TW202122460A - Methacrylate polyphenyl ether as well as preparation method and application thereof - Google Patents

Abstract

The invention provides methacrylate polyphenyl ether as well as a preparation method and application thereof, and relates to the technical field of polymer synthesis. The methacrylate polyphenyl etherhas a structure as shown in a formula I. The methacrylate polyphenyl ether derivative has the characteristics of small molecular weight, good distributivity and high solvent selectivity, is applied to a resin composition and is prepared into a laminated board, and has the advantages of good heat resistance, stable structure, good toughness and the like.

Description

Methacrylate polyphenylene ether and its preparation method and application

The invention relates to the technical field of polymer synthesis, in particular to a methacrylate polyphenylene ether and a preparation method and application thereof.

Polyphenylene ether is a class of engineering plastics with excellent performance. Among them, the polymer obtained by oxidative polymerization using 2,6-dimethylphenol as a raw material is a representative one. Polyphenylene ether is called PPO in the United States and PPE in Japan, and its molecular weight is generally 30,000 to 50,000. Polyphenylene ether resin has the characteristics of hydrolysis resistance, insulation, flame retardancy, low dielectric constant (Dk), low dissipation factor (dissipation factor, Df), etc., and is widely used in automobiles, electronic appliances, cable, wire, etc. Printed circuit boards, integrated circuit boards and other fields.

However, the existing polyphenylene ether resins still have some shortcomings in application, such as: insufficient heat resistance when making printed circuit substrates, and the glass transition temperature of PCB substrates is lower than the dip soldering temperature, and processing is likely to occur above 200 ℃ Deformation; limited adhesion to circuit copper foil and other materials, easy to fall off; large molecular weight, more restrictions when used with other materials. These shortcomings limit the further application of polyphenylene ether resin in industry.

Based on this, it is necessary to solve the problem of insufficient heat resistance of existing polyphenylene ether resins and provide a methacrylate polyphenylene ether with the advantages of small molecular weight, good distribution and high solvent selectivity.

化學式(I)A methacrylate polyphenylene ether whose structure is shown in the following chemical formula (I):

Chemical formula (I)

Wherein, m+n=5~50, the number average molecular weight Mn is 1000~6000; R is a cycloalkyl group or an asymmetric branched chain alkyl group, and the cycloalkyl group is cyclopentyl, cyclohexyl, cycloheptyl, 3 -Methylcyclohexyl, 3-methylcycloheptyl or 3,5-dimethylcyclohexyl, the asymmetric branched alkyl group is methylethyl, methylpropyl, ethylpropyl, methyl Butyl or ethylbutyl.

The above-mentioned methacrylate polyphenylene ether has the advantages of small molecular weight, good distribution and high solvent selectivity; applied to plastic compositions, it has good heat resistance, good structural stability, good toughness, and high solvent selectivity. The polymer has the advantages of small molecular weight and good distribution.

Among them, polyphenylene ether or methacrylate polyphenylene ether in which R is an asymmetric branched chain alkyl group and cycloalkyl group has better performance than products in which R is a symmetric branched chain alkyl group. Furthermore, the product performance of polyphenylene ether or methacrylate polyphenylene ether with R being a cycloalkyl group is the best.

Preferably, R is a cycloalkyl group, and the number average molecular weight Mn is 2700-3200.

In one of the embodiments, R is cyclohexyl, and the number average molecular weight Mn is 2700-3100.

In one of the embodiments, R is cyclopentyl, and the number average molecular weight Mn is 2700-3100.

In one of the embodiments, R is methyl ethyl, and the number average molecular weight Mn is 2800-3200.

One aspect of the present invention also provides a method for preparing the above-mentioned methacrylate polyphenylene ether, which includes the following steps:

Substitution reaction: mixing toluene, triethylamine, methacrylic acid chloride, and polyphenylene ether, heating and reacting to obtain methacrylate polyphenylene ether.

In one of the embodiments, the heating temperature is 40-60°C, and the reaction time is 6-8 hours.

In one of the embodiments, the following steps are further included after the substitution reaction step:

Neutralization: neutralization by adding acid; preferably, neutralization by adding hydrochloric acid;

Precipitation: adding toluene for extraction, retaining the toluene layer, adding methanol to precipitate a solid, and vacuum drying to obtain refined methacrylate polyphenylene ether; preferably, the drying temperature is 120°C.

