Methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product, method for producing the same, and use thereof

Abstract

The application discloses a methacrylate-terminated polyphenylene ether / carbon hydrocarbon resin composite cured product and a preparation method and application thereof. A methacrylate-terminated polyphenylene ether and a carbon hydrocarbon resin with a mass ratio of 100:(11-67) are dissolved in an organic solvent, a free radical initiator is added, heating is carried out at 50-70 DEG C for 20-40 min, vacuum drying is carried out, and then heat treatment is carried out at 140-160 DEG C for 5-20 min, and the product is crushed into powder and molded into a shape. The methacrylate-terminated polyphenylene ether / carbon hydrocarbon resin composite cured product has low dielectric loss, high glass transition temperature, good thermal stability, good mechanical properties and excellent hydrophobicity, excellent comprehensive performance, and can fully meet the strict requirements of 5G / 6G communication high-frequency copper-clad plate substrates, and can be used for preparing high-frequency copper-clad plates, high-frequency printed circuit boards, 5G / 6G communication substrates, millimeter wave radar substrates or aerospace electronic packaging materials.

Description

Technical Field

[0001] This invention relates to the field of high-frequency electronic materials technology, and in particular to a composite cured product formed by free radical crosslinking and curing of methacrylate-terminated low molecular weight polyphenylene ether and butadiene-styrene copolymer. This invention also relates to a method for preparing this composite cured product and its application in high-frequency copper-clad laminates. Background Technology

[0002] With the large-scale commercialization of 5G technology and the rapid development of next-generation communication technology (6G), electronic devices are facing unprecedented demands for signal transmission rate, bandwidth capacity, and reliability. This demand directly impacts the core supporting material—the substrate material of the printed circuit board (PCB)—copper clad laminate (CCL). In high-frequency, high-speed scenarios, the signal transmission rate is inversely proportional to the square root of the dielectric constant of the dielectric material, while transmission loss is positively correlated with both the dielectric constant and dielectric loss. Therefore, to achieve low-latency, low-attenuation signal transmission, the CCL substrate must simultaneously possess a low dielectric constant (D). k <2.8) and ultra-low dielectric loss (D f <0.005).

[0003] As electronic devices evolve towards higher integration and performance, the widespread adoption of lead-free soldering processes (processing temperatures reaching 250-260℃) places higher demands on the heat resistance of substrates. CCL substrates must possess a high glass transition temperature (T0). g >180℃) and high thermal decomposition temperature (T d 5% The temperature must be above 400 °C to ensure dimensional stability and structural integrity during processing and service. In addition, the substrate must have excellent mechanical properties (including sufficient tensile strength, flexural strength and impact toughness), low moisture absorption and good processing flowability.

[0004] Among numerous high-frequency CCL matrix resin materials, hydrocarbon resins and polyphenylene ether (PPO) have attracted widespread attention due to their unique performance advantages. Hydrocarbon resins (such as butadiene-styrene copolymers) have molecular chains composed only of carbon and hydrogen elements, exhibiting extremely low polarity and excellent dielectric properties (D...). k ≈2.2~2.4, D f It has a molecular weight of approximately 0.001~0.003 and extremely low hygroscopicity. However, its molecular backbone is mainly aliphatic, and the cross-linking network is not dense enough, resulting in a low Tg. gIts low temperature (usually below 90 °C) and insufficient mechanical strength (tensile strength < 40 MPa) make it difficult to meet the requirements of high-performance CCLs.

