A silica-filled PPO resin-based copper clad laminate and its preparation method

Abstract

The present invention relates to the field of PPO resin copper clad laminates, and specifically discloses a silica-filled PPO resin-based copper clad laminate and a preparation method thereof. In the present invention, silica is reacted with acryloyl chloride to obtain vinylated silica; using AIBN as an initiator, under ultraviolet light irradiation, the vinyl group on the vinylated silica reacts with the mercapto group on 5-fluoro-2-mercaptobenzyl alcohol to obtain fluorinated silica; the fluorinated silica is reacted with acryloyl chloride again to obtain modified silica; the polyphenylene oxide is made into small molecules and hydroxyl groups are introduced at both ends, and then it is reacted with acryloyl chloride to obtain modified polyphenylene oxide; the polyphenylene oxide, the modified polyphenylene oxide, the modified silica, benzoyl peroxide, and N,N-dimethylformamide are uniformly mixed to prepare a PPO resin composition prepreg; the glass fiber cloth is immersed in the PPO resin composition prepreg, dried to obtain a semi-cured sheet, the semi-cured sheets are laminated, copper foils are covered on both sides, and pressed to obtain a copper clad laminate.

Description

Technical Field

[0001] The present invention relates to the technical field of PPO resin copper clad laminates, and specifically relates to a silica-filled PPO resin-based copper clad laminate and a preparation method thereof. Background Art

[0002] With the development of technology, the requirements for materials in today's electronic products are getting higher and higher. As the basic material of electronic components, the copper clad laminate has a great impact on its performance. PPO resin (polyphenylene oxide) has excellent thermal stability and mechanical strength and is widely used in copper clad laminates. However, the pure PPO resin-based copper clad laminate still needs to be further improved in terms of wear resistance, fatigue resistance and strength to meet the requirements of current products.

[0003] Silica is added to the PPO resin to improve the performance of the copper clad laminate. Silica has advantages such as good thermal conductivity, high strength, and low coefficient of thermal expansion. Filling it into the PPO resin matrix can effectively improve the mechanical properties, thermal conductivity, fatigue resistance and wear resistance of the copper clad laminate. However, the poor compatibility between silica and PPO resin leads to a decrease in the mechanical properties of the copper clad laminate, and the solvent resistance of the copper clad laminate also needs to be improved. Summary of the Invention

[0004] The purpose of the present invention is to provide a silica-filled PPO resin-based copper clad laminate and a preparation method thereof to solve the problems mentioned in the above background art.

[0005] A silica-filled PPO resin-based copper clad laminate and a preparation method thereof include the following operating steps:

[0006] Step 1: (1) React silica with acryloyl chloride to obtain vinylated silica; (2) Mix vinylated silica, 5-fluoro-2-mercaptobenzyl alcohol, azobisisobutyronitrile, and tetrahydrofuran evenly, and react at room temperature under ultraviolet light irradiation to obtain fluorinated silica; (3) Stir and react fluorinated silica with acryloyl chloride under ice-water bath conditions for 4 to 6 hours to obtain modified silica;

[0007] Step 2: (1) Add polyphenylene oxide and tetramethylbisphenol A to a toluene solution, react at 80°C to 90°C for 30 to 50 minutes, dropwise add a toluene solution of benzoyl peroxide, and continue to react for 3 to 5 hours, then purify to obtain small molecule polyphenylene oxide; (2) React small molecule polyphenylene oxide with acryloyl chloride to obtain modified polyphenylene oxide;

[0008] Step 3: Uniformly mix polyphenylene oxide, modified polyphenylene oxide, modified silica, benzoyl peroxide, and N,N-dimethylformamide to prepare a PPO resin composition prepreg;

[0009] Step 4: Immerse the fiberglass cloth in the PPO resin composition prepreg, perform a roller leveling treatment, and dry it to obtain a semi-cured sheet. Stack 5 to 7 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a PPO resin-based copper clad laminate containing 65wt% to 70wt% of the PPO resin composition.

