Low-loss resin plug hole high-frequency high-speed circuit board and preparation method thereof

Abstract

The invention discloses a low-loss resin plug hole high-frequency high-speed circuit board and a preparation method thereof, and belongs to the technical field of circuit board preparation. The preparation method of the low-loss resin hole-plugging high-frequency high-speed circuit board comprises the following steps: step 1, adding a composite heat stabilizer into polyphenyl ether, and stirring and mixing to obtain matrix resin; 2, mixing and stirring a low-loss auxiliary agent and matrix resin, adding acetone at the same time, and carrying out vacuum defoaming treatment to obtain composite resin; and 3, drilling holes in the circuit board crude product, then cleaning, drying, filling the composite resin into the holes, curing, grinding, welding resistors, capacitors and chip components on the circuit board crude product filled with the composite resin, and after the assembly is completed, obtaining the low-loss resin hole-plugging high-frequency and high-speed circuit board. The circuit board prepared by the method has excellent thermal stability, heat and humidity resistance, low dielectric loss and dielectric constant.

Description

Technical Field

[0001] The present invention belongs to the technical field of circuit board preparation, and particularly relates to a low-loss resin plug hole high-frequency and high-speed circuit board and a preparation method thereof. Background Art

[0002] With the wide application of 5G technology and the continuous advancement of 6G technology research, the importance of high-frequency and high-speed circuit boards in high-end electronic manufacturing fields such as communication, aerospace, and intelligent vehicles has become increasingly prominent. As a key carrier for signal transmission, the performance of high-frequency and high-speed circuit boards directly determines the overall performance and reliability of electronic devices. However, traditional high-frequency and high-speed circuit boards have many deficiencies in terms of loss and heat resistance performance, severely restricting their further development.

[0003] Patent CN115433451B discloses a high-speed low-loss resin composition and its application. The resin composition includes at least one of a resin compound, a benzocyclobutene compound and its derivatives, a promoter, and a filler mixture. This invention discloses the application of a high-speed low-loss resin composition in the preparation of prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards. The cured product of the prepared resin composition has excellent heat and moisture resistance, a relatively high glass transition temperature, a low dielectric constant, a low dielectric loss, a low coefficient of expansion, and excellent heat resistance, and at the same time has good processability, which can fully meet the requirements of high-performance printed circuit boards for high frequency and high speed. However, there is still room for improvement in the dielectric loss, dielectric constant, and thermal stability performance of the circuit boards prepared by this method. Summary of the Invention

[0004] The purpose of the present invention is to provide a low-loss resin plug hole high-frequency and high-speed circuit board and a preparation method thereof, which are used to solve the technical problems of poor dielectric loss, dielectric constant, and thermal stability performance of circuit boards in the prior art.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions: The present invention provides a preparation method for a low-loss resin plug hole high-frequency and high-speed circuit board, including the following steps: Step 1: Add a composite heat stabilizer to polyphenylene ether and stir and mix to obtain a matrix resin; Step 2: Mix and stir the low-loss additive with the matrix resin, and at the same time add acetone for vacuum degassing treatment to obtain a composite resin; Step 3: Drill holes in the rough circuit board, then clean and dry it, fill the composite resin into the holes, cure and grind it. At the same time, solder resistors, capacitors, and chip components to the rough circuit board filled with the composite resin. After assembly is completed, a low-loss resin plug hole high-frequency and high-speed circuit board is obtained.

[0006] Preferably, in the first step, the dosage ratio of the composite heat stabilizer to the polyphenylene ether is (4 - 10) g : (88 - 95) g, the mixing and stirring temperature is 110 - 130 °C, the stirring speed is 200 - 500 rpm, and the stirring time is 30 - 60 min.

[0007] Preferably, the preparation method of the composite heat stabilizer comprises the following steps: Q1: Add 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine, and polyphosphoric acid into a container, heat and stir for reaction. After the reaction is completed, purify to obtain Product 1; add Product 1, methyl bromoacetate, and cesium carbonate into a container, then add acetonitrile, stir at room temperature for reaction. After the reaction is completed, purify to obtain Product 2; Q2: Add Product 2 and lithium aluminum hydride into a container, then add tetrahydrofuran, stir at room temperature for reaction, add distilled water, perform negative pressure treatment, and purify to obtain Product 3; Q3: Add Product 3, isocyanatoethyl methacrylate, and dibutyltin dilaurate into a container, then add tetrahydrofuran, stir at room temperature, perform negative pressure concentration, and purify to obtain the composite heat stabilizer.

