CN117241479B - High-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant and preparation method thereof - Google Patents
High-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant and preparation method thereof Download PDFInfo
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 36
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- ACXJHSWQLRWWMJ-UHFFFAOYSA-N 2,5-bis(ethenyl)benzene-1,4-diamine Chemical compound NC1=CC(C=C)=C(N)C=C1C=C ACXJHSWQLRWWMJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 29
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 28
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Abstract
The invention relates to the technical field of copper-clad plates, and particularly discloses a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant and a preparation method thereof. The method comprises the following steps: reacting 2, 5-divinyl-p-phenylenediamine with pyromellitic dianhydride to obtain polyimide; the pretreated ceramic powder reacts with gamma-methacryloxypropyl trimethoxy silane to obtain alkenyl modified ceramic powder; pre-irradiating polytetrafluoroethylene micro powder, and reacting with polyimide and alkenyl modified ceramic powder to obtain modified ceramic powder; preparing polytetrafluoroethylene micro powder, modified ceramic powder and surfactant solution into polytetrafluoroethylene glue solution; placing the glass fiber into polytetrafluoroethylene glue solution for dipping, drying and sintering after the dipping is completed to obtain dipping films; copper foil is coated on the upper and lower surfaces of the impregnated film, and the copper-clad plate is manufactured by hot pressing. The copper-clad plate has the characteristics of high dielectric constant, low dielectric loss, low temperature drift coefficient and the like.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant and a preparation method thereof.
Background
The copper-clad plate, which is called copper-clad laminate, has important application as a base material of the electronic industry and mainly comprises a substrate and copper foil. The base plate of the copper-clad plate is generally an insulating laminated plate made of high-molecular synthetic insulating resin and reinforcing materials, wherein the common high-molecular synthetic resin comprises phenolic resin, epoxy resin, polytetrafluoroethylene and the like, and the common reinforcing materials comprise wood pulp paper, glass fiber cloth and the like.
The polytetrafluoroethylene-based high-frequency copper-clad plate material with high dielectric constant is widely applied to the high-tech fields such as aviation, aerospace and the like. In the prior art, ceramic filler is adopted to fill, glass fiber is woven to be a reinforcing material, a polytetrafluoroethylene high-frequency copper-clad plate with high dielectric constant is developed, various degrees of circuit miniaturization can be realized, and the novel high-dielectric-constant polytetrafluoroethylene high-frequency copper-clad plate is widely applied to microstrip antennas, ground radar monitoring systems, miniaturized circuit patch antennas, low-noise power amplifiers, aircraft anti-collision systems and the like. However, the high-frequency polytetrafluoroethylene copper-clad plate with high dielectric constant has an obvious defect that the dielectric constant has larger change along with the change of the use temperature, particularly under the high frequency, namely the temperature drift coefficient of the dielectric constant is larger, the change of the dielectric constant can be caused under the condition of large difference of the use environment temperature, the phase difference is generated, and the signal transmission is influenced.
Chinese patent CN109336461B discloses a PTFE-based microwave composite dielectric substrate and a preparation method thereof, wherein high-dielectric perovskite ceramic and polytetrafluoroethylene are mixed, molded and subjected to vacuum hot pressing to obtain the PTFE-based microwave composite dielectric substrate, but the surface energy of PTFE is low, the action force between the PTFE and the high-dielectric perovskite ceramic is weak, the compatibility is poor, and the mixing mode of the high-dielectric perovskite ceramic and the polytetrafluoroethylene is dry mixing, so that the mixing is uneven easily caused, and the stability of the performance of a dielectric material is further influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant and a preparation method thereof, which are used for solving the problems of large temperature drift coefficient and the like of the polytetrafluoroethylene high-frequency copper-clad plate in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant comprises the following steps:
Step one, adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving, dropwise adding pyromellitic dianhydride solution after complete dissolution, reacting, adding 3-methylpyridine and acetic anhydride after reaction, continuing the reaction, precipitating, filtering, washing and drying after the reaction is finished to obtain polyimide;
Step two, ceramic powder is sintered, crushed and screened to obtain pretreated ceramic powder, the pretreated ceramic powder is added into gamma-methacryloxypropyl trimethoxysilane solution for reaction, and after the reaction is finished, the ceramic powder is filtered, washed and dried to obtain alkenyl modified ceramic powder;
pre-irradiating polytetrafluoroethylene micro powder, adding the pre-irradiated polytetrafluoroethylene micro powder into a surfactant solution, stirring to obtain polytetrafluoroethylene suspension, adding polyimide, alkenyl modified ceramic powder, a polymerization inhibitor and a sensitizer into the polytetrafluoroethylene suspension, reacting, purifying after the reaction is finished, and drying to obtain modified ceramic powder;
step three, adding polytetrafluoroethylene micro powder and modified ceramic powder into the surfactant solution, and stirring to obtain polytetrafluoroethylene glue solution;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for impregnation, drying and sintering after the impregnation is finished, and repeating the impregnation, drying and sintering treatment for 3 times to obtain an impregnated film;
And fifthly, covering copper foils on the upper surface and the lower surface of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing to obtain the high-frequency copper-clad plate with high dielectric constant and low-temperature drift coefficient.