[0010] Further, in the step (1), the mass ratio of silica to acryloyl chloride is (4 - 6):1; the reaction time is 4 to 6 hours.

[0011] Further, in the step (2), the raw materials of the fluorinated silica include the following components: by weight, 1 to 3 parts of vinylated silica, 5 to 15 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.05 to 0.1 part of azobisisobutyronitrile, 25 to 75 parts of tetrahydrofuran; the conditions of ultraviolet lamp irradiation are: emission wavelength 350nm - 365nm, light intensity 50% - 100%, 80mW / cm 2 ~100mW / cm 2 , and the reaction time is 20 to 30 minutes;

[0012] Further, in the step (3), the mass ratio of fluorinated silica to acryloyl chloride is (3 - 5):0.8; the reaction time is 5 to 7 hours.

[0013] Further, in the step (1) of the second step, the raw materials of the small molecule polyphenylene ether include the following components: by weight, 15 to 20 parts of polyphenylene ether, 1 to 3 parts of tetramethylbisphenol A, 0.2 to 0.5 part of benzoyl peroxide, 60 to 80 parts of toluene.

[0014] Further, in the step (2) of the second step, the mass ratio of the small molecule polyphenylene ether to acryloyl chloride is (1 - 3):0.5; the reaction time is 6 to 9 hours.

[0015] Further, in the third step, the raw materials of the PPO resin composition prepreg include the following components: by weight, 70 to 100 parts of polyphenylene ether, 20 to 30 parts of modified polyphenylene ether, 10 to 15 parts of modified silica, 0.02 to 0.05 part of benzoyl peroxide, 60 to 80 parts of N,N-dimethylformamide.

[0016] Further, in the fourth step, the drying temperature is 80°C to 95°C, and the pressing program of the vacuum laminator: the temperature is 90°C to 220°C, the vacuum degree is 80 bar to 140 bar, and the time is 3 to 5 hours.

[0017] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0018] (1) Silica has a high specific surface area and unique morphology. When used as a filler, it can effectively enhance the strength of PPO resin. Its relatively high specific surface area can effectively absorb and conduct heat, thereby improving the heat resistance of PPO resin. However, the dispersibility of silica in PPO resin is poor, so its surface is treated to improve the compatibility between silica and PPO resin.

[0019] (2) The hydroxyl groups on silica react with acryloyl chloride to introduce vinyl groups on its surface. Then it reacts with 5-fluoro-2-mercaptobenzyl alcohol to introduce solvent-resistant fluorinated groups, obtaining fluorinated silica. The silica containing fluorine groups has solvent resistance, which can thus improve the solvent resistance of the copper clad laminate. The fluorinated silica is modified again to increase its chain length, so that a more compact network structure can be formed with polyphenylene ether, thereby improving the thermal stability and mechanical properties of the polyphenylene ether resin.

[0020] (3) Miniaturizing polyphenylene ether can improve the fluidity of silica in the PPO resin composition, thereby improving the mechanical properties and processing properties of the PPO resin. The hydroxyl groups on the miniaturized polyphenylene ether react with acryloyl chloride to obtain a modified PPO resin, which can improve its compatibility with the modified silica. Detailed implementation manners

[0021] The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0022] In this embodiment, it should be noted that the following parts are parts by mass; there are no special restrictions on the purchase manufacturers of all raw materials involved in the present invention. Exemplarily, they include: the CAS number of N,N-dimethylformamide is 68-12-2, the CAS number of acryloyl chloride is 814-68-6, the CAS number of azobisisobutyronitrile (AIBN) is 78-67-1, the CAS number of tetrahydrofuran is 109-99-9, the CAS number of 5-fluoro-2-mercaptobenzyl alcohol is 870703-84-7, the CAS number of tetramethylbisphenol A is 203578-30-7, the CAS number of benzoyl peroxide is 94-36-0, the CAS number of purchased silica is 7631-86-9, and the CAS number of polyphenylene ether (PPO resin) is 31533-76-3.