[0008] In the above process, the synthesis reaction formula of the composite heat stabilizer is as follows:

[0009] The mass spectrometry analysis results of Product 1 are: m / z: 281.15 (100.0%), 282.16 (18.6%), 283.16 (1.8%), 282.15 (1.1%); the mass spectrometry analysis results of Product 2 are: m / z: 353.17 (100.0%), 354.18 (22.0%), 355.18 (2.9%), 354.17 (1.1%); the mass spectrometry analysis results of Product 3 are: m / z: 325.18 (100.0%), 326.18 (21.7%), 327.19 (2.1%); the mass spectrometry analysis results of the composite heat stabilizer are: m / z: 635.30 (100.0%), 636.30 (36.5%), 637.30 (8.6%), 636.29 (1.8%).

[0010] Preferably, in Q1, the dosage ratio of 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine and polyphosphoric acid is (1.425 - 1.883) g : (1.725 - 2.221) g : (0.185 - 0.208) g, the heating and stirring reaction temperature is 160 - 180 °C, and the heating and stirring reaction time is 10 - 12 h; the dosage ratio of product 1, methyl bromoacetate, cesium carbonate and acetonitrile is (2.11 - 2.39) g : (1.65 - 2.04) g : (4.56 - 5.02) g : (30 - 45) mL, and the room temperature stirring reaction time is 12 - 16 h.

[0011] Preferably, in Q2, the dosage ratio of product 2, lithium aluminum hydride and tetrahydrofuran is (1.02 - 1.37) g : (0.84 - 0.99) g : (20 - 30) mL, and the room temperature stirring reaction time is 8 - 10 h; in Q3, the dosage ratio of product 3, isocyanatoethyl methacrylate, dibutyltin dilaurate and tetrahydrofuran is (0.92 - 1.24) g : (1.01 - 1.43) g : (0.05 - 0.07) mL : (20 - 25) mL, and the room temperature stirring time is 2 - 4 h.

[0012] Preferably, in the second step, the dosage ratio of the low-loss additive, matrix resin and acetone is (20 - 40) g : (65 - 85) g : (18 - 26) mL.

[0013] Preferably, the preparation method of the low-loss additive includes the following steps: S1: Under a nitrogen atmosphere, add hexafluorobisphenol A and anhydrous aluminum chloride into a container, slowly raise the temperature, and then add dicyclopentadiene dropwise into the container through a constant pressure dropping funnel. After the dropping is completed, continue the reaction. After the reaction is completed, cool down, add toluene and an aqueous sodium hydroxide solution, stir, filter, separate the liquid, wash the organic phase, rotary evaporate, wash, separate the liquid, dry, concentrate, and purify to obtain monomer A; S2: Under a nitrogen atmosphere, add monomer A into N-methylpyrrolidone, slowly raise the temperature, and then successively add 4-bromobenzocyclobutene, cesium carbonate, 2,2,6,6-tetramethyl-3,5-heptanedione and copper chloride. Keep the temperature for the reaction. After the reaction is completed, cool down, add petroleum ether and hydrochloric acid, stir, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain the low-loss additive.

[0014] In the above process, the synthesis reaction formula of the low-loss additive is as follows:

[0015] The mass spectrometry analysis results of monomer A are: m / z: 836.27 (100.0%), 837.28 (46.0%), 838.28 (11.2%), 839.28 (1.8%); the mass spectrometry analysis results of the low-loss additive are: m / z: 1244.46 (100.0%), 1245.46 (80.0%), 1246.47 (33.1%), 1247.47 (9.1%), 1248.47 (1.8%).

[0016] Preferably, in S1, the dosage ratio of hexafluorobisphenol A, anhydrous aluminum chloride, dicyclopentadiene, toluene and aqueous sodium hydroxide solution is (4.535 - 4.959) g : (0.32 - 0.47) g : (2.13 - 2.96) g : (20 - 30) mL : (0.36 - 0.62) mL. Slowly heat up to 110 - 120 °C, and continue the reaction for 4 - 6 h. The mass fraction of the aqueous sodium hydroxide solution is 5 wt%, and the stirring time is 30 - 45 min.

[0017] Preferably, in S2, the dosage ratio of monomer A, N-methylpyrrolidone, 4-bromobenzocyclobutene, cesium carbonate, 2,2,6,6-tetramethyl-3,5-heptanedione, copper(I) chloride, petroleum ether and hydrochloric acid is (2.85 - 3.54) g : (20 - 25) mL : (4.12 - 4.83) g : (6.12 - 6.78) g : (0.174 - 0.192) g : (1.01 - 1.43) g : (20 - 25) mL : (1 - 4) mL. Slowly heat up to 110 - 120 °C, and keep the temperature for 20 - 28 h. The concentration of hydrochloric acid is 1 mol / L, and the stirring time is 30 - 45 min.

