Thermosetting polyphenyl ether as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of thermosetting polyphenyl ether, and particularly relates to thermosetting polyphenyl ether as well as a preparation method and application thereof. The preparation method of the thermosetting polyphenyl ether comprises the following steps: mixing a copper catalyst, an amine compound, an organic acid compound, an organic acid ester compound, monohydric phenol, dihydric phenol and a solvent, reacting, and removing the copper catalyst to prepare a dihydroxy-terminated polyphenyl ether solution; and mixing an end-capping catalyst, an alkenylation reagent and the dihydroxy-terminated polyphenyl ether solution, reacting, separating and purifying to obtain the thermosetting polyphenyl ether. The organic acid compound and the organic acid ester compound are simultaneously added in the oxidative copolymerization process, the organic acid compound and the organic acid ester compound have a synergistic effect and are combined with other components, so that the chromaticity of the thermosetting polyphenyl ether can be obviously reduced, and the platinum-cobalt chromaticity value of a 50wt% butanone solution can be as low as 14-16; meanwhile, the intrinsic viscosity and the molecular structure of the thermosetting polyphenyl ether are not obviously changed.

Description

Technical Field

[0001] The invention belongs to the technical field of thermosetting polyphenylene ether, and particularly relates to a thermosetting polyphenylene ether and a preparation method and application thereof. Background Art

[0002] Polyphenylene ether resin has good heat resistance, flame retardancy, low water absorption and dimensional stability, especially in a wide frequency and temperature range can maintain excellent dielectric properties, is one of the ideal materials for high-frequency and high-speed copper clad laminate. However, conventional molecular weight polyphenylene ether has a high melting temperature and high melt viscosity, which makes it difficult to directly apply to copper clad laminate. At the same time, polyphenylene ether solution has high viscosity, poor glass fiber permeability, and is thermoplastic, which cannot meet the process requirements of copper clad laminate manufacturing. Usually, polyphenylene ether needs to be modified into a low molecular weight thermosetting resin to adapt to the curing formula system of copper clad laminate.

[0003] The typical preparation method of low molecular weight thermosetting polyphenylene ether resin is to first use monophenol and diphenol to oxidize copolymer to form a dihydroxy polyphenylene ether solution, remove the solvent and organic amine compounds by high temperature devolatilization to form a dihydroxy polyphenylene ether solid; then react the dihydroxy polyphenylene ether with an olefinic agent in a benign solvent to form a thermosetting polyphenylene ether with a diolefinic group. Generally, conventional molecular weight polyphenylene ether has a lower chromaticity, while thermosetting polyphenylene ether often has a higher chromaticity due to the particularity and complexity of the preparation process. The platinum-cobalt chromaticity value of the 50% butanone solution of the thermosetting polyphenylene ether products currently on the market is between 16 and 18, which is a high chromaticity value.

[0004] As signal transmission further develops towards high speed, high-speed copper clad laminates have become the mainstream of servers, and the application end has higher and higher requirements for the chromaticity of high-speed copper clad laminate resin raw materials. In order to reduce the chromaticity of conventional molecular weight polyphenylene ether products, the prior art discloses a method for decolorizing polyphenylene ether resins, which decolorizes polyphenylene ether by contacting with a hydroxyl compound containing a hydroxyl group or a double bond or aromatic bond at a specific position in the molecule in a molten state or in a solution. This decolorization method is to decolorize the product end and introduce new impurity compounds, which is not suitable for electronic thermosetting polyphenylene ether resins with high purity requirements. At present, there are no reports on reducing or regulating the chromaticity of thermosetting polyphenylene ether resins.

[0005] Therefore, it is of great significance to provide a method for preparing a thermosetting polyphenylene ether with low chroma. Summary of the invention

[0006] The present invention aims to solve one or more technical problems existing in the above-mentioned prior art, and at least provide a beneficial choice or create conditions. Specifically, the present invention provides a method for preparing a thermosetting polyphenylene ether, which has a lower chromaticity and can well meet the requirements of copper clad laminates for the chromaticity of resin raw materials.

