A composite filler reinforced copper clad plate substrate material with excellent dielectric properties

Abstract

This invention relates to the field of dielectric materials technology, specifically to a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties. This material addresses the problems of high dielectric constant, high dielectric loss, and poor bending performance in existing copper clad laminate substrate materials. The matrix material incorporates benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane-modified boron nitride. The benzocyclobutene structure has low dielectric properties, reducing electronic polarizability; tetraphenylethylene increases free volume, hindering electron transfer and lowering the dielectric constant; the rigid structure of POSS inhibits chain segment movement, reducing dielectric loss; and the boron nitride in the piperazine-based hyperbranched polysiloxane-modified boron nitride has a low dielectric constant, the piperazine ring reduces the molar polarizability of the molecular chain, lowering the dielectric constant; and the siloxane segments provide a flexible buffer layer, improving the bending strength of the material. This results in good stability of the material under high-frequency application conditions.

Description

Technical Field

[0001] This invention relates to the field of dielectric materials technology, specifically to a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties. Background Technology

[0002] Copper-clad laminate (CCL) substrate materials are widely used in the electronics industry, especially in printed circuit board (PCB) manufacturing. The structure of this material includes an insulating substrate and a copper foil layer, which is tightly bonded to the substrate using chemical or physical methods to provide excellent electrical and mechanical properties. Most CCL substrate materials use insulating substrates with high dielectric constants, which limits the dielectric performance at high frequencies and leaves room for improvement in bending properties, particularly important for small electronic devices that require both durability and flexibility. Therefore, this invention provides a composite filler-reinforced CCL substrate material with excellent dielectric properties, applicable to the manufacture of modern high-frequency electronic products, improving overall product performance. Summary of the Invention

[0003] In order to overcome the above-mentioned technical problems, the present invention aims to provide a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, which solves the problems of high dielectric constant, high dielectric loss and poor bending performance of existing copper clad laminate substrate materials.

[0004] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties, comprising the following parts by weight: 30-50 parts of polyphenylene ether resin, 20-30 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 10-20 parts of piperazine-modified polysiloxane-modified boron nitride, and 130-150 parts of xylene. The benzocyclobutene-tetraphenylethylene grafted POSS is prepared by the following steps: Step A1: Add 4-chlorodiphenylmethane and tetrahydrofuran to a three-necked flask equipped with a thermometer and a stirrer, stir for 5-10 min, transfer to an ice bath, add n-butyllithium / hexane solution dropwise at 0-5℃ and stir for 15-30 min, add 4-bromobenzoylbenzene / tetrahydrofuran solution dropwise, stir and react at room temperature for 12 h, add to saturated ammonium chloride solution, extract with dichloromethane, combine organic phases, dry with anhydrous sodium sulfate, filter, evaporate the filtrate to dryness, add toluene and p-toluenesulfonic acid to a two-necked flask equipped with a stirrer and a reflux condenser, react for 12 h, evaporate to dryness, use dichloromethane / n-hexane mixed solvent as eluent, purify by silica gel column chromatography to obtain bromophenyl-chlorophenyl-diphenylethylene;

[0005] Step A2: Add bromophenyl-chlorophenyl-diphenylethylene, N-Boc-4-aminophenylboronic acid pinacol ester, tetrahydrofuran, and tetra(triphenylphosphine)palladium to a three-necked flask equipped with a thermometer and a stirrer. Stir for 5 min, add sodium carbonate solution dropwise, purge with nitrogen three times, and stir at 85°C for 8 h. Separate and combine the organic phases, recrystallize with methanol-water solution, and purify by silica gel column chromatography using petroleum ether as eluent. Add the organic phases, along with methanol and dichloromethane, to a three-necked flask equipped with a stirrer and a spherical condenser. Purge with argon three times, stir for 30-40 min under an argon atmosphere, add concentrated hydrochloric acid dropwise, and react for 10-12 h. Adjust the pH to 7 with saturated sodium carbonate solution, filter, wash the filter residue 3-5 times with deionized water, and dry to obtain 4-aminophenyl-chlorophenyl-diphenylethylene.

[0006] Step A3: 4-Aminophenyl-chlorophenyl-diphenylethylene, 4-vinylaniline, tris(dibenzylacetone)palladium, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl and sodium tert-butoxide were added to a Schlenk tube equipped with a stirrer. The mixture was purged three times with argon. Toluene was added under an argon atmosphere, and the mixture was stirred at 110°C for 14 h. After cooling to room temperature, the mixture was filtered, and the filtrate was evaporated to dryness. The filtrate was purified by silica gel column chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent to obtain vinylphenyl-amino-diphenylethylene.

[0007] Step A4: Add vinylphenyl-amino-diphenylethylene, 4-aldehyde benzocyclobutene and anhydrous ethanol to a three-necked flask equipped with a thermometer and a stirrer, add 4A molecular sieve and stir the reaction at 60°C for 10 h, cool to room temperature, filter, wash the filter residue with ethanol solution 3-5 times, dry, and obtain benzocyclobutene-vinyltetraphenylethylene.

[0008] Step A5: Add (3-mercaptopropyl)trimethoxysilane, anhydrous methanol, and concentrated hydrochloric acid to a three-necked flask equipped with a stirrer, thermometer, and reflux condenser. Stir for 5 min, add deionized water, and react at 90°C for 8-12 h. Let stand at 0-5°C for 30 min, pour off the supernatant, add dichloromethane and stir, add ice-cold methanol to precipitate, repeat three times, dry, and add benzocyclobutene-vinyltetraphenylethylene, azobisisobutyronitrile, and anhydrous toluene to a two-necked flask equipped with a thermometer. Vacuum and purge with nitrogen, transfer to an oil bath, and react at 65°C for 72 h. Quench with ice water, stir and dropwise add to methanol at room temperature, collect the precipitate by centrifugation, add to toluene, and precipitate with methanol 2-3 times to obtain benzocyclobutene-tetraphenylethylene-grafted POSS.

[0009] In a preferred embodiment of the present invention, the ratio of 4-chlorodiphenylmethane, tetrahydrofuran, n-butyllithium / hexane solution, 4-bromobenzoylbenzene / tetrahydrofuran solution, toluene, and p-toluenesulfonic acid in step A1 is 47.6-95.2 mmol: 80-160 mL: 23.75-47.5 mL: 40-80 mL: 200-400 mL: 2-4 g.

[0010] In a preferred embodiment of the present invention, the molar concentration of the n-butyllithium / hexane solution in step A1 is 1.6 mol / L.

