CN116478520A - Low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material and preparation method thereof - Google Patents

Low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material and preparation method thereof Download PDF

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CN116478520A
CN116478520A CN202211680142.8A CN202211680142A CN116478520A CN 116478520 A CN116478520 A CN 116478520A CN 202211680142 A CN202211680142 A CN 202211680142A CN 116478520 A CN116478520 A CN 116478520A
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dielectric
low
flame retardant
retardant
polycarbonate material
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朱爱华
周志敏
赵志刚
程方清
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Shanghai Changwei Jinci Engineering Plastic Co ltd
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Shanghai Changwei Jinci Engineering Plastic Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation

Abstract

The invention discloses a low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material which is prepared from the following components in percentage by mass: 43-82% of siloxane copolycarbonate resin, 9.8-25% of chopped low-dielectric glass fiber, 5-15% of modified hollow glass beads, 1-10% of polyphosphate flame retardant, 1-4% of polyphenyl siloxane flame retardant, 0.1-1% of silane coupling agent, 1-5% of organosilicon toughening agent and 0.1-2% of auxiliary agent. The invention adopts the combination of the chopped low dielectric glass fiber and the modified hollow glass microsphere, is applied to the siloxane copolycarbonate resin, has excellent comprehensive performance, obtains lower dielectric constant and dielectric loss, and meets the use requirement of 5G.

Description

Low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material and preparation method thereof
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a low-dielectric, halogen-free, flame-retardant, weather-resistant and reinforced polycarbonate material and a preparation method thereof.
Background
The fifth generation mobile phone mobile communication standard, also called fifth generation mobile communication technology, is abbreviated as 5G. The difference between the 5G mobile communication and the previous four-generation mobile communication is that the previous four-generation mobile communication is a single technology, and the 5G is the sum of the previous four-generation mobile communication, so that the peak rate of the 5G mobile communication is higher, safer and wider in coverage range. The 5G mobile communication makes up for the loopholes existing in the 4G mobile communication, the technology is more advanced, the current demands of people on the network can be met, and the method is a mainstream trend developed in a future period of time. The 5G communication adopts millimeter wave band, and has the greatest advantages of high propagation speed and great penetration force and attenuation. Thus, 5G requires that the dielectric constant and dielectric loss of the propagation medium material be small to achieve efficient reception and transmission, and remain stable over a wide frequency range. The dielectric constant of the 5G device for low dielectric materials is less than 3 and is far less than the standard that the 4G device requires between 3.4 and 3.7 for dielectric constant. High frequency high speed transmission also places demands on composite materials used in smartphones, requiring low dielectric loss at high frequency voltages. Therefore, reducing the dielectric constant and dielectric loss of the material is an urgent need for 5G communication. In addition, the 5G smart terminals and base stations will be developed toward miniaturization, lightness and thinness, requiring that the composite materials used therein have excellent mechanical properties and melt molding processability to be molded into high-strength thin-wall structural parts.
The polycarbonate is widely used in the technical fields of electronic appliances, automobiles, machine manufacturing, computers and the like because of the characteristics of heat resistance, flame retardance, good impact resistance, easiness in processing and molding, low cost and the like. The Polycarbonate (PC) can further improve the strength, fatigue resistance, stress cracking resistance and the like after being reinforced by glass fibers, and is used for preparing outer frames, middle frames and bases of electrical equipmentStation radomes and like structure packaging components. However, the PC composite material is reinforced by common alkali-free glass fiber (E-glass fiber), because the E-glass fiber has higher Dk (6.80-7.10, 1 MHz) and Df (6.00 x 10) -3 1 MHz), the filling of which leads to the deterioration of the dielectric properties of PC, and the appearance of the reinforced floating fiber is more obvious due to the orientation of the alkali-free glass fiber, which is difficult to meet the 5G application requirement. The dielectric constant of the common PC is 3.0-3.1, the dielectric loss is 0.009, and after the glass fiber is reinforced and modified, the dielectric constant of the common PC is 3.5, the dielectric loss is 0.009, and the requirements of 5G equipment cannot be met. In addition, the common polycarbonate has insufficient flame retardance and cannot meet the situation of high or high flame retardance grade requirement.
