CN102350825B - Process for preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal method - Google Patents
Process for preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 24
- 239000011737 fluorine Substances 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000000839 emulsion Substances 0.000 claims abstract description 57
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000005096 rolling process Methods 0.000 claims abstract description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical group CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229940043279 diisopropylamine Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910004247 CaCu Inorganic materials 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 238000004891 communication Methods 0.000 description 6
- 230000008054 signal transmission Effects 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000010365 information processing Effects 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- AMVVEDHCBDQBJL-UHFFFAOYSA-N [Ca][Zr] Chemical compound [Ca][Zr] AMVVEDHCBDQBJL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention relates to a process for preparing a fluorine-containing high polymer high frequency circuit board material by a hydrothermal method, which belongs to the high frequency circuit substrate material field. The method comprises the following steps: uniformly mixing a polytetrafluoroethylene emulsion (PTFE), a fluoroethylenepropylene emulsion (FEP) and a polyfluoroalkoxy emulsion (PFA), adding salts, then adding a molecule guiding agent and a molecular weight regulator, uniformly mixing, adding in a reaction vessel for performing hydrothermal reaction to complete high-molecular secondary polymerization, acquiring a substance of dielectric inorganic compound nanoparticles coated with high-molecular, filtering, washing, drying, removing end group, sintering, rolling, cladding copper to obtain the high frequency circuit board material with different dielectric constants finally. The prepared high frequency circuit board is capable of satisfying each basic index of the high frequency circuit board, and has the advantages of adjustable dielectric constant, low loss, good mechanical property and the like; the dielectric constant can be adjusted by the circuit board according to the generated dielectric inorganic compound content, the range of the dielectric constant is 2-35 which can satisfy the different requirements.
Description
Technical field
The present invention relates to the preparation method of HF link plate material, particularly adopt the process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal, belong to high-frequency circuit board Material Field.
Background technology
Fluorine-containing polymer high-frequency circuit board refers to compound other material of fluorine-containing polymer, and as pottery, glass fabric, nonwoven, the high frequency of producing covers copper circuit board.
In the high-speed signal transmission lines of printed circuit board wire, can be divided at present two large classes: a class is high-frequency signal transmission electronic product, this series products is relevant with wireless electromagnetic wave, it is with sine wave, to carry out the product of signal transmission, as radar, radio and television, mobile phone, microwave communication and optical-fibre communications etc.; Another kind of is the electronic product of high-speed logic signal transmission class, this series products is with digital data transmission, equally also relevant with the transmission of electromagnetic square wave, this series products starts to be mainly used in the aspects such as computer, has now been generalized to rapidly on the electronic product of household electrical appliances and communication.The development of the communication technology and the information processing technology, improves constantly its operating frequency.
Reach at a high speed and transmit, microwave high-frequency printed board baseplate material is being had to clear and definite requirement aspect electrical characteristic.Aspect high speed transmission, realize the low-loss of signal transmission, low delay, must select the baseplate material that dielectric constant and dielectric loss angle tangent are less, fluorine-containing polymer is exactly wherein a kind of.Fluorine-containing polymer has following feature: 1. dielectric constant (ε) and dielectric loss angle tangent (tan δ) minimum, and dielectric constant (ε) is stable under high frequency; 2. good mechanical property; 3. hot property is high; 4. high with metal adhesive strength; 5. chemical-resistance is good; 6. excellent in cushion effect.So the high frequency substrate material that fluorine-containing polymer is best suited for is also the maximum microwave high-frequency printed circuit board base board material of the amount of employing nowadays.
Through the development of nearly more than ten years, fluorine-containing polymer high-frequency circuit board has entered the comparatively ripe research and development phase at present.The current all kinds of fluorine-containing polymer high-frequency circuit boards of U.S. Rogers company, its dielectric constant is in 2 left and right.Domestic R&D work mainly contains: the composite panel for high-frequency circuit board of Hsinchu County, Taiwan Province Industrial Technology Research Institute; The method for producing printed circuit board for local region high frequency circuit by half-addition of Dongguan ShengYi Electronics Co., Ltd has the region of requirement to embed Rogers sheet material to high frequency characteristics on common sheet material.Fluorine-containing polymer high-frequency circuit board is the hard foundation stone of mechanics of communication of new generation and information processing technology revolution, and home products cannot meet high-frequency circuit needs at all, import Rogers sheet material is expensive, so that research and development have fluorine-containing polymer high-frequency circuit board and the novel preparation technology of independent intellectual property right is significant to domestic mechanics of communication and information processing technology industry.
