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

Abstract

The present invention discloses a low-loss resin-plugged high-frequency and high-speed circuit board and a preparation method thereof, which belongs to the technical field of circuit board preparation. The preparation method of the low-loss resin-plugged high-frequency and high-speed circuit board comprises the following steps: Step 1: Add a composite thermal stabilizer to polyphenylene ether, stir and mix to obtain a matrix resin; Step 2: Mix and stir a low-loss additive with the matrix resin, and add acetone at the same time, vacuum degassing to obtain a composite resin; Step 3: Drill holes on the rough product of the circuit board, then clean and dry, fill the composite resin into the hole, solidify, grind, and at the same time weld resistors, capacitors, and chip components to the rough product of the circuit board filled with the composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed circuit board is obtained. The circuit board prepared by this method has excellent thermal stability, moisture and heat resistance, low dielectric loss and dielectric constant.

Description

Technical Field

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

[0002] With the widespread adoption of 5G technology and the continued advancement of 6G research, high-frequency, high-speed circuit boards are becoming increasingly important in high-end electronics manufacturing, including communications, aerospace, and smart cars. As a key carrier of signal transmission, the performance of high-frequency, high-speed circuit boards directly determines the overall performance and reliability of electronic devices. However, traditional high-frequency, high-speed circuit boards suffer from numerous deficiencies in terms of loss and heat resistance, severely hindering their further development.

[0003] Patent CN115433451B discloses a high-speed, low-loss resin composition and its application. The resin composition includes a resin compound, at least one of a benzocyclobutene compound and its derivatives, a accelerator, and a filler mixture. The 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 foil-clad laminates, and wiring boards. The cured product of the prepared resin composition has excellent heat and moisture resistance, a high glass transition temperature, a low dielectric constant, low dielectric loss, a low coefficient of expansion, and excellent heat resistance. It also has good processability and can fully meet the high-frequency and high-speed requirements of high-performance printed circuit boards. However, the dielectric loss, dielectric constant, and thermal stability of the circuit boards prepared by this method still have room for improvement. Summary of the Invention

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

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The present invention provides a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0007] Step 1: Add the composite heat stabilizer to the polyphenylene ether, stir and mix, and obtain a base resin;

[0008] Step 2: Mixing the low-loss additive and the base resin, adding acetone, and vacuum degassing to obtain a composite resin;

[0009] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0010] Preferably, in step 1, the usage ratio of the composite heat stabilizer and 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.

[0011] Preferably, the preparation method of the composite thermal stabilizer comprises the following steps:

[0012] Q1: 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine, and polyphosphoric acid were added to a container, heated and stirred for reaction, and purified after the reaction to obtain product 1; product 1, methyl bromoacetate, and cesium carbonate were added to a container, and then acetonitrile was added, stirred for reaction at room temperature, and purified after the reaction to obtain product 2;

[0013] Q2: Add product 2 and lithium aluminum hydride to a container, then add tetrahydrofuran, stir at room temperature for reaction, add distilled water, treat under negative pressure, and purify to obtain product 3;

[0014] Q3: Product 3, isocyanoethyl methacrylate and dibutyltin dilaurate are added to a container, and then tetrahydrofuran is added. The mixture is stirred at room temperature, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0015] In the above process, the synthetic reaction formula of the composite thermal stabilizer is as follows:

[0016]

[0017] The results of mass spectrometry analysis of product 1 were: m / z: 281.15 (100.0%), 282.16 (18.6%), 283.16 (1.8%), 282.15 (1.1%); the results of mass spectrometry analysis of product 2 were: m / z: 353.17 (100.0%), 354.18 (22.0%), 355.18 (2.9%), 354.17 (1.1%); the results of mass spectrometry analysis of product 3 were: m / z: 325.18 (100.0%), 326.18 (21.7%), 327.19 (2.1%); the results of mass spectrometry analysis of composite thermal stabilizer were: m / z: 635.30 (100.0%), 636.30 (36.5%), 637.30 (8.6%), 636.29 (1.8%).

[0018] Preferably, in Q1, the amount 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 amount 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 stirring reaction time at room temperature is 12-16 h.