The traditional brominated flame retardant has high flame retardant efficiency, but generates a large amount of smoke, tetrabromodibenzodioxane, tetrabromodibenzofuran and other cancerogenic substances in the combustion and thermal cracking processes; although the low-molecular phosphate flame retardant avoids harmful substances generated in the combustion process of a brominated flame retardant system, the low-molecular phosphate flame retardant has low melting point and high volatility, and is easy to cause great reduction of heat resistance of materials and volatilization loss in the forming process; the sulfonate flame retardant accelerates the carbonization rate of bisphenol A polycarbonate during combustion, promotes the molecular crosslinking of the polymer, has small addition amount and high efficiency, can keep the material transparent, but can not meet the flame retardant requirement of thin-wall parts; the phosphazene flame retardant has the advantages of excellent flame retardance, water resistance, oxidation resistance, thermal stability, molding processability, low smoke generation amount during combustion or thermal cracking, and the like, but has larger addition amount, and influences the heat resistance and the light transmittance of the material after the phosphazene flame retardant is added; the traditional polysiloxane flame retardant is important for researchers due to excellent processability, flame retardance and good mechanical properties, is particularly friendly to the environment, but has poor thin-wall flame retardant effect when being singly used, has large addition amount and high cost, and is generally used as a synergistic flame retardant for compounding. The phenyl organosiloxane flame retardant has better thermal stability, higher thermal decomposition activation energy and thermal decomposition temperature, and better flame retardant effect, and the higher the phenyl content of the silicon flame retardant, the denser the carbon layer formed after the prepared flame retardant material is combusted, and the better the flame retardant effect.
Patent publication No. CN115124826AThe application 'a glass fiber reinforced polycarbonate material and a preparation method thereof' discloses a glass fiber reinforced polycarbonate material and a preparation method and application thereof, wherein the glass fiber reinforced polycarbonate material comprises the following components in parts by weight: 40-95 parts of polycarbonate, 1-40 parts of alkali-free glass fiber and 1-40 parts of porous glass fiber; siO in the porous glass fiber 2 The mass percentage content of (2) is more than or equal to 95 percent. The invention combines the alkali-free glass fiber with low dielectric loss and the porous glass fiber and modifies the polycarbonate, thereby comprehensively improving the dielectric property, mechanical property and processability of the material, leading the material to have high impact toughness, good mechanical property and good processing property, having lower dielectric loss and dielectric constant, achieving the performance balance in a plurality of aspects such as excellent dielectric property, processability, comprehensive mechanical property and the like, and meeting the requirements of the fields such as high-frequency communication equipment, automobile parts, electric appliances and the like. The invention compounds the alkali-free glass fiber with low dielectric loss and the porous glass fiber, and modifies the polycarbonate, the dielectric constant of the modified material at 5GHz is 2.9-3.25, and the appearance fiber floating is obvious due to the orientation of the glass fiber. In addition, the material does not modify the flame retardance and weather resistance, can not meet the occasion with higher requirements on flame retardance grade, and can not be suitable for outdoor use.
Patent application publication No. CN113416401A, low dielectric glass fiber reinforced PC/PPO composite material and preparation thereof, discloses a low dielectric glass fiber reinforced PC/PPO composite material and a preparation method thereof. The PC/PPO composite material comprises the following components in percentage by mass: 29.8 to 41.5 percent of polycarbonate, 29.7 to 38.0 percent of modified polyphenyl ether, 20.0 to 40.0 percent of chopped low dielectric glass fiber, 0.1 to 0.4 percent of antioxidant and 0.3 to 0.6 percent of dispersing agent; the Dk of the composite material is reduced to 2.83-3.10, and Df is reduced to 1.53 multiplied by 10 -3 ～2.40×10 -3 The application requirement of 5G/6G on low dielectric materials can be met, and the good compatibility and the lower melt viscosity ensure that the composite material has high mechanical property and excellent molding processability. The patent application with publication number CN105440628A discloses a reinforced flame-retardant PC/PPO composite material, which comprises the following components: 20-30 parts of PC resin,14.9-22 parts of PPO (polyphenyl ether), 3-5.2 parts of PC-PPO block copolymer, 5-8 parts of SEBS graft, 5-8 parts of polypropylene elastomer graft, 0.5-1 part of amino modified silicone oil, 0.5-1 part of amino silane coupling agent and 20-30 parts of glass fiber; composite flame retardants, antioxidants and light stabilizers. The composite materials disclosed in the two patents have good tensile strength, rigidity and high-low temperature toughness, but the PPO material has high viscosity and high rigidity, so that the processing fluidity of the material is low, and thin-wall parts are difficult to prepare.