[0023] Example 1: Step 1: (1) Place silica in a tube furnace and dry it at 100 °C for 2 hours. Add it to N,N-dimethylformamide and ultrasonically disperse it for 20 minutes at a power of 100 W to obtain a homogeneous dispersion. Under ice-water bath conditions, drop acryloyl chloride into the dispersion. The mass ratio of silica to acryloyl chloride is 4:1. Stir and react for 4 hours. After centrifugation, dry the precipitate to obtain vinylated silica. (2) Dissolve vinylated silica and AIBN in tetrahydrofuran, stir and react for 40 minutes, then add 5-fluoro-2-mercaptobenzyl alcohol and mix evenly. Place it under ultraviolet light (emission wavelength is 350 nm, light intensity is 50%, 50 mW / cm 2 ) and irradiate for 20 minutes. Finally, wash and dry it to obtain fluorinated silica. The raw materials of fluorinated silica include the following components: 1 part of vinylated silica, 5 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.05 part of AIBN, and 25 parts of tetrahydrofuran. (3) Add fluorinated silica to N,N-dimethylformamide and ultrasonically disperse it for 20 minutes at a power of 100 W to obtain a homogeneous dispersion. Under ice-water bath conditions, drop acryloyl chloride and stir and react for 5 hours to obtain modified silica. The mass ratio of fluorinated silica to acryloyl chloride is 3:0.8;

[0024] Step 2: (1) Add polyphenylene ether and tetramethylbisphenol A to toluene, react at 80 °C for 30 minutes, drop benzoyl peroxide toluene solution, and continue to react for 3 hours. Cool to room temperature, add it to methanol, and the mass ratio of it to methanol is 6:1. Stir rapidly for 40 minutes, filter, collect the filtrate, add the filtrate to methanol and stir to precipitate a solid. Filter, wash and dry to obtain small molecule polyphenylene ether. The raw materials of small molecule polyphenylene ether include the following components: by weight, 15 parts of polyphenylene ether, 1 part of tetramethylbisphenol A, 0.2 part of benzoyl peroxide, and 60 parts of toluene. (2) Add small molecule polyphenylene ether to N,N-dimethylformamide and ultrasonically disperse it for 20 minutes at a power of 100 W. Under ice-water bath conditions, drop acryloyl chloride and stir and react for 6 hours. Filter, wash and dry to obtain modified polyphenylene ether. The mass ratio of small molecule polyphenylene ether to acryloyl chloride is 1.7:0.5;

[0025] Step 3: Mix 70 parts of polyphenylene ether, 20 parts of modified polyphenylene ether, 10 parts of modified silica, 0.02 part of benzoyl peroxide, and 65 parts of N,N-dimethylformamide evenly to make a PPO resin composition prepreg;

[0026] Step 4: Immerse the fiberglass cloth in the PPO resin composition prepreg, perform a roller leveling treatment, and dry it at 90 °C for 1 hour to obtain a semi-cured sheet. Stack 4 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a copper clad laminate with a PPO resin composition content of 65 wt%. The pressing procedure is as follows: press at 100 °C and 90 bar for 20 minutes; press at 160 °C and 120 bar for 2 hours; press at 220 °C and 140 bar for 2 hours.