[0018] A low-loss resin plugging high-frequency and high-speed circuit board prepared by using the preparation method of the low-loss resin plugging high-frequency and high-speed circuit board.

[0019] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are: 1. The present invention first uses 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine, methyl bromoacetate and isocyanatoethyl methacrylate as the main raw materials to prepare a composite heat stabilizer. Subsequently, hexafluorobisphenol A, dicyclopentadiene and 4-bromobenzocyclobutene are used as the main raw materials to prepare a low-loss additive. Applying the two to the preparation process of the circuit board can effectively improve the thermal stability and damp-heat performance of the circuit board, and can also endow it with low dielectric loss and dielectric constant.

[0020] 2. The composite heat stabilizer prepared in the present invention is applied to the preparation process of circuit boards, enabling them to have excellent heat stability, low dielectric loss and dielectric constant, and also excellent heat and humidity resistance. The composite heat stabilizer can disperse heat energy through conjugated π electrons, inhibit the movement of molecular chains. The steric hindrance effect can hinder the sliding of molecular chain segments, and the three-dimensional cross-linked structure restricts the freedom of molecular chains, making the circuit boards have excellent heat stability. The low polarity and conjugated system of the composite heat stabilizer can also endow the circuit boards with low dielectric loss and dielectric constant. At the same time, the hydrophobic effect, hydrogen bond network and densified cross-linked structure of the composite heat stabilizer also endow the circuit boards with excellent heat and humidity resistance.

[0021] 3. The low-loss additive prepared in the present invention is mixed with the matrix resin to obtain a composite resin, which is then applied to circuit boards, enabling them to have low dielectric loss, dielectric constant and excellent heat stability. The low-polarity groups, conjugated system and cross-linked network contained in the low-loss additive endow the circuit boards with low dielectric loss and dielectric constant. At the same time, the rigid structure contained can disperse heat energy through conjugated π electrons, inhibit the thermal movement of molecular chains, and improve heat stability. Detailed implementation manners

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0023] Example 1: This example discloses a preparation method of a composite heat stabilizer, including the following steps: Q1: Add 1.654 g of 5-aminosalicylic acid, 1.992 g of 4-tert-butylbenzene-1,2-diamine and 0.194 g of polyphosphoric acid into a container, heat and stir at 160 °C for 12 h. After the reaction, purify to obtain Product 1; Add 2.25 g of Product 1, 1.84 g of methyl bromoacetate and 4.74 g of cesium carbonate into a container, then add 37.5 mL of acetonitrile, stir at room temperature for 14 h. After the reaction, purify to obtain Product 2; Q2: Add 1.19 g of Product 2 and 0.91 g of lithium aluminum hydride into a container, then add 25 mL of tetrahydrofuran, stir at room temperature for 10 h, add distilled water, perform negative pressure treatment, and purify to obtain Product 3; Q3: Add 1.08 g of Product 3, 1.24 g of isocyanatoethyl methacrylate and 0.06 mL of dibutyltin dilaurate into a container, then add 22.5 mL of tetrahydrofuran, stir at room temperature for 4 h, concentrate under negative pressure, and purify to obtain the composite heat stabilizer.

[0024] This embodiment discloses a preparation method of a low-loss additive, comprising the following steps: S1: Under a nitrogen atmosphere, add 4.742 g of hexafluorobisphenol A and 0.39 g of anhydrous aluminum chloride into a container, slowly heat up to 120 °C, then add 2.58 g of dicyclopentadiene dropwise into the container through a constant-pressure dropping funnel. After the dropping is completed, continue the reaction for 6 h. After the reaction ends, cool down, add 25 mL of toluene and 0.48 mL of a sodium hydroxide aqueous solution with a mass fraction of 5 wt%, stir for 30 min, filter, separate the liquid, wash the organic phase, rotary evaporate, wash, separate the liquid, dry, concentrate, and purify to obtain monomer A; S2: Under a nitrogen atmosphere, add 3.14 g of monomer A into 22.5 mL of N-methylpyrrolidone, slowly heat up to 120 °C, then sequentially add 4.45 g of 4-bromobenzocyclobutene, 6.45 g of cesium carbonate, 0.183 g of 2,2,6,6-tetramethyl-3,5-heptanedione, and 1.22 g of copper chloride. Keep the temperature for reaction for 24 h. After the reaction ends, cool down the temperature, add 22.5 mL of petroleum ether and 2.5 mL of hydrochloric acid with a concentration of 1 mol / L, stir for 45 min, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain the low-loss additive.

