Then, 200 g of saturated ammonium sulfate solution was added, stirred and dispersed uniformly, and the temperature of the mixed solution was maintained below 50° C., 400 g of dichloroethane and 100 g of cyclohexane were added for extraction and separation, and the aqueous phase was extracted once again with 200 g of dichloroethane and 50 g of cyclohexane, and the organic phases were combined;

[0115] (3) The combined organic phases were washed three times with a saturated aqueous ammonium sulfate solution, each time with 200 g of a desaturated ammonium sulfate solution until the pH of the aqueous phase was 3-4. The washed organic phases were then dried over 50 g of anhydrous magnesium sulfate at room temperature at 20° C. for 2 hours, filtered, and the filter residue was washed with 50 g of propyl acetate to obtain an anhydrous peracid solution, which was divided into three equal portions. One equal portion was subjected to the subsequent test of Example 1, and the other two equal portions were simultaneously subjected to the test of step (4) of Examples 8-9.

[0116] (4) Take one aliquot of the mixture, add 32.1 g (0.15 mol) of low-halogen diallylphenyl allyl ether (halogen content 0.50 ppm) at 10-15°C, stir and mix, and react at 30-35°C for 23 hours after 1 hour;

[0117] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0118] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 30°C for 2 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 50°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 80°C and distilled under a vacuum degree of -0.098 to -0.099 MPa for 1 hour to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0119] The epoxy value was measured by the hydrochloric acid-acetone method and was 1.09 mol / 100 g.

[0120] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - Ion chromatography method), and the total halogen content of this epoxy resin was 1.5ppm, which is a low-halogen epoxy resin.

[0121] Example 8:

[0122] 8-1: Low halogen bisphenol A diallyl ether

[0123] Preparation of (CH2=CHCH2O-Ph-C(CH3)2-Ph-O-CH2CH=CH2)

[0124] Proceed with reference to the method of Example 3-1:

[0125] (1) In a 1000 ml four-necked flask equipped with a reflux cooler, 114 g (0.5 mol) of bisphenol A, 200 ml of acetone, and 91.8 g (1.2 mol) of allyl chloride were added at room temperature, and 165.6 g (1.2 mol) of solid potassium carbonate was added under stirring. The mixture was then heated to 50° C. and reacted for 18 hours, followed by cooling.

[0126] (2) Add 1000 ml of deionized water and 300 ml of toluene, stir and separate to remove the lower aqueous phase, wash the upper oil phase with 10% NaOH and centrifuge for separation twice, using 100 g of 10% NaOH each time, and finally wash with 150 g of deionized water three times until neutral, then add 20 g of anhydrous magnesium sulfate, dry at room temperature at 25°C for 8 hours, and filter;

[0127] (3) The obtained filtrate is subjected to reduced pressure distillation to remove the solvent to obtain the residue which is bisphenol A diallyl ether (CH2=CHCH2O-Ph-C(CH3)2-Ph-O-CH2CH=CH2).

[0128] The halogen content of this compound was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products-ion chromatography), and the total halogen content was 0.89 ppm, indicating a low-halogen diene compound.

[0129] 8-2: Epoxidation reaction

[0130] Steps (1) to (3) are the same as in Example 7;

[0131] (4) Take out an equal portion of the anhydrous peroxy acid prepared in Example 7 and add 46.2 g (0.15 mol) of low-halogen bisphenol A diallyl ether at 10-15°C.

[0132] (CH2=CHCH2O-Ph-C(CH3)2-Ph-O-CH2CH=CH2, total halogen content is 0.89ppm), stirred and mixed, and reacted at 45-50°C for 10 hours;

[0133] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0134] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 30°C for 2 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 50°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 90°C and distilled under a vacuum degree of -0.098 to -0.099 MPa for 1 hour to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0135] The epoxy value of the epoxy resin was measured by the hydrochloric acid-acetone method to be 0.575 mol / 100 g, which is close to the complete oxidation of the two allyl groups (the epoxy value of the completely epoxidized epoxy resin is 0.588 mol / 100 g).

[0136] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - Ion chromatography method), and the total halogen content of this epoxy resin was 2.9ppm, which is a low-halogen epoxy resin;

[0137] Example 9:

[0138] 9-1: Preparation of low-halogen polyalkenyl compound 2,2'-diallylbisphenol A diallyl ether (CH2=CHCH2O-Ph(CH2CH=CH2)-C(CH3)2-Ph(CH2CH=CH2)-O-CH2CH=CH2)

[0139] Proceed with reference to the method of Example 8-1:

[0140] (1) In a 1000 ml four-necked flask equipped with a reflux cooling device, 154 g (0.5 mol) of 2,2'-diallylbisphenol A, 300 ml of acetone, and 91.8 g (1.2 mol) of allyl chloride were added at room temperature, and 165.6 g (1.2 mol) of solid potassium carbonate was added under stirring. The mixture was then heated to 50°C and reacted for 24 hours, followed by cooling.