The reaction formula for synthesizing methacrylate polyphenylene ether is as follows:

化學式(II)In one of the embodiments, the structure of the polyphenylene ether is shown in the following chemical formula (II):

Chemical formula (II)

Preferably, the molecular weight of the polyphenylene ether is 2700-3200. The polyphenylene ether of this molecular weight has better performance in all aspects.

In one of the embodiments, the polyphenylene ether is prepared by the following method:

Preparation of intermediates: mix sulfuric acid, dehydrating agent, 2,6-dimethylphenol, _{and n-hexane (Hexane) containing dichloromethane (CH 2} Cl ₂ ), add alkanone, and control the reaction temperature to 65~75 ℃, React for 20-28 hours, add alkali to neutralize, add dichloromethane (CH ₂ Cl ₂ ) for extraction, add n-hexane (Hexane) to precipitate a solid, that is, a refined polyphenylene ether intermediate is obtained. The alkanone is selected from: cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclohexanone, 3-methylcycloheptanone, 3,5-dimethylcyclohexanone, methyl ethyl ketone , Methyl acetone, ethyl acetone, propyl acetone, methyl butanone or, one of ethyl butanone. Preferably, the dehydrating agent is magnesium sulfate.

Reaction: mixing toluene, metal catalyst, triethylamine and the above polyphenylene ether intermediate to obtain a pre-reaction solution; dissolving 2,6-dimethylphenol in toluene to obtain a 2,6-dimethylphenol solution; Under oxygen conditions, add the 2,6-dimethylphenol solution to the pre-reaction solution and react for 6-8 hours to obtain polyphenylene ether. Preferably, the molar ratio of 2,6-dimethylphenol to toluene used in the preparation of the 2,6-dimethylphenol solution is (3-16):1. Preferably, the metal catalyst is copper chloride (CuCl ₂ ).

In one of the embodiments, the reaction step in the preparation method of polyphenylene ether further includes the following steps:

Removal of impurities: add EDTA aqueous solution to adsorb the metal catalyst, mix at 20-30 ℃ for 8-12 hours, heat to 50-60 ℃, mix for 1-3 hours, separate into layers, and retain the toluene solution layer.

Neutralization: Add acid to neutralize, mix for 20-40 minutes, separate into layers, and retain the toluene solution layer. Preferably, the acid is hydrochloric acid.

Precipitation: Mix methanol and toluene solution layer, stirring at 3000~4000 rpm, the product precipitates quickly.

Drying: filter and place the solid product at 75~85 ℃ for vacuum drying for 14~18 hours.

化學式(III)；Among them, the structure of the polyphenylene ether intermediate is shown in the following chemical formula (III):

Chemical formula (III);

R is cycloalkyl or asymmetric branched alkyl; said cycloalkyl is cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl or 3,5-di Methyl cyclohexyl; the asymmetric branched alkyl group is methyl ethyl, methyl propyl, ethyl propyl, propyl propyl, methyl butyl or ethyl butyl.

The reaction formula for the synthesis of polyphenylene ether is as follows:

In one aspect, the present invention also provides an application of the above methacrylate polyphenylene ether in the preparation of epoxy resins and laminates.

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

The methacrylate polyphenylene ether of the present invention has the advantages of small molecular weight, good distribution and high solvent selectivity; applied to plastic compositions, it has good heat resistance, good structural stability, good toughness, and solvent selectivity. High, low polymer molecular weight and good distribution.

In order to facilitate the understanding of the present invention, preferred embodiments are given below to describe the present invention more fully. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.

The test methods and instruments involved in the following examples, comparative examples and application examples are as follows:

(1) Nuclear magnetic resonance (NMR) analysis: Varian's nuclear magnetic resonance spectrometer (model: Mercury-VX200 MHz).

(2) Infrared spectrum analysis: Infrared spectrometer from Bio-RAD (model: FTS-3000).

(3) Differential scanning calorimetry (DSC) analysis: Perkin-Elmer's differential scanning calorimetry (model: DSC 7).

