CN112194877B - Quartz glass filler, resin composition and copper-clad plate - Google Patents
Quartz glass filler, resin composition and copper-clad plate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a quartz glass filler, wherein the mass content of silicon dioxide in the quartz glass filler is more than or equal to 99.5%, the mass content of aluminum oxide is less than or equal to 0.2%, the mass content of water is less than or equal to 0.0005%, the mass content of sodium oxide is less than 0.01%, the mass content of potassium oxide is less than 0.01%, the mass content of lithium oxide is less than 0.01%, the mass content of calcium oxide is less than 0.01%, the mass content of magnesium oxide is less than 0.01%, the mass content of barium oxide is less than 0.01%, the mass content of strontium oxide is less than 0.01%, the mass content of ferric oxide is less than 0.01%, the mass content of titanium dioxide is less than 0.01%, the dielectric constant of the quartz glass filler is 3.5-3.8, the dielectric loss is 0.0001-0.001, and the hydrophobicity is more than or equal to 24 hours.
Description
The invention is a divisional application with application date of 2017, 9 and 22, application number of 2017108646472, and name of quartz glass filler, resin composition and copper-clad plate.
Technical Field
The invention belongs to the field of copper-clad plates, and particularly relates to a quartz glass filler, a resin composition and a copper-clad plate.
Background
The copper-clad plate is a plate-shaped material which is prepared by impregnating insulating paper, glass fiber cloth or other fiber materials with resin, coating copper foil on one surface or two surfaces and carrying out hot pressing, and is a basic material of a PCB.
The quartz glass (the mass content of silicon dioxide is 98.5-99.7%, the mass content of aluminum oxide is 0.1-0.3%, the mass content of water is 0.1-0.3%, the mass content of sodium oxide is 0.05-0.1%, the mass content of potassium oxide is 0.05-0.1%, the mass content of lithium oxide is 0.05-0.1%, the mass content of calcium oxide is 0.05-0.1%, the mass content of magnesium oxide is 0.05-0.1%, the mass content of barium oxide is 0.05-0.1%, the mass content of strontium oxide is 0.05-0.1%, the mass content of ferric oxide is 0.05-0.2%, the mass content of titanium dioxide is 0.05-0.1%), the dielectric constant is more than 3.8, the dielectric loss is more than 0.001, and is the material with the lowest dielectric constant and dielectric loss in the current easily obtained fillers, is used in the copper-clad laminate, has the smallest influence on the dielectric performance, and can replace high-cost low-dielectric-constant copper-clad laminate and low-dielectric-medium resin with the lowest loss, therefore, a great amount of quartz glass powder is used as a filler in the copper clad laminate with low dielectric constant and low dielectric loss. With the improvement of the requirements of the copper-clad plate on dielectric constant and dielectric loss (dielectric constant is less than 3.8, and dielectric loss is less than 0.001), the current quartz glass can not meet the requirements of the copper-clad plate. The main reasons that the current quartz glass powder cannot meet the requirements of copper-clad plates on higher dielectric constant and dielectric loss are as follows: 1. the quartz glass structure has broken bonds among elements, so that a plurality of small gap structures are formed, the silicon-oxygen structure is changed into a silicon-oxygen structure due to broken bonds, the silicon-oxygen structure is easy to adsorb water in the atmosphere to form hydroxyl (the hydroxyl belongs to a mode of existence of water, and the lower the water content is, the lower the hydroxyl content is), and the gap structures are easy to adsorb the water in the atmosphere due to capillary action, so that the hydroxyl content of the quartz glass is higher; 2. if the quartz glass contains lithium, sodium and potassium elements or calcium, magnesium, barium and strontium elements or iron and titanium elements, the elements exist in the quartz glass in an ionic form, the ions are easy to hydrate, and the adsorbed water also exists in a hydroxyl form, so that the higher content of the elements is another reason for the high hydroxyl content of the quartz glass, and the elements are easy to polarize, so that the dielectric constant and the dielectric loss of the material are increased. The quartz glass powder has high hydrophilicity due to high hydroxyl content, so that the quartz glass powder is not beneficial to dispersion in the polymer resin and is easy to agglomerate; in addition, hydroxyl is a polar group, and easy polarization causes high dielectric constant and dielectric loss of the material. 3. Quartz glass, when it is not transparent, does not form a complete glass state, and other crystal forms of quartz or impurities exist in the material, while the dielectric constant and dielectric loss of the non-glass state quartz glass are high; meanwhile, impurities in the material are also metal ions, which can cause the dielectric constant and dielectric loss of the material to increase. 4. The high water absorption of the material can cause the material to easily absorb water (the dielectric constant is approximately equal to 80) in the storage process, so that the dielectric constant of the material is increased, and the performance of the copper-clad plate is deteriorated.
