CN119119711A - A low dielectric constant glass fiber reinforced polyphenylene ether composition and its preparation method and application - Google Patents
A low dielectric constant glass fiber reinforced polyphenylene ether composition and its preparation method and application Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 229920001955 polyphenylene ether Polymers 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 26
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 32
- 238000001125 extrusion Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000004611 light stabiliser Substances 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012963 UV stabilizer Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004734 Polyphenylene sulfide Substances 0.000 abstract description 12
- 229920000069 polyphenylene sulfide Polymers 0.000 abstract description 12
- 239000011342 resin composition Substances 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 229920000426 Microplastic Polymers 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000012681 fiber drawing Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- -1 phosphorus compound Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polyphenyl ether composition, in particular to a polyphenyl ether composition reinforced by glass fibers with low dielectric constant, a preparation method and application thereof, and the polyphenyl ether composition comprises, by mass, 25-60% of polyphenyl ether, 10-40% of glass fibers with low dielectric constant and low loss, 0.1-50% of inorganic filler, 0.1-10% of processing aid, and carbon doped silicon oxide as a coupling agent, wherein the dielectric constant of the glass fibers with low dielectric constant and low loss is less than 3.8 and the dielectric loss is less than 0.001 under the condition of 1 MHz. Compared with the prior art, the invention solves the problems of the prior art that the polyphenylene sulfide resin composition has high processing difficulty, insufficient batch stability and high hygroscopicity, and the glass fiber and the polyphenyl ether have good combination degree, can fully exert the performance advantages of the polyphenyl ether, effectively reduce the water absorption rate of the composition, and has high overall production efficiency and excellent product quality.
Description
Technical Field
The invention relates to a polyphenyl ether composition, in particular to a polyphenyl ether composition reinforced by glass fibers with low dielectric constant, and a preparation method and application thereof.
Background
With the advent of the 5G age, humans entered a new age of the communication revolution, and the 5G age was mainly characterized by high speed, low power consumption and low latency, and the most important characteristic was ultrafast data processing and transmission. The 5G era is not limited to mobile phone communication, and from smart cities to unmanned vehicles, conditions of high speed, low power consumption and low time delay are required to be achieved, so that the 5G era has higher requirements on a new generation of Printed Circuit Boards (PCBs), and the new generation of printed circuit boards mainly show high-speed and high-frequency characteristics. In order to satisfy the performance of the printed circuit board, a material having a low dielectric constant and a low dielectric loss is particularly important at a high frequency.
Glass fibers and resins are used as the reinforcing material for the substrate of the printed circuit board, and in general, when an alternating current flows through the glass material, the glass material absorbs the flow of the current in an endothermic manner, and the absorbed dielectric loss energy depends on the dielectric constant and dielectric tangent of the glass material used, and is proportional to the dielectric constant and dielectric tangent, respectively, and is generally represented by the formula w= KfV 2 xepsilon tan delta, wherein W is the dielectric loss energy, K is the constant, f is a frequency, V 2 represents the potential gradient, epsilon represents the dielectric constant, and tan delta represents the dielectric tangent. From the above equation, the higher the frequency, the larger the dielectric constant and dielectric tangent, and the larger the dielectric loss.
At present, a glass fiber reinforced epoxy resin board is used as a 4G communication circuit board substrate in the market, and a glass fiber reinforced polyphenylene sulfide composition is used as a 5G antenna oscillator. However, since polyphenylene sulfide resin itself is a semi-crystalline material, the fluidity is ultra high and the processing difficulty is great, so that most of polyphenylene sulfide needs to be modified by glass fibers to greatly improve the temperature resistance. However, the molding difficulty is still high, flash is easy to occur in the molded product, extra labor is needed for trimming, the production efficiency is low, and the 40% glass fiber reinforced polyphenylene sulfide composition supplied in the market at present has unstable dielectric properties, and the dielectric constants are different along with the different raw material batches, so that the stability of the product is difficult to ensure. The E-glass fiber is commonly used for the printed circuit board at present, the dielectric constant is about 6.5-7.2 and the dielectric tangent is about 12 multiplied by 10 -4 at the room temperature under the condition of the frequency of 1MHz, so that the E-glass fiber generally generates relatively high dielectric loss and cannot meet the requirements of the high-frequency high-speed printed circuit board in the 5G era, and the 40% glass fiber reinforced polyphenylene sulfide composition cannot stably control the dielectric constant within a certain range due to the large difference of different batches of glass fibers, so that the line impedance of the circuit board after the assembly of the later stage is seriously defective. Through testing, the dielectric constants of the 40% glass fiber reinforced polyphenylene sulfide composition are all larger than 4.2 at high frequency, the test values of dielectric loss at high frequency are all larger than 0.006, signal delay is easy to generate, the requirement of 5G for future high-frequency development is not met, meanwhile, the 40% glass fiber reinforced polyphenylene sulfide composition is large in hygroscopicity, and the circuit is affected by moisture when the composition is used in an outdoor 5G base station for a long time.
