CN115926381A - Silicon dioxide filled epoxy resin copper-clad plate and preparation method thereof - Google Patents
Silicon dioxide filled epoxy resin copper-clad plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of copper-clad plates, in particular to a silicon dioxide filled epoxy resin copper-clad plate and a preparation method thereof. The epoxy resin is a high-insulation material, and the graphene is added to endow the epoxy resin with good antistatic capability; and the silicon dioxide has high dielectric strength and excellent chemical stability, and can improve the light stability, heat resistance and chemical stability of the material after being blended with the epoxy resin. In order to avoid the agglomeration phenomenon when the silicon dioxide and the graphene are directly blended with the polymer resin, the surface of the silicon dioxide is modified, the modified silicon dioxide is grafted to the surface of the graphene oxide through the electrostatic action, and finally the graphene oxide is reduced to obtain the reduced graphene oxide-silicon dioxide composite material. The reduced graphene oxide-silicon dioxide composite material can improve the heat resistance and the antistatic property of the epoxy resin, can play a role in toughening and modifying, and can improve the mechanical property.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a silicon dioxide filled epoxy resin copper-clad plate and a preparation method thereof.
Background
With the progress of scientific technology, the electronic technology is more and more widely applied in various industries, electronic equipment gradually develops towards the direction of high frequency, high speed, high power and high integration at a high speed, the number of components loaded on a copper-clad plate is more and more, and the power consumption is more and more. High power consumption can cause temperature rise, so when the copper-clad plate is prepared, the selection of a material with good heat resistance is particularly important.
The epoxy resin is a thermosetting polymer resin, has high crosslinking density, small shrinkage, high mechanical strength, good cohesiveness, heat resistance, chemical corrosion resistance and the like after being cured, and is used as a base material of the copper clad laminate. In the preparation process of the copper-clad plate, a welding technology is required. The traditional welding technology uses tin-lead alloy as welding flux, although the cost is low and the product quality is good, lead as a poisonous heavy metal pollutes the environment, so the lead-free welding technology is produced at the same time. The lead-free soldering technique operates at higher temperatures than conventional soldering. The epoxy resin is used as a heat-sensitive substance, is extremely easy to burn, is not only not beneficial to welding processing, but also can be burnt due to overheating in the using process, and the probability of fire occurrence is increased. Therefore, it is necessary to modify the epoxy resin copper clad laminate to improve the heat resistance and flame retardancy of the copper clad laminate.
Disclosure of Invention
The invention aims to provide a silicon dioxide filled epoxy resin copper-clad plate and a preparation method thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
step 1: after drying nano silicon dioxide powder in vacuum, mixing the dried nano silicon dioxide powder with gamma-aminopropyltriethoxysilane, adding the mixture into xylene, stirring and heating for reaction, washing and drying to obtain modified silicon dioxide;
step 2: adding modified silicon dioxide and graphene oxide into an ethanol solution, mechanically stirring for 10-12 h, performing suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing the graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH value to 9-10, adding hydrazine hydrate, stirring for 20-30 min, heating to 80-90 ℃, continuously stirring for reaction for 2-4 h, and performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating bisphenol A epoxy resin at 50-65 ℃, adding a curing agent, acetone, a flame retardant and a reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 10-15 min, coating copper foil on the resin glue solution, placing in a hot press at 80-95 ℃ for 2-4 h, and curing for 1-2 h to obtain the epoxy resin copper-clad plate.
Further, in the step 1, the dosage of each component is 30-50 parts of nano silicon dioxide, 5-8 parts of gamma-aminopropyltriethoxysilane and 400-500 parts of xylene by weight.
Further, in the step 1, the reaction temperature is 120-130 ℃, and the reaction time is 3-4 h.
Further, in the step 2, the use amounts of the components are 10-20 parts by weight of modified silicon dioxide, 5-10 parts by weight of graphene oxide and 500-600 parts by weight of ethanol solution.
Further, in the step 3, the usage amounts of the components are 15-22 parts by weight of graphene oxide-silicon dioxide composite material and 60-100 parts by weight of hydrazine hydrate.
Further, in step 4, 160-200 parts by weight of bisphenol A epoxy resin, 35-50 parts by weight of curing agent, 25-30 parts by weight of acetone, 22-28 parts by weight of flame retardant and 24-32 parts by weight of reduced graphene oxide-silicon dioxide composite material.