[0005] To address the aforementioned issues, existing technologies attempt to chemically modify polyphenylene ether (PPE) to combine with hydrocarbon resins at the molecular level. For example, Chinese patent application CN121159796A discloses a low-dielectric thermosetting PPE-hydrocarbon resin polymer and its preparation method. This technology reduces the molecular weight of PPE through a redistribution reaction and grafts allyl groups onto its ends. Then, the allyl double bonds crosslink with the double bonds on the hydrocarbon resin. Due to the low reactivity of the allyl double bonds, the crosslinking network is not dense enough, requiring the introduction of small-molecule crosslinking agents (such as triallyl isocyanurate) to increase the crosslinking density. This technology solves the system compatibility problem to some extent, achieving a balance between the flexibility of the hydrocarbon resin and the rigidity of the PPE. However, this technology uses an allyl-terminated PPE / hydrocarbon resin composite system, whose terminal double bonds have low reactivity, requiring the addition of small-molecule crosslinking agents to increase the crosslinking density. Furthermore, the residual polar groups introduced by the small-molecule crosslinking agents significantly increase the dielectric constant and dielectric loss. Meanwhile, the low reactivity of the allyl double bond results in insufficient density of the crosslinked network and limited mechanical strength. Tests show that the dielectric constant of the material obtained by this technology is as high as 2.81 (1 MHz), the dielectric loss is as high as 0.0041 (1 MHz), and the tensile strength is only 46.7 MPa. The overall performance needs to be improved. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a low dielectric loss (D) dielectric material. f <0.0026@1 MHz), high glass transition temperature (T g >180.0 ℃), good thermal stability (T d 5% A methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product with a temperature greater than 430.0 °C and good mechanical properties as well as excellent hydrophobic properties.

[0007] Another objective of this invention is to provide a method for preparing the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product, which is simple in process, controllable in operation, and suitable for large-scale production.

[0008] Another object of the present invention is to provide the application of the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product in the preparation of high-frequency copper-clad laminates, high-frequency printed circuit boards, 5G / 6G communication substrates, millimeter-wave radar substrates or aerospace electronic packaging materials.

[0009] To achieve the above objectives, the present invention adopts the following technical solution.

[0010] A methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product, characterized in that it is obtained by dissolving methacrylate-terminated polyphenylene ether and hydrocarbon resin in an organic solvent at a mass ratio of 100:(11~67), adding a free radical initiator, heating at 50~70 °C for 20~40 min, vacuum drying, heat treatment at 140~160 °C for 5~20 min, pulverizing the product into powder, and molding; the methacrylate-terminated polyphenylene ether has the following structural formula (I):

[0011]

[0012] Equation (I)

[0013] R is: , , One of them; m and n are the same or different positive integers, m≤22, n≤22; m+n=10~23;

[0014] The hydrocarbon resin is a butadiene-styrene copolymer.

[0015] To further achieve the objectives of this invention, preferably, the free radical initiator is one or two of bis(tert-butylperoxyisopropylbenzene), dicumyl peroxide, or tert-butyl peroxide.

[0016] Preferably, the amount of the free radical initiator is 0.25 to 2.0% of the total mass of the methacrylate-terminated polyphenylene ether and the hydrocarbon resin.

[0017] Preferably, the number average molecular weight of the methacrylate-terminated polyphenylene ether is 1700–3000 g / mol;

[0018] The butadiene-styrene copolymer has a number average molecular weight of 4000-5000 g / mol and a 1,2-vinyl content of 60-80%.

[0019] Preferably, the vacuum drying temperature is 50–80 °C and the time is 4–8 h.

[0020] Preferably, the organic solvent is one or two of butanone, toluene, xylene, or cyclohexane; the amount of organic solvent used is 3 to 10 times the total mass of methacrylate-terminated polyphenylene ether and hydrocarbon resin.

[0021] Preferably, the molding temperature is 190–230 °C, the pressure is 1–10 MPa, and the time is 60–120 min.

[0022] Preferably, the molding temperature is 200~220 ℃, the pressure is 4~6 MPa, and the time is 85~95 min.

[0023] The method for preparing the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product includes the following steps:

[0024] (1) Dissolve methacrylate-terminated polyphenylene ether and hydrocarbon resin in an organic solvent according to the ratio, stir until completely dissolved, add free radical initiator, and continue stirring until homogeneous to obtain resin solution;

[0025] (2) Heat the obtained resin solution at 50-70 °C for 20-40 min and dry it under vacuum to obtain a dry resin mixture;

[0026] (3) Heat-treat the resin mixture obtained in step (2) at 140-160 °C for 5-20 min to obtain a pre-cured resin;

[0027] (4) The pre-cured resin obtained in step (3) is crushed into powder and molded to obtain methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product.

