Modified spherical silica powder for copper-clad plate and preparation method of modified spherical silica powder

Abstract

The invention discloses modified spherical silica powder for a copper-clad plate, and the modified spherical silica powder is prepared from the following components in parts by weight: 1-2 parts of spherical silica powder of 0.1-100 microns, 10-36 parts of hydrogen peroxide solution of which the mass fraction is 5-8%, 8-24 parts of methylbenzene, 0.2-0.8 part of silane coupling agent and 0.006-0.024 part of catalyst. A preparation method of the modified spherical silica powder comprises the following steps: preparing raw materials: cleaning and drying the raw materials; surface treatment: reacting the silica powder with a hydrogen peroxide solution, filtering and cleaning, filtering and cleaning to be neutral after the reaction is finished, modification reaction: adding a silane coupling agent and a catalyst into the spherical silica powder subjected to surface activation for reaction modification, cleaning and drying, and cooling, cleaning and drying after the reaction is finished to obtain the finished product modified spherical silica powder. The invention belongs to the technical field of material modification, and particularly relates to modified spherical silica powder for a copper-clad plate and a preparation method of the modified spherical silica powder.

Description

Technical Field

[0001] The invention belongs to the technical field of material modification, and specifically refers to modified spherical silicon powder for copper-clad plates and a preparation method thereof. Background Art

[0002] In the modern electronics industry, the performance requirements of copper clad laminates are becoming increasingly stringent. Spherical silicon powder has great application potential in the field of copper clad laminates due to its low expansion coefficient, high insulation and good chemical stability.

[0003] However, the surface of the original spherical silica powder is hydrophilic, and there are compatibility issues between it and the organic resin matrix, which makes it difficult to disperse evenly during the preparation process of the copper clad laminate, thereby affecting the overall performance of the copper clad laminate, such as reducing mechanical strength and affecting the stability of electrical properties. Therefore, it is of great significance to develop an effective modification method to improve the compatibility and interfacial bonding strength of spherical silica powder with the resin matrix. Summary of the invention

[0004] The technical problem to be solved by the present invention is that the compatibility between unmodified spherical silicon powder and the organic resin matrix is ​​poor, resulting in weak interface bonding force and poor use effect of the copper clad laminate.

[0005] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0006] A modified spherical silicon micropowder for copper-clad laminates comprises the following formula in parts by weight: 1-2 parts of spherical silicon micropowder with a size of 0.1-100 microns, 10-36 parts of a hydrogen peroxide solution with a mass fraction of 5-8%, 8-24 parts of toluene, 0.2-0.8 parts of a silane coupling agent, and 0.006-0.024 parts of a catalyst.

[0007] Furthermore, the silane coupling agent is vinylphenyl glycidyl ether trimethoxysilane.

[0008] Furthermore, the catalyst is dibutyltin dilaurate, and its usage is 2-3% of the mass of the silane coupling agent.

[0009] A method for preparing modified spherical silicon powder for copper clad laminates comprises the following steps:

[0010] (1) Raw material preparation: Spherical silicon micropowder with a particle size range of 0.1-100 μm is selected as the basic raw material, which is placed in a vacuum oven and dried at a temperature of 100-150°C for 2-4 hours to ensure that the moisture and impurities adsorbed on the surface of the silicon micropowder are completely removed;

[0011] (2) Surface treatment: Slowly add the dried spherical silicon powder into a 5-8% hydrogen peroxide solution, where the mass ratio of silicon powder to hydrogen peroxide solution is 1:10-1:18, and then place it in an ultrasonic oscillator for 1 hour;

[0012] (3) Filtration and cleaning: After the reaction is completed, filter with a microporous filter membrane and rinse repeatedly with deionized water until the pH value of the filtrate stabilizes at around 7 to ensure that the surface of the silicon micropowder is neutral and there is no residual hydrogen peroxide;

[0013] (4) Modification reaction: The surface activated spherical silicon powder is uniformly dispersed in a toluene solution that has been treated with dehydration and deoxygenation, and the mass ratio of silicon powder to toluene is maintained at 1:8-1:12. Then, a silane coupling agent (vinylphenyl glycidyl ether trimethoxysilane) is weighed and added to the reaction system at a mass ratio of 0.4:1-0.2:1 of the silane coupling agent (vinylphenyl glycidyl ether trimethoxysilane to) silicon powder. A catalyst (dibutyltin dilaurate) is introduced. Under the protection of high-purity nitrogen, the reaction system is slowly heated to 70-80°C and stirred for reaction for 4-6 hours at a magnetic stirrer speed of 700-800 rpm.

