Alkyl-substituted aromatic hydrocarbon modified epoxy resin and preparation method thereof

Abstract

The invention discloses alkyl-substituted aromatic hydrocarbon modified epoxy resin and a preparation method thereof, and relates to the technical field of resin. The molecular structural formula of the alkyl substituted aromatic hydrocarbon modified epoxy resin disclosed by the invention is as follows: # imgabs0 #. The synthesized alkyl-substituted aromatic hydrocarbon modified epoxy resin contains more alkyl substituent groups, so that the synthesized modified epoxy resin integrally has lower polarity and excellent electrochemical performance. In addition, in the synthesis process of the alkyl substituted aromatic hydrocarbon modified epoxy resin, any highly toxic gas raw material is not adopted, and a large amount of harmful waste liquid is not generated in the synthesis process; the synthesis reaction difficulty is low, the potential safety hazard is low, the operation is simple and convenient, and the industrial large-scale production is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of resins, and in particular to a modified epoxy resin and a preparation method thereof; more particularly, the present invention relates to an alkyl-substituted aromatic hydrocarbon-modified epoxy resin and a preparation method thereof. Background Art

[0002] Epoxy resins have excellent mechanical properties, electrical insulation, and adhesion, and are widely used in various fields such as coatings, adhesives, laminates, and electronic packaging. The NC-2000 and NC-3000 series epoxy resins invented by Nippon Kayaku Co., Ltd. have structures shown in Formulas 1 and 2, respectively:

[0003]

[0004] Formula 1;

[0005]

[0006] Formula 2.

[0007] Conventional general-purpose novolac epoxy resins include phenol-type novolac epoxy resins and o-cresol-type novolac epoxy resins, and their structures are shown in Formula 3 and Formula 4, respectively:

[0008]

[0009] Formula 3;

[0010]

[0011] Formula 4.

[0012] As can be seen, the main difference between the molecular structure of NC-2000 and NC-3000 epoxy resins and general-purpose novolac epoxy resins is the insertion of a low-polarity benzene ring or biphenyl structure between the phenol-epoxy groups. Therefore, compared with traditional novolac epoxy resins, NC-2000 and NC-3000 epoxy resins have better electrical properties, such as low dielectric constant and low dielectric loss.

[0013] Taking the synthesis of NC-2000 epoxy resin as an example, the prior art generally uses p-xylene as a raw material, first synthesizing p-dichlorobenzyl (structural formula shown in Formula 5 below) through a free radical chlorination reaction; then the p-dichlorobenzyl is further hydrolyzed into p-xylene dimethanol (structural formula shown in Formula 6 below); then the p-xylene dimethanol is reacted with phenol under strongly acidic conditions to synthesize a polyphenol compound (structural formula shown in Formula 7 below); finally, the polyphenol compound is reacted with epichlorohydrin to obtain the target product; wherein:

[0014]

[0015] Formula 5;

[0016]

[0017] Formula 6;

[0018]

[0019] Formula seven.

[0020] The above-mentioned synthesis reaction has the following problems or drawbacks: the reaction process requires the use of highly toxic chlorine as a raw material, and the chlorination reaction produces a large amount of waste hydrochloric acid. In addition, the above-mentioned synthesis reaction requires a reaction vessel that can withstand strong acid corrosion. In summary, the above-mentioned synthesis reaction is difficult, requires high equipment requirements, and is highly dangerous.

[0021] Based on the above reasons, this application is filed. Summary of the Invention

[0022] Based on the above reasons, in view of the problems or defects existing in the prior art, the purpose of the present invention is to provide a class of alkyl-substituted aromatic hydrocarbon-modified epoxy resins and a preparation method thereof, so as to solve or at least partially solve the above technical defects existing in the prior art: in the process of synthesizing the alkyl-substituted aromatic hydrocarbon-modified epoxy resin of the present invention, no highly toxic gas raw materials are used, and no large amount of harmful waste liquid is generated during the synthesis process; and the synthesis reaction of the present invention is low in difficulty, has low safety hazards, and is simple to operate, which is conducive to industrial large-scale production; in addition, the alkyl-substituted aromatic hydrocarbon-modified epoxy resin synthesized by the present invention has lower polarity and better electrochemical performance.

[0023] In order to achieve one of the above purposes of the present invention, the technical solution adopted by the present invention is as follows:

[0024] The present invention provides an alkyl-substituted aromatic hydrocarbon modified epoxy resin, the molecular structure of which is shown in the following formula VIII: wherein: A represents an alkyl-substituted aromatic hydrocarbon compound; -OG represents ; B represents a substituted or unsubstituted phenolic compound;

[0025] ;

[0026] Formula eight.

[0027] Specifically, in the above technical solution, in Formula 8, the H on the aromatic ring of A is substituted by a substituent R, which can be monosubstituted, disubstituted or polysubstituted; (n) Where n is an integer of 1 to 4, representing the number of aromatic ring substituents R on the aromatic ring A; the substituents R at different substitution positions are the same or different; the substituent R is C1 to C 10 of alkyl.

[0028] Specifically, in the above technical solution, in Formula 8, the phenolic compound is an aromatic hydrocarbon compound containing a phenolic hydroxyl group, and the H on the aromatic ring B is substituted by a substituent R or is unsubstituted, and the substitution can be monosubstituted, disubstituted or polysubstituted; R on the aromatic ring B is (m) Where m is an integer of 0 to 4; represents the number of substituents R on the aromatic ring B; the substituents R at different substitution positions are the same or different; the substituent R is C1 to C 10 of alkyl.

[0029] Specifically, the above technical solution is as follows: （n） In the process, OG is synthesized by reacting an aromatic hydrocarbon compound containing a phenolic hydroxyl group with epichlorohydrin; OG （n） Here, n represents the number of phenolic hydroxyl group-containing aromatic hydrocarbon compounds substituted by phenolic hydroxyl groups, which can be monosubstituted, disubstituted or polysubstituted; n is an integer of 1 to 4.