[0141] (2) Add 1000 ml of deionized water and 300 ml of toluene, stir and separate to remove the lower aqueous phase, wash the upper oil phase with 10% NaOH and centrifuge for separation twice, using 100 g of 10% NaOH each time, and finally wash with 150 g of deionized water three times until neutral, then add 20 g of anhydrous magnesium sulfate, dry at room temperature at 25°C for 8 hours, and filter;

[0142] (3) The obtained filtrate is subjected to reduced pressure distillation to remove the solvent to obtain the residue which is 2,2'-diallylbisphenol A diallyl ether (CH2=CHCH2O-Ph(CH2CH=CH2)-C(CH3)2-Ph(CH2CH=CH2)-O-CH2CH=CH2).

[0143] The halogen content of this compound was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products-ion chromatography), and the total halogen content was 0.93 ppm, which was a low-halogen tetraallyl organic compound.

[0144] 9-2: Epoxidation reaction

[0145] Steps (1) to (3) are the same as in Example 7;

[0146] (4) Take out one equal portion of the anhydrous peroxy acid prepared in Example 7, add 77.6 g (0.2 mol) of low-halogen 2,2'-diallylbisphenol A diallyl ether (CH2=CHCH2O-Ph(CH2CH=CH2)-C(CH3)2-Ph(CH2CH=CH2)-O-CH2CH=CH2, total halogen content of 0.93 ppm) at 10-15°C, stir and mix, and react at 30-35°C for 47 hours;

[0147] (5) cooling, filtering, and washing the filtrate with 10% inorganic NaOH aqueous solution and 5% sodium sulfite solution multiple times, with the temperature of the mixed solution not exceeding 40° C. each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase;

[0148] (6) The organic phase was dried over 50 g of anhydrous magnesium sulfate at room temperature at 30°C for 2 hours, filtered, and the filtrate was subjected to reduced pressure distillation. The organic solvent was first distilled at 50°C under a vacuum degree of -0.06 to -0.07 MPa to recover the organic solvent, and then the temperature was raised to 90°C and the reduced pressure distillation was carried out at a vacuum degree of -0.098 to -0.099 MPa for 1.5 hours to remove the residual solvent. The residual liquid obtained was epoxy resin.

[0149] Its epoxy value, measured using the hydrochloric acid-acetone method, is 0.616 mol / 100 g. The number of epoxy groups is between 2 and 3 (the epoxy value of the product of epoxidation of two olefin groups in 2,2'-diallyl bisphenol A diallyl ether is 0.476 mol / 100 g, and the epoxy value of the product of epoxidation of three olefin groups is 0.688 mol / 100 g), making it a polyepoxy epoxy resin.

[0150] The halogen content was tested (GB / T37861-2019 Determination of halogen content of electronic and electrical products - Ion chromatography method), and the total halogen content of this epoxy resin was 3.7 ppm, which is a low-halogen epoxy resin.

[0151] As can be seen from the test results of the above examples, the present invention uses C5-C10 halogen-free monocarboxylic acids to prepare an anhydrous peroxyacid solution, and epoxidizes halogen-free or low-halogen di- or polyolefin-based compounds. The entire process does not introduce an organic metal catalyst, and can produce high-epoxy value and halogen-free or low-halogen high-purity epoxy resins. The halogen content is less than 10 ppm, which is much lower than the halogen content of several hundred ppm in the low-halogen epoxy resins of the prior art.

