Amino-terminated polyphenyl ether modified bismaleimide and preparation method thereof

Abstract

The invention provides a preparation method of polyphenyl ether modified bismaleimide, which comprises the following steps: in the presence of a basic catalyst, preparing nitrated polyphenyl ether from double-terminal hydroxyl polyphenyl ether; carrying out hydrogenation reaction on the nitrated polyphenyl ether in the presence of a catalyst to obtain amino-terminated polyphenyl ether; the preparation method comprises the following steps: dissolving bismaleimide resin, amino modified polyphenyl ether resin and a peroxyisopropyl benzene compound in bisphenol A to obtain a premix; and curing the premix. By introducing amino-terminated polyphenyl ether into a bismaleimide system, the prepared bismaleimide resin modified material is excellent in dielectric property, heat resistance and the like, solves the problem of poor dielectric property of the traditional bismaleimide material, can be used in the field of low-dielectric and high-temperature-resistant materials, and has wide application prospects. For example, the method can be applied to copper-clad plates and other fields.

Description

Technical Field

[0001] The present invention relates to the field of thermosetting resins, and in particular to a modified bismaleimide resin and a preparation method thereof. Background Art

[0002] Bismaleimide resins, due to their excellent mechanical properties, heat resistance, and solvent resistance, play a vital role in composite materials and structural adhesives for aerospace, electronics, and other fields. However, with the advancement of cutting-edge technology, particularly in the copper-clad laminate (CCL) field, the demand for BMI resin matrices with excellent thermal stability and dielectric properties has become increasingly urgent. Existing BMI resin materials no longer meet the performance requirements of high-integration, lower-power products, necessitating the development of BMI resin systems with superior dielectric properties and high heat resistance.

[0003] Polyphenylene ether (PPE) is one of the five most commonly used engineering plastics in the world. As a polymer material, it possesses excellent mechanical properties, thermal stability, flame retardancy, and dielectric properties, finding important applications in electronics, intelligent manufacturing, printed circuits, aerospace, and military equipment. SABIC has launched Noryl-SA90, a low-molecular-weight PPE, which has found widespread application in high-speed and high-frequency copper cladding. Modified PPE with amino end groups can be introduced into a bismuth system via a Michael addition reaction, improving its dielectric and heat resistance.

[0004] In summary, the existing technology urgently needs to solve the problem of poor dielectric properties of traditional bismaleimide materials and / or improve the application capabilities of bismaleimide in the fields of low dielectric and high temperature resistant materials. Summary of the Invention

[0005] To address the above-mentioned problems, the present invention provides polyphenylene ether-modified bismaleimide and a preparation method thereof. By introducing amino-terminated polyphenylene ether into a bismaleimide system, the prepared bismaleimide resin-modified material exhibits excellent dielectric properties and heat resistance, thereby overcoming the problem of poor dielectric properties of traditional bismaleimide materials. The material can be used in the fields of low dielectric and high-temperature resistant materials, for example, in fields such as copper-clad laminates, and has guiding significance for the preparation of other materials with similar properties.

[0006] The first aspect of the present invention aims to provide a method for preparing polyphenylene ether modified bismaleimide, which comprises first preparing amino-terminated polyphenylene ether, preferably using dihydroxy-terminated polyphenylene ether (PPO) as a raw material, preparing a nitroated aromatic compound in the presence of an alkaline catalyst, further hydrogenating the amino-terminated polyphenylene ether, and then preparing polyphenylene ether modified bismaleimide.

[0007] The method of the present invention comprises the following steps: Step 1: preparing nitrated polyphenylene ether from dihydroxy-terminated polyphenylene ether in the presence of a basic catalyst; Step 2: In the presence of a catalyst, the nitrated polyphenylene ether is subjected to a hydrogenation reaction to obtain an amino-terminated polyphenylene ether; Step 3, dissolving bisphenol A, amino-modified polyphenylene ether resin, and cumene peroxide compound in bisphenol A to obtain a premix; Step 4: solidify the premix.

[0008] According to the present invention, the PPO has a structure as shown in the following formula:

[0009] in, The value of x+y is 2-100, preferably 5-50.

