Composite insulating circuit board with ceramic filler reinforced layer and method for manufacturing the same

Abstract

The application discloses a kind of composite insulating circuit board with ceramic filler reinforcing layer and preparation method thereof, belong to circuit board preparation technical field.The kind of composite insulating circuit board with ceramic filler reinforcing layer, comprising the following steps: step one: after drying, ceramic filler is added to silane coupling agent mixed solution, stirring mixes, dry, obtain pretreated ceramic filler;Step two: pretreated ceramic filler, modified composite resin, curing agent and N, N-dimethylformamide are added to reaction container, stirring, grinding, obtain mixed slurry;Step three: mixed slurry is coated on the surface of metal substrate, solidification treatment, cover copper foil, form metal substrate-mixed slurry-copper foil structure, high temperature and high pressure treatment, make circuit diagram, surface oxidation resistance treatment, obtain a kind of composite insulating circuit board with ceramic filler reinforcing layer.The circuit board prepared by the method has excellent dielectric properties and heat resistance.

Description

Technical Field

[0001] This invention belongs to the field of circuit board material preparation technology, specifically relating to a composite insulating circuit board with a ceramic filler reinforcement layer and its preparation method. Background Technology

[0002] In the rapid development of modern electronics industry, circuit boards (PCBs), as key foundational components of electronic devices, directly impact the overall performance and reliability of electronic products. Traditional PCB materials are increasingly revealing limitations in the face of increasingly complex electronic applications. On one hand, as electronic devices move towards miniaturization and high integration, the density of components on PCBs increases dramatically, leading to a sharp rise in heat generated during operation. Traditional PCB materials, such as ordinary epoxy glass cloth substrates, have poor thermal conductivity, making it difficult to dissipate heat effectively. This results in excessively high localized temperatures on the PCB, affecting the performance and lifespan of electronic components, and potentially causing component damage and equipment failure. On the other hand, in special applications requiring high insulation and mechanical strength, such as aerospace and new energy vehicles, traditional PCB materials struggle to simultaneously meet stringent insulation and mechanical performance requirements. In complex operating environments, PCBs may be affected by mechanical stress, humidity, chemical corrosion, and other factors, easily leading to decreased insulation performance and insufficient mechanical strength, affecting the stable operation of electronic systems. Therefore, developing a new type of PCB material with superior comprehensive performance has become an urgent industry need to overcome these problems.

[0003] Patent CN111087843B discloses a high-dielectric insulating film material and its preparation method. The insulating film material is characterized by a three-layer structure: its insulating polymer composite is made of a thin film material, and a protective film covers the surface of the insulating polymer composite. The insulating polymer composite is made of a conductive paste containing a composite dielectric filler, which is composed of boron nitride nanosheets and inorganic ceramic ions. The high-dielectric insulating film material preparation method and materials described in this invention are simple, have low dielectric loss, and can be applied to semiconductor electronic packaging such as printed circuit boards, substrates, and carriers. However, the insulating film material in the aforementioned patent still has room for improvement in terms of insulation and heat resistance. Regarding insulation performance, although a composite dielectric filler is used, the dispersion uniformity of boron nitride nanosheets and inorganic filler ions may be limited. Local aggregation may lead to local electric field concentration, increasing the risk of leakage current and reducing overall insulation performance. Furthermore, the interfacial bonding between different materials may not be tight enough, with micro-gaps providing channels for charge conduction. In terms of heat resistance, the insulating polymer composite, as the main load-bearing structure, is prone to thermal motion of its polymer chains at high temperatures, which leads to material softening, decreased mechanical properties, and thus affects heat resistance stability. At the same time, high temperature may weaken the interfacial interaction between the composite dielectric filler and the polymer, destroy the internal structure of the material, and limit its long-term stable application in higher temperature environments. Summary of the Invention

[0004] The purpose of this invention is to provide a composite insulating circuit board with a ceramic filler reinforcement layer and its preparation method, so as to solve the technical problem of poor dielectric and heat resistance properties of circuit boards in the prior art.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a method for preparing a composite insulating circuit board containing a ceramic filler reinforcement layer, comprising the following steps:

[0007] Step 1: After drying the ceramic filler, add it to ethanol containing silane coupling agent KH-560, stir and mix, and then dry to obtain the pretreated ceramic filler.

[0008] Step 2: Add the pretreated ceramic filler, modified composite resin, curing agent and N,N-dimethylformamide into the reaction vessel, stir and grind to obtain a mixed slurry;

[0009] Step 3: The mixed slurry is evenly coated onto the cleaned metal substrate surface and cured. Then, copper foil is covered on the surface of the mixed slurry to form a metal substrate-mixed slurry-copper foil structure. The structure is then subjected to high temperature and high pressure treatment to create a circuit diagram and surface anti-oxidation treatment to obtain a composite insulating circuit board with a ceramic filler reinforcement layer.

[0010] Preferably, in step one, the ratio of ceramic filler, silane coupling agent KH-560, and ethanol is (80-100) g: (0.5-2) g: (100-120) mL; in step two, the ratio of pretreated ceramic filler, modified composite resin, curing agent, and N,N-dimethylformamide is (50-85) g: (25-45) g: (20-32) g: (120-150) mL, and the modified composite resin is prepared from 80-100 parts of polymeric resin and 10-15 parts of modified insulating organic material.

