CN107722518A - A kind of new low-k PTFE based composites and preparation method thereof - Google Patents
A kind of new low-k PTFE based composites and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides a kind of new low-k PTFE based composites and preparation method thereof, new low-k PTFE based composites are made up of PTFE, modified ceramic powder and fluorinated graphene, and the mass fraction that its raw material components and each component account for raw material gross mass is respectively：PTFE 35~70%, modified ceramic powder 24~59%, fluorinated graphene 1~6%.Modified ceramic powder is handled using complex fire resistant coupling agent, and wherein coupling agent accounts for the quality 0.5~2.5% of ceramic powder.The consistency of composite can be lifted using high temperature resistant coupling agent, reduces the porosity of composite inner, meanwhile, the dielectric properties, mechanical performance and heat endurance of composite can be improved by adding a small amount of fluorinated graphene.Composite prepared by the present invention has excellent combination property, and processing technology is simple, has good application prospect.
Description
Technical field
The invention belongs to microwave dielectric material field, more particularly to a kind of new low-k PTFE based composites and
Its preparation method.
Background technology
With the continuous development of electronic information technologies, people to the high speed of communication apparatus, efficiently require more and more higher, pass
The glass epoxy printed board of system can not meet the requirement of current high-frequency microwave printed circuit board (PCB), and PTFE bases is compound
Material can meet the basic demand of microwave circuit boards well：Than relatively low dielectric constant and dielectric loss, suitable heat is swollen
Swollen coefficient, acceptable thermal conductivity, suitable hygroscopicity and mechanical property, excellent chemical resistance and it is good can
Processability.The composite of PTFE bases, it is the filler that certain content is added in PTFE, so as to reduce its high thermal expansion system
Number, while thermal conductivity can also be increased, elevating mechanism performance.Presently, Inorganic Fillers Filled PTFE moulding process is simple, system
Standby cost is low, has a good application prospect.
Inorganic filler is mixed by coupling agent modified with PTFE, can increase both compatibility, but presently, very
More researchers or enterprise all do not account for coupling agent itself some performances composite can also be produced in itself it is unfavorable
Influence, if wherein the boiling point of coupling agent is than relatively low, then during Composite Sintering, can occur because temperature is too high
Decompose, so as to produce a number of space in the composite, reduce the overall compactness of composite, while can also increase
The possibility of big composite water imbibition, then influences overall performance.It is therefore necessary to before modified inorganic filler, select resistance to height
The coupling agent of temperature is tested to carry out.
Graphene has high specific surface area, and a small amount of graphene is added in system can just be such that it is formed in high polymer
The structural form of cross network, while graphene also has excellent electric property and mechanical performance, and each fluorine atom is placed on often
On individual single carbon atom, it is possible to obtain pure fluorinated graphene, the fluorinated graphene of height fluorination has perfect insulation
Characteristic；The presence of fluorine atom can reduce graphenic surface energy, increase hydrophobicity, improve heat endurance, chemical stability and resist
Corrosive power, therefore fluorinated graphene has fine with the structure and performance of two kinds of materials of graphene and polytetrafluoroethylene (PTFE)
Application prospect.
A kind of low dielectric constant polymers of the A of patent CN 103772981-fluorinated graphene composite and its preparation side
Method, describe using polymer epoxy or polyimides as matrix, add a small amount of fluorinated graphene and be prepared into composite, lead to
Dielectric constant can be reduced by crossing introducing father element, while improve the original mechanical property of composite and thermal stability.Specially
The polymer that profit is related to or can not exclusively be adapted to high-frequency microwave circuit board.
The preparation method of patent CN102604282 A nano-particles filled PTFE composites, is described nano-particle
Surface modification is carried out by coupling agent to mix with PTFE, then molding sintering is molded, and can effectively lift the mechanics of composite
Performance, anti-wear performance, reduce coefficient of friction.Its silane coupler used and titanate coupling agent are essentially all some boiling points
In 100~200 DEG C or so of coupling agent, it is certain to that pyrolytic occurs when being sintered more than 360 DEG C, in composite wood
More spaces is formed in material, increases the water absorption rate of material, reduces consistency.
