A thermosetting polyphenyl ether and a method for preparing and using the same

Abstract

The present application belongs to the technical field of thermosetting polyphenyl ether, and particularly relates to a thermosetting polyphenyl ether, 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, a monohydric phenol, a dihydric phenol and a solvent, reacting, removing the copper catalyst, and obtaining a double-end hydroxyl polyphenyl ether solution; mixing a capping catalyst, an alkenylating agent and the double-end hydroxyl polyphenyl ether solution, reacting, and separating and purifying to obtain the thermosetting polyphenyl ether. In the process of oxidative copolymerization, the organic acid compound and the organic acid ester compound are simultaneously added, the two compounds synergize, and in combination with other components, the colority of the thermosetting polyphenyl ether can be obviously reduced, and the platinum-cobalt colority value of a 50wt% butanone solution can be as low as 14-16; at the same time, the inherent viscosity and the molecular structure of the thermosetting polyphenyl ether are not obviously changed.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of thermosetting polyphenyl ether, and particularly relates to a thermosetting polyphenyl ether, a preparation method and application thereof. BACKGROUND

[0002] Polyphenyl ether resin has good heat resistance, flame retardance, low water absorption and dimensional stability, and can maintain excellent dielectric properties in a wide frequency and temperature range, and is one of ideal materials for high-frequency high-speed copper-clad plates. However, polyphenyl ether with a conventional molecular weight has a high melting temperature and a large melt viscosity, and is difficult to be directly applied to a copper-clad plate. Meanwhile, polyphenyl ether solution has a large viscosity and poor glass fiber impregnation, and is thermoplastic, which cannot meet the process requirements of the copper-clad plate manufacturing. Generally, polyphenyl ether needs to be modified into a low-molecular-weight thermosetting resin to adapt to the curing formula system of the copper-clad plate.

[0003] A typical production method of low-molecular-weight thermosetting polyphenyl ether resin is to first use a monohydric phenol and a dihydric phenol to oxidatively copolymerize to form a dihydroxyl polyphenyl ether solution, remove the solvent and an organic amine compound by high-temperature devolatilization to form a dihydroxyl polyphenyl ether solid, and then make the dihydroxyl polyphenyl ether react with an alkenylating agent in a good solvent to form a thermosetting polyphenyl ether with double end alkenyl groups. Generally, polyphenyl ether with a conventional molecular weight has a low colority, while the thermosetting polyphenyl ether often has a high colority due to the particularity and complexity of the preparation process. The platinum-cobalt colority value of the 50% butanone solution of the thermosetting polyphenyl ether product currently sold on the market is between 16 and 18, and the colority value is high.

[0004] With the further development of signal transmission towards high speed, high-speed copper-clad plates have become mainstream of servers, and the colority requirement of the resin raw material of the high-speed copper-clad plate is also higher and higher. For reducing the colority of polyphenyl ether products with a conventional molecular weight, the existing technology discloses a method for decolorizing polyphenyl ether resin, which makes the polyphenyl ether decolorize by contacting with a hydroxyl compound containing a hydroxyl group or a double bond or an aromatic bond at a specific position in the molecule in a molten state or a solution. The decolorizing method is to decolorize the product end, and introduces new impurity compounds, which is not suitable for electronic thermosetting polyphenyl ether resin with high purity requirements. At present, there is no report on reducing or regulating the colority of thermosetting polyphenyl ether resin.

[0005] Therefore, it is of great significance to provide a preparation method of thermosetting polyphenyl ether with low colority. SUMMARY

[0006] The present application aims to solve one or more technical problems in the prior art, and at least provide a beneficial choice or create conditions. Specifically, the present application provides a preparation method of thermosetting polyphenyl ether, which has a low colority and can well meet the colority requirement of the resin raw material of the copper-clad plate.