[0007] The inventive concept of the present invention: The preparation method of the thermosetting polyphenylene ether of the present invention comprises the following steps: mixing a copper catalyst, an amine compound, an organic acid compound, an organic acid ester compound, a monohydric phenol, a dihydric phenol and a solvent, reacting, removing the copper catalyst, and obtaining a dihydroxy-terminated polyphenylene ether solution; mixing a capping catalyst, an olefination agent and the dihydroxy-terminated polyphenylene ether solution, reacting, separating and purifying, and obtaining the thermosetting polyphenylene ether. The present invention can significantly reduce the chromaticity of the thermosetting polyphenylene ether by simultaneously adding an organic acid compound and an organic acid ester compound during the oxidative copolymerization reaction, and the platinum-cobalt chromaticity value of its 50wt% butanone solution can be as low as 14-15. At the same time, the characteristic viscosity and molecular structure of the thermosetting polyphenylene ether do not undergo significant changes, and can well meet the requirements of the copper clad laminate for the chromaticity of the resin raw materials.

[0008] Therefore, a first aspect of the present invention provides a method for preparing a thermosetting polyphenylene ether.

[0009] Specifically, the preparation method of the thermosetting polyphenylene ether comprises the following steps:

[0010] (1) mixing a copper catalyst, an amine compound, an organic acid compound, an organic acid ester compound, a monohydric phenol, a dihydric phenol and a solvent, reacting them, removing the copper catalyst, and preparing a dihydroxy-terminated polyphenylene ether solution;

[0011] (2) mixing the end-capping catalyst, the olefination agent and the dihydroxy-terminated polyphenylene ether solution obtained in step (1), reacting, separating and purifying, and obtaining the thermosetting polyphenylene ether.

[0012] Preferably, in step (1), the copper catalyst comprises at least one of copper bromide and cuprous bromide.

[0013] Preferably, in step (1), the amine compound comprises at least one monovalent secondary amine.

[0014] Further preferably, in step (1), the amine compound includes di-n-butylamine.

[0015] Preferably, in step (1), the amine compound further comprises at least one of a monoprimary amine, a monotertiary amine and a diamine.

[0016] Further preferably, in step (1), the amine compound also includes at least one of n-butylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethyl-n-butylamine, N,N-dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylpropylenediamine and tetramethylbutylenediamine.

[0017] Preferably, in step (1), the organic acid compound comprises at least one of acrylic acid and methacrylic acid.

[0018] Preferably, in step (1), the organic acid ester compound comprises at least one of methyl acrylate and methyl methacrylate.

[0019] Preferably, in step (1), the monohydric phenol includes 2,6-dimethylphenol.

[0020] Preferably, in step (1), the dihydric phenol includes tetramethyl bisphenol A.

[0021] Preferably, in step (1), the solvent comprises toluene.

[0022] Specifically, the solvent is a benign solvent for polyphenylene ether.

[0023] Preferably, in step (1), the molar ratio of the monohydric secondary amine to the monohydric phenol is (0.005-0.015):1; further preferably, in step (1), the molar ratio of the monohydric secondary amine to the monohydric phenol is (0.008-0.012):1.

[0024] Preferably, in step (1), the molar ratio of the organic acid compound to the monoamine is (0.1-1):1; further preferably, in step (1), the molar ratio of the organic acid compound to the monoamine is (0.3-0.7):1.

[0025] Preferably, in step (1), the molar ratio of the organic acid ester compound to the monoamine is (0.3-1.5):1; further preferably, in step (1), the molar ratio of the organic acid ester compound to the monoamine is (0.5-1.3):1.

[0026] Preferably, in step (1), the molar ratio of the monohydric phenol to the dihydric phenol is (2-30):1; further preferably, in step (1), the molar ratio of the monohydric phenol to the dihydric phenol is (2-20):1.

[0027] Preferably, in step (1), the reaction temperature is 15-65°C. More preferably, in step (1), the reaction temperature is 20-60°C.

[0028] Preferably, in step (1), the reaction time is 2-5 h; further preferably, in step (1), the reaction time is 3-4 h.

[0029] Specifically, in step (1), the reaction is an oxidative copolymerization reaction.

[0030] Preferably, the process of removing the copper catalyst comprises: mixing the product after the reaction with a chelating agent, reacting, liquid-liquid separation, removing the heavy phase copper catalyst solution, and obtaining the dihydroxy-terminated polyphenylene ether solution.

[0031] Specifically, the heavy phase copper catalyst solution is removed, and the obtained light phase is the dihydroxy-terminated polyphenylene ether solution.

[0032] Preferably, the chelating agent comprises trisodium nitrilotriacetate.

