CN114133699A - Housing containing nano inorganic mullite alumina hollow micro-beads for 5G communication - Google Patents

Housing containing nano inorganic mullite alumina hollow micro-beads for 5G communication Download PDF

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CN114133699A
CN114133699A CN202111264475.8A CN202111264475A CN114133699A CN 114133699 A CN114133699 A CN 114133699A CN 202111264475 A CN202111264475 A CN 202111264475A CN 114133699 A CN114133699 A CN 114133699A
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nano inorganic
epoxy resin
alumina hollow
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CN114133699B (en
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熊云峰
陈汉明
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Aneng Guangzhou Science And Technology Co ltd
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Aneng Guangzhou Science And Technology Co ltd
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Abstract

The invention belongs to the technical field of outer covers for 5G communication, and particularly discloses an outer cover for 5G communication containing nano inorganic mullite alumina hollow microspheres, which is prepared from the following raw materials in parts by weight: 1-3 parts of an anti-aging agent, 1-3 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 3-15 parts of a linear phenol-formaldehyde resin, 5-25 parts of a bisphenol A novolac epoxy resin, 10-20 parts of a modified glass fiber, 10-30 parts of an o-cresol novolac epoxy resin, 10-35 parts of a phosphorus-containing and nitrogen-containing novolac epoxy resin, 15-35 parts of an auxiliary agent, 10-45 parts of a phenol type novolac epoxy resin and 15-80 parts of nano inorganic mullite alumina hollow microspheres. The housing for 5G communication containing the nano inorganic mullite-alumina hollow microspheres has good dielectric constant, dielectric loss and strength.

Description

Housing containing nano inorganic mullite alumina hollow micro-beads for 5G communication
Technical Field
The invention relates to the technical field of outer covers for 5G communication, in particular to an outer cover for 5G communication containing nano inorganic mullite-alumina hollow microspheres.
Background
From the large emergence of big and brother in 1973, the emergence of signals of 1G to the evolution of 2G, 3G, 4G and now 5G, the evolution of each generation brings about the speed increase and the massive increase of transmission contents; in brief, 5G is a fifth generation communication technology, and is mainly characterized by millimeter-scale wavelength, ultra-wideband, ultra-high speed, and ultra-low time delay. 1G realizes analog voice communication, and the mobile phone can only make a call without a screen; 2G realizes the digitization of voice communication, and the functional machine has a small screen and can send short messages; 3G realizes multimedia communication of pictures and the like besides voice, and pictures can be seen when the screen is enlarged; 4G realizes local high-speed internet access, and a large-screen intelligent machine can watch short videos, but has good urban signals and poor signals for the old. 1G ~4G all aim at more convenient and fast's communication between the people, and 5G will realize at any time, with the place, everything interconnection, let the mankind dare to expect to participate in through the direct broadcast mode no time difference with everything on the earth in step, need realize 5G completely, its requirement to the signal will get into brand-new notion, and as carrying and realizing 5G signal carrier, need accomplish to be as far as possible to be close to with the direction of signal zero loss, and the appearance of hollow microballon and regard hollow microballon as the filling medium preparation finished product, realize the high speed of signal and low-loss probably.
Patent CN112724515A discloses a beautifying antenna housing substrate and a preparation method thereof, which comprises the following components in parts by weight: 55-70 parts of polypropylene resin, 5-15 parts of modified hollow glass beads, 5-15 parts of modified glass fibers, 10-15 parts of toughening agent, 3-5 parts of compatilizer, 0.3-0.6 part of antioxidant, 0.3-0.6 part of lubricant and 0.1-0.3 part of anti-ultraviolet agent. According to the description in paragraph 0071, the prepared beautifying radome material has the dielectric constant of 2.258, the dielectric loss of 0.00152 and the notch impact strength of 18.42 MPa, and the dielectric constant and the dielectric loss are still to be reduced and the strength is still to be improved.
Disclosure of Invention
The invention provides a housing for 5G communication containing nano inorganic mullite alumina hollow microspheres, which has good dielectric constant, dielectric loss and strength.
