PPO resin copper-clad plate with high peel strength and high durability and preparation method thereof

Abstract

The invention discloses a PPO resin copper-clad plate with high peel strength and high durability, and particularly relates to the technical field of copper-clad plates, the PPO resin copper-clad plate comprises a glue solution, an electronic glass fabric and a copper foil, the glue solution and the electronic glass fabric are impregnated, then the glue solution and the copper foil are subjected to compression molding, and the glue solution comprises the following raw materials: polystyrene resin, a curing agent, a composite filler and the balance of modified polyphenyl ether; the composite filler is prepared from the following raw materials: silicone master batch, modified nano clay, white carbon black and mesoporous silica. According to the invention, the polyphenyl ether is firstly activated by using a polyoxyethylene surfactant, so that the dispersity of the polyphenyl ether is better, then the polyphenyl ether is modified by using lauryl mercaptan and dicumyl peroxide, so that the polyphenyl ether is subjected to grafting reaction, long-chain alkyl is introduced in the polymerization process, the molecular weight distribution is controlled, and the flowability is improved; therefore, the melt index of the glue solution is improved, and the peel strength of the glue solution with electronic glass fiber cloth and copper foil sheets is relatively good.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of copper clad plate, more particularly, the present application relates to a kind of high peel strength high durable PPO resin copper clad plate and preparation method thereof. BACKGROUND

[0002] Copper Clad Laminate (full name Copper Clad Laminate, English abbreviation CCL) is a product made of wood pulp paper or glass fiber cloth as reinforcing material, impregnated with resin, single-sided or double-sided copper foil, and hot-pressed. Copper clad plate is the basic material of electronic industry, mainly used for processing and manufacturing printed circuit board (PCB), widely used in television, radio, computer, computer, mobile communication and other electronic products. Copper clad plate has a history of nearly 100 years, which is a technology development history that cannot be separated from the development of electronic information industry, especially the development of PCB industry. The development of copper clad plate began in the early 20th century. At that time, the manufacture of copper clad plate with epoxy resin, reinforcing material and substrate had made gratifying progress.

[0003] Polyphenyl ether is a high-strength engineering plastic, and its chemical name is poly-2,6-dimethyl-1,4-phenyl ether, which is simply called PPO or PPE. PPO is non-toxic, transparent, and has small relative density, and has excellent mechanical strength, creep resistance, stress relaxation resistance, heat resistance, water vapor resistance, water resistance, dimensional stability. Good electrical performance in a wide temperature and frequency range, PPO resin can be used in copper clad plate material.

[0004] Polyphenyl ether has good mechanical properties, heat resistance, stability and chemical stability when applied to copper clad plate. However, it has some disadvantages, such as poor melt index of PPO resin when applied to copper clad plate, resulting in poor flowability of PPO resin, low peel strength when contacting with electronic glass fiber cloth and copper foil, and sometimes cannot meet the use requirements of people. SUMMARY

[0005] In order to overcome the above-mentioned defects of the prior art, the embodiments of the present application provide a kind of high peel strength high durable PPO resin copper clad plate and preparation method thereof, the problem to be solved by the present application is: how to improve the peel strength of copper clad plate, so that the stability of copper clad plate is better.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme: a kind of high peel strength high durable PPO resin copper clad plate, including glue solution, electronic glass fiber cloth and copper foil, the glue solution is impregnated with electronic glass fiber cloth, and then is pressed into shape with copper foil, the glue solution includes: polystyrene resin 19.8-32.5%, curing agent 2.5-6.5%, composite filler 15-25%, and the rest is modified polyphenyl ether, calculated according to weight percentage.

[0007] The composite filler comprises the following raw materials by weight: silicone masterbatch 40-62 parts, modified nanoclay 30-45 parts, white carbon black 15-25 parts, and mesoporous silica 10-20 parts.

[0008] In a preferred embodiment, the glue solution comprises, by weight percentage: polystyrene resin 25-28%, curing agent 3.5-5.5%, composite filler 18-22%, and the rest is modified polyphenyl ether.

[0009] The composite filler comprises the following raw materials by weight: silicone masterbatch 45-55 parts, modified nanoclay 35-40 parts, white carbon black 18-22 parts, and mesoporous silica 13-17 parts.