[0011] In a preferred embodiment of the present invention, the molar concentration of the 4-bromobenzoylbenzene / tetrahydrofuran solution in step A1 is 0.95 mmol / mL.

[0012] In a preferred embodiment of the present invention, the volume ratio of dichloromethane to n-hexane in the dichloromethane / n-hexane mixed solvent in step A1 is 1:10.

[0013] In a preferred embodiment of the present invention, the ratio of the amounts of bromophenyl-chlorophenyl-diphenylethylene, N-Boc-4-aminophenylboronic acid pinacol ester, tetrahydrofuran, tetra(triphenylphosphine)palladium, sodium carbonate solution, methanol, dichloromethane, and concentrated hydrochloric acid in step A2 is 0.1-0.2 mmol: 0.3-0.6 mmol: 70-140 mL: 0.01-0.02 mmol: 1.5-3 mL: 8-16 mL: 2-4 mL: 0.1-0.2 mL.

[0014] In a preferred embodiment of the present invention, the molar concentration of the sodium carbonate solution in step A2 is 0.3 mmol / mL.

[0015] In a preferred embodiment of the present invention, the volume ratio of methanol to water in the methanol-water solution in step A2 is 4:1.

[0016] In a preferred embodiment of the present invention, the molar concentration of the concentrated hydrochloric acid in step A2 is 12 mol / L.

[0017] In a preferred embodiment of the present invention, the ratio of 4-aminophenyl-chlorophenyl-diphenylethylene, 4-vinylaniline, tridibenzylacetone dipalladium, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, sodium tert-butoxide, and toluene in step A3 is 0.5-1 mmol: 0.6-1.2 mmol: 7-14 mg: 14-28 mg: 96-192 mg: 5-10 mL.

[0018] In a preferred embodiment of the present invention, the volume ratio of petroleum ether to dichloromethane in the petroleum ether / dichloromethane mixed solvent in step A3 is 10:1.

[0019] In a preferred embodiment of the present invention, the ratio of vinylphenyl-amino-diphenylethylene, 4-aldehyde benzocyclobutene, 4A molecular sieve and anhydrous ethanol in step A4 is 0.5-1 mmol: 0.5-1 mmol: 2-4 g: 15-30 mL.

[0020] In a preferred embodiment of the present invention, the ethanol solution in step A4 has a mass fraction of 95%.

[0021] In a preferred embodiment of the present invention, the ratio of (3-mercaptopropyl)trimethoxysilane, anhydrous methanol, concentrated hydrochloric acid, deionized water, benzocyclobutene-vinyltetraphenylethylene, azobisisobutyronitrile, and anhydrous toluene in step A5 is 2.15-4.3 mmol: 11-22 mL: 0.05-0.1 mL: 0.1-0.2 mL: 2.37-4.74 mmol: 0.024-0.048 mmol: 10-20 mL.

[0022] In a preferred embodiment of the present invention, the molar concentration of the concentrated hydrochloric acid in step A5 is 12 mol / L.

[0023] In a preferred embodiment of the present invention, the piperazine-based hyperbranched polysiloxane-modified boron nitride is prepared by the following steps: Step B1: Add boron nitride, glucose and deionized water to a ball mill jar, ball mill at 700 r / min for 6 h, filter, wash with pure water 5-7 times, place in a drying oven and dry at 80℃ for 12 h, add with sodium hydroxide solution to a reaction vessel, react at 120℃ for 12 h, sonicate for 1-2 h to obtain hydroxylated boron nitride; Step B2: 3-glycidyl etheroxypropyltrimethoxysilane and ethanol were added to a reaction vessel, nitrogen gas was introduced, the temperature was raised to 60°C, deionized water was added, the pH was adjusted to 10 with sodium hydroxide solution, the mixture was stirred and kept at the temperature for 4 hours, the pH was adjusted to 7 with tartaric acid solution, the mixture was filtered, the filtrate was distilled under reduced pressure, and 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine and dimethyl sulfoxide were added to a three-necked flask equipped with a stirrer and thermometer, nitrogen gas was introduced, the mixture was stirred at 40°C for 1 hour, and the reaction was carried out for 7 hours. The mixture was added to methanol, filtered, the residue was washed three times with methanol, dried, and then added to a three-necked flask equipped with a stirrer and thermometer with hydroxylated boron nitride and N-methylpyrrolidone, nitrogen gas was introduced, the reaction was carried out at 70°C for 72 hours, and then added to methanol, filtered, the residue was washed three times with methanol, and dried to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride.

[0024] In a preferred embodiment of the present invention, the ratio of boron nitride, glucose, deionized water and sodium hydroxide solution used in step B1 is 4-8g: 4-8g: 128-256mL: 10-20mL.

[0025] In a preferred embodiment of the present invention, the molar concentration of the sodium hydroxide solution in step B1 is 5 mol / L.

[0026] In a preferred embodiment of the present invention, the ratio of 3-glycidoxypropyltrimethoxysilane, ethanol, deionized water, 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine, dimethyl sulfoxide, hydroxylated boron nitride, and N-methylpyrrolidone in step B2 is 6-12g: 5.1-10.2mL: 0.65-1.3g: 5-10g: 150-300mL: 4-8g: 150-300mL.

[0027] In a preferred embodiment of the present invention, the molar concentration of the sodium hydroxide solution in step B2 is 1 mol / L.

[0028] In a preferred embodiment of the present invention, the molar concentration of the tartaric acid solution in step B2 is 0.67 mol / L.

[0029] Secondly, this application provides a method for preparing a composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step 1: Weigh out 30-50 parts of polyphenylene ether resin, 20-30 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 10-20 parts of piperazine-modified hyperbranched polysiloxane-modified boron nitride, and 130-150 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701; Step 2: Add polyphenylene ether resin, benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 240-270℃ and 20-40MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0030] The beneficial effects of this invention are: The present invention provides a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties. Benzocyclobutene-tetraphenylethylene is introduced on the surface of POSS to obtain benzocyclobutene-tetraphenylethylene-grafted POSS, and then piperazine-based polysiloxane is synthesized to modify boron nitride. This ensures that the high-frequency copper clad laminate has low dielectric constant and low dielectric loss while possessing high bending strength.