Patent application publication No. CN114716802A, a low dielectric cell phone middle frame substrate and a preparation method thereof, discloses a low dielectric cell phone middle frame substrate and a preparation method thereof, and the cell phone middle frame substrate comprises the following components in parts by weight: 55-70 parts of polycarbonate, 10-25 parts of polyethylene terephthalate, 10-18 parts of modified hollow glass microspheres, 5-15 parts of toughening agent, 3-8 parts of dispersing agent, 0.4-1 part of antioxidant and 0.5-1.5 parts of lubricant. The mobile phone middle frame substrate has the advantages of better dielectric property, excellent mechanical property, light weight, low cost and easy processing. The dielectric constant of the base material obtained by the invention is 2.601-2.723, the dielectric loss is 0.00257-0.0036, and the dielectric property is excellent; notched impact strength of 20.22-24.40KJ/m 2 The tensile strength is 36-45MPa, the bending strength is 58-70MPa, the mechanical property is excellent, and the specific gravity is 0.956-0.993g/cm 3 The specific gravity is small and the weight is light. But the strength is lower, and the use requirements of a middle frame, an antenna housing and the like cannot be met.
The structure composition of the chopped low dielectric glass fiber (D-glass fiber) contains more low-polarity components, has Dk (4.20-4.80, 1 MHz) and Df (1.00 x 10) lower than that of the E-glass fiber -3 1 MHz), patent application publication No. WO2017203467A1 uses D-glass fibers instead of E-glass fibers to reinforcement-modify PC, and Dk and Df of the composite material are reduced by 4.2% and 6.8%, respectively, when the glass fiber content is 20wt% as well. It can be seen that the modification of PC is carried out by using D-glass fiber instead of E-glass fiber, the reduction degree of Dk and Df of the obtained composite material is very limited, and the requirement of 5G application cannot be met.
Therefore, reducing the dielectric properties and dielectric loss of the reinforced polycarbonate material and improving the strength, flame retardance, weather resistance and fiber floating of the material are still important to the research in the field.
Disclosure of Invention
The invention aims to provide a low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material.
The invention further aims to provide a preparation method of the low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material, which is prepared from the following components in percentage by mass: 43-82% of siloxane copolycarbonate resin, 9.8-25% of chopped low-dielectric glass fiber, 5-15% of modified hollow glass beads, 1-10% of polyphosphate flame retardant, 1-4% of polyphenyl siloxane flame retardant, 0.1-1% of silane coupling agent, 1-5% of organosilicon toughening agent and 0.1-2% of auxiliary agent.
The low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material is prepared from the following components in percentage by mass: 55.4% of siloxane copolycarbonate resin, 20% of chopped low-dielectric glass fiber, 10% of modified hollow glass beads, 7% of polyphosphate flame retardant, 3% of polyphenyl siloxane flame retardant, 0.3% of silane coupling agent, 3% of organosilicon toughening agent and 1.3% of auxiliary agent.
The siloxane copolycarbonate resin is a polycarbonate resin obtained by copolymerizing bisphenol A and siloxane, the relative molecular weight of the siloxane copolycarbonate resin is 25000-32000, the siloxane content is 5-20%, and FG1760 of Nippon light Xingxing Co., ltd., 8000-05 of LG chemistry is specifically selected. The structure is as follows:
wherein R is 1 、R 2 Each independently selected from C1-C10 alkyl, C6-C18 aryl, alkoxylated C1-C10 alkyl, C6-C18 aryl, preferably methyl, phenyl.
The chopped low dielectric glass fiber, siO 2 The mass percentage content of the polymer is more than or equal to 90 percent, the dielectric constant is 4.2 to 4.6,the dielectric loss is 0.0020-0.0030, and is purchased from Taishan glass fiber Co., ltd, model number is TLD-CS310-3.0-T436S.
The particle diameter of the modified hollow glass microsphere is 15-20 mu m, and the density is 0.125-0.60g/cm 3 The strength is 82MPa-124MPa, the dielectric constant is 1.2-2.0, the dielectric loss is 0.001-0.002, and the material is purchased from 3M company in the United states, and the model is 1M16K.
The relative molecular weight of the polyphosphate flame retardant is 40000-50000, and the structure is as follows:
manufactured by FRX Polymers, usa, model number HM1100.