[0010] In a preferred embodiment, the glue solution comprises, by weight percentage: polystyrene resin 26.5%, curing agent 4.5%, composite filler 20%, and the rest is modified polyphenyl ether.

[0011] The composite filler comprises the following raw materials by weight: silicone masterbatch 50 parts, modified nanoclay 38 parts, white carbon black 20 parts, and mesoporous silica 15 parts.

[0012] In a preferred embodiment, the curing agent is a mixture of diamino diphenyl sulfone and m-phenylenediamine, and the mass ratio of the diamino diphenyl sulfone and m-phenylenediamine is 1:1.

[0013] In a preferred embodiment, the preparation method of the modified polyphenyl ether is as follows:

[0014] A polyoxyethylene surfactant is added to the weighed polyphenyl ether, and after mixing uniformly, the pre-treated polyphenyl ether is obtained by granulating in a twin-screw extruder. The pre-treated polyphenyl ether is dissolved in toluene, 1-5 wt% of dodecyl mercaptan and 0.1-1 wt% of dicumyl peroxide are added to the dissolved solution, and after stirring and mixing uniformly, the reaction is carried out under nitrogen protection at a temperature of 70-90°C for 4-8h. After the reaction is completed, the modified polyphenyl ether is obtained by precipitation, filtration, washing, and drying.

[0015] In a preferred embodiment, the addition amount of the polyoxyethylene surfactant is 1.5-4.5% of the weight of the polyphenyl ether, and the precipitation time after the reaction is completed is 2-4h. The filtrate is washed with deionized water three times, and after the washing is completed, the drying is carried out at 45-55°C for 30-50min.

[0016] In a preferred embodiment, the preparation method of the modified nanoclay is as follows: the selected nanoclay is placed in an oven and dried at 75-85℃ for 10-12h to remove water, the dried nanoclay is dispersed in a mixture of ethanol and water, 3-5wt% silane coupling agent is added to the mixture, and the mixture is stirred and reacted at 75-85℃ for 3-5h, then filtered, washed, and dried at 50-60℃ to obtain the modified nanoclay.

[0017] In a preferred embodiment, the preparation method of the composite filler is as follows: the weighed modified nanoclay, silicone masterbatch, white carbon black, and mesoporous silica are mixed uniformly to obtain the composite filler.

[0018] The application also provides a preparation method of a high-strength and high-durability PPO resin copper-clad plate, which specifically comprises the following steps:

[0019] Step one: the polystyrene resin, curing agent, composite filler, and modified polyphenylene ether are weighed according to the above weight percentage, the weighed polystyrene resin and modified polyphenylene ether are mixed uniformly, then the curing agent and composite filler are added and placed in an emulsifying kettle, emulsification and high-speed shearing treatment are performed in the emulsifying kettle to obtain a glue solution for standby;

[0020] Step two: the electronic glass fiber cloth is impregnated in the glue solution prepared in step one, and the impregnated electronic glass fiber cloth is subjected to baking treatment to obtain a prepreg;

[0021] Step three: the prepreg prepared in step two is laminated with a copper foil sheet, and then compression bonding treatment is performed to obtain the high-strength and high-durability PPO resin copper-clad plate.

[0022] In a preferred embodiment, in the process of impregnating the electronic glass fiber cloth in the glue solution in step two, ultrasonic oscillation treatment is performed, and the baking treatment is performed by using an oven with a segmented temperature gradient, the baking temperature varies in the range of 50-180℃, and the baking temperature gradually changes from low to high and then from high to low.

[0023] The technical effects and advantages of the application are as follows:

[0024] 1. The high peel strength and high durability PPO resin copper-clad plate produced by the present application adopts polystyrene resin and modified polyphenyl ether as raw materials, the compatibility of polystyrene resin and polyphenyl ether is good, the fluidity of polystyrene resin is good, the melt index of the glue solution can be significantly improved, the dispersibility of polyphenyl ether is better by activating treatment of polyphenyl ether with polyoxyethylene surfactant, then the polyphenyl ether is modified by dodecyl mercaptan and dicumyl peroxide, so that the polyphenyl ether grafting reaction occurs, long-chain alkyl is introduced in the polymerization process, the molecular weight distribution is controlled, the fluidity is improved, and the melt index of the glue solution is improved, so that the peel strength of the glue solution and the electronic glass fiber cloth and the copper foil is good.