[0011] Preferably, the method for preparing the polymeric resin includes the following steps:

[0012] Q1: 3,5-Di(trifluoromethyl)aniline and 2,4-dinitrofluorobenzene were added to ethanol, stirred and mixed, and reacted in an ice-salt bath. After the reaction was completed, the mixture was filtered and dried under vacuum to obtain intermediate 1. Intermediate 1 was added to an aqueous ethanol solution, and then sodium bicarbonate and sodium sulfide were added in sequence. The mixture was heated and stirred to react. After the reaction was completed, the mixture was cooled and added to distilled water to precipitate a solid. The solid was filtered and dried to obtain intermediate 2.

[0013] Q2: Add intermediate 2 and triethylamine to a container containing tetrahydrofuran, then slowly add tetrahydrofuran containing dissolved 4-nitrobenzoyl chloride to the container, stir the reaction, filter, vacuum dry, dissolve in γ-butyrolactone, add p-toluenesulfonic acid and heat the reaction, after the reaction is complete, cool, dilute, filter, wash, vacuum dry, recrystallize to obtain intermediate 3;

[0014] Q3: Add intermediate 3 and Pd / C to a container containing 1,4-dioxane, heat and add hydrazine hydrate, reflux the reaction, filter after the reaction is complete, add to ice water, filter again, recrystallize, filter under vacuum and dry under vacuum to obtain intermediate 4.

[0015] Q4: Under nitrogen atmosphere, intermediate 4, bisphenol A type diether dianhydride and m-cresol are added to a container, heated and stirred, then heated and stirred again, then isoquinoline is added, and the reaction is continued to be heated. After the reaction is completed, the mixture is cooled, crushed, washed, filtered, and vacuum dried to obtain the polymer resin.

[0016] The synthesis reaction formula for the polymer resin in the above process is as follows:

[0017]

[0018] The mass spectrometry analysis results of intermediate 1 were: m / z: 395.03 (100.0%), 396.04 (15.4%), 397.04 (1.9%), 396.03 (1.1%); those of intermediate 2 were: m / z: 365.06 (100.0%), 366.06 (16.3%), 367.07 (1.1%); those of intermediate 3 were: m / z: 496.06 (100.0%), 497.06 (24.3%), 498.07 (2.5%), 498.06 (1.2%); and those of intermediate 4 were: m / z: 436.11 (100.0%), 437.12 (22.9%), 438.12. (2.5%), 437.11 (1.5%).

[0019] Preferably, in Q1, the ratio of 3,5-bis(trifluoromethyl)aniline, 2,4-dinitrofluorobenzene, and ethanol is (10.89-14.48) g : (9.12-9.88) g : (100-120) mL, the reaction time in an ice-salt bath is 16-20 h, the vacuum drying temperature is 78-82 °C, and the time is 20-24 h; the ratio of intermediate 1, aqueous ethanol solution, sodium bicarbonate, and sodium sulfide is (14.12-14.84) ​​g : (100-120) mL : (3.78-4.02) g : (3.48-3.72) g, the volume fraction of the aqueous ethanol solution is 75 wt%, the heating and stirring reaction temperature is 80-84 °C, and the time is 10-12 h.

[0020] Preferably, in Q2, the ratio of intermediate 2, triethylamine, 4-nitrobenzoyl chloride, γ-butyrolactone, and p-toluenesulfonic acid is (22.12-22.98) g : (7.46-8.12) g : (14.12-14.89) g : (200-220) mL : (12.28-14.58) g, the stirring reaction temperature is 6-8℃, the time is 5-8 h, and the heating reaction temperature is 180-220℃, the time is 4-6 h.

[0021] Preferably, in Q3, the ratio of intermediate 3, Pd / C, 1,4-dioxane, and hydrazine hydrate is (17.012-17.124) g : (0.8-1.2) g : (100-120) mL : (17.2-18.1) mL, the heating temperature is 80-82℃, and the reflux reaction time is 14-18 h; in Q4, the ratio of intermediate 4, bisphenol A type diether dianhydride, m-cresol, and isoquinoline is (2.012-2.165) g : (2.12-2.34) g : (8.8-12.2) g : (0.288-0.354) g, the heating and stirring are carried out at 80-100℃ for 2-3 h, the temperature is raised to 145-150℃ and stirred for 4-6 h, and the reaction is carried out at 200-205℃ for 5-7 h.

[0022] Preferably, the method for preparing the modified insulating organic material includes the following steps:

[0023] S1: Under argon protection, 4-bromophenol, cesium carbonate and dimethyl sulfoxide were added to a container, stirred at room temperature, and then 1,2-dibromotetrafluoroethane was added. The mixture was heated to react. After the reaction was completed, the mixture was filtered, extracted, washed, dried, filtered, concentrated, purified, and distilled under reduced pressure to obtain a colorless and transparent liquid a.

[0024] S2: Under argon protection, zinc powder and acetonitrile are added to a container. Under heating conditions, colorless and transparent liquid a is added and the reaction is refluxed. After the reaction is completed, the mixture is filtered, concentrated, and purified to obtain colorless oily liquid b.