Summary of the invention
The object of the present invention is to provide a kind of process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal, this HF link plate can meet the requirement of microwave high-frequency printed board substrate completely, and its dielectric constant can regulate according to the content of the inorganic compound generating, and meets different high-frequency circuit demands.
The concrete technical scheme that the present invention adopts is as follows:
A kind of process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal, it is characterized in that: it is by ptfe emulsion (PTFE), perfluoroethylene-propylene emulsion (FEP), after tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) mixes, first add salt, add again molecular guide agent and molecular weight regulator, after mixing, add and in reactor, carry out hydro-thermal reaction and complete macromolecule after polymerization, and obtain the material of the coated dielectric inorganic compound nano-particle of macromolecule, then after filtration, washing, dry, remove end group, sintering, rolling, cover copper, finally obtain the HF link plate material of differing dielectric constant.
Described hydro-thermal reaction has experienced two processes, and the one, macromolecule after polymerization generates dielectric inorganic compound nano-particle simultaneously, and the 2nd, the coated dielectric inorganic compound nano-particle generating of macromolecule.
Described dielectric inorganic compound nano-particle is mainly zirconates, titanate, zirconium titanate or CaCu 3 Ti 4 O etc., and wherein the dielectric constant of CaCu 3 Ti 4 O (CCTO) can be up to more than 10000.
The concrete technology step of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal of the present invention is as follows:
A, ptfe emulsion (PTFE), perfluoroethylene-propylene emulsion (FEP), tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) are mixed and are mixed well according to 6 ~ 7:3 ~ 4:7 ~ 9 (w) after, first add 5 ~ 35% (w) salt, the molecular weight regulator that adds again the molecular guide agent and 0 ~ 10% (w) of 0 ~ 10% (w), mixes and obtains mixed emulsion.
The concentration of described ptfe emulsion (PTFE) is 50% (w), and the concentration of perfluoroethylene-propylene emulsion (FEP) is that the concentration of 50% (w), tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) is 30% (w).
Described salts reaction thing is selected from the nitrate of calcium, magnesium, zirconium, strontium, barium, zinc or copper; Or the acetate of calcium, magnesium, zirconium, strontium or barium; Also or the sulfate of zinc or copper; Positive butyl titanate etc. also.
Described molecular guide agent is selected from diisopropylamine.
Described molecular weight regulator is selected from the different monooctyl ester of 3-mercaptopropionic acid (IOMP), modification mercaptan, isopropyl alcohol or alkyl hydrosulfide.
B, the mixed emulsion that steps A is made add reactor, with the heating rate of 0.5 ~ 1.5 ℃/min, are warmed up to after 180 ~ 250 ℃, and under the pressure of 2 ~ 8Mpa, reaction 2 ~ 48hour, obtains the material of the coated dielectric inorganic compound nano-particle of macromolecule.
The reacted product particle of C, filtration step B, first with deionized water washing 3 ~ 5 times, then under 80 ~ 100 ℃ of environment of temperature dry 2 ~ 5hour, then pack in the ultraviolet light pipe of wavelength X <200nm logical ammonia into degraded end group.
D, the product particle after step C processes after sintering 10 ~ 48hour, is positioned over immediately in milling train and is rolled at 200 ~ 280 ℃ the thin plate that 0.1 ~ 3mm is thick at 320 ~ 380 ℃.
E, in vacuum, temperature is 300 ~ 365 ℃, pressure is under 20 ~ 50Mpa environment, thin plate one or two sides is mixed to electrolytic copper foil and make single or double copper-clad plate material.
Technical advantage of the present invention shows following 3 points:
The organic phase of A, fluorine-containing polymer HF link plate material mainly contains three kinds, wherein PTFE mainly provides dielectric properties, FEP mainly provides thermoplastic property, and PFA mainly provides thermoplasticity and mechanical performance, and can improve the adhesive property of whole fluorine-containing polymer HF link plate material.
The dielectric constant of B, fluorine-containing polymer HF link plate material can regulate according to the content of the inorganic compound generating, and meets different high-frequency circuit demands, especially the actual needs of alternating-current resistance reactance coupling.