[0030] Furthermore, in the above technical solution, in the structural formula of formula 8, n represents the average degree of polymerization, and the value of n is any value between 1 and 50.

[0031] Preferably, in the above technical solution, the average degree of polymerization n is any value between 1 and 10.

[0032] Further preferably, in the above technical solution, the average degree of polymerization n is any value between 1.5 and 5.

[0033] Furthermore, in the above technical solution, the molecular structure of the alkyl-substituted aromatic hydrocarbon modified epoxy resin is shown in Formula 9 below:

[0034]

[0035] Formula nine.

[0036] It can be seen that the structure of the alkyl-substituted aromatic hydrocarbon-modified epoxy resin shown in Formula 9 is basically similar to that of the NC-2000 epoxy resin, except that the benzene ring of the intermediate structure contains more alkyl substituents. It is precisely based on the design of this special structure that the modified epoxy resin synthesized by the present invention has lower polarity and excellent electrochemical properties as a whole.

[0037] A second object of the present invention is to provide a method for preparing the above-mentioned alkyl-substituted aromatic hydrocarbon-modified epoxy resin, the method comprising the following steps:

[0038] (1) Alkyl-substituted aromatic hydrocarbon compounds and aldehyde compounds are used as reaction materials, and addition reaction occurs under strong acid conditions to generate aromatic hydrocarbon resins;

[0039] (2) using the aromatic hydrocarbon resin and phenolic compound as reaction raw materials, a polycondensation reaction occurs under strong acid conditions to generate a polyphenol compound;

[0040] (3) using the polyphenol compound and epichlorohydrin as reaction materials, a condensation reaction occurs in the presence of an acid-binding agent to generate the alkyl-substituted aromatic hydrocarbon modified epoxy resin;

[0041] Alternatively, the polyphenol compound is reacted with allyl chloride and peroxyacetic acid in sequence to generate the alkyl-substituted aromatic hydrocarbon modified epoxy resin.

[0042] Furthermore, in the above technical solution, in the alkyl-substituted aromatic hydrocarbon compound in step (1), the aromatic hydrocarbon is benzene or a condensed-ring aromatic hydrocarbon, and the aromatic ring of the aromatic hydrocarbon contains at least one vacant site available for reaction.

[0043] Specifically, in the above technical solution, the condensed-ring aromatic hydrocarbon refers to a polycyclic organic compound composed of two or more benzene rings sharing a ring edge. For example, the condensed-ring aromatic hydrocarbon can be at least one of naphthalene, anthracene, phenanthrene, pyrene, or higher condensed-ring aromatic hydrocarbons.

[0044] Furthermore, in the above technical solution, the alkyl-substituted aromatic hydrocarbon compound in step (1) is at least one of an alkyl-substituted benzene compound, an alkyl-substituted naphthalene compound, an alkyl-substituted anthracene compound, an alkyl-substituted phenanthrene compound or an alkyl-substituted pyrene compound.

[0045] Specifically, the structural formula of the alkyl-substituted aromatic hydrocarbon compounds described in some aspects of the present invention is shown in Formula 10 below.

[0046] ; ; ;

[0047] (A) (B) (C)

[0048] ;

[0049] (D) (E)

[0050] Formula 10.

[0051] Furthermore, in the above technical solution, the aromatic ring in the alkyl-substituted aromatic hydrocarbon compound in step (1) is preferably a benzene ring structure. That is, the alkyl-substituted aromatic hydrocarbon compound is an alkyl-substituted benzene compound, as shown in (A) in Formula 10.

[0052] Specifically, in Formula 10 (A), H on the benzene ring is monosubstituted, disubstituted, trisubstituted, tetrasubstituted or pentasubstituted by a substituent R; n is an integer from 1 to 5, and n represents the number of substituents R on the benzene ring; when n=1, it means that H on the benzene ring is monosubstituted by a substituent R; when n=2, it means that H on the benzene ring is disubstituted by a substituent R; when n=3, it means that H on the benzene ring is trisubstituted by a substituent R; when n=4, it means that H on the benzene ring is tetrasubstituted by a substituent R; when n=5, it means that H on the benzene ring is pentasubstituted by a substituent R; the substituents R at different substitution positions are the same or different; the substituent R is C1~C 10 of alkyl.

[0053] Preferably, in the above technical solution, n is 2 to 3.

[0054] Preferably, in the above technical solution, when n=2, the disubstitution is meta-disubstitution, that is, 1,3-alkylbenzene.

[0055] Preferably, in the above technical solution, when n=3, the tri-substitution is o-, m-, and p-tri-substitution, that is, 1,3,5-alkylbenzene.

[0056] More preferably, the alkyl-substituted benzene compound is a composition, comprising 1,3-alkylbenzene and 1,3,5-alkylbenzene, wherein the total mass of the 1,3-alkylbenzene and 1,3,5-alkylbenzene is not less than 30% of the total mass of the composition.

[0057] More preferably, the alkyl-substituted benzene compound is a composition, comprising 1,3-alkylbenzene and 1,3,5-alkylbenzene, wherein the total mass of the 1,3-alkylbenzene and 1,3,5-alkylbenzene is greater than 60% of the total mass of the composition.

[0058] Preferably, in the above technical solution, the substituent R is a C1~C4 alkyl group.

[0059] More preferably, in the above technical solution, the substituent R is a C1 alkyl group.