[0014] (5) Cleaning and drying: After the reaction is completed, the reaction mixture is naturally cooled to room temperature and filtered using a vacuum filtration device. The filtered silicon micropowder is washed with toluene and ethanol respectively to completely remove impurities such as unreacted silane coupling agent and catalyst. Finally, the washed modified spherical silicon micropowder is placed in a vacuum oven at 100-150°C and dried for 3-6 hours to obtain a finished modified spherical silicon micropowder.

[0015] The present invention adopts the above structure to achieve the following beneficial effects: the present invention provides a modified spherical silicon micropowder for copper clad laminates and a preparation method thereof, which successfully solves the problem of poor compatibility between spherical silicon micropowder and resin matrix through a unique multi-functional group grafting design and precise preparation process control, significantly improves various properties of copper clad laminates, and shows extremely broad application prospects and huge market potential in the field of electronic materials. DETAILED DESCRIPTION

[0016] The technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] The present invention provides a modified spherical silicon powder for copper clad laminate and a preparation method thereof:

[0018] Embodiment 1:

[0019] Accurately weigh 50g of spherical silicon powder with a particle size of 80 microns, place it in a vacuum oven, set the temperature to 120°C, and dry it for 3 hours to remove moisture and impurities on the surface of the silicon powder;

[0020] The dried spherical silicon powder was slowly added into 800 g of 6% hydrogen peroxide solution (mass ratio of silicon powder to hydrogen peroxide solution was 1:16), and then placed in an ultrasonic oscillator for 1 hour;

[0021] The reacted solution was filtered through a 0.22 μm microporous filter membrane, and the silicon powder was repeatedly washed with deionized water until the pH value of the filtrate was stabilized at about 7;

[0022] The cleaned spherical silicon powder is evenly dispersed in 600g of toluene solution that has been dehydrated and deoxygenated (the mass ratio of silicon powder to toluene is 1:11). Weigh 10g of vinylphenyl glycidyl ether trimethoxysilane (the mass ratio of silane coupling agent to silicon powder is 0.2:1) and add it to the reaction system, and then add 0.3g of dibutyltin dilaurate (2% of the mass of the silane coupling agent) as a catalyst. Under the protection of high-purity nitrogen, the reaction system is heated to 75°C at a heating rate of 1°C / min, and the reaction is stirred at a magnetic stirrer speed of 800rpm for 5 hours;

[0023] After the reaction is completed, it is naturally cooled to room temperature, filtered with a vacuum filtration device, and the silicon micropowder is washed with toluene and ethanol three times respectively. Finally, the silicon micropowder is placed in a vacuum oven at 120°C and dried for 4 hours to obtain a finished modified spherical silicon micropowder.

[0024] Embodiment 2:

[0025] Accurately weigh 30g of spherical silicon micropowder with a particle size of 50 microns, place it in a vacuum oven, set the temperature to 130°C, and dry it for 2.5 hours to remove moisture and impurities on the surface of the silicon micropowder;

[0026] The dried spherical silicon powder was slowly added into 540 g of 8% hydrogen peroxide solution (mass ratio of silicon powder to hydrogen peroxide solution was 1:18), and then placed in an ultrasonic oscillator for 1 hour;

[0027] The reacted solution was filtered through a 0.22 μm microporous filter membrane, and the silicon powder was repeatedly washed with deionized water until the pH value of the filtrate was stabilized at about 7;

[0028] The cleaned spherical silicon powder is evenly dispersed in 360g of toluene solution that has been dehydrated and deoxygenated (the mass ratio of silicon powder to toluene is 1:12). Weigh 9g of vinylphenyl glycidyl ether trimethoxysilane (the mass ratio of silane coupling agent to silicon powder is 0.3:1) and add it to the reaction system, and then add 0.27g of dibutyltin dilaurate (3% of the mass of the silane coupling agent) as a catalyst. Under the protection of high-purity nitrogen, the reaction system is heated to 78°C at a heating rate of 1°C / min, and the reaction is stirred at a magnetic stirrer speed of 800rpm for 4.5 hours;

[0029] After the reaction is completed, it is naturally cooled to room temperature, filtered with a vacuum filtration device, and the silicon micropowder is washed with toluene and ethanol three times respectively. Finally, the silicon micropowder is placed in a vacuum oven at 130°C and dried for 3.5 hours to obtain a finished modified spherical silicon micropowder.