[0019] Preferably, in Q2, the amount 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 stirring reaction time at room temperature is 8-10 h; in Q3, the amount 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, and the stirring time at room temperature is 2-4 h.

[0020] Preferably, in step 2, the usage ratio of the low-loss additive, the base resin and acetone is (20-40) g: (65-85) g: (18-26) mL.

[0021] Preferably, the method for preparing the low-loss additive comprises the following steps:

[0022] S1: Under a nitrogen atmosphere, hexafluorobisphenol A and anhydrous aluminum chloride are added to a container, the temperature is slowly increased, and then dicyclopentadiene is added dropwise to the container through a constant pressure dropping funnel. After the addition is complete, the reaction is continued. After the reaction is completed, the reaction is cooled, toluene and a sodium hydroxide aqueous solution are added, the mixture is stirred, filtered, separated, the organic phase is washed, rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A;

[0023] 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. The temperature is kept for reaction. After the reaction is completed, the temperature is lowered, petroleum ether and hydrochloric acid are added, the mixture is stirred, filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss additive.

[0024] In the above process, the synthesis reaction formula of the low-loss additive is as follows:

[0025]

[0026] The results of mass spectrometry analysis of monomer A were: m / z: 836.27 (100.0%), 837.28 (46.0%), 838.28(11.2%), 839.28 (1.8%); the results of mass spectrometry analysis of the low-loss additive were: m / z: 1244.46 (100.0%), 1245.46 (80.0%), 1246.47 (33.1%), 1247.47 (9.1%), 1248.47 (1.8%).

[0027] Preferably, in S1, the amount 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, the temperature is slowly raised to 110-120°C, the reaction time is continued for 4-6 hours, the mass fraction of the sodium hydroxide aqueous solution is 5wt%, and the stirring time is 30-45 minutes.

[0028] Preferably, in S2, the amount 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, the temperature is slowly raised to 110-120°C, the reaction time is kept warm for 20-28 h, the concentration of hydrochloric acid is 1 mol / L, and the stirring time is 30-45 min.

[0029] A low-loss resin-plugged-hole high-frequency and high-speed circuit board is prepared by adopting the method for preparing a low-loss resin-plugged-hole high-frequency and high-speed circuit board.

[0030] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0031] 1. The present invention first uses 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine, methyl bromoacetate and isocyanoethyl methacrylate as main raw materials to prepare a composite thermal stabilizer, and then uses hexafluorobisphenol A, dicyclopentadiene and 4-bromobenzocyclobutene as main raw materials to prepare a low-loss additive. Applying both to the preparation process of circuit boards can effectively improve the thermal stability and wet-heat performance of the circuit boards, and can also make them have low dielectric loss and dielectric constant.

[0032] 2. The present invention applies the prepared composite thermal stabilizer to the preparation process of the circuit board, which can make it have excellent thermal stability, low dielectric loss and dielectric constant, and excellent moisture and heat resistance. The composite thermal stabilizer can disperse thermal energy through conjugated π electrons, inhibit the movement of molecular chains, and the steric hindrance effect can hinder the sliding of molecular chain segments. The three-dimensional cross-linked structure limits the freedom of the molecular chain, so that the circuit board has excellent thermal stability. The low polarity and conjugated system of the composite thermal stabilizer can also make the circuit board have low dielectric loss and dielectric constant. At the same time, the hydrophobic effect, hydrogen bond network and densified cross-linked structure of the composite thermal stabilizer also make the circuit board have excellent moisture and heat resistance.