[0060] Similarly, in the compounds represented by (B), (C), (D) or (E) in Formula 10, the H on the naphthalene ring, anthracene ring, phenanthrene ring or pyrene ring is monosubstituted, disubstituted, trisubstituted, tetrasubstituted or pentasubstituted by a substituent R; n is an integer from 1 to 5, and n represents the number of substituents R on the naphthalene ring, anthracene ring, phenanthrene ring or pyrene ring; when n=1, it means that the H on the naphthalene ring, anthracene ring, phenanthrene ring or pyrene ring is monosubstituted by a substituent R; when n=2, it means that the H on the naphthalene ring , anthracene, phenanthrene or pyrene ring is disubstituted by a substituent R; when n=3, it means that the H on the naphthalene ring, anthracene ring, phenanthrene ring or pyrene ring is trisubstituted by a substituent R; when n=4, it means that the H on the naphthalene ring, anthracene ring, phenanthrene ring or pyrene ring is tetrasubstituted by a substituent R; when n=5, it means that the H on the naphthalene ring, anthracene ring, phenanthrene ring or pyrene ring is pentasubstituted by a substituent R; the substituents R at different substitution positions are the same or different; the substituent R is C1~C 10 of alkyl.

[0061] Furthermore, in the above technical solution, the aldehyde compound in step (1) is a C1~C20 aldehyde compound.

[0062] Furthermore, in the above technical solution, the aldehyde compound is a C1~C10 aldehyde compound.

[0063] Preferably, in the above technical solution, the aldehyde compound is formaldehyde, polyoxymethylene (POM) and aldehydes that can provide formyl groups, such as benzaldehyde.

[0064] Further preferably, in the above technical solution, the aldehyde compound is formaldehyde or polyoxymethylene.

[0065] Furthermore, in the above technical solution, the molar ratio of the alkyl-substituted aromatic hydrocarbon compound to the aldehyde compound in step (1) is 1:(1-3), preferably 1:2.

[0066] Furthermore, in the above technical solution, the molar ratio of the alkyl-substituted aromatic hydrocarbon compound to the strong acid in step (1) is 4:1.

[0067] Furthermore, in the above technical solution, the phenolic compound in step (2) is an aromatic hydrocarbon compound containing 1 to 4 phenolic hydroxyl groups.

[0068]

[0069] Formula 12;

[0070] Wherein: Ar2- represents an aromatic ring, including a substituted or unsubstituted benzene ring or a condensed ring, and the substituted group is an alkyl group; the H on the aromatic ring is monosubstituted, disubstituted, trisubstituted or tetrasubstituted by a phenolic hydroxyl group (-OH); n is an integer from 1 to 4, and n represents the number of phenolic hydroxyl groups on the aromatic ring; when n=1, it means that the H on the aromatic ring is monosubstituted by a phenolic hydroxyl group; when n=2, it means that the H on the aromatic ring is disubstituted by a phenolic hydroxyl group; when n=3, it means that the H on the aromatic ring is trisubstituted by a phenolic hydroxyl group; when n=4, it means that the H on the aromatic ring is tetrasubstituted by a phenolic hydroxyl group.

[0071] Furthermore, in the above technical solution, the condensed ring is at least one of a naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring or other higher condensed rings.

[0072] Preferably, in the above technical solution, Ar2- is a benzene ring or a naphthalene ring; more preferably, it is a benzene ring.

[0073] Furthermore, in the above technical solution, the alkyl group is C1~C 10 of alkyl.

[0074] Preferably, in the above technical solution, the alkyl group is a C1~C4 alkyl group, more preferably a C1 alkyl group.

[0075] Furthermore, in the above technical solution, when Ar2- is a benzene ring, the number of alkyl substitutions on the benzene ring is 0 to 4.

[0076] Furthermore, in the above technical solution, when Ar2- is a naphthalene ring, the number of alkyl substitutions on the naphthalene ring is 0 to 6.

[0077] Furthermore, in the above technical solution, when Ar2- is an anthracene ring, a phenanthrene ring, a pyrene ring or a higher condensed ring, the aromatic ring Ar2- contains at least one vacant position available for substitution.

[0078] Furthermore, in the above technical solution, the phenolic compound is at least one of phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, 2,6-diethylphenol, 2,6-diisopropylphenol, resorcinol, phloroglucinol, 1-naphthol, 2-naphthol, 1,9-dinaphthol, 2,8-dinaphthol, 1,8-dinaphthol, etc.

[0079] Furthermore, in the above technical solution, the mass ratio of the strong acid to the phenolic compound in step (2) is 1-5:100. In a preferred embodiment of the present invention, the mass ratio of the strong acid to the phenolic compound is 3:100.

[0080] Furthermore, in the above technical solution, the molar ratio of the aromatic hydrocarbon resin to the phenolic compound in step (2) is (0-1):1, but not equal to 0.

[0081] Furthermore, in the above technical solution, the strong acid in step (1) and step (2) is at least one of concentrated sulfuric acid or concentrated hydrochloric acid.

[0082] Specifically, in the above technical solution, the method of sequentially reacting the polyphenol compound with allyl chloride and peroxyacetic acid to produce the target product in step (3) is an allyl peroxide method. The mechanism of the allyl peroxide method is as follows: first, the polyphenol compound is reacted with allyl chloride and an acid-binding agent to produce an allyl ether, and then the allyl ether is reacted with peroxyacetic acid to produce the alkyl-substituted aromatic hydrocarbon-modified epoxy resin.

[0083] Furthermore, in the above technical solution, the acid binding agent in step (3) is selected from one of triethylamine, pyridine, sodium hydroxide or sodium carbonate.

[0084] Furthermore, in the above technical solution, in step (3), the mass ratio of epichlorohydrin to polyphenol compound is (1-10): 1. In a preferred embodiment of the present invention, the mass ratio of epichlorohydrin to polyphenol compound is (1-5): 1.

[0085] Furthermore, in the above technical solution, in step (3), the mass ratio of the acid-binding agent to the polyphenol compound is 0.1-1:1. In a preferred embodiment of the present invention, the mass ratio of the acid-binding agent to the polyphenol compound is 0.1-0.5:1.

[0086] Furthermore, in the above technical solution, the mass ratio of the allyl chloride to the polyphenol intermediate 1 in step (3) is (0.1-1):1.