[0025] 2. The present application adds a composite filler, which contains silicone masterbatch, modified nano-clay, white carbon black and mesoporous silica, the silicone masterbatch migrates to form a lubricating layer during the melting process of PPO resin and polystyrene resin, which can reduce the flow resistance, the white carbon black has adsorption effect, which can avoid the generation of bubbles during the pressing forming process, and can improve the strength of the copper-clad plate, the nano-clay as a filler can improve the flame retardancy and strength of the copper-clad plate, and can improve the interfacial compatibility of nano-clay and PPO resin under the auxiliary action of silane coupling agent, the interlayer distance of modified nano-clay is increased, the clay layers are uniformly dispersed, and part of them are in single-layer peeling state. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments in the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0027] Embodiment 1:

[0028] The present application provides a high peel strength and high durability PPO resin copper-clad plate, which comprises a glue solution, an electronic glass fiber cloth and a copper foil, the glue solution is impregnated with the electronic glass fiber cloth, and then is pressed and formed with the copper foil, the glue solution comprises, by weight percentage: polystyrene resin 19.8%, curing agent 2.5%, composite filler 15%, and the rest is modified polyphenyl ether.

[0029] The composite filler comprises the following raw materials by weight: silicone masterbatch 40 parts, modified nano-clay 30 parts, white carbon black 15 parts and mesoporous silica 10 parts.

[0030] In a preferred embodiment, the curing agent is a mixture of diamino diphenyl sulfone and m-phenylenediamine, and the mass ratio of diamino diphenyl sulfone and m-phenylenediamine is 1:1.

[0031] In a preferred embodiment, the preparation method of the modified polyphenylene ether is as follows:

[0032] The polyoxyethylene surfactant is added to the weighed polyphenylene ether, which is mixed uniformly and then granulated in a twin-screw extruder to obtain pretreated polyphenylene ether. The pretreated polyphenylene ether is dissolved in toluene, 3wt% dodecyl mercaptan and 0.5wt% dicumyl peroxide are added to the solution, which is stirred and mixed uniformly, and then reacted for 6h under nitrogen protection at 80℃. After the reaction is completed, the modified polyphenylene ether is obtained by precipitation, filtration, washing and drying.

[0033] In a preferred embodiment, the addition amount of the polyoxyethylene surfactant is 3% of the weight of the polyphenylene ether, the precipitation time after the reaction is completed is 3h, and the filter is washed with deionized water three times, and then dried at 50℃ for 40min.

[0034] In a preferred embodiment, the preparation method of the modified nanoclay is as follows: the selected nanoclay is placed in an oven and dried at 80℃ for 11h to remove water, and then dispersed in a mixture of ethanol and water. 4wt% silane coupling agent is added to the mixture, which is stirred and reacted at 80℃ for 4h. After the reaction is completed, the modified nanoclay is obtained by filtration, washing and drying at 55℃.

[0035] In a preferred embodiment, the preparation method of the composite filler is as follows: the weighed modified nanoclay, silicone master batch, white carbon black and mesoporous silica are mixed uniformly to obtain the composite filler.

[0036] The application also provides a preparation method of a PPO resin copper-clad plate with high peeling strength and high durability, which specifically comprises the following steps:

[0037] Step one: the polystyrene resin, curing agent, composite filler and modified polyphenylene ether are weighed according to the weight percentage, the weighed polystyrene resin and modified polyphenylene ether are mixed uniformly, then the curing agent and composite filler are added and placed in an emulsifying kettle, and emulsification and high-speed shearing treatment are performed in the emulsifying kettle to obtain a glue solution for standby use;

[0038] Step two: the electronic glass fiber cloth is impregnated in the glue solution prepared in step one, and the impregnated electronic glass fiber cloth is subjected to baking treatment to obtain a prepreg;

[0039] Step three: the prepreg prepared in step two is laminated with a copper foil sheet, and then compression bonding treatment is performed to obtain a PPO resin copper-clad plate with high peeling strength and high durability.