[0028] The present invention also provides the application of the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product in the preparation of high-frequency copper-clad laminates, high-frequency printed circuit boards, 5G / 6G communication substrates, millimeter-wave radar substrates or aerospace electronic packaging materials.

[0029] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0030] (1) The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product obtained by the present invention has excellent thermal properties, with a glass transition temperature above 180 ℃, a heat distortion temperature above 150 ℃, a 5% thermal weight loss temperature above 430 ℃, and a coefficient of thermal expansion below 70 ppm / ℃. Compared with the prior art, the glass transition temperature is increased by 30 ℃ and the heat distortion temperature is increased by 40 ℃.

[0031] (2) The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product obtained in this invention has both excellent mechanical and dielectric properties. Its tensile strength reaches more than 50 MPa, its flexural strength reaches more than 90 MPa, and its notched impact strength remains above 1.0 kJ / m², achieving a good balance between strength and toughness; its water absorption rate is less than 0.30 wt%, and its water contact angle is greater than 120°, exhibiting excellent moisture resistance and surface hydrophobicity; its dielectric constant is less than 2.6, and its dielectric loss is less than 0.003.

[0032] (3) This invention uses industrial raw materials and conventional solution blending-hot pressing curing process. The preparation method is simple and easy to industrialize. The resulting material fully meets the performance requirements of high-frequency copper clad laminate substrate (D). k <2.8, Df <0.005, T g >180 ℃, T d 5% (>400 ℃), applicable to 5G / 6G communication base stations, millimeter-wave radar, high-frequency and high-speed printed circuit boards, radio frequency identification and aerospace electronic packaging and other fields. Attached Figure Description

[0033] Figure 1 The image shows the 1H NMR spectrum of the methyl methacrylate-terminated polyphenylene ether selected in Example 1. Detailed Implementation

[0034] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be described in detail below through specific embodiments. However, the scope of protection of this invention is not limited to the following embodiments. All equivalent substitutions or improvements made based on the technical concept of this invention should be included within the scope of protection of this invention. The raw materials used in the embodiments are all commercially available analytical grade or industrial grade products, and the detection methods used, unless otherwise specified, are conventional methods in the art.

[0035] Methacrylate-terminated polyphenylene ether is a substance disclosed in the art. Although the prior art has used this type of substance to improve dielectric properties by compounding it with resins such as epoxy, cyanate, and bismaleimide, it is usually only used as an additive (in amounts less than 50 wt%), and often requires the addition of small molecule crosslinking agents such as triallyl isocyanurate to increase the crosslinking density, resulting in small molecule residues that degrade dielectric properties.

[0036] The methacrylate-terminated polyphenylene ether used in this invention, abbreviated as VLWPPO, is also a commercially available substance, such as SABIC's NORYL™ SA9000, but VLWPPO has a low molecular weight ( Typical values ​​are around 2300, high end-capping degree (vinyl functionality around 1.9), excellent organic solvent solubility (>50 wt% in toluene / methyl ethyl ketone), and low dielectric constant (around 2.54 @ 1 MHz). The methacrylate-terminated polyphenylene ether of the present invention has the following structural formula (Ⅰ):

[0037]

[0038] Equation (I)

[0039] R is: , , One of them; m and n are the same or different positive integers, m≤22, n≤22; m+n=10~23.

[0040] This invention discovers that by dissolving VLWPPO and BSC in an organic solvent and controlling the mass ratio of VLWPPO to BSC to be 100:(11~67), cross-linking and curing can be achieved through the action of a free radical initiator, thus obtaining a methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product. However, this cross-linking and curing requires first heating the product with the added free radical initiator at 50~70 °C for 20~40 min, vacuum drying, and then heat-treating the resulting dried product at 140~160 °C for 5~20 min. The product is then pulverized into powder and molded to obtain the target product.