[0087] Compared with the prior art, the present invention has the following beneficial effects:

[0088] (1) The alkyl-substituted aromatic hydrocarbon modified epoxy resin synthesized in the present invention contains more alkyl substituents, so that the modified epoxy resin synthesized in the present invention has lower polarity and excellent electrochemical properties as a whole.

[0089] (2) No highly toxic gas raw materials are used in the process of synthesizing the alkyl-substituted aromatic hydrocarbon-modified epoxy resin of the present invention, and no large amount of hazardous waste liquid is generated during the synthesis process; and the synthesis reaction of the present invention has low difficulty, low safety risks, and simple operation, which is conducive to industrial large-scale production.

[0090] (3) The alkyl-substituted aromatic hydrocarbon modified epoxy resin synthesized in the present invention has low polarity and better electrical properties. DETAILED DESCRIPTION

[0091] The present invention is further described in detail below through an implementation case. This implementation case is implemented based on the technology of the present invention. Detailed implementation methods and specific operating procedures are now given to illustrate the creativity of the present invention, but the protection scope of the present invention is not limited to the following implementation case.

[0092] Based on the information contained in this application, it will be readily apparent to those skilled in the art that various changes can be made to the precise description of the present invention. It should be understood that the scope of the present invention is not limited to the defined processes, properties, or components, as these embodiments and other descriptions are provided only to illustrate specific aspects of the present invention.

[0093] In order to better understand the present invention and not to limit the scope of the present invention, all numbers used in this application to express amounts, percentages, and other numerical values should be understood to be modified by the word "about" in all cases. Therefore, unless otherwise specified, the numerical parameters listed in the specification are approximate values, which may be changed according to the different ideal properties to be obtained. Each numerical parameter should at least be regarded as obtained based on the reported significant figures and by conventional rounding methods.

[0094] The equipment and raw materials used in the present invention can be purchased from the market or are commonly used in the art. The methods in the following examples are all conventional methods in the art unless otherwise specified.

[0095] H Magnetic Resonance Spectroscopy ( 1 H-NMR) characterization and analysis

[0096] The proton spectrum is the most common spectrum. Proton NMR spectra can provide important structural information, including chemical shifts, coupling constants, peak splitting, and peak area. Peak area is proportional to the number of hydrogen atoms, so it can quantitatively reflect the information about hydrogen nuclei.

[0097] The nuclear magnetic resonance hydrogen spectrum testing method used in the present invention is as follows:

[0098] 15 mg of the internal standard was dissolved in 750 μL of deuterated chloroform (CDCl3). The resulting solution was placed in the sample feeder of a nuclear magnetic resonance instrument (Bruker AVANCE 500NMR). After shimming, analysis was performed using a 5 mm probe (BBFO Smart probe). Tetramethylsilane was used as the reference substance, with a resonance frequency of 500 MHz, a pulse width of 10 μs, a pulse delay of 2 seconds, 32 accumulations, and a chemical shift of 0 ppm. Scanning was performed at 25°C. The internal standard can be the resin prepared in each step of each example, such as m-xylene resin, a polyphenol intermediate, or an epoxy resin.

[0099] Example 1

[0100] The present embodiment provides a method for preparing an alkyl-substituted aromatic hydrocarbon-modified epoxy resin, the method comprising the following steps:

[0101] (1) Synthetic meta-xylene resin

[0102] 1 mol of meta-xylene, 162 g of a 37% formaldehyde aqueous solution (2 mol of formaldehyde), and 0.25 mol of concentrated sulfuric acid (98% concentration) are sequentially added to a reactor 1; after the addition is completed, the mixture is mixed evenly, and the resulting mixed reaction solution 1 is refluxed at 100-110° C. for 4 hours, and toluene is added to the reaction system; the reaction is continued for 2 hours; after the reaction is completed, the resulting product is allowed to stand, separated, and the lower acid liquid is separated; the resulting upper organic layer is washed with hot water 2-3 times; the solvent and a small amount of unreacted meta-xylene are distilled off at approximately 90 kPa and 150° C. to obtain 160 g of the meta-xylene resin, and then the meta-xylene resin is completely dissolved in 500 mL of toluene to obtain a toluene solution of the meta-xylene resin; wherein the mass of the added toluene is 30% of the mass of the mixed reaction solution 1.

[0103] (2) Synthesis of polyphenol intermediate 1 using phenol and m-xylene resin as raw materials

[0104] 300 g of phenol and 24.3 g of 37 wt % concentrated hydrochloric acid were sequentially added to a reaction kettle 2, and the obtained mixed reaction liquid 2 was heated to 110° C. Then, the entire toluene solution of the meta-xylene resin obtained in step (1) was added to the reaction system in batches, and the mixture was reacted at reflux temperature for 5 hours. After the reaction was completed, the solvent and residual phenol, the generated water and the catalyst hydrogen chloride were evaporated under reduced pressure to obtain the polyphenol intermediate 1.

[0105] (3) Synthesize epoxy resin 1 using polyphenol intermediate 1 and epichlorohydrin as raw materials

[0106] 205 g of the polyphenol intermediate 1 obtained in step (2) and 370 g of epichlorohydrin were added to a reactor 3 in sequence, stirred and dissolved uniformly to obtain a mixed reaction solution 3; then 100 g of a 40% NaOH aqueous solution was added dropwise to the mixed reaction solution 3, and the pressure of the reaction system was controlled to -0.6±0.1 bar to allow water and epichlorohydrin in the reaction system to azeotrope; while the NaOH aqueous solution was added dropwise, water in the reaction system was removed through a water separator, and the epichlorohydrin was returned to the reactor 3, and the reaction was carried out at 60±5°C for 6 hours. After the reaction was completed, the obtained product was washed with water, distilled, and refined in sequence to obtain epoxy resin 1.

[0107] Structural test results and analysis

[0108] (1) The m-xylene resin prepared in step (1) of Example 1 was 1 The results of H-NMR characterization are shown in Table 1.