[0025] S3: Slowly add a mixed solution of tetrahydrofuran containing colorless oily liquid b to a container containing magnesium powder, methyltrimethoxysilane and tetrahydrofuran. Stir at room temperature and allow the reaction to proceed. After the reaction is complete, add toluene, filter, concentrate, and distill under reduced pressure to obtain the modified insulating organic compound.

[0026] The synthesis reaction formula for the modified insulating organic material in the above process is as follows:

[0027] The mass spectrometry analysis results of colorless transparent liquid a are: m / z: 351.85 (100.0%), 349.86 (51.4%), 353.85 (48.6%), 352.86 (8.7%), 350.86 (4.5%), 354.86 (4.3%); the mass spectrometry analysis results of colorless oily liquid b are: m / z: 251.94 (100.0%), 253.94 (97.5%), 252.94 (8.7%), 254.94 (8.5%); the mass spectrometry analysis results of modified insulating organic material are: m / z: 278.06 (100.0%), 279.06 (17.2%), 280.06 (4.6%).

[0028] Preferably, in S1, the ratio of 4-bromophenol, cesium carbonate, dimethyl sulfoxide, and 1,2-dibromotetrafluoroethane is (17.12-17.48) g : (48.38-49.23) g : (180-200) mL : (50.92-52.34) g, stirred at room temperature for 10-12 h, heated to 45-55℃ for 20-24 h; in S2, the ratio of zinc powder, acetonitrile, and colorless transparent liquid a is (21.21-25.43) g : (100-120) mL : (61.22-64.34) g, heated to 80-90℃, and refluxed for 20-24 h.

[0029] Preferably, in step S3, the ratio of magnesium powder, methyltrimethoxysilane, colorless oily liquid b, and toluene is (18.88-19.98) g : (66.12-66.88) g : (40.02-42.28) g : (100-120) mL, and the stirring time at room temperature is 20-24 h.

[0030] As a preferred embodiment, a composite insulating circuit board containing a ceramic filler reinforcement layer is prepared using the above-described preparation method.

[0031] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0032] 1. The present invention applies the prepared polymer resin and modified insulating organic material to an insulating composite circuit board with a ceramic filler reinforcement layer, which can effectively improve the heat resistance and dielectric properties, and the addition of ceramic filler can effectively improve its thermal conductivity.

[0033] 2. This invention applies the prepared polymeric resin to a composite insulating circuit board with a ceramic filler reinforcement layer, which can effectively improve its dielectric and heat resistance properties. The fluorine atoms introduced into the polymeric resin have low polarity, and the trifluoromethyl side groups create a large number of "free volumes" in the polymer segments. The synergistic effect of the two significantly reduces the dielectric constant of the material. The rigid structure contained in the polymeric resin restricts the movement of rigid chain segments, further reducing dielectric loss. Moreover, the main chain of the polymeric resin is composed of aromatic rings and five-membered imide rings, which makes the molecular chain extremely rigid. The carbonyl group contained therein is a strongly polar group, and there are strong dipole-dipole interactions and π-π stacking effects between the molecular chains, which effectively improves the heat resistance of the material.

[0034] 3. This invention applies the prepared modified insulating organic material to a composite insulating circuit board with a ceramic filler reinforcement layer, which can effectively improve its dielectric properties, interfacial compatibility, and thermal stability. The carbon-fluorine bonds introduced in the modified insulating organic material have low polarizability, and the fluorinated segments can create huge molecular-level holes in the polymer matrix, significantly reducing the dielectric constant of the material. As a small molecule, the segments can interpenetrate between the main chains of the polymer resin, reducing the tight packing between polymer chains and further reducing dielectric loss. At the same time, the fluorinated segments have excellent thermal stability, thereby improving the thermal stability of the circuit board. Detailed Implementation

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1: This example discloses a method for preparing a polymeric resin, including the following steps:

[0037] Q1: 12.68 g of 3,5-bis(trifluoromethyl)aniline and 9.65 g of 2,4-dinitrofluorobenzene were added to 110 mL of ethanol, stirred and mixed, and reacted in an ice-salt bath for 18 h. After the reaction was completed, the mixture was filtered and dried under vacuum at 80 °C for 24 h to obtain intermediate 1. 14.52 g of intermediate 1 was added to 120 mL of 75 vt% ethanol aqueous solution, and then 3.85 g of sodium bicarbonate and 3.61 g of sodium sulfide were added sequentially. The mixture was heated and stirred at 80 °C for 12 h. After the reaction was completed, the mixture was cooled, added to distilled water, and a solid precipitated. The solid was filtered and dried to obtain intermediate 2.

[0038] Q2: 22.55g of intermediate 2 and 7.82g of triethylamine were added to a container containing 100mL of tetrahydrofuran. Then, 50mL of tetrahydrofuran containing 14.51g of 4-nitrobenzoyl chloride was slowly added to the container. The mixture was stirred at 6°C for 6 hours. After the reaction was completed, the mixture was filtered, dried under vacuum, dissolved in 210mL of γ-butyrolactone, and 13.33g of p-toluenesulfonic acid was added. The mixture was heated at 200°C for 6 hours. After the reaction was completed, the mixture was cooled, diluted, filtered, washed, dried under vacuum, and recrystallized to obtain intermediate 3.