[0041] On the one hand, the terminal double bonds of VLWPPO exhibit significantly higher reactivity than allyl ethers due to the electron-withdrawing effect of the ester groups. This allows it to directly form a dense and uniform cross-linked network via free radical initiation without the need for additional small molecule cross-linking agents, thus avoiding the degradation of high-frequency dielectric properties caused by residual cross-linking agents. On the other hand, the realization of the above-mentioned functions of VLWPPO requires a combination of heating and drying processes and heat treatment at a defined temperature. This ensures that the cured methacrylate-terminated polyphenylene ether / hydrocarbon resin composite can form a dense cross-linked network without the addition of any small molecule cross-linking agents, achieving low dielectric loss (D). f ≤0.0026@1MHz) and high heat resistance (T g >180.0 ℃).

[0042] The free radical initiator of the present invention is a commonly used initiator in the art, preferably one or two of bis-tert-butylperoxyisopropylbenzene, diisopropylbenzene peroxide or tert-butyl peroxide; the amount used is preferably 0.25 to 2.0% of the total mass of methacrylate-terminated polyphenylene ether and hydrocarbon resin.

[0043] The organic solvent only needs to be able to dissolve VLWPPO and BSC, preferably one or two of methyl ethyl ketone, toluene, xylene or cyclohexane; the amount of organic solvent used is 3 to 10 times the total mass of methacrylate-terminated polyphenylene ether and hydrocarbon resin.

[0044] Vacuum drying is a conventional drying method, with the preferred temperature being 50–80 °C and the time being 4–8 h.

[0045] Compression molding is a common molding method. Preferably, the compression molding temperature of this invention is 190–230 °C, the pressure is 1–10 MPa, and the time is 60–120 min. More preferably, the compression molding temperature is 200–220 °C, the pressure is 4–6 MPa, and the time is 85–95 min.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0047] The testing methods and instruments involved in the embodiments and comparative examples of this invention are as follows:

[0048] (1) Nuclear magnetic resonance hydrogen spectrum (¹H NMR) analysis: A Bruker AVANCE III HD 600 nuclear magnetic resonance spectrometer was used, with deuterated chloroform (CDCl3) as solvent and tetramethylsilane (TMS) as internal standard.

[0049] (2) Dynamic thermomechanical analysis (DMA): A TA Q800 DMA instrument was used in the three-point bending mode, with a frequency of 1 Hz and a heating rate of 3 ℃ / min.

[0050] (3) Heat distortion temperature (HDT) test: The HV-3000 heat distortion temperature tester of Power Crystal Science was used according to ASTM D648 standard.

[0051] (4) Coefficient of thermal expansion (CTE) test: The German Netzsch TMA-402F3 thermodynamic analyzer was used in compression mode with a heating rate of 5 ℃ / min.

[0052] (5) Thermogravimetric analysis (TGA): A Netzsch TG 209F1 TGA instrument was used in Germany under a nitrogen atmosphere at a heating rate of 20℃ / min.

[0053] (6) Tensile property test: The Japanese Shimadzu AGX electronic universal testing machine was used, according to ASTM D638 standard.

[0054] (7) Bending performance test: The Shimadzu AGS-10KNI universal mechanical testing machine was used according to ASTM D790 standard.

[0055] (8) Notched impact strength test: The German Zwick 5113 digital pendulum impact tester was used, according to ASTM D256 standard.

[0056] (9) Water absorption test: according to ASTM D570-98 standard, soak in deionized water for 48 h.

[0057] (10) Water contact angle test: The German KRUSS DSA100 contact angle measuring instrument was used, and the seat drop method was employed.

[0058] (11) Dielectric performance test: Agilent ALPHA-ANB broadband dielectric spectrometer was used, with a frequency range of 100Hz to 1MHz.