Polyphenylene ether resins are also a material for circuit boards suitable for use in high-frequency electronic devices because polyphenylene ether resins have good high-frequency characteristics such as low dielectric constant, low dielectric loss, and the like. However, polyphenylene ether resins have the disadvantage of poor moldability and therefore cannot be used alone, but can only be used in the form of a mixture with a fully compatible polystyrene-based resin or with a plasticizer triphenyl phosphate. Although polystyrene resin can increase the fluidity of polyphenylene ether resin, the introduction of the polyphenylene ether resin reduces the flame retardance and the heat resistance of the polyphenylene ether resin, and the processing requirements of the flexible copper-clad plate cannot be met, while the mixture of the plasticizer and the triphenyl phosphate can increase the fluidity and the flame retardance of the polyphenylene ether resin, but has larger loss on the temperature resistance. Glass fibers are typically added to enhance heat resistance.
The low dielectric constant glass fibers available on the market at present are only suitable for PA, PBT and PPS, and there is no low dielectric constant glass fiber suitable for polyphenylene ether. The existing glass fiber with low dielectric constant is used for modifying polyphenyl ether, and then the glass fiber is found to have poor dielectric property and high moisture absorption rate, so that the glass fiber is not beneficial to processing in the downstream PCB industry. As in the prior art CN113652074a, a polyphenylene oxide substrate for a high-frequency high-speed copper-clad plate and a preparation method and application thereof are disclosed. The polyphenyl ether base material comprises, by mass, 30-90% of polyphenyl ether resin, 10-40% of glass fibers, 0.1-50% of inorganic filler, 0.01-0.5% of antioxidant, 0.01-0.5% of light stabilizer, 0.01-0.5% of release agent, 0.1-10% of processing aid and 0-20% of plasticizer. According to the scheme, the polyphenylene oxide forms an orderly arranged crystalline structure through interaction between the processing aid (nano-scale siloxane) and the polyphenylene oxide, so that the fluidity can be increased to adapt to the requirement of a downstream production process. However, as shown in conclusion 3, the main improvement of the scheme is only fluidity, and the influence on the dielectric property directly related to the property of the end product is small, and the influence of the environmental humidity on the dielectric property of the material is not considered, so that the dielectric property of the product under the high humidity environment is greatly changed due to insufficient bonding degree of the polyphenyl ether and the glass fiber, and finally the performance requirement cannot be met, and the practical application environment is not met.
Accordingly, studies on a composition using a polyphenylene ether resin as a high-frequency electronic substrate are required to propose a polyphenylene ether resin composition having a low dielectric constant, low dielectric loss, and suitable for downstream PCB processing.
Disclosure of Invention
The invention aims to solve at least one of the problems and provide a low-dielectric-constant glass fiber reinforced polyphenyl ether composition, a preparation method and application thereof, so as to solve the problems of high processing difficulty, insufficient batch stability and high hygroscopicity of the polyphenyl thioether resin composition in the prior art.
The aim of the invention is achieved by the following technical scheme:
The invention discloses a low-dielectric-constant glass fiber reinforced polyphenyl ether composition, which comprises the following components in parts by mass:
the low-dielectric-constant low-loss glass fiber has a dielectric constant of less than 3.8 and a dielectric loss of less than 0.001 under the condition of 1MHz, and the surface of the low-dielectric-constant low-loss glass fiber is coated with carbon-doped silicon oxide as a coupling agent.
Preferably, the low dielectric constant and low loss glass fiber comprises the following components, by mass, 50-52% of silicon dioxide, 13-15% of aluminum oxide, 24-26% of boron oxide, 3-5% of calcium oxide, 3-5% of magnesium oxide and 0.1-1.5% of zirconium oxide.
The low-dielectric constant low-loss glass fiber is prepared by mixing the components, melting for the first time, quenching to obtain broken glass, melting for the second time to obtain glass fiber precursor, immersing the glass fiber precursor in carbon-doped silicon oxide, transferring into a preheated oven to remove surface bubbles, transferring into a vacuum oven to be dried and solidified, and finally chopping by a chopping machine.
Preferably, the primary melting temperature is 1300-1550 ℃, the secondary melting temperature is 1300-1350 ℃, the heat preservation is 0.5-1h, the surface bubble removal is carried out in a 50-80 ℃ oven, and the drying and solidification are carried out in three steps, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours.
Preferably, the weight of the carbon-doped silicon oxide is 0.1-5% of that of the glass fiber.
Preferably, the inorganic filler comprises one or more of titanium dioxide, aluminum oxide, kaolin and talcum powder, and the processing aid comprises an antioxidant, a light stabilizer, a release agent, a UV stabilizer and a lubricant.