[0039] Q3: Add 17.063g of intermediate 3 and 1g of Pd / C to a container containing 110mL of 1,4-dioxane, heat at 80℃, add 17.6mL of hydrazine hydrate, reflux for 16h, filter after the reaction is complete, add to ice water, filter again, recrystallize, filter under vacuum, and dry under vacuum to obtain intermediate 4.

[0040] Q4: Under nitrogen atmosphere, 2.083g of intermediate 4, 2.23g of bisphenol A type diether dianhydride and 10.5g of m-cresol were added to a container, heated and stirred at 80℃ for 3h, then heated and stirred at 150℃ for 6h, then 0.311g of isoquinoline was added, and the reaction was continued at 200℃ for 6h. After the reaction was completed, the mixture was cooled, pulverized, washed, filtered, and vacuum dried to obtain the polymer resin.

[0041] This embodiment discloses a method for preparing a modified insulating organic material, including the following steps:

[0042] S1: Under argon protection, 17.25 g of 4-bromophenol, 48.91 g of cesium carbonate and 190 mL of dimethyl sulfoxide were added to a container and stirred at room temperature for 12 h. Then, 51.17 g of 1,2-dibromotetrafluoroethane was added and the mixture was heated at 50 °C for 24 h. After the reaction was completed, the mixture was filtered, extracted, washed, dried, filtered, concentrated, purified and distilled under reduced pressure to obtain a colorless and transparent liquid a.

[0043] S2: Under argon protection, 23.32g of zinc powder and 100mL of acetonitrile were added to a container. Under heating at 90℃, 62.87g of colorless and transparent liquid a was added. The mixture was refluxed for 24h. After the reaction was completed, the mixture was filtered, concentrated, and purified to obtain colorless oily liquid b.

[0044] S3: Slowly add 20 mL of a tetrahydrofuran mixture containing 41.15 g of colorless oily liquid b to a container containing 19.38 g of magnesium powder, 66.55 g of methyltrimethoxysilane and 180 mL of tetrahydrofuran. Stir at room temperature for 24 h to allow the reaction to proceed. After the reaction is complete, add 110 mL of toluene, filter, concentrate, and distill under reduced pressure to obtain the modified insulating organic compound.

[0045] This embodiment discloses a method for preparing a composite insulating circuit board containing a ceramic filler reinforcement layer, including the following steps:

[0046] Step 1: After drying 90g of ceramic filler, add it to 110mL of ethanol containing 1.25g of silane coupling agent KH-560, stir and mix, and dry to obtain pretreated ceramic filler;

[0047] Step 2: Add 62.5g of pretreated ceramic filler, 35g of modified composite resin (add 90 parts of polymerized resin to 200 parts of N,N-dimethylacetamide, stir and mix, then add 12.5 parts of modified insulating organic material and mix evenly), 26g of curing agent and 135mL of N,N-dimethylformamide to the reaction vessel, stir and grind to obtain a mixed slurry;

[0048] Step 3: The mixed slurry is evenly coated onto the cleaned metal substrate surface and cured. Then, copper foil is covered on the surface of the mixed slurry to form a metal substrate-mixed slurry-copper foil structure. The structure is then subjected to high temperature and high pressure treatment to create a circuit diagram and surface anti-oxidation treatment to obtain a composite insulating circuit board with a ceramic filler reinforcement layer.

[0049] Example 2: This example discloses a method for preparing a polymeric resin, including the following steps:

[0050] Q1: 10.89 g of 3,5-bis(trifluoromethyl)aniline and 9.12 g of 2,4-dinitrofluorobenzene were added to 120 mL of ethanol, stirred and mixed, and reacted in an ice-salt bath for 18 h. After the reaction was completed, the mixture was filtered and dried under vacuum at 80 °C for 24 h to obtain intermediate 1. 14.12 g of intermediate 1 was added to 110 mL of 75 vt% ethanol aqueous solution, and then 3.78 g of sodium bicarbonate and 3.48 g of sodium sulfide were added sequentially. The mixture was heated and stirred at 80 °C for 12 h. After the reaction was completed, the mixture was cooled, added to distilled water, and a solid precipitated. The solid was filtered and dried to obtain intermediate 2.

[0051] Q2: 22.12 g of intermediate 2 and 7.46 g of triethylamine were added to a container containing 100 mL of tetrahydrofuran. Then, 50 mL of tetrahydrofuran containing 14.12 g of 4-nitrobenzoyl chloride was slowly added to the container. The mixture was stirred at 6 °C for 6 h. After the reaction was completed, the mixture was filtered, dried under vacuum, dissolved in 220 mL of γ-butyrolactone, and 12.28 g of p-toluenesulfonic acid was added. The mixture was heated at 200 °C for 6 h. After the reaction was completed, the mixture was cooled, diluted, filtered, washed, dried under vacuum, and recrystallized to obtain intermediate 3.

[0052] Q3: Add 17.012 g of intermediate 3 and 0.8 g of Pd / C to a container containing 100 mL of 1,4-dioxane, heat at 80 °C, add 17.2 mL of hydrazine hydrate, reflux for 16 h, filter after the reaction is complete, add to ice water, filter again, recrystallize, filter under vacuum, and dry under vacuum to obtain intermediate 4.