[0059] Example 1

[0060] Weigh 100 g of VLWPPO-1 ( =1700 g / mol, Saudi Basic Industries Corporation) and 33 g BSC ( =4000 g / mol, 1,2-vinyl content 60%, Clayville Corporation) was dissolved in 500 mL of butanone and stirred at room temperature until completely dissolved. 0.53 g of bis-tert-butylperoxyisopropylbenzene was added, and stirring was continued for 1 h to obtain a resin solution. The mixed solution was transferred to a tray lined with a polyimide film, heated at 50 °C for 20 min, and vacuum dried at 50 °C for 4 h to obtain a dried resin mixture. The dried resin mixture was heat-treated in a 140 °C forced-air oven for 5 min to obtain a pre-cured resin. The pre-cured resin was pulverized into powder using a high-speed pulverizer, and then the powder was placed in a mold. Both sides of the mold were covered with release film and steel plate, and the mold was pressed at 190 °C and about 1 MPa for 60 min to obtain a cured sample.

[0061] The methacrylate polyphenylene ether (VLWPPO-1) used was Figure 1 of 1 1H NMR confirmed its molecular structure as formula (II): the chemical shifts of approximately 6.8~6.9 ppm in the 1H NMR spectrum correspond to the terminal methyl hydrogen, the chemical shifts of approximately 6.2~6.5 ppm correspond to the phenyl ring hydrogen of the polyphenylene ether main chain, the chemical shifts of approximately 5.6 ppm correspond to the terminal double bond hydrogen, the chemical shifts of approximately 1.9~2.1 ppm correspond to the methyl hydrogen on the benzene ring, and the chemical shifts of approximately 1.5 ppm correspond to the intermediate methyl hydrogen.

[0062]

[0063] Formula (II)

[0064] Where m and n are both positive integers, and satisfy 3≤m≤7, 7≤n≤3, and m+n=10.

[0065] Example 2

[0066] Weigh 100 g of VLWPPO-2 ( =2300 g / mol) and 33 g BSC ( =4500 g / mol, 1,2-vinyl content 70%) was dissolved in 600 mL toluene and stirred at room temperature until completely dissolved. 0.67 g of dicumyl peroxide was added and stirring was continued for 1 h to obtain a resin solution. The mixed solution was transferred to a tray lined with a polyimide film and heated at 60 °C for 25 min, then vacuum dried at 60 °C for 5 h to obtain a dried resin mixture. The dried resin mixture was heat-treated in a 150 °C forced-air oven for 10 min to obtain a pre-cured resin. The pre-cured resin was pulverized into powder using a high-speed pulverizer, and then the powder was placed in a mold. Both sides of the mold were covered with release film and steel plate, and the mold was molded at 200 °C and about 5 MPa for 90 min to obtain a cured sample.

[0067] The molecular structural formula of the VLWPPO-2 used is formula (Ⅲ):

[0068]

[0069] Formula (III)

[0070] Where m and n are both positive integers, and satisfy 6≤m≤12, 12≤n≤6, and m+n=18.

[0071] Example 3

[0072] Weigh 100 g of VLWPPO-3 ( =3000 g / mol) and 25 g BSC ( =5000 g / mol, 1,2-vinyl content of 80% was dissolved in 600 mL xylene and stirred at room temperature until completely dissolved. 1.25 g of tert-butyl peroxide was added and stirring was continued for 1 h to obtain a resin solution. The mixed solution was transferred to a tray lined with a polyimide film and heated at 70 °C for 30 min, then vacuum dried at 70 °C for 6 h to obtain a dried resin mixture. The dried resin mixture was heat-treated in a 160 °C forced-air oven for 20 min to obtain a pre-cured resin. The pre-cured resin was pulverized into powder using a high-speed pulverizer, and then the powder was placed in a mold. Both sides of the mold were covered with release film and steel plate, and the mold was molded at 210 °C and a pressure of about 10 MPa for 120 min to obtain a cured sample.