[0109] Table 1 Meta-xylene resin prepared in Example 1 1 H-NMR test results table

[0110]

[0111] As can be seen from Table 1, 1 In H-NMR, hydrogen on the carbon of the benzene ring produces multiple peak signals with chemical shifts at 6.9~7.1ppm and an integrated area of 100; the αH of the diether carbon-oxygen single bond produces a single peak signal with a chemical shift at 4.59ppm and an integrated area of 6.1; the methylene hydrogen of benzyl alcohol produces a single peak signal with a chemical shift at 4.52ppm and an integrated area of 35.9; the methylene hydrogen of benzyl ether produces a single peak signal with a chemical shift at 4.42ppm and an integrated area of 52.2; the methylene hydrogen of diphenylmethane produces a single peak signal with a chemical shift at 3.96ppm and an integrated area of 4.5; the hydroxyl hydrogen of benzyl alcohol produces a broad peak signal with a chemical shift at 2.56ppm and an integrated area of 37.6; the methyl hydrogen of toluene produces a single peak signal with a chemical shift at 2.28ppm and an integrated area of 296.6.

[0112] Moreover, it can be seen from the integrated area in Table 1 that the ratio of the number of hydrogen atoms on the benzene ring carbon, the number of hydrogen atoms in the diphenylmethane methylene group, the number of hydrogen atoms in the benzyl ether methylene group, the number of hydrogen atoms in the benzyl alcohol methylene group, and the number of hydrogen atoms alpha to the diether carbon-oxygen single bond is 100:9:104:72:12.

[0113] Based on the above analysis, it can be proved that the compound synthesized in step (1) of Example 1 of the present invention is the target compound, namely, m-xylene resin.

[0114] (2) The polyphenol intermediate 1 prepared in step (2) of Example 1 was subjected to 1 The results of H-NMR characterization are shown in Table 2.

[0115] Table 2 Polyphenol intermediate 1 prepared in Example 1 1 H-NMR test results table

[0116]

[0117] From Table 2, we can see that 1In H-NMR, the meta-hydrogen of phenol and the hydrogen of xylene produced multiple peak signals with chemical shifts at 6.9~7.15ppm and an integrated area of 100; the ortho-para hydrogen of phenol produced multiple peak signals with chemical shifts at 6.6~6.7ppm and an integrated area of 47.3; the phenolic hydroxyl hydrogen produced a broad peak signal with a chemical shift at 5.11ppm and an integrated area of 29.5; the methylene hydrogen of xylene produced a single peak signal with a chemical shift at 3.96ppm and an integrated area of 1.8; the methylene hydrogen of benzylphenol produced multiple peak signals with a chemical shift at 3.86~3.94ppm and an integrated area of 41.1; the methyl hydrogen of toluene produced a single peak signal with a chemical shift at 2.28ppm and an integrated area of 123.2.

[0118] In addition, it can be seen from the integrated area in Table 2 that the ratio of the number of phenol ring hydrogens, the number of alkylbenzene ring hydrogens, the number of diphenylmethane methylene hydrogens, the number of benzyl ether methylene hydrogens, the number of benzyl alcohol methylene hydrogens, and the number of α hydrogens of diether carbon-oxygen single bonds is 140:100:192:0:0:0.

[0119] Based on the above analysis, it can be proved that the compound synthesized in step (2) of Example 1 of the present invention is a polyphenol compound.

[0120] Furthermore, it was found through testing that the average molecular weight of the compound synthesized in step (2) of Example 1 of the present invention was 675, and the average functionality was 3.3, that is, the phenolic hydroxyl equivalent was 205 g / mol.

[0121] (III) Epoxy resin 1 prepared in step (3) of Example 1 was subjected to 1 The results of H-NMR characterization are shown in Table 3.

[0122] Table 3 Epoxy resin 1 prepared in Example 1 1 H-NMR test results table

[0123]

[0124] From Table 3 we can see that 1In H-NMR, the meta-hydrogen of phenol and the hydrogen of xylene produced multiple peak signals with chemical shifts of 6.9~7.15ppm and an integrated area of 100; the ortho-para hydrogen of phenol produced multiple peak signals with chemical shifts of 6.6~6.7ppm and an integrated area of 47.3; the epoxy hydrogen 1 produced multiple peak signals with chemical shifts of 4.16ppm and an integrated area of 32.7; the methylene hydrogen of xylene produced a single peak signal with chemical shifts of 3.96ppm and an integrated area of 1.8; the methylene hydrogen of benzyl (propylene oxide) phenol .... And epoxy hydrogen 2 produced multiple peak signals with chemical shifts at 3.86~3.94ppm and an integrated area of 41.1; epoxy hydrogen 3 produced multiple peak signals with chemical shifts at 3.31 and an integrated area of 30.3; epoxy hydrogen 4 produced multiple peak signals with chemical shifts at 2.85 and an integrated area of 31.6; epoxy hydrogen 5 produced multiple peak signals with chemical shifts at 2.71 and an integrated area of 30.5; toluene methyl hydrogen produced a single peak signal with a chemical shift at 2.28ppm and an integrated area of 123.2.

[0125] The above-mentioned epoxy hydrogen 1 (H ), epoxy hydrogen 2 (H ), epoxy hydrogen 3 (H <c>), epoxy hydrogen 4 (H <d>), epoxy hydrogen 5 (H <e>) is shown in the following formula 13:

[0126]

[0127] Formula 13.

[0128] Example 2

[0129] The present embodiment provides a method for preparing an alkyl-substituted aromatic hydrocarbon-modified epoxy resin, the method comprising the following steps:

[0130] (1) Synthetic meta-xylene resin

[0131] The steps are exactly the same as step (1) of Example 1.