[0053] Q4: Under nitrogen atmosphere, 2.012g of intermediate 4, 2.12g of bisphenol A type diether dianhydride and 12.2g of m-cresol were added to a container, heated and stirred at 80℃ for 3h, then heated and stirred at 150℃ for 6h, then 0.288g of isoquinoline was added, and the reaction was continued at 200℃ for 6h. After the reaction was completed, the mixture was cooled, pulverized, washed, filtered, and vacuum dried to obtain the polymer resin.

[0054] This embodiment discloses a method for preparing a modified insulating organic material, including the following steps:

[0055] S1: Under argon protection, 17.12 g of 4-bromophenol, 48.38 g of cesium carbonate and 180 mL of dimethyl sulfoxide were added to a container and stirred at room temperature for 12 h. Then, 50.92 g of 1,2-dibromotetrafluoroethane was added and the mixture was heated at 50 °C for 24 h. After the reaction was completed, the mixture was filtered, extracted, washed, dried, filtered, concentrated, purified and distilled under reduced pressure to obtain a colorless and transparent liquid a.

[0056] S2: Under argon protection, 21.21g of zinc powder and 110mL of acetonitrile were added to a container. Under heating at 90℃, 61.22g of colorless and transparent liquid a was added. The mixture was refluxed for 24h. After the reaction was completed, the mixture was filtered, concentrated, and purified to obtain colorless oily liquid b.

[0057] S3: Slowly add 20 mL of a tetrahydrofuran mixture containing 40.02 g of colorless oily liquid b to a container containing 18.88 g magnesium powder, 66.12 g methyltrimethoxysilane and 180 mL tetrahydrofuran. Stir at room temperature for 24 h to allow the reaction to proceed. After the reaction is complete, add 100 mL toluene, filter, concentrate, and distill under reduced pressure to obtain the modified insulating organic compound.

[0058] This embodiment discloses a method for preparing a composite insulating circuit board containing a ceramic filler reinforcement layer, including the following steps:

[0059] Step 1: After drying 80g of ceramic filler, add it to 100mL of ethanol containing 0.5g of silane coupling agent KH-560, stir and mix, and dry to obtain pretreated ceramic filler;

[0060] Step 2: Add 50g of pretreated ceramic filler, 25g of modified composite resin (add 80 parts of polymerized resin to 200 parts of N,N-dimethylacetamide, stir and mix, then add 15 parts of modified insulating organic material and mix evenly), 32g of curing agent and 150mL of N,N-dimethylformamide to the reaction vessel, stir and grind to obtain a mixed slurry;

[0061] Step 3: The mixed slurry is evenly coated onto the cleaned metal substrate surface and cured. Then, copper foil is covered on the surface of the mixed slurry to form a metal substrate-mixed slurry-copper foil structure. The structure is then subjected to high temperature and high pressure treatment to create a circuit diagram and surface anti-oxidation treatment to obtain a composite insulating circuit board with a ceramic filler reinforcement layer.

[0062] Example 3: This example discloses a method for preparing a polymeric resin, including the following steps:

[0063] Q1: 14.48 g of 3,5-bis(trifluoromethyl)aniline and 9.88 g of 2,4-dinitrofluorobenzene were added to 100 mL of ethanol, stirred and mixed, and reacted in an ice-salt bath for 18 h. After the reaction was completed, the mixture was filtered and dried under vacuum at 80 °C for 24 h to obtain intermediate 1. 18.84 g of intermediate 1 was added to 100 mL of 75 vt% ethanol aqueous solution, and then 4.02 g of sodium bicarbonate and 3.72 g of sodium sulfide were added sequentially. The mixture was heated and stirred at 80 °C for 12 h. After the reaction was completed, the mixture was cooled, added to distilled water, and a solid precipitated. The solid was filtered and dried to obtain intermediate 2.

[0064] Q2: 22.98 g of intermediate 2 and 8.12 g of triethylamine were added to a container containing 100 mL of tetrahydrofuran. Then, 50 mL of tetrahydrofuran containing 14.89 g of 4-nitrobenzoyl chloride was slowly added to the container. The mixture was stirred at 6 °C for 6 h. After the reaction was completed, the mixture was filtered, dried under vacuum, dissolved in 200 mL of γ-butyrolactone, and 14.58 g of p-toluenesulfonic acid was added. The mixture was heated at 200 °C for 6 h. After the reaction was completed, the mixture was cooled, diluted, filtered, washed, dried under vacuum, and recrystallized to obtain intermediate 3.

[0065] Q3: Add 17.124 g of intermediate 3 and 1.2 g of Pd / C to a container containing 120 mL of 1,4-dioxane, heat at 80 °C, add 18.1 mL of hydrazine hydrate, reflux for 16 h, filter after the reaction is complete, add to ice water, filter again, recrystallize, filter under vacuum, and dry under vacuum to obtain intermediate 4.

[0066] Q4: Under nitrogen atmosphere, 2.165g of intermediate 4, 2.34g of bisphenol A type diether dianhydride and 8.8g of m-cresol were added to a container, heated and stirred at 80℃ for 3h, then heated and stirred at 150℃ for 6h, then 0.354g of isoquinoline was added, and the reaction was continued at 200℃ for 6h. After the reaction was completed, the mixture was cooled, pulverized, washed, filtered, and vacuum dried to obtain the polymer resin.