[0025] This embodiment discloses a preparation method of a low-loss resin plugging hole high-frequency and high-speed circuit board, comprising the following steps: Step 1: Add 7 g of a composite heat stabilizer into 91 g of polyphenylene ether, stir and mix at 120 °C and 500 rpm for 60 min to obtain a matrix resin; Step 2: Mix and stir 30 g of the low-loss additive with 75 g of the matrix resin, and simultaneously add 22 mL of acetone, and perform vacuum defoaming treatment to obtain a composite resin; Step 3: Drill holes in the rough circuit board, then perform cleaning and drying. Fill the composite resin into the holes, cure, grind, and simultaneously weld resistors, capacitors, and chip components onto the rough circuit board filled with the composite resin. After the assembly is completed, obtain the low-loss resin plugging hole high-frequency and high-speed circuit board.

[0026] Example 2: This embodiment discloses a preparation method of a composite heat stabilizer, comprising the following steps: Q1: Add 1.425 g of 5-aminosalicylic acid, 1.725 g of 4-tert-butylbenzene-1,2-diamine, and 0.185 g of polyphosphoric acid into a container, heat and stir at 160 °C for 12 h. After the reaction ends, purify to obtain product 1; Add 2.11 g of product 1, 1.65 g of methyl bromoacetate, and 4.56 g of cesium carbonate into a container, then add 30 mL of acetonitrile, stir at room temperature for 14 h. After the reaction ends, purify to obtain product 2; Q2: Add 1.02 g of product 2 and 0.84 g of lithium aluminum hydride into a container, then add 20 mL of tetrahydrofuran. After stirring at room temperature for 10 h, add distilled water, perform negative pressure treatment, and purification to obtain product 3; Q3: Add 0.92 g of product 3, 1.01 g of isocyanatoethyl methacrylate, and 0.05 mL of dibutyltin dilaurate into a container, then add 25 mL of tetrahydrofuran. Stir at room temperature for 4 h, perform negative pressure concentration, and purification to obtain the composite heat stabilizer.

[0027] This example discloses a preparation method of a low-loss additive, including the following steps: S1: Under a nitrogen atmosphere, add 4.535 g of hexafluorobisphenol A and 0.32 g of anhydrous aluminum chloride into a container, slowly heat up to 120 °C, and then add 2.13 g of dicyclopentadiene dropwise into the container through a constant pressure dropping funnel. After the dropping is completed, continue the reaction for 6 h. After the reaction ends, cool down, add 20 mL of toluene and 0.36 mL of a 5 wt% sodium hydroxide aqueous solution, stir for 30 min, filter, separate the liquid, wash the organic phase, perform rotary evaporation, wash, separate the liquid, dry, concentrate, and purify to obtain monomer A; S2: Under a nitrogen atmosphere, add 2.85 g of monomer A into 25 mL of N-methylpyrrolidone, slowly heat up to 120 °C, and then successively add 4.12 g of 4-bromobenzocyclobutene, 6.12 g of cesium carbonate, 0.174 g of 2,2,6,6-tetramethyl-3,5-heptanedione, and 1.01 g of cuprous chloride. Keep the temperature for reaction for 24 h. After the reaction ends, cool down the temperature, add 25 mL of petroleum ether and 1 mL of 1 mol / L hydrochloric acid, stir for 45 min, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain the low-loss additive.

[0028] This example discloses a preparation method of a low-loss resin plug-hole high-frequency high-speed circuit board, including the following steps: Step 1: Add 4 g of the composite heat stabilizer into 88 g of polyphenylene ether, stir and mix at 120 °C and 500 rpm for 60 min to obtain the matrix resin; Step 2: Mix and stir 40 g of the low-loss additive with 65 g of the matrix resin, and at the same time add 18 mL of acetone, and perform vacuum degassing treatment to obtain the composite resin; Step 3: Drill holes in the rough circuit board, then perform cleaning and drying. Fill the composite resin into the holes, cure, grind, and at the same time weld resistors, capacitors, and chip components to the rough circuit board filled with the composite resin. After assembly is completed, obtain the low-loss resin plug-hole high-frequency high-speed circuit board.

[0029] Example 3: This example discloses a preparation method of a composite heat stabilizer, including the following steps: Q1: Add 1.883 g of 5-aminosalicylic acid, 2.221 g of 4-tert-butylbenzene-1,2-diamine, and 0.208 g of polyphosphoric acid into a container, heat and stir at 160 °C for 12 h. After the reaction, purify to obtain Product 1; add 2.39 g of Product 1, 2.04 g of methyl bromoacetate, and 5.02 g of cesium carbonate into a container, then add 45 mL of acetonitrile, stir at room temperature for 14 h. After the reaction, purify to obtain Product 2; Q2: Add 1.37 g of Product 2 and 0.99 g of lithium aluminum hydride into a container, then add 30 mL of tetrahydrofuran, stir at room temperature for 10 h, add distilled water, perform negative pressure treatment, and purify to obtain Product 3; Q3: Add 1.24 g of Product 3, 1.43 g of isocyanatoethyl methacrylate, and 0.07 mL of dibutyltin dilaurate into a container, then add 20 mL of tetrahydrofuran, stir at room temperature for 4 h, perform negative pressure concentration, and purify to obtain the composite heat stabilizer.