[0007] The present application provides a method for preparing a thermosetting polyphenyl ether, comprising 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 double-end hydroxyl polyphenyl ether solution; mixing a capping catalyst, an alkenylating agent and the double-end hydroxyl polyphenyl ether solution, reacting, separating and purifying, and obtaining the thermosetting polyphenyl ether. The present application can significantly reduce the color of the thermosetting polyphenyl ether by simultaneously adding an organic acid compound and an organic acid ester compound in the oxidative copolymerization process, and the platinum-cobalt color value of a 50wt% butanone solution of the thermosetting polyphenyl ether can be as low as 14-15. Meanwhile, the intrinsic viscosity and the molecular structure of the thermosetting polyphenyl ether do not change significantly, and the color requirement of the resin raw material for the copper-clad plate can be well met.

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

[0009] Specifically, the method for preparing the thermosetting polyphenyl 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, removing the copper catalyst, and obtaining a double-end hydroxyl polyphenyl ether solution;

[0011] (2) mixing a capping catalyst, an alkenylating agent and the double-end hydroxyl polyphenyl ether solution obtained in step (1), reacting, separating and purifying, and obtaining the thermosetting polyphenyl 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 monohydric secondary amine.

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

[0015] Preferably, in step (1), the amine compound further comprises at least one of a monohydric primary amine, a monohydric tertiary amine and a dihydric amine.

[0016] Further preferably, in step (1), the amine compound further comprises 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 comprises 2,6-dimethylphenol.

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

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

[0022] In particular, the solvent is a good solvent for polyphenyl 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 monohydric secondary amine is (0.1-1):1; further preferably, in step (1), the molar ratio of the organic acid compound to the monohydric secondary amine is (0.3-0.7):1.

[0025] Preferably, in step (1), the molar ratio of the organic acid ester compound to the monohydric secondary amine is (0.3-1.5):1; further preferably, in step (1), the molar ratio of the organic acid ester compound to the monohydric secondary amine 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 temperature of the reaction is 15-65℃, further preferably, in step (1), the temperature of the reaction is 20-60℃.

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

[0029] In particular, 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, to obtain the double-end hydroxyl polyphenyl ether solution.

[0031] Specifically, the light phase obtained by removing the heavy phase copper catalyst solution is the double-end hydroxyl polyphenyl ether solution.

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

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

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

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

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

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

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

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

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

[0041] Preferably, the solvent is a poor solvent of polyphenyl ether; further preferably, the poor solvent of polyphenyl ether comprises C1-C4 alkyl alcohol; more preferably, the poor solvent of polyphenyl ether is methanol.

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

[0043] The second aspect of the present application provides a thermosetting polyphenyl ether.

[0044] Specifically, the thermosetting polyphenyl ether is prepared by the preparation method of the first aspect of the present application, and the platinum-cobalt color value of a 50wt% butanone solution of the thermosetting polyphenyl ether is 14-16.

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

[0046] The third aspect of the present application provides a use of the preparation method of the thermosetting polyphenyl ether of the first aspect of the present application in the field of electronic materials.

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

[0048] (1) In the present application, monohydric phenol and dihydric phenol are subjected to oxidative copolymerization in a good solvent of polyphenyl ether in the presence of copper catalyst, amine compound, organic acid compound and organic acid ester compound, and after removal of the copper catalyst, an alkenyl reaction is further carried out to obtain thermosetting polyphenyl ether. In the present application, by simultaneously adding organic acid compound and organic acid ester compound in the process of oxidative copolymerization, the color of the thermosetting polyphenyl ether can be significantly reduced, and the platinum-cobalt color value of a 50wt% butanone solution of the thermosetting polyphenyl ether can be as low as 14-15. At the same time, the intrinsic viscosity and molecular structure of the thermosetting polyphenyl ether are not significantly changed. The low-color thermosetting polyphenyl ether resin prepared by the present application is used to prepare high-frequency high-speed copper-clad plate, and the color of the product is also significantly reduced.