The invention adopts the following technical scheme for solving the technical problems:
the outer cover containing the nano inorganic mullite alumina hollow microspheres for 5G communication is prepared from the following raw materials in parts by weight: 1-3 parts of an anti-aging agent, 1-3 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 3-15 parts of a linear phenol-formaldehyde resin, 5-25 parts of a bisphenol A novolac epoxy resin, 10-20 parts of a modified glass fiber, 10-30 parts of an o-cresol novolac epoxy resin, 10-35 parts of a phosphorus-containing and nitrogen-containing novolac epoxy resin, 15-35 parts of an auxiliary agent, 10-45 parts of a phenol type novolac epoxy resin and 15-80 parts of nano inorganic mullite alumina hollow microspheres.
As a preferable scheme, the 5G communication housing containing the nano inorganic mullite alumina hollow microspheres is prepared from the following raw materials in parts by weight: 1-2 parts of an anti-aging agent, 1-2.5 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 3-10 parts of linear phenol-formaldehyde resin, 5-20 parts of bisphenol A novolac epoxy resin, 10-18 parts of modified glass fiber, 10-20 parts of o-cresol-formaldehyde epoxy resin, 10-30 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin, 15-30 parts of an auxiliary agent, 10-40 parts of phenol type novolac epoxy resin and 15-60 parts of nano inorganic mullite alumina hollow microspheres.
As a preferable scheme, the 5G communication housing containing the nano inorganic mullite alumina hollow microspheres is prepared from the following raw materials in parts by weight: 1.5 parts of an anti-aging agent, 2 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 8 parts of linear phenol-formaldehyde resin, 12 parts of bisphenol A novolac epoxy resin, 15 parts of modified glass fiber, 15 parts of o-cresol-formaldehyde epoxy resin, 20 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin, 22 parts of an auxiliary agent, 25 parts of phenol type novolac epoxy resin and 29.5 parts of nano inorganic mullite alumina hollow microspheres.
As a preferable scheme, the preparation method of the modified glass fiber comprises the following steps:
s1, adding 10-20 parts by weight of glass fiber, 4-10 parts by weight of hydrogen peroxide and 1-5 parts by weight of citric acid into 70-90 parts by weight of hydrochloric acid aqueous solution, and uniformly stirring at a rotating speed of 100-600 rpm to obtain glass fiber pretreatment solution;
s2, adding 1-4 parts by weight of aminoethoxy aminopropyl trimethoxysilane and 1-4 parts by weight of heptadecafluorodecyl triethoxysilane into 20-40 parts by weight of deionized water to prepare a modification solution;
s3, dropping 1 part by weight of the modified liquid into 3-6 parts by weight of the glass fiber pretreatment liquid, performing ultrasonic treatment at 60-80 ℃, stirring at 300-800 rpm for 1-5 hours, filtering, and drying to obtain the modified glass fiber.
Preferably, the hydrochloric acid aqueous solution in S1 is a hydrochloric acid aqueous solution with a molar concentration of 1-5 mol/L.
As a preferable scheme, the ultrasonic treatment power is 200-600W, and the ultrasonic treatment time is 30-60 min.
As a preferable scheme, the preparation method of the nano inorganic mullite alumina hollow microsphere comprises the following steps:
s11, adding 40-52 parts by weight of mullite, 20-35 parts by weight of alumina, 8-20 parts by weight of silica, 1-4 parts by weight of magnesium oxide and 0.8-2 parts by weight of zinc oxide into a ball mill, and uniformly ball-milling at the rotating speed of 500-800 rpm to obtain mixed powder;
s2, adding 8-20 parts by weight of the mixed powder into 30-50 parts by weight of deionized water, adding 0.5-1 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulated substance;
s3, sintering the granules at 850-1000 ℃ for 40-70 min, and then sintering at 1300-1600 ℃ for 30-60 min to obtain a precursor;
s4, uniformly dispersing 10 parts by weight of the precursor in 30-60 parts by weight of deionized water, adding 1-4 parts by weight of cyclodextrin and 0.5-1 part by weight of KH550, uniformly stirring at a rotating speed of 100-600 rpm, filtering, and drying to obtain the nano inorganic mullite-alumina hollow microspheres.