[0030] This example discloses a preparation method of a low-loss additive, including the following steps: S1: Under a nitrogen atmosphere, add 4.959 g of hexafluorobisphenol A and 0.47 g of anhydrous aluminum chloride into a container, slowly heat up to 120 °C, then add 2.96 g of dicyclopentadiene dropwise into the container through a constant pressure dropping funnel. After the dropping is completed, continue the reaction for 6 h. After the reaction, cool down, add 30 mL of toluene and 0.62 mL of a 5 wt% sodium hydroxide aqueous solution, stir for 30 min, filter, separate the liquid, wash the organic phase, perform rotary evaporation, wash, separate the liquid, dry, concentrate, and purify to obtain Monomer A; S2: Under a nitrogen atmosphere, add 3.54 g of Monomer A into 20 mL of N-methylpyrrolidone, slowly heat up to 120 °C, then add 4.83 g of 4-bromobenzocyclobutene, 6.78 g of cesium carbonate, 0.192 g of 2,2,6,6-tetramethyl-3,5-heptanedione, and 1.43 g of copper chloride in sequence, keep the temperature for reaction for 24 h. After the reaction, cool down the temperature, add 20 mL of petroleum ether and 4 mL of 1 mol / L hydrochloric acid, stir for 45 min, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain the low-loss additive.

[0031] This example discloses a preparation method of a low-loss resin plugging high-frequency and high-speed circuit board, including the following steps: Step 1: Add 10 g of the composite heat stabilizer into 95 g of polyphenylene ether, stir and mix at 120 °C and 500 rpm for 60 min to obtain the matrix resin; Step 2: Mix and stir 20 g of the low-loss additive with 85 g of the matrix resin, and simultaneously add 26 mL of acetone, perform vacuum degassing treatment to obtain the composite resin; Step 3: Drill holes in the rough circuit board, then clean, dry it, fill the holes with composite resin, cure, grind, and at the same time solder resistors, capacitors, and chip components to the rough circuit board filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed circuit board is obtained.

[0032] Example 4: This example discloses a preparation method of a composite heat stabilizer, which includes the following steps: Q1: Add 1.571 g of 5-aminosalicylic acid, 1.836 g of 4-tert-butylbenzene-1,2-diamine, and 0.189 g of polyphosphoric acid into a container, heat and stir at 160 °C for 12 h. After the reaction, purify to obtain Product 1; add 2.18 g of Product 1, 1.71 g of methyl bromoacetate, and 4.63 g of cesium carbonate into a container, then add 32 mL of acetonitrile, stir at room temperature for 14 h. After the reaction, purify to obtain Product 2; Q2: Add 1.11 g of Product 2 and 0.86 g of lithium aluminum hydride into a container, then add 22 mL of tetrahydrofuran, stir at room temperature for 10 h, add distilled water, perform negative pressure treatment, and purify to obtain Product 3; Q3: Add 0.99 g of Product 3, 1.15 g of isocyanatoethyl methacrylate, and 0.06 mL of dibutyltin dilaurate into a container, then add 21 mL of tetrahydrofuran, stir at room temperature for 4 h, perform negative pressure concentration, and purify to obtain the composite heat stabilizer.

[0033] This example discloses a preparation method of a low-loss additive, which includes the following steps: S1: Under a nitrogen atmosphere, add 4.613 g of hexafluorobisphenol A and 0.35 g of anhydrous aluminum chloride into a container, slowly heat up to 120 °C, and then add 2.38 g of dicyclopentadiene dropwise into the container through a constant pressure dropping funnel. After the dropping is completed, continue the reaction for 6 h. After the reaction, cool down, add 22 mL of toluene and 0.41 mL of a 5 wt% sodium hydroxide aqueous solution, stir for 30 min, filter, separate the liquid, wash the organic phase, perform rotary evaporation, wash, separate the liquid, dry, concentrate, and purify to obtain Monomer A; S2: Under a nitrogen atmosphere, add 3.01 g of Monomer A into 21 mL of N-methylpyrrolidone, slowly heat up to 120 °C, and then successively add 4.27 g of 4-bromobenzocyclobutene, 6.23 g of cesium carbonate, 0.179 g of 2,2,6,6-tetramethyl-3,5-heptanedione, and 1.17 g of copper(I) chloride, keep the temperature for reaction for 24 h. After the reaction, cool down, add 21 mL of petroleum ether and 2 mL of 1 mol / L hydrochloric acid, stir for 45 min, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain the low-loss additive.