(4) Gel permeation chromatography (GPC) analysis: Waters Colloidal Chromatography Analyzer (model: waters 600).

(5) Glass transition temperature test: Use a dynamic mechanical analyzer (DMA) to measure the glass transition temperature (Tg). The test specification for the glass transition temperature adopts the IPC-TM-650.2.4.25C and 24C test methods of The Institute for Interconnecting and Packaging Electronic Circuits (IPC).

(6) Dielectric constant and dissipation factor measurement: According to ASTM D150, the dielectric constant (Dk) and dissipation factor (Df) are calculated at a working frequency of 1 MHz (GHz).

(7) Water absorption test: Carry out pressure cooker test (PCT) test, put the laminate in a pressure vessel, and test for 2 hours at 121 ℃, saturated humidity (100%RH) and 2 atmospheres. The high humidity resistance of the laminated board.

(8) 288 ℃ solder resistance and heat resistance test: immerse the test piece that has been steamed in a PCT pressure cooker for 2 hours into a 288 ℃ soldering furnace, and record the time required for the test piece to burst and delamination.

(9) Thermal expansion coefficient test and Z-axis expansion rate: measured by TA 2940 thermal expansion analyzer of TA Instrument company, measuring temperature is 50 ℃ ~ 260 ℃, heating rate is 5 ℃/min, measuring sample 3×3 mm Thermal expansion coefficient and Z-axis expansion coefficient in the thickness direction (Z-axis direction) of laminate samples of ^{2 sizes.}

(10) Thermal decomposition temperature test: Use a thermogravimetric analyzer (TGA) to measure the temperature when the quality is reduced by 5% compared with the initial quality, which is the thermal decomposition temperature.

(11) Toughness test: Lay the laminated board flat on a flat jig, use a cross-shaped metal jig to vertically contact the surface of the laminated board, and then apply vertical pressure, then remove the cross jig and observe the cross shape of the laminated board For traces, check the surface of the laminate. If there is no white wrinkles, it is judged as good, slightly white lines are normal, and those with cracks or breaks are considered bad.

Example 1

A methacrylate polyphenylene ether prepared by the following method:

In a 500 mL three-necked round bottom flask, 100 g of polyphenylene ether with cyclohexyl R and 300 g of toluene were sequentially added, and stirred at room temperature (about 20 ℃) for about 30 minutes. After the polyphenylene ether is dissolved, 17.33 g of methacrylic acid chloride is pre-dissolved in 52 g of toluene and stirred evenly (molar ratio is 8:1), added to the above flask, and the reaction is continued for 30 minutes. Then 25.18 g of triethylamine (the molar ratio of triethylamine to methacrylic acid chloride is 1.5:1) was pre-dissolved in 75.5 g of toluene, stirred evenly, and then added to the above flask in batches. Heat to 50°C and stir for 5 hours to complete the reaction. Add hydrochloric acid for neutralization, add methanol for extraction, save the toluene layer, add methanol to precipitate a solid, filter, and vacuum dry the solid to obtain 90 g of light gray powder.

化學式(IV)The structure of the obtained methacrylate polyphenylene ether is as follows:

Chemical formula (IV)

Among them, m+n=20~24, and the number average molecular weight Mn=2800~3200.

The polyphenylene ether in which R is a cyclohexyl group is prepared by the following method:

Preparation of intermediate: control the reflux condensation temperature to 0 ℃, add 600 mL of _{Hexane containing dichloromethane (CH 2} Cl ₂ ), 0.8 g sulfuric acid and 2 g dehydrating agent magnesium sulfate into a 1000 mL four-neck flask, Add 57.3 g of 2,6-dimethylphenol, and then add 9.2 g of cyclohexanone in batches, control the reaction temperature to 70° C., and react for 24 hours to obtain the initial product. To the initial product, an aqueous solution of sodium bicarbonate was added for neutralization, dichloromethane (CH ₂ Cl ₂ ) was added for extraction, and n-hexane (Hexane) was added to precipitate a solid, and 18.1 g of refined product was obtained.