Preferably, the polyphenylene ether composition further comprises 0 to 30% by mass of polystyrene and/or 0 to 20% by mass of plasticizer.
In a second aspect, the present invention discloses a process for preparing a low dielectric constant glass fiber reinforced polyphenylene ether composition as defined in any one of the preceding claims, comprising the steps of:
Firstly premixing polyphenyl ether and a processing aid, and then adding an inorganic filler for mixing to obtain a premix;
Premix is added into a main feeder of the double-screw extruder, and low-dielectric constant and low-loss glass fiber is added into a side feeder of the double-screw extruder for extrusion granulation.
Preferably, the polyphenylene ether and the processing aid are premixed at 500-700rpm for 8-10min, mixed at 200-300rpm for 30-45s after the inorganic filler is added, the temperature of the feeding zone of the twin-screw extruder is 50-100 ℃, the temperature of the melting zone is 280-300 ℃, the temperature of the mixing zone is 280-310 ℃, the temperature of the dispersing zone is 280-320 ℃, the rotating speed is 280-350rpm, and the total extrusion speed is 25-50kg/h.
The invention discloses an application of the low dielectric constant glass fiber reinforced polyphenyl ether composition in high-frequency electronic equipment.
The working principle of the invention is as follows:
The carbon-doped silicon oxide molecules are easy to form three ring-opened silicon-oxygen bonds at high temperature, so that grafting can be conveniently formed by combining the carbon-doped silicon oxide molecules with terminal hydroxyl groups of polyphenyl ether molecules in a double-screw extruder, the combination degree between glass fibers and polyphenyl ether is improved, the temperature resistance, the impact resistance and the rigidity of the polymer are further enhanced, and the water absorption rate of a molded product of the polymer is reduced. According to the prior researches (Wang Juan, wang Jianghua. Influence factor study of water absorption on dielectric constant and dielectric loss angle [ J ]. Printed circuit information, 2010 (11): 4.DOI:10.3969/J. Issn.1009-0096.2010.11.005.) it is known that the influence of water absorption of a material on dielectric constant and dielectric loss is proportional, so that the smaller the water absorption of the material is, the smaller the dielectric constant and dielectric loss of a copper-clad plate prepared from the material are.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a low-dielectric-constant glass fiber reinforced polyphenyl ether composition and a preparation method thereof, and a copper-clad plate prepared from the low-dielectric-constant glass fiber reinforced polyphenyl ether composition has the advantages of low dielectric constant, extremely small high-frequency dielectric loss performance, excellent temperature resistance, good processability and the like. The circuit board made of the substrate material can be widely used for 5G base station antenna oscillators, vehicle information and communication systems, electronic toll collection systems, radomes (including aircrafts, ships, ground and vehicle-mounted radars), military antennas and the like.
1. The polyphenylene oxide resin has the greatest advantages of being capable of providing low dielectric constant and low dielectric loss and conforming to the processing characteristics of copper-clad plate materials. The circuit board manufactured by the method is not only suitable for the requirements of the existing high-frequency high-speed circuit board, but also brings possibility for the development of more 5G products in the future due to the characteristics of low density, high flame retardant property, environmental protection process route and the like.
2. The low-dielectric-constant low-loss glass fiber reinforced polyphenyl ether resin composition and the preparation method thereof can improve the rigidity and the temperature resistance of polyphenyl ether resin, so that the polyphenyl ether resin composition can pass the standard test in the downstream PCB manufacturing process.
3. The inorganic phosphorus compound (plasticizer triphenyl phosphate) can improve the flame retardant capability, and the inorganic fillers such as titanium dioxide, alumina, kaolin, talcum powder and the like can reduce the expansion coefficient and improve the heat resistance.
4. The carbon doped silicon oxide (SiCO) is used as a coupling agent, so that the prepared glass fiber with low dielectric constant and low loss can form grafting with the hydroxyl end groups of polyphenyl ether molecules, the bonding degree of the glass fiber is improved, and the water absorption rate of a molding product is greatly reduced.
5. The double-screw extruder is utilized to uniformly mix the formula, then the mixture is molded and granulated, the produced product has good moldability, is easy to process, can not generate the injection molding problems such as flash, and has high production efficiency.
Drawings
Fig. 1 is a schematic structural diagram of a preparation flow of a twin screw extruder.
Fig. 2 is a schematic structural view of a glass fiber drawing test wire.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
In the following description, unless otherwise indicated, the reagents employed are conventional commercial products and the methods employed are means well known in the art.
A low dielectric constant and low loss glass fiber reinforced polyphenyl ether composition. The composition comprises the following components:
The low-dielectric-constant low-loss glass fiber has a dielectric constant of less than 3.8, a dielectric loss of less than 0.001, a glass density of 2.28-2.32 and a thermal expansion coefficient of less than 3.5, wherein the borosilicate glass fiber comprises 50-52% by mass of silicon dioxide, 13-15% by mass of aluminum oxide, 24-26% by mass of boron oxide, 3-5% by mass of calcium oxide, 3-5% by mass of magnesium oxide and 0.1-1.5% by mass of zirconium oxide.