[0073] The molecular structural formula of VLWPPO-3 used is formula (Ⅳ):

[0074]

[0075] Equation (Ⅳ)

[0076] Where m and n are both positive integers, and satisfy 8≤m≤15, 15≤n≤8, and m+n=23.

[0077] Example 4

[0078] Weigh 100 g of VLWPPO-2 ( =1700 g / mol, where m and n are both positive integers and satisfy 3≤m≤7, 7≤n≤3, m+n=10) and 41 g BSC ( =5000 g / mol, 1,2-vinyl content of 80% was dissolved in 700 mL of cyclohexane and stirred at room temperature until completely dissolved. 2.82 g of bis-tert-butylperoxyisopropylbenzene was added and stirring was continued for 1 h to obtain a resin solution. The mixed solution was transferred to a tray lined with a polyimide film and heated at 65 ℃ for 35 min, then vacuum dried at 80 ℃ for 7 h to obtain a dried resin mixture. The dried resin mixture was heat-treated in a 155 ℃ forced-air oven for 15 min to obtain a pre-cured resin. The pre-cured resin was pulverized into powder using a high-speed pulverizer, and then the powder was placed in a mold. Both sides of the mold were covered with release film and steel plate, and the mold was molded at 220 ℃ and about 5 MPa pressure for 80 min to obtain a cured sample.

[0079] Example 5

[0080] Weigh 100 g of VLWPPO-3 ( =2300 g / mol, where m and n are both positive integers and satisfy 6≤m≤12, 12≤n≤6, m+n=18) and 11 g BSC ( =4500 g / mol, 1,2-vinyl content 70%) was dissolved in 450 mL of butanone and stirred at room temperature until completely dissolved. 0.56 g of bis-tert-butylperoxyisopropylbenzene was added and stirring was continued for 1 h to obtain a resin solution. The mixed solution was transferred to a tray lined with a polyimide film and heated at 70 ℃ for 40 min, then vacuum dried at 55 ℃ for 8 h to obtain a dried resin mixture. The dried resin mixture was heat-treated in a 145 ℃ forced-air oven for 13 min to obtain a pre-cured resin. The pre-cured resin was pulverized into powder using a high-speed pulverizer, and then the powder was placed in a mold. Both sides of the mold were covered with release film and steel plate, and the mold was pressed at 230 ℃ and about 4 MPa pressure for 85 min to obtain a cured sample.

[0081] Example 6

[0082] Weigh 100 g of VLWPPO-1 ( =2300 g / mol, where m and n are both positive integers and satisfy 6≤m≤12, 12≤n≤6, m+n=18) and 67 g BSC ( =4500 g / mol, 1,2-vinyl content 70%) was dissolved in 700 mL of butanone and stirred at room temperature until completely dissolved. 0.84 g of bis-tert-butylperoxyisopropylbenzene was added and stirring was continued for 1 h to obtain a resin solution. The mixed solution was transferred to a tray lined with a polyimide film and heated at 60 ℃ for 30 min, then vacuum dried at 65 ℃ for 6 h to obtain a dried resin mixture. The dried resin mixture was heat-treated in a 155 ℃ forced-air oven for 10 min to obtain a pre-cured resin. The pre-cured resin was pulverized into powder using a high-speed pulverizer, and then the powder was placed in a mold. Both sides of the mold were covered with release film and steel plate, and the mold was pressed at 210 ℃ and about 6 MPa for 95 min to obtain a cured sample.

[0083] Comparative Example

[0084] Using an allyl-terminated polyphenylene ether / hydrocarbon resin cured product disclosed in CN121159796A as a comparative example, its preparation method is as follows:

[0085] 100 g of di-terminated allyl polyphenylene ether ( =3000 g / mol), 100g BSC ( =4500 g / mol, 1,2 vinyl content of 70%), 30 g triallyl isocyanurate and 1.73 g di-tert-butylperoxyisopropylbenzene were uniformly mixed and placed in a vacuum dryer at 70 ℃ for 6 h to remove residual solvent; pre-cured at 150 ℃ for 30 min and hot-pressed at 190 ℃ for 4 h to obtain allyl-terminated polyphenylene ether / hydrocarbon resin composite cured product.