[0132] (2) Synthesis of polyphenol intermediate 2 using o-cresol and m-xylene resin as raw materials

[0133] 345 g of o-cresol and 28 g of 37 wt % concentrated hydrochloric acid were sequentially added to a reaction kettle 4, and the obtained mixed reaction liquid 4 was heated to 110° C. Then, the toluene solution of all the m-xylene resin obtained in step (1) was added to the reaction system in batches, and the mixture was reacted at reflux temperature for 7 hours. After the reaction was completed, the solvent and residual o-cresol, the generated water and the catalyst hydrogen chloride were evaporated under reduced pressure to obtain the polyphenol intermediate 2.

[0134] (3) Using polyphenol intermediate 2 and epichlorohydrin as raw materials, epoxy resin 2 was synthesized

[0135] 219 g of the polyphenol intermediate 2 obtained in step (2) and 370 g of epichlorohydrin were added to a reactor 5 in sequence, stirred and dissolved uniformly to obtain a mixed reaction solution 5; then 100 g of a 40% NaOH aqueous solution was added dropwise to the mixed reaction solution 5, and the pressure of the reaction system was controlled to -0.6±0.1 bar to allow water and epichlorohydrin in the reaction system to azeotrope; while the NaOH aqueous solution was added dropwise, water in the reaction system was removed through a water separator, and the epichlorohydrin was returned to the reactor 5, and the reaction was carried out at 60±5°C for 6 hours. After the reaction was completed, the obtained product was washed with water, distilled, and refined in sequence to obtain epoxy resin 2.

[0136] Structural test results and analysis

[0137] (1) The polyphenol intermediate 2 prepared in step (2) of Example 2 was subjected to 1 The results of H-NMR characterization are shown in Table 4.

[0138] Table 4 Polyphenol intermediate 2 prepared in Example 2 1 H-NMR test results table

[0139]

[0140] From Table 4 we can see that 1 In H-NMR, the meta-hydrogen of phenol and the hydrogen of xylene produced multiple peak signals with chemical shifts at 6.9~7.15ppm and an integrated area of 100; the ortho-para hydrogen of phenol produced multiple peak signals with chemical shifts at 6.6~6.7ppm and an integrated area of 17.8; the phenolic hydroxyl hydrogen produced a broad peak signal with a chemical shift at 5.15ppm and an integrated area of 29.5; the methylene hydrogen of xylene produced a single peak signal with a chemical shift at 3.96ppm and an integrated area of 1.8; the methylene hydrogen of benzylphenol produced multiple peak signals with a chemical shift at 3.86~3.94ppm and an integrated area of 41.1; the methyl hydrogen of toluene produced a single peak signal with a chemical shift at 2.28ppm and an integrated area of 123.2; the methyl hydrogen of cresol produced a single peak signal with a chemical shift at 2.24ppm and an integrated area of 93.8.

[0141] In addition, it can be seen from the integrated area in Table 4 that the ratio of the number of ring hydrogens of o-cresol, the number of ring hydrogens of alkylbenzene, the number of methylene hydrogens of diphenylmethane, the number of methylene hydrogens of benzyl ether, the number of methylene hydrogens of benzyl alcohol, and the number of alpha hydrogens of diether carbon-oxygen single bonds is 142:100:190:0:0:0.

[0142] Based on the above analysis, it can be proved that the compound synthesized in step (2) of Example 2 of the present invention is a polyphenol compound.

[0143] Furthermore, it was found through testing that the average molecular weight of the compound synthesized in step (2) of Example 2 of the present invention was 722, and the average functionality was 3.3, that is, the phenolic hydroxyl equivalent was 219 g / mol.

[0144] (2) Epoxy resin 2 prepared in step (3) of Example 2 was subjected to 1 The results of H-NMR characterization are shown in Table 5.

[0145] Table 5 Epoxy resin 2 prepared in Example 2 1 H-NMR test results table

[0146]

[0147] From Table 5, we can see that 1 In H-NMR, the meta-hydrogen of phenol and the hydrogen of xylene produced multiple peak signals with chemical shifts at 6.9~7.15ppm and an integrated area of 100; the ortho-para hydrogen of phenol produced multiple peak signals with chemical shifts at 6.6~6.7ppm and an integrated area of 17.8; the hydroxyl hydrogen of phenol produced a broad peak signal with a chemical shift at 5.15ppm and an integrated area of 29.5; the epoxy hydrogen 1 produced a multiple peak signal with a chemical shift at 4.15ppm and an integrated area of 28.2; the methylene hydrogen of xylene produced a single peak signal with a chemical shift at 3.96ppm and an integrated area of 1.8; the methylene hydrogen and Epoxy hydrogen 2 produced multiple peak signals with a chemical shift of 3.86~3.94ppm and an integrated area of 69.8; epoxy hydrogen 3 produced multiple peak signals with a chemical shift of 3.32 and an integrated area of 30.3; epoxy hydrogen 4 produced multiple peak signals with a chemical shift of 2.84 and an integrated area of 28.9; epoxy hydrogen 5 produced multiple peak signals with a chemical shift of 2.72 and an integrated area of 31.4; toluene methyl hydrogen produced a single peak signal with a chemical shift of 2.28ppm and an integrated area of 123.2; toluene glycidylphenol produced a single peak signal with a chemical shift of 2.24ppm and an integrated area of 93.8.

[0148] Example 3

[0149] The present embodiment provides a method for preparing an alkyl-substituted aromatic hydrocarbon-modified epoxy resin, the method comprising the following steps:

[0150] (1) Synthetic meta-xylene resin

[0151] The steps are exactly the same as step (1) of Example 1.

[0152] (2) Synthesis of polyphenol intermediate 3 using mixed cresol and m-xylene resin as raw materials

[0153] 345 g of mixed cresol and 28 g of concentrated hydrochloric acid with a concentration of 37 wt% are added to the reaction kettle 6 in sequence, and the obtained mixed reaction liquid 6 is heated to 110° C. Then, the toluene solution of all the m-xylene resin obtained in step (1) is added to the reaction system in batches, and the reaction is carried out at reflux temperature for 7 hours. After the reaction is completed, the solvent and residual o-cresol, the generated water and the catalyst hydrogen chloride are evaporated under reduced pressure to obtain the polyphenol intermediate 3.