Preferably, in the first step, the dissolution conditions are as follows: under the protection of inert gas, the dissolution temperature is controlled to be 0-5 ℃.
Preferably, in the first step, the mass ratio of the 2, 5-divinyl-p-phenylenediamine, the N, N-dimethylacetamide, the pyromellitic dianhydride solution, the 3-methylpyridine and the acetic anhydride is 16 (150-200): (65-70): (9.5-10): (100-105); the reaction conditions are as follows: reacting for 36-48h at 0-5 ℃ under the protection of inert gas; the conditions for continuing the reaction were: reacting for 36-48h under the protection of inert gas at the temperature of 0-5 ℃.
Preferably, the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide, wherein the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide is 1:2.
Preferably, in the second step, the conditions for sintering the ceramic powder are as follows: sintering for 1-3h at 950-1150 ℃ in air atmosphere.
Preferably, in the second step, the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxysilane solution is 1:55-65; the reaction conditions are as follows: reacting at 60-70 deg.C for 60-90min.
Further, the gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and ethanol water solution, wherein the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the ethanol water solution is 0.5-1:54.5-64.
Further, the aqueous ethanol solution is a 95wt% aqueous ethanol solution.
Preferably, the ceramic powder comprises microwave dielectric ceramic powder.
Preferably, in the second step, the pre-irradiation treatment is performed on the polytetrafluoroethylene micro powder, including: and placing polytetrafluoroethylene micropowder in 60 Co radiation source under air atmosphere and at room temperature for gamma-ray radiation treatment, wherein the radioactivity is 1.85 multiplied by 10 14 Bq, and the radiation time is 1-2h.
Further, the grain diameter of the polytetrafluoroethylene micro powder is 5-20 mu m.
Preferably, in the second step, the mass of polytetrafluoroethylene micro powder, surfactant solution, polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer is (30-50): 100-200): 20-30): 20-40): 0.01-0.05: (0.15-0.25, and the reaction conditions are as follows: reacting for 4-6h under the protection of inert gas at 65-75 ℃.
Further, the surfactant solution is prepared from ethoxy perfluorooctyl alcohol and deionized water, wherein the mass ratio of the ethoxy perfluorooctyl alcohol to the deionized water is 1:10.
Further, the polymerization inhibitor comprises ferrous ammonium sulfate, and the sensitizer comprises concentrated sulfuric acid.
Further, the concentrated sulfuric acid comprises 98wt% sulfuric acid.
Preferably, in the second step, the purifying includes: centrifuging, removing supernatant, washing the centrifugated precipitate, centrifuging again, and repeating the washing and centrifuging process for 8-10 times.
Preferably, in the third step, the mass ratio of the polytetrafluoroethylene micro powder to the modified ceramic powder to the surfactant solution is (100-200)/(200-300)/(200-400).
Further, the surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is (5-10): 100.
Further, the nonionic surfactant comprises propylene glycol block polyether and branched alcohol polyoxyethylene ether.
Further, the mass ratio of the propylene glycol block polyether to the branched alcohol polyoxyethylene ether is 1:1.
Preferably, in the fourth step, the soaking temperature is 10-25 ℃, the soaking time is 10-20min, and the bath ratio is 1:10; the drying conditions are as follows: drying at 100deg.C for 10-20min; the sintering conditions are as follows: sintering at 400 deg.c for 5-10min.