[0010] In step 1 of the present invention, the double-terminated hydroxyl polyphenylene ether and the halogen nitrobenzene compound react in a solvent to obtain the nitrated polyphenylene ether. The p-halogen nitrobenzene is selected from one or two of p-fluoronitrobenzene, p-chloronitrobenzene, p-iodine nitrobenzene and p-bromonitrobenzene. Preferably, the molar ratio of halogen nitrobenzene to double-terminated hydroxyl polyphenylene ether is (1-100):1, preferably (1-50):1. The solvent is an organic solvent, The alkaline catalyst is selected from one or more of organic bases, alkali metal hydrides, alkali metal hydroxides, alkali metal carbonate compounds and alkali metal bicarbonate compounds. The molar ratio of the alkaline catalyst to the double-terminated hydroxyl polyphenylene ether is (0.5-100):1, preferably (1-60):1. The reaction temperature is 20 to 200°C, preferably 40 to 160°C.

[0011] The reaction time is 1 to 100 hours, preferably 2 to 50 hours.

[0012] In step 2 of the present invention, the catalyst is preferably a palladium-carbon catalyst. Preferably, the mass ratio of the palladium-carbon catalyst to the nitrated polyphenylene ether is 1:(10-500), preferably 1:(50-200). The nitropolyphenylene ether is subjected to a hydrogenation reaction in a solvent in a high-temperature and high-pressure reactor. The solvent is selected from one or more of tetrahydrofuran, chloroform, ethanol, water, toluene, xylene, dichloromethane, N,N-dimethylformamide, and N,N-dimethylacetamide. The pressure after hydrogenation is 0.05-5 MPa, preferably 0.4-2 MPa, and the reaction temperature is 40-180° C., preferably 60-140° C.

[0013] In step 2, after the reaction is completed, post-treatment is performed, and the reaction mixture is precipitated, washed, filtered and dried to finally obtain amino-terminated polyphenylene ether. The precipitant is an alcohol, preferably a lower alcohol, such as a fatty alcohol having 1 to 6 carbon atoms. The washing agent is preferably the same alcohol as the precipitant, such as methanol.

[0014] The vacuum drying temperature is 50 to 95° C., preferably 60 to 90° C., and the drying time is 10 to 50 h, preferably 15 to 30 h.

[0015] According to the present invention, the APPO can be represented by the following formula:

[0016] in, The value of x+y is 2-100, preferably 5-50, more preferably 10-20.

[0017] In step 3 of the present invention, the bismaleimide resin is selected from one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylene bismaleimide, 1,1'-(methylenebis(2-ethyl-6-methyl-4,1-phenylene))bismaleimide, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, bisphenol A is preferably 2,2'-allyl bisphenol A (DBA), and the cumene peroxide compound is di-tert-butylperoxyisopropylbenzene (BIBP). Preferably, the mass ratio of DBA to BIBP is 10~100:1, preferably 20~60:1.

[0018] In step 4 of the present invention, the premix is preferably cured in a hot press at a certain pressure and a preset temperature. The curing conditions are: constant temperature of 170-180° C. for 2-4 hours, constant temperature of 110-170° C. for 1.5-2 hours, constant temperature of 160-180° C. for 1.5-4 hours, and constant temperature of 240-250° C. for 2-4 hours.

[0019] In another aspect, the present invention provides a bismaleimide-modified material (named AD-BMI), which is prepared according to the method described above. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The following is a reaction formula for curing the premix to obtain a bismaleimide-modified material, as well as the structural formulas of the reaction components and the resulting cured product; Figure 2 The NMR spectrum of the nitro-terminated modified polyphenylene ether prepared in the pre-example is shown; Figure 3 The NMR spectrum of the amino-terminated modified polyphenylene ether prepared in the pre-example is shown; Figure 4 The infrared spectra of the nitro-terminated modified polyphenylene ether and the amino-terminated modified polyphenylene ether prepared in the examples are shown; Figure 5 The infrared spectra of the curing component used in Example 1 and the prepared amino-modified polyphenylene ether-modified bismaleimide resin cured product (AD-BMI) are shown. DETAILED DESCRIPTION

[0021] The present invention will be described in detail below through specific embodiments, and the features and advantages of the present invention will become clearer and more distinct with these descriptions.

[0022] According to one aspect of the present invention, a method for modifying bismaleimide with polyphenylene ether is provided, comprising first preparing amino-terminated polyphenylene ether, and then preparing polyphenylene ether-modified bismaleimide.