[0033] Preferably, the reaction temperature is 50-90°C, and the reaction time is 30-90 min; further preferably, the reaction temperature is 60-80°C, and the reaction time is 55-65 min.

[0034] Preferably, in step (2), the capping catalyst comprises 4-dimethylaminopyridine.

[0035] Preferably, in step (2), the alkenylating agent comprises at least one of acrylic anhydride and methacrylic anhydride; further preferably, in step (2), the alkenylating agent is methacrylic anhydride.

[0036] Specifically, in order to avoid introducing new impurities during the synthesis process, the organic acid compound used in step (1) is preferably the acid corresponding to the alkenylating agent.

[0037] Preferably, in step (2), the reaction temperature is 80-120°C; further preferably, in step (2), the reaction temperature is 90-110°C.

[0038] Preferably, in step (2), the reaction time is 1-5 h; further preferably, in step (2), the reaction time is 2-4 h.

[0039] Specifically, in step (2), the reaction is an olefination reaction.

[0040] Preferably, in step (2), the separation and purification method comprises: adding the product obtained by the reaction into a solvent for precipitation, separation, washing, and drying.

[0041] Preferably, the solvent is a poor solvent for polyphenylene ether; further preferably, the poor solvent for polyphenylene ether includes C1-C4 alkyl alcohol; further preferably, the poor solvent for polyphenylene ether is methanol.

[0042] Preferably, in step (2), before the separation and purification, the process further includes washing, filtering and concentrating the thermosetting polyphenylene ether solution obtained by the olefination reaction.

[0043] A second aspect of the present invention provides a thermosetting polyphenylene ether.

[0044] Specifically, the thermosetting polyphenylene ether is prepared by the preparation method described in the first aspect of the present invention, and the platinum-cobalt chromaticity value of a 50 wt % butanone solution of the thermosetting polyphenylene ether is 14-16.

[0045] Preferably, the platinum-cobalt chromaticity value of a 50 wt % butanone solution of the thermosetting polyphenylene ether is 14-15.

[0046] The third aspect of the present invention provides an application of the method for preparing the thermosetting polyphenylene ether according to the first aspect of the present invention in the field of preparing electronic materials.

[0047] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0048] (1) The present invention conducts an oxidative copolymerization reaction of monohydric phenol and dihydric phenol in a benign solvent of polyphenylene ether in the presence of a copper catalyst, an amine compound, an organic acid compound and an organic acid ester compound, and further conducts an olefination reaction after removing the copper catalyst to obtain a thermosetting polyphenylene ether. The present invention can significantly reduce the chromaticity of the thermosetting polyphenylene ether by simultaneously adding an organic acid compound and an organic acid ester compound during the oxidative copolymerization reaction, and the platinum-cobalt chromaticity value of its 50wt% butanone solution can be as low as 14-15. At the same time, the intrinsic viscosity and molecular structure of the thermosetting polyphenylene ether do not undergo significant changes. The low-chromaticity thermosetting polyphenylene ether resin prepared by the present invention is used to prepare high-frequency and high-speed copper-clad laminates, and the chromaticity of the products thereof will also be significantly reduced.

[0049] (2) In the oxidative copolymerization process of the present invention, the organic acid compound and the organic acid ester compound must be present at the same time. If either of them is missing, even if the content of the other component is increased, the purpose of effectively reducing the chromaticity of the thermosetting polyphenylene ether cannot be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a hydrogen nuclear magnetic resonance spectrum of the thermosetting polyphenylene ether prepared in Example 1 of the present invention;

[0051] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the thermosetting polyphenylene ether prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0052] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0053] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0054] In Examples 1-4 and Comparative Examples 1-5, the relationship between the addition amounts of the relevant raw material components is shown in Table 1.