CN102503115B discloses a production method of low-hydroxyl quartz glass fibers, wherein quartz glass rods with the diameter of 15-40 mm are fed into a vacuum dehydroxylation furnace, the vacuum degree of the vacuum dehydroxylation furnace is controlled within 10Mpa, then the temperature is raised to 1000-1100 ℃, and the constant temperature is maintained for 0.5-2 hours. Because the quartz glass is a high-viscosity supercooled liquid, hydroxyl groups among quartz glass lattices cannot be discharged in the temperature range, and meanwhile, the time is short and the hydroxyl groups cannot be discharged well within 0.5-2 hours, the method is found out to be incapable of achieving the effect that the hydroxyl groups can be controlled to be about 5ppm by using the method through practical verification, the quartz glass rod is a solidified whole, the hydroxyl groups are difficult to remove, the hydroxyl groups in the lattices are difficult to remove, and because the hydroxyl group removal is a reversible process, if the material for removing the hydroxyl groups is stored in the air, the material for removing the hydroxyl groups can absorb moisture in the air and regenerate the hydroxyl groups, the hydroxyl groups can be generated after the hydroxyl groups are removed by using the method, and the hydroxyl groups in the quartz glass rod cannot be removed and can be removed only by crushing the material into small particles.
CN106430912A discloses a preparation method of low-hydroxyl quartz glass andquartz glass, which is a first loose silica body prepared by chemical vapor deposition of a silicon-containing raw material, wherein the first loose silica body has pores and hydroxyl groups; introducing dehydroxylation airflow into the first silicon dioxide loose body, and obtaining a second silicon dioxide loose body after dehydroxylation airflow dehydroxylates the first silicon dioxide loose body at the dehydroxylation temperature; and sintering the second silicon dioxide loose body at the sintering temperature, and cooling to obtain a quartz glass finished product. In the invention, the hydroxyl groups in the crystal lattice can not be removed by the method that the dehydroxylation gas flow reacts with the hydroxyl groups in the surface of the quartz glass. The dehydroxylating gas stream is defined to include a dehydroxylating gas comprising chlorine Cl2SOCl, sulfur oxychloride2At least one of (1). By using the dehydroxylation gas, chlorine ions are contained on the surface of the quartz glass, and the two gases are toxic gases and are extremely harmful to the environment, while the chlorine ions can increase the dielectric constant and dielectric loss of the material, and the dielectric constant and dielectric loss of the quartz glass with the chlorine ions on the surface are higher than those of the quartz glass with the same amount of hydroxyl groups. In the invention, the silicon-containing raw material is limited to comprise silicon tetrachloride, monosilane, disilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, decatetramethylcyclohexasiloxane, hexadecamethyloctasiloxane, octadecylcyclononasiloxane or icosylcyclododecasiloxane. The high-purity quartz glass prepared by using the materials has the disadvantages of high cost and extremely low yield, and the by-products produced either pollute the environment or increase the carbon emission. The invention limits the combustion flame to be formed by mutually combusting at least one of hydrogen, methane and acetylene as fuel gas and oxygen or air as combustion-supporting gas. In fact, these fuel gases generate hydroxyl groups with the silica structure of the silica glass during combustion, and therefore the obtained material still contains a large amount of hydroxyl groups.
Disclosure of Invention
The invention aims to provide a quartz glass filler with low hydroxyl content, low dielectric constant (3.5-3.8) and low dielectric loss (0.0001-0.001), a preparation method thereof and application thereof in a copper-clad plate.
In order to solve the technical problems, the invention adopts the following technical scheme:
an object of the present invention is to provide a silica glass filler, wherein the silica glass filler has a silica content of 99.5% by mass or more, an alumina content of 0.2% by mass or less, a water content of 0.0005% by mass or less, a sodium oxide content of less than 0.01% by mass, a potassium oxide content of less than 0.01% by mass, a lithium oxide content of less than 0.01% by mass, a calcium oxide content of less than 0.01% by mass, a magnesium oxide content of less than 0.01% by mass, a barium oxide content of less than 0.01% by mass, a strontium oxide content of less than 0.01% by mass, an iron oxide content of less than 0.01% by mass, and a titanium dioxide content of less than 0.01% by mass, and the silica glass filler has a dielectric constant of 3.5 to 3.8, a dielectric loss of 0.0001 to 0.001, and a hydrophobicity of 24 hours or more.
Preferably, the quartz glass filler has a dielectric constant of 3.5 to 3.7 and a dielectric loss of 0.0001 to 0.0008.
Preferably, the quartz glass filler has a water absorption of < 5%, more preferably < 4.5%.
According to one embodiment, the quartz glass filler is obtained by firstly processing a quartz glass raw material into primary quartz glass powder, then performing vacuum heating treatment on the primary quartz glass powder, and finally performing surface modification treatment; the mass content of silicon dioxide in the primary quartz glass powder is more than or equal to 99.5%, the mass content of aluminum oxide is less than or equal to 0.2%, the mass content of water is less than or equal to 2%, the mass content of sodium oxide is less than 0.01%, the mass content of potassium oxide is less than 0.01%, the mass content of lithium oxide is less than 0.01%, the mass content of calcium oxide is less than 0.01%, the mass content of magnesium oxide is less than 0.01%, the mass content of barium oxide is less than 0.01%, the mass content of strontium oxide is less than 0.01%, the mass content of ferric oxide is less than 0.01%, the mass content of titanium dioxide is less than 0.01%, and the maximum particle size of the primary quartz glass powder is less than or equal to 15 microns.