Further, in step 4, the curing agent is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, maleic anhydride, tetraethylenepentamine, and phthalic anhydride.
Further, in step 4, the accelerator is any one of N, N-dimethylbenzylamine, N-dimethylurea, dimethylimidazolium urea, and 2-ethyl-4-methylimidazole.
Further, in step 4, the flame retardant is any one or more of magnesium hydroxide, decabromodiphenylethane, kaolin and antimony trioxide.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the graphene-silicon dioxide composite material is added in the process of preparing the epoxy resin copper-clad plate, so that the performance of the copper-clad plate is improved. The epoxy resin is a high-insulation material, and the copper-clad plate can be endowed with good antistatic capability by adding the graphene. The silicon dioxide has high dielectric strength and excellent chemical stability, can permeate the interior of the material after being blended with the epoxy resin, and can generate an effect with unsaturated bonds of a polymer chain, so that the light stability, the heat resistance and the chemical stability of the material are improved. According to the invention, the surface of the silicon dioxide is modified, the modified silicon dioxide is grafted to the surface of the graphene oxide under the electrostatic action, and finally the graphene oxide is reduced to obtain the reduced graphene oxide-silicon dioxide composite material, so that the problem of agglomeration when the silicon dioxide and the graphene are blended with epoxy resin is avoided. In addition, the reduced graphene oxide-silicon dioxide can also play a role in toughening and modifying, and the mechanical property of the epoxy resin is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The main materials and their sources in the following examples are as follows:
nano-silica was purchased from Jiangsu Huimei Su-Sprite technologies, inc.; gamma-aminopropyltriethoxysilane (CAS number 919-30-2) was purchased from alatin; graphene oxide was purchased from nanotechnology ltd, amanita, zhejiang; ethanol (CAS number 64-17-5) was purchased from Maxin; sodium hydroxide (CAS number 1310-73-2) was purchased from Chinese medicine; hydrazine hydrate (CAS number: 7803-57-8) was purchased from alatin; bisphenol A epoxy resin E51 is purchased from Lin Yuanhua, and has an average molecular weight of 4500-5000; ethylenediamine (CAS number: 107-15-3) purchased from national medicine; acetone (CAS number 67-64-1) was purchased from Aladdin; decabromodiphenylethane (CAS number: 84852-53-9) was purchased from Shanghai Kernel chemical Co., ltd.
Example 1:
step 1: drying nano silicon dioxide powder for 24 hours at the temperature of 100 ℃, adding 30g of nano silicon dioxide and 5g of gamma-aminopropyltriethoxysilane into 400g of dimethylbenzene, heating the system to 120 ℃, stirring for reaction for 3 hours, washing and drying to obtain modified silicon dioxide;
step 2: adding 10g of modified silicon dioxide and 5g of graphene oxide into 500g of ethanol solution, mechanically stirring for 10 hours, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing 15g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH value to 9, adding 60g of hydrazine hydrate, stirring for 20min, heating to 90 ℃, continuously stirring for reaction for 2h, performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating 160kg of bisphenol A epoxy resin at 50 ℃, adding 35kg of ethylenediamine, 25kg of acetone, 22kg of decabromodiphenylethane and 24kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 10min, coating copper foil on the resin glue solution, placing in a hot press at 80 ℃ for 2h, and curing for 2h to obtain the epoxy resin copper-clad plate.
Example 2:
step 1: drying nano silicon dioxide powder for 27h at 105 ℃ under vacuum condition, adding 35g of nano silicon dioxide and 5.6g of gamma-aminopropyltriethoxysilane into 450g of xylene, heating the system to 125 ℃, stirring for reaction for 3.5h, washing and drying to obtain modified silicon dioxide;
and 2, step: adding 13g of modified silicon dioxide and 6g of graphene oxide into 550g of ethanol solution, mechanically stirring for 11 hours, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing 18g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH to 9.5, adding 70g of hydrazine hydrate, stirring for 25min, heating to 85 ℃, continuously stirring for reaction for 2.5h, and performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating 165kg of bisphenol A epoxy resin at 55 ℃, adding 38kg of ethylenediamine, 27kg of acetone, 23kg of decabromodiphenylethane and 25kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying for 12min at 75 ℃, coating copper foil on the resin glue solution, putting the resin glue solution in a hot press at 85 ℃ for 3h, and curing for 1.5h to obtain the epoxy resin copper-clad plate.