[0030] Embodiment three:

[0031] Accurately weigh 80g of spherical silicon powder with a particle size of 5 microns, place it in a vacuum oven, set the temperature to 140°C, and dry it for 4 hours to remove moisture and impurities on the surface of the silicon powder;

[0032] The dried spherical silicon powder was slowly added into 1280 g of 5% hydrogen peroxide solution (mass ratio of silicon powder to hydrogen peroxide solution was 1:16), and then placed in an ultrasonic oscillator for 1 hour;

[0033] The reacted solution was filtered through a 0.22 μm microporous filter membrane, and the silicon powder was repeatedly washed with deionized water until the pH value of the filtrate was stabilized at about 7;

[0034] The cleaned spherical silicon powder is evenly dispersed in 960g of toluene solution that has been dehydrated and deoxygenated (the mass ratio of silicon powder to toluene is 1:12). Weigh 16g of vinylphenyl glycidyl ether trimethoxysilane (the mass ratio of silane coupling agent to silicon powder is 0.2:1) and add it to the reaction system, and then add 0.48g of dibutyltin dilaurate (3% of the mass of the silane coupling agent) as a catalyst. Under the protection of high-purity nitrogen, the reaction system is heated to 80°C at a heating rate of 1°C / min, and the reaction is stirred at a magnetic stirrer speed of 700rpm for 6 hours;

[0035] After the reaction is completed, it is naturally cooled to room temperature, filtered with a vacuum filtration device, and the silicon micropowder is washed three times with toluene and ethanol respectively. Finally, the silicon micropowder is placed in a vacuum oven at 150°C and dried for 6 hours to obtain a finished modified spherical silicon micropowder.

[0036] The present invention and its embodiments are described above, and such description is not restrictive. What is shown in the embodiments is only a few embodiments of the present invention, and the actual steps and formulas are not limited thereto. In short, if a person of ordinary skill in the art is inspired by it, and does not depart from the purpose of the invention, a structural mode and an embodiment similar to the technical solution can be designed without creativity, and all of them should belong to the protection scope of the present invention.

Claims

1. A modified spherical silicon powder for copper clad laminate, the formula composition of which is as follows by weight: 1-2 parts of spherical silicon powder with a size of 0.1-100 microns, 10-36 parts of hydrogen peroxide solution with a mass fraction of 5-8%, 8-24 parts of toluene, 0.2-0.8 parts of silane coupling agent, and 0.006-0.024 parts of catalyst.

2. The modified spherical silicon powder for copper clad laminate and the preparation method thereof according to claim 1, characterized in that: The silane coupling agent is vinylphenyl glycidyl ether trimethoxysilane.

3. The modified spherical silicon powder for copper clad laminate and the preparation method thereof according to claim 1, characterized in that: The catalyst is dibutyltin dilaurate, and its usage is 2-3% of the mass of the silane coupling agent.

4. The method for preparing modified spherical silicon powder for copper clad laminate according to claims 1 to 3 comprises the following steps: (1) Raw material preparation: Spherical silicon micropowder with a particle size range of 0.1-100 μm is selected as the basic raw material, which is placed in a vacuum oven and dried at a temperature of 100-150°C for 2-4 hours to ensure that the moisture and impurities adsorbed on the surface of the silicon micropowder are completely removed; (2) Surface treatment: Slowly add the dried spherical silicon powder into a 5-8% hydrogen peroxide solution, where the mass ratio of silicon powder to hydrogen peroxide solution is 1:10-1:18, and then place it in an ultrasonic oscillator for 1 hour; (3) Filtration and cleaning: After the reaction is completed, filter with a microporous filter membrane and rinse repeatedly with deionized water until the pH value of the filtrate stabilizes at around 7 to ensure that the surface of the silicon micropowder is neutral and there is no residual hydrogen peroxide; (4) Modification reaction: The surface activated spherical silicon powder is uniformly dispersed in a toluene solution that has been treated with dehydration and deoxygenation, and the mass ratio of silicon powder to toluene is maintained at 1:8-1:

12. Then, a silane coupling agent is weighed and added to the reaction system at a mass ratio of silane coupling agent to silicon powder of 0.4:1-0.2:

1. A catalyst is introduced. Under the protection of high-purity nitrogen, the reaction system is slowly heated to 70-80°C, and the reaction is stirred for 4-6 hours at a magnetic stirrer speed of 700-800 rpm. (5) Cleaning and drying: After the reaction is completed, the reaction mixture is naturally cooled to room temperature and filtered using a vacuum filtration device. The filtered silicon micropowder is washed with toluene and ethanol respectively to completely remove impurities such as unreacted silane coupling agent and catalyst. Finally, the washed modified spherical silicon micropowder is placed in a vacuum oven at 100-150°C and dried for 3-6 hours to obtain a finished modified spherical silicon micropowder.