[0033] 3. The present invention mixes the prepared low-loss additive with a matrix resin to obtain a composite resin, and applies it to a circuit board, so that it has low dielectric loss, dielectric constant and excellent thermal stability. The low-polarity groups, conjugated system and cross-linked network contained in the low-loss additive give the circuit board low dielectric loss and dielectric constant. At the same time, the rigid structure contained therein can disperse thermal energy through conjugated π electrons, inhibit the thermal motion of the molecular chain, and improve thermal stability. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0035] Example 1: This example discloses a method for preparing a composite thermal stabilizer, comprising the following steps:

[0036] Q1: 1.654 g of 5-aminosalicylic acid, 1.992 g of 4-tert-butylbenzene-1,2-diamine, and 0.194 g of polyphosphoric acid were added to a container, heated and stirred at 160°C for 12 h, and purified after completion of the reaction to obtain product 1; 2.25 g of product 1, 1.84 g of methyl bromoacetate, and 4.74 g of cesium carbonate were added to a container, and then 37.5 mL of acetonitrile was added, and the mixture was stirred at room temperature for 14 h. After completion of the reaction, purified to obtain product 2;

[0037] Q2: 1.19 g of product 2 and 0.91 g of lithium aluminum hydride were added to a container, followed by 25 mL of tetrahydrofuran. After stirring at room temperature for 10 h, distilled water was added, and the mixture was treated under negative pressure and purified to obtain product 3.

[0038] Q3: 1.08 g of product 3, 1.24 g of isocyanoethyl methacrylate and 0.06 mL of dibutyltin dilaurate were added to a container, and then 22.5 mL of tetrahydrofuran was added. The mixture was stirred at room temperature for 4 h, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0039] This embodiment discloses a method for preparing a low-loss additive, comprising the following steps:

[0040] S1: Under a nitrogen atmosphere, 4.742 g of hexafluorobisphenol A and 0.39 g of anhydrous aluminum chloride were added to a container, and the temperature was slowly raised to 120°C. Then, 2.58 g of dicyclopentadiene was added dropwise to the container through a constant pressure dropping funnel. After the addition was complete, the reaction was continued for 6 hours. After the reaction was completed, the reaction was cooled, 25 mL of toluene and 0.48 mL of a 5 wt% sodium hydroxide aqueous solution were added, and the mixture was stirred for 30 minutes. The mixture was filtered, separated, and the organic phase was washed. The mixture was rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A.

[0041] S2: Under a nitrogen atmosphere, 3.14 g of monomer A was added to 22.5 mL of N-methylpyrrolidone, and the temperature was slowly raised to 120°C. Then, 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 cuprous chloride were added in sequence. The mixture was kept warm for 24 hours. After the reaction was completed, the temperature was lowered, 22.5 mL of petroleum ether and 2.5 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred for 45 minutes. The mixture was filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss auxiliary agent.

[0042] This embodiment discloses a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0043] Step 1: Add 7 g of composite heat stabilizer to 91 g of polyphenylene ether, stir and mix at 120°C and 500 rpm for 60 min to obtain a base resin;

[0044] Step 2: 30 g of low-loss additive was mixed with 75 g of base resin, and 22 mL of acetone was added, and vacuum degassing was performed to obtain a composite resin;

[0045] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0046] Example 2: This example discloses a method for preparing a composite thermal stabilizer, comprising the following steps:

[0047] Q1: 1.425 g of 5-aminosalicylic acid, 1.725 g of 4-tert-butylbenzene-1,2-diamine, and 0.185 g of polyphosphoric acid were added to a container, heated and stirred at 160°C for 12 h, and purified after the reaction to obtain product 1; 2.11 g of product 1, 1.65 g of methyl bromoacetate, and 4.56 g of cesium carbonate were added to a container, and then 30 mL of acetonitrile was added, and the mixture was stirred at room temperature for 14 h. After the reaction, purified to obtain product 2;

[0048] Q2: 1.02 g of product 2 and 0.84 g of lithium aluminum hydride were added to a container, followed by 20 mL of tetrahydrofuran. After stirring at room temperature for 10 h, distilled water was added, and the mixture was treated under negative pressure and purified to obtain product 3.

[0049] Q3: 0.92 g of product 3, 1.01 g of isocyanoethyl methacrylate and 0.05 mL of dibutyltin dilaurate were added to a container, and then 25 mL of tetrahydrofuran was added. The mixture was stirred at room temperature for 4 h, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0050] This embodiment discloses a method for preparing a low-loss additive, comprising the following steps:

[0051] S1: Under a nitrogen atmosphere, 4.535 g of hexafluorobisphenol A and 0.32 g of anhydrous aluminum chloride were added to a container, and the temperature was slowly raised to 120°C. Then, 2.13 g of dicyclopentadiene was added dropwise to the container through a constant pressure dropping funnel. After the addition was complete, the reaction was continued for 6 hours. After the reaction was completed, the reaction was cooled, 20 mL of toluene and 0.36 mL of a 5 wt% sodium hydroxide aqueous solution were added, and the mixture was stirred for 30 minutes. The mixture was filtered, separated, and the organic phase was washed. The mixture was rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A.