[0055] Table 1: Relationship of the amount of relevant raw material components added in Examples 1-4 and Comparative Examples 1-5

[0056]

[0057] Example 1

[0058] A method for preparing a thermosetting polyphenylene ether comprises the following steps:

[0059] (1) Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 30.8 g of tetramethylbisphenol A (0.108 mol) and 500.0 g of toluene to a reaction kettle, stir and dissolve, then add 2.5 g of di-n-butylamine (0.019 mol), 4.5 g of N,N-dimethylcyclohexylamine, 1.0 g of methacrylic acid (0.012 mol), 1.8 g of methyl methacrylate (0.018 mol) and 2.60 g of cuprous bromide solution (preliminarily prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, introduce oxygen, and react at 40° C. for 4 h; after the reaction is completed, add 30 g of 10 wt% trisodium nitrilotriacetate solution, stir and react at 70° C. for 60 min, then stand and remove the aqueous phase to obtain a dihydroxy-terminated polyphenylene ether solution;

[0060] (2) Add 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride to the double-terminated hydroxyl polyphenylene ether solution, and react at 100° C. for 3 h. After the reaction, distill and concentrate the resulting solution to 570 g. Then, add 3000 g of methanol to precipitate, filter, wash with methanol three times, and vacuum dry at 100° C. for 8 h to obtain a thermosetting polyphenylene ether.

[0061] Example 2

[0062] A method for preparing a thermosetting polyphenylene ether comprises the following steps:

[0063] (1) Add 220.0 g of 2,6-dimethylphenol (1.803 mol), 30.8 g of tetramethylbisphenol A (0.108 mol) and 500.0 g of toluene to a reaction kettle, stir and dissolve, then add 2.1 g of di-n-butylamine (0.016 mol), 4.5 g of N,N-dimethyl-n-butylamine, 1.1 g of methacrylic acid (0.013 mol), 1.0 g of methyl methacrylate (0.010 mol) and 2.86 g of cuprous bromide solution (preliminarily prepared with 0.22 g of cuprous oxide and 2.64 g of hydrobromic acid), mix well, introduce oxygen, and react at 35° C. for 4 h; after the reaction is completed, add 33 g of 10 wt% trisodium nitrilotriacetate solution, stir and react at 60° C. for 60 min, then stand and remove the aqueous phase to obtain a dihydroxy-terminated polyphenylene ether solution;

[0064] (2) 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to the dihydroxy-terminated polyphenylene ether solution, and the mixture was reacted at 100° C. for 3 h. After the reaction, the resulting solution was concentrated to 590 g by distillation, and then added to 3000 g of methanol to precipitate. The precipitate was filtered, washed with methanol for 3 times, and vacuum dried at 100° C. for 8 h to obtain a thermosetting polyphenylene ether.

[0065] Example 3

[0066] A method for preparing a thermosetting polyphenylene ether comprises the following steps:

[0067] (1) Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 34.2 g of tetramethylbisphenol A (0.120 mol) and 500.0 g of toluene to a reaction kettle, stir and dissolve, then add 2.1 g of di-n-butylamine (0.016 mol), 4.5 g of N,N-dimethylcyclohexylamine, 0.5 g of methacrylic acid (0.006 mol), 2.0 g of methyl methacrylate (0.020 mol) and 2.60 g of cuprous bromide solution (preliminarily prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, introduce oxygen, and react at 40° C. for 4 h; after the reaction is completed, add 30 g of 10 wt% trisodium nitrilotriacetate solution, stir and react at 65° C. for 60 min, then stand and remove the aqueous phase to obtain a dihydroxy-terminated polyphenylene ether solution;

[0068] (2) Add 4.3 g of 4-dimethylaminopyridine and 58.0 g of methacrylic anhydride to the double-terminated hydroxyl polyphenylene ether solution, and react at 100° C. for 3 h. After the reaction, distill and concentrate the resulting solution to 570 g. Then, add 3000 g of methanol to precipitate, filter, wash with methanol three times, and vacuum dry at 100° C. for 8 h to obtain a thermosetting polyphenylene ether.

[0069] Example 4

[0070] A method for preparing a thermosetting polyphenylene ether comprises the following steps:

[0071] (1) Add 200.0 g of 2,6-dimethylphenol (1.639 mol), 34.2 g of tetramethylbisphenol A (0.120 mol) and 500.0 g of toluene to a reaction kettle, stir and dissolve, then add 2.3 g of di-n-butylamine (0.018 mol), 2.5 g of N,N-dimethylcyclohexylamine, 0.5 g of tetramethylethylenediamine, 0.7 g of methacrylic acid (0.008 mol), 1.0 g of methyl methacrylate (0.010 mol) and 2.60 g of cuprous bromide solution (preliminarily prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid), mix well, introduce oxygen, and react at 40° C. for 3 h; after the reaction is completed, add 30 g of 10 wt% trisodium nitrilotriacetate solution, stir and react at 75° C. for 60 min, then stand and remove the aqueous phase to obtain a dihydroxy-terminated polyphenylene ether solution;

[0072] (2) Add 4.3 g of 4-dimethylaminopyridine and 58.0 g of methacrylic anhydride to the double-terminated hydroxyl polyphenylene ether solution, and react at 100° C. for 3 h. After the reaction, distill and concentrate the resulting solution to 570 g. Then, add 3000 g of methanol to precipitate, filter, wash with methanol three times, and vacuum dry at 100° C. for 8 h to obtain a thermosetting polyphenylene ether.