[0154] The mixed cresol consists of three isomers: o-cresol, m-cresol and p-cresol, wherein the mass ratio of o-cresol, m-cresol and p-cresol is 12.1:45.7:42.2.

[0155] (3) Using polyphenol intermediate 3 and epichlorohydrin as raw materials, epoxy resin 3 was synthesized

[0156] 220 g of the polyphenol intermediate 3 obtained in step (2) and 370 g of epichlorohydrin were added to a reaction kettle 7 in sequence, stirred and dissolved uniformly to obtain a mixed reaction solution 7; then 100 g of a 40% NaOH aqueous solution was added dropwise to the mixed reaction solution 7, and the pressure of the reaction system was controlled to -0.6±0.1 bar to allow water and epichlorohydrin in the reaction system to azeotrope; while the NaOH aqueous solution was added dropwise, water in the reaction system was removed through a water separator, and the epichlorohydrin was returned to the reaction kettle 7, and the reaction was carried out at 60±5°C for 6 hours. After the reaction was completed, the obtained product was washed with water, distilled, and refined in sequence to obtain epoxy resin 3.

[0157] Test results and analysis

[0158] (1) The polyphenol intermediate 3 prepared in step (2) of Example 3 was subjected to 1 The results of H-NMR characterization are shown in Table 6.

[0159] Table 6 Polyphenol intermediate 3 prepared in Example 3 1 H-NMR test results table

[0160]

[0161] From Table 6, we can see that 1 In H-NMR, the meta-hydrogen of phenol and the hydrogen of xylene produced multiple peak signals with chemical shifts at 6.9~7.15ppm and an integrated area of 100; the ortho-para-hydrogen of phenol produced multiple peak signals with chemical shifts at 6.6~6.7ppm and an integrated area of 23.4; the phenolic hydroxyl hydrogen produced a broad peak signal with a chemical shift at 5.13ppm and an integrated area of 30.8; the methylene hydrogen of xylene produced a single peak signal with a chemical shift at 3.95ppm and an integrated area of 1.9; the methylene hydrogen of benzylphenol produced multiple peak signals with a chemical shift at 3.85~3.95ppm and an integrated area of 43.0; the methyl hydrogen of toluene and methyl cresol produced multiple peak signals with chemical shifts at 2.2~2.3ppm and an integrated area of 227.1.

[0162] Moreover, it can be seen from the integrated area in Table 6 that the ratio of the number of ring hydrogens of mixed cresol, the number of ring hydrogens of alkylbenzene, the number of methylene hydrogens of diphenylmethane, the number of methylene hydrogens of benzyl ether, the number of methylene hydrogens of benzyl alcohol, and the number of α hydrogens of diether carbon-oxygen single bonds is 152:100:195:0:0:0.

[0163] Based on the above analysis, it can be proved that the compound synthesized in step (2) of Example 3 of the present invention is a polyphenol compound.

[0164] Furthermore, it was found through testing that the average molecular weight of the compound synthesized in step (2) of Example 3 of the present invention was 748, and the average functionality was 3.4, that is, the phenolic hydroxyl equivalent was 220 g / mol.

[0165] Structural testing and characterization results

[0166] (2) Epoxy resin 3 prepared in step (3) of Example 3 was subjected to 1 The results of H-NMR characterization are shown in Table 7.

[0167] Table 7 Epoxy resin 3 prepared in Example 3 1 H-NMR test results table

[0168]

[0169] From Table 7, we can see that 1 In H-NMR, the meta-hydrogen of phenol and the hydrogen of xylene produced multiple peak signals with chemical shifts at 6.9~7.15ppm and an integrated area of 100; the ortho-para hydrogen of phenol produced multiple peak signals with chemical shifts at 6.6~6.7ppm and an integrated area of 23.4; the epoxy hydrogen 1 produced multiple peak signals with chemical shifts at 4.16ppm and an integrated area of 30.3; the methylene hydrogen of xylene produced a single peak signal with chemical shifts at 3.95ppm and an integrated area of 1.9; the methylene hydrogen of benzylphenol and Epoxy hydrogen 2 produced a multiple peak signal with a chemical shift of 3.85~3.95ppm and an integrated area of 76.2; epoxy hydrogen 3 produced a multiple peak signal with a chemical shift of 3.93 and an integrated area of 33.2; epoxy hydrogen 4 produced a multiple peak signal with a chemical shift of 3.31 and an integrated area of 27.8; epoxy hydrogen 5 produced a multiple peak signal with a chemical shift of 2.85 and an integrated area of 31.5; epoxy hydrogen 6 produced a multiple peak signal with a chemical shift of 2.71 and an integrated area of 29.6;

[0170] Toluene methyl hydrogen and toluene epoxypropylphenol produced multiple peak signals with chemical shifts ranging from 2.2 to 2.3 and an integrated area of 227.1.

[0171] Example 4

[0172] The present embodiment provides a method for preparing an alkyl-substituted aromatic hydrocarbon-modified epoxy resin, the method comprising the following steps:

[0173] (1) Synthetic meta-xylene resin

[0174] The steps are exactly the same as step (1) of Example 1.

[0175] (2) Synthesis of polyphenol intermediate 1 using phenol and m-xylene resin as raw materials

[0176] The steps are exactly the same as step (2) in Example 1.

[0177] (3) Using polyphenol intermediate 1 and allyl chloride as raw materials, allyl ether intermediate 1 was synthesized

[0178] 205 g of the polyphenol intermediate 1 obtained in step (2) and 76.5 g of allyl chloride were added to a reaction kettle 8 in sequence, stirred and dissolved uniformly, to obtain a mixed reaction solution 8; 100 g of a 40% aqueous NaOH solution was then added dropwise to the mixed reaction solution 8, and the mixture was reacted at 60±5°C for 4 hours. After the reaction, the obtained product was washed with water, distilled, and refined in sequence to obtain the allyl ether intermediate 1;

[0179] (4) Synthesis of epoxy resin by oxidation method

[0180] After dissolving the allyl ether intermediate 1 in glacial acetic acid, a 30% aqueous hydrogen peroxide solution was added dropwise to oxidize the allyl groups to epoxy groups. After the addition was complete, the reaction was continued at 60°C for 3 hours. The resulting product was distilled and purified to obtain epoxy resin 4.