The content of the invention
The invention provides a kind of new low-k PTFE based composites and preparation method thereof, its object is to gram
Take the deficiencies in the prior art, there is provided a kind of that there are high-compactness, low water absorbable, excellent dielectric properties and other ratios
Such as good mechanical performance, the PTFE composite of dimensional stability, the composite mainly by PTFE, modified ceramic powder and
Fluorinated graphene is formed.The technical scheme is that provide a kind of low-k PTFE composite woods of excellent combination property
Material, by
35~70%wt% PTFE
1~6wt% fluorinated graphene
24~59wt% modified ceramic powder
0.5~2.5wt% of ceramic powder quality composite coupler.
PTFE of the present invention is polytetrafluoroethylpowder powder.
The coupling agent be butyl titanate, three iso stearate isopropyl titanates, 1H, 1H, 2H, the second of 2H- perfluoro decyls three
One or both of TMOS.
Present invention also offers the preparation method of above-mentioned fluoropolymer composite, it is concretely comprised the following steps：
(1) ceramic powder and ethanol, are mixed into 0.5~1h at room temperature, subsequent dropwise addition ceramic powder quality 0.5~
2.5% high temperature resistant coupling agent, while deionized water is added, pH=3~5 are adjusted using acetic acid, 65 DEG C is warming up to, continues to mix
1~3h, after filtering, washing, product is placed at 110 DEG C and dries 3h, ground, sieve at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Finely dispersed graphene oxide dispersion is obtained, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining,
A certain amount of hydrofluoric acid is added simultaneously, and is gently mixed, then heating response for a period of time, drops at a certain temperature by reactor
To room temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder
Body；
(3), obtained modified ceramic powder in (2) and fluorinated graphene powder and PTFE powders are mixed according to a certain percentage
Close, drying, add a certain amount of lubricant, infiltrate, the idiosome of definite shape is extruded into by extruder, then passes through idiosome
Two rollers repeatedly roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, 230~250 DEG C
Lower 24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned over and is cold-pressed under 45~60MPa
0.5~1.0h, it is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 360~380 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 360~380 DEG C with 0.5 DEG C/min, is incubated 1h, then, with 1.5 DEG C/
Temperature is down to 160 DEG C from 260 DEG C by min, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
The beneficial effect that the present invention is reached：
(1), present invention employs high temperature resistant coupling agent, especially in conjunction with fluorine-containing coupling agent is employed, can effectively strengthen
Modified effect, preferably improve the interface binding power between inorganic filler and fluoropolymer, reduce the overall porosity of system,
Consistency is lifted, improves the overall performance of composite；
(2), the present invention using high fluorination the filling-modified PTFE of fluorinated graphene, can be effectively reduced dielectric constant and
Dielectric loss, improve the mechanical performance and chemically-resistant/thermodynamic property of composite.Patent and document before is few in detail
Be related to.
Embodiment
With reference to instantiation, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：
Raw material：
Polytetrafluoroethylpowder powder, density 2.17/g/cm3, 1 μm of particle diameter, 40g；
Fluorinated graphene, 1g；
SiO2, 5 μm of particle diameter, 59g；
Coupling agent, butyl titanate, 0.295g.