[0023] In the present invention, dihydroxy-terminated polyphenylene ether (PPO) is used as a raw material to prepare a nitro aromatic compound in the presence of an alkaline catalyst, and then further hydrogenated to prepare amino-terminated polyphenylene ether, which specifically includes the following steps 1 and 2.

[0024] Step 1: preparing nitrated polyphenylene ether from dihydroxy-terminated polyphenylene ether in the presence of a basic catalyst.

[0025] In the present invention, the double-terminated hydroxyl polyphenylene ether (PPO) has a structure shown in the following formula:

[0026] in, The value of x+y is 2-100, preferably 5-50, more preferably 10-20.

[0027] According to a preferred embodiment of the present invention, the double-terminated hydroxyl polyphenylene ether and the p-halogen nitrobenzene compound are reacted in a solvent to obtain the nitrated polyphenylene ether.

[0028] The p-halogen nitrobenzene is selected from one or two of p-fluoronitrobenzene, p-chloronitrobenzene, p-iodine nitrobenzene and p-bromonitrobenzene.

[0029] According to an embodiment of the present invention, the molar ratio of the p-halogen nitrobenzene to the dihydroxy-terminated polyphenylene ether is (1-100):1, preferably (1-50):1, and more preferably (1-20):1.

[0030] The solvent is an organic solvent, preferably one or more selected from the group consisting of benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0031] In the present invention, the alkaline catalyst is selected from one or more of organic bases, alkali metal hydrides, alkali metal hydroxides, alkali metal carbonate compounds and alkali metal bicarbonate compounds.

[0032] The molar ratio of the alkaline catalyst to the dihydroxy-terminated polyphenylene ether is (0.5-100):1, preferably (1-60):1, and more preferably (1-20):1.

[0033] In step 1, the reaction temperature is 20-200°C, preferably 40-160°C, more preferably 60-120°C.

[0034] The reaction time is 1 to 100 hours, preferably 2 to 50 hours, and more preferably 2 to 30 hours.

[0035] According to the present invention, after the reaction is completed, post-treatment is performed, including precipitation, washing, filtering and drying of the reaction mixture, to finally obtain 35 g of nitrated polyphenylene ether.

[0036] To this end, in step 1, after stopping the reaction, a precipitant is added to the supernatant of the reaction mixture for precipitation. The precipitant is an alcohol, preferably a lower alcohol, such as a fatty alcohol with 1 to 6 carbon atoms, more preferably methanol.

[0037] A detergent is added to the precipitate for washing. The detergent may be an alcohol, preferably the same alcohol as the precipitant, such as methanol.

[0038] Repeat the above washing and filtering steps multiple times, preferably 2 to 3 times, until no reaction solvent is present in the product, and finally vacuum dry the product at a drying temperature of 50 to 95° C., preferably 60 to 90° C., for 10 to 50 h, preferably 15 to 30 h.

[0039] Step 2: In the presence of a catalyst, the nitrated polyphenylene ether is subjected to a hydrogenation reaction to obtain an amino-terminated polyphenylene ether.

[0040] In step 2, the catalyst is preferably a palladium-carbon catalyst. Preferably, the mass ratio of the palladium-carbon catalyst to the nitrated polyphenylene ether is 1:(10-500), preferably 1:(50-200), and more preferably 1:(80-150).

[0041] According to a preferred embodiment, the nitrated polyphenylene ether is hydrogenated in a solvent in a high-temperature and high-pressure reactor.

[0042] The solvent is an organic solvent, preferably one or more selected from tetrahydrofuran, chloroform, ethanol, water, toluene, xylene, dichloromethane, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0043] The pressure after hydrogenation is 0.05-5 MPa, preferably 0.4-2 MPa.

[0044] The reaction temperature is 40-180°C, preferably 60-140°C, more preferably 80-120°C.

[0045] The reaction time is 1 to 50 hours, preferably 2 to 30 hours, more preferably 2 to 15 hours.

[0046] In step 2, after the reaction is completed, post-treatment is performed, and the reaction mixture is precipitated, washed, filtered and dried to finally obtain amino-terminated polyphenylene ether, also known as amino-terminated polyphenylene ether polyol.

[0047] To this end, in step 2, after stopping the reaction, a precipitant is added to the supernatant of the reaction mixture for precipitation. The precipitant is an alcohol, preferably a lower alcohol, such as a fatty alcohol with 1 to 6 carbon atoms, and more preferably methanol.