[0040] In a preferred embodiment, the step two electronic glass fiber cloth is subjected to ultrasonic oscillation treatment during the impregnation in the glue solution, and is subjected to baking treatment by using an oven with a segmented temperature gradient, the baking temperature varies in the range of 90 DEG C, the baking temperature gradually changes from low to high and then from high to low. 2 The pressing pressure in the step three pressing treatment is 40 kg / m

[0041] Example 2

[0042] Different from example 1, the glue solution comprises, by weight percentage, polystyrene resin 26.5%, curing agent 4.5%, composite filler 20%, and the rest is modified polyphenyl ether.

[0043] Example 3

[0044] Different from examples 1-2, the glue solution comprises, by weight percentage, polystyrene resin 32.5%, curing agent 6.5%, composite filler 25%, and the rest is modified polyphenyl ether.

[0045] Example 4

[0046] Different from example 1, the composite filler comprises the following raw materials by weight: silicone masterbatch 50 parts, modified nano-clay 38 parts, white carbon black 20 parts, and mesoporous silica 15 parts.

[0047] Example 5

[0048] Different from examples 1 and 4, the composite filler comprises the following raw materials by weight: silicone masterbatch 62 parts, modified nano-clay 45 parts, white carbon black 25 parts, and mesoporous silica 20 parts.

[0049] Comparative Example 1

[0050] The application provides a high-stripping-strength and high-durability PPO resin copper-clad plate, comprising a glue solution, electronic glass fiber cloth, and a copper foil, the glue solution is impregnated with the electronic glass fiber cloth and then is pressed and formed with the copper foil, the glue solution comprises, by weight percentage, polystyrene resin 19.8%, curing agent 2.5%, composite filler 15%, and the rest is polyphenyl ether.

[0051] The composite filler comprises the following raw materials by weight: silicone masterbatch 40 parts, modified nano-clay 30 parts, white carbon black 15 parts, and mesoporous silica 10 parts.

[0052] In a preferred embodiment, the curing agent is a mixture of diaminodiphenyl sulfone and m-phenylenediamine, and the mass ratio of diaminodiphenyl sulfone and m-phenylenediamine is 1:1.

[0053] In a preferred embodiment, the preparation method of the modified nanoclay is as follows: the selected nanoclay is placed in an oven, dried at 80℃ for 11h to remove water, the dried nanoclay is dispersed in a mixture of ethanol and water, 4wt% silane coupling agent is added to the mixture, stirred and reacted at 80℃ for 4h, and then filtered, washed, and dried at 55℃ to obtain the modified nanoclay.

[0054] In a preferred embodiment, the preparation method of the composite filler is as follows: the weighed modified nanoclay, silicone master batch, white carbon black, and mesoporous silica are mixed uniformly to obtain the composite filler.

[0055] The application also provides a preparation method of the PPO resin copper-clad plate with high peeling strength and high durability, which specifically comprises the following steps:

[0056] Step one: the polystyrene resin, curing agent, composite filler, and polyphenylene ether are weighed according to the above weight percentage, the weighed polystyrene resin and polyphenylene ether are mixed uniformly, then the curing agent and composite filler are added and placed in an emulsifying kettle, and emulsification and high-speed shearing treatment are performed in the emulsifying kettle to obtain a glue solution for standby;

[0057] Step two: the electronic glass fiber cloth is impregnated in the glue solution prepared in step one, and the impregnated electronic glass fiber cloth is subjected to baking treatment to obtain a prepreg;

[0058] Step three: the prepreg prepared in step two is laminated with a copper foil, and then compression bonding treatment is performed to obtain the PPO resin copper-clad plate with high peeling strength and high durability.

[0059] In a preferred embodiment, in the process of impregnating the electronic glass fiber cloth in the glue solution in step two, ultrasonic oscillation treatment is performed, and the baking treatment is performed by using an oven with a segmented temperature gradient, the baking temperature changes from low to high and then from high to low, the compression bonding pressure in step three is 40kg / m2, the compression bonding temperature is 170℃, the high-speed shearing of the emulsifying kettle adopts a pipeline high-speed shearing technology, the speed of the high-speed shearing is 4000r / min, and the time of the high-speed shearing is 1.5h.

[0060] Comparative Example 2:

[0061] The application provides a high-stripping-strength and high-durability PPO resin copper-clad plate, which comprises a glue solution, electronic glass fiber cloth and a copper foil sheet, the glue solution is impregnated with the electronic glass fiber cloth, and then is formed with the copper foil sheet, and the glue solution comprises, in percentage by weight, 19.8% of polystyrene resin, 2.5% of curing agent, 15% of composite filler, and the rest is modified polyphenylene ether.