Method：
(1), by SiO20.5h is mixed at room temperature with ethanol, and SiO is then added dropwise2The high temperature resistant coupling of quality 0.5%
Agent, while deionized water is added, pH=3 is adjusted using acetic acid, is warming up to 65 DEG C, continues to mix 1h, will after filtering, washing
Product, which is placed at 110 DEG C, dries 3h, grinds, sieves at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Finely dispersed graphene oxide dispersion is obtained, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining,
A certain amount of hydrofluoric acid is added simultaneously, and is gently mixed, then heating response for a period of time, drops at a certain temperature by reactor
To room temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder
Body；
(3), by obtained modified SiO in (1), (2)2Mixed according to a certain percentage with fluorinated graphene powder and PTFE powders
Close, drying, add a certain amount of lubricant, infiltrate, the idiosome of definite shape is extruded into by extruder, then passes through idiosome
Two rollers repeatedly roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, at 230 DEG C
24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned over and is cold-pressed 0.5h under 45MPa,
It is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 360~380 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 360 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
Embodiment 2
Raw material：
Polytetrafluoroethylpowder powder, density 2.17/g/cm3, 1 μm of particle diameter, 70g；
Fluorinated graphene, 6g；
SiO2, 15 μm, 24g；
Coupling agent, three iso stearate isopropyl titanates, 0.6g.
Method：
(1), by SiO21h is mixed at room temperature with ethanol, and SiO is then added dropwise2The high temperature resistant coupling of quality 2.5%
Agent, while deionized water is added, pH=5 is adjusted using acetic acid, is warming up to 65 DEG C, continues to mix 3h, will after filtering, washing
Product, which is placed at 110 DEG C, dries 3h, grinds, sieves at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Finely dispersed graphene oxide dispersion is obtained, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining,
A certain amount of hydrofluoric acid is added simultaneously, and is gently mixed, then heating response for a period of time, drops at a certain temperature by reactor
To room temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder
Body；
(3), by obtained modified SiO in (1), (2)2With self-control fluorinated graphene powder with PTFE powders according to certain ratio
Example mixing, drying, adds a certain amount of lubricant, infiltrates, and the idiosome of definite shape is extruded into by extruder, then by idiosome
Repeatedly rolled by two rollers so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, 250 DEG C
Lower 24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned under 60MPa and is cold-pressed 1.0h, with
It is placed on and can be sintered according to following condition in the sintering furnace of accurate temperature controlling afterwards：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 380 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 380 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
Embodiment 3
Raw material：
Polytetrafluoroethylpowder powder, density 2.17/g/cm3, 1 μm of particle diameter, 35g；
Fluorinated graphene, 6g；
Magnesium silicate, 15 μm, 59g；
Coupling agent, 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes, 1.18g；
Method：
(1) magnesium silicate and ethanol, are mixed into 0.8h at room temperature, the high temperature resistant of magnesium silicate quality 2% is then added dropwise
Coupling agent, while deionized water is added, pH=4 is adjusted using acetic acid, is warming up to 65 DEG C, continues to mix 2h, through filtering, washing
Afterwards, product is placed at 110 DEG C and dries 3h, ground, sieve at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Finely dispersed graphene oxide dispersion is obtained, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining,
A certain amount of hydrofluoric acid is added simultaneously, and is gently mixed, then heating response for a period of time, drops at a certain temperature by reactor
To room temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder
Body；
(3), by obtained modified magnesium silicate in (1), (2) and fluorinated graphene powder and PTFE powders according to a certain percentage
Mixing, drying, adds a certain amount of lubricant, infiltrates, the idiosome of definite shape is extruded into by extruder, then leads to idiosome
Cross two rollers repeatedly to roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, at 240 DEG C
24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned over and is cold-pressed under 45~60MPa
1.0h, it is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 370 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 370 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
Embodiment 4：
Polytetrafluoroethylpowder powder, density 2.17/g/cm3, 1 μm of particle diameter, 70g；
Fluorinated graphene, 1g；
Magnesium silicate, 5 μm, 29g；
Coupling agent, butyl titanate and three iso stearate isopropyl titanate mixtures, mass ratio 1: 1,0.58g；
Method：
(1) magnesium silicate and ethanol, are mixed into 0.5h at room temperature, the high temperature resistant of magnesium silicate quality 2% is then added dropwise