C, be used for regulating the inorganic compound of dielectric constant can select compared with multiple types, be not subject to the market supply and demand, many condition restriction such as chemical reaction.
The specific embodiment
embodiment 1
A, tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) of the perfluoroethylene-propylene emulsion (FEP) of the ptfe emulsion of 2.048L (PTFE), 1.024L, 3.926L is mixed and is mixed well after, first add 897.4g zirconium nitrate Zr (NO
3)
4with 434.4g calcium nitrate Ca (NO
3)
2, then add 80g diisopropylamine and 70g isopropyl alcohol, mix and obtain mixed emulsion.
The concentration of described ptfe emulsion (PTFE) is 50% (w), and the concentration of perfluoroethylene-propylene emulsion (FEP) is that the concentration of 50% (w), tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) is 30% (w).
B, the mixed emulsion that steps A is made add 10L autoclave, dress still ratio is 70.5%, is warmed up to after 200 ℃, with the heating rate of 1 ℃/min under the pressure of 4Mpa, reaction 48hour, obtains the material that macromolecule is coated dielectric inorganic compound nano-particle.
The reacted product particle of C, filtration step B, first with deionized water washing 5 times, then under 100 ℃ of environment of temperature dry 2hour, then pack in the ultraviolet light pipe of wavelength X=100nm logical ammonia into degraded end group.
D, the product particle after step C processes after sintering 36hour, is positioned over immediately in milling train and is rolled at 260 ℃ the thin plate that 1mm is thick at 350 ℃.
E, in vacuum, temperature is 340 ℃, pressure is under 30Mpa environment, thin plate one or two sides is mixed to electrolytic copper foil and make single or double copper-clad plate material.
After tested
1, calcium zirconate CaZrO in the product particle of step C
3nano-particle content is 14.9% (w), and PTFE content is 32.1% (w), and FEP content is 16.1% (w), and PFA content is 36.9% (w).
2, step e copper coin dielectric material performance is: under 1MHz, and ε
r=2.7, tan δ=3 * 10
-4; Under 10GHz, ε
r=2.8, tan δ=8 * 10
-4.
embodiment 2
A, tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) of the perfluoroethylene-propylene emulsion (FEP) of the ptfe emulsion of 1.982L (PTFE), 1.038L, 3.980L is mixed and is mixed well after, first add 1.1164kg barium nitrate Ba (NO
3)
2with the positive butyl titanate C of 1.4538kg
16h
36o
4ti, then add 90g diisopropylamine and the different monooctyl ester of 80g 3-mercaptopropionic acid (IOMP), mix and obtain mixed emulsion.
The concentration of described ptfe emulsion (PTFE) is 50% (w), and the concentration of perfluoroethylene-propylene emulsion (FEP) is that the concentration of 50% (w), tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) is 30% (w).
B, the mixed emulsion that steps A is made add 10L autoclave, dress still ratio is 72.6%, is warmed up to after 180 ℃, with the heating rate of 0.5 ℃/min under the pressure of 5Mpa, reaction 36hour, obtains the material that macromolecule is coated dielectric inorganic compound nano-particle.
The reacted product particle of C, filtration step B, first with deionized water washing 4 times, then under 90 ℃ of environment of temperature dry 4hour, then pack in the ultraviolet light pipe of wavelength X=160nm logical ammonia into degraded end group.
D, the product particle after step C processes after sintering 24hour, is positioned over immediately in milling train and is rolled at 200 ℃ the thin plate that 0.5mm is thick at 345 ℃.
E, in vacuum, temperature is 365 ℃, pressure is under 20Mpa environment, thin plate one or two sides is mixed to electrolytic copper foil and make single or double copper-clad plate material.
After tested
1, in the product particle of step C, barium titanate nano granule content is 26.9% (w), and PTFE content is 26.8% (w), and FEP content is 14% (w), and PFA content is 32.3% (w).
2, step e copper coin dielectric material performance is: under 1MHz, and ε
r=6.1, tan δ=2 * 10
-3; Under 10GHz, ε
r=6.2, tan δ=6.7 * 10
-4.
embodiment 3
A, tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) of the perfluoroethylene-propylene emulsion (FEP) of the ptfe emulsion of 1.920L (PTFE), 1.047L, 4.030L is mixed and is mixed well after, first add 1.3802kg calcium nitrate Ca (NO
3)
2, the positive butyl titanate C of 1.4305kg
16h
36o
4ti and 1.418kg zirconium nitrate Zr (NO
3)
4, then add 100g diisopropylamine and 90g alkyl hydrosulfide, mix and obtain mixed emulsion.