As a preferable scheme, the spray granulation specifically comprises: the inlet temperature of hot air is 85-95 ℃, the outlet temperature is 55-70 ℃, and the inlet air volume is 120-150 m3Per hour, the outlet air volume is 150-200 m3The rotation speed is 12000-16000 r/min.
Preferably, the antioxidant is antioxidant 4020.
As a preferable scheme, the auxiliary agent comprises a cross-linking agent, a lubricant, a light stabilizer and an antioxidant in a weight ratio of 10-15: 1-4: 1-4: 1-3, the cross-linking agent is styrene, the lubricant is zinc stearate, the antioxidant is antioxidant 1010, and the light stabilizer is light stabilizer UV 326.
The invention has the beneficial effects that: the housing for 5G communication containing the nano inorganic mullite-alumina hollow microspheres has good dielectric constant, dielectric loss and strength; under the resin systems of the linear phenol formaldehyde resin, the bisphenol A novolac epoxy resin, the o-cresol novolac epoxy resin, the phosphorus-containing and nitrogen-containing novolac epoxy resin and the phenol novolac epoxy resin, the 5G communication outer cover with good dielectric constant, dielectric loss and strength is prepared by adding the nano inorganic mullite alumina hollow microspheres and the modified glass fibers.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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.
In the present invention, the parts are all parts by weight unless otherwise specified.
Example 1
The outer cover containing the nano inorganic mullite alumina hollow microspheres for 5G communication is prepared from the following raw materials in parts by weight: 1.5 parts of an anti-aging agent 4020, 2 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 8 parts of linear phenol-formaldehyde resin (PF-8020-65M), 12 parts of bisphenol A novolac epoxy resin (EPIKOTE 5520-W-60A), 15 parts of modified glass fiber, 15 parts of o-cresol novolac epoxy resin (EOCN 6850), 20 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin (DOPOPIN-630), 22 parts of an auxiliary agent, 25 parts of phenol type novolac epoxy resin (EPON SU-8) and 29.5 parts of nano inorganic mullite alumina hollow microspheres.
The auxiliary agent comprises a cross-linking agent, a lubricant, a light stabilizer and an antioxidant according to the weight ratio of 14: 3: 3: 2, the cross-linking agent is styrene, the lubricant is zinc stearate, the antioxidant is antioxidant 1010, and the light stabilizer is light stabilizer UV 326.
The preparation method of the modified glass fiber comprises the following steps:
s1, adding 12 parts by weight of glass fiber, 6 parts by weight of hydrogen peroxide and 3 parts by weight of citric acid into 79 parts by weight of hydrochloric acid aqueous solution with the molar concentration of 4mol/L, and uniformly stirring at the rotating speed of 400rpm to obtain glass fiber pretreatment solution;
s2, adding 3 parts by weight of aminoethoxy aminopropyl trimethoxysilane and 2 parts by weight of heptadecafluorodecyl triethoxysilane into 35 parts by weight of deionized water to prepare a modification liquid;
s3, dropping 1 part by weight of the modified solution into 4 parts by weight of the glass fiber pretreatment solution, carrying out ultrasonic treatment at 70 ℃ for 50min at 500W, stirring at 600rpm for 4h, filtering, and drying to obtain the modified glass fiber.