Coupling agent, while deionized water is added, pH=3 is adjusted using acetic acid, is warming up to 65 DEG C, continues to mix 3h, through filtering, washing
Afterwards, product is placed at 110 DEG C and dries 3h, ground, sieve at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Finely dispersed graphene oxide dispersion is obtained, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining,
A certain amount of hydrofluoric acid is added simultaneously, and is gently mixed, then heating response for a period of time, drops at a certain temperature by reactor
To room temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder
Body；
(3), by obtained modified magnesium silicate in (1), (2) and fluorinated graphene powder and PTFE powders according to a certain percentage
Mixing, drying, adds a certain amount of lubricant, infiltrates, the idiosome of definite shape is extruded into by extruder, then leads to idiosome
Cross two rollers repeatedly to roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, at 230 DEG C
24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned over and is cold-pressed 1.0h under 50MPa,
It is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 380 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 380 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
Embodiment 5：
Polytetrafluoroethylpowder powder, density 2.17/g/cm3, 1 μm of particle diameter, 55g；
Fluorinated graphene, 3g；
Calcium silicates, 5 μm, 42g；
Coupling agent, butyl titanate and 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane mixture, mass ratio 2:
1,0.84g；
Method：
(1) calcium silicates and ethanol, are mixed into 0.5h at room temperature, the high temperature resistant of calcium silicates quality 2% is then added dropwise
Coupling agent, while deionized water is added, pH=3 is adjusted using acetic acid, is warming up to 65 DEG C, continues to mix 3h, through filtering, washing
Afterwards, product is placed at 110 DEG C and dries 3h, ground, sieve at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Finely dispersed graphene oxide dispersion is obtained, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining,
A certain amount of hydrofluoric acid is added simultaneously, and is gently mixed, then heating response for a period of time, drops at a certain temperature by reactor
To room temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder
Body；
(3), by obtained modified calcium silicates in (1), (2) and fluorinated graphene powder and PTFE powders according to a certain percentage
Mixing, drying, adds a certain amount of lubricant, infiltrates, the idiosome of definite shape is extruded into by extruder, then leads to idiosome
Cross two rollers repeatedly to roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, at 250 DEG C
24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned over and is cold-pressed 1.0h under 50MPa,
It is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 365 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 365 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
Embodiment 6：
Polytetrafluoroethylpowder powder, density 2.17/g/cm3, 1 μm of particle diameter, 45g；
Fluorinated graphene, 2g；
Calcium silicates, 15 μm, 53g；
Coupling agent, three iso stearate isopropyl titanates and 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane mixture,
Mass ratio is 3: 1,1.06g；
Method：
(1) calcium silicates and ethanol, are mixed into 1h at room temperature, the high temperature resistant that calcium silicates quality 2% is then added dropwise is even
Join agent, while add deionized water, pH=5 is adjusted using acetic acid, is warming up to 65 DEG C, continue to mix 2h, after filtering, washing,
Product is placed at 110 DEG C and dries 3h, grinds, sieve at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can obtain
Score
Uniform graphene oxide dispersion is dissipated, above-mentioned dispersion liquid is added to the reactor containing polytetrafluoroethyllining lining
In, while add a certain amount of hydrofluoric acid, and be gently mixed, then by reactor at a certain temperature one section of heating response when
Between, room temperature is down to, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtain fluorographite
Alkene powder；
(3), by obtained modified calcium silicates in (1), (2) and fluorinated graphene powder and PTFE powders according to a certain percentage
Mixing, drying, adds a certain amount of lubricant, infiltrates, the idiosome of definite shape is extruded into by extruder, then leads to idiosome
Cross two rollers repeatedly to roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, at 245 DEG C
24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, is positioned over and is cold-pressed under 45~60MPa
1.0h, it is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, will according to 1 DEG C/min
Temperature rises to 260 DEG C from 160 DEG C, is incubated 1h, and temperature is eventually raised into 375 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 375 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
Examples detailed above is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by examples detailed above
System, other it is any without departing from spirit of the invention with made under principle modification, modification, replacement, combine, simplification is equivalent
Substitute mode, be included within protection scope of the present invention.