[0062] The composite filler comprises raw materials in the following weight parts: 40 parts of silicone masterbatch, 15 parts of white carbon black and 10 parts of mesoporous silica.

[0063] In a preferred embodiment, the curing agent is a mixture of diaminodiphenyl sulfone and m-phenylenediamine, and the mass ratio of the diaminodiphenyl sulfone and the m-phenylenediamine is 1:1.

[0064] In a preferred embodiment, the preparation method of the modified polyphenylene ether is as follows:

[0065] The polyoxyethylene surfactant is added to the weighed polyphenylene ether, and after uniform mixing, the pretreated polyphenylene ether is granulated in a twin-screw extruder, the pretreated polyphenylene ether is dissolved in toluene, 3wt% of dodecyl mercaptan and 0.5wt% of dicumyl peroxide are added to the dissolution solution, after uniform stirring and mixing, the reaction is carried out under nitrogen protection at a temperature of 80℃ for 6h, and after the reaction is completed, the modified polyphenylene ether is obtained by precipitation, filtration, washing and drying.

[0066] In a preferred embodiment, the addition amount of the polyoxyethylene surfactant is 3% of the weight of the polyphenylene ether, the precipitation time after the reaction is completed is 3h, the filter is washed with deionized water for three times, and after the washing is completed, the filter is dried at 50℃ for 40min.

[0067] In a preferred embodiment, the preparation method of the composite filler is as follows: the weighed silicone masterbatch, white carbon black and mesoporous silica are uniformly mixed to obtain the composite filler.

[0068] The application further provides a preparation method of the high-stripping-strength and high-durability PPO resin copper-clad plate, which specifically comprises the following steps:

[0069] Step one: the polystyrene resin, the curing agent, the composite filler and the modified polyphenylene ether are weighed according to the above weight percentage, the weighed polystyrene resin and the modified polyphenylene ether are uniformly mixed, then the curing agent and the composite filler are added and placed in an emulsifying kettle, and emulsification and high-speed shearing treatment are carried out in the emulsifying kettle to obtain the glue solution for standby use;

[0070] Step two: the electronic glass fiber cloth is impregnated in the glue solution prepared in step one, and the impregnated electronic glass fiber cloth is subjected to baking treatment to obtain a prepreg;

[0071] Step three: stack the prepreg prepared in step two with copper foil, and then perform a pressing treatment to obtain the PPO resin copper-clad plate with high peeling strength and high durability.

[0072] In a preferred embodiment, during the step two of impregnating the electronic glass fiber cloth in the glue solution, ultrasonic oscillation treatment is performed, and a segmented temperature gradient baking treatment is performed using an oven, with the baking temperature changing from low to high and then from high to low, the range of the baking temperature being 90 DEG C. 2 The pressing pressure in the step three of the pressing treatment is 40 kg / m

[0073] Comparative example 3:

[0074] The application provides a PPO resin copper-clad plate with high peeling strength and high durability, which comprises a glue solution, an electronic glass fiber cloth and a copper foil.

[0075] The composite filler comprises the following raw materials in parts by weight: silicone masterbatch 40 parts, white carbon black 15 parts and mesoporous silica 10 parts.

[0076] In a preferred embodiment, the curing agent is a mixture of diamino diphenyl sulfone and m-phenylenediamine, and the mass ratio of the diamino diphenyl sulfone to the m-phenylenediamine is 1:1.

[0077] In a preferred embodiment, the preparation method of the composite filler is as follows: the weighed silicone masterbatch, white carbon black and mesoporous silica are uniformly mixed to obtain the composite filler.

[0078] The application further provides a preparation method of the PPO resin copper-clad plate with high peeling strength and high durability.

[0079] Step one: the polystyrene resin, the curing agent, the composite filler and the polyphenyl ether are weighed according to the above weight percentage, the weighed polystyrene resin and polyphenyl ether are uniformly mixed, then the curing agent and the composite filler are added and placed in an emulsifying kettle, and emulsification and high-speed shearing treatment are performed in the emulsifying kettle to obtain the glue solution for standby use;

[0080] Step two: the electronic glass fiber cloth is impregnated in the glue solution prepared in step one, and the impregnated electronic glass fiber cloth is baked to obtain a prepreg;

[0081] Step three: stack the prepreg prepared in step two with copper foil, and then press and process to obtain the high peel strength and high durability PPO resin copper clad plate.