Preferably, the mass content of the silicon dioxide in the quartz glass raw material is more than or equal to 99.7Percent, mass content of aluminium oxide less than or equal to 0.2 percent and H2The mass content of O is less than or equal to 0.2 percent, the mass content of sodium oxide is less than 0.01 percent, the mass content of potassium oxide is less than 0.01 percent, the mass content of lithium oxide is less than 0.01 percent, the mass content of calcium oxide is less than 0.01 percent, the mass content of magnesium oxide is less than 0.01 percent, the mass content of barium oxide is less than 0.01 percent, the mass content of strontium oxide is less than 0.01 percent, the mass content of ferric oxide is less than 0.01 percent, and the mass content of titanium dioxide is less than 0.01 percent.
In the invention, the quartz glass raw material is purchased by lithopone ore product trade limited in Lingshu county, and then is automatically melted into quartz glass and ground into quartz glass powder by my company.
According to a preferred embodiment, the method for processing the primary quartz glass powder from the quartz glass raw material comprises the following steps: melting the quartz glass raw material at 1700-1950 ℃ for 8-16 hours to form quartz glass melt, cooling the quartz glass melt, crushing, selecting transparent quartz glass particles, and grinding the quartz glass particles to powder with the maximum particle size of less than or equal to 15 microns, namely the primary quartz glass powder.
According to a further preferable mode, the melting temperature is 1800-1900 ℃, and the melting time is 10-14 hours.
According to a further preferred mode, the primary quartz glass powder has a maximum particle size of 8 μm or less.
According to a further preferred mode, the grinding treatment is carried out by one of a ball mill, a jet mill or a vibration mill.
According to a further preferable mode, after cooling the quartz glass melt, the quartz glass melt is firstly crushed into large-particle materials of 4-5 cm, then colorless and transparent quartz glass blocks without bubbles and impurities are manually selected, then the quartz glass blocks are crushed into small-particle materials of 1-2 mm, and then the quartz glass particles are selected by a high-gradient magnetic separator. According to one embodiment, the method for vacuum heat treatment of the primary quartz glass powder comprises the following steps: using a reactor having a first chamber and a second chamber which are relatively independent of each other, soThe reactor has heating and vacuum pumping functions, and the primary quartz glass powder is first placed in the first chamber under the vacuum degree of 10-1～10-5mpa, heat preservation for 5-10 hours at 1400-1600 ℃, then moving to the second chamber, and keeping the vacuum degree at 10 DEG C-1～10-5mpa, cooling to 25-30 ℃, and transferring the materials into a vacuumized ton bag with an inner membrane.
Preferably, the reactor is a roller kiln.
Preferably: the temperature reduction range is 3 ℃/min to 5 ℃/min.
According to the invention, the quartz glass powder is adopted, so that a large number of gaps are exposed, hydroxyl groups in crystal lattices are easy to be removed at a high temperature, and the material is cooled and packaged at a vacuum state, so that the material can not absorb moisture to generate hydroxyl groups.
According to a further preferred mode, the primary quartz glass powder is filled into a sagger made of quartz glass, and then the sagger is placed into the first chamber for heat preservation and the second chamber for temperature reduction.
According to a preferred mode, the surface modification treatment is carried out using a titanate coupling agent having the following structural formula:
Further preferably, the titanate coupling agent has the following structural formula:
further preferably, the feeding amount of the titanate coupling agent is 0.5-4% of the mass of the primary quartz glass powder.
More preferably, the feeding amount of the titanate coupling agent is 1-3.5% of the mass of the primary quartz glass powder.
Most preferably, the feeding amount of the titanate coupling agent is 2-3% of the mass of the primary quartz glass powder.
In the invention, the synthetic route of the titanate coupling agent is as follows:
1、
2、
3、
4、
5、
6、
the synthesis method of the titanate coupling agent comprises the following steps:
step (1), adding TiCl into a reaction kettle4And C2H5OH, reacting at 60-120 ℃ for 3 to8 hours to give C2H5OTiCl3。
Step (2), adding the C into a reaction kettle2H5OTiCl3And C6H4OHCL, reacting at 60-120 ℃ under 4-6 atmospheric pressures to obtain C2H5OTi(OC6H4Cl)3。
Step (3) adding ClCH into a reaction kettle2CH2CH3And Mg, in the presence of ether, reacting at 50-60 ℃ to obtain ClMgCH2CH2CH3。
Step (4), adding the C into a reaction kettle2H5OTi(OC6H4Cl)3And said ClMgCH2CH2CH3In the presence of diethyl ether to give C2H5OTi(OC6H4 CH2CH2CH3)3。
Step (5), adding the C into a reaction kettle2H5OTi(OC6H4 CH2CH2CH3)3Introduction of Cl2Then preparing C by illumination2H5OTi(OC6H4 CH2CH2CH2Cl)3。
Step (6), adding the C into a reaction kettle2H5OTi(OC6H4 CH2CH2CH2Cl)3And
and reacting for 5-8 hours at 60-120 ℃ under 2-4 atmospheric pressures to obtain the titanate coupling agent.
Preferably, said TiCl4And said C2H5The feeding molar ratio of OH is 1-2: 1.
preferably, said C2H5OTiCl3And said C6H4The feeding molar ratio of OHCl is 1: 3 to 3.5.
Preferably, said ClCH2CH2CH3And the feeding molar ratio of Mg is 1: 1 to 1.5.