The preparation method of the nano inorganic mullite alumina hollow microsphere comprises the following steps:
s11, adding 48 parts by weight of mullite, 32 parts by weight of alumina, 16 parts by weight of silicon dioxide, 3 parts by weight of magnesium oxide and 1 part by weight of zinc oxide into a ball mill, and uniformly ball-milling at the rotating speed of 600rpm to obtain mixed powder;
s2, adding 15 parts by weight of the mixed powder into 35 parts by weight of deionized water, adding 0.6 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulated substance; the spray granulation specifically comprises the following steps: the inlet temperature of hot air is 90 ℃, the outlet temperature is 65 ℃, and the inlet air quantity is 140m3H, outlet air volume 180m3H, the rotating speed is 15000 r/min;
s3, sintering the granules at 950 ℃ for 50min, and then sintering at 1500 ℃ for 40min to obtain a precursor;
s4, uniformly dispersing 10 parts by weight of the precursor in 36.2 parts by weight of deionized water, adding 3 parts by weight of cyclodextrin and 0.8 part by weight of KH550, uniformly stirring at the rotating speed of 500rpm, filtering, and drying to obtain the nano inorganic mullite-alumina hollow microspheres.
The preparation method of the 5G communication outer cover containing the nano inorganic mullite alumina hollow microspheres comprises the following steps:
(1) adding o-cresol formaldehyde epoxy resin, phenol novolac epoxy resin and bisphenol A novolac epoxy resin into a reaction kettle, uniformly stirring at the rotating speed of 200rpm, adding phosphorus-containing and nitrogen-containing novolac epoxy resin, linear phenol formaldehyde resin and resorcinol bis (2, 6-dimethylphenyl) phosphate, and uniformly stirring to obtain a first slurry;
(2) uniformly mixing the anti-aging agent 4020, the modified glass fiber, the auxiliary agent and the nano inorganic mullite alumina hollow microspheres to obtain a second slurry;
(3) adding the second slurry into the reaction kettle in the step (1), and uniformly mixing to obtain glue;
(4) adding glue into a dipping tank of a gluing machine, dipping electronic-grade glass fiber insulating cloth into the dipping tank for 4 minutes, drying and cooling to obtain a semi-solidified sheet, respectively adding a layer of polyethylene film with the thickness of 40 micrometers on the upper surface and the lower surface of the semi-solidified sheet, adding a mirror surface stainless steel plate with the thickness of 1.5mm on the polyethylene film on one surface, putting the semi-solidified sheet into high-temperature pressing equipment, pressing and molding for 4 hours at the temperature of 200 ℃, and cooling to obtain the 5G communication outer cover containing the nano mullite inorganic alumina hollow microspheres.
Example 2
The outer cover containing the nano inorganic mullite alumina hollow microspheres for 5G communication is prepared from the following raw materials in parts by weight: 1 part of an anti-aging agent 4020, 3 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 3 parts of linear phenol formaldehyde resin (PF-8020-65M), 25 parts of bisphenol A novolac epoxy resin (EPIKOTE 5520-W-60A), 10 parts of modified glass fiber, 30 parts of o-cresol formaldehyde epoxy resin (EOCN 6850), 10 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin (DOPOPIN-630), 35 parts of an auxiliary agent, 10 parts of phenol type novolac epoxy resin (EPON SU-8) and 30 parts of nano inorganic mullite alumina hollow microspheres.
The auxiliary agent comprises a cross-linking agent, a lubricant, a light stabilizer and an antioxidant according to the weight ratio of 14: 3: 3: 2, the cross-linking agent is styrene, the lubricant is zinc stearate, the antioxidant is antioxidant 1010, and the light stabilizer is light stabilizer UV 326.
The preparation method of the modified glass fiber comprises the following steps:
s1, adding 15 parts by weight of glass fiber, 5 parts by weight of hydrogen peroxide and 1 part by weight of citric acid into 79 parts by weight of hydrochloric acid aqueous solution with the molar concentration of 3mol/L, and uniformly stirring at the rotating speed of 400rpm to obtain glass fiber pretreatment solution;
s2, adding 4 parts by weight of aminoethoxy aminopropyl trimethoxysilane and 1 part by weight of heptadecafluorodecyl triethoxysilane into 35 parts by weight of deionized water to prepare a modification liquid;
s3, dropping 1 part by weight of the modified solution into 4 parts by weight of the glass fiber pretreatment solution, carrying out ultrasonic treatment at 70 ℃ for 50min at 300W, stirring at 500rpm for 2h, filtering, and drying to obtain the modified glass fiber.