Example 3:
step 1: drying the nano silicon dioxide powder for 28 hours at the temperature of 110 ℃ under vacuum, adding 40g of nano silicon dioxide and 6.5g of gamma-aminopropyltriethoxysilane into 420g of dimethylbenzene, heating the system to 125 ℃, stirring for reaction for 3.5 hours, washing and drying to obtain modified silicon dioxide;
step 2: adding 14g of modified silicon dioxide and 7.4g of graphene oxide into 540g of ethanol solution, mechanically stirring for 11h, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing 18.5g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH value to 10, adding 76g of hydrazine hydrate, stirring for 30min, heating to 80 ℃, continuously stirring for reaction for 3h, performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating 170kg of bisphenol A epoxy resin at 60 ℃, adding 39kg of ethylenediamine, 27kg of acetone, 25kg of decabromodiphenylethane and 27kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 13min, coating copper foil on the resin glue solution, putting the resin glue solution in a hot press at 85 ℃ for 4h, and curing for 1h to obtain the epoxy resin copper-clad plate.
Example 4:
step 1: drying the nano silicon dioxide powder for 23-36 h under the vacuum condition of 110 ℃, adding 42g of nano silicon dioxide and 6.9g of gamma-aminopropyltriethoxysilane into 450g of dimethylbenzene, heating the system to 125 ℃, stirring for reaction for 4h, washing and drying to obtain modified silicon dioxide;
step 2: adding 16g of modified silicon dioxide and 8g of graphene oxide into 560g of ethanol solution, mechanically stirring for 12h, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing 19g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH to 9, adding 85g of hydrazine hydrate, stirring for 30min, heating to 80 ℃, continuously stirring for reaction for 2h, performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating 185kg of bisphenol A epoxy resin at 60 ℃, adding 41kg of ethylenediamine, 27kg of acetone, 24kg of decabromodiphenylethane and 28kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying for 13min at 75 ℃, coating copper foil on the resin glue solution, putting the resin glue solution in a 90 ℃ hot press for 4h, and curing for 1-2 h to obtain the epoxy resin copper-clad plate.
Example 5:
step 1: drying the nano silicon dioxide powder for 23-36 h under the vacuum condition of 115 ℃, adding 45g of nano silicon dioxide and 7g of gamma-aminopropyltriethoxysilane into 475g of xylene, heating the system to 125 ℃, stirring for reaction for 3h, washing and drying to obtain modified silicon dioxide;
step 2: adding 17g of modified silicon dioxide and 8.5g of graphene oxide into 580g of ethanol solution, mechanically stirring for 10 hours, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing 20g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH value to 9, adding 80g of hydrazine hydrate, stirring for 30min, heating to 90 ℃, continuously stirring for reaction for 3h, performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating 190kg of bisphenol A epoxy resin at 65 ℃, adding 45kg of ethylenediamine, 27kg of acetone, 26kg of decabromodiphenylethane and 30kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying for 15min at 75 ℃, coating copper foil on the resin glue solution, putting the resin glue solution in a 90 ℃ hot press for 4h, and curing for 1h to obtain the epoxy resin copper-clad plate.
Example 6:
step 1: drying the nano silicon dioxide powder for 36 hours at the temperature of 120 ℃ under vacuum, adding 50g of nano silicon dioxide and 8g of gamma-aminopropyltriethoxysilane into 500g of xylene, heating the system to 130 ℃, stirring for reaction for 4 hours, washing and drying to obtain modified silicon dioxide;
step 2: adding 20g of modified silicon dioxide and 10g of graphene oxide into 600g of ethanol solution, mechanically stirring for 12 hours, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: dispersing 22g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH value to 10, adding 100g of hydrazine hydrate, stirring for 30min, heating to 90 ℃, continuously stirring for reaction for 4h, performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating 200kg of bisphenol A epoxy resin at 65 ℃, adding 50kg of ethylenediamine, 30kg of acetone, 28kg of decabromodiphenylethane and 32kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 15min, coating copper foil on the resin glue solution, putting the resin glue solution in a hot press at 95 ℃ for 4h, and curing for 2h to obtain the epoxy resin copper-clad plate.