The concentration of described ptfe emulsion (PTFE) is 50% (w), and the concentration of perfluoroethylene-propylene emulsion (FEP) is that the concentration of 50% (w), tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) is 30% (w).
B, the mixed emulsion that steps A is made add 10L autoclave, dress still ratio is 73.4%, is warmed up to after 220 ℃, with the heating rate of 1.5 ℃/min under the pressure of 6.5Mpa, reaction 24hour, obtains the material that macromolecule is coated dielectric inorganic compound nano-particle.
The reacted product particle of C, filtration step B, first with deionized water washing 4 times, then under 95 ℃ of environment of temperature dry 3hour, then pack in the ultraviolet light pipe of wavelength X=130nm logical ammonia into degraded end group.
D, the product particle after step C processes after sintering 24hour, is positioned over immediately in milling train and is rolled at 280 ℃ the thin plate that 1.5mm is thick at 380 ℃.
E, in vacuum, temperature is 350 ℃, pressure is under 35Mpa environment, thin plate one or two sides is mixed to electrolytic copper foil and make single or double copper-clad plate material.
After tested
1, zirconium calcium titanate CaTi in the product particle of step C
0.5zr
0.5o
3nano-particle content is 31.4% (w), and PTFE content is 24.4% (w), and FEP content is 13.5% (w), and PFA content is 30.7% (w).
2, step e copper coin dielectric material performance is: under 1MHz, and ε
r=4.2, tan δ=3 * 10
-4; Under 10GHz, ε
r=4.3, tan δ=1.2 * 10
-3.
embodiment 4
A, tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) of the perfluoroethylene-propylene emulsion (FEP) of the ptfe emulsion of 1.885L (PTFE), 1.077L, 4.038L is mixed and is mixed well after, first add 322.2g calcium nitrate Ca (NO
3)
2, 941.4g copper sulphate CuSO
4with the positive butyl titanate C of 677.6g
16h
36o
4ti, then add 100g diisopropylamine and 100g modification mercaptan, mix and obtain mixed emulsion.
The concentration of described ptfe emulsion (PTFE) is 50% (w), and the concentration of perfluoroethylene-propylene emulsion (FEP) is that the concentration of 50% (w), tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion (PFA) is 30% (w).
B, the mixed emulsion that steps A is made add 10L autoclave, dress still ratio is 73.1%, is warmed up to after 160 ℃, with the heating rate of 1 ℃/min under the pressure of 6Mpa, reaction 24hour, obtains the material that macromolecule is coated dielectric inorganic compound nano-particle.
The reacted product particle of C, filtration step B, first with deionized water washing 3 times, then under 80 ℃ of environment of temperature dry 2hour, then pack in the ultraviolet light pipe of wavelength X=180nm logical ammonia into degraded end group.
D, the product particle after step C processes after sintering 45hour, is positioned over immediately in milling train and is rolled at 250 ℃ the thin plate that 1mm is thick at 350 ℃.
E, in vacuum, temperature is 345 ℃, pressure is under 40Mpa environment, thin plate one or two sides is mixed to electrolytic copper foil and make single or double copper-clad plate material.
After tested
1, in the product particle of step C, CaCu 3 Ti 4 O CCTO nano-particle content is 31.1% (w), and PTFE content is 24.1% (w), and FEP content is 13.8% (w), and PFA content is 31% (w).
2, step e copper coin dielectric material performance is: under 1MHz, and ε
r=13.2, tan δ=9 * 10
-4;
Under 10GHz, ε
r=13.3, tan δ=5 * 10
-3.