[0082] In a preferred embodiment, the step two electronic glass fiber cloth is subjected to ultrasonic oscillation treatment during the impregnation in the glue solution, and is subjected to baking treatment using an oven with a segmented temperature gradient, the baking temperature changes from low to high and then from high to low, the baking temperature change range is 90℃, the pressing pressure in the pressing treatment in the step three is 40kg / m 2 , the pressing temperature is 170℃, the high-speed shearing of the emulsification kettle adopts pipeline high-speed shearing technology, the high-speed shearing rate is 4000r / min, and the high-speed shearing time is 1.5h.

[0083] Select the high peel strength and high durability PPO resin copper clad plates produced by examples 1-5 as experimental group 1, experimental group 2, experimental group 3, experimental group 4 and experimental group 5 respectively, and select the PPO resin copper clad plates produced by comparative examples 1-3 as control group 1, control group 2 and control group 3 respectively, and test the peel strength and bending strength of the selected copper clad plates.

[0084] Bending strength: the bending strength is detected according to the standard GB / T1449-2005.

[0085] Peel strength: the peel strength performance is detected according to the detection standard GB / T36476-2018

[0086] The measurement results are shown in Table 1.

[0087] Bending strength (MPa) Peeling strength (N / mm) Experiment group 1 635.3 1.89 Experiment group 2 640.2 2.12 Experiment group 3 638.5 2.03 Experiment group 4 645.0 2.20 Experiment group 5 637.4 2.06 Control group 1 633.8 1.54 Control group 2 612.7 1.66 Control group 3 610.8 1.28

[0088] Table 1

[0089] As shown in Table 1, the copper-clad plate produced by the embodiment has good bending strength and peeling strength. Compared with Example 1 and Comparative Example 1, the bending strength does not change much, but the peeling strength is obviously reduced, because the unmodified polyphenyl ether is used. Compared with Example 1 and Comparative Example 2, the bending strength and peeling strength are both reduced, because the modified nano-clay is not added. Therefore, the polystyrene resin and the modified polyphenyl ether are used as raw materials in the present application. The compatibility of the polystyrene resin and the polyphenyl ether is good, and the flowability of the polystyrene resin is good, so that the melt index of the glue solution can be significantly improved. The polyphenyl ether is activated by using a polyoxyethylene surfactant, so that the dispersibility of the polyphenyl ether is better. Then, the polyphenyl ether is modified by using dodecyl mercaptan and dicumyl peroxide, so that the polyphenyl ether undergoes grafting reaction, long-chain alkyl is introduced in the polymerization process, the flowability is controlled, and the melt index of the glue solution is improved. Therefore, the peeling strength of the glue solution, the electronic glass fiber cloth and the copper foil is good. The nano-clay is used as a filler, so that the flame retardance and the strength of the copper-clad plate are improved. Under the auxiliary action of the silane coupling agent, the interface compatibility of the nano-clay and the PPO resin is improved. After the modification, the interlayer spacing of the nano-clay is increased, the clay layers are uniformly dispersed, and part of the clay layers is in a single-layer peeling state.

[0090] Finally, the above only describes the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A high peel strength and high durability PPO resin copper clad plate comprising a glue solution, an electronic glass fiber cloth and a copper foil sheet, the glue solution being impregnated with the electronic glass fiber cloth and then being compression molded with the copper foil sheet, characterized in that; The glue liquid comprises, in percentage by weight: polystyrene resin 19.8-32.5%, curing agent 2.5-6.5%, composite filler 15-25%, and the rest is modified polyphenyl ether; ​ The composite filler comprises the following raw materials in parts by weight: silicone masterbatch 40-62 parts, modified nanoclay 30-45 parts, white carbon black 15-25 parts, and mesoporous silica 10-20 parts.