[0049] (2) In the present application, organic acid compound and organic acid ester compound must exist simultaneously in the process of oxidative copolymerization, and the absence of any one of them, even if the content of the other component is increased, cannot achieve the purpose of effectively reducing the color of the thermosetting polyphenyl ether. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the thermosetting polyphenyl ether prepared in Example 1 of the present application is shown in the following figure.

[0051] Figure 2 The nuclear magnetic resonance hydrogen spectrum of the thermosetting polyphenyl ether prepared in Comparative Example 1 of the present application is shown in the following figure. DETAILED DESCRIPTION

[0052] In order to make those skilled in the art more clearly understand the technical scheme of the present application, the following examples are given for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the present application.

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

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

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

[0056]

[0057] Example 1

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

[0059] (1) 200.0 g of 2,6-dimethylphenol (1.639 mol), 30.8 g of tetramethyl bisphenol A (0.108 mol), and 500.0 g of toluene were added to a reaction kettle, and after stirring and dissolving, 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 a cuprous bromide solution (freshly prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added, mixed uniformly, oxygen was introduced, and reaction was performed at 40°C for 4 h; after the reaction was completed, 30 g of a 10 wt% solution of trisodium nitrilotriacetate was added, stirring was performed at 70°C for 60 min, and then the aqueous phase was removed by standing, thereby obtaining a solution of a dihydroxyl-terminated polyphenylene ether;

[0060] (2) 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added to the dihydroxyl-terminated polyphenylene ether solution, and reaction was performed at 100°C for 3 h; after the reaction was completed, the obtained solution was distilled and concentrated to 570 g, and then 3000 g of methanol was added, and the precipitate was separated by filtration, washed with methanol three times, and dried at 100°C under vacuum for 8 h, thereby obtaining a thermosetting polyphenylene ether.

[0061] Example 2

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

[0063] (1) 220.0 g of 2,6-dimethylphenol (1.803 mol), 30.8 g of tetramethyl bisphenol A (0.108 mol), and 500.0 g of toluene were added to a reaction kettle, and after stirring and dissolving, 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 a cuprous bromide solution (freshly prepared with 0.22 g of cuprous oxide and 2.64 g of hydrobromic acid) were added, mixed uniformly, oxygen was introduced, and reaction was performed at 35°C for 4 h; after the reaction was completed, 33 g of a 10 wt% solution of trisodium nitrilotriacetate was added, stirring was performed at 60°C for 60 min, and then the aqueous phase was removed by standing, thereby obtaining a solution of a dihydroxyl-terminated polyphenylene ether;

[0064] (2) To the solution of the di-hydroxyl terminated polyphenylene ether, 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added and reacted at 100°C for 3 h. After the reaction was completed, the resulting solution was distilled and concentrated to 590 g, then added to 3000 g of methanol, precipitated and separated by filtration, washed with methanol three times, and dried at 100°C under vacuum for 8 h to obtain a thermosetting polyphenylene ether.

[0065] Example 3

[0066] A method for preparing a thermosetting polyphenylene ether, comprising the steps of:

[0067] (1) In a reaction kettle, 200.0 g of 2,6-dimethylphenol (1.639 mol), 34.2 g of tetramethyl bisphenol A (0.120 mol) and 500.0 g of toluene were added, stirred and dissolved, then 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 (freshly prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added, mixed uniformly, oxygen was introduced, and reacted at 40°C for 4 h. After the reaction was completed, 30 g of 10 wt% of trisodium nitrilotriacetate solution was added, stirred at 65°C for 60 min, then the aqueous phase was removed after standing to obtain a di-hydroxyl terminated polyphenylene ether solution;

[0068] (2) To the solution of the di-hydroxyl terminated polyphenylene ether, 4.3 g of 4-dimethylaminopyridine and 52.0 g of methacrylic anhydride were added and reacted at 100°C for 3 h. After the reaction was completed, the resulting solution was distilled and concentrated to 590 g, then added to 3000 g of methanol, precipitated and separated by filtration, washed with methanol three times, and dried at 100°C under vacuum for 8 h to obtain a thermosetting polyphenylene ether.