[0027] Example 2: Step 1: (1) Place silicon dioxide in a tube furnace and dry it at 100 °C for 2 hours. Add it to N,N-dimethylformamide and ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniform dispersion. Under the condition of an ice-water bath, drop acryloyl chloride into the dispersion. The mass ratio of silicon dioxide to acryloyl chloride is 5:1. Stir and react for 5 hours. After centrifugation, dry the precipitate to obtain vinylated silicon dioxide. (2) Dissolve vinylated silicon dioxide and AIBN in tetrahydrofuran, stir and react for 40 minutes, then add 5-fluoro-2-mercaptobenzyl alcohol, mix evenly, and place it under ultraviolet light (emission wavelength is 365 nm, light intensity is 100%, 100 mW / cm 2 ) irradiate for 20 minutes, and finally wash and dry it to obtain fluorinated silicon dioxide. The raw materials of fluorinated silicon dioxide include the following components: 2 parts of vinylated silicon dioxide, 10 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.07 part of AIBN, and 50 parts of tetrahydrofuran. (3) Add fluorinated silicon dioxide to N,N-dimethylformamide and ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniform dispersion. Under the condition of an ice-water bath, drop acryloyl chloride and stir and react for 5 hours to obtain modified silicon dioxide. The mass ratio of fluorinated silicon dioxide to acryloyl chloride is 3.5:0.8;

[0028] Step 2: (1) Add polyphenylene oxide and tetramethylbisphenol A to toluene, react at 85 °C for 40 minutes, drop benzoyl peroxide toluene solution, continue to react for 4 hours, cool to room temperature, add it to methanol, and the mass ratio of it to methanol is 6:1. Stir rapidly for 40 minutes, filter, collect the filtrate, add the filtrate to methanol and stir to precipitate a solid, filter, wash and dry to obtain small molecule polyphenylene oxide. The raw materials of small molecule polyphenylene oxide include the following components: by weight, 17 parts of polyphenylene oxide, 1.5 parts of tetramethylbisphenol A, 0.25 part of benzoyl peroxide, and 65 parts of toluene. (2) Add small molecule polyphenylene oxide to N,N-dimethylformamide and ultrasonically disperse it at a power of 100 W for 20 minutes. Under the condition of an ice-water bath, drop acryloyl chloride, stir and react for 8 hours, filter, wash and dry to obtain modified polyphenylene oxide. The mass ratio of small molecule polyphenylene oxide to acryloyl chloride is 2:0.5;

[0029] Step 3: 85 parts of polyphenylene ether, 20 parts of modified polyphenylene ether, 12 parts of modified silica, 0.03 part of benzoyl peroxide, and 70 parts of N,N-dimethylformamide are uniformly mixed to prepare a PPO resin composition prepreg;

[0030] Step 4: Immerse a glass fiber cloth in the PPO resin composition prepreg, roll it to make it flat, dry it at 95 °C for 1 hour to obtain a semi-cured sheet. Stack 5 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a copper clad laminate with a PPO resin composition content of 68%; the pressing process is pressing at 100 °C and 90 bar for 20 minutes; pressing at 160 °C and 120 bar for 2 hours; pressing at 220 °C and 140 bar for 2 hours.

[0031] Example 3: Step 1: (1) Place silica in a tube furnace and dry it at 100 °C for 2 hours. Add it to N,N-dimethylformamide and ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniform dispersion; under the condition of an ice-water bath, drop acryloyl chloride into the dispersion. The mass ratio of silica to acryloyl chloride is 6:1, stir and react for 6 hours, and after centrifugation, dry the precipitate to obtain vinylated silica; (2) Dissolve vinylated silica and AIBN in tetrahydrofuran, stir and react for 40 minutes, then add 5-fluoro-2-mercaptobenzyl alcohol, mix uniformly, and place it under ultraviolet light (emission wavelength is 365 nm, light intensity is 80%, 80 mW / cm 2 ) irradiate for 20 minutes, and finally wash and dry it to obtain fluorinated silica; the raw materials of fluorinated silica include the following components: 2.5 parts of vinylated silica, 12 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.1 part of AIBN, and 60 parts of tetrahydrofuran; (3) Add fluorinated silica to N,N-dimethylformamide, ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniform dispersion, and drop acryloyl chloride under the condition of an ice-water bath, stir and react for 7 hours to obtain modified silica. The mass ratio of fluorinated silica to acryloyl chloride is 4.5:0.8;