[0052] S2: Under a nitrogen atmosphere, 2.85 g of monomer A was added to 25 mL of N-methylpyrrolidone, and the temperature was slowly raised to 120°C. Then, 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 were added in sequence. The mixture was kept warm for 24 hours. After the reaction was completed, the temperature was lowered, 25 mL of petroleum ether and 1 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred for 45 minutes. The mixture was filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss auxiliary agent.

[0053] This embodiment discloses a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0054] Step 1: Add 4 g of composite heat stabilizer to 88 g of polyphenylene ether, stir and mix at 120°C and 500 rpm for 60 min to obtain a base resin;

[0055] Step 2: 40 g of low-loss additive was mixed with 65 g of base resin, and 18 mL of acetone was added, and vacuum degassing was performed to obtain a composite resin;

[0056] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0057] Example 3: This example discloses a method for preparing a composite thermal stabilizer, comprising the following steps:

[0058] Q1: 1.883 g of 5-aminosalicylic acid, 2.221 g of 4-tert-butylbenzene-1,2-diamine, and 0.208 g of polyphosphoric acid were added to a container, heated and stirred at 160°C for 12 h, and purified after completion of the reaction to obtain product 1; 2.39 g of product 1, 2.04 g of methyl bromoacetate, and 5.02 g of cesium carbonate were added to a container, and then 45 mL of acetonitrile was added, and the mixture was stirred at room temperature for 14 h. After completion of the reaction, purified to obtain product 2;

[0059] Q2: 1.37 g of product 2 and 0.99 g of lithium aluminum hydride were added to a container, followed by 30 mL of tetrahydrofuran. After stirring at room temperature for 10 h, distilled water was added, and the mixture was treated under negative pressure and purified to obtain product 3.

[0060] Q3: 1.24 g of product 3, 1.43 g of isocyanoethyl methacrylate and 0.07 mL of dibutyltin dilaurate were added to a container, and then 20 mL of tetrahydrofuran was added. The mixture was stirred at room temperature for 4 h, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0061] This embodiment discloses a method for preparing a low-loss additive, comprising the following steps:

[0062] S1: Under a nitrogen atmosphere, 4.959 g of hexafluorobisphenol A and 0.47 g of anhydrous aluminum chloride were added to a container, and the temperature was slowly raised to 120°C. Then, 2.96 g of dicyclopentadiene was added dropwise to the container through a constant pressure dropping funnel. After the addition was complete, the reaction was continued for 6 hours. After the reaction was completed, the reaction was cooled, 30 mL of toluene and 0.62 mL of a 5 wt% sodium hydroxide aqueous solution were added, and the mixture was stirred for 30 minutes. The mixture was filtered, separated, and the organic phase was washed. The mixture was rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A.

[0063] S2: Under a nitrogen atmosphere, 3.54 g of monomer A was added to 20 mL of N-methylpyrrolidone, and the temperature was slowly raised to 120°C. Then, 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 cuprous chloride were added in sequence. The mixture was kept warm for 24 hours. After the reaction was completed, the temperature was lowered, 20 mL of petroleum ether and 4 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred for 45 minutes. The mixture was filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss additive.