[0034] This embodiment discloses a preparation method of a low-loss resin plug hole high-frequency and high-speed circuit board, including the following steps: Step 1: Add 6 g of composite heat stabilizer to 90 g of polyphenylene ether, stir and mix at 120 °C and 500 rpm for 60 min to obtain a matrix resin; Step 2: Mix and stir 25 g of low-loss additive with 70 g of matrix resin, and simultaneously add 19 mL of acetone, and perform vacuum defoaming treatment to obtain a composite resin; Step 3: Drill holes in the rough circuit board, then clean and dry it. Fill the composite resin into the holes, cure and grind it. At the same time, weld resistors, capacitors, and chip components to the rough circuit board filled with the composite resin. After assembly, a low-loss resin plug hole high-frequency and high-speed circuit board is obtained.

[0035] Example 5: This embodiment discloses a preparation method of a composite heat stabilizer, including the following steps: Q1: Add 1.723 g of 5-aminosalicylic acid, 2.017 g of 4-tert-butylbenzene-1,2-diamine, and 0.199 g of polyphosphoric acid to a container, heat and stir at 160 °C for 12 h. After the reaction, purify to obtain Product 1; Add 2.31 g of Product 1, 1.98 g of methyl bromoacetate, and 4.98 g of cesium carbonate to a container, then add 42 mL of acetonitrile, stir at room temperature for 14 h. After the reaction, purify to obtain Product 2; Q2: Add 1.28 g of Product 2 and 0.95 g of lithium aluminum hydride to a container, then add 28 mL of tetrahydrofuran, stir at room temperature for 10 h, add distilled water, perform negative pressure treatment, and purify to obtain Product 3; Q3: Add 1.17 g of Product 3, 1.29 g of isocyanatoethyl methacrylate, and 0.05 mL of dibutyltin dilaurate to a container, then add 24 mL of tetrahydrofuran, stir at room temperature for 4 h, concentrate under negative pressure, and purify to obtain the composite heat stabilizer.

[0036] This embodiment discloses a preparation method of a low-loss additive, including the following steps: S1: Under a nitrogen atmosphere, add 4.871 g of hexafluorobisphenol A and 0.42 g of anhydrous aluminum chloride to a container, slowly heat up to 120 °C, and then add 2.71 g of dicyclopentadiene dropwise to the container through a constant pressure dropping funnel. After the dropping is completed, continue the reaction for 6 h. After the reaction, cool down, add 28 mL of toluene and 0.54 mL of a 5 wt% sodium hydroxide aqueous solution, stir for 30 min, filter, separate the liquid, wash the organic phase, rotary evaporate, wash, separate the liquid, dry, concentrate, and purify to obtain monomer A; S2: Under a nitrogen atmosphere, add 3.37 g of monomer A to 24 mL of N-methylpyrrolidone, slowly heat up to 120 °C, then successively add 4.62 g of 4-bromobenzocyclobutene, 6.57 g of cesium carbonate, 0.188 g of 2,2,6,6-tetramethyl-3,5-heptanedione, and 1.35 g of cuprous chloride, keep the temperature for reaction for 24 h. After the reaction is completed, cool down, add 24 mL of petroleum ether and 3 mL of 1 mol / L hydrochloric acid, stir for 45 min, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain a low-loss auxiliary agent.

[0037] This example discloses a preparation method of a low-loss resin plug-hole high-frequency and high-speed circuit board, including the following steps: Step 1: Add 8 g of a composite heat stabilizer to 92 g of polyphenylene ether, stir and mix at 120 °C and 500 rpm for 60 min to obtain a matrix resin. Step 2: Mix and stir 35 g of a low-loss auxiliary agent with 80 g of the matrix resin, and at the same time add 24 mL of acetone, and perform vacuum degassing treatment to obtain a composite resin. Step 3: Drill holes in the rough circuit board, then clean and dry it, fill the composite resin into the holes, cure and grind it. At the same time, solder resistors, capacitors, and chip components to the rough circuit board filled with the composite resin. After assembly is completed, a low-loss resin plug-hole high-frequency and high-speed circuit board is obtained.