[0067] This embodiment discloses a method for preparing a modified insulating organic material, including the following steps:

[0068] S1: Under argon protection, 17.48 g of 4-bromophenol, 49.23 g of cesium carbonate and 200 mL of dimethyl sulfoxide were added to a container and stirred at room temperature for 12 h. Then, 52.34 g of 1,2-dibromotetrafluoroethane was added and the mixture was heated at 50 °C for 24 h. After the reaction was completed, the mixture was filtered, extracted, washed, dried, filtered, concentrated, purified and distilled under reduced pressure to obtain a colorless and transparent liquid a.

[0069] S2: Under argon protection, 25.43g of zinc powder and 120mL of acetonitrile were added to a container. Under heating at 90℃, 64.34g of colorless and transparent liquid a was added. The mixture was refluxed for 24h. After the reaction was completed, the mixture was filtered, concentrated, and purified to obtain colorless oily liquid b.

[0070] S3: Slowly add 20 mL of a tetrahydrofuran mixture containing 42.28 g of colorless oily liquid b to a container containing 19.98 g magnesium powder, 66.88 g methyltrimethoxysilane and 180 mL tetrahydrofuran. Stir at room temperature for 24 h to allow the reaction to proceed. After the reaction is complete, add 120 mL toluene, filter, concentrate, and distill under reduced pressure to obtain the modified insulating organic compound.

[0071] This embodiment discloses a method for preparing a composite insulating circuit board containing a ceramic filler reinforcement layer, including the following steps:

[0072] Step 1: After drying 100g of ceramic filler, add it to 120mL of ethanol containing 2g of silane coupling agent KH-560, stir and mix, and dry to obtain pretreated ceramic filler;

[0073] Step 2: Add 85g of pretreated ceramic filler, 45g of modified composite resin (add 100 parts of polymerized resin to 200 parts of N,N-dimethylacetamide, stir and mix, then add 10 parts of modified insulating organic material and mix evenly), 20g of curing agent and 120mL of N,N-dimethylformamide to the reaction vessel, stir and grind to obtain a mixed slurry;

[0074] Step 3: The mixed slurry is evenly coated onto the cleaned metal substrate surface and cured. Then, copper foil is covered on the surface of the mixed slurry to form a metal substrate-mixed slurry-copper foil structure. The structure is then subjected to high temperature and high pressure treatment to create a circuit diagram and surface anti-oxidation treatment to obtain a composite insulating circuit board with a ceramic filler reinforcement layer.

[0075] Example 4: This example discloses a method for preparing a polymeric resin, including the following steps:

[0076] Q1: 11.78 g of 3,5-bis(trifluoromethyl)aniline and 9.38 g of 2,4-dinitrofluorobenzene were added to 105 mL of ethanol, stirred and mixed, and reacted in an ice-salt bath for 18 h. After the reaction was completed, the mixture was filtered and dried under vacuum at 80 °C for 24 h to obtain intermediate 1. 14.32 g of intermediate 1 was added to 105 mL of 75 vt% ethanol aqueous solution, and then 3.81 g of sodium bicarbonate and 3.51 g of sodium sulfide were added sequentially. The mixture was heated and stirred at 80 °C for 12 h. After the reaction was completed, the mixture was cooled, added to distilled water, and a solid precipitated. The solid was filtered and dried to obtain intermediate 2.

[0077] Q2: 22.37 g of intermediate 2 and 7.61 g of triethylamine were added to a container containing 100 mL of tetrahydrofuran. Then, 50 mL of tetrahydrofuran containing 14.32 g of 4-nitrobenzoyl chloride was slowly added to the container. The mixture was stirred at 6 °C for 6 h. After the reaction was completed, the mixture was filtered, dried under vacuum, dissolved in 205 mL of γ-butyrolactone, and 13.87 g of p-toluenesulfonic acid was added. The mixture was heated at 200 °C for 6 h. After the reaction was completed, the mixture was cooled, diluted, filtered, washed, dried under vacuum, and recrystallized to obtain intermediate 3.

[0078] Q3: Add 17.035g of intermediate 3 and 0.9g of Pd / C to a container containing 105mL of 1,4-dioxane, heat at 80℃, add 17.3mL of hydrazine hydrate, reflux for 16h, filter after the reaction is complete, add to ice water, filter again, recrystallize, filter under vacuum, and dry under vacuum to obtain intermediate 4.

[0079] Q4: Under nitrogen atmosphere, 2.045g of intermediate 4, 2.18g of bisphenol A type diether dianhydride and 9.2g of m-cresol were added to a container, heated and stirred at 80℃ for 3h, then heated and stirred at 150℃ for 6h, then 0.297g of isoquinoline was added, and the reaction was continued at 200℃ for 6h. After the reaction was completed, the mixture was cooled, pulverized, washed, filtered, and vacuum dried to obtain the polymer resin.