[0032] Step 2: (1) Add polyphenylene ether and tetramethylbisphenol A into toluene, react at 90 °C for 45 minutes, dropwise add benzoyl peroxide toluene solution, continue to react for 5 hours, cool to room temperature, add it into methanol, and the mass ratio of it to methanol is 6:1. Stir rapidly for 40 minutes, filter, collect the filtrate, add the filtrate into methanol and stir to precipitate solids, filter, wash and dry to obtain low-molecular-weight polyphenylene ether. The raw materials of the low-molecular-weight polyphenylene ether include the following components: by weight, 20 parts of polyphenylene ether, 2 parts of tetramethylbisphenol A, 0.3 part of benzoyl peroxide, and 70 parts of toluene; (3) Add the low-molecular-weight polyphenylene ether into N,N-dimethylformamide, disperse it by ultrasonic wave at a power of 100 W for 20 minutes, dropwise add acryloyl chloride under the condition of ice-water bath, stir and react for 9 hours, filter, wash and dry to obtain modified polyphenylene ether. The mass ratio of the low-molecular-weight polyphenylene ether to acryloyl chloride is 3:0.5;

[0033] Step 3: Mix 90 parts of polyphenylene ether, 20 parts of modified polyphenylene ether, 15 parts of modified silica, 0.04 part of benzoyl peroxide, and 80 parts of N,N-dimethylformamide evenly to prepare a PPO resin composition prepreg;

[0034] Step 4: Immerse the glass fiber cloth in the PPO resin composition prepreg, roll and process it to be flat, dry it at 95 °C for 1 hour to obtain a semi-cured sheet. Stack 6 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a copper-clad laminate with a PPO resin composition content of 70%. The pressing procedure is: press at 100 °C and 90 bar for 20 minutes; press at 160 °C and 120 bar for 2 hours; press at 220 °C and 140 bar for 2 hours.

[0035] Comparative Example 1: Step 1: (1) Place silica in a tube furnace and dry it at 100 °C for 2 hours, add it into N,N-dimethylformamide, disperse it by ultrasonic wave at a power of 100 W for 20 minutes to obtain a uniform dispersion; under the condition of ice-water bath, dropwise add acryloyl chloride into the dispersion, and the mass ratio of silica to acryloyl chloride is 5:1. Stir and react for 5 hours, centrifuge and dry the precipitate to obtain vinylated silica; (2) Dissolve vinylated silica and AIBN in tetrahydrofuran, stir and react for 40 minutes, then add 5-fluoro-2-mercaptobenzyl alcohol, mix evenly, and place it under ultraviolet light (emission wavelength is 365 nm, light intensity is 100%, 100 mW / cm 2)Irradiate for 20 minutes, and finally wash and dry it to obtain fluorinated silica; the raw materials of the fluorinated silica include the following components: 2 parts of vinylated silica, 10 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.07 part of AIBN, and 50 parts of tetrahydrofuran; (3) Add the fluorinated silica to N,N-dimethylformamide, ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniformly dispersed solution, dropwise add acryloyl chloride under ice-water bath conditions, and stir and react for 5 hours to obtain modified silica; the mass ratio of the fluorinated silica to acryloyl chloride is 3.5:0.8;

[0036] Step 2: (1) Add polyphenylene oxide and tetramethylbisphenol A to toluene, react at 85 °C for 40 minutes, dropwise add a toluene solution of benzoyl peroxide, continue to react for 4 hours, cool to room temperature, add it to methanol, and the mass ratio of it to methanol is 6:1. Stir rapidly for 40 minutes, filter, collect the filtrate, add the filtrate to methanol and stir to precipitate solids, filter, wash and dry to obtain small molecule polyphenylene oxide; the raw materials of the small molecule polyphenylene oxide include the following components: by weight, 17 parts of polyphenylene oxide, 1.5 parts of tetramethylbisphenol A, 0.25 part of benzoyl peroxide, and 65 parts of toluene;