The preparation method of the nano inorganic mullite alumina hollow microsphere comprises the following steps:
s11, adding 50 parts by weight of mullite, 35 parts by weight of alumina, 12 parts by weight of silicon dioxide, 2 parts by weight of magnesium oxide and 1 part by weight of zinc oxide into a ball mill, and uniformly ball-milling at the rotating speed of 600rpm to obtain mixed powder;
s2, adding 15 parts by weight of the mixed powder into 35 parts by weight of deionized water, adding 1 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulated substance; the spray granulation specifically comprises the following steps: the inlet temperature of hot air is 90 ℃, the outlet temperature is 65 ℃, and the inlet air quantity is 140m3H, outlet air volume 180m3H, the rotating speed is 15000 r/min;
s3, sintering the granules at 950 ℃ for 50min, and then sintering at 1500 ℃ for 40min to obtain a precursor;
s4, uniformly dispersing 10 parts by weight of the precursor in 36.2 parts by weight of deionized water, adding 3 parts by weight of cyclodextrin and 0.8 part by weight of KH550, uniformly stirring at the rotating speed of 500rpm, filtering, and drying to obtain the nano inorganic mullite-alumina hollow microspheres.
The preparation method of the 5G communication outer cover containing the nano inorganic mullite alumina hollow microspheres comprises the following steps:
(1) adding o-cresol formaldehyde epoxy resin, phenol novolac epoxy resin and bisphenol A novolac epoxy resin into a reaction kettle, uniformly stirring at the rotating speed of 200rpm, adding phosphorus-containing and nitrogen-containing novolac epoxy resin, linear phenol formaldehyde resin and resorcinol bis (2, 6-dimethylphenyl) phosphate, and uniformly stirring to obtain a first slurry;
(2) uniformly mixing the anti-aging agent 4020, the modified glass fiber, the auxiliary agent and the nano inorganic mullite alumina hollow microspheres to obtain a second slurry;
(3) adding the second slurry into the reaction kettle in the step (1), and uniformly mixing to obtain glue;
(4) adding glue into a dipping tank of a gluing machine, dipping electronic-grade glass fiber insulating cloth into the dipping tank for 4 minutes, drying and cooling to obtain a semi-solidified sheet, respectively adding a layer of polyethylene film with the thickness of 40 micrometers on the upper surface and the lower surface of the semi-solidified sheet, adding a mirror surface stainless steel plate with the thickness of 1.5mm on the polyethylene film on one surface, putting the semi-solidified sheet into high-temperature pressing equipment, pressing and molding for 4 hours at the temperature of 200 ℃, and cooling to obtain the 5G communication outer cover containing the nano mullite inorganic alumina hollow microspheres.
Example 3
The outer cover containing the nano inorganic mullite alumina hollow microspheres for 5G communication is prepared from the following raw materials in parts by weight: 3 parts of an anti-aging agent 4020, 1 part of resorcinol bis (2, 6-dimethylphenyl) phosphate, 15 parts of linear phenol formaldehyde resin (PF-8020-65M), 5 parts of bisphenol A novolac epoxy resin (EPIKOTE 5520-W-60A), 14 parts of modified glass fiber, 10 parts of o-cresol formaldehyde epoxy resin (EOCN 6850), 35 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin (DOPOPIN-630), 15 parts of an auxiliary agent, 45 parts of phenol type novolac epoxy resin (EPON SU-8) and 15 parts of nano inorganic mullite alumina hollow microspheres.
The auxiliary agent comprises a cross-linking agent, a lubricant, a light stabilizer and an antioxidant according to the weight ratio of 14: 3: 3: 2, the cross-linking agent is styrene, the lubricant is zinc stearate, the antioxidant is antioxidant 1010, and the light stabilizer is light stabilizer UV 326.