[0048] A detergent is added to the precipitate for washing. The detergent may be an alcohol, preferably the same alcohol as the precipitant, such as methanol.

[0049] Repeat the above washing and filtering steps multiple times, preferably 2 to 3 times, until no reaction solvent is present in the product, and finally vacuum dry the product at a drying temperature of 50 to 95° C., preferably 60 to 90° C., for 10 to 50 h, preferably 15 to 30 h.

[0050] The amino-terminated polyphenylene ether is amino-terminated polyphenylene ether diamine (APPO), which can be represented by the following formula:

[0051] in, The value of x+y is 2-100, preferably 5-50, more preferably 10-20.

[0052] Step 3: dissolving the bisphenol A resin, amino-modified polyphenylene ether resin, and cumene peroxide compounds in bisphenol A to obtain a premix.

[0053] In this step, the bismaleimide resin used is also called bismaleimide resin (BMI), which is a bismaleimide substance, preferably selected from one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylene bismaleimide, 1,1'-(methylenebis(2-ethyl-6-methyl-4,1-phenylene))bismaleimide, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane.

[0054] In the present invention, the bisphenol A is preferably 2,2'-allylbisphenol A (DBA), and the molar ratio of DBA to BMI is 1:0.8-2.0, preferably 1:1.0-1.5.

[0055] The cumene peroxide compound is preferably di-tert-butylcumene peroxide (BIBP). Preferably, the mass ratio of bisphenol A to BIBP is 10-100:1, preferably 20-60:1.

[0056] In the present invention, the preparation of the premix in step 3 is carried out under nitrogen protection. In order to facilitate dissolution, it is preferably heated, for example, to 50-180° C., preferably 80-150° C., more preferably 100-120° C., so that the bismaleimide resin, amino-modified polyphenylene ether resin, and BIBP are dissolved in DBA.

[0057] Step 4: solidify the premix.

[0058] In the present invention, the premix is cured in a hot press, preferably at a certain pressure and a preset temperature.

[0059] According to a preferred embodiment of the present invention, the curing conditions are: constant temperature of 170-180°C for 2-4 hours, constant temperature of 110-170°C for 1.5-2 hours, constant temperature of 160-180°C for 1.5-4 hours, and constant temperature of 240-250°C for 2-4 hours.

[0060] Through the above steps, the premix is cured to obtain a bismaleimide modified material. The structural formula of the reaction components and the obtained cured product is as follows: Figure 1 shown.

[0061] The above method of the present invention and the bismaleimide modified material prepared thereby can achieve the following beneficial effects: the prepared bismaleimide modified material has the performance advantages of polyphenylene ether, such as dielectric properties, heat resistance, etc., and can thus be applied to fields such as copper clad laminates. Example

[0062] Preliminary embodiment In a three-necked round-bottom flask equipped with a reflux condenser, 40.00 g (25.04 mmol) of double-terminated hydroxyl polyphenylene ether (PPO, purchased from Saudi Basic Industries (China) Co., Ltd., model Noryl SA90, molecular weight 1600, x+y=10), 11.76 g (74.72 mmol) of p-chloronitrobenzene (purchased from Anaiji Chemical) and 10.32 (74.48 mmol) of K2CO3 (purchased from Tianjin Damao Chemical Reagent Factory) were added to 200 mL of N,N-dimethylformamide (DMF), and the mixture was stirred and refluxed at 80°C for 24 h to stop the reaction.

[0063] The supernatant of the reaction mixture was dropped into anhydrous methanol for precipitation. The resulting off-white precipitate was further obtained by suction filtration, and the filter cake was washed with anhydrous methanol. Repeat the above vacuum filtration step and wash with anhydrous methanol 2 to 3 times until there is no reaction solvent in the product. Finally, the product was dried in a vacuum oven at 80 ° C for 24 hours. 35.96g of nitroated polyphenylene ether was obtained with a yield of about 93%, named NPPO, and its nuclear magnetic spectrum is as follows Figure 2 As shown by Figure 2 It can be seen that there is a characteristic peak a at a chemical shift of 8.23, a characteristic peak b at chemical shifts of 7.03 and 6.95, and a characteristic peak c at a chemical shift of 1.67. The corresponding substituents are shown in Figure 2 Its infrared spectrum is as follows Figure 4 shown (middle curve).