[0152] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for preparing a halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid, characterized in that: The method comprises the following preparation steps: (1) Under cooling at 5-30°C in a water bath, first mix and stir the C5-C10 halogen-free monocarboxylic acid and liquid strong acid to disperse uniformly, then add hydrogen peroxide solution dropwise while stirring, keeping the temperature of the mixture not exceeding 50°C during the addition process. After the addition is completed, keep the mixture at 10-40°C for 3-24 hours to obtain a crude halogen-free peroxycarboxylic acid mixture; (2) Then add sulfate solid or saturated solution, stir and disperse evenly, maintain the temperature of the mixed solution below 50°C, add non-water-soluble organic solvent to perform extraction and liquid separation or / and centrifugal separation, re-extract the aqueous phase with non-water-soluble organic solvent or / and centrifuge for 1-2 times, and combine the organic phases; (3) washing the combined organic phases 2 to 4 times with a saturated sulfate aqueous solution until the pH of the aqueous phase is 3 to 6, drying the washed organic phases, filtering, and washing the filter residue with an ester solvent and / or the organic solvent in step (2), or without washing the filter residue, to obtain an anhydrous peroxycarboxylic acid solution; (4) stirring and mixing the olefin compound and the anhydrous peroxycarboxylic acid solution at 15-60° C. and reacting for 6-72 hours in a molar ratio of the active olefin group to the monocarboxylic acid charged in step (1) of 1:0.5-2.5, wherein the active olefin group is C=C, excluding the benzene ring; (5) Cooling, filtering, and washing the filtrate multiple times, with the temperature of the mixed solution not exceeding 40°C each time, and finally washing with deionized water multiple times until the pH value is neutral to obtain an organic phase; (6) The organic phase is dried and filtered, and the filtrate is subjected to reduced pressure distillation to recover the distillate organic solvent. The residue obtained is a halogen-free or low-halogen anti-corrosion epoxy resin; The C5-C10 halogen-free monocarboxylic acid in step (1) is a halogen-free monocarboxylic acid containing an alicyclic, aliphatic or aromatic group; The olefinic compound in step (4) is a halogen-free or low-halogen compound containing an olefinic group, wherein the olefinic group is R 1 R 2 C=CR 3 -, where R 1 ,R 2 ,R 3 =H or alkyl, selected from organosilicon compounds containing vinyl or allyl groups and non-silicon compounds containing vinyl, allyl or 2-propenyl groups.

2. The preparation method according to claim 1, characterized in that The C5-C10 halogen-free monocarboxylic acid in step (1) includes one or more of cyclohexanecarboxylic acid, cyclohexylacetic acid, 3-cyclohexylpropionic acid, 4-cyclohexylbutyric acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, benzoic acid, phenylacetic acid, and 3-phenylpropionic acid; The vinyl or allyl organosilicon compound in step (4) is one or more of triallylphenylsilane, trivinylphenylsilane, tetraallylsilane, trivinyltrimethylcyclotrisiloxane, tetravinyltetramethylcyclotetrasiloxane, methylvinylpolysiloxane, methylvinylphenylpolysiloxane and methylallylpolysiloxane; The non-silicon compound containing vinyl, allyl or 2-propenyl is one or more of divinylbenzene, trivinylbenzene, allylphenyl allyl ether, diallylphenyl allyl ether, di(2-propenyl)phenyl-2-propenyl ether, bisphenol A diallyl ether, 2,2'-diallylbisphenol A diallyl ether, and bis or polymaleimides.

3. The preparation method according to claim 1, wherein The liquid strong acid in step (1) is one or more of C1-C3 n-alkylsulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, nitric acid or their aqueous solutions with a concentration of 60 wt % or more.

4. The preparation method according to claim 3, characterized in that In step (1), the molar ratio of the C5-C10 halogen-free monocarboxylic acid to the liquid strong acid and hydrogen peroxide is 1:0.5-5:1-3, where the molar ratio is based on pure acid and hydrogen peroxide; The aqueous hydrogen peroxide solution in step (1) is an aqueous hydrogen peroxide solution with a content of more than 30 wt %.

5. The preparation method according to claim 4, characterized in that The non-water-soluble organic solvent in step (2) is cyclohexane, methylcyclohexane, ethylcyclohexane, n-hexane, n-heptane, dichloroethane, or chloroform; the ester solvent includes one or more of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, and ethyl butyrate, and the total amount of the organic solvent is 2 to 10 times the total mass of the monocarboxylic acid.

6. The preparation method according to claim 5, characterized in that The sulfate in step (2) is ammonium sulfate, sodium sulfate, or potassium sulfate; The drying is carried out using an inorganic desiccant, wherein the inorganic desiccant is anhydrous sodium sulfate or anhydrous magnesium sulfate, the drying time is 1 to 12 hours, and the temperature is room temperature.

7. The preparation method according to claim 6, characterized in that The washing in step (5) is performed multiple times with an inorganic alkali aqueous solution and an inorganic reducing agent solution, wherein the inorganic alkali aqueous solution is an aqueous solution of potassium carbonate, sodium carbonate, potassium hydroxide, or sodium hydroxide containing less than 30 wt %, and the inorganic reducing agent solution is an aqueous solution of sulfite or thiosulfate containing 2 to 15 wt %; The reduced pressure distillation temperature does not exceed 100° C., and the reduced pressure distillation vacuum degree is -0.06 to -0.0998 MPa.

8. A halogen-free or low-halogen anti-corrosion epoxy resin prepared by epoxidation of an olefin-based anhydrous peroxy acid, characterized in that: Prepared by the method according to any one of claims 1 to 7.

9. Use of the halogen-free or low-halogen anti-corrosion epoxy resin according to claim 8 in the fields of electronics and new energy, anti-corrosion adhesives, packaging materials and protective materials.

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