[0086] The performance test results of the cured products of Examples 1-6 and the comparative examples are shown in Table 1.

[0087] Table 1. Performance test results of the cured products prepared in the examples and comparative examples.

[0088] The test results from the examples and comparative examples show that:

[0089] The VLWPPO / BSC composite cured products prepared in each embodiment of this invention exhibit excellent comprehensive properties. The glass transition temperature of all embodiments is increased to above 180 °C, the heat distortion temperature reaches above 150 °C, the 5% thermogravimetric temperature exceeds 430 °C, and the coefficient of thermal expansion is controlled below 70 ppm / °C, indicating that the composite cured products of this invention possess excellent heat resistance and dimensional stability. Simultaneously, the tensile strength of all embodiments reaches above 50 MPa, the flexural strength reaches above 90 MPa, and the notched impact strength remains above 1.0 kJ / m², achieving a good strength-toughness balance. The water absorption rate is below 0.30 wt%, and the water contact angle is greater than 120°, exhibiting excellent moisture resistance and surface hydrophobicity. The dielectric constant is below 2.6, and the dielectric loss is below 0.003, demonstrating excellent high-frequency dielectric properties.

[0090] Compared with the allyl-terminated polyphenylene ether / hydrocarbon resin composite cured products of the comparative example, the composite cured products of the various embodiments of the present invention have achieved significant improvements in all aspects of performance. Regarding heat resistance, the glass transition temperature, heat distortion temperature, and 5% thermogravimetric temperature of the cured products of the present invention are all significantly increased, while the coefficient of thermal expansion is significantly reduced, indicating that their heat resistance and dimensional stability are significantly superior to the comparative example. In terms of mechanical properties, the tensile strength, flexural strength, and notched impact strength of the cured products of the present invention are mostly significantly higher than those of the comparative example, achieving a comprehensive optimization of strength-toughness balance. Regarding hydrophobic properties, the water contact angle of the cured products of the present invention is significantly increased, and the water absorption rate is significantly reduced, exhibiting superior surface hydrophobicity and moisture resistance. Regarding dielectric properties, the dielectric constant and dielectric loss of the cured products of the present invention are significantly lower than those of the comparative example, with significantly better high-frequency dielectric properties, and all properties fully meet the stringent performance requirements of 5G / 6G communication high-frequency copper-clad laminate substrates.

[0091] The present invention provides a methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product and its preparation method, which uses readily available raw materials, has a simple process, clear parameters, and is suitable for industrial production. The resulting composite cured product exhibits low dielectric loss (Dk). f <0.0026@1 MHz), high glass transition temperature (T g >180.0 ℃), high thermal stability (T d 5% With a temperature of >430.0 ℃, good mechanical properties and excellent hydrophobic properties, it fully meets the stringent requirements of high-frequency copper-clad laminate substrates for 5G / 6G communication.