Preferably, said C2H5OTi(OC6H4 CH2CH2CH3)3And said Cl2The feeding molar ratio of (A) to (B) is 2-3: 1.
preferably, the intensity of the illumination is 40-60 cd.
Preferably, said C2H5OTi(OC6H4 CH2CH2CH2Cl)3And said
The feeding molar ratio of (1): 4 to 5.
Another object of the present invention is to provide a method for preparing the above quartz glass filler, comprising the steps of:
melting a quartz glass raw material at 1700-1950 ℃ for 8-16 hours to form a quartz glass melt, cooling the quartz glass melt, crushing, selecting transparent quartz glass particles, and grinding the quartz glass particles to powder with the maximum particle size of less than or equal to 15 microns, namely the primary quartz glass powder.
Step (2), adopting a reactor with a first chamber and a second chamber which are relatively independent, wherein the reactor has the functions of heating and vacuumizing, and the primary quartz glass powder is firstly placed in the first chamber under the vacuum degree of 10-1～10-5mpa, heat preservation for 5-10 hours at 1400-1600 ℃, then moving to the second chamber, and keeping the vacuum degree at 10 DEG C-1～10-5mpa, cooling to 25-30 ℃, and transferring the materials into a vacuumized ton bag with an inner membrane.
Further preferably: the reactor is a roller kiln.
Further preferably: the temperature reduction range is 3 ℃/min to 5 ℃/min.
And (3) carrying out surface modification treatment on the primary quartz glass powder treated in the step (2) by using a coupling agent to obtain the quartz glass filler.
Further preferably, the feeding amount of the coupling agent is 0.5-4% of the mass of the primary quartz glass powder.
More preferably, the feeding amount of the coupling agent is 1-3.5% of the mass of the primary quartz glass powder.
Most preferably, the feeding amount of the coupling agent is 2-3% of the mass of the primary quartz glass powder.
Further preferably, the coupling agent and the primary quartz glass powder treated in the step (2) are added into a high-speed mixer, mixed for 8-12 minutes at 2000-4000 rpm and at 110-150 ℃, and then air draft is started to ensure that the vacuum degree of the high-speed mixer is 10-1～10-5mpa, finishing the surface modification treatment.
According to a preferred mode, the maximum grain size of the primary quartz glass powder is less than or equal to 8 m.
According to a preferred mode, the grinding treatment is performed by one of a ball mill, a jet mill or a vibration mill.
According to a preferable mode, after being cooled, the quartz glass melt is firstly crushed into large-particle materials of 4-5 cm, then colorless and transparent quartz glass blocks without bubbles and impurities are manually selected, then the quartz glass blocks are crushed into small-particle materials of 1-2 mm, and then the quartz glass particles are selected through a color selector and a high-gradient magnetic separator.
According to a preferred mode, the primary silica glass frit is filled in a sagger made of silica glass, and then the sagger is put into the first chamber for heat preservation.
According to a preferred mode, the coupling agent is a titanate coupling agent.
The third purpose of the invention is to provide the application of the quartz glass filler in preparing the copper-clad plate.
It is a fourth object of the present invention to provide a resin composition comprising a filler, said filler being all or part of said silica glass filler.
The fifth purpose of the invention is to provide a copper-clad plate, which comprises a resin composition, wherein the resin composition comprises a filler, and the whole or part of the filler is the quartz glass filler.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, a large amount of internal gaps of the crystal are exposed by adopting the ground primary quartz glass powder, and hydroxyl in the crystal lattice is easy to be removed at a high temperature, so that the dielectric constant and the dielectric loss are reduced due to the reduction of the hydroxyl; the invention further shields the silicon oxygen group through the coupling effect of the self-synthesized titanate coupling agent with high hydrophobicity and high dispersibility, so that the silicon oxygen group can not absorb moisture in the air again to generate hydroxyl, and the manufactured product is stored in vacuum, so that the material can not absorb moisture, and the improvement of dielectric constant and dielectric loss is restrained.
Because the quartz glass filler has low hydroxyl content and is treated by the titanate coupling agent with high hydrophobicity and high dispersion, the quartz glass filler is easy to be mixed with high molecular resin, the dielectric constant and the dielectric loss are reduced, and compared with the prior quartz glass powder used as the filler copper-clad plate, the quartz glass filler has lower dielectric constant and lower dielectric loss, the water absorption of the material is lower, and the prepared material cannot cause the dielectric property deterioration due to moisture absorption.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. Not indicated, "%" is mass percent. The raw materials in the invention are all available in the market.
The test method comprises the following steps:
hydrophobicity: a10 g sample is taken and placed in a beaker filled with 500ml pure water, the material is observed to sink, and when the material does not sink for 24 hours, the material is considered to have good hydrophobicity.
Dielectric constant and dielectric loss test: 25% of filler, 15% of polyphenylene ether resin (Asahi Kasei, 500H), 20% of bisphenol F type epoxy resin (Changchun chemical industry, BFE170), 20% of cyanate ester (bisphenol A type cyanate ester, Wuqiao resin factory in Yangzhou city, Jiangsu province), 10% of dicyandiamide (ISO, Zhengzhouzhi Zhi teleproducts Limited) and 10% of glass cloth (2116, Chongqing International composite) are prepared into prepregs with 60% of resin and 25% of filler, and then a network analyzer is used for testing the dielectric constant and the dielectric loss of the prepregs at 10 GHZ.