Reaction: Take a 5 L four-neck round bottom flask, control the stirring speed at 150~200 rpm, add 1.3 L toluene, 30 g copper chloride (CuCl ₂ ), 120 g tri-ethylamine (Tri-ethylamine), and continue to pass in Oxygen, add 280 g of the above polyphenylene ether intermediate to completely dissolve; dissolve 800 g of 2,6-dimethylphenol in 1L of toluene, add the 2,6-dimethylphenol solution into a four-necked round bottom bottle, Stirring was continued for 7 hours, and oxygen flow was stopped after stirring. Transfer the above reaction solution to a 12 L round bottom flask, add 820 mL 0.1N EDTA aqueous solution, stir at room temperature for 6 hours, heat to 50-60 ℃, and continue to stir for 2 hours. Collect the toluene solution layer, add 10 L of methanol to the toluene solution layer, stir quickly to precipitate a large amount of precipitation, continue stirring at room temperature for at least 1 hour, and then filter the precipitated product and dry it in a vacuum oven (80 ℃, 16 hours), Obtain 850~950 g of light gray powder.

化學式(V)The structure of the above-mentioned polyphenylene ether intermediate is shown in the chemical formula (V):

Chemical formula (V)

化學式(VI)The structure of the above polyphenylene ether is shown in the chemical formula (VI):

Chemical formula (VI)

The hydrogen spectrum, carbon spectrum and infrared spectrum results of the polyphenylene ether intermediate shown in chemical formula (V) are shown in Figures 1-3; after testing, the compound has a melting point of 202.23°C. The infrared spectrum of the polyphenylene ether shown in the chemical formula (VI) is shown in FIG. 4. The infrared spectrum of the methacrylate polyphenylene ether shown in the chemical formula (VI) is shown in FIG. 5. After testing, polyphenylene ether and methacrylate polyphenylene ether have good solubility for benzene, ketones, amide, pyridine, etc.

Example 2

A methacrylate polyphenylene ether. The difference from Example 1 is that 9.2 g of cyclohexanone is replaced with 7.8 g of cyclopentanone, correspondingly R is cyclopentyl, and finally 84 g of light gray powder is obtained, m+n = 20~23, number average molecular weight Mn=2800~3100.

化學式(VII)The structure of the methacrylate polyphenylene ether is as follows:

Chemical formula (VII)

化學式(VIII)The structure of the polyphenylene ether intermediate involved in the preparation process is shown in the chemical formula (VIII):

Chemical formula (VIII)

化學式(IX)The structure of the polyphenylene ether involved in the preparation process is shown in the chemical formula (IX):

Chemical formula (IX)

The results of hydrogen spectrum, carbon spectrum and infrared spectrum of the polyphenylene ether intermediate shown in chemical formula (VIII) are shown in Figures 6-8; after testing, the compound has a melting point of 176.4°C. The infrared spectrum of the polyphenylene ether shown in the chemical formula (IX) is shown in FIG. 9. The infrared spectrum of the methacrylate polyphenylene ether shown in the chemical formula (VII) is shown in FIG. 10. After testing, polyphenylene ether and methacrylate polyphenylene ether have good solubility for benzene, ketones, amide, pyridine, etc.

Example 3

A methacrylate polyphenylene ether. The difference from Example 1 is that 9.2 g of cyclohexanone is replaced with 8.8 g of methyl ethyl ketone, correspondingly R is methyl ethyl, and 88 g of light gray powder is finally obtained, m +n= 20~23, number average molecular weight Mn=2700~3100.

化學式(X)The structure of the methacrylate polyphenylene ether is as follows chemical formula (X):

Chemical formula (X)

化學式(XI)The structure of the polyphenylene ether intermediate involved in the preparation process is shown in the chemical formula (XI):

Chemical formula (XI)

化學式(XII)The structure of the polyphenylene ether involved in the preparation process is shown in the chemical formula (XII):

Chemical formula (XII)

After testing, polyphenylene ether and methacrylate polyphenylene ether have good solubility for benzene, ketones, amide, pyridine, etc.

Example 4

A methacrylate polyphenylene ether, which is different from Example 1 in that the amount of 2,6-dimethylphenol used when preparing the polyphenylene ether is 500 g. The molecular weight of the obtained methacrylate polyphenylene ether is 1500-2000.