[0038] Example 6: This example discloses a preparation method of a composite heat stabilizer, including the following steps: Q1: Add 1.623 g of 5-aminosalicylic acid, 1.983 g of 4-tert-butylbenzene-1,2-diamine, and 0.191 g of polyphosphoric acid to a container, heat and stir at 160 °C for 12 h. After the reaction is completed, purify to obtain product 1; add 2.28 g of product 1, 1.78 g of methyl bromoacetate, and 4.81 g of cesium carbonate to a container, then add 35 mL of acetonitrile, stir at room temperature for 14 h. After the reaction is completed, purify to obtain product 2. Q2: Add 1.21 g of product 2 and 0.92 g of lithium aluminum hydride to a container, then add 26 mL of tetrahydrofuran, stir at room temperature for 10 h, add distilled water, perform negative pressure treatment, and purify to obtain product 3. Q3: Add 1.21 g of product 3, 1.37 g of isocyanatoethyl methacrylate, and 0.07 mL of dibutyltin dilaurate to a container, then add 23 mL of tetrahydrofuran, stir at room temperature for 4 h, perform negative pressure concentration, and purify to obtain the composite heat stabilizer.

[0039] This example discloses a preparation method of a low-loss auxiliary agent, including the following steps: S1: Under a nitrogen atmosphere, add 4.711 g of hexafluorobisphenol A and 0.45 g of anhydrous aluminum chloride into a container, slowly heat up to 120 °C, then add 2.87 g of dicyclopentadiene dropwise into the container through a constant-pressure dropping funnel. After the dropping is completed, continue the reaction for 6 h. After the reaction ends, cool down, add 26 mL of toluene and 0.45 mL of a 5 wt% sodium hydroxide aqueous solution, stir for 30 min, filter, separate the liquid, wash the organic phase, rotary evaporate, wash, separate the liquid, dry, concentrate, and purify to obtain monomer A; S2: Under a nitrogen atmosphere, add 2.97 g of monomer A into 23 mL of N-methylpyrrolidone, slowly heat up to 120 °C, then sequentially add 4.58 g of 4-bromobenzocyclobutene, 6.65 g of cesium carbonate, 0.181 g of 2,2,6,6-tetramethyl-3,5-heptanedione, and 1.31 g of copper(I) chloride, keep the temperature for reaction for 24 h. After the reaction ends, cool down the temperature, add 23 mL of petroleum ether and 2.5 mL of 1 mol / L hydrochloric acid, stir for 45 min, filter, wash, separate the liquid, extract, dry, concentrate, and purify to obtain the low-loss auxiliary agent.

[0040] This example discloses a preparation method of a low-loss resin plug-hole high-frequency and high-speed circuit board, including the following steps: Step 1: Add 5 g of the composite heat stabilizer into 93 g of polyphenylene ether, stir and mix at 120 °C and 500 rpm for 60 min to obtain the matrix resin; Step 2: Mix and stir 28 g of the low-loss auxiliary agent with 71 g of the matrix resin, and at the same time add 20 mL of acetone, and perform vacuum degassing treatment to obtain the composite resin; Step 3: Drill holes on the rough circuit board, then wash and dry. Fill the composite resin into the holes, cure, grind, and at the same time weld resistors, capacitors, and chip components to the rough circuit board filled with the composite resin. After the assembly is completed, a low-loss resin plug-hole high-frequency and high-speed circuit board is obtained.

[0041] Comparative Example 1: Compared with Example 1, in the process of preparing the low-loss resin plug-hole high-frequency and high-speed circuit board in Comparative Example 1, the composite heat stabilizer is not added, and other conditions remain unchanged.

[0042] Comparative Example 2: Compared with Example 1, in the process of preparing the low-loss resin plug-hole high-frequency and high-speed circuit board in Comparative Example 2, the low-loss auxiliary agent is not added, and other conditions remain unchanged.

[0043] Experimental Example: The performance of the low-loss resin-plugged via high-frequency and high-speed circuit boards prepared in Examples 1-6 and Comparative Examples 1-2 was tested. The heat resistance of the samples was tested according to GB / T 2423.2-2008, the damp heat resistance of the samples was tested according to GB / T 2423.4-2008, and the dielectric loss and dielectric constant of the samples were tested according to GB / T 1409-2006. The test results are shown in Table 1: Table 1 Project Whether there are cracks and delaminations Moisture absorption rate / % Dielectric constant Dielectric loss factor Example 1 None 0.13 2.11 0.0012 Example 2 None 0.17 2.13 0.0013 Example 3 None 0.16 2.21 0.0015 Example 4 None 0.18 2.24 0.0015 Example 5 None 0.14 2.18 0.0013 Example 6 None 0.15 2.17 0.0015 Comparative Example 1 There are cracks and delaminations 0.48 3.25 0.0027 Comparative Example 2 There are cracks and delaminations 0.17 3.28 0.0029 It can be seen from the test results in Table 1 that the low-loss resin-plugged via high-frequency and high-speed circuit boards prepared in Examples 1-6 of the present invention have excellent thermal stability, damp heat resistance, low dielectric loss and dielectric constant. By comparing Comparative Example 1 with Examples 1-6, it can be seen that adding a composite heat stabilizer can endow the circuit board with excellent thermal stability, damp heat resistance, low dielectric loss and dielectric constant; by comparing Comparative Example 2 with Examples 1-6, it can be seen that adding a low-loss additive can endow the circuit board with low dielectric loss, dielectric constant and excellent thermal stability.