The preparation method of the modified glass fiber comprises the following steps:
s1, adding 20 parts by weight of glass fiber, 10 parts by weight of hydrogen peroxide and 1 part by weight of citric acid into 90 parts by weight of hydrochloric acid aqueous solution with the molar concentration of 1mol/L, and uniformly stirring at the rotating speed of 300rpm to obtain glass fiber pretreatment solution;
s2, adding 2 parts by weight of aminoethoxy aminopropyl trimethoxysilane and 4 parts by weight of heptadecafluorodecyl triethoxysilane into 34 parts by weight of deionized water to prepare a modification liquid;
s3, dropping 1 part by weight of the modified solution into 3 parts by weight of the glass fiber pretreatment solution, carrying out ultrasonic treatment at 65 ℃ for 50min at 500W, stirring at 600rpm for 4h, filtering, and drying to obtain the modified glass fiber.
The preparation method of the nano inorganic mullite alumina hollow microsphere comprises the following steps:
s11, adding 40 parts by weight of mullite, 20 parts by weight of alumina, 20 parts by weight of silica, 1 part by weight of magnesia and 2 parts by weight of zinc oxide into a ball mill, and uniformly ball-milling at the rotating speed of 600rpm to obtain mixed powder;
s2, adding 15 parts by weight of the mixed powder into 35 parts by weight of deionized water, adding 1 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulated substance; the spray granulation specifically comprises the following steps: the inlet temperature of hot air is 90 ℃, the outlet temperature is 65 ℃, and the inlet air quantity is 140m3H, outlet air volume 180m3H, the rotating speed is 15000 r/min;
s3, sintering the granules at 950 ℃ for 50min, and then sintering at 1500 ℃ for 40min to obtain a precursor;
s4, uniformly dispersing 10 parts by weight of the precursor in 36.2 parts by weight of deionized water, adding 3 parts by weight of cyclodextrin and 0.8 part by weight of KH550, uniformly stirring at the rotating speed of 500rpm, filtering, and drying to obtain the nano inorganic mullite-alumina hollow microspheres.
The preparation method of the 5G communication outer cover containing the nano inorganic mullite alumina hollow microspheres comprises the following steps:
(1) adding o-cresol formaldehyde epoxy resin, phenol novolac epoxy resin and bisphenol A novolac epoxy resin into a reaction kettle, uniformly stirring at the rotating speed of 200rpm, adding phosphorus-containing and nitrogen-containing novolac epoxy resin, linear phenol formaldehyde resin and resorcinol bis (2, 6-dimethylphenyl) phosphate, and uniformly stirring to obtain a first slurry;
(2) uniformly mixing the anti-aging agent 4020, the modified glass fiber, the auxiliary agent and the nano inorganic mullite alumina hollow microspheres to obtain a second slurry;
(3) adding the second slurry into the reaction kettle in the step (1), and uniformly mixing to obtain glue;
(4) adding glue into a dipping tank of a gluing machine, dipping electronic-grade glass fiber insulating cloth into the dipping tank for 4 minutes, drying and cooling to obtain a semi-solidified sheet, respectively adding a layer of polyethylene film with the thickness of 40 micrometers on the upper surface and the lower surface of the semi-solidified sheet, adding a mirror surface stainless steel plate with the thickness of 1.5mm on the polyethylene film on one surface, putting the semi-solidified sheet into high-temperature pressing equipment, pressing and molding for 4 hours at the temperature of 200 ℃, and cooling to obtain the 5G communication outer cover containing the nano mullite inorganic alumina hollow microspheres.
Comparative example 1
Comparative example 1 is different from example 1 in that comparative example 1 adopts the same amount of hollow glass microspheres instead of the nano inorganic mullite alumina hollow microspheres, and the rest is the same.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the preparation method of the nano inorganic mullite alumina hollow microsphere in the comparative example 2 is different from that in the example 1, and the rest is the same.
In the comparative example, the hollow microspheres of nano inorganic mullite alumina were obtained after granulation and sintering.