Example 5

A methacrylate polyphenylene ether, which is different from Example 1 in that the amount of 2,6-dimethylphenol used in the preparation of the polyphenylene ether is 1200 g. The molecular weight of the obtained methacrylate polyphenylene ether is 4800~6000.

Comparative example 1

A methacrylate polyphenylene ether. The difference from Example 1 is that the amount of methacrylic acid chloride is changed to 10 g, and 85 g of light gray powder is finally obtained.

Detected by GPC, there are a large number of high peaks in the spectrum at the same time, and the peak value is the index of the phenyl ether intermediate shown in the chemical formula (V).

Application Examples

Add high bromine epoxy resin (Hexion 523), bisphenol A cyanate (Mitsubishi Gas), the methacrylate polyphenylene ether of Example 1, and the hardener diamino two into the agitator at room temperature. Phenyl sulphur, hardening accelerator 2-methylimidazole and cyclohexanone, the parts by weight of the above raw materials are as shown in Table 1, and mixed with a stirrer for 2 to 4 hours to obtain the resin composition R1. A similar method is used to prepare the resin composition R2-R5.

Then use a roll coater to coat the resin composition R1 on the 7628 glass fiber cloth. The weight ratio of the resin composition to the glass fiber cloth is 43%. After the coating is completed, heat and dry it at 170~180 ℃ for 2-5 minutes. Prepare a semi-hardened prepreg. Laminate eight pieces of prepreg, and laminate a 1-ounce copper foil on each of the outermost layers on both sides, and perform hot pressing. The hot pressing conditions are: heating up to 200 ℃ at a heating rate of 2.0 ℃/min. At 200 ℃, heat pressing at a total pressure of 25 kg/cm ² (initial pressure of 12 kg/cm ² ) for 90 minutes to obtain a laminated board A1. Laminated boards A2-A5 were prepared using the same method.

Table 2 shows the analysis results of the glass transition temperature (Tg), dielectric constant, dissipation factor, water absorption, thermal expansion coefficient, Z-axis expansion rate, thermal decomposition temperature, and toughness of the obtained laminates A1-A5. [Table 1] Raw materials and ratio of resin composition Cyanate resin Tetrabromo epoxy resin Methacrylate polyphenylene ether hardener 2-methylimidazole Cyclohexanone A1 A2 A3 A4 A5 Resin composition R1 150 100 30 / / / / 25 0.1 200 Resin composition R2 150 100 / 30 / / / 25 0.1 200 Resin composition R3 150 100 / / 30 / / 25 0.1 200 Resin composition R4 150 100 / / / 30 / 25 0.1 200 Resin composition R5 150 100 / / / / 30 25 0.1 200 [Table 2] Performance of laminated board Glass transition temperature (Tg) (℃) Dielectric constant (Dk) (1 MHz) Dissipation factor (Df) (1 MHz) Water absorption (%) Coefficient of thermal expansion (ppm/℃) Z-axis direction expansion (%) Thermal decomposition temperature (℃) toughness Laminated board A1 198 3.45 0.0045 0.21 40 2.3 396 good Laminated board A2 195 3.49 0.0043 0.23 49 2.6 394 good Laminated board A3 193 3.48 0.0042 0.23 52 2.7 392 good Laminated board A4 190 3.89 0.0051 0.23 55 2.8 392 good Laminated board A5 196 3.4 0.041 0.22 59 3.3 395 general

It can be seen from Table 2 that the laminated board prepared by using the methacrylate polyphenylene ether of the present invention has excellent heat resistance, water absorption and electrical properties (low Dk and Df). The R of the methacrylate polyphenylene ether in the laminates A1 and A2 is a cycloalkyl group, and its overall performance is better than that of A3. Laminated board R4 uses polyphenylene ether units with a lower polymerization content, so it is slightly higher than laminated board R1 in terms of dielectric constant and dispersion factor. The laminated board R5 uses a higher polymerized polyphenylene ether unit, although the dielectric constant and dispersion factor are relatively better than R1, but because the higher polymerized polyphenylene ether unit has a lower relative glue density, it will be slightly Affects the structure, the advantage of low water absorption, and the thermal decomposition temperature is slightly worse than R1.