[0031] To prepare a composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties, benzocyclobutene-tetraphenylethylene grafted with POSS was first prepared. 4-Chlorodiphenylmethane reacted with 4-bromobenzoylbenzene to obtain bromophenyl-chlorophenyl-diphenylethylene. Bromophenyl-chlorophenyl-diphenylethylene reacted with N-Boc-4-aminophenylboronic acid pinacol ester, followed by deprotection of the amino group using concentrated hydrochloric acid to obtain 4-aminophenyl-chlorophenyl-diphenylethylene. 4-Aminophenyl-chlorophenyl-diphenylethylene reacted with 4-vinylaniline to synthesize vinylphenyl-amino-diphenylethylene. The amino group in vinylphenyl-amino-diphenylethylene reacted with the aldehyde group in 4-aldehyde benzocyclobutene to obtain benzocyclobutene. The dehydration condensation of cyclobutene-vinyltetraphenylethylene and (3-mercaptopropyl)trimethoxysilane synthesizes mercapto-POSS. The mercapto group is then used to perform a click reaction with the vinyl group in benzocyclobutene-vinyltetraphenylethylene to obtain benzocyclobutene-tetraphenylethylene-grafted POSS. The tetraphenylethylene structure can hinder the close packing of molecular chains, increase the inter-chain structure, impede the transfer of charge, and reduce the dielectric constant. The benzocyclobutene group itself has low dielectric properties; its introduction reduces electronic polarizability and improves dielectric performance. The POSS cage structure introduces nanocavities, increasing the free volume. The POSS nanocage provides rigidity reinforcement and inhibits chain segment movement, achieving the goal of reducing the dielectric constant and dielectric loss of the material. Next, piperazine-based hyperbranched polysiloxane-modified boron nitride was prepared. Boron nitride was hydroxylated using sodium hydroxide solution, followed by dehydration condensation of 3-glycidoxypropyltrimethoxysilane to obtain hyperbranched polysiloxane. The amino group in 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine underwent a ring-opening reaction with the epoxy group in the hyperbranched polysiloxane. After adding hydroxylated boron nitride, B-OH and Si-OH condensed to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride. The six-membered nitrogen-containing piperazine ring reduces the molar polarizability of the molecular chain and lowers the dielectric constant. The hyperbranched structure, with its highly branched and deformable characteristics, can buffer stress. The polysiloxane segments provide a flexible buffer layer, which helps improve the bending strength of the material. Simultaneously, the low-polarity segments of the polysiloxane chain further reduce dielectric loss. Boron nitride itself has a low dielectric constant; its addition to the matrix material improves the dielectric properties and bending strength of the material, ensuring the durability and reliability of the copper-clad laminate in complex applications. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1:

[0034] This embodiment describes a method for preparing a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step S1: 47.6 mmol of 4-chlorodiphenylmethane and 80 mL of tetrahydrofuran were added to a three-necked flask equipped with a thermometer and a stirrer. The mixture was stirred for 5 min, transferred to an ice bath, and 23.75 mL of 1.6 mol / L n-butyllithium / hexane solution was added dropwise at 0 °C. The mixture was stirred for 15 min, and 40 mL of 0.95 mmol / mL 4-bromobenzoylbenzene / tetrahydrofuran solution was added dropwise. The mixture was stirred at room temperature for 12 h. The mixture was then added to a saturated ammonium chloride solution and extracted with dichloromethane. The combined organic phases were dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness. The filtrate was added to a two-necked flask equipped with a stirrer and a reflux condenser with 200 mL of toluene and 2 g of p-toluenesulfonic acid. The mixture was reacted for 12 h and evaporated to dryness. The filtrate was purified by silica gel column chromatography using a dichloromethane / n-hexane mixed solvent (dichloromethane to n-hexane volume ratio of 1:10) as the eluent to obtain bromophenyl-chlorophenyl-diphenylethylene. Step S2: Add 0.1 mmol of bromophenyl-chlorophenyl-diphenylethylene, 0.3 mmol of N-Boc-4-aminophenylboronic acid pinacol ester, 70 mL of tetrahydrofuran, and 0.01 mmol of tetra(triphenylphosphine)palladium to a three-necked flask equipped with a thermometer and a stirrer. Stir for 5 min, then add 1.5 mL of 0.3 mmol / mL sodium carbonate solution dropwise. Purge the mixture three times with nitrogen and stir at 85 °C for 8 h. Combine the organic phases and recrystallize with a methanol-water solution (methanol to water volume ratio of 4:1). Elute with petroleum ether and purify by silica gel column chromatography. Add the purified organic phase, along with 8 mL of methanol and 2 mL of dichloromethane, to a three-necked flask equipped with a stirrer and a spherical condenser. Purge the mixture three times with argon and stir for 30 min under an argon atmosphere. Add 0.1 mL of sodium carbonate solution dropwise. 12 mol / L concentrated hydrochloric acid was used to react for 10 h. The pH was adjusted to 7 with saturated sodium carbonate solution. The mixture was filtered, and the residue was washed three times with deionized water and dried to obtain 4-aminophenyl-chlorophenyl-diphenylethylene. Step S3: 0.5 mmol of 4-aminophenyl-chlorophenyl-diphenylethylene, 0.6 mmol of 4-vinylaniline, 7 mg of tridibenzylacetone dipalladium, 14 mg of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl and 96 mg of sodium tert-butoxide were added to a Schlenk tube equipped with a stirrer. The mixture was purged three times with argon gas. Under an argon atmosphere, 5 mL of toluene was added, and the mixture was stirred at 110 °C for 14 h. After cooling to room temperature, the mixture was filtered, and the filtrate was evaporated to dryness. The solution was purified by silica gel column chromatography using a petroleum ether / dichloromethane mixed solvent (petroleum ether to dichloromethane volume ratio of 10:1) as the eluent to obtain vinylphenyl-amino-diphenylethylene. Step S4: Add 0.5 mmol vinylphenyl-amino-diphenylethylene, 0.5 mmol 4-aldehyde benzocyclobutene and 15 mL anhydrous ethanol to a three-necked flask equipped with a thermometer and a stirrer. Add 2 g of 4A molecular sieve and stir the reaction at 60 °C for 10 h. Cool to room temperature, filter, wash the filter residue three times with 95% ethanol solution, and dry to obtain benzocyclobutene-vinyltetraphenylethylene. Step S5: 2.15 mmol (3-mercaptopropyl)trimethoxysilane, 11 mL anhydrous methanol, and 0.05 mL 12 mol / L concentrated hydrochloric acid were added to a three-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred for 5 min, 0.1 mL deionized water was added, and the mixture was reacted at 90 °C for 8 h. The mixture was allowed to stand at 0 °C for 30 min, the supernatant was poured off, dichloromethane was added and stirred, and ice-cold methanol was added to precipitate the precipitate. This process was repeated three times. The mixture was dried, and 2.37 mmol benzocyclobutene-vinyltetraphenylethylene, 0.024 mmol azobisisobutyronitrile, and 10 mL anhydrous toluene were added to a two-necked flask equipped with a thermometer. The mixture was evacuated and purged with nitrogen, then transferred to an oil bath and reacted at 65 °C for 72 h. The reaction was quenched with ice water, and the mixture was added dropwise to methanol at room temperature with stirring. The precipitate was collected by centrifugation and added to toluene. The mixture was then precipitated twice with methanol to obtain benzocyclobutene-tetraphenylethylene-grafted POSS. Step S6: Add 4g boron nitride, 4g glucose and 128mL deionized water to a ball mill jar, ball mill at 700r / min for 6h, filter, wash 5 times with pure water, place in a drying oven and dry at 80℃ for 12h, add 10mL 5mol / L sodium hydroxide solution to a reaction vessel, react at 120℃ for 12h, and sonicate for 1h to obtain hydroxylated boron nitride; Step S7: Add 6g of 3-glycidyl etheroxypropyltrimethoxysilane and 5.1mL of ethanol to a reaction vessel, purge with nitrogen, heat to 60℃, add 0.65g of deionized water, adjust the pH to 10 with 1mol / L sodium hydroxide solution, stir and maintain the temperature for 4h, adjust the pH to 7 with 0.67mol / L tartaric acid solution, filter, distill the filtrate under reduced pressure, and add 5g of 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine and 150mL of dimethyl sulfoxide to a three-necked flask equipped with a stirrer and thermometer, purge with nitrogen, stir at 40℃ for 1h, react for 7h, add to methanol, filter, wash the residue three times with methanol, dry, and add 4g of hydroxylated boron nitride and 150mL of dimethyl sulfoxide... N-methylpyrrolidone was added to a three-necked flask equipped with a stirrer and a thermometer, nitrogen gas was introduced, and the reaction was carried out at 70°C for 72 h. The mixture was then added to methanol, filtered, and the filter residue was washed three times with methanol and dried to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride. Step S8: Weigh out 30 parts of polyphenylene ether resin, 20 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 10 parts of piperazine-modified hyperbranched polysiloxane-modified boron nitride, and 130 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701. Step S9: Add polyphenylene ether resin, benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 240℃ and 20MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0035] Example 2:

[0036] This embodiment describes a method for preparing a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step S1: 71.4 mmol of 4-chlorodiphenylmethane and 120 mL of tetrahydrofuran were added to a three-necked flask equipped with a thermometer and a stirrer. The mixture was stirred for 7 min, transferred to an ice bath, and 32.625 mL of 1.6 mol / L n-butyllithium / hexane solution was added dropwise at 3 °C. The mixture was stirred for 22 min, and 60 mL of 0.95 mmol / mL 4-bromobenzoylbenzene / tetrahydrofuran solution was added dropwise. The mixture was stirred at room temperature for 12 h, added to a saturated ammonium chloride solution, and extracted with dichloromethane. The combined organic phases were dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness. The filtrate was added to a two-necked flask equipped with a stirrer and a reflux condenser with 300 mL of toluene and 3 g of p-toluenesulfonic acid. The mixture was reacted for 12 h, evaporated to dryness, and purified by silica gel column chromatography using a dichloromethane / n-hexane mixed solvent (dichloromethane to n-hexane volume ratio of 1:10) as the eluent to obtain bromophenyl-chlorophenyl-diphenylethylene. Step S2: Add 0.15 mmol of bromophenyl-chlorophenyl-diphenylethylene, 0.45 mmol of N-Boc-4-aminophenylboronic acid pinacol ester, 105 mL of tetrahydrofuran, and 0.015 mmol of tetra(triphenylphosphine)palladium to a three-necked flask equipped with a thermometer and a stirrer. Stir for 5 min, then add 2.25 mL of 0.3 mmol / mL sodium carbonate solution dropwise. Purge the mixture three times with nitrogen and stir at 85 °C for 8 h. Combine the organic phases and recrystallize from a methanol-water solution (methanol to water volume ratio of 4:1). Elute with petroleum ether and purify by silica gel column chromatography. Add the purified organic phase, along with 12 mL of methanol and 3 mL of dichloromethane, to a three-necked flask equipped with a stirrer and a spherical condenser. Purge the mixture three times with argon and stir for 35 min under an argon atmosphere. Add 0.15 mL of argon solution dropwise. 12 mol / L concentrated hydrochloric acid was used to react for 11 h. The pH was adjusted to 7 with saturated sodium carbonate solution. The mixture was filtered, and the residue was washed four times with deionized water and dried to obtain 4-aminophenyl-chlorophenyl-diphenylethylene. Step S3: 0.75 mmol of 4-aminophenyl-chlorophenyl-diphenylethylene, 0.9 mmol of 4-vinylaniline, 10.5 mg of tris(dibenzylacetone)palladium, 21 mg of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl and 144 mg of sodium tert-butoxide were added to a Schlenk tube equipped with a stirrer. The mixture was purged three times with argon gas. Under an argon atmosphere, 7.5 mL of toluene was added, and the mixture was stirred at 110 °C for 14 h. After cooling to room temperature, the mixture was filtered, and the filtrate was evaporated to dryness. The filtrate was purified by silica gel column chromatography using a petroleum ether / dichloromethane mixed solvent (petroleum ether to dichloromethane volume ratio of 10:1) as the eluent to obtain vinylphenyl-amino-diphenylethylene. Step S4: Add 0.75 mmol vinylphenyl-amino-diphenylethylene, 0.75 mmol 4-aldehyde benzocyclobutene and 22.5 mL anhydrous ethanol to a three-necked flask equipped with a thermometer and a stirrer. Add 3 g of 4A molecular sieve and stir the reaction at 60 °C for 10 h. Cool to room temperature, filter, wash the filter residue four times with 95% ethanol solution, and dry to obtain benzocyclobutene-vinyltetraphenylethylene. Step S5: 3.225 mmol (3-mercaptopropyl)trimethoxysilane, 16.5 mL anhydrous methanol, and 0.075 mL 12 mol / L concentrated hydrochloric acid were added to a three-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred for 5 min, then 0.15 mL deionized water was added and the mixture was reacted at 90 °C for 10 h. After standing at 2 °C for 30 min, the supernatant was decanted, dichloromethane was added and stirred, and then ice-cold methanol was added to precipitate the product. This process was repeated three times. The product was dried and then added to a two-necked flask equipped with a thermometer along with 3.555 mmol benzocyclobutene-vinyltetraphenylethylene, 0.036 mmol azobisisobutyronitrile, and 15 mL anhydrous toluene. The mixture was evacuated and purged with nitrogen, then transferred to an oil bath and reacted at 65 °C for 72 h. The reaction was quenched with ice water and then added dropwise to methanol at room temperature with stirring. The precipitate was collected by centrifugation and added to toluene. The product was then precipitated twice with methanol to obtain benzocyclobutene-tetraphenylethylene-grafted POSS. Step S6: Add 6g boron nitride, 4-8g glucose and 192mL deionized water to a ball mill jar, ball mill at 700r / min for 6h, filter, wash 6 times with pure water, place in a drying oven and dry at 80℃ for 12h, add 15mL of 5mol / L sodium hydroxide solution to a reaction vessel, react at 120℃ for 12h, and sonicate for 1.5h to obtain hydroxylated boron nitride; Step S7: Add 9g of 3-glycidyl etheroxypropyltrimethoxysilane and 7.65mL of ethanol to a reaction vessel, purge with nitrogen, heat to 60℃, add 0.975g of deionized water, adjust the pH to 10 with 1mol / L sodium hydroxide solution, stir and maintain the temperature for 4h, adjust the pH to 7 with 0.67mol / L tartaric acid solution, filter, distill the filtrate under reduced pressure, and add it to a three-necked flask equipped with a stirrer and thermometer with 7.5g of 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine and 225mL of dimethyl sulfoxide. Purge with nitrogen, stir at 40℃ for 1h, react for 7h, add to methanol, filter, wash the residue three times with methanol, dry, and add to 6g of hydroxylated boron nitride and 225mL of dimethyl sulfoxide. N-methylpyrrolidone was added to a three-necked flask equipped with a stirrer and a thermometer, nitrogen gas was introduced, and the reaction was carried out at 70°C for 72 h. The mixture was then added to methanol, filtered, and the filter residue was washed three times with methanol and dried to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride. Step S8: Weigh out 40 parts of polyphenylene ether resin, 25 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 15 parts of piperazine-based hyperbranched polysiloxane-modified boron nitride, and 140 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701. Step S9: Add polyphenylene ether resin, benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 255℃ and 30MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0037] Example 3:

[0038] This embodiment describes a method for preparing a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step S1: 95.2 mmol of 4-chlorodiphenylmethane and 160 mL of tetrahydrofuran were added to a three-necked flask equipped with a thermometer and a stirrer. The mixture was stirred for 10 min, transferred to an ice bath, and 47.5 mL of 1.6 mol / L n-butyllithium / hexane solution was added dropwise at 5 °C. The mixture was stirred for 30 min, and 80 mL of 0.95 mmol / mL 4-bromobenzoylbenzene / tetrahydrofuran solution was added dropwise. The mixture was stirred at room temperature for 12 h. The mixture was then added to a saturated ammonium chloride solution and extracted with dichloromethane. The combined organic phases were dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness. The filtrate was added to a two-necked flask equipped with a stirrer and a reflux condenser with 400 mL of toluene and 4 g of p-toluenesulfonic acid. The mixture was reacted for 12 h and evaporated to dryness. The filtrate was purified by silica gel column chromatography using a dichloromethane / n-hexane mixed solvent (dichloromethane to n-hexane volume ratio of 1:10) as the eluent to obtain bromophenyl-chlorophenyl-diphenylethylene. Step S2: Add 0.2 mmol of bromophenyl-chlorophenyl-diphenylethylene, 0.6 mmol of N-Boc-4-aminophenylboronic acid pinacol ester, 140 mL of tetrahydrofuran, and 0.02 mmol of tetra(triphenylphosphine)palladium to a three-necked flask equipped with a thermometer and a stirrer. Stir for 5 min, add 3 mL of 0.3 mmol / mL sodium carbonate solution dropwise, purge three times with nitrogen, and stir at 85 °C for 8 h. Combine the organic phases and recrystallize with a methanol-water solution (methanol to water volume ratio of 4:1). Elute with petroleum ether and purify by silica gel column chromatography. Add the purified organic phase, along with 16 mL of methanol and 4 mL of dichloromethane, to a three-necked flask equipped with a stirrer and a spherical condenser. Purge three times with argon, stir for 40 min under an argon atmosphere, and add 0.2 mL of sodium carbonate solution dropwise. 12 mol / L concentrated hydrochloric acid was used to react for 12 h. The pH was adjusted to 7 with saturated sodium carbonate solution. The mixture was filtered, and the residue was washed 5 times with deionized water and dried to obtain 4-aminophenyl-chlorophenyl-diphenylethylene. Step S3: 1 mmol of 4-aminophenyl-chlorophenyl-diphenylethylene, 1.2 mmol of 4-vinylaniline, 14 mg of tridibenzylacetone dipalladium, 28 mg of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl and 192 mg of sodium tert-butoxide were added to a Schlenk tube equipped with a stirrer. The mixture was purged three times with argon gas. Under an argon atmosphere, 10 mL of toluene was added, and the mixture was stirred at 110 °C for 14 h. After cooling to room temperature, the mixture was filtered, and the filtrate was evaporated to dryness. The filtrate was purified by silica gel column chromatography using a petroleum ether / dichloromethane mixed solvent (petroleum ether to dichloromethane volume ratio of 10:1) as the eluent to obtain vinylphenyl-amino-diphenylethylene. Step S4: Add 1 mmol vinylphenyl-amino-diphenylethylene, 1 mmol 4-aldehyde benzocyclobutene and 30 mL anhydrous ethanol to a three-necked flask equipped with a thermometer and a stirrer. Add 4 g of 4A molecular sieve and stir the reaction at 60 °C for 10 h. Cool to room temperature, filter, wash the filter residue 5 times with 95% ethanol solution, and dry to obtain benzocyclobutene-vinyltetraphenylethylene. Step S5: 4.3 mmol (3-mercaptopropyl)trimethoxysilane, 22 mL anhydrous methanol, and 0.1 mL 12 mol / L concentrated hydrochloric acid were added to a three-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred for 5 min, 0.2 mL deionized water was added, and the mixture was reacted at 90 °C for 12 h. After standing at 5 °C for 30 min, the supernatant was decanted, dichloromethane was added and stirred, and ice-cold methanol was added to precipitate the product. This process was repeated three times. The product was dried, and 4.74 mmol benzocyclobutene-vinyltetraphenylethylene, 0.048 mmol azobisisobutyronitrile, and 20 mL anhydrous toluene were added to a two-necked flask equipped with a thermometer. The mixture was evacuated and purged with nitrogen, then transferred to an oil bath and reacted at 65 °C for 72 h. The reaction was quenched with ice water, and the product was added dropwise to methanol at room temperature with stirring. The precipitate was collected by centrifugation and added to toluene. The product was then precipitated three times with methanol to obtain benzocyclobutene-tetraphenylethylene-grafted POSS. Step S6: Add 8g boron nitride, 8g glucose and 256mL deionized water to a ball mill jar, ball mill at 700r / min for 6h, filter, wash 7 times with pure water, place in a drying oven and dry at 80℃ for 12h, add 20mL 5mol / L sodium hydroxide solution to a reaction vessel, react at 120℃ for 12h, sonicate for 2h to obtain hydroxylated boron nitride; Step S7: Add 12g of 3-glycidyl etheroxypropyltrimethoxysilane and 10.2mL of ethanol to a reaction vessel, purge with nitrogen, heat to 60℃, add 1.3g of deionized water, adjust the pH to 10 with 1mol / L sodium hydroxide solution, stir and maintain the temperature for 4h, adjust the pH to 7 with 0.67mol / L tartaric acid solution, filter, distill the filtrate under reduced pressure, and add it to a three-necked flask equipped with a stirrer and thermometer with 10g of 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine and 300mL of dimethyl sulfoxide. Purge with nitrogen, stir at 40℃ for 1h, react for 7h, add to methanol, filter, wash the residue three times with methanol, dry, and add to 8g of hydroxylated boron nitride and 300mL of dimethyl sulfoxide. N-methylpyrrolidone was added to a three-necked flask equipped with a stirrer and a thermometer, nitrogen gas was introduced, and the reaction was carried out at 70°C for 72 h. The mixture was then added to methanol, filtered, and the filter residue was washed three times with methanol and dried to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride. Step S8: Weigh out 50 parts of polyphenylene ether resin, 30 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 20 parts of piperazine-modified hyperbranched polysiloxane-modified boron nitride, and 150 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701. Step S9: Add polyphenylene ether resin, benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 270℃ and 40MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0039] Comparative Example 1: This comparative example illustrates a method for preparing a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step S1: 4.3 mmol (3-mercaptopropyl)trimethoxysilane, 22 mL anhydrous methanol and 0.1 mL 12 mol / L concentrated hydrochloric acid were added to a three-necked flask equipped with a stirrer, thermometer and reflux condenser. The mixture was stirred for 5 min, 0.2 mL deionized water was added and the mixture was reacted at 90 °C for 12 h. The mixture was then allowed to stand at 5 °C for 30 min. The supernatant was poured off, dichloromethane was added and stirred, and then ice-cold methanol was added to precipitate the product. This process was repeated three times and the mixture was dried to obtain mercapto POSS. Step S2: Add 8g boron nitride, 8g glucose and 256mL deionized water to a ball mill jar, ball mill at 700r / min for 6h, filter, wash 7 times with pure water, place in a drying oven and dry at 80℃ for 12h, add 20mL 5mol / L sodium hydroxide solution to a reaction vessel, react at 120℃ for 12h, sonicate for 2h to obtain hydroxylated boron nitride; Step S3: Add 12g of 3-glycidyl etheroxypropyltrimethoxysilane and 10.2mL of ethanol to a reaction vessel, purge with nitrogen, heat to 60℃, add 1.3g of deionized water, adjust the pH to 10 with 1mol / L sodium hydroxide solution, stir and maintain the temperature for 4h, adjust the pH to 7 with 0.67mol / L tartaric acid solution, filter, distill the filtrate under reduced pressure, and add it to a three-necked flask equipped with a stirrer and thermometer with 10g of 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine and 300mL of dimethyl sulfoxide. Purge with nitrogen, stir at 40℃ for 1h, react for 7h, add to methanol, filter, wash the residue three times with methanol, dry, and add to 8g of hydroxylated boron nitride and 300mL of dimethyl sulfoxide. N-methylpyrrolidone was added to a three-necked flask equipped with a stirrer and a thermometer, nitrogen gas was introduced, and the reaction was carried out at 70°C for 72 h. The mixture was then added to methanol, filtered, and the filter residue was washed three times with methanol and dried to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride. Step S4: Weigh out 50 parts of polyphenylene ether resin, 30 parts of mercapto POSS, 20 parts of piperazine-based hyperbranched polysiloxane-modified boron nitride, and 150 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701. Step S5: Add polyphenylene ether resin, mercapto POSS and piperazine-based hyperbranched polysiloxane-modified boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 270℃ and 40MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0040] Comparative Example 2: This comparative example illustrates a method for preparing a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step S1: 95.2 mmol of 4-chlorodiphenylmethane and 160 mL of tetrahydrofuran were added to a three-necked flask equipped with a thermometer and a stirrer. The mixture was stirred for 10 min, transferred to an ice bath, and 47.5 mL of 1.6 mol / L n-butyllithium / hexane solution was added dropwise at 5 °C. The mixture was stirred for 30 min, and 80 mL of 0.95 mmol / mL 4-bromobenzoylbenzene / tetrahydrofuran solution was added dropwise. The mixture was stirred at room temperature for 12 h. The mixture was then added to a saturated ammonium chloride solution and extracted with dichloromethane. The combined organic phases were dried with anhydrous sodium sulfate, filtered, and the filtrate was evaporated to dryness. The filtrate was added to a two-necked flask equipped with a stirrer and a reflux condenser with 400 mL of toluene and 4 g of p-toluenesulfonic acid. The mixture was reacted for 12 h and evaporated to dryness. The filtrate was purified by silica gel column chromatography using a dichloromethane / n-hexane mixed solvent (dichloromethane to n-hexane volume ratio of 1:10) as the eluent to obtain bromophenyl-chlorophenyl-diphenylethylene. Step S2: Add 0.2 mmol of bromophenyl-chlorophenyl-diphenylethylene, 0.6 mmol of N-Boc-4-aminophenylboronic acid pinacol ester, 140 mL of tetrahydrofuran, and 0.02 mmol of tetra(triphenylphosphine)palladium to a three-necked flask equipped with a thermometer and a stirrer. Stir for 5 min, add 3 mL of 0.3 mmol / mL sodium carbonate solution dropwise, purge three times with nitrogen, and stir at 85 °C for 8 h. Combine the organic phases and recrystallize with a methanol-water solution (methanol to water volume ratio of 4:1). Elute with petroleum ether and purify by silica gel column chromatography. Add the purified organic phase, along with 16 mL of methanol and 4 mL of dichloromethane, to a three-necked flask equipped with a stirrer and a spherical condenser. Purge three times with argon, stir for 40 min under an argon atmosphere, and add 0.2 mL of sodium carbonate solution dropwise. 12 mol / L concentrated hydrochloric acid was used to react for 12 h. The pH was adjusted to 7 with saturated sodium carbonate solution. The mixture was filtered, and the residue was washed 5 times with deionized water and dried to obtain 4-aminophenyl-chlorophenyl-diphenylethylene. Step S3: 1 mmol of 4-aminophenyl-chlorophenyl-diphenylethylene, 1.2 mmol of 4-vinylaniline, 14 mg of tridibenzylacetone dipalladium, 28 mg of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl and 192 mg of sodium tert-butoxide were added to a Schlenk tube equipped with a stirrer. The mixture was purged three times with argon gas. Under an argon atmosphere, 10 mL of toluene was added, and the mixture was stirred at 110 °C for 14 h. After cooling to room temperature, the mixture was filtered, and the filtrate was evaporated to dryness. The filtrate was purified by silica gel column chromatography using a petroleum ether / dichloromethane mixed solvent (petroleum ether to dichloromethane volume ratio of 10:1) as the eluent to obtain vinylphenyl-amino-diphenylethylene. Step S4: Add 1 mmol vinylphenyl-amino-diphenylethylene, 1 mmol 4-aldehyde benzocyclobutene and 30 mL anhydrous ethanol to a three-necked flask equipped with a thermometer and a stirrer. Add 4 g of 4A molecular sieve and stir the reaction at 60 °C for 10 h. Cool to room temperature, filter, wash the filter residue 5 times with 95% ethanol solution, and dry to obtain benzocyclobutene-vinyltetraphenylethylene. Step S5: 4.3 mmol (3-mercaptopropyl)trimethoxysilane, 22 mL anhydrous methanol, and 0.1 mL 12 mol / L concentrated hydrochloric acid were added to a three-necked flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred for 5 min, 0.2 mL deionized water was added, and the mixture was reacted at 90 °C for 12 h. After standing at 5 °C for 30 min, the supernatant was decanted, dichloromethane was added and stirred, and ice-cold methanol was added to precipitate the product. This process was repeated three times. The product was dried, and 4.74 mmol benzocyclobutene-vinyltetraphenylethylene, 0.048 mmol azobisisobutyronitrile, and 20 mL anhydrous toluene were added to a two-necked flask equipped with a thermometer. The mixture was evacuated and purged with nitrogen, then transferred to an oil bath and reacted at 65 °C for 72 h. The reaction was quenched with ice water, and the product was added dropwise to methanol at room temperature with stirring. The precipitate was collected by centrifugation and added to toluene. The product was then precipitated three times with methanol to obtain benzocyclobutene-tetraphenylethylene-grafted POSS. Step S6: Add 8g boron nitride, 8g glucose and 256mL deionized water to a ball mill jar, ball mill at 700r / min for 6h, filter, wash 7 times with pure water, place in a drying oven and dry at 80℃ for 12h, add 20mL 5mol / L sodium hydroxide solution to a reaction vessel, react at 120℃ for 12h, sonicate for 2h to obtain hydroxylated boron nitride; Step S7: Weigh out 50 parts of polyphenylene ether resin, 30 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 20 parts of hydroxylated boron nitride, and 150 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701. Step S8: Add polyphenylene ether resin, benzocyclobutene-tetraphenylethylene grafted POSS and hydroxylated boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 270℃ and 40MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0041] Comparative Example 3: This comparative example illustrates a method for preparing a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties, comprising the following steps: Step S1: 4.3 mmol (3-mercaptopropyl)trimethoxysilane, 22 mL anhydrous methanol and 0.1 mL 12 mol / L concentrated hydrochloric acid were added to a three-necked flask equipped with a stirrer, thermometer and reflux condenser. The mixture was stirred for 5 min, 0.2 mL deionized water was added and the mixture was reacted at 90 °C for 12 h. The mixture was then allowed to stand at 5 °C for 30 min. The supernatant was poured off, dichloromethane was added and stirred, and then ice-cold methanol was added to precipitate the product. This process was repeated three times and the mixture was dried to obtain mercapto POSS. Step S2: Add 8g boron nitride, 8g glucose and 256mL deionized water to a ball mill jar, ball mill at 700r / min for 6h, filter, wash 7 times with pure water, place in a drying oven and dry at 80℃ for 12h, add 20mL 5mol / L sodium hydroxide solution to a reaction vessel, react at 120℃ for 12h, sonicate for 2h to obtain hydroxylated boron nitride; Step S3: Weigh out 50 parts of polyphenylene ether resin, 30 parts of mercapto POSS, 20 parts of hydroxylated boron nitride and 150 parts of xylene according to the following weight parts; wherein, the polyphenylene ether resin is of type PX1005X-701; Step S4: Add polyphenylene ether resin, mercapto POSS and hydroxylated boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 270℃ and 40MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