[0064] This embodiment discloses a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0065] Step 1: Add 10 g of composite heat stabilizer to 95 g of polyphenylene ether, stir and mix at 120°C and 500 rpm for 60 min to obtain a base resin;

[0066] Step 2: 20 g of low-loss additive was mixed with 85 g of base resin, and 26 mL of acetone was added, and vacuum degassing was performed to obtain a composite resin;

[0067] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0068] Example 4: This example discloses a method for preparing a composite thermal stabilizer, comprising the following steps:

[0069] Q1: 1.571 g of 5-aminosalicylic acid, 1.836 g of 4-tert-butylbenzene-1,2-diamine, and 0.189 g of polyphosphoric acid were added to a container, heated and stirred at 160°C for 12 h, and purified after completion of the reaction to obtain product 1; 2.18 g of product 1, 1.71 g of methyl bromoacetate, and 4.63 g of cesium carbonate were added to a container, and then 32 mL of acetonitrile was added, stirred at room temperature for 14 h, and purified after completion of the reaction to obtain product 2;

[0070] Q2: 1.11 g of product 2 and 0.86 g of lithium aluminum hydride were added to a container, followed by 22 mL of tetrahydrofuran. After stirring at room temperature for 10 h, distilled water was added, and the mixture was treated under negative pressure for purification to obtain product 3.

[0071] Q3: 0.99 g of product 3, 1.15 g of isocyanoethyl methacrylate and 0.06 mL of dibutyltin dilaurate were added to a container, and then 21 mL of tetrahydrofuran was added. The mixture was stirred at room temperature for 4 h, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0072] This embodiment discloses a method for preparing a low-loss additive, comprising the following steps:

[0073] S1: Under a nitrogen atmosphere, 4.613 g of hexafluorobisphenol A and 0.35 g of anhydrous aluminum chloride were added to a container, and the temperature was slowly raised to 120°C. Then, 2.38 g of dicyclopentadiene was added dropwise to the container through a constant pressure dropping funnel. After the addition was complete, the reaction was continued for 6 hours. After the reaction was completed, the reaction was cooled, 22 mL of toluene and 0.41 mL of a 5 wt% sodium hydroxide aqueous solution were added, and the mixture was stirred for 30 minutes. The mixture was filtered, separated, and the organic phase was washed. The mixture was rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A.

[0074] S2: Under a nitrogen atmosphere, 3.01 g of monomer A was added to 21 mL of N-methylpyrrolidone, and the temperature was slowly raised to 120°C. Then, 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 cuprous chloride were added in sequence. The mixture was kept warm for 24 hours. After the reaction was completed, the temperature was lowered, 21 mL of petroleum ether and 2 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred for 45 minutes. The mixture was filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss additive.

[0075] This embodiment discloses a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0076] 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 base resin;

[0077] Step 2: 25 g of low-loss additive was mixed with 70 g of base resin, and 19 mL of acetone was added, and vacuum degassing was performed to obtain a composite resin;

[0078] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0079] Example 5: This example discloses a method for preparing a composite thermal stabilizer, comprising the following steps:

[0080] Q1: 1.723 g of 5-aminosalicylic acid, 2.017 g of 4-tert-butylbenzene-1,2-diamine, and 0.199 g of polyphosphoric acid were added to a container, heated and stirred at 160°C for 12 h, and purified after completion of the reaction to obtain product 1; 2.31 g of product 1, 1.98 g of methyl bromoacetate, and 4.98 g of cesium carbonate were added to a container, and then 42 mL of acetonitrile was added, and the mixture was stirred at room temperature for 14 h. After completion of the reaction, it was purified to obtain product 2;

[0081] Q2: 1.28 g of product 2 and 0.95 g of lithium aluminum hydride were added to a container, followed by 28 mL of tetrahydrofuran. After stirring at room temperature for 10 h, distilled water was added, and the mixture was treated under negative pressure and purified to obtain product 3.

[0082] Q3: 1.17 g of product 3, 1.29 g of isocyanoethyl methacrylate and 0.05 mL of dibutyltin dilaurate were added to a container, and then 24 mL of tetrahydrofuran was added. The mixture was stirred at room temperature for 4 h, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0083] This embodiment discloses a method for preparing a low-loss additive, comprising the following steps:

[0084] S1: Under a nitrogen atmosphere, 4.871 g of hexafluorobisphenol A and 0.42 g of anhydrous aluminum chloride were added to a container, and the temperature was slowly raised to 120°C. Then, 2.71 g of dicyclopentadiene was added dropwise to the container through a constant pressure dropping funnel. After the addition was complete, the reaction was continued for 6 hours. After the reaction was completed, the reaction was cooled, 28 mL of toluene and 0.54 mL of a 5 wt% sodium hydroxide aqueous solution were added, and the mixture was stirred for 30 minutes. The mixture was filtered, separated, and the organic phase was washed. The mixture was rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A.