The polyphenyl siloxane flame retardant is octaphenyl cyclotetrasiloxane, and the molecular structure is as follows:
the preparation method comprises the following steps: 200g of diphenyl dimethoxy silane, 320g of acetone and 8g of deionized water are put into a three-port bottle provided with a stirring device, a condenser and a thermometer, the three-port bottle is fully stirred to be uniformly mixed, 0.05g of NaOH is dissolved in a beaker containing 20g of methanol, the three-port bottle is put into the three-port bottle after being uniformly mixed, the temperature is raised to 55 ℃, the reflux is started, the reaction is carried out for 4 hours, the three-port bottle is subjected to suction filtration after the reaction is finished, the three-port bottle is washed with absolute ethyl alcohol for 3 times, the three-port bottle is washed with deionized water until filtrate is neutral, and the eight-phenyl cyclotetrasiloxane in a white crystal shape is obtained after vacuum drying. Wherein diphenyldimethoxysilane, acetone, methylene chloride, potassium hydroxide and methanol are used commercially (specific references: yang Rui, etc., research on a high-phenyl-content silicone flame-retardant polycarbonate, [ engineering science and technology, 2021, 195-202.)
The silane coupling agent is at least one selected from gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane or gamma-glycidoxypropyl triethoxy silane. Gamma-glycidoxypropyl trimethoxysilane was purchased from boiling chemical Co., ltd and model KH560.
The organosilicon toughening agent is a core-shell graft copolymer with a core of silicon rubber-acrylic ester and a shell of polymethyl methacrylate, and the silicon content is 70-80 percent, and can be selected from Mitsubishi positive company of Japan, and the model is SX005.
The auxiliary agent is prepared from an antioxidant, a light stabilizer, a processing aid and toner.
The antioxidant is at least one of phosphite antioxidant 168, S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076, and more preferably is a mixture of antioxidant S-9228 and antioxidant 1076.
The light stabilizer is cyanoacrylate ultraviolet absorber, and is purchased from BASF corporation and is of the model Uvinul 3030.
The processing aid is at least one selected from polyethylene wax, oxidized polyethylene wax and pentaerythritol stearate, and more preferably pentaerythritol stearate.
The toner is mainly composed of pigment and lubricant EBS, wherein the pigment is phthalocyanine blue, phthalocyanine green, BR red, HG yellow, 3R blue and the like, and can be purchased from Coryn chemical industry (China); pigment and lubricant EBS according to 1:10 ratio dilution.
The second aspect of the invention provides a preparation method of the low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material, which comprises the following steps:
adding a silane coupling agent into the siloxane copolycarbonate resin, and mixing in a high-speed mixer; adding the polyphosphate flame retardant, the polyphenyl siloxane flame retardant, the organosilicon toughening agent and the auxiliary agent into a high-speed mixer, mixing at a high speed for 6-8 minutes, uniformly mixing, and then feeding the mixture into a double-screw extruder through a main feeder; the chopped low dielectric glass fiber and the modified hollow glass beads are fed into a double-screw extruder from the side feeding of the 4 th section and the 5 th section of the extruder respectively, and are granulated after melt blending; the low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material is obtained.
The temperature of the 11 region of the twin-screw extruder is respectively set to 250 ℃, 260 ℃, 270 DEG C270 ℃, 260 ℃ and 260 DEG C260 ℃, 260 ℃; the obtained pellets were dried at 120℃for 4 hours and then injection molded into standard bars at 280-290 ℃.
The silicone copolycarbonate resin was dried at 110℃for 6 hours in a forced air dryer.
The polyphosphate flame retardant is dried in a vacuum oven at 100 ℃ for 6 hours.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
(1) The short-cut low-dielectric glass fiber and the modified hollow glass microsphere are adopted for compounding, so that the modified hollow glass microsphere is applied to siloxane copolycarbonate resin, has excellent comprehensive performance, obtains lower dielectric constant and dielectric loss, and meets the use requirement of 5G.
(2) The flame retardant is compounded by the polyphosphate flame retardant and the polyphenyl siloxane flame retardant, is applied to the siloxane copolycarbonate resin, has obvious flame retardant synergistic effect, and can meet the thin-wall flame retardant requirement.
(3) The addition of the toughening agent with high silicon content not only improves the impact resistance of the material, but also is beneficial to improving the flame retardant property.
(4) The material has excellent weather resistance and can meet the requirement of 5G outdoor use.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Polycarbonate resin used in comparative example: bisphenol A type aromatic polycarbonate resin purchased from Kochia company has a relative molecular weight of 20000-30000 and a model 2805.