[0069] Example 4

[0070] A method for preparing a thermosetting polyphenylene ether, comprising the steps of:

[0071] (1) In a reaction kettle, 200.0 g of 2,6-dimethylphenol (1.639 mol), 34.2 g of tetramethyl bisphenol A (0.120 mol) and 500.0 g of toluene were added, after stirring and dissolving, 2.3 g of di-n-butylamine (0.018 mol), 2.5 g of N,N-dimethylcyclohexylamine, 0.5 g of tetramethyl ethylenediamine, 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 (freshly prepared with 0.20 g of cuprous oxide and 2.40 g of hydrobromic acid) were added, mixed uniformly, oxygen was introduced, and reacted at 40°C for 3h; after the reaction was completed, 30 g of 10wt% nitrilotriacetic acid trisodium solution was added, stirred at 75°C for 60 min, and then the aqueous phase was removed after standing to obtain a double-end hydroxyl polyphenyl ether solution;

[0072] (2) 4.3 g of 4-dimethylaminopyridine and 58.0 g of methacrylic anhydride were added to the double-end hydroxyl polyphenyl ether solution, and reacted at 100°C for 3h; after the reaction was completed, the obtained solution was concentrated by distillation to 570 g, then added into 3000 g of methanol, precipitated and separated, washed with methanol for 3 times, and vacuum dried at 100°C for 8h to obtain a thermosetting polyphenyl ether.

[0073] Comparative Example 1

[0074] The difference between Comparative Example 1 and Example 1 is only that Comparative Example 1 does not add methacrylic acid and methyl methacrylate, and the others are the same as Example 1.

[0075] Comparative Example 2

[0076] The difference between Comparative Example 2 and Example 1 is only that Comparative Example 2 does not add methyl methacrylate, and the others are the same as Example 1.

[0077] Comparative Example 3

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

[0079] Comparative Example 4

[0080] The difference between Comparative Example 4 and Example 1 is only that Comparative Example 4 does not add methacrylic acid, and the others are the same as Example 1.

[0081] Comparative Example 5

[0082] The difference between Comparative Example 5 and Example 1 is only that Comparative Example 5 does not add methacrylic acid, and the amount of methyl methacrylate is increased to 2.963 g (0.030 mol), and the others are the same as Example 1.

[0083] Performance Test

[0084] 1. Nuclear magnetic resonance test

[0085] The thermosetting polyphenyl ether prepared in Example 1 and Comparative Example 1 was subjected to nuclear magnetic resonance test, and the nuclear magnetic resonance hydrogen spectrum of the thermosetting polyphenyl ether prepared in Example 1 and Comparative Example 1 is shown in Figure 1 and 2 wherein the abscissa f1 (ppm) represents chemical shift.

[0086] Figure 1 and Figure 2 In the above, the peak No. 1 at 6.98 ppm is the proton peak on the benzene ring of tetramethyl bisphenol A unit, the peak No. 2 at 6.48 ppm is the proton peak on the benzene ring in the polyphenyl ether repeating unit, and the peak No. 3 at 6.37 ppm and the peak No. 4 at 5.74 ppm are the proton peaks of =CH2 on the terminal methyl methacryl group of the molecular chain, respectively. Figure 1 and 2 It can be seen from the above that the addition of methacrylic acid and methyl methacrylate in the process of oxidative copolymerization does not have obvious influence on the structure of the final product.