[0037] Step 3: 85 parts of polyphenylene oxide, 20 parts of modified polyphenylene oxide, 12 parts of modified silica, 0.03 part of benzoyl peroxide, and 70 parts of N,N-dimethylformamide are uniformly mixed to prepare a PPO resin composition prepreg;

[0038] Step 4: Immerse the glass fiber cloth in the PPO resin composition prepreg, roll and process it to be flat, dry it at 95 °C for 1 hour to obtain a semi-cured sheet. Stack 5 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a copper clad laminate with a PPO resin composition content of 68%; the pressing procedure is to press at 100 °C and 90 bar for 20 minutes; press at 160 °C and 120 bar for 2 hours; press at 220 °C and 140 bar for 2 hours;

[0039] Comparative Example 1 is based on Example 2, and the small molecule polyphenylene oxide is not modified.

[0040] Comparative Example 2: Step 1: (1) Place silica in a tube furnace and dry it at 100 °C for 2 hours. Add it to N,N-dimethylformamide and ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniformly dispersed solution; under ice-water bath conditions, dropwise add acryloyl chloride to the dispersion. The mass ratio of silica to acryloyl chloride is 5:1. Stir and react for 5 hours, and dry the precipitate after centrifugation to obtain vinylated silica;

[0041] Step 2: (1) Add polyphenylene ether and tetramethylbisphenol A to toluene, react at 85 °C for 40 minutes, dropwise add benzoyl peroxide toluene solution, continue to react for 4 hours, cool to room temperature, add it to methanol, and the mass ratio of it to methanol is 6:1. Stir rapidly for 40 minutes, filter, collect the filtrate, add the filtrate to methanol and stir to precipitate solids, filter, wash and dry to obtain small molecule polyphenylene ether; the raw materials of the small molecule polyphenylene ether include the following components: by weight, 17 parts of polyphenylene ether, 1.5 parts of tetramethylbisphenol A, 0.25 parts of benzoyl peroxide, and 65 parts of toluene; (3) Add the small molecule polyphenylene ether to N,N-dimethylformamide, ultrasonically disperse it at a power of 100 W for 20 minutes, dropwise add acryloyl chloride under ice-water bath conditions, stir and react for 8 hours, filter, wash and dry to obtain modified polyphenylene ether; the mass ratio of the small molecule polyphenylene ether to acryloyl chloride is 2:0.5;

[0042] Step 3: 85 parts of polyphenylene ether, 20 parts of modified polyphenylene ether, 12 parts of modified silica, 0.03 parts of benzoyl peroxide, 70 parts of N,N-dimethylformamide, are uniformly mixed to make a PPO resin composition prepreg;

[0043] Step 4: Immerse the glass fiber cloth in the PPO resin composition prepreg, roll and process it to be flat, dry it at 95 °C for 1 hour to obtain a semi-cured sheet. Stack 5 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a copper clad laminate with a PPO resin composition content of 68%; the pressing procedure is to press at 100 °C and 90 bar for 20 minutes; press at 160 °C and 120 bar for 2 hours; press at 220 °C and 140 bar for 2 hours;

[0044] Comparative Example 2 is based on Example 2, and the modified silica is changed to vinylated silica.