[0073] Comparative Example 1

[0074] The only difference between Comparative Example 1 and Example 1 is that methacrylic acid and methyl methacrylate are not added in Comparative Example 1, and the other parts are the same as Example 1.

[0075] Comparative Example 2

[0076] The difference between Comparative Example 2 and Example 1 is that no methyl methacrylate is added in Comparative Example 2, and the other parts are the same as Example 1.

[0077] Comparative Example 3

[0078] The difference between Comparative Example 3 and Example 1 is that methyl methacrylate is not added in Comparative Example 3, and the added amount of methacrylic acid is increased to 2.548 g (0.030 mol), and the rest is the same as Example 1.

[0079] Comparative Example 4

[0080] The difference between Comparative Example 4 and Example 1 is that no methacrylic acid is added in Comparative Example 4, and the other steps are the same as Example 1.

[0081] Comparative Example 5

[0082] The difference between Comparative Example 5 and Example 1 is that methacrylic acid is not added in Comparative Example 5, and the addition amount of methyl methacrylate is increased to 2.963 g (0.030 mol), and the rest is the same as Example 1.

[0083] Performance Testing

[0084] 1. MRI test

[0085] The thermosetting polyphenylene ether prepared in Example 1 and Comparative Example 1 were subjected to nuclear magnetic resonance tests, and the nuclear magnetic resonance hydrogen spectra of the thermosetting polyphenylene ether prepared in Example 1 and Comparative Example 1 were as follows: Figure 1 and 2 As shown, the abscissa f1 (ppm) represents the chemical shift.

[0086] Figure 1 and Figure 2 In the graph, the peak 1 at 6.98ppm is the proton peak on the benzene ring of the tetramethyl bisphenol A unit, the peak 2 at 6.48ppm is the proton peak on the benzene ring in the polyphenylene ether repeating unit, the peak 3 at 6.37ppm and the peak 4 at 5.74ppm are the proton peaks of =CH2 on the methyl propylene group at the end of the molecular chain. Figure 1 and 2 It can be seen that the addition of methacrylic acid and methyl methacrylate during the oxidative copolymerization process did not have a significant effect on the structure of the final product.

[0087] 2. Intrinsic viscosity and color value test

[0088] The intrinsic viscosity and chromaticity value of the thermosetting polyphenylene ether prepared in Examples 1-4 and Comparative Examples 1-5 were tested respectively, and the testing method was as follows:

[0089] Intrinsic viscosity: Chloroform was used as solvent and the intrinsic viscosity of thermosetting polyphenylene ether was tested using an Ubbelohde viscometer at 30°C.

[0090] Chromaticity value: 15 g of thermosetting polyphenylene ether resin and 15 g of butanone were sequentially added into a sealed conical flask, stirred to dissolve, and then a platinum-cobalt colorimeter was used to test the platinum-cobalt chromaticity value of a 50 wt% butanone solution of the thermosetting polyphenylene ether resin at 25°C.

[0091] The test results of the intrinsic viscosity and chromaticity value of the thermosetting polyphenylene ether resin of Examples 1-4 and Comparative Examples 1-5 are shown in Table 2.

[0092] Table 2: Intrinsic viscosity and chromaticity values ​​of thermosetting polyphenylene ether resins of Examples 1-4 and Comparative Examples 1-5

[0093]

[0094]

[0095] As can be seen from Table 2, the present invention adds methacrylic acid and methyl methacrylate during the oxidative copolymerization reaction, so that the platinum-cobalt chromaticity value of the 50 wt % butanone solution of the finally synthesized thermosetting polyphenylene ether product is 14-16, which has a lower chromaticity value.

[0096] Compared with Example 1, Comparative Example 1 did not add methacrylic acid and methacrylate during the oxidative copolymerization reaction, so that its chromaticity value was 16.9, which was significantly higher than that of Example 1, but its intrinsic viscosity did not change significantly.