Hydroxyl group content: hydroxyl is a existence mode of moisture, and the change of the weight of the material before and after the test is carried out through high-temperature calcination of the material, namely the change condition of the hydroxyl is obtained.
Water absorption: the material was exposed to 85% relative humidity at 85 ℃ for 24h, dried to constant weight at 105 ℃ and the water absorption was compared to the ratio of water before and after exposure (post exposure/pre exposure) 100%.
Example 1 preparation of a quartz glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0004％,Li2O：0.0003％,CaO：0.0005％，MgO：0.0002％,BaO：0.0003％,SrO：0.0005％,Fe2O3：0.0006％,TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
This is a preferred example: the quartz glass filler prepared by the above method has a chemical composition of SiO2：99.68％，Al2O3：0.15％，H2O：0.00036％,Na2O：0.0005％，K2O：0.0003％,Li2O：0.0002％,CaO：0.0004％，MgO：0.0002％,BaO：0.0002％,SrO：0.0003％,Fe2O3：0.0007％,TiO2: 0.0006%, hydrophobicity: good, dielectric constant: 3.52, dielectric loss: 0.0003, water absorption rate of 4.2%, and in the preferred example, the oxide of alkali metal, alkaline earth metal and transition metal is small, and the hydroxyl content is small, the water absorption rate is low, and the dielectric constant and dielectric loss of the material are low by the optimal coupling agent treatment amount and the optimal processing technology treatment.
Comparative example 1 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0169％，K2O：0.0004％,Li2O：0.0003％,CaO：0.0005％，MgO：0.0002％,BaO：0.0003％,SrO：0.0005％,Fe2O3：0.0006％,TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00045％,Na2O：0.0153％，K2O：0.0003％,Li2O：0.0005％,CaO：0.0003％，MgO：0.0004％,BaO：0.0002％,SrO：0.0006％,Fe2O3：0.0003％,TiO2: 0.0004% of water repellentProperty: good, dielectric constant: 3.86, dielectric loss: 0.0025, water absorption: 9.25% of Na2The increase of the O content increases the hydroxyl content of the material, the water absorption of the material increases, and the dielectric constant and the dielectric loss become large.
Comparative example 2 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0005％，K2O：0.0172％,Li2O：0.0003％,CaO：0.0005％，MgO：0.0002％,BaO：0.0003％,SrO：0.0005％,Fe2O3：0.0006％,TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and then starting air draft to ensure that the temperature is highVacuum degree of the fast mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00045％,Na2O：0.0004％，K2O：0.0163％,Li2O：0.0003％,CaO：0.0004％，MgO：0.0001％,BaO：0.0002％,SrO：0.0005％,Fe2O3：0.0006％,TiO2: 0.0004%, hydrophobicity: good, dielectric constant: 3.84, dielectric loss: 0.0022, water absorption: 9.05%, K2The increase of the O content increases the hydroxyl content of the material, the water absorption of the material increases, and the dielectric constant and the dielectric loss become large.
Comparative example 3 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0193％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 ℃ for 7 hours, and then moving to the temperatureIn the second chamber, at a vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00043％,Na2O：0.0005％，K2O：0.0003％,Li2O：0.0178％,CaO：0.0004％，MgO：0.0001％,BaO：0.0002％,SrO：0.0005％,Fe2O3：0.0005％,TiO2: 0.0004%, hydrophobicity: good, dielectric constant: 3.82, dielectric loss: 0.0020, water absorption: 8.95% of Li2The increase of the O content increases the hydroxyl content of the material, the water absorption of the material increases, and the dielectric constant and the dielectric loss become large.
Comparative example 4 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0003％，CaO：0.0156％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00042％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0154％，MgO：0.0001％，BaO：0.0002％，SrO：0.0005％，Fe2O3：0.0005％，TiO2: 0.0004%, hydrophobicity: good, dielectric constant: 3.82, dielectric loss: 0.0020, water absorption: 8.70%, the content of CaO is increased, the content of hydroxyl groups in the material is increased, the water absorption of the material is increased, and the dielectric constant and the dielectric loss are increased.
Comparative example 5 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0193％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling by taking 3-5 ℃/min as a cooling range, and transferring the material into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃;
step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00042％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0006％，MgO：0.0181％，BaO：0.0002％，SrO：0.0005％，Fe2O3：0.0005％，TiO2: 0.0004% of water, sparseWater-based: good, dielectric constant: 3.80, dielectric loss: 0.0018, water absorption: 8.62%, the content of MgO increased, the content of hydroxyl group increased, the water absorption increased, and the dielectric constant and dielectric loss increased.
Comparative example 6 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0143％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to enable the primary quartz glass powder to be subjected to air draftThe vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00042％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0006％，MgO：0.0001％，BaO：0.0142％，SrO：0.0005％，Fe2O3：0.0005％，TiO2: 0.0004%, hydrophobicity: good, dielectric constant: 3.88, dielectric loss: 0.0029, water absorption: 8.52%, the BaO content increases, the hydroxyl content of the material increases, the water absorption of the material increases, and the dielectric constant and the dielectric loss become large.