Preferably, in the fifth step, the hot pressing condition is: hot pressing at 370deg.C under 400PSI pressure for 100-120min.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, polytetrafluoroethylene is used as a resin matrix for preparing the copper-clad plate, and the copper-clad plate has the advantages of high insulation resistance, good processing performance, small dielectric loss and the like, and by adding the ceramic powder with high dielectric property, the dielectric constant of the copper-clad plate can be effectively improved, and the prepared copper-clad plate has the characteristics of high dielectric constant, low dielectric loss, low temperature drift coefficient and the like, and even under high frequency, the dielectric constant has small change along with the use temperature, the signal transmission stability is high, and the copper-clad plate can be applied to equipment for preparing miniaturized microstrip antennas and the like;
The ceramic powder is subjected to modification treatment, wherein the surface of the ceramic powder can be oxidized at high temperature by sintering treatment, and a large number of hydroxyl groups exist on the surface of the oxidized ceramic powder, so that the reaction of the ceramic powder and gamma-methacryloxypropyl trimethoxy silane is facilitated, and alkenyl modified ceramic powder is prepared; reacting 2, 5-divinyl-p-phenylenediamine with pyromellitic dianhydride to prepare polyimide containing alkenyl; the polytetrafluoroethylene micro powder is irradiated under the air condition to generate chain end peroxy free radicals (chain end free radicals-CF 2-CF2 -O-), and the polytetrafluoroethylene subjected to irradiation treatment can be subjected to copolymerization grafting with alkenyl modified ceramic powder and polyimide containing alkenyl to prepare modified ceramic powder; the existence of polytetrafluoroethylene molecules in the modified ceramic powder effectively solves the problems of weak acting force and poor compatibility between the inorganic ceramic material and polytetrafluoroethylene, and improves the stability of the performance of the copper-clad plate; the polyimide has good electrical insulation, high dielectric strength, small dielectric loss and small frequency change of electrical properties, and can be used for performance complementation with polytetrafluoroethylene by introducing the polyimide, so that the comprehensive performance of the insulating resin is improved.
Drawings
FIG. 1 is a flow chart of a preparation process of the modified ceramic powder;
FIG. 2 is a line graph showing the results of measurement of the dielectric constants of the copper clad laminates produced in examples 1 to 4 and comparative examples 1 to 3 of the present invention;
FIG. 3 is a line graph showing the results of measuring the dielectric loss values of the copper-clad laminates produced in examples 1 to 4 and comparative examples 1 to 3 of the present invention;
FIG. 4 is a line graph showing the results of measurement of the temperature drift coefficients of the copper-clad plates produced in examples 1 to 4 and comparative examples 1 to 3 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
Adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving the N, N-dimethylacetamide under the protection of nitrogen at the temperature of 0 ℃, dropwise adding pyromellitic dianhydride solution after the complete dissolution, reacting for 48 hours under the protection of nitrogen at the temperature of 0 ℃, adding 3-methylpyridine and acetic anhydride after the reaction is finished, continuing to react for 48 hours under the protection of nitrogen at the temperature of 0 ℃, precipitating with methanol after the reaction is finished, filtering, washing with methanol, and drying for 24 hours at the temperature of 60 ℃ to obtain polyimide;
Wherein the mass ratio of the 2, 5-divinyl-p-phenylenediamine to the N, N-dimethylacetamide to the pyromellitic dianhydride solution to the 3-picoline to the acetic anhydride is 16:150:65:9.5:100;
the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide, and the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide is 1:2.
Sintering ceramic powder for 3 hours at 950 ℃, crushing, screening, taking pretreated ceramic powder with the particle size of 10 mu m, adding the pretreated ceramic powder into gamma-methacryloxypropyl trimethoxysilane solution, reacting for 90 minutes at 60 ℃, filtering after the reaction is finished, washing with ethanol, drying for 5 hours at 120 ℃, crushing, and sieving with a 325-mesh sieve to obtain alkenyl modified ceramic powder;
Wherein the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxysilane solution is 1:55, the gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and 95wt% ethanol aqueous solution, and the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the 95wt% ethanol aqueous solution is 0.5:54.5;
Placing polytetrafluoroethylene micropowder in 60 Co radioactive source under air atmosphere and room temperature for gamma-ray irradiation treatment, wherein the radioactivity is 1.85 multiplied by 10 14 Bq, the irradiation time is 1h, adding the polytetrafluoroethylene micropowder into surfactant solution after the pre-irradiation treatment is completed, stirring for 30min at the speed of 1000r/min to obtain polytetrafluoroethylene suspension, adding polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer into the polytetrafluoroethylene suspension, reacting for 6h under the protection of nitrogen and the temperature of 65 ℃, centrifuging for 10min at the speed of 3000r/min after the reaction is completed, removing supernatant, washing centrifugal precipitate with deionized water, centrifuging for 10min at the speed of 3000r/min again, repeating the washing and centrifuging processes for 8 times, and drying for 24h at the temperature of 60 ℃ to obtain modified ceramic powder;