The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the various technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and their description is relatively specific and detailed, but they should not be understood as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Figure 1 is a hydrogen spectrum of the polyphenylene ether intermediate in Example 1; Figure 2 is a carbon spectrum of the polyphenylene ether intermediate in Example 1; Figure 3 is an infrared spectrogram of the polyphenylene ether intermediate in Example 1; Figure 4 is an infrared spectrogram of polyphenylene ether in Example 1; Figure 5 is an infrared spectrogram of methacrylate polyphenylene ether in Example 1; Figure 6 is a hydrogen spectrum of the polyphenylene ether intermediate in Example 2; Figure 7 is a carbon spectrum of the polyphenylene ether intermediate in Example 2; Figure 8 is an infrared spectrogram of the polyphenylene ether intermediate in Example 2; Figure 9 is an infrared spectrogram of polyphenylene ether in Example 2; FIG. 10 is an infrared spectrum diagram of methacrylate polyphenylene ether in Example 2. FIG.

Claims (10)

A methacrylate polyphenylene ether, characterized in that its structure is shown in the following chemical formula (I):

Chemical formula (I) where m+n=5-50, the number-average molecular weight Mn is 1000-6000; R is a cycloalkyl group or an asymmetric branched chain alkyl group, and the cycloalkyl group is a cyclopentyl group, a cyclohexyl group, and a cycloalkyl group. Heptyl, 3-methylcyclohexyl, 3-methylcycloheptyl or 3,5-dimethylcyclohexyl, the asymmetric branched alkyl group is methyl ethyl, methyl propyl, ethyl propyl Group, methylbutyl or ethylbutyl. The methacrylate polyphenylene ether according to claim 1, wherein R is a cycloalkyl group, and the number average molecular weight Mn is 2700-3200. The methacrylate polyphenylene ether according to claim 2, wherein R is a cyclohexyl group, and the number average molecular weight Mn is 2700-3100. The methacrylate polyphenylene ether according to claim 2, wherein R is cyclopentyl and the number average molecular weight Mn is 2700-3100. A method for preparing methacrylate polyphenylene ether according to any one of claims 1 to 4, characterized in that it comprises the following steps: Substitution reaction: mixing toluene, triethylamine, methacrylic acid chloride, and polyphenylene ether, heating and reacting to obtain methacrylate polyphenylene ether. The preparation method according to claim 5, wherein the heating temperature is 40-60°C, and the reaction time is 6-8 hours. The preparation method according to claim 5 or 6, characterized in that, after the substitution reaction step, it further comprises the following steps: Neutralization: Add acid to neutralize; Precipitation: adding toluene for extraction, keeping the toluene layer, adding methanol to precipitate a solid, and vacuum drying to obtain refined methacrylate polyphenylene ether. The preparation method according to claim 5, wherein the structure of the polyphenylene ether is shown in the following chemical formula (II):

Chemical formula (II). The preparation method according to claim 8, characterized in that the polyphenylene ether is prepared by the following method: preparation intermediate: sulfuric acid, dehydrating agent, 2,6-dimethylphenol, containing dichloromethane (CH ₂ Cl ₂ ) mixed with Hexane, add alkanone, control the reaction temperature to 65~75 ℃, react for 20~28 hours, add alkali to neutralize, add dichloromethane (CH ₂ Cl ₂ ) for extraction, add Hexane precipitates solids to obtain refined polyphenylene ether intermediates; the alkanone is selected from cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclohexanone, and 3-methylcyclohexanone. One of heptanone, 3,5-dimethylcyclohexanone, methyl ethyl ketone, methyl acetone, ethyl acetone, propyl acetone, methyl butanone or ethyl butanone; reaction: toluene, The metal catalyst, triethylamine and the above-mentioned polyphenylene ether intermediate are mixed to obtain a pre-reaction liquid; 2,6-dimethylphenol is dissolved in toluene to obtain a 2,6-dimethylphenol solution; under oxygen conditions , Add the 2,6-dimethylphenol solution to the pre-reaction solution and react to obtain polyphenylene ether. An application of the methacrylate polyphenylene ether described in any one of claims 1 to 4 in the preparation of epoxy resins and laminates.

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