Comparative example 7 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0175％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, keeping the temperature at 1450 ℃ for 7 hours, and then moving to the placeIn the second chamber, the vacuum degree is 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00042％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0006％，MgO：0.0001％，BaO：0.0002％，SrO：0.0168％，Fe2O3：0.0005％，TiO2: 0.0004%, hydrophobicity: good, dielectric constant: 3.86, dielectric loss: 0.0025, water absorption: 8.60%, the SrO content is increased, the hydroxyl content of the material is increased, the water absorption of the material is increased, and the dielectric constant and the dielectric loss are increased.
Comparative example 8 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0162％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling by taking 3-5 ℃/min as a cooling range, and transferring the material into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃;
step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00042％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0006％，MgO：0.0001％，BaO：0.0002％，SrO：0.0006％，Fe2O3：0.0160％，TiO2: 0.0004%, hydrophobicity: good, dielectric constant: 3.83, dielectric loss: 0.0016, water absorption: 7.50% of Fe2O3The content is increased, the hydroxyl content of the material is increased, the water absorption of the material is increased, and the dielectric constant and the dielectric loss are increased.
Comparative example 9 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0005％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0185 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 2.5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.70％，Al2O3：0.16％，H2O：0.00042％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0006％，MgO：0.0001％，BaO：0.0002％，SrO：0.0006％，Fe2O3：0.0007％，TiO2: 0.0179%, hydrophobicity: good, dielectric constant: 3.87, dielectric loss: 0.0030, water absorption: 7.20% of TiO2The content is increased, the hydroxyl content of the material is increased, the water absorption of the material is increased, and the dielectric constant and the dielectric loss are increased.
Comparative example 10 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0004％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.68％，Al2O3：0.15％，H2O：0.00038％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0004％，MgO：0.0002％，BaO：0.0002％，SrO：0.0003％，Fe2O3：0.0007％，TiO2: 0.0006%, hydrophobicity: poor (sinking when put in water), dielectric constant: 3.76, dielectric loss: 0.0008, water absorption of 15.2 percent, no treatment by using a coupling agent, and high water absorption of the material.
Comparative example 11 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0004％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the degree of vacuum in the first chamber is 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, and then adding a titanate coupling agent, wherein the dosage of the titanate coupling agent is the dosage of the titanate coupling agent in the step (5)0.3% of the treated primary silica glass powder by weight, and then mixed at 3000rpm at 115 ℃ for 10 minutes, and then the draft was turned on so that the degree of vacuum of the high-speed mixer was 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.68％，Al2O3：0.15％，H2O：0.00038％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0004％，MgO：0.0002％，BaO：0.0002％，SrO：0.0003％，Fe2O3：0.0007％，TiO2: 0.0006%, hydrophobicity: difference (put in water, all sink after 20 minutes), dielectric constant: 3.76, dielectric loss: 0.0008 percent, water absorption of 13.8 percent, less treatment amount of a coupling agent and high water absorption of the material.
Comparative example 12 preparation of silica glass filler:
step (1) using a catalyst having SiO2：99.75％，Al2O3：0.12％，H2O：0.10％，Na2O：0.0006％，K2O：0.0004％，Li2O：0.0003％，CaO：0.0005％，MgO：0.0002％，BaO：0.0003％，SrO：0.0005％，Fe2O3：0.0006％，TiO2: 0.0005 percent of high-purity quartz glass raw material is melted in an electric arc furnace for 12 hours at 1850 ℃ to form uniform quartz glass melt.
And (2) after the quartz glass melt is cooled, pouring out the molten ingot, crushing the molten ingot into large-particle materials of 4cm, and manually selecting colorless and transparent quartz glass blocks without bubbles and impurities.
And (3) finely crushing the quartz glass blocks into small granular materials with the particle size of 1mm, and selecting transparent quartz glass granules by a high-gradient magnetic separator.
And (4) performing ball milling on the material processed in the step (3) until the maximum particle size of the material is 7.5 microns to obtain primary quartz glass powder.
Step (5), the ground primary quartz glass powder is filled into a sagger made of quartz glass, and the sagger is arranged in the first chamberIn a vacuum degree of 10-3mpa, temperature 1450 deg.C for 7 hr, moving to the second chamber, and vacuum degree of 10-3mpa, cooling with the cooling range of 3-5 ℃/min, and transferring the materials into a vacuumized ton bag with an inner film when the temperature is cooled to 28 ℃.
Step (6), conveying the primary quartz glass powder treated in the step (5) to a high-speed mixer, adding a titanate coupling agent, wherein the use amount of the titanate coupling agent is 5% of the weight of the primary quartz glass powder treated in the step (5), mixing for 10 minutes at 3000rpm and 115 ℃, and starting air draft to ensure that the vacuum degree of the high-speed mixer is 10-3mpa, and obtaining the quartz glass powder filler.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.68％，Al2O3：0.15％，H2O：0.00038％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0004％，MgO：0.0002％，BaO：0.0002％，SrO：0.0003％，Fe2O3：0.0007％，TiO2: 0.0006%, hydrophobicity: difference (put in water, all sink after 20 minutes), dielectric constant: 3.76, dielectric loss: 0.008, water absorption of 4.0 percent, high treatment capacity of the coupling agent, low water absorption of the material, but increased dielectric loss mainly caused by slow dipole moment polarization in the coupling agent.