[0097] Compared with Example 1, Comparative Example 2 did not add methyl methacrylate during the oxidative copolymerization reaction, so that its chromaticity value was 16.4, which was slightly improved compared with Comparative Example 1, but still significantly higher than Example 1. Comparative Example 3 did not add methyl methacrylate during the oxidative copolymerization reaction, and the amount of methacrylic acid was further increased on the basis of Comparative Example 2, and its chromaticity value was 16.3, which was not significantly improved compared with Comparative Example 2, indicating that when only methacrylic acid was added during the oxidative copolymerization reaction, even if its amount was further increased, the chromaticity of the thermosetting polyphenylene ether could not be effectively reduced.

[0098] Compared with Example 1, Comparative Example 4 did not add methacrylic acid during the oxidative copolymerization reaction, so that its chromaticity value was 16.3, which was slightly improved compared with Comparative Example 1, but still significantly higher than Example 1. Comparative Example 5 did not add methacrylic acid during the oxidative copolymerization reaction, and the amount of methacrylate was further increased on the basis of Comparative Example 4, and its chromaticity value was 16.3, which was not significantly improved compared with Comparative Example 4, indicating that when only methacrylate was added during the oxidative copolymerization reaction, even if its amount was further increased, the chromaticity of the thermosetting polyphenylene ether could not be effectively reduced.

[0099] In summary, the present invention simultaneously adds an organic acid compound and an organic acid ester compound during the oxidative copolymerization process, and the two act synergistically, and in combination with other components, the chromaticity of the thermosetting polyphenylene ether can be significantly reduced, and the platinum-cobalt chromaticity value of its 50wt% butanone solution can be as low as 14-16, or even reduced to 14-15; at the same time, the intrinsic viscosity and molecular structure of the thermosetting polyphenylene ether do not undergo significant changes.

[0100] The above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing a thermosetting polyphenylene ether, characterized in that: The following steps are involved: (1) mixing a copper catalyst, an amine compound, an organic acid compound, an organic acid ester compound, a monohydric phenol, a dihydric phenol and a solvent, reacting them, removing the copper catalyst, and preparing a dihydroxy-terminated polyphenylene ether solution; (2) mixing the end-capping catalyst, the olefination agent and the dihydroxy-terminated polyphenylene ether solution obtained in step (1), reacting, separating and purifying, and obtaining the thermosetting polyphenylene ether.

2. The preparation method according to claim 1, characterized in that: In step (1), the copper catalyst includes at least one of copper bromide and cuprous bromide; and / or the amine compound includes at least one monoamine; and / or the organic acid compound includes at least one of acrylic acid and methacrylic acid; and / or the organic acid ester compound includes at least one of methyl acrylate and methyl methacrylate; and / or the monophenol includes 2,6-dimethylphenol; and / or the diphenol includes tetramethyl bisphenol A; and / or the solvent includes toluene.

3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of the monohydric secondary amine to the monohydric phenol is (0.005-0.015):1; and / or the molar ratio of the monohydric phenol to the dihydric phenol is (2-30):

1.

4. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of the organic acid compound to the monoamine is (0.1-1):1; and / or the molar ratio of the organic acid ester compound to the monoamine is (0.3-1.5):

1.

5. The preparation method according to claim 1, characterized in that: In step (1), the reaction temperature is 15-65°C.

6. The preparation method according to claim 1, characterized in that: The process of removing the copper catalyst comprises: mixing the product after the reaction with a chelating agent, reacting, liquid-liquid separation, removing the heavy phase copper catalyst solution, and obtaining the dihydroxy-terminated polyphenylene ether solution.

7. The preparation method according to claim 1, characterized in that: In step (2), the capping catalyst includes 4-dimethylaminopyridine; and / or the olefination agent includes at least one of acrylic anhydride and methacrylic anhydride.

8. The preparation method according to claim 1, characterized in that: In step (2), the reaction temperature is 80-120°C.

9. A thermosetting polyphenylene ether, characterized in that: The thermosetting polyphenylene ether is prepared by the preparation method according to any one of claims 1 to 8, wherein the platinum-cobalt chromaticity value of a 50wt% butanone solution of the thermosetting polyphenylene ether is 14-16.

10. Application of the preparation method according to any one of claims 1 to 8 in the field of preparing electronic materials.

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