[0085] S2: Under a nitrogen atmosphere, 3.37 g of monomer A was added to 24 mL of N-methylpyrrolidone, and the temperature was slowly raised to 120°C. Then, 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 were added in sequence. The mixture was kept warm for 24 hours. After the reaction was completed, the temperature was lowered, 24 mL of petroleum ether and 3 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred for 45 minutes. The mixture was filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss auxiliary agent.

[0086] This embodiment discloses a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0087] Step 1: Add 8 g of composite heat stabilizer to 92 g of polyphenylene ether, stir and mix at 120°C and 500 rpm for 60 min to obtain a base resin;

[0088] Step 2: 35g of low-loss additive and 80g of base resin were mixed and stirred, and 24mL of acetone was added at the same time, and vacuum degassing was performed to obtain a composite resin;

[0089] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0090] Example 6: This example discloses a method for preparing a composite thermal stabilizer, comprising the following steps:

[0091] Q1: 1.623 g of 5-aminosalicylic acid, 1.983 g of 4-tert-butylbenzene-1,2-diamine, and 0.191 g of polyphosphoric acid were added to a container, heated and stirred at 160°C for 12 h, and purified after the reaction to obtain product 1; 2.28 g of product 1, 1.78 g of methyl bromoacetate, and 4.81 g of cesium carbonate were added to a container, and then 35 mL of acetonitrile was added, and the mixture was stirred at room temperature for 14 h. After the reaction, it was purified to obtain product 2;

[0092] Q2: 1.21 g of product 2 and 0.92 g of lithium aluminum hydride were added to a container, followed by 26 mL of tetrahydrofuran. After stirring at room temperature for 10 h, distilled water was added, and the mixture was treated under negative pressure and purified to obtain product 3.

[0093] Q3: 1.21 g of product 3, 1.37 g of isocyanoethyl methacrylate and 0.07 mL of dibutyltin dilaurate were added to a container, and then 23 mL of tetrahydrofuran was added. The mixture was stirred at room temperature for 4 h, concentrated under negative pressure, and purified to obtain a composite thermal stabilizer.

[0094] This embodiment discloses a method for preparing a low-loss additive, comprising the following steps:

[0095] S1: Under a nitrogen atmosphere, 4.711 g of hexafluorobisphenol A and 0.45 g of anhydrous aluminum chloride were added to a container, and the temperature was slowly raised to 120°C. Then, 2.87 g of dicyclopentadiene was added dropwise to the container through a constant pressure dropping funnel. After the addition was complete, the reaction was continued for 6 hours. After the reaction was completed, the reaction was cooled, 26 mL of toluene and 0.45 mL of a 5 wt% sodium hydroxide aqueous solution were added, and the mixture was stirred for 30 minutes. The mixture was filtered, separated, and the organic phase was washed. The mixture was rotary evaporated, washed, separated, dried, concentrated, and purified to obtain monomer A.

[0096] S2: Under a nitrogen atmosphere, 2.97 g of monomer A was added to 23 mL of N-methylpyrrolidone, and the temperature was slowly raised to 120°C. Then, 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 cuprous chloride were added in sequence. The mixture was kept warm for 24 hours. After the reaction was completed, the temperature was lowered, 23 mL of petroleum ether and 2.5 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred for 45 minutes. The mixture was filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss auxiliary agent.

[0097] This embodiment discloses a method for preparing a low-loss resin-plugged high-frequency and high-speed circuit board, comprising the following steps:

[0098] Step 1: Add 5 g of composite heat stabilizer to 93 g of polyphenylene ether, stir and mix at 120°C and 500 rpm for 60 min to obtain a base resin;

[0099] Step 2: 28g of low-loss additive and 71g of base resin were mixed and stirred, and 20mL of acetone was added, and vacuum degassing was performed to obtain a composite resin;

[0100] Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify and grind them, and solder resistors, capacitors and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-plugged high-frequency and high-speed PCB is obtained.