The glass fiber is prepared through weighing glass fiber components in proportion, mixing, high temperature smelting in electric furnace at 1300-1550 deg.c for 5-10 hr, quenching to obtain broken glass, and secondary smelting in the glass fiber drawing test line at 1300-1350 deg.c for 0.5-1 hr to obtain glass fiber filament with low dielectric constant and fiber diameter of 4-15 microns. The glass fiber precursor is immersed in a container, and carbon doped silicon oxide (SiCO) produced by Hybrid Plastics company of America is added as a coupling agent, wherein the mass ratio of the carbon doped silicon oxide (SiCO) accounts for 0.1-5% of the coupling agent. The impregnated glass fiber precursor is placed in an oven at 50-80 ℃ for preheating, and surface bubbles are removed. And then placing the mixture into a vacuum oven, and setting the drying temperature of three stages, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours, so that the mixture is completely cured. The glass fiber precursor thus obtained has low dielectric constant and low loss, few surface defects and no bubbles. And then the glass fiber is prepared into chopped yarn with the length of about 1-13mm by a chopping machine.
The carbon-doped silicon oxide molecules are easy to form three ring-opened silicon-oxygen bonds at high temperature, and are combined with hydroxyl end groups of polyphenyl ether molecules in a double-screw extruder to form grafts, so that the combination degree of glass fibers is improved, the temperature resistance, the impact resistance and the rigidity of the polymer are enhanced, and the water absorption rate of a molded product of the polymer is reduced. The molded product includes injection molded products, heat extruded sheets, films, drawn products, die cast products, hot pressed sheets and the like. There are researches showing that the influence of water absorption on dielectric constant and dielectric loss angle is in direct proportion to the influence of water absorption of materials on dielectric constant and dielectric loss, and the smaller the water absorption of materials is, the smaller the dielectric constant and dielectric loss of copper-clad plates prepared from the copper-clad plates are.
The inorganic filler comprises one or more of titanium dioxide, aluminum oxide, kaolin and talcum powder.
The processing aid includes an antioxidant, a light stabilizer, a mold release agent, a UV stabilizer, a lubricant, etc., and is added in an appropriate amount as needed to improve or increase the corresponding properties without affecting other properties of the resin composition.
The preparation method of the resin composition comprises the steps of premixing polyphenyl ether resin and a processing aid by utilizing a double-screw extruder production line, setting the rotating speed of a blade to be 500-700 rpm in a high-speed mixer, adding inorganic fillers such as titanium dioxide, barium titanate and the like after mixing for 8-10 minutes, setting the rotating speed of slurry to be 200-300 rpm, and mixing for 30-45 seconds to obtain the premix. The premix was placed in the main feeder and the low dielectric constant low loss glass fiber was placed in the side feeder. Setting the temperature of a feeding area of the twin-screw extruder to be 50-100 ℃, the temperature of a melting area to be 280-300 ℃, the temperature of a mixing area to be 280-310 ℃ and the temperature of a dispersing area to be 280-320 ℃. The rotational speed of the twin-screw extruder is set to 280-350RPM, and the total extrusion speed is 25-50kg/h. The modified granulation is carried out according to the following process (figure 1) to obtain the product.
In the following examples, blue star LXR series is adopted for polyphenyl ether, glass fiber is purchased from Zaoqing international composite material CPIC, inorganic filler is purchased from Komu chemistry, american Hybrid Plastics are adopted as processing aids (the selected processing aids meet the functional requirements, no special limitation is imposed on specific types), zhenjiang Qimei chemical is adopted as polystyrene, and plasticizer (triphenyl phosphate) is derived from Zhejiang Mo Cheng.
Comparative example 1
The glass fiber was weighed according to the following proportions, with 50% by mass of silica, 15% by mass of alumina, 25% by mass of boron oxide, 5% by mass of calcium oxide, 4% by mass of magnesium oxide and 1% by mass of zirconium oxide. Mixing uniformly, placing in a crucible, melting at high temperature in an electric furnace at 1350 ℃, preserving heat for 8 hours, quenching to obtain broken glass, and secondarily melting for 0.5 hour by using a glass fiber drawing experiment line at 1350 ℃ to obtain a glass fiber precursor with low dielectric constant and low loss, wherein the fiber diameter is about 13 microns. The glass fiber precursor is immersed in a container and an impregnating compound for 30 minutes, and the immersed glass fiber precursor is placed in a 50 ℃ oven for preheating, so that surface bubbles are removed. And then placing the mixture into a vacuum oven, and setting the drying temperature of three stages, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours, so that the mixture is completely cured. The glass fiber precursor with low dielectric constant and low loss has few surface defects and no bubbles, and the glass fiber is prepared into chopped yarn A (with unmodified surface) with the length of about 4mm by a chopping machine.