[0181] In addition, the epoxy resins 1-4 prepared in Examples 1-4 may all contain the following end-capping structures, as shown in Formulas 14, 15, and 16 below; wherein: 1 、R 2 、R 3 , or R 4 All are methyl.

[0182]

[0183] Formula 14;

[0184]

[0185] Formula 15;

[0186]

[0187] Formula 16.

[0188] Performance testing:

[0189] Epoxy Resins 1, 2, and 3 synthesized in Examples 1-3, along with NC-2000, NC-3000, a general-purpose o-cresol-type epoxy novolac resin (DIC N-665-EXP), and a general-purpose phenol-type epoxy novolac resin (DIC N-770) from the prior art, were used as a curing agent using thermoplastic novolac resin (softening point 80°C) to prepare cured resin blocks. The dielectric constant and dielectric loss of these blocks were tested according to the national standard GB / T 5597-1999. The specific test methods for dielectric constant (Dk) and dielectric dissipation factor (Df) are as follows:

[0190] According to the national standard GB / T 5597-1999, the test method for the microwave complex dielectric constant of solid dielectrics, the dielectric constant (real part of the relative dielectric constant, ε', the same below) and loss factor (electrical loss tangent, tanδ, the same below) of the test sample were measured at 25°C and an operating frequency of 9.5 GHz.

[0191] The test results are shown in Table 8 below.

[0192] Table 8 Dielectric properties of epoxy resins 1-4 synthesized in Examples 1-4 and epoxy resins in the prior art

[0193] Test results table

[0194] Resin type Dielectric constant Dissipation Factor Epoxy resin 1 3.15 0.022 Epoxy resin 2 3.12 0.021 Epoxy resin 3 3.10 0.019 Epoxy resin 4 3.13 0.020 NC-2000 3.20 0.025 NC-3000 3.15 0.026 DIC N-665-EXP 3.30 0.032 DIC N-770 3.30 0.033 < / e> < / d> < / c>

Claims

1. An alkyl-substituted aromatic hydrocarbon modified epoxy resin, characterized in that: Its molecular structure is shown in the following formula 8: Wherein: A represents an alkyl-substituted aromatic hydrocarbon compound; -OG represents ; B represents a substituted or unsubstituted phenolic compound; ； Formula eight.

2. The alkyl-substituted aromatic hydrocarbon modified epoxy resin according to claim 1, wherein: The H on the aromatic ring of A is substituted by a substituent R, which may be monosubstituted, disubstituted or polysubstituted; (n) Where n is an integer of 1 to 4, representing the number of aromatic ring substituents R on the aromatic ring A; the substituents R at different substitution positions are the same or different; the substituent R is C1 to C 10 of alkyl.

3. The alkyl-substituted aromatic hydrocarbon modified epoxy resin according to claim 1, wherein: In Formula 8, the phenolic compound is an aromatic hydrocarbon compound containing a phenolic hydroxyl group, wherein the H on the aromatic ring B is substituted by a substituent R or is unsubstituted, and the substitution may be monosubstituted, disubstituted or polysubstituted; R on the aromatic ring B is (m) Where m is an integer of 0 to 4; represents the number of substituents R on the aromatic ring B; the substituents R at different substituent positions are the same or different; the substituent R is C1 to C 10 of alkyl.

4. The alkyl-substituted aromatic hydrocarbon modified epoxy resin according to claim 1, wherein: Type 8 OG （n） In the process, OG is synthesized by reacting an aromatic hydrocarbon compound containing a phenolic hydroxyl group with epichlorohydrin; OG （n） Here, n represents the number of phenolic hydroxyl group-containing aromatic hydrocarbon compounds substituted by phenolic hydroxyl groups, which can be monosubstituted, disubstituted or polysubstituted; n is an integer of 1 to 4.

5. The alkyl-substituted aromatic hydrocarbon modified epoxy resin according to claim 1, wherein: In the structural formula (8), n represents the average degree of polymerization, and the value of n is any value between 1 and 50.

6. The method for preparing an alkyl-substituted aromatic hydrocarbon-modified epoxy resin according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: (1) Alkyl-substituted aromatic hydrocarbon compounds and aldehyde compounds are used as reaction materials, and addition reaction occurs under strong acid conditions to generate aromatic hydrocarbon resins; (2) using the aromatic hydrocarbon resin and phenolic compound as reaction raw materials, a polycondensation reaction occurs under strong acid conditions to generate a polyphenol compound; (3) using the polyphenol compound and epichlorohydrin as reaction materials, a condensation reaction occurs in the presence of an acid-binding agent to generate the alkyl-substituted aromatic hydrocarbon modified epoxy resin; Alternatively, the polyphenol compound is reacted with allyl chloride and peroxyacetic acid in sequence to generate the alkyl-substituted aromatic hydrocarbon modified epoxy resin.

7. The preparation method according to claim 6, characterized in that: In step (1), the molar ratio of the alkyl-substituted aromatic hydrocarbon compound to the aldehyde compound is 1:(1-3).

8. The preparation method according to claim 6, characterized in that: The molar ratio of the aromatic hydrocarbon resin to the phenolic compound in step (2) is (0-1):1, but not equal to 0.

9. The preparation method according to claim 6, characterized in that: The mass ratio of epichlorohydrin to polyphenol compound in step (3) is (1-10):

1.

10. The preparation method according to claim 6, characterized in that: The mass ratio of the allyl chloride to the polyphenol intermediate 1 in step (3) is (0.1-1):1.

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