[0080] This embodiment discloses a method for preparing a modified insulating organic material, including the following steps:

[0081] S1: Under argon protection, 17.18 g of 4-bromophenol, 48.57 g of cesium carbonate and 185 mL of dimethyl sulfoxide were added to a container and stirred at room temperature for 12 h. Then, 51.07 g of 1,2-dibromotetrafluoroethane was added and the mixture was heated at 50 °C for 24 h. After the reaction was completed, the mixture was filtered, extracted, washed, dried, filtered, concentrated, purified and distilled under reduced pressure to obtain a colorless and transparent liquid a.

[0082] S2: Under argon protection, 21.18g of zinc powder and 105mL of acetonitrile were added to a container. Under heating at 90℃, 62.12g of colorless and transparent liquid a was added. The mixture was refluxed for 24h. After the reaction was completed, the mixture was filtered, concentrated, and purified to obtain colorless oily liquid b.

[0083] S3: Slowly add 20 mL of a tetrahydrofuran mixture containing 41.02 g of colorless oily liquid b to a container containing 19.18 g magnesium powder, 66.37 g methyltrimethoxysilane and 180 mL tetrahydrofuran. Stir at room temperature for 24 h to allow the reaction to proceed. After the reaction is complete, add 105 mL toluene, filter, concentrate, and distill under reduced pressure to obtain the modified insulating organic compound.

[0084] This embodiment discloses a method for preparing a composite insulating circuit board containing a ceramic filler reinforcement layer, including the following steps:

[0085] Step 1: After drying 85g of ceramic filler, add it to 105mL of ethanol containing 0.78g of silane coupling agent KH-560, stir and mix, and dry to obtain pretreated ceramic filler;

[0086] Step 2: Add 55g of pretreated ceramic filler, 30g of modified composite resin (add 85 parts of polymer resin to 200 parts of N,N-dimethylacetamide, stir and mix, then add 11 parts of modified insulating organic material and mix evenly), 23g of curing agent and 130mL of N,N-dimethylformamide to the reaction vessel, stir and grind to obtain a mixed slurry;

[0087] Step 3: The mixed slurry is evenly coated onto the cleaned metal substrate surface and cured. Then, copper foil is covered on the surface of the mixed slurry to form a metal substrate-mixed slurry-copper foil structure. The structure is then subjected to high temperature and high pressure treatment to create a circuit diagram and surface anti-oxidation treatment to obtain a composite insulating circuit board with a ceramic filler reinforcement layer.

[0088] Comparative Example 1: Compared with Example 1, in the process of preparing the composite insulating circuit board with ceramic filler reinforcement layer, the polymer resin in the modified composite resin of Comparative Example 1 was replaced with epoxy resin, while other conditions remained unchanged.

[0089] Comparative Example 2: Compared with Example 1, in the process of preparing the composite insulating circuit board with ceramic filler reinforcement layer, no modified insulating organic material was added to the modified composite resin, and all other conditions remained unchanged.

[0090] Performance testing:

[0091] The composite insulating circuit boards with ceramic filler reinforcement layers prepared according to Examples 1-4 and Comparative Examples 1-2 were subjected to performance tests. The heat resistance of the samples was tested according to GB / T 11026.8-2014, and the dielectric properties of the samples were tested according to GB / T 31838.8-2024. The test results are shown in Table 1.

[0092] Table 1

[0093] project Aging temperature / ℃ Relative permittivity Dielectric loss factor Example 1 283 2.7 0.008 Example 2 278 2.8 0.008 Example 3 279 2.8 0.009 Example 4 281 2.8 0.009 Comparative Example 1 186 4.0 0.017 Comparative Example 2 198 3.9 0.018

[0094] As shown in Table 1, the prepared composite insulated circuit board exhibits excellent heat resistance and dielectric properties. A comparison between Comparative Example 1 and Examples 1-4 reveals that the use of polymeric resin effectively improves its heat resistance and dielectric properties; a comparison between Comparative Example 2 and Examples 1-4 reveals that the use of modified insulating organic materials effectively improves its heat resistance and dielectric properties.