This chopped yarn A was used for modifying the polyphenylene ether composition, and the composition 1 was weighed in the following ratio, and plastic pellets were obtained by a twin-screw extrusion line.
The preparation method comprises the following steps:
1) Premixing polyphenyl ether resin, polystyrene, a processing aid antioxidant and a processing aid light stabilizer, controlling the rotating speed of a blade to be 500 revolutions per minute in a high-speed mixer, mixing for 8 minutes, adding inorganic filler talcum powder, controlling the rotating speed of slurry to be 200 revolutions per minute, and mixing for 30 seconds to obtain the premix.
2) The premix was placed in the main feeder of the twin-screw extrusion line and the chopped yarn a was placed in the side feeder of the twin-screw extrusion line. The twin screw extruder feed zone temperature was controlled at 50 ℃, melt zone temperature 280 ℃, mixing zone temperature 280 ℃, dispersion zone temperature 280 ℃ and twin screw extruder speed 280RPM with a total extrusion speed of 25kg/h. The modified granulation was performed according to the following procedure (fig. 1) to obtain composition 1.
Comparative example 2
The glass fiber was weighed according to the following proportions, with 50% by mass of silica, 15% by mass of alumina, 25% by mass of boron oxide, 5% by mass of calcium oxide, 4% by mass of magnesium oxide and 1% by mass of zirconium oxide. Mixing uniformly, placing in a crucible, melting at high temperature in an electric furnace at 1350 ℃, preserving heat for 8 hours, quenching to obtain broken glass, and secondarily melting for 0.5 hour by using a glass fiber drawing experiment line at 1350 ℃ to obtain a glass fiber precursor with low dielectric constant and low loss, wherein the fiber diameter is about 13 microns. The glass fiber precursor is immersed in a container and an impregnating compound for 30 minutes, and the immersed glass fiber precursor is placed in a 50 ℃ oven for preheating, so that surface bubbles are removed. And then placing the mixture into a vacuum oven, and setting the drying temperature of three stages, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours, so that the mixture is completely cured. The glass fiber precursor with low dielectric constant and low loss has few surface defects and no bubbles, and the glass fiber is prepared into chopped yarn A (with unmodified surface) with the length of about 4mm by a chopping machine.
This chopped yarn A was used for modifying the polyphenylene ether composition, and composition 2 was weighed in the following ratio, and plastic pellets were obtained by a twin-screw extrusion line.
The preparation method comprises the following steps:
1) Premixing polyphenyl ether resin, plasticizer, processing aid antioxidant and processing aid light stabilizer, controlling the rotating speed of a blade to be 500 revolutions per minute in a high-speed mixer, mixing for 8 minutes, adding inorganic filler talcum powder, controlling the rotating speed of slurry to be 200 revolutions per minute, and mixing for 30 seconds to obtain premix.
2) The premix was placed in the main feeder of the twin-screw extrusion line and the chopped yarn a was placed in the side feeder of the twin-screw extrusion line. The twin screw extruder feed zone temperature was controlled at 50 ℃, melt zone temperature 280 ℃, mixing zone temperature 280 ℃, dispersion zone temperature 280 ℃ and twin screw extruder speed 280RPM with a total extrusion speed of 25kg/h. The modified granulation was performed according to the following procedure (fig. 1) to obtain composition 2.
Example 1
The glass fiber was weighed according to the following proportions, with 50% by mass of silica, 15% by mass of alumina, 25% by mass of boron oxide, 5% by mass of calcium oxide, 4% by mass of magnesium oxide and 1% by mass of zirconium oxide. Mixing uniformly, placing in a crucible, melting at high temperature in an electric furnace at 1350 ℃, preserving heat for 8 hours, quenching to obtain broken glass, and secondarily melting for 0.5 hour by using a glass fiber drawing experiment line at 1350 ℃ to obtain a glass fiber precursor with low dielectric constant and low loss, wherein the fiber diameter is about 13 microns. The glass fiber precursor was immersed in a container and impregnating agent for 30 minutes, and carbon doped Silica (SiCO) produced by Hybrid Plastics, inc. of America was added as a coupling agent in a mass ratio of 3% of the coupling agent. The impregnated glass fiber precursor is placed in an oven at 50 ℃ for preheating, and surface bubbles are removed. And then placing the mixture into a vacuum oven, and setting the drying temperature of three stages, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours, so that the mixture is completely cured. The glass fiber precursor with low dielectric constant and low loss has few surface defects and no bubbles, and the glass fiber is prepared into chopped yarn B (surface modification) with the length of about 4mm by a chopped machine.
This chopped yarn B was used for modifying the polyphenylene ether composition, and the composition 3 was weighed in the following ratio, and plastic pellets were obtained by a twin-screw extrusion line.