[0045] Comparative Example 3: Step 1: (1) Place silica in a tube furnace and dry it at 100 °C for 2 hours. Add it to N,N-dimethylformamide and ultrasonically disperse it at a power of 100 W for 20 minutes to obtain a uniform dispersion; under ice-water bath conditions, dropwise add acryloyl chloride to the dispersion, and the mass ratio of silica to acryloyl chloride is 5:1. Stir and react for 5 hours, centrifuge and dry the precipitate to obtain vinylated silica; (2) Dissolve vinylated silica and AIBN in tetrahydrofuran, stir and react for 40 minutes, then add 5-fluoro-2-mercaptobenzyl alcohol, mix evenly, and place it under ultraviolet light (emission wavelength is 365 nm, light intensity is 100%, 100 mW / cm 2)Irradiate for 20 minutes, and finally wash and dry it to obtain fluorinated silica; the raw materials of fluorinated silica include the following components: 2 parts of vinylated silica, 10 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.07 part of AIBN, and 50 parts of tetrahydrofuran; (3) Add the fluorinated silica into N,N-dimethylformamide, ultrasonically disperse it for 20 minutes at a power of 100 W to obtain a uniformly dispersed solution, dropwise add acryloyl chloride under ice-water bath conditions, and stir and react for 5 hours to obtain modified silica; the mass ratio of fluorinated silica to acryloyl chloride is 3.5:0.8;

[0046] Step 3: 85 parts of polyphenylene ether, 12 parts of modified silica, 0.03 part of benzoyl peroxide, and 70 parts of N,N-dimethylformamide are uniformly mixed to prepare a PPO resin composition prepreg;

[0047] Step 4: Immerse the glass fiber cloth in the PPO resin composition prepreg, roll and process it flat, dry it at 95°C for 1 hour to obtain a semi-cured sheet. Stack 5 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a copper clad laminate with a PPO resin composition content of 68%; the pressing procedure is to press at 100°C and 90 bar for 20 minutes; press at 160°C and 120 bar for 2 hours; press at 220°C and 140 bar for 2 hours;

[0048] Comparative Example 3 is based on Example 2, and no modified polyphenylene ether is added.

[0049] Detection Experiment 1: Detect the samples of Examples 1 to 3 and Comparative Examples 1 to 3 according to the standards of GB / T2571-1981 and GB / T2571-1995 respectively. At room temperature, the impact rate of the impact strength is 2.9 m / s, and the loading rate of the flexural strength is 2 mm / min.

[0050]

[0051]

[0052] Table 1

[0053] Detection Experiment 2: Solvent resistance performance test: Cut the copper clad laminates of Example 2 and Comparative Examples 1 to 3 into 80 mm × 50 nm × 4 nm, according to the standard of GB / T6968—2011. Calculate the mass change rate of the copper clad laminate immersed in toluene: Weigh the copper clad laminates of Examples 1 to 3 and Comparative Examples 1 to 3, record the weight as M1, after weighing, immerse the samples in toluene for 5, 40, and 160 hours, take out the samples at the corresponding time points, dry them and weigh them, record as m2, and calculate the mass change rate according to the formula (M1 - m2) / M1 × 100%; the test data are shown in Table 1.

[0054]

[0055] Conclusion: Comparative Example 1 is based on Example 2. Without modifying the small molecule polyphenylene ether, the dispersibility of the modified silica in the PPO resin is reduced, resulting in a decrease in the impact strength and flexural strength of the copper clad laminate. It can be seen from Table 2 that the solvent resistance of Comparative Example 1 is lower than that of Example 2. Comparative Example 2 is based on Example 2, and the modified silica is changed to vinylated silica. The vinyl group on the silica can react with the hydroxyl group on the modified polyphenylene ether, but the reaction is slow, resulting in lower impact resistance and flexural strength of Comparative Example 2 compared to Example 2. However, due to the absence of fluorinated groups, its mass change rate increases with time, leading to a decrease in its solvent resistance. Comparative Example 3 is based on Example 2. Without adding the modified polyphenylene ether, the compatibility between the polyphenylene ether and the modified silica is reduced, resulting in uneven distribution of the silica containing fluorine groups in the polyphenylene ether, and finally leading to a decrease in the impact strength, flexural strength and solvent resistance of the copper clad laminate.