Comparative example 13 preparation of silica glass filler:
step (1), according to example 1, but melting at 1680 ℃ for 12 h.
And (4) conclusion: the melting temperature is low, the material can not be melted, and the quartz glass can not be formed.
Comparative example 14 preparation of silica glass filler:
step (1), according to example 1, but melting was carried out at 1850 ℃ for 7 hours.
And (4) conclusion: short melting time, material melting, inability to form transparent quartz glass, hydrophobicity: good, dielectric constant: 3.92, dielectric loss: 0.0020, water absorption: 4.6 percent, is not transparent quartz glass, and has high dielectric constant and high dielectric loss.
Comparative example 15 preparation of silica glass filler:
step (1), according to example 1, but the melting was carried out for 8h at 2000 ℃.
And (4) conclusion: the melting temperature is too high, the melting time is short, the material can be melted, but a large amount of quartz vapor is formed to block an exhaust pipeline.
Comparative example 16 preparation of silica glass filler:
step (1) according to the embodiment 1, the temperature is reduced at the vacuum degree of 1mpa and the temperature reduction range of 3-5 ℃/min, and when the temperature is cooled to 28 ℃, the material is transferred to a vacuumized ton bag with an inner film.
The quartz glass filler prepared by the above method has a chemical composition of SiO2：99.68％，Al2O3：0.15％，H2O：0.00106％，Na2O：0.0005％，K2O：0.0003％，Li2O：0.0002％，CaO：0.0004％，MgO：0.0002％，BaO：0.0002％，SrO：0.0003％，Fe2O3：0.0007％，TiO2: 0.0006%, hydrophobicity: good, dielectric constant: 3.76, dielectric loss: 0.0009, water absorption of 5.3 percent, insufficient vacuum degree, insufficient removal of hydroxyl groups of the material, high dielectric constant and high dielectric loss.
Comparative example 17, commercial quartz glass powder (525ari, Silico mining):
the chemical composition of the step (1) is as follows: SiO 22：98.68％，Al2O3：0.13％，H2O：0.11％，Na2O：0.058％，K2O：0.067％，Li2O：0.062％，CaO：0.059％，MgO：0.071％，BaO：0.058％，SrO：0.053％，Fe2O3：0.052％，TiO2：0.073％。
Hydrophobicity: difference (put in water, all sink after 5 minutes), dielectric constant: 3.92, dielectric loss: 0.0032, water absorption of 15.6 percent, high water absorption of the material, high dielectric constant and large dielectric loss.
Example 2 preparation of coupling agent:
1. 80mol of TiCl are added into a clean reaction kettle4(titanium tetrachloride, Chrysanthemum morifolium chemical Co., Ltd.) and 50mol of C2H5OH (DY-01233, east China chemical Co., Ltd., Jiangsu province) at 115 ℃ for 5 hours under one atmosphere, and then 50mol of C was obtained by rectification2H5OTiCl3。
2. 50mol of C from 1 are reacted in a clean reactor2H5OTiCl3And 150mol of C6H4OHCL (BT/5218-557 Enoka, Luke chemical Co., Ltd.) prepared 50mol of C at 105 ℃ under 5 atm2H5OTi(OC6H4Cl)3。
3. 50mol of ClCH are put into a clean reaction kettle2CH2CH3And 60mol of Mg (FM1, Shandong Fuwang chemical Co., Ltd.) in 200mol of Et2Preparing 50mol of ClMgCH in O (diethyl ether, Suzhou chemical industry) solvent at 55 ℃ and 1 atmospheric pressure2CH2CH3。
4. Into the reaction vessel of the above 3, 50mol of C obtained in the above 2 was charged2H5OTi(OC6H4Cl)3By rectification to obtain 50mol C2H5OTi(OC6H4 CH2CH2CH3)3。
5. 50mol C obtained from the above 42H5OTi(OC6H4 CH2CH2CH3)3Putting the mixture into a clean reaction kettle, and introducing 20mol of Cl2(6061AL, Heng shui city peach city Xin Hai chemical instruments Co., Ltd.), and then the 20mol C is prepared by illumination (light intensity 50cd) and rectification2H5OTi(OC6H4 CH2CH2CH2Cl)3。
6. Prepared by the above 5
(styrene, Zhengzhou Yuqiang)Import and export trade Limited company) into a clean reaction kettle, reacting for 6 hours at 112 ℃ under 3 atmospheric pressures, and rectifying to obtain 20mol
Claims (10)
1. A silica glass filler characterized by: the quartz glass filler contains more than or equal to 99.5% of silicon dioxide by mass, less than or equal to 0.2% of aluminum oxide by mass, less than or equal to 0.0005% of water by mass, less than 0.01% of sodium oxide by mass, less than 0.01% of potassium oxide by mass, less than 0.01% of lithium oxide by mass, less than 0.01% of calcium oxide by mass, less than 0.01% of magnesium oxide by mass, less than 0.01% of barium oxide by mass, less than 0.01% of strontium oxide by mass, less than 0.01% of ferric oxide by mass, less than 0.01% of titanium dioxide by mass, and has a dielectric constant of 3.5-3.8, a dielectric loss of 0.0001-0.001 and hydrophobicity of more than or equal to 24 hours;
the quartz glass filler is obtained by processing a quartz glass raw material into primary quartz glass powder, then carrying out vacuum heating treatment on the primary quartz glass powder, and finally carrying out surface modification treatment by adopting a titanate coupling agent;
the titanate coupling agent has the following structural formula:
2. the quartz glass filler according to claim 1, characterized in that: the mass content of silicon dioxide in the quartz glass raw material is more than or equal to 99.7 percent, the mass content of aluminum oxide is less than or equal to 0.2 percent, and H2The mass content of O is less than or equal to 0.2 percent, the mass content of sodium oxide is less than 0.01 percent, the mass content of potassium oxide is less than 0.01 percent, the mass content of lithium oxide is less than 0.01 percent, and the mass content of calcium oxide is less than0.01 percent, less than 0.01 percent of magnesium oxide, less than 0.01 percent of barium oxide, less than 0.01 percent of strontium oxide, less than 0.01 percent of ferric oxide and less than 0.01 percent of titanium dioxide;
the mass content of silicon dioxide in the primary quartz glass powder is more than or equal to 99.5 percent, the mass content of aluminum oxide is less than or equal to 0.2 percent, the mass content of water is less than or equal to 0.2 percent, the mass content of sodium oxide is less than 0.01 percent, the mass content of potassium oxide is less than 0.01 percent, the mass content of lithium oxide is less than 0.01 percent, the mass content of calcium oxide is less than 0.01 percent, the mass content of magnesium oxide is less than 0.01 percent, the mass content of barium oxide is less than 0.01 percent, the mass content of strontium oxide is less than 0.01 percent, the mass content of ferric oxide is less than 0.01 percent, and the mass content of titanium dioxide is less than 0.01 percent;
the maximum particle size of the primary quartz glass powder is less than or equal to 15 microns.
3. The quartz glass filler according to claim 1, characterized in that: the feeding amount of the titanate coupling agent is 1-4% of the mass of the primary quartz glass powder.
4. The quartz glass filler according to claim 3, characterized in that: the feeding amount of the titanate coupling agent is 1-3.5% of the mass of the primary quartz glass powder.
5. The quartz glass filler according to claim 1 or 2, characterized in that: the method for processing the primary quartz glass powder from the quartz glass raw material comprises the following steps: melting the quartz glass raw material at 1700-1950 ℃ for 8-16 hours to form quartz glass melt, cooling the quartz glass melt, crushing, selecting transparent quartz glass particles, and grinding the quartz glass particles to powder with the maximum particle size of less than or equal to 15 microns, namely the primary quartz glass powder.
6. The quartz glass filler according to claim 5, characterized in that: after cooling the quartz glass melt, firstly crushing the quartz glass melt into large-particle materials of 4-5 cm, then manually selecting colorless and transparent quartz glass blocks, crushing the quartz glass blocks into small-particle materials of 1-2 mm, and then selecting the quartz glass particles through a high-gradient magnetic separator.
7. The quartz glass filler according to claim 1 or 2, characterized in that: the method for carrying out vacuum heating treatment on the primary quartz glass powder comprises the following steps: adopting a reactor with a first chamber and a second chamber which are relatively independent, wherein the reactor has the functions of heating and vacuumizing, the primary quartz glass powder is firstly placed in the first chamber, and the vacuum degree is 10-1～10-5Heat preservation is carried out for 5-10 hours under the conditions of MPa and the temperature of 1400-1600 ℃, and then the vacuum chamber is moved into the second chamber with the vacuum degree of 10-1～10-5And (5) when the temperature is reduced to 25-30 ℃ under the MPa, transferring the material into a vacuumized ton bag with an inner film.
8. A method for producing a silica glass filler according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
melting a quartz glass raw material at 1700-1950 ℃ for 8-16 hours to form a quartz glass melt, cooling the quartz glass melt, crushing, selecting transparent quartz glass particles, and grinding the quartz glass particles to obtain powder with the maximum particle size of less than or equal to 15 microns, namely the primary quartz glass powder;
step (2), adopting a reactor with a first chamber and a second chamber which are relatively independent, wherein the reactor has the functions of heating and vacuumizing, and the primary quartz glass powder is firstly placed in the first chamber under the vacuum degree of 10-1～10- 5Heat preservation is carried out for 5-10 hours under the conditions of MPa and the temperature of 1400-1600 ℃, and then the vacuum chamber is moved into the second chamber with the vacuum degree of 10-1～10-5Cooling to 25-30 ℃ under MPa, and transferring the material into a vacuumized ton bag with an inner film;
and (3) carrying out surface modification treatment on the primary quartz glass powder treated in the step (2) by using a coupling agent to obtain the quartz glass filler.
9. A resin composition comprising a filler, characterized in that: the filler is entirely or partially the silica glass filler according to any one of claims 1 to 7.
10. A copper-clad plate is characterized in that: comprising the quartz glass filler of any of claims 1 to 7.
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| CN101215074B (en) * | 2008-01-17 | 2010-12-15 | 徐传龙 | Production technique for drawing crystal powder used for low-hydroxyl quartz glass soft pipe and pipe drawing method |
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