The preparation method comprises the following steps:
1) Premixing polyphenyl ether resin, plasticizer, processing aid antioxidant and processing aid light stabilizer, controlling the rotating speed of a blade to be 500 revolutions per minute in a high-speed mixer, mixing for 8 minutes, adding inorganic filler talcum powder, controlling the rotating speed of slurry to be 200 revolutions per minute, and mixing for 30 seconds to obtain premix.
2) The premix was placed in the main feeder of the twin-screw extrusion line and the chopped yarn B was placed in the side feeder of the twin-screw extrusion line. The twin screw extruder feed zone temperature was controlled at 50 ℃, melt zone temperature 280 ℃, mixing zone temperature 280 ℃, dispersion zone temperature 280 ℃ and twin screw extruder speed 280RPM with a total extrusion speed of 25kg/h. Modified granulation was performed according to the following procedure (fig. 1) to obtain composition 3.
Example 2
The glass fiber was weighed according to the following proportions, with 50% by mass of silica, 15% by mass of alumina, 25% by mass of boron oxide, 5% by mass of calcium oxide, 4% by mass of magnesium oxide and 1% by mass of zirconium oxide. Mixing uniformly, placing in a crucible, melting at high temperature in an electric furnace at 1350 ℃, preserving heat for 8 hours, quenching to obtain broken glass, and secondarily melting for 0.5 hour by using a glass fiber drawing experiment line at 1350 ℃ to obtain a glass fiber precursor with low dielectric constant and low loss, wherein the fiber diameter is about 13 microns. The glass fiber precursor was immersed in a container and impregnating agent for 30 minutes, and carbon doped Silica (SiCO) produced by Hybrid Plastics, inc. of America was added as a coupling agent in a mass ratio of 3% of the coupling agent. The impregnated glass fiber precursor is placed in an oven at 50 ℃ for preheating, and surface bubbles are removed. And then placing the mixture into a vacuum oven, and setting the drying temperature of three stages, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours, so that the mixture is completely cured. The glass fiber precursor with low dielectric constant and low loss has few surface defects and no bubbles, and the glass fiber is prepared into chopped yarn B (surface modification) with the length of about 4mm by a chopped machine.
This chopped yarn B was used for the modified polyphenylene ether composition, and composition 4 was weighed in the following ratio, and plastic pellets were obtained by a twin-screw extrusion line.
The preparation method comprises the following steps:
1) Premixing polyphenyl ether resin, polystyrene, a processing aid antioxidant and a processing aid light stabilizer, controlling the rotating speed of a blade to be 500 revolutions per minute in a high-speed mixer, mixing for 8 minutes, adding inorganic filler titanium dioxide, controlling the rotating speed of slurry to be 200 revolutions per minute, and mixing for 30 seconds to obtain the premix.
2) The premix was placed in the main feeder of the twin-screw extrusion line and the chopped yarn B was placed in the side feeder of the twin-screw extrusion line. The twin screw extruder feed zone temperature was controlled at 50 ℃, melt zone temperature 280 ℃, mixing zone temperature 280 ℃, dispersion zone temperature 280 ℃ and twin screw extruder speed 280RPM with a total extrusion speed of 25kg/h. The modified granulation was performed according to the following procedure (fig. 1) to obtain composition 4.
Comparative example 3
Low dielectric constant glass fiber ECS309-3-K/HL, fiber diameter 13 microns, purchased from Chongqing composite International Inc. CPIC was designated as cut yarn C. This chopped yarn C was used for modifying the polyphenylene ether composition, and the composition 5 was weighed in the following ratio, and plastic pellets were obtained by a twin-screw extrusion line.
The preparation method comprises the following steps:
1) Premixing polyphenyl ether resin, polystyrene, a processing aid antioxidant and a processing aid light stabilizer, controlling the rotating speed of a blade to be 500 revolutions per minute in a high-speed mixer, mixing for 8 minutes, adding inorganic filler titanium dioxide, controlling the rotating speed of slurry to be 200 revolutions per minute, and mixing for 30 seconds to obtain the premix.
2) The premix was placed in the main feeder of the twin-screw extrusion line and the chopped yarn B was placed in the side feeder of the twin-screw extrusion line. The twin screw extruder feed zone temperature was controlled at 50 ℃, melt zone temperature 280 ℃, mixing zone temperature 280 ℃, dispersion zone temperature 280 ℃ and twin screw extruder speed 280RPM with a total extrusion speed of 25kg/h. Modified granulation was performed according to the following procedure (fig. 1) to obtain composition 5.
Comparative example 4
Low dielectric constant glass fiber ECS301HP-3-K/HL, available from Chongqing composite International Inc. CPIC, having a fiber diameter of 13 microns was designated as cut yarn D. This chopped yarn D was used for modifying the polyphenylene ether composition, and the composition 6 was weighed in the following ratio, and plastic pellets were obtained by a twin-screw extrusion line.