[0087] 2. Intrinsic viscosity and color value test

[0088] The thermosetting polyphenyl ether prepared in Example 1-4 and Comparative Example 1-5 was subjected to intrinsic viscosity and color value test, and the test method is as follows:

[0089] Intrinsic viscosity: chloroform was used as solvent, and the intrinsic viscosity of the thermosetting polyphenyl ether was tested at 30℃ using an Ubbelohde viscometer;

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

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

[0092] Table 2: Intrinsic viscosity and color value of the thermosetting polyphenyl ether resin of Example 1-4 and Comparative Example 1-5

[0093]

[0094]

[0095] It can be seen from Table 2 that the addition of methacrylic acid and methyl methacrylate in the process of oxidative copolymerization makes the platinum-cobalt color value of the 50wt% butanone solution of the final synthesized thermosetting polyphenyl ether product be 14-16, which has a lower color value.

[0096] Compared with Example 1, the Comparative Example 1 did not add methacrylic acid and methacrylic ester in the oxidative copolymerization reaction, so that the color value thereof was 16.9, which was obviously higher than that of Example 1, but the inherent viscosity thereof did not change obviously.

[0097] Compared with Example 1, the Comparative Example 2 did not add methyl methacrylate in the oxidative copolymerization reaction, so that the color value thereof was 16.4, which was slightly improved compared with Comparative Example 1, but was still obviously higher than that of Example 1. The Comparative Example 3 did not add methyl methacrylate in the oxidative copolymerization reaction, and further increased the amount of methacrylic acid based on Comparative Example 2, so that the color value thereof was 16.3, which was not obviously improved compared with Comparative Example 2, which indicated that when only methacrylic acid was added in the oxidative copolymerization reaction, even if the amount thereof was further increased, the color value of the thermosetting polyphenyl ether could not be effectively reduced.

[0098] Compared with Example 1, the Comparative Example 4 did not add methacrylic acid in the oxidative copolymerization reaction, so that the color value thereof was 16.3, which was slightly improved compared with Comparative Example 1, but was still obviously higher than that of Example 1. The Comparative Example 5 did not add methacrylic acid in the oxidative copolymerization reaction, and further increased the amount of methacrylic ester based on Comparative Example 4, so that the color value thereof was 16.3, which was not obviously improved compared with Comparative Example 4, which indicated that when only methacrylic ester was added in the oxidative copolymerization reaction, even if the amount thereof was further increased, the color value of the thermosetting polyphenyl ether could not be effectively reduced.

[0099] In summary, the organic acid compound and the organic acid ester compound are simultaneously added in the oxidative copolymerization process according to the present application, the two compounds synergistically act, and in combination with other components, the color value of the thermosetting polyphenyl ether can be obviously reduced, the platinum-cobalt color value of the 50wt% butanone solution thereof can be as low as 14-16, or even 14-15; at the same time, the inherent viscosity and the molecular structure of the thermosetting polyphenyl ether do not change obviously.

[0100] The above examples are only used to illustrate the technical solutions of the present application, but not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A method for preparing 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 the mixture, removing the copper catalyst and obtaining a dihydroxy-terminated polyphenylene ether solution; (2) mixing the end-capping catalyst, the alkenylating agent and the dihydroxy-terminated polyphenylene ether solution obtained in step (1), reacting, separating and purifying, and obtaining the thermosetting polyphenylene ether; The organic acid compound includes at least one of acrylic acid and methacrylic acid; the organic acid ester compound includes at least one of methyl acrylate and methyl methacrylate; The amine compound includes at least one monovalent secondary amine; The molar ratio of the organic acid compound to the monoamine is (0.1-1):1; the molar ratio of the organic acid ester compound to the monoamine is (0.3-1.5):

1.

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 monohydric phenol includes 2,6-dimethylphenol; and / or the dihydric phenol 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 1, characterized in that In step (1), the reaction temperature is 15-65°C.

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

6. 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.

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

8. A thermosetting polyphenylene ether, characterized in that Prepared by the preparation method according to any one of claims 1 to 7, the platinum-cobalt chromaticity value of a 50wt% butanone solution of the thermosetting polyphenylene ether is 14-16.

9. Use of the preparation method according to any one of claims 1 to 7 in the field of preparing electronic materials.

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