The preparation method of the nano inorganic mullite alumina hollow microsphere comprises the following steps:
s11, adding 48 parts by weight of mullite, 32 parts by weight of alumina, 16 parts by weight of silicon dioxide, 3 parts by weight of magnesium oxide and 1 part by weight of zinc oxide into a ball mill, and uniformly ball-milling at the rotating speed of 600rpm to obtain mixed powder;
s2, adding 15 parts by weight of the mixed powder into 35 parts by weight of deionized water, adding 0.6 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulated substance; the spray granulation specifically comprises the following steps: the inlet temperature of hot air is 90 ℃, the outlet temperature is 65 ℃, and the inlet air quantity is 140m3H, outlet air volume 180m3H, the rotating speed is 15000 r/min;
s3, sintering the granules at 950 ℃ for 50min, and then sintering at 1500 ℃ for 40min to obtain the nano inorganic mullite alumina hollow microspheres.
Comparative example 3
Comparative example 3 differs from example 1 in that comparative example 3 does not contain the modified glass fiber, and the other is the same.
Comparative example 4
Comparative example 4 differs from example 1 in that comparative example 4 uses glass fibers instead of modified glass fibers, all other things being equal.
Comparative example 5
Comparative example 5 is different from example 1 in that comparative example 5 shows a modified glass fiber having a different production method from example 1, and the other steps are the same.
In the comparative example, the modified glass fiber is only pretreated and is not treated by the modifying solution.
The preparation method of the modified glass fiber comprises the following steps:
s1, adding 12 parts by weight of glass fiber, 6 parts by weight of hydrogen peroxide and 3 parts by weight of citric acid into 79 parts by weight of hydrochloric acid aqueous solution with the molar concentration of 4mol/L, stirring uniformly at the rotating speed of 400rpm, filtering and drying to obtain the modified glass fiber.
TABLE 1 Performance test results of the outer covers described in examples 1 to 3 and comparative examples 1 to 5
Figure DEST_PATH_IMAGE001
As can be seen from table 1, the enclosures prepared according to the present invention have good dielectric constant, dielectric loss, and strength.
Comparing example 1 with comparative examples 1-2, it can be seen that the nano inorganic mullite alumina hollow microspheres of the present invention can significantly improve dielectric constant, dielectric loss and strength. In the preparation method of the nano inorganic mullite-alumina hollow microsphere, cyclodextrin and KH550 are adopted for treatment after sintering, so that the dielectric constant, dielectric loss and strength can be obviously improved.
Comparing example 1 with comparative examples 3-5, it can be seen that the modified glass fiber described herein can significantly improve dielectric constant, dielectric loss, and strength.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. The outer cover containing the nano inorganic mullite alumina hollow microspheres for 5G communication is characterized by being prepared from the following raw materials in parts by weight: 1-3 parts of an anti-aging agent, 1-3 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 3-15 parts of a linear phenol-formaldehyde resin, 5-25 parts of a bisphenol A novolac epoxy resin, 10-20 parts of a modified glass fiber, 10-30 parts of an o-cresol novolac epoxy resin, 10-35 parts of a phosphorus-containing and nitrogen-containing novolac epoxy resin, 15-35 parts of an auxiliary agent, 10-45 parts of a phenol type novolac epoxy resin and 15-80 parts of nano inorganic mullite alumina hollow microspheres.
2. The housing containing the nano inorganic mullite alumina hollow micro beads for 5G communication as claimed in claim 1, is characterized by being prepared from the following raw materials in parts by weight: 1-2 parts of an anti-aging agent, 1-2.5 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 3-10 parts of linear phenol-formaldehyde resin, 5-20 parts of bisphenol A novolac epoxy resin, 10-18 parts of modified glass fiber, 10-20 parts of o-cresol-formaldehyde epoxy resin, 10-30 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin, 15-30 parts of an auxiliary agent, 10-40 parts of phenol type novolac epoxy resin and 15-60 parts of nano inorganic mullite alumina hollow microspheres.