Comparative example 1:
no reduced graphene oxide-silica composite was added.
Step 1: heating 160kg of bisphenol A epoxy resin at 50 ℃, adding 35kg of ethylenediamine, 25kg of acetone and 22kg of decabromodiphenylethane, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 10min, coating copper foil on the resin glue solution, placing in a hot press at 80 ℃ for 2h, and curing for 2h to obtain the epoxy resin copper-clad plate.
Comparative example 2:
directly blending the graphene oxide and the nano silicon dioxide.
Step 1: adding 13g of nano-silica and 6g of graphene oxide into 550g of ethanol solution, mechanically stirring for 11 hours, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silica composite material, and storing at 120 ℃ for later use;
step 2: dispersing 18g of graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH to 9.5, adding 70g of hydrazine hydrate, stirring for 25min, heating to 85 ℃, continuously stirring for reaction for 2.5h, and performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and step 3: heating 165kg of bisphenol A epoxy resin at 55 ℃, adding 38kg of ethylenediamine, 27kg of acetone, 23kg of decabromodiphenylethane and 25kg of reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 12min, coating copper foil on the resin glue solution, putting the resin glue solution in a hot press at 85 ℃ for 3h, and curing for 1.5h to obtain the epoxy resin copper-clad plate.
Comparative example 3:
and blending the graphene and the silicon dioxide to prepare the copper-clad plate.
Step 1: drying the nano silicon dioxide powder for 28 hours at the temperature of 110 ℃ under vacuum, adding 40g of nano silicon dioxide and 6.5g of gamma-aminopropyltriethoxysilane into 420g of dimethylbenzene, heating the system to 125 ℃, stirring for reaction for 3.5 hours, washing and drying to obtain modified silicon dioxide;
step 2: adding 14g of modified silicon dioxide and 7.4g of graphene into 540g of ethanol solution, mechanically stirring for 11 hours, carrying out suction filtration, drying and sieving to obtain a graphene-silicon dioxide composite material, and storing at 120 ℃ for later use;
and step 3: heating 170kg of bisphenol A epoxy resin at 60 ℃, adding 39kg of ethylenediamine, 27kg of acetone, 25kg of decabromodiphenylethane and 27kg of graphene-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 13min, coating copper foil on the resin glue solution, putting the resin glue solution in a hot press at 85 ℃ for 4h, and curing for 1h to obtain the epoxy resin copper-clad plate.
Experiment:
the epoxy resins prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to a performance test. Wherein:
flame retardancy: testing according to the method specified in UL 94;
and (3) testing tensile strength: according to GB/T1040-92, the rubber was cut into a dumbbell shape (size: 4 mm. Times.75 mm. Times.2 mm), placed in an electronic universal tester (product No. AG-201, shimadzu, japan) and subjected to a tensile test at a tensile rate of 100mm/min;
and (3) volume resistivity test: volume resistivity testing was performed according to GB/T1410-2006 using a high insulation resistance tester (cat 4399A, agilent, USA);
thermal stability: heating to 500 deg.C at a rate of 5 deg.C/min in nitrogen environment, and recording the temperature T of 10% heat loss 10％ ；
The results of the experiments are shown in the following table.
And (4) conclusion: data of examples 1 to 6 show that the copper-clad plate prepared by blending the reduced graphene oxide-silicon dioxide composite material and the epoxy resin has good antistatic property, heat resistance and tensile strength. The modified silicon dioxide surface contains amino groups, and can be grafted with graphene oxide through electrostatic interaction, so that the dispersibility of the graphene oxide is improved, and the reduced graphene oxide obtained through reduction reaction also has good dispersibility, and the performance of the epoxy resin can be improved. In addition, amino and hydroxyl on the surface of the silicon dioxide can react with C-O-C in the epoxy resin to play a role in autocatalysis and crosslinking promotion, so that the mechanical property of the product is improved.