[0064] In a 500 mL high-temperature autoclave, 30.00 g (18.80 mmol) of nitropolyphenylene ether (NPPO) and 0.24 (2.26 mmol) of Pd / C (purchased from Anaiji Chemical) were added to 110 mL of tetrahydrofuran (THF) and 60 mL of anhydrous ethanol (EtOH), and the mixture was reacted at 100 ° C and a hydrogen pressure of 1.11 MPa for 10 h, and the reaction was stopped.

[0065] The supernatant of the reaction mixture was dropped into anhydrous methanol for precipitation, and the resulting off-white precipitate was further obtained by suction filtration and the filter cake was washed with anhydrous methanol. Repeat the above vacuum filtration step and wash with anhydrous methanol 2 to 3 times until there is no reaction solvent in the product. Finally, the product was dried in a vacuum oven at 80°C for 24 hours. 27.82g of amino-terminated polyphenylene ether was obtained with a yield of about 90%, named APPO, and its NMR spectrum is as follows Figure 3 As shown by Figure 3 It can be seen that there is a characteristic peak a at a chemical shift of 4.66, a characteristic peak b at a chemical shift of 7.03, and a characteristic peak c at a chemical shift of 1.67, and the corresponding substituents are shown in Figure 3 Its infrared spectrum is as follows Figure 4 shown (upper curve).

[0066] Example 1 Weigh 4 g of 2,2'-diallylbisphenol A (DBA, purchased from Anaiji Chemical), 0.25 g of APPO and 0.1 g of di-tert-butylperoxyisopropylbenzene (BIBP, purchased from Anaiji Chemical), add them into a three-necked flask equipped with a magnetic stirrer and nitrogen protection, heat them to 120 ° C in an oil bath to completely dissolve them, and after they are completely dissolved, add 6 g of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane (BMI, purchased from Yamato Chemical Co., Ltd. of Japan) in three batches and stir until they are completely dissolved.

[0067] The curing reaction was carried out in a hot press. The hot press pressure was set to 5.2 tons. The temperature was gradually increased according to a certain procedure (as shown in Table 1). The temperature was maintained at 116.6°C for about 2 hours, 163.5°C for about 4 hours, and 190.9°C for about 1 hour. The curing reaction was completed to obtain 10g of modified bismaleimide resin AD-BMI. After multiple washings with tetrahydrofuran, it was found that the quality of the cured product remained basically unchanged. Its infrared spectrum is shown in FIG. Figure 5 shown.

[0068] The obtained modified resin was made into a membrane for performance testing, and the obtained performance parameters are shown in Table 2 below.

[0069] Examples 2-4 The premix was prepared in a similar manner to Example 1. Some of the experimental conditions are shown in Table 1 below.

[0070] Table 1: Experimental conditions for preparing modified bismaleimide resin in the examples

[0071] After the curing reaction was completed by gradient temperature increase, the modified bismaleimide resin was obtained. It was made into a film and performance tested. The performance parameters obtained are shown in Table 2 below: Table 2: Properties of modified bismaleimide resin prepared in the examples

[0072] Comparative Example 1 Weigh 4 g of 2,2'-diallylbisphenol A (DBA) and 0.1 g of di-tert-butylperoxyisopropylbenzene (BIBP) into a three-necked flask equipped with a magnetic stirrer and nitrogen protection, heat to 120 °C in an oil bath to completely dissolve it. After it is completely dissolved, add 6 g of BMI in three batches and stir until it is completely dissolved.

[0073] The curing reaction was carried out under a hot press, and the hot press pressure was set to 5 tons. According to the preset program (107.0℃: 2h, 158.8℃: 2h, 193.1℃: 1h), the temperature was increased gradually to complete the curing reaction, and 9.5g of modified bismaleimide resin was obtained. It was made into a film for performance testing. The obtained performance parameters were: dielectric constant D k is 2.99, dielectric loss D f is 0.027, and the thermal weight loss temperature is T d5% It is 392℃.

[0074] The present invention has been described in detail above with reference to specific embodiments and / or exemplary examples and the accompanying drawings. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A method for preparing polyphenylene ether modified bismaleimide, comprising first preparing amino-terminated polyphenylene ether and then preparing polyphenylene ether modified bismaleimide.