[0042] Performance testing: The dielectric constant and dielectric loss of the samples from Examples 1-3 and Comparative Examples 1-3 were obtained according to the IPC-TM-650 test method. The bending strength of the samples from Examples 1-3 and Comparative Examples 1-3 was tested using an electronic universal testing machine in accordance with GB / T4722-2017.

[0043] Referring to the table above, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the substrate material prepared by adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride has good dielectric and mechanical properties. Based on the comparison between Example 3 and Comparative Example 1, it can be seen that the dielectric constant of the substrate material prepared by adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-modified hyperbranched polysiloxane to modify boron nitride is lower than that of the substrate material prepared by adding mercapto POSS and piperazine-modified hyperbranched polysiloxane to modify boron nitride. This indicates that adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-modified hyperbranched polysiloxane to modify boron nitride can improve the dielectric properties of the material. Based on the comparison between Example 3 and Comparative Example 1, it can be seen that the dielectric constant of the substrate material prepared by adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride is lower than that of the substrate material prepared by adding benzocyclobutene-tetraphenylethylene grafted POSS and hydroxylated boron nitride. This indicates that adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride can improve the dielectric properties of the material. Based on the comparison between Example 3 and Comparative Example 1, it can be seen that the dielectric constant of the substrate material prepared by adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride is lower than that of the substrate material prepared by adding mercapto POSS and hydroxylated boron nitride. This indicates that adding benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride can improve the dielectric properties of the material.