Wherein, the mass ratio of polytetrafluoroethylene micro powder, surfactant solution, polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer is 30:100:20:20:0.01:0.15, the surfactant solution is prepared by ethoxy perfluorooctyl alcohol and deionized water, the mass ratio of ethoxy perfluorooctyl alcohol to deionized water is 1:10, the polymerization inhibitor is ferrous ammonium sulfate, and the sensitizer is 98wt% sulfuric acid;
Adding polytetrafluoroethylene micropowder and modified ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micropowder to the modified ceramic powder to the surfactant solution is 100:200:200, and stirring for 30min at the speed of 1000r/min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 5:100, and the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at the temperature of 10 ℃ for 20min with the bath ratio of 1:10, drying at the temperature of 100 ℃ for 10min after the soaking is completed, sintering at the temperature of 400 ℃ for 5min, and repeating the soaking, drying and sintering treatment for 3 times to obtain a soaking film;
step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 100min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
Example 2
The embodiment discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving under the protection of nitrogen at the temperature of 5 ℃, dropwise adding pyromellitic dianhydride solution after complete dissolution, reacting for 36 hours under the protection of nitrogen at the temperature of 5 ℃, adding 3-methylpyridine and acetic anhydride after the reaction is finished, continuing to react for 36 hours under the protection of nitrogen at the temperature of 5 ℃, precipitating with methanol after the reaction is finished, filtering, washing with methanol, and drying for 24 hours at the temperature of 60 ℃ to obtain polyimide;
Wherein the mass ratio of the 2, 5-divinyl-p-phenylenediamine to the N, N-dimethylacetamide to the pyromellitic dianhydride solution to the 3-picoline to the acetic anhydride is 16:200:70:10:105;
the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide, and the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide is 1:2.
Sintering ceramic powder for 1h at 1150 ℃, crushing, screening, taking pretreated ceramic powder with the particle size of 10 mu m, adding the pretreated ceramic powder into gamma-methacryloxypropyl trimethoxysilane solution, reacting for 60min at 70 ℃, filtering after the reaction is finished, washing with ethanol, drying for 5h at 120 ℃, crushing, and sieving with a 325-mesh sieve to obtain alkenyl modified ceramic powder;
Wherein the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxysilane solution is 1:65, the gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and 95wt% ethanol aqueous solution, and the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the 95wt% ethanol aqueous solution is 1:64;
Placing polytetrafluoroethylene micropowder in 60 Co radioactive source under air atmosphere and room temperature for gamma-ray irradiation treatment, wherein the radioactivity is 1.85 multiplied by 10 14 Bq, the irradiation time is 2 hours, adding the polytetrafluoroethylene micropowder into surfactant solution after the pre-irradiation treatment is completed, stirring for 60 minutes at the speed of 800r/min to obtain polytetrafluoroethylene suspension, adding polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer into the polytetrafluoroethylene suspension, reacting for 4 hours at the temperature of 75 ℃ under the protection of nitrogen, centrifuging for 10 minutes at the speed of 3000r/min after the reaction is completed, removing supernatant, washing centrifugal precipitate with deionized water, centrifuging for 10 minutes at the speed of 3000r/min again, repeating the washing and centrifuging processes for 10 times, and drying for 24 hours at the temperature of 60 ℃ to obtain modified ceramic powder;
wherein, the mass ratio of polytetrafluoroethylene micro powder, surfactant solution, polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer is 50:200:30:40:0.05:0.25, the surfactant solution is prepared by ethoxy perfluorooctyl alcohol and deionized water, the mass ratio of ethoxy perfluorooctyl alcohol to deionized water is 1:10, the polymerization inhibitor is ferrous ammonium sulfate, and the sensitizer is 98wt% sulfuric acid;
adding polytetrafluoroethylene micropowder and modified ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micropowder to the modified ceramic powder to the surfactant solution is 200:300:400, and stirring at the speed of 800r/min for 60min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 10:100, and the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at 25 ℃ for 10min with a bath ratio of 1:10, drying at 100 ℃ for 20min after the soaking is completed, sintering at 400 ℃ for 10min, and repeating the soaking, drying and sintering treatment for 3 times to obtain a soaking film;
step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 120min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
Example 3
The embodiment discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
Step one, adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving the N, N-dimethylacetamide under the protection of nitrogen at the temperature of 2 ℃, dropwise adding pyromellitic dianhydride solution after the complete dissolution, then reacting for 45 hours under the protection of nitrogen at the temperature of 2 ℃, adding 3-methylpyridine and acetic anhydride after the reaction is finished, continuing to react for 45 hours under the protection of nitrogen at the temperature of 2 ℃, precipitating with methanol after the reaction is finished, filtering, washing with methanol, and drying for 24 hours at the temperature of 60 ℃ to obtain polyimide;
Wherein the mass ratio of the 2, 5-divinyl-p-phenylenediamine to the N, N-dimethylacetamide to the pyromellitic dianhydride solution to the 3-picoline to the acetic anhydride is 16:165:67:9.6:102;
the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide, and the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide is 1:2.