[0044] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

[0045] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific embodiments. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art in the relevant technical field can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A method for preparing a low-loss resin plugged high-frequency and high-speed circuit board, characterized in that: The following steps are involved: Step 1: adding the composite heat stabilizer to the polyphenylene ether, stirring and mixing, to obtain a base resin; Step 2: Mix and stir the low-loss additive and the base resin, add acetone, and perform vacuum degassing to obtain a composite resin; Step 3: Drill holes on the rough circuit board, then clean and dry it, fill the holes with composite resin, cure it, grind it, and solder resistors, capacitors, and chip components to the rough circuit board filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed circuit board is obtained.

2. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 1, characterized in that: In the step 1, the usage ratio of the composite heat stabilizer and the polyphenylene ether is (4-10) g: (88-95) g.

3. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 1, characterized in that: The preparation method of the composite thermal stabilizer comprises the following steps: Q1: Add 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine and polyphosphoric acid to a container, heat and stir to react, purify after the reaction is completed, and obtain product 1; add product 1, methyl bromoacetate and cesium carbonate to a container, then add acetonitrile, stir at room temperature to react, purify after the reaction is completed, and obtain product 2; Q2: Add product 2 and lithium aluminum hydride into a container, then add tetrahydrofuran, stir at room temperature for reaction, add distilled water, treat under negative pressure, and purify to obtain product 3; Q3: Add product 3, isocyanoethyl methacrylate and dibutyltin dilaurate into a container, then add tetrahydrofuran, stir at room temperature, concentrate under negative pressure, and purify to obtain a composite thermal stabilizer.

4. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 3, characterized in that: In the Q1, the dosage ratio of 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine and polyphosphoric acid is (1.425-1.883) g: (1.725-2.221) g: (0.185-0.208) g; the dosage ratio of product 1, methyl bromoacetate, cesium carbonate and acetonitrile is (2.11-2.39) g: (1.65-2.04) g: (4.56-5.02) g: (30-45) mL.

5. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 3, characterized in that: In Q2, the usage ratio of product 2, lithium aluminum hydride and tetrahydrofuran is (1.02-1.37) g: (0.84-0.99) g: (20-30) mL; in Q3, the usage ratio of product 3, isocyanoethyl methacrylate, dibutyltin dilaurate and tetrahydrofuran is (0.92-1.24) g: (1.01-1.43) g: (0.05-0.07) mL: (20-25) mL.

6. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 1, characterized in that: In the step 2, the usage ratio of the modified resin, the base resin and acetone is (20-40) g: (65-85) g: (18-26) mL.

7. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 1, characterized in that: The preparation method of the low-loss auxiliary agent comprises the following steps: S1: Under a nitrogen atmosphere, hexafluorobisphenol A and anhydrous aluminum chloride are added to a container, the temperature is slowly raised, and then dicyclopentadiene is added dropwise to the container through a constant pressure dropping funnel. After the addition is completed, the reaction is continued. After the reaction is completed, the reaction is cooled, toluene and sodium hydroxide aqueous solution are added, stirred, filtered, separated, the organic phase is washed, rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A; S2: Under a nitrogen atmosphere, monomer A is added to N-methylpyrrolidone, the temperature is slowly raised, and then 4-bromobenzocyclobutene, cesium carbonate, 2,2,6,6-tetramethyl-3,5-heptanedione and cuprous chloride are added in sequence, and the temperature is kept for reaction. After the reaction is completed, the temperature is lowered, petroleum ether and hydrochloric acid are added, and the mixture is stirred, filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss additive.

8. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 7, characterized in that: In the S1, the usage ratio of hexafluorobisphenol A, anhydrous aluminum chloride, dicyclopentadiene, toluene and sodium hydroxide aqueous solution is (4.535-4.959) g: (0.32-0.47) g: (2.13-2.96) g: (20-30) mL: (0.36-0.62) mL.

9. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 7, characterized in that: In S2, the usage ratio of monomer A, N-methylpyrrolidone, 4-bromobenzocyclobutene, cesium carbonate, 2,2,6,6-tetramethyl-3,5-heptanedione, cuprous chloride, petroleum ether and hydrochloric acid is (2.85-3.54) g: (20-25) mL: (4.12-4.83) g: (6.12-6.78) g: (0.174-0.192) g: (1.01-1.43) g: (20-25) mL: (1-4) mL.

10. A low-loss resin-plugged high-frequency and high-speed circuit board prepared by the method according to any one of claims 1 to 9.

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