[0095] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0096] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a composite insulating circuit board containing a ceramic filler reinforcement layer, characterized in that, Includes the following steps: Step 1: After drying the ceramic filler, add it to ethanol containing silane coupling agent KH-560, stir and mix, and then dry to obtain the pretreated ceramic filler. Step 2: Add the pretreated ceramic filler, modified composite resin, curing agent and N,N-dimethylformamide into the reaction vessel, stir and grind to obtain a mixed slurry; Step 3: The mixed slurry is evenly coated on the cleaned metal substrate surface and cured. Then, copper foil is covered on the surface of the mixed slurry to form a metal substrate-mixed slurry-copper foil structure. Then, it is subjected to high temperature and high pressure treatment to make the circuit diagram and surface anti-oxidation treatment to obtain a composite insulating circuit board with a ceramic filler reinforcement layer. The modified composite resin is prepared from 80-100 parts of polymer resin and 10-15 parts of modified insulating organic material; The method for preparing the polymeric resin includes the following steps: Q1: 3,5-Di(trifluoromethyl)aniline and 2,4-dinitrofluorobenzene were added to ethanol, stirred and mixed, and reacted in an ice-salt bath. After the reaction was completed, the mixture was filtered and dried under vacuum to obtain intermediate 1. Intermediate 1 was added to an aqueous ethanol solution, and then sodium bicarbonate and sodium sulfide were added in sequence. The mixture was heated and stirred to react. After the reaction was completed, the mixture was cooled and added to distilled water to precipitate a solid. The solid was filtered and dried to obtain intermediate 2. Q2: Add intermediate 2 and triethylamine to a container containing tetrahydrofuran, then slowly add tetrahydrofuran containing dissolved 4-nitrobenzoyl chloride to the container, stir the reaction, filter, vacuum dry, dissolve in γ-butyrolactone, add p-toluenesulfonic acid and heat the reaction, after the reaction is complete, cool, dilute, filter, wash, vacuum dry, recrystallize to obtain intermediate 3; Q3: Add intermediate 3 and Pd / C to a container containing 1,4-dioxane, heat and add hydrazine hydrate, reflux the reaction, filter after the reaction is complete, add to ice water, filter again, recrystallize, filter under vacuum and dry under vacuum to obtain intermediate 4. Q4: Under nitrogen atmosphere, intermediate 4, bisphenol A type diether dianhydride and m-cresol were added to a container, heated and stirred, then heated and stirred again, then isoquinoline was added, and the reaction was continued to be heated. After the reaction was completed, the mixture was cooled, crushed, washed, filtered, and vacuum dried to obtain the polymer resin. The method for preparing the modified insulating organic material includes the following steps: S1: Under argon protection, 4-bromophenol, cesium carbonate and dimethyl sulfoxide were added to a container, stirred at room temperature, and then 1,2-dibromotetrafluoroethane was added. The mixture was heated to react. After the reaction was completed, the mixture was filtered, extracted, washed, dried, filtered, concentrated, purified, and distilled under reduced pressure to obtain a colorless and transparent liquid a. S2: Under argon protection, zinc powder and acetonitrile are added to a container. Under heating conditions, colorless and transparent liquid a is added and the reaction is refluxed. After the reaction is completed, the mixture is filtered, concentrated, and purified to obtain colorless oily liquid b. S3: Slowly add a mixed solution of tetrahydrofuran containing colorless oily liquid b to a container containing magnesium powder, methyltrimethoxysilane and tetrahydrofuran. Stir at room temperature and allow the reaction to proceed. After the reaction is complete, add toluene, filter, concentrate, and distill under reduced pressure to obtain the modified insulating organic compound.

2. The method for preparing a composite insulating circuit board with a ceramic filler reinforcement layer according to claim 1, characterized in that, In step one, the ratio of ceramic filler, silane coupling agent KH-560 and ethanol is (80-100) g: (0.5-2) g: (100-120) mL; in step two, the ratio of pretreated ceramic filler, modified composite resin, curing agent and N,N-dimethylformamide is (50-85) g: (25-45) g: (20-32) g: (120-150) mL.

3. The method for preparing a composite insulating circuit board with a ceramic filler reinforcement layer according to claim 1, characterized in that, In Q1, the ratio of 3,5-bis(trifluoromethyl)aniline, 2,4-dinitrofluorobenzene, and ethanol is (10.89-14.48) g : (9.12-9.88) g : (100-120) mL; the ratio of intermediate 1, aqueous ethanol solution, sodium bicarbonate, and sodium sulfide is (14.12-14.84) ​​g : (100-120) mL : (3.78-4.02) g : (3.48-3.72) g.

4. The method for preparing a composite insulating circuit board with a ceramic filler reinforcement layer according to claim 1, characterized in that, In Q2, the ratio of intermediate 2, triethylamine, 4-nitrobenzoyl chloride, γ-butyrolactone, and p-toluenesulfonic acid is (22.12-22.98) g : (7.46-8.12) g : (14.12-14.89) g : (200-220) mL : (12.28-14.58) g.

5. The method for preparing a composite insulating circuit board with a ceramic filler reinforcement layer according to claim 1, characterized in that, In Q3, the ratio of intermediate 3, Pd / C, 1,4-dioxane and hydrazine hydrate is (17.012-17.124) g : (0.8-1.2) g : (100-120) mL : (17.2-18.1) mL; in Q4, the ratio of intermediate 4, bisphenol A type diether dianhydride, m-cresol and isoquinoline is (2.012-2.165) g : (2.12-2.34) g : (8.8-12.2) g : (0.288-0.354) g.

6. The method for preparing a composite insulating circuit board with a ceramic filler reinforcement layer according to claim 1, characterized in that, In S1, the ratio of 4-bromophenol, cesium carbonate, dimethyl sulfoxide, and 1,2-dibromotetrafluoroethane is (17.12-17.48) g : (48.38-49.23) g : (180-200) mL : (50.92-52.34) g; in S2, the ratio of zinc powder, acetonitrile, and colorless transparent liquid a is (21.21-25.43) g : (100-120) mL : (61.22-64.34) g.

7. The method for preparing a composite insulating circuit board with a ceramic filler reinforcement layer according to claim 1, characterized in that, In S3, the ratio of magnesium powder, methyltrimethoxysilane, colorless oily liquid b, and toluene is (18.88-19.98) g : (66.12-66.88) g : (40.02-42.28) g : (100-120) mL.

8. A composite insulating circuit board containing a ceramic filler reinforcement layer, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.

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