Sintering ceramic powder for 2 hours at 1000 ℃, crushing, screening, taking pretreated ceramic powder with the particle size of 10 mu m, adding the pretreated ceramic powder into gamma-methacryloxypropyl trimethoxysilane solution, reacting for 70 minutes at 65 ℃, filtering after the reaction is finished, washing with ethanol, drying for 5 hours at 120 ℃, crushing, and sieving with a 325-mesh sieve to obtain alkenyl modified ceramic powder;
wherein, the 1:60 gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and 95wt% ethanol aqueous solution, and the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the 95wt% ethanol aqueous solution is 0.6:59.4;
Placing polytetrafluoroethylene micropowder in 60 Co radioactive source under air atmosphere and room temperature for gamma-ray irradiation treatment, wherein the radioactivity is 1.85 multiplied by 10 14 Bq, the irradiation time is 1.5h, adding the polytetrafluoroethylene micropowder into surfactant solution after the pretreatment is completed, stirring the polytetrafluoroethylene micropowder for 20min at the speed of 1200r/min to obtain polytetrafluoroethylene suspension, adding polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer into the polytetrafluoroethylene suspension, reacting for 5h at the temperature of 70 ℃ under the protection of nitrogen, centrifuging for 10min at the speed of 3000r/min after the reaction is completed, removing supernatant, washing centrifugal precipitate with deionized water, centrifuging for 10min at the speed of 3000r/min again, repeating the washing and centrifuging processes for 8 times, and drying for 24h at the temperature of 60 ℃ to obtain modified ceramic powder;
Wherein, the mass ratio of polytetrafluoroethylene micro powder, surfactant solution, polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer is 35:130:24:28:0.02:0.18, the surfactant solution is prepared by ethoxy perfluorooctyl alcohol and deionized water, the mass ratio of ethoxy perfluorooctyl alcohol to deionized water is 1:10, the polymerization inhibitor is ferrous ammonium sulfate, and the sensitizer is 98wt% sulfuric acid;
Adding polytetrafluoroethylene micropowder and modified ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micropowder to the modified ceramic powder to the surfactant solution is 130:240:270, and stirring for 20min at the speed of 1200r/min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 6.5:100, the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at 15 ℃ for 15min with a bath ratio of 1:10, drying at 100 ℃ for 15min after the soaking is completed, sintering at 400 ℃ for 5min, and repeating the soaking, drying and sintering processes for 3 times to obtain a soaking film;
Step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 110min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
Example 4
The embodiment discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
Adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving under the protection of nitrogen at the temperature of 3 ℃, dropwise adding pyromellitic dianhydride solution after complete dissolution, reacting for 40 hours under the protection of nitrogen at the temperature of 3 ℃, adding 3-methylpyridine and acetic anhydride after the reaction is finished, continuing to react for 40 hours under the protection of nitrogen at the temperature of 3 ℃, precipitating with methanol after the reaction is finished, filtering, washing with methanol, and drying for 24 hours at the temperature of 60 ℃ to obtain polyimide;
Wherein the mass ratio of the 2, 5-divinyl-p-phenylenediamine to the N, N-dimethylacetamide to the pyromellitic dianhydride solution to the 3-picoline to the acetic anhydride is 16:180:68:9.8:104;
the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide, and the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide is 1:2.