[0092] The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured material obtained by this invention can be widely used in communication base stations, millimeter-wave radar, high-frequency and high-speed printed circuit boards, radio frequency identification, and aerospace electronic packaging. Among these applications, communication base stations require the substrate to have ultra-low dielectric loss (DL) in the millimeter-wave band.f ≤0.002~0.005), the material D obtained in this invention f With a dielectric constant as low as 0.0020, signal integrity can be effectively guaranteed; millimeter-wave radar needs to maintain stable dielectric properties over a wide temperature range of -40 to 125 °C and withstand automotive-grade vibration and shock. The material T obtained in this invention... g With a temperature reaching 184.8 ℃ and a notched impact strength of 1.72 kJ / m², it meets the requirements for heat resistance and impact resistance; high-frequency and high-speed printed circuit boards are subject to T g Strict requirements are placed on the material's temperature (>180 °C) and low coefficient of thermal expansion (CTE < 70 ppm / °C) to prevent thermal delamination and impedance mismatch in multilayer boards. The material obtained in this invention has a CTE of 65.4 ppm / °C, meeting application requirements. RFID tags need to withstand high temperature and high humidity (85 °C / 85%RH) environments to prevent signal drift; the material obtained in this invention has a water absorption rate of only 0.23 wt% and a T0.05. d 5 The temperature reaches 443.2 ℃, exhibiting excellent resistance to damp heat aging; aerospace electronic packaging for T g The material T obtained in this invention has extremely high requirements for long-term service reliability, and also needs to possess high strength, toughness, and dimensional stability. g With a temperature of 184.8 °C, tensile strength of 54.5 MPa, flexural strength of 100.0 MPa, and CTE of 65.4 ppm / °C, the material meets the requirements of most aerospace applications. Therefore, it is evident that the performance indicators of the material obtained in this embodiment meet or exceed the key requirements of applications in communication base stations, millimeter-wave radar, high-frequency and high-speed printed circuit boards, radio frequency identification, and aerospace electronic packaging.

[0093] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product, characterized in that, The product is obtained by dissolving methacrylate-terminated polyphenylene ether and hydrocarbon resin in an organic solvent at a mass ratio of 100:(11~67), adding a free radical initiator, heating at 50~70℃ for 20~40 min, vacuum drying, heat treatment at 140~160℃ for 5~20 min, pulverizing the product into powder, and molding it. The methacrylate-terminated polyphenylene ether has the following structural formula (I): Equation (I) R is , , One of them; m and n are the same or different positive integers, m≤22, n≤22; m+n=10~23; The hydrocarbon resin is a butadiene-styrene copolymer.

2. The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 1, characterized in that, The free radical initiator is one or two of bis(tert-butylperoxyisopropylbenzene), diisopropylbenzene peroxide, or tert-butyl peroxide.

3. The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 2, characterized in that, The amount of the free radical initiator is 0.25 to 2.0% of the total mass of the methacrylate-terminated polyphenylene ether and the hydrocarbon resin.

4. The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 1, characterized in that, The number-average molecular weight of the methacrylate-terminated polyphenylene ether is 1700–3000 g / mol; The butadiene-styrene copolymer has a number average molecular weight of 4000-5000 g / mol and a 1,2-vinyl content of 60-80%.

5. The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 1, characterized in that, The vacuum drying temperature is 50–80 °C, and the time is 4–8 h.

6. The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 1, characterized in that, The organic solvent is one or two of butanone, toluene, xylene, or cyclohexane; the amount of organic solvent used is 3 to 10 times the total mass of methacrylate-terminated polyphenylene ether and hydrocarbon resin.

7. The methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 1, characterized in that, The molding temperature is 190–230 °C, the pressure is 1–10 MPa, and the time is 60–120 min.

8. The method for preparing the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 7, characterized in that, The molding temperature is 200~220 ℃, the pressure is 4~6 MPa, and the time is 85~95 min.

9. The method for preparing the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to claim 1, characterized in that, Includes the following steps: (1) Dissolve methacrylate-terminated polyphenylene ether and hydrocarbon resin in an organic solvent according to the ratio, stir until completely dissolved, add free radical initiator, and continue stirring until homogeneous to obtain resin solution; (2) Heat the obtained resin solution at 50-70 °C for 20-40 min and dry it under vacuum to obtain a dry resin mixture; (3) Heat-treat the resin mixture obtained in step (2) at 140-160 °C for 5-20 min to obtain a pre-cured resin; (4) The pre-cured resin obtained in step (3) is crushed into powder and molded to obtain methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product.

10. The application of the methacrylate-terminated polyphenylene ether / hydrocarbon resin composite cured product according to any one of claims 1-8 in the preparation of high-frequency copper-clad laminates, high-frequency printed circuit boards, 5G / 6G communication substrates, millimeter-wave radar substrates, or aerospace electronic packaging materials.

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