The preparation method comprises the following steps:
1) Premixing polyphenyl ether resin, a plasticizer, a processing aid antioxidant and a processing aid light stabilizer, controlling the rotating speed of a blade to be 500 revolutions per minute in a high-speed mixer, mixing for 8 minutes, adding inorganic filler titanium dioxide, controlling the rotating speed of slurry to be 200 revolutions per minute, and mixing for 30 seconds to obtain the premix.
2) The premix was placed in the main feeder of the twin-screw extrusion line and the chopped yarn B was placed in the side feeder of the twin-screw extrusion line. The twin screw extruder feed zone temperature was controlled at 50 ℃, melt zone temperature 280 ℃, mixing zone temperature 280 ℃, dispersion zone temperature 280 ℃ and twin screw extruder speed 280RPM with a total extrusion speed of 25kg/h. Modified granulation was performed according to the following procedure (fig. 1) to obtain composition 5.
Comparative example 5
This comparative example is a PPS composition purchased from selainius 1140L4.
The compositions of the above examples and comparative examples were tested for dielectric constant and dielectric loss at different frequencies by a quasi-optical cavity method, for heat distortion temperature by an ISO 75-2/A method, for water absorption by a constant temperature and humidity oven under different conditions, and the test results are shown in tables 1 to 3.
TABLE 1 dielectric constants (DK) and dielectric losses (Df) of the resin compositions of examples 1 and 2 and comparative examples 1 to 5 at different frequencies
From Table 1, it is concluded that the dielectric loss of the polyphenylene ether resin composition was better than that of the polyphenylene sulfide resin composition, that of the compositions 4 and 5 were higher than that of the compositions 1, that of the compositions 2 and 3 and 6, because titanium dioxide was contained in the system, and that of the anatase type titanium dioxide was 48.
TABLE 2 Heat distortion temperatures (°C) of the resin compositions of examples 1,2 and comparative examples 1-5
From Table 2, it is concluded that the heat distortion temperatures of polyphenylene ether composition 1, composition 4 and composition 5, each containing polystyrene groups, are less than 170℃and fail to meet the requirements for downstream processing of PCBs.
TABLE 3 dielectric constants and dielectric losses at 20GHz with different humidity for the resin compositions of examples 1, 2 and comparative examples 1-5
From Table 3, it is concluded that the permittivity of the PPS composition drifts with increasing relative humidity, which is not satisfactory for the PCB industry, where the permittivity drifts within + -0.1, and that the dielectric loss increases with increasing relative humidity. Composition 3 exhibited the best performance, with dielectric constant and dielectric loss remaining almost unchanged with changes in relative humidity. Composition 1, composition 2 and composition 4 exhibited acceptable properties. Composition 5 and composition 6 because glass fiber is not suitable for modification of polyphenyl ether, polyphenyl ether resin and glass fiber have poor binding force, the surface of a test sample is uneven, and water molecules are easy to adsorb, so that the dielectric loss of the test sample is greatly increased along with the rise of relative humidity.
From a combination of the performance tests of tables 1-3, the formulations of composition 3 (example 1) and composition 4 (example 2) have optimal results, stable and excellent dielectric constants and dielectric losses, both at high frequencies at different frequencies and at different relative humidities, and heat distortion temperatures that are sufficient to meet downstream PCB processing requirements. In the formulation of the composition 2 (comparative example 2) and the composition 3 (example 1), the glass fibers are all prepared from the same proportion and raw materials, and compared with the two groups of properties, the modified glass fibers provided by the scheme can still maintain excellent dielectric constant and dielectric loss under high humidity and high frequency, so that the bonding degree between the modified glass fibers and the polyphenyl ether is fully improved, the water absorption is lower, and the influence on the dielectric constant and the dielectric loss is small.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The low dielectric constant glass fiber reinforced polyphenyl ether composition is characterized by comprising the following components in parts by mass:
25-60% of polyphenyl ether;
10-40% of low-dielectric constant low-loss glass fiber;
0.1-50% of inorganic filler;
0.1-10% of processing aid;
the low-dielectric-constant low-loss glass fiber has a dielectric constant of less than 3.8 and a dielectric loss of less than 0.001 under the condition of 1MHz, and the surface of the low-dielectric-constant low-loss glass fiber is coated with carbon-doped silicon oxide as a coupling agent.
2. The low dielectric constant glass fiber reinforced polyphenylene ether composition according to claim 1, wherein the low dielectric constant low loss glass fiber comprises the following components by mass percent, 50-52% of silicon dioxide, 13-15% of aluminum oxide, 24-26% of boron oxide, 3-5% of calcium oxide, 3-5% of magnesium oxide and 0.1-1.5% of zirconium oxide.