2. The high peel strength and high durability PPO resin copper-clad plate according to claim 1, characterized in that: The glue liquid comprises, in percentage by weight: polystyrene resin 25-28%, curing agent 3.5-5.5%, composite filler 18-22%, and the rest is modified polyphenyl ether; The composite filler comprises the following raw materials in parts by weight: silicone masterbatch 45-55 parts, modified nanoclay 35-40 parts, white carbon black 18-22 parts, and mesoporous silica 13-17 parts.

3. The high peel strength and high durability PPO resin copper-clad plate according to claim 1, characterized in that: The glue liquid comprises, in percentage by weight: polystyrene resin 26.5%, curing agent 4.5%, composite filler 20%, and the rest is modified polyphenyl ether; The composite filler comprises the following raw materials in parts by weight: silicone masterbatch 50 parts, modified nanoclay 38 parts, white carbon black 20 parts, and mesoporous silica 15 parts.

4. The high peel strength and high durability PPO resin copper-clad plate according to claim 1, characterized in that: The curing agent is a mixture of diamino diphenyl sulfone and m-phenylenediamine, and the mass ratio of the diamino diphenyl sulfone to the m-phenylenediamine is 1:

1.

5. The high peel strength and high durability PPO resin copper-clad plate according to claim 1, characterized in that: The preparation method of the modified polyphenyl ether is: The weighed polyphenyl ether is added with a polyoxyethylene surfactant, and after being uniformly mixed, the mixture is placed in a twin-screw extruder for granulation to obtain pretreated polyphenyl ether. The pretreated polyphenyl ether is dissolved in toluene, 1-5 wt% of dodecyl mercaptan and 0.1-1 wt% of dicumyl peroxide are added to the solution, and after being uniformly stirred, the mixture is reacted under nitrogen protection at a temperature of 70-90°C for 4-8 hours. After the reaction is completed, the modified polyphenyl ether is obtained by precipitation, filtration, washing, and drying.

6. The high peel strength and high durability PPO resin copper-clad plate according to claim 5, characterized in that: The addition amount of the polyoxyethylene surfactant is 1.5-4.5% of the weight of the polyphenyl ether. After the reaction is completed, the precipitation time is 2-4 hours. The filtrate is washed with deionized water for three times, and after the washing is completed, the filtrate is dried at 45-55°C for 30-50 minutes.

7. The high peel strength and high durability PPO resin copper-clad plate according to claim 1, characterized in that: The preparation method of the modified nanoclay is: the selected nanoclay is placed in an oven and dried at 75-85°C for 10-12 hours to remove water. The dried nanoclay is dispersed in a mixture of ethanol and water, 3-5 wt% of a silane coupling agent is added to the mixture, and the mixture is stirred and reacted at 75-85°C for 3-5 hours. After the reaction is completed, the modified nanoclay is obtained by filtration, washing, and drying at 50-60°C.

8. The high peel strength and high durability PPO resin copper-clad plate according to claim 7, characterized in that: The preparation method of the composite filler is: the weighed modified nanoclay, silicone masterbatch, white carbon black, and mesoporous silica are uniformly mixed to obtain the composite filler.

9. The method according to any one of claims 1-8, characterized in that: Specifically comprising the following steps: Step one: the polystyrene resin, curing agent, composite filler, and modified polyphenyl ether are weighed according to the above weight percentage, the weighed polystyrene resin and modified polyphenyl ether are uniformly mixed, then the curing agent and composite filler are added and placed in an emulsifying kettle, and emulsification and high-speed shearing treatment are performed in the emulsifying kettle to obtain the glue liquid for standby use. Step two: dipping the electronic fiberglass cloth in the glue solution prepared in step one, and baking the electronic fiberglass cloth after the dipping to prepare a prepreg; Step three: laminating the prepreg prepared in step two with a copper foil sheet, and then performing a pressing treatment to obtain a PPO resin copper-clad plate with high peel strength and high durability.

10. The method of claim 9, wherein the PPO resin copper clad plate has high peel strength and durability. The step two electronic glass fiber cloth is subjected to ultrasonic oscillation treatment in the process of impregnation in glue solution, and is subjected to baking treatment by using an oven with segmented temperature gradient, the baking temperature changes in the range of 50-180℃, the baking temperature gradually changes from low to high and then from high to low, and the pressing pressure in the pressing treatment in the step three is 38-42 kg / m 2 , and the pressing temperature is 160-180℃.