Claims (6)
1. a kind of new low-k PTFE based composites and preparation method thereof, it is characterised in that its raw material components and each group
The mass fraction for point accounting for raw material gross mass is respectively：PTFE 35~70%, modified ceramic powder 24~59%, fluorinated graphene 1~
6%.Ceramic powder is surface-treated using high temperature resistant coupling agent, and coupling agent accounts for SiO2The 0.5~2.5% of quality.
2. a kind of new low-k PTFE based composites according to claim 1 and preparation method thereof, its feature
It is PTFE powders to be the PTFE.
3. a kind of new low-k PTFE based composites according to claim 1 and preparation method thereof, its feature
It is the fluorinated graphene of high degree of fluorination to be the fluorinated graphene.
4. a kind of new low-k PTFE based composites according to claim 1 and preparation method thereof, its feature
It is amorphous melt of si O to be the ceramic powder2, calcium silicates or magnesium silicate, 5~15 μm of particle diameter.
5. a kind of new low-k PTFE based composites according to claim 1 and preparation method thereof, its feature
It is that the coupling agent has good resistance to elevated temperatures, there is very high boiling point, is butyl titanate, three iso stearate metatitanic acids
One or both of isopropyl ester, 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes.
6. a kind of new low-k PTFE based composites and preparation method thereof as claimed in claim 1, are by following
What step was realized：
(1) ceramic powder and ethanol, are mixed into 0.5~1h at room temperature, ceramic powder quality 0.5~2.5% is then added dropwise
High temperature resistant coupling agent, while deionized water is added, pH=3~5 are adjusted using acetic acid, 65 DEG C is warming up to, continues 1~3h of mixing,
After filtering, washing, product is placed at 110 DEG C and dries 3h, ground, sieve at room temperature；
(2), graphene oxide is evenly spread in deionized water, ultrasonic vibration 1h, filtered, removed insoluble matter, can be divided
Uniform graphene oxide dispersion is dissipated, above-mentioned dispersion liquid is added in the reactor containing polytetrafluoroethyllining lining, simultaneously
A certain amount of hydrofluoric acid is added, and is gently mixed, then heating response for a period of time, is down to room at a certain temperature by reactor
Temperature, repeatedly washing is carried out to pH value in 7 or so (neutrality) with deionized water, filtering, dries, obtains fluorinated graphene powder；
(3), obtained modified ceramic powder in (1), (2) and fluorinated graphene powder and PTFE powders are mixed according to a certain percentage
Close, drying, add a certain amount of lubricant, infiltrate, the idiosome of definite shape is extruded into by extruder, then passes through idiosome
Two rollers repeatedly roll so that sheet is presented in final PTFE composite, PTFE sheet is placed in baking oven, 230~250 DEG C
Lower 24h；
(4) obtained multi-disc in (3), is dried into sheet material at room temperature to be overlapped mutually, be positioned under 45~60MPa cold pressing 0.5~
1.0h, it is subsequently placed at and can be sintered according to following condition in the sintering furnace of accurate temperature controlling：
Temperature-rise period：Temperature is risen to 160 DEG C from room temperature according to 1.5 DEG C/min, is incubated 1h, then, according to 1 DEG C/min by temperature
260 DEG C are risen to from 160 DEG C, is incubated 1h, temperature is eventually raised to 360~380 DEG C according to 0.5 DEG C/min, is incubated 2h；
Temperature-fall period：Temperature is down to 260 DEG C from 360~380 DEG C with 0.5 DEG C/min, is incubated 1h, then, will with 1.5 DEG C/min
Temperature is down to 160 DEG C from 260 DEG C, is incubated 0.5h, finally, room temperature is cooled the temperature to according to 2 DEG C/min rate of temperature fall.
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