With example 1 as a reference, comparative example 1 shows that, without adding the reduced graphene oxide-silica composite, the tensile strength and thermal stability of the epoxy resin are reduced, while the volume resistivity is increased; by taking the example 2 as a reference, the data of the comparative example 2 show that after the graphene oxide and the nano-silica are directly blended, the dispersibility of the graphene oxide and the nano-silica in the epoxy resin is poor, so that the tensile strength of the epoxy resin is reduced; in the embodiment, the nano silicon dioxide modified by the gamma-aminopropyltriethoxysilane and the graphene oxide can be grafted on the surface of the graphene oxide through electrostatic interaction, and the graphene oxide has a stable net structure, so that the dispersity of the graphene oxide is improved while the aggregation of the silicon dioxide is avoided, and the reduced graphene oxide-silicon dioxide composite material obtained through the reduction reaction has good compatibility with epoxy resin; the data of comparative example 3 show that the epoxy resin prepared by directly blending modified silicon dioxide and graphene has poor performance, mainly because the graphene has fewer functional group components on the molecular structure and is difficult to generate electrostatic interaction with the modified silicon dioxide, so that the dispersion performance of the graphene cannot be improved, the compatibility of the graphene and the epoxy resin after blending is poor, and the performance improvement effect on the epoxy resin is poor.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a silicon dioxide filled epoxy resin copper-clad plate is characterized by comprising the following steps: the method comprises the following steps:
step 1: vacuum drying the nano silicon dioxide powder, mixing the nano silicon dioxide powder with gamma-aminopropyl triethoxysilane, adding the mixture into dimethylbenzene, stirring, heating for reaction, washing and drying to obtain modified silicon dioxide;
step 2: adding modified silicon dioxide and graphene oxide into an ethanol solution, mechanically stirring for 10-12 h, carrying out suction filtration, drying and sieving to obtain a graphene oxide-silicon dioxide composite material for later use;
and step 3: dispersing the graphene oxide-silicon dioxide composite material in deionized water, adding a sodium hydroxide solution to adjust the pH value to 9-10, adding hydrazine hydrate, stirring for 20-30 min, heating to 80-90 ℃, continuously stirring for reaction for 2-4 h, performing suction filtration, washing and drying to obtain a reduced graphene oxide-silicon dioxide composite material;
and 4, step 4: heating bisphenol A epoxy resin at 50-65 ℃, adding a curing agent, acetone, a flame retardant and a reduced graphene oxide-silicon dioxide composite material, and uniformly mixing to obtain a resin glue solution; and coating the resin glue solution on glass fiber cloth, drying at 75 ℃ for 10-15 min, coating copper foil on the resin glue solution, and carrying out hot pressing and curing to obtain the epoxy resin copper-clad plate.
2. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 1, the dosage of each component is 30-50 parts of nano silicon dioxide, 5-8 parts of gamma-aminopropyl triethoxysilane and 400-500 parts of dimethylbenzene by weight.
3. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 1, the reaction temperature is 120-130 ℃, and the reaction time is 3-4 h.
4. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 2, the dosage of each component is 10-20 parts of modified silicon dioxide, 5-10 parts of graphene oxide and 500-600 parts of ethanol solution by weight.
5. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 3, the usage amount of each component is 15-22 parts by weight of graphene oxide-silicon dioxide composite material and 60-100 parts by weight of hydrazine hydrate.
6. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 4, the components comprise, by weight, 160-200 parts of bisphenol A epoxy resin, 35-50 parts of a curing agent, 25-30 parts of acetone, 22-28 parts of a flame retardant and 24-32 parts of a reduced graphene oxide-silicon dioxide composite material.
7. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 4, the curing agent is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, maleic anhydride, tetraethylenepentamine and phthalic anhydride; the accelerator is any one of N, N-dimethylbenzylamine, N-dimethyl urea, dimethyl imidazole urea and 2-ethyl-4-methylimidazole; the flame retardant is any one or more of magnesium hydroxide, decabromodiphenylethane, kaolin and antimony trioxide.
8. The method for preparing the silica-filled epoxy resin copper-clad plate according to claim 1, which is characterized in that: in the step 4, the hot pressing temperature is 80-95 ℃, and the hot pressing time is 2-4 h; the curing time is 1-2 h.
9. The epoxy resin copper-clad plate prepared by the preparation method of the silica filled epoxy resin copper-clad plate according to any one of claims 1 to 8.
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| CN116512702A (en) * | 2023-05-06 | 2023-08-01 | 江苏耀鸿电子有限公司 | High-frequency high-speed PPO resin-based copper-clad plate and preparation process thereof |
| CN117467195A (en) * | 2023-10-23 | 2024-01-30 | 宿迁海岳新材料技术有限公司 | Graphene material and preparation method thereof |
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