[0056] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a silica-filled PPO resin-based copper clad laminate, characterized in that: It includes the following operation steps: S1: (1) React silica with acryloyl chloride under an ice-water bath condition to obtain vinylated silica; (2) Mix vinylated silica, 5-fluoro-2-mercaptobenzyl alcohol, azobisisobutyronitrile, and tetrahydrofuran evenly, and react at room temperature under ultraviolet light irradiation to obtain fluorinated silica; (3) React the fluorinated silica with acryloyl chloride again under an ice-water bath to obtain modified silica; S2: (1) Add polyphenylene oxide and tetramethylbisphenol A to a toluene solution, stir at 80°C - 90°C for 30 - 50 minutes, dropwise add a toluene solution of benzoyl peroxide, and continue to react for 3 - 5 hours, then purify to obtain small molecule polyphenylene oxide; (2) React the small molecule polyphenylene oxide with acryloyl chloride to obtain modified polyphenylene oxide; S3: Uniformly mix polyphenylene oxide, modified polyphenylene oxide, modified silica, benzoyl peroxide, and N,N-dimethylformamide to prepare a PPO resin composition prepreg; S4: Immerse a glass fiber cloth in the PPO resin composition prepreg, perform a roller leveling treatment, and dry to obtain a semi-cured sheet; Stack 5 - 7 layers of the semi-cured sheets, cover both sides with copper foil, and press them on a vacuum laminator to obtain a PPO resin-based copper clad laminate containing 65wt% - 70wt% of the PPO resin composition; In S1(1), the mass ratio of silica to acryloyl chloride is (4 - 6):1; In S1(2), the raw materials of the fluorinated silica include the following components: by weight, 1 - 3 parts of vinylated silica, 5 - 15 parts of 5-fluoro-2-mercaptobenzyl alcohol, 0.05 - 0.1 part of azobisisobutyronitrile, and 25 - 75 parts of tetrahydrofuran; In S1(3), the mass ratio of the fluorinated silica to acryloyl chloride is (3 - 5):0.8; In S2(1), the raw materials of the small molecule polyphenylene oxide include the following components: by weight, 15 - 20 parts of polyphenylene oxide, 1 - 3 parts of tetramethylbisphenol A, 0.2 - 0.5 part of benzoyl peroxide, and 60 - 80 parts of toluene; In S2(2), the mass ratio of the small molecule polyphenylene oxide to acryloyl chloride is (1 - 3):0.5; In S3, the raw materials of the PPO resin composition prepreg include the following components: by weight, 70 - 100 parts of polyphenylene oxide, 20 - 30 parts of modified polyphenylene oxide, 10 - 15 parts of modified silica, 0.02 - 0.05 part of benzoyl peroxide, and 60 - 90 parts of N,N-dimethylformamide.

2. The preparation method of a silica-filled PPO resin-based copper clad laminate according to claim 1, wherein: In S1(1), the reaction time is 4 - 6 hours.

3. The preparation method of a silica-filled PPO resin-based copper clad laminate according to claim 1, wherein: In S1(2), the conditions for ultraviolet lamp irradiation are as follows: emission wavelength is 350 nm to 365 nm, light intensity is 50% to 100%, 80 mW / cm 2 ~100 mW / cm 2 , and the reaction time is 20 to 30 minutes.

4. The preparation method of a silica-filled PPO resin-based copper clad laminate according to claim 1, characterized in that: In S1(3), the reaction time is 5 - 7 hours.

5. The preparation method of a silica-filled PPO resin-based copper clad laminate according to claim 1, characterized in that: In S2(2), the reaction time is 6 - 9 hours.

6. The preparation method of a silica-filled PPO resin-based copper clad laminate according to claim 1, characterized in that: In S4, the drying temperature is 80°C - 95°C, and the pressing program of the vacuum laminator: the temperature is 90°C - 220°C, the vacuum degree is 80 bar - 140 bar, and the time is 3 - 5 hours.

7. A copper clad laminate prepared by the preparation method of a silica-filled PPO resin-based copper clad laminate according to any one of claims 1 - 6.

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