3. The low dielectric constant glass fiber reinforced polyphenyl ether composition as set forth in claim 2, wherein the low dielectric constant low loss glass fiber is prepared through the steps of mixing the components, melting for the first time, quenching to obtain broken glass, melting for the second time to obtain glass fiber precursor, immersing the glass fiber precursor in carbon doped silica, transferring to a preheated oven to remove surface bubbles, transferring to a vacuum oven to dry and solidify, and finally chopping by a chopping machine.
4. The glass fiber reinforced polyphenylene ether composition with low dielectric constant according to claim 3, wherein the primary melting temperature is 1300-1550 ℃ and the heat preservation is 5-10 hours, the secondary melting temperature is 1300-1350 ℃ and the heat preservation is 0.5-1 hour, the surface bubble removal is carried out in a 50-80 ℃ oven, and the drying and curing are carried out in three steps, namely, drying at 50 ℃ for 1 hour, drying at 100 ℃ for 2 hours and drying at 120 ℃ for 4 hours.
5. The low dielectric constant glass fiber reinforced polyphenylene ether composition of claim 1, wherein the carbon doped silica is present in an amount of 0.1 to 5% by weight of the glass fiber.
6. The low dielectric constant glass fiber reinforced polyphenyl ether composition as set forth in claim 1, wherein the inorganic filler comprises one or more of titanium dioxide, aluminum oxide, kaolin and talcum powder, and the processing aid comprises an antioxidant, a light stabilizer, a release agent, a UV stabilizer and a lubricant.
7. The low dielectric constant glass fiber reinforced polyphenylene ether composition according to claim 1, further comprising 0 to 30% by mass of polystyrene and/or 0 to 20% by mass of plasticizer.
8. A method for preparing the low dielectric constant glass fiber reinforced polyphenylene ether composition of any one of claims 1 to 7, comprising the steps of:
Firstly premixing polyphenyl ether and a processing aid, and then adding an inorganic filler for mixing to obtain a premix;
Premix is added into a main feeder of the double-screw extruder, and low-dielectric constant and low-loss glass fiber is added into a side feeder of the double-screw extruder for extrusion granulation.
9. The method for preparing a low dielectric constant glass fiber reinforced polyphenylene ether composition according to claim 8, wherein the polyphenylene ether and the processing aid are premixed at 500-700rpm for 8-10min, and mixed at 200-300rpm for 30-45s after adding the inorganic filler, wherein the temperature of the feeding zone of the twin-screw extruder is 50-100 ℃, the temperature of the melting zone is 280-300 ℃, the temperature of the mixing zone is 280-310 ℃, the temperature of the dispersing zone is 280-320 ℃, the rotating speed is 280-350rpm, and the total extrusion speed is 25-50kg/h.
10. Use of the low dielectric constant glass fiber reinforced polyphenylene ether composition as defined in any one of claims 1 to 7 in high frequency electronic devices.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5884844A (en) * | 1981-11-16 | 1983-05-21 | Asahi Shiyueebell Kk | Resin composition |
| CN102993683A (en) * | 2012-11-27 | 2013-03-27 | 广东生益科技股份有限公司 | Resin composition and use thereof |
| JP2017141314A (en) * | 2016-02-08 | 2017-08-17 | 三菱瓦斯化学株式会社 | Prepreg |
| CN110951177A (en) * | 2019-12-13 | 2020-04-03 | Oppo广东移动通信有限公司 | Nano-injection composite material and preparation method thereof, housing assembly and electronic device |
| CN113416401A (en) * | 2021-06-10 | 2021-09-21 | 华南理工大学 | Low-dielectric glass fiber reinforced PC/PPO composite material and preparation method thereof |
| CN113652074A (en) * | 2020-09-17 | 2021-11-16 | 上海恒什塑料技术有限公司 | Polyphenyl ether base material for high-frequency high-speed copper-clad plate and preparation method and application thereof |
-
2024
- 2024-03-13 CN CN202410285816.7A patent/CN119119711A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5884844A (en) * | 1981-11-16 | 1983-05-21 | Asahi Shiyueebell Kk | Resin composition |
| CN102993683A (en) * | 2012-11-27 | 2013-03-27 | 广东生益科技股份有限公司 | Resin composition and use thereof |
| JP2017141314A (en) * | 2016-02-08 | 2017-08-17 | 三菱瓦斯化学株式会社 | Prepreg |
| CN110951177A (en) * | 2019-12-13 | 2020-04-03 | Oppo广东移动通信有限公司 | Nano-injection composite material and preparation method thereof, housing assembly and electronic device |
| CN113652074A (en) * | 2020-09-17 | 2021-11-16 | 上海恒什塑料技术有限公司 | Polyphenyl ether base material for high-frequency high-speed copper-clad plate and preparation method and application thereof |
| CN113416401A (en) * | 2021-06-10 | 2021-09-21 | 华南理工大学 | Low-dielectric glass fiber reinforced PC/PPO composite material and preparation method thereof |
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