[0101] Comparative Example 1: Compared with Example 1, in the process of preparing the low-loss resin-plugged high-frequency and high-speed circuit board in Comparative Example 1, no composite thermal stabilizer is added, and other conditions remain unchanged.

[0102] Comparative Example 2: Compared with Example 1, in Comparative Example 2, during the process of preparing the low-loss resin-plugged high-frequency and high-speed circuit board, no low-loss additive was added, and other conditions remained unchanged.

[0103] Experimental Example: The performance of the low-loss resin-plugged high-frequency, high-speed circuit boards prepared in Examples 1-6 and Comparative Examples 1-2 was tested. The heat resistance of the samples was tested in accordance with GB / T 2423.2-2008, the moisture and heat resistance of the samples was tested in accordance with GB / T 2423.4-2008, and the dielectric loss and dielectric constant of the samples were tested in accordance with GB / T 1409-2006. The test results are shown in Table 1:

[0104] Table 1

[0105] project Are there cracks or delamination? 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 Cracks and delamination 0.48 3.25 0.0027 Comparative Example 2 Cracks and delamination 0.17 3.28 0.0029

[0106] The test results in Table 1 show that the low-loss resin-plugged high-frequency, high-speed circuit boards prepared in Examples 1-6 of the present invention exhibit excellent thermal stability, moisture and heat resistance, low dielectric loss, and dielectric constant. A comparison of Comparative Example 1 with Examples 1-6 shows that the addition of a composite thermal stabilizer can impart excellent thermal stability, moisture and heat resistance, low dielectric loss, and dielectric constant to the circuit boards. A comparison of Comparative Example 2 with Examples 1-6 shows that the addition of a low-loss additive can impart low dielectric loss, dielectric constant, and excellent thermal stability to the circuit boards.

[0107] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

[0108] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only 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: Add the composite heat stabilizer to the polyphenylene ether, stir and mix, and obtain a base resin; Step 2: Mixing the low-loss additive and the base resin, adding acetone, and vacuum degassing to obtain a composite resin; Step 3: Drill holes on the rough PCB, then clean and dry them, fill the holes with composite resin, solidify them, grind them, and solder resistors, capacitors, and chip components to the rough PCB filled with composite resin. After assembly, a low-loss resin-filled high-frequency and high-speed PCB is obtained. The preparation method of the composite heat stabilizer comprises the following steps: Q1: 5-aminosalicylic acid, 4-tert-butylbenzene-1,2-diamine, and polyphosphoric acid were added to a container, heated and stirred for reaction, and purified after the reaction to obtain product 1; product 1, methyl bromoacetate, and cesium carbonate were added to a container, and then acetonitrile was added, stirred for reaction at room temperature, and purified after the reaction to obtain product 2; Q2: Add product 2 and lithium aluminum hydride to 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 to a container, then add tetrahydrofuran, stir at room temperature, concentrate under negative pressure, and purify to obtain a composite thermal stabilizer; The preparation method of the low-loss additive comprises the following steps: S1: Under a nitrogen atmosphere, hexafluorobisphenol A and anhydrous aluminum chloride are added to a container, the temperature is slowly increased, and then dicyclopentadiene is added dropwise to the container through a constant pressure dropping funnel. After the addition is complete, the reaction is continued. After the reaction is completed, the reaction is cooled, toluene and a sodium hydroxide aqueous solution are added, the mixture is 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. The temperature is kept for reaction. After the reaction is completed, the temperature is lowered, petroleum ether and hydrochloric acid are added, the mixture is stirred, filtered, washed, separated, extracted, dried, concentrated, and purified to obtain a low-loss additive.

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: In Q1, the usage 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 usage 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.

4. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 1, 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.

5. 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 the acetone is (20-40) g: (65-85) g: (18-26) 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 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.

7. The method for preparing a low-loss resin plugged high-frequency and high-speed circuit board according to claim 1, 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.

8. A low-loss resin-plugged high-frequency and high-speed circuit board prepared by the method according to any one of claims 1 to 7.

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