Claims (5)
1. the process of a preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal, it is characterized in that: it is by ptfe emulsion, perfluoroethylene-propylene emulsion, after tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion mixes, first add salt, add again molecular guide agent and molecular weight regulator, after mixing, add and in reactor, carry out hydro-thermal reaction and complete macromolecule after polymerization, and obtain the material of the coated dielectric inorganic compound nano-particle of macromolecule, then after filtration, washing, dry, remove end group, sintering, rolling, cover copper, finally obtain the HF link plate material of differing dielectric constant,
Concrete technology step is as follows:
A, ptfe emulsion, perfluoroethylene-propylene emulsion, tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion are mixed and are mixed well according to the weight ratio of 6 ~ 7:3 ~ 4:7 ~ 9 after, first add 5 ~ 35 wt% salts, add again the molecular guide agent of 0 ~ 10 wt% and the molecular weight regulator of 0 ~ 10 wt%, mix and obtain mixed emulsion;
B, the mixed emulsion that steps A is made add reactor, with the heating rate of 0.5 ~ 1.5 ℃/min, are warmed up to after 180 ℃ ~ 250 ℃, and under the pressure of 2 ~ 8Mpa, reaction 2 ~ 48hour, obtains the material of the coated dielectric inorganic compound nano-particle of macromolecule;
The reacted product particle of C, filtration step B, first with deionized water washing 3 ~ 5 times, then under 80 ~ 100 ℃ of environment of temperature dry 2 ~ 5hour, then pack in the ultraviolet light pipe of wavelength X <200nm logical ammonia into degraded end group;
D, the product particle after step C processes after sintering 10 ~ 48hour, is positioned over immediately in milling train and is rolled at 200 ~ 280 ℃ the thin plate that 0.1 ~ 3mm is thick at 320 ~ 380 ℃;
E, in vacuum, temperature is 300 ~ 365 ℃, pressure is under 20 ~ 50Mpa environment, thin plate one or two sides is mixed to electrolytic copper foil and make single or double copper-clad plate material;
The concentration of described ptfe emulsion is 50wt%, and the concentration of perfluoroethylene-propylene emulsion is that the concentration of 50 wt%, tetrafluoroethene-perfluor n-propyl vinyl ether copolymer emulsion is 30 wt%;
Described salt is selected from the nitrate of calcium, magnesium, zirconium, strontium, barium, zinc or copper; Or the acetate of calcium, magnesium, zirconium, strontium or barium; Also or the sulfate of zinc or copper; Also or positive butyl titanate.
2. the process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal according to claim 1, is characterized in that: described molecular guide agent is selected from diisopropylamine.
3. the process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal according to claim 1, is characterized in that: described molecular weight regulator is selected from the different monooctyl ester of 3-mercaptopropionic acid, modification mercaptan, isopropyl alcohol or alkyl hydrosulfide.
4. the process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal according to claim 1, is characterized in that: described dielectric inorganic compound nano-particle is zirconates, titanate, zirconium titanate or CaCu 3 Ti 4 O.
5. the process of preparing fluorine-containing high polymer high frequency circuit board material by hydrothermal according to claim 4, is characterized in that: described dielectric inorganic compound DIELECTRIC CONSTANTS
rin 30 ~ 10000 scopes, wherein the dielectric constant of CaCu 3 Ti 4 O is up to more than 10000.
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| CN107382291A (en) * | 2017-06-22 | 2017-11-24 | 庐江县典扬电子材料有限公司 | The preparation method of the copper-clad plate base materials of 2.2≤Dk ＜ 6.5 |
| CN107311517A (en) * | 2017-06-29 | 2017-11-03 | 安徽升鸿电子有限公司 | The method that Dk ＞ 10 copper-clad plate base material is made using turning mode |
| CN107509311A (en) * | 2017-06-29 | 2017-12-22 | 安徽升鸿电子有限公司 | The method that the copper-clad plate base material of 6.5≤Dk≤10 is made using turning mode |
| CN107278037A (en) * | 2017-06-29 | 2017-10-20 | 安徽升鸿电子有限公司 | The copper-clad plate of 6.5≤Dk≤10 is made using turning hot pressing mode |
| CN114644846A (en) * | 2020-12-17 | 2022-06-21 | 常熟三爱富中昊化工新材料有限公司 | Fluorine-containing polymer emulsion copper-clad plate and preparation method thereof |
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| EP1225194A2 (en) * | 2001-01-17 | 2002-07-24 | Air Products And Chemicals, Inc. | Method of forming a dielectric interlayer film with organosilicon precursors |
| CN101942180A (en) * | 2010-09-08 | 2011-01-12 | 广东生益科技股份有限公司 | Epoxy resin composition and copper clad laminate manufactured by using same |
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| CN101942180A (en) * | 2010-09-08 | 2011-01-12 | 广东生益科技股份有限公司 | Epoxy resin composition and copper clad laminate manufactured by using same |
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