Sintering ceramic powder for 2 hours at 1050 ℃, crushing, screening, taking pretreated ceramic powder with the particle size of 10 mu m, adding the pretreated ceramic powder into gamma-methacryloxypropyl trimethoxysilane solution, reacting for 80 minutes at 65 ℃, filtering after the reaction is finished, washing with ethanol, drying for 5 hours at 120 ℃, crushing, and sieving with a 325-mesh sieve to obtain alkenyl modified ceramic powder;
Wherein the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxysilane solution is 1:60, the gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and 95wt% ethanol aqueous solution, and the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the 95wt% ethanol aqueous solution is 0.8:59.2;
Placing polytetrafluoroethylene micropowder in 60 Co radioactive source under air atmosphere and room temperature for gamma-ray irradiation treatment, wherein the radioactivity is 1.85 multiplied by 10 14 Bq, the irradiation time is 1h, adding the polytetrafluoroethylene micropowder into surfactant solution after the pre-irradiation treatment is completed, stirring for 30min at the speed of 1000r/min to obtain polytetrafluoroethylene suspension, adding polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer into the polytetrafluoroethylene suspension, reacting for 5h at the temperature of 60 ℃ under the protection of nitrogen, centrifuging for 10min at the speed of 3000r/min after the reaction is completed, removing supernatant, washing centrifugal precipitate with deionized water, centrifuging for 10min at the speed of 3000r/min again, repeating the washing and centrifuging processes for 10 times, and drying for 24h at the temperature of 60 ℃ to obtain modified ceramic powder;
Wherein, the mass ratio of polytetrafluoroethylene micro powder, surfactant solution, polyimide, alkenyl modified ceramic powder, polymerization inhibitor and sensitizer is 45:170:26:35:0.04:0.22, the surfactant solution is prepared by ethoxy perfluorooctyl alcohol and deionized water, the mass ratio of ethoxy perfluorooctyl alcohol to deionized water is 1:10, the polymerization inhibitor is ferrous ammonium sulfate, and the sensitizer is 98wt% sulfuric acid;
adding polytetrafluoroethylene micropowder and modified ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micropowder to the modified ceramic powder to the surfactant solution is 170:265:340, and stirring for 30min at the speed of 1000r/min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 8:100, the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1.
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at 20 ℃ for 15min with a bath ratio of 1:10, drying at 100 ℃ for 10min after the soaking is completed, sintering at 400 ℃ for 5min, and repeating the soaking, drying and sintering treatment for 3 times to obtain a soaking film;
Step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 110min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
Comparative example 1
The comparative example discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving under the protection of nitrogen at the temperature of 5 ℃, dropwise adding pyromellitic dianhydride solution after complete dissolution, reacting for 36 hours under the protection of nitrogen at the temperature of 5 ℃, adding 3-methylpyridine and acetic anhydride after the reaction is finished, continuing to react for 36 hours under the protection of nitrogen at the temperature of 5 ℃, precipitating with methanol after the reaction is finished, filtering, washing with methanol, and drying for 24 hours at the temperature of 60 ℃ to obtain polyimide;
Wherein the mass ratio of the 2, 5-divinyl-p-phenylenediamine to the N, N-dimethylacetamide to the pyromellitic dianhydride solution to the 3-picoline to the acetic anhydride is 16:200:70:10:105;
the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide, and the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide is 1:2.
Sintering ceramic powder for 1h at 1150 ℃, crushing, screening, taking pretreated ceramic powder with the particle size of 10 mu m, adding the pretreated ceramic powder into gamma-methacryloxypropyl trimethoxysilane solution, reacting for 60min at 70 ℃, filtering after the reaction is finished, washing with ethanol, drying for 5h at 120 ℃, crushing, and sieving with a 325-mesh sieve to obtain alkenyl modified ceramic powder;
Wherein the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxysilane solution is 1:65, the gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and 95wt% ethanol aqueous solution, and the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the 95wt% ethanol aqueous solution is 1:64;
Adding polytetrafluoroethylene micro powder, polyimide and alkenyl modified ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micro powder to the polyimide to the alkenyl modified ceramic powder to the surfactant solution is 325:75:100:200, and stirring for 60min at the speed of 800r/min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 10:100, and the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at 25 ℃ for 10min with a bath ratio of 1:10, drying at 100 ℃ for 20min after the soaking is completed, sintering at 400 ℃ for 10min, and repeating the soaking, drying and sintering treatment for 3 times to obtain a soaking film;
step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 120min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