2. The preparation method according to claim 1, characterized in that Using dihydroxy-terminated polyphenylene ether (PPO) as a raw material, a nitro aromatic compound is prepared in the presence of an alkaline catalyst, and then further hydrogenated to prepare amino-terminated polyphenylene ether, preferably including the following steps: Step 1: preparing nitrated polyphenylene ether from dihydroxy-terminated polyphenylene ether in the presence of a basic catalyst; Step 2: In the presence of a catalyst, the nitrated polyphenylene ether is subjected to a hydrogenation reaction to obtain an amino-terminated polyphenylene ether.

3. The preparation method according to claim 2, characterized in that PPO has the following structure: ； in, The value of x+y is 2-100, preferably 5-50.

4. The preparation method according to claim 2, characterized in that In step 1, a double-terminated hydroxyl polyphenylene ether and a halogen nitrobenzene compound react in a solvent to obtain a nitrated polyphenylene ether. The p-halogen nitrobenzene is selected from one or two of p-fluoronitrobenzene, p-chloronitrobenzene, p-iodine nitrobenzene and p-bromonitrobenzene. Preferably, the molar ratio of halogen nitrobenzene to double-terminated hydroxyl polyphenylene ether is (1-100):1, preferably (1-50):

1. The solvent is an organic solvent.

5. The preparation method according to any one of claims 2 to 4, characterized in that: In step 1, the alkaline catalyst is selected from one or more of an organic base, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate compound and an alkali metal bicarbonate compound. The molar ratio of the alkaline catalyst to the double-terminated hydroxyl polyphenylene ether is (0.5-100):1, preferably (1-60):

1. The reaction temperature is 20-200°C, preferably 40-160°C. The reaction time is 1 to 100 hours, preferably 2 to 50 hours.

6. The preparation method according to any one of claims 2 to 4, characterized in that: In step 2, the catalyst is preferably a palladium-carbon catalyst, Preferably, the mass ratio of palladium carbon catalyst to nitroated polyphenylene ether is 1:(10-500), preferably 1:(50-200), The nitropolyphenylene ether is subjected to a hydrogenation reaction in a solvent in a high-temperature and high-pressure reactor. The solvent is selected from one or more of tetrahydrofuran, chloroform, ethanol, water, toluene, xylene, dichloromethane, N,N-dimethylformamide, and N,N-dimethylacetamide. The pressure after hydrogenation is 0.05-5 MPa, preferably 0.4-2 MPa, and the reaction temperature is 40-180° C., preferably 60-140° C.

7. The preparation method according to any one of claims 2 to 6, characterized in that: In step 2, after the reaction is completed, post-treatment is performed, and the reaction mixture is precipitated, washed, filtered and dried to finally obtain amino-terminated polyphenylene ether. The precipitant is an alcohol, preferably a lower alcohol, such as a fatty alcohol having 1 to 6 carbon atoms. The washing agent is preferably the same alcohol as the precipitant, such as methanol. The vacuum drying temperature is 50 to 95° C., preferably 60 to 90° C., and the drying time is 10 to 50 h, preferably 15 to 30 h.

8. The preparation method according to any one of claims 1 to 7, characterized in that The amino-terminated polyphenylene ether (APPO) can be represented by the following formula: ； in, The value of x+y is 2-100, preferably 5-50, more preferably 10-20.

9. The preparation method according to any one of claims 2 to 8, characterized in that: The following steps are also included: Step 3, dissolving bisphenol A, amino-modified polyphenylene ether resin, and cumene peroxide compound in bisphenol A to obtain a premix; Step 4, curing the premix; In step 3, the bismaleimide resin is selected from one or more of N,N'-(4,4'-methylenediphenyl)bismaleimide, N,N'-m-phenylene bismaleimide, 1,1'-(methylenebis(2-ethyl-6-methyl-4,1-phenylene))bismaleimide, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, bisphenol A is preferably 2,2'-allyl bisphenol A (DBA), and the cumene peroxide compound is di-tert-butyl peroxide isopropylbenzene (BIBP). Preferably, the mass ratio of DBA to BIBP is 10-100:1, preferably 20-60:

1. In step 4, the premix is cured in a hot press, preferably at a certain pressure and a preset temperature. The curing conditions are: 170-180° C. for 2-4 hours, 110-170° C. for 1.5-2 hours, 160-180° C. for 1.5-4 hours, and 240-250° C. for 2-4 hours.

10. A bismaleimide-modified material prepared according to the method of any one of claims 1 to 9.

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