[0044] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0045] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties, characterized in that, Includes the following components by weight: 30-50 parts of polyphenylene ether resin, 20-30 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 10-20 parts of piperazine-modified polysiloxane-modified boron nitride, and 130-150 parts of xylene. The benzocyclobutene-tetraphenylethylene grafted POSS is prepared by the following steps: Step A1: React 4-chlorodiphenylmethane, tetrahydrofuran, n-butyllithium / hexane solution and 4-bromobenzoylbenzene / tetrahydrofuran solution, and react with toluene and p-toluenesulfonic acid to obtain bromophenyl-chlorophenyl-diphenylethylene; Step A2: Reaction of bromophenyl-chlorophenyl-diphenylethylene, N-Boc-4-aminophenylboronic acid pinacol ester, tetrahydrofuran, tetra(triphenylphosphine)palladium and sodium carbonate solution, followed by reaction with methanol, dichloromethane and concentrated hydrochloric acid to obtain 4-aminophenyl-chlorophenyl-diphenylethylene; Step A3: 4-Aminophenyl-chlorophenyl-diphenylethylene, 4-vinylaniline, tridibenzylacetone dipalladium, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, sodium tert-butoxide and toluene are reacted to obtain vinylphenyl-amino-diphenylethylene; Step A4: Reaction of vinylphenyl-amino-diphenylethylene, 4-aldehyde benzocyclobutene and anhydrous ethanol yields benzocyclobutene-vinyltetraphenylethylene; Step A5: (3-mercaptopropyl)trimethoxysilane, anhydrous methanol, concentrated hydrochloric acid and deionized water are reacted with benzocyclobutene-vinyltetraphenylethylene, azobisisobutyronitrile and anhydrous toluene to obtain benzocyclobutene-tetraphenylethylene grafted POSS.

2. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 1, characterized in that, In step A1, the molar ratio of 4-chlorodiphenylmethane, tetrahydrofuran, n-butyllithium / hexane solution, 4-bromobenzoylbenzene / tetrahydrofuran solution, toluene, and p-toluenesulfonic acid is 47.6-95.2 mmol: 80-160 mL: 23.75-47.5 mL: 40-80 mL: 200-400 mL: 2-4 g; the molar concentration of the n-butyllithium / hexane solution is 1.6 mol / L; and the molar concentration of the 4-bromobenzoylbenzene / tetrahydrofuran solution is 0.95 mmol / mL.

3. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 1, characterized in that, In step A2, the ratio of the amounts of bromophenyl-chlorophenyl-diphenylethylene, N-Boc-4-aminophenylboronic acid pinacol ester, tetrahydrofuran, tetra(triphenylphosphine)palladium, sodium carbonate solution, methanol, dichloromethane, and concentrated hydrochloric acid is 0.1-0.2 mmol : 0.3-0.6 mmol : 70-140 mL : 0.01-0.02 mmol : 1.5-3 mL : 8-16 mL : 2-4 mL : 0.1-0.2 mL; the molar concentration of the sodium carbonate solution is 0.3 mmol / mL.

4. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 1, characterized in that, The ratio of 4-aminophenyl-chlorophenyl-diphenylethylene, 4-vinylaniline, tridibenzylacetone dipalladium, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, sodium tert-butoxide, and toluene in step A3 is 0.5-1 mmol. 0.6-1.2mmol: 7-14mg: 14-28mg: 96-192mg: 5-10mL.

5. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 1, characterized in that, The ratio of vinylphenyl-amino-diphenylethylene, 4-aldehyde benzocyclobutene, 4A molecular sieve and anhydrous ethanol used in step A4 is 0.5-1 mmol: 0.5-1 mmol: 2-4 g: 15-30 mL.

6. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 1, characterized in that, In step A5, the ratio of (3-mercaptopropyl)trimethoxysilane, anhydrous methanol, concentrated hydrochloric acid, deionized water, benzocyclobutene-vinyltetraphenylethylene, azobisisobutyronitrile, and anhydrous toluene is 2.15-4.3 mmol: 11-22 mL: 0.05-0.1 mL: 0.1-0.2 mL: 2.37-4.74 mmol: 0.024-0.048 mmol: 10-20 mL; the molar concentration of the concentrated hydrochloric acid is 12 mol / L.

7. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 1, characterized in that, The piperazine-based hyperbranched polysiloxane-modified boron nitride is prepared by the following steps: Step B1: Ball mill boron nitride, glucose and deionized water, wash, dry, react with sodium hydroxide solution, and sonicate to obtain hydroxylated boron nitride; Step B2: React 3-glycidoxypropyltrimethoxysilane with ethanol, add deionized water and react, stir with 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine and dimethyl sulfoxide and react, react with hydroxylated boron nitride and N-methylpyrrolidone to obtain piperazine-based hyperbranched polysiloxane-modified boron nitride.

8. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 7, characterized in that, In step B1, the ratio of boron nitride, glucose, deionized water, and sodium hydroxide solution is 4-8g:4-8g:128-256mL:10-20mL; the molar concentration of the sodium hydroxide solution is 5mol / L.

9. The composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties according to claim 7, characterized in that, The ratio of 3-glycidyl etheroxypropyltrimethoxysilane, ethanol, deionized water, 1-(4-aminophenyl)-4-(4-hydroxyphenyl)piperazine, dimethyl sulfoxide, hydroxylated boron nitride, and N-methylpyrrolidone in step B2 is 6-12g: 5.1-10.2mL: 0.65-1.3g: 5-10g: 150-300mL: 4-8g: 150-300mL.

10. A composite filler-reinforced copper-clad laminate substrate material with excellent dielectric properties as described in any one of claims 1-9, characterized in that, Includes the following steps: Step 1: Weigh out 30-50 parts of polyphenylene ether resin, 20-30 parts of benzocyclobutene-tetraphenylethylene grafted POSS, 10-20 parts of piperazine-modified hyperbranched polysiloxane-modified boron nitride, and 130-150 parts of xylene according to the following weight proportions; wherein, the polyphenylene ether resin is of type PX1005X-701; Step 2: Add polyphenylene ether resin, benzocyclobutene-tetraphenylethylene grafted POSS and piperazine-based hyperbranched polysiloxane modified boron nitride to a ball mill jar, mix, add to xylene and mix evenly, coat onto a release film, air dry and then pulverize, place in a mold and hot press at 240-270℃ and 20-40MPa to obtain a composite filler-reinforced copper clad laminate substrate material with excellent dielectric properties.

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