3. The housing containing the nano inorganic mullite alumina hollow micro beads for 5G communication as claimed in claim 1, is characterized by being prepared from the following raw materials in parts by weight: 1.5 parts of an anti-aging agent, 2 parts of resorcinol bis (2, 6-dimethylphenyl) phosphate, 8 parts of linear phenol-formaldehyde resin, 12 parts of bisphenol A novolac epoxy resin, 15 parts of modified glass fiber, 15 parts of o-cresol-formaldehyde epoxy resin, 20 parts of phosphorus-containing and nitrogen-containing novolac epoxy resin, 22 parts of an auxiliary agent, 25 parts of phenol type novolac epoxy resin and 29.5 parts of nano inorganic mullite alumina hollow microspheres.
4. The housing for 5G communication containing the nano inorganic mullite alumina hollow micro beads as claimed in claim 1, wherein the preparation method of the modified glass fiber is as follows:
s1, adding 10-20 parts by weight of glass fiber, 4-10 parts by weight of hydrogen peroxide and 1-5 parts by weight of citric acid into 70-90 parts by weight of hydrochloric acid aqueous solution, and uniformly stirring at a rotating speed of 100-600 rpm to obtain glass fiber pretreatment solution;
s2, adding 1-4 parts by weight of aminoethoxy aminopropyl trimethoxysilane and 1-4 parts by weight of heptadecafluorodecyl triethoxysilane into 20-40 parts by weight of deionized water to prepare a modification solution;
s3, dropping 1 part by weight of the modified liquid into 3-6 parts by weight of the glass fiber pretreatment liquid, performing ultrasonic treatment at 60-80 ℃, stirring at 300-800 rpm for 1-5 hours, filtering, and drying to obtain the modified glass fiber.
5. The cover for 5G communication containing the nano inorganic mullite alumina hollow beads as claimed in claim 4, wherein the hydrochloric acid aqueous solution in S1 is hydrochloric acid aqueous solution with a molar concentration of 1-5 mol/L.
6. The cover for 5G communication containing the nano inorganic mullite alumina hollow bead as claimed in claim 4, wherein the ultrasonic treatment power is 200-600W, and the ultrasonic treatment time is 30-60 min.
7. The housing for 5G communication containing the nano inorganic mullite alumina hollow bead as claimed in claim 1, wherein the preparation method of the nano inorganic mullite alumina hollow bead is as follows:
s11, adding 40-52 parts by weight of mullite, 20-35 parts by weight of alumina, 8-20 parts by weight of silica, 1-4 parts by weight of magnesium oxide and 0.8-2 parts by weight of zinc oxide into a ball mill, and uniformly ball-milling at the rotating speed of 500-800 rpm to obtain mixed powder;
s2, adding 8-20 parts by weight of the mixed powder into 30-50 parts by weight of deionized water, adding 0.5-1 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulated substance;
s3, sintering the granules at 850-1000 ℃ for 40-70 min, and then sintering at 1300-1600 ℃ for 30-60 min to obtain a precursor;
s4, uniformly dispersing 10 parts by weight of the precursor in 30-60 parts by weight of deionized water, adding 1-4 parts by weight of cyclodextrin and 0.5-1 part by weight of KH550, uniformly stirring at a rotating speed of 100-600 rpm, filtering, and drying to obtain the nano inorganic mullite-alumina hollow microspheres.
8. The housing for 5G communication containing the nano inorganic mullite alumina hollow micro beads as claimed in claim 7, wherein the spray granulation is specifically as follows: the inlet temperature of hot air is 85-95 ℃, the outlet temperature is 55-70 ℃, and the inlet air volume is 120-150 m3Per hour, the outlet air volume is 150-200 m3The rotation speed is 12000-16000 r/min.
9. The housing for 5G communication containing the nano inorganic mullite alumina hollow microspheres as claimed in claim 1, wherein the anti-aging agent is anti-aging agent 4020.
10. The housing containing the nano inorganic mullite alumina hollow microspheres for 5G communication as claimed in claim 1, wherein the auxiliary agent comprises a cross-linking agent, a lubricant, a light stabilizer and an antioxidant in a weight ratio of 10-15: 1-4: 1-4: 1-3, the cross-linking agent is styrene, the lubricant is zinc stearate, the antioxidant is antioxidant 1010, and the light stabilizer is light stabilizer UV 326.
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