Comparative example 2
The comparative example discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
Sintering ceramic powder for 1h at 1150 ℃, crushing, screening, taking pretreated ceramic powder with the particle size of 10 mu m, adding the pretreated ceramic powder into gamma-methacryloxypropyl trimethoxysilane solution, reacting for 60min at 70 ℃, filtering after the reaction is finished, washing with ethanol, drying for 5h at 120 ℃, crushing, and sieving with a 325-mesh sieve to obtain alkenyl modified ceramic powder;
Wherein the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxysilane solution is 1:65, the gamma-methacryloxypropyl trimethoxysilane solution is prepared from gamma-methacryloxypropyl trimethoxysilane and 95wt% ethanol aqueous solution, and the mass ratio of the gamma-methacryloxypropyl trimethoxysilane to the 95wt% ethanol aqueous solution is 1:64;
Adding polytetrafluoroethylene micropowder and alkenyl modified ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micropowder to the alkenyl modified ceramic powder to the surfactant solution is 325:175:200, and stirring at the speed of 800r/min for 60min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 10:100, and the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at 25 ℃ for 10min with a bath ratio of 1:10, drying at 100 ℃ for 20min after the soaking is completed, sintering at 400 ℃ for 10min, and repeating the soaking, drying and sintering treatment for 3 times to obtain a soaking film;
step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 120min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
Comparative example 3
The comparative example discloses a preparation method of a high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which comprises the following steps:
step one, adding polytetrafluoroethylene micro powder and ceramic powder into a surfactant solution, wherein the mass ratio of the polytetrafluoroethylene micro powder to the ceramic powder to the surfactant solution is 325:175:200, and stirring for 60min at the speed of 800r/min to obtain polytetrafluoroethylene glue solution;
The surfactant solution is prepared from nonionic surfactant and deionized water, wherein the mass ratio of the nonionic surfactant to the deionized water is 10:100, and the nonionic surfactant comprises propylene glycol block polyether F-68 and branched secondary alcohol polyoxyethylene (5) ether S50, and the mass ratio of the propylene glycol block polyether F-68 to the branched secondary alcohol polyoxyethylene (5) ether S50 is 1:1;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for soaking at 25 ℃ for 10min with a bath ratio of 1:10, drying at 100 ℃ for 20min after the soaking is completed, sintering at 400 ℃ for 10min, and repeating the soaking, drying and sintering treatment for 3 times to obtain a soaking film;
step five, covering copper foils on the upper and lower surfaces of the impregnated film, placing the impregnated film between two steel plates, and hot-pressing the impregnated film under the following conditions: and hot-pressing for 120min at the temperature of 370 ℃ and the pressure of 400PSI to obtain the high-frequency copper-clad plate with low-temperature drift coefficient and high dielectric constant.
In the above examples and comparative examples, ceramic powders were purchased from Katian electro-optic materials Co., ltd., model: BST, molecular formula: ba 0.7Sr0.3TiO3; polytetrafluoroethylene micropowder was purchased from the company dongguan city mountain-plasticization limited, cat No.: SY39 with an average particle size of 10 μm; copper foil was purchased from Dongguan city, dingsheng adhesive products, inc., cat#: ds007-1, thickness: 0.05mm; glass fiber cloth is purchased from Changzhou city Ruishan New Material technology Co., ltd., product number: electronic grade glass fiber cloth, specification: 7628.
Test examples
Performance tests were performed on the copper clad laminates prepared in examples 1 to 4 and comparative examples 1 to 3:
the temperature drift coefficient (TCR), dielectric constant (DK) and dielectric loss value (DF) of the copper-clad plate were measured, and the measurement results are shown in table 1:
TABLE 1
| DK(10GHz) | DF(10GHz) | TCR(ppm/℃) | |
| Example 1 | 10.3 | 0.0041 | 7.2 |
| Example 2 | 9.2 | 0.0052 | 11.6 |
| Example 3 | 9.9 | 0.0044 | 8.5 |
| Example 4 | 9.5 | 0.0047 | 10.1 |
| Comparative example 1 | 8.8 | 0.0055 | 12.3 |
| Comparative example 2 | 8.5 | 0.0062 | 12.7 |
| Comparative example 3 | 8.0 | 0.0067 | 13.1 |
As can be seen from Table 1, the copper-clad plate prepared by the method has the characteristics of high dielectric constant, low dielectric loss and low temperature drift coefficient. Compared with the embodiment 2, in the comparative example 1, the alkenyl modified ceramic powder is not connected with polytetrafluoroethylene molecules through copolymerization grafting, and has weak interaction force and poor compatibility with polytetrafluoroethylene, so that the dielectric property of the copper-clad plate is reduced; compared with comparative example 1, in comparative example 2, the alkenyl modified ceramic powder was not connected to polytetrafluoroethylene molecules by co-grafting, and at the same time, polyimide was not added, resulting in further decrease in dielectric properties of the copper-clad plate; compared with comparative example 2, the ceramic powder is not modified and has poorer compatibility with polytetrafluoroethylene, and the copper-clad plate has worst dielectric property.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient is characterized by comprising the following steps of:
Step one, adding 2, 5-divinyl-p-phenylenediamine into N, N-dimethylacetamide, dissolving, dropwise adding pyromellitic dianhydride solution after complete dissolution, reacting, adding 3-methylpyridine and acetic anhydride after reaction, continuing the reaction, precipitating, filtering, washing and drying after the reaction is finished to obtain polyimide;
Step two, ceramic powder is sintered, crushed and screened to obtain pretreated ceramic powder, the pretreated ceramic powder is added into gamma-methacryloxypropyl trimethoxysilane solution for reaction, and after the reaction is finished, the ceramic powder is filtered, washed and dried to obtain alkenyl modified ceramic powder;
pre-irradiating polytetrafluoroethylene micro powder, adding the pre-irradiated polytetrafluoroethylene micro powder into a surfactant solution, stirring to obtain polytetrafluoroethylene suspension, adding polyimide, alkenyl modified ceramic powder, a polymerization inhibitor and a sensitizer into the polytetrafluoroethylene suspension, reacting, purifying after the reaction is finished, and drying to obtain modified ceramic powder;
step three, adding polytetrafluoroethylene micro powder and modified ceramic powder into the surfactant solution, and stirring to obtain polytetrafluoroethylene glue solution;
Step four, arranging glass fibers in polytetrafluoroethylene glue solution for impregnation, drying and sintering after the impregnation is finished, and repeating the impregnation, drying and sintering treatment to obtain an impregnated film;
and fifthly, coating copper foils on the upper surface and the lower surface of the impregnated film, and hot-pressing to obtain the high-frequency copper-clad plate with high dielectric constant and low-temperature drift coefficient.
2. The preparation method of the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 1, wherein in the first step, the mass ratio of 2, 5-divinyl-p-phenylenediamine, N-dimethylacetamide, pyromellitic dianhydride solution, 3-methylpyridine and acetic anhydride is 16 (150-200): (65-70): (9.5-10): (100-105); the reaction conditions are as follows: reacting for 36-48h at 0-5 ℃ under the protection of inert gas; the conditions for continuing the reaction were: reacting for 36-48h under the protection of inert gas at the temperature of 0-5 ℃.
3. The method for preparing the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 2, wherein the pyromellitic dianhydride solution is prepared from pyromellitic dianhydride and N, N-dimethylacetamide in a mass ratio of 1:2.
4. The method for preparing the high-frequency copper-clad plate with high dielectric constant and low-temperature drift coefficient according to claim 1, wherein in the second step, the sintering condition of the ceramic powder is as follows: sintering for 1-3h at 950-1150 ℃ in air atmosphere.
5. The method for preparing the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 1, wherein in the second step, the mass ratio of the pretreated ceramic powder to the gamma-methacryloxypropyl trimethoxy silane solution is 1:55-65; the reaction conditions are as follows: reacting at 60-70 deg.C for 60-90min.
6. The preparation method of the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 1, wherein in the second step, the mass ratio of polytetrafluoroethylene micro powder to surfactant solution to polyimide to alkenyl modified ceramic powder to polymerization inhibitor to sensitizer is (30-50), the mass ratio of (100-200), the mass ratio of (20-30), the mass ratio of (20-40), the mass ratio of (0.01-0.05) to (0.15-0.25) is as follows: reacting for 4-6h under the protection of inert gas at 65-75 ℃.
7. The method for preparing the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 1, wherein in the third step, the mass ratio of polytetrafluoroethylene micro powder to modified ceramic powder to surfactant solution is (100-200): 200-300): 200-400.
8. The method for preparing the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 1, wherein in the fourth step, the dipping temperature is 10-25 ℃, the dipping time is 10-20min, and the bath ratio is 1:10; the drying conditions are as follows: drying at 100deg.C for 10-20min; the sintering conditions are as follows: sintering at 400 deg.c for 5-10min.
9. The method for preparing the high-frequency copper-clad plate with the high dielectric constant and the low-temperature drift coefficient according to claim 1, wherein in the fifth step, the hot pressing condition is as follows: hot pressing at 370deg.C under 400PSI pressure for 100-120min.
10. A high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant, which is prepared by the preparation method of the high-frequency copper-clad plate with a low-temperature drift coefficient and a high dielectric constant according to any one of claims 1 to 9.
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| CN115503306A (en) * | 2022-09-22 | 2022-12-23 | 泰州市旺灵绝缘材料厂 | Ultrathin superfine glass fiber cloth ceramic high-frequency copper foil-clad substrate and manufacturing process |
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