TABLE 1 comparative examples 1-4 and examples 1-5 Components and proportions
Table 2 comparative examples 5-7 and example 6 Components and proportions
The preparation method comprises the following steps:
firstly, drying siloxane copolycarbonate resin or bisphenol A polycarbonate resin for 6 hours at 110 ℃ of a blast drier, and drying a polyphosphate flame retardant in a vacuum oven at 100 ℃ for 6 hours; then adding the silane coupling agent into PC resin according to the proportion, and mixing for 1 minute in a high-speed mixer; adding the polyphosphate flame retardant, the polyphenyl siloxane flame retardant, the organosilicon toughening agent and the auxiliary agent into a high-speed mixer, mixing at a high speed for 6-8 minutes, uniformly mixing, and then feeding the mixture into a double-screw extruder through a main feeder; the chopped low dielectric glass fiber and the modified hollow glass microsphere are fed into a double-screw extruder from the side feeding of the 4 th section and the 5 th section of the extruder respectively, and are granulated after melt blending.
The temperature of the 11 region of the twin-screw extruder was set at 250 ℃, 260 ℃, 270 ℃ respectively 270 ℃, 260 ℃ and 260 ℃. The obtained granules are dried for 4 hours at 120 ℃ and then are subjected to injection molding at 280-290 ℃ to form standard sample bars, thus obtaining the composite material.
Evaluation of implementation Effect
The samples obtained in examples 1 to 8 and comparative examples 1 to 5 above were tested for mechanical properties according to the American Society for Testing and Materials (ASTM) standard, for flame retardant properties according to the UL94 standard, for dielectric constant and dielectric loss according to the ASTM ES 7-83 standard, for flame retardancy according to the UL94 standard, for weather resistance (15 cycles) according to GB/T2423-2013 procedure B, and for color change grey scale after weathering according to ISO 105-A02. The test results are shown in the following table:
TABLE 3 Properties of comparative examples 1-4 and examples 1-5
Table 4 Properties of comparative examples 5-7 and example 6
The test performance results of tables 3 and 4 show that:
(1) Comparative examples 1-5 and comparative example 5 found that the addition of modified hollow glass microspheres significantly reduced the density, dielectric constant and dielectric loss of the composite material because the hollow glass microspheres contained a large number of microscopic holes (air, dielectric constant 1, dielectric loss 0) so that the hollow glass microspheres had low dielectric constant and dielectric loss; and the micropores can generate capillary phenomenon, so that the combination property of the PC resin in a molten state is improved, and the comprehensive mechanical property of the material is improved. However, in comparative example 5, the content of hollow glass fiber was added alone, and the strength and modulus of the material were very low, failing to meet the use requirements. The low dielectric glass fiber contains 90% or more of SiO as compared with the conventional glass fiber 2 Substantially free of MgO, li 2 O、Na 2 O、K 2 O and TiO 2 The dielectric constant and dielectric loss are low. The low dielectric glass fiber and the hollow glass microsphere are matched to obtain the low dielectric composite material with excellent comprehensive performance, and the optimal proportion is the example 2.
(2) Comparative example 2 and comparative example 2 found that the siloxane copolycarbonate resin, in addition to having good low temperature and weather resistance properties, also has lower dielectric constant and dielectric loss, and is more suitable for use in 5G scenes, as compared to the conventional bisphenol a polycarbonate resin. This is due to the si—o bond contained in the molecular chain, which generally has a low dipole moment and a low polarization strength due to the Si atom contained therein.
(3) Comparative example 2 and comparative examples 1 and 3 found that the use of the combination of polyphosphate flame retardant and polyphenylsiloxane flame retardant for reinforcing siloxane copolycarbonate resin has excellent combination properties, does not affect dielectric properties, and can meet the requirements of high heat resistance and high flame retardance. It was found from comparative examples 1 and 2 that the flame retardant effect was not good and the flame retardant requirement could not be satisfied when the polyphosphate flame retardant was used alone or the polyphenylsiloxane flame retardant was used alone. The molecular chain of the silicon flame retardant is Si-O bond, the bond energy is higher, the thermal stability is excellent, the organic silicon can promote the generation of a carbon layer during combustion, the formation of smoke and the development of flame are prevented, and the flame retardant effect is improved. The phenyl organosilicon flame retardant has better flame retardant effect due to higher thermal decomposition activation energy and thermal decomposition temperature; and the higher the phenyl content is, the more compact the carbon layer is formed after combustion, and the better the flame retardant effect is.
(4) Comparative example 2, comparative example 7, found that the composite material has excellent weather resistance by incorporating cyanoacrylate-based ultraviolet absorber, and can satisfy outdoor use. Comparative examples 2, 6 and comparative example 6 find that: the toughening agent with high silicon content is added, so that the impact resistance of the material is improved, the flame retardant property is improved, and the dielectric property is reduced; however, as the amount of the additive increases, the strength of the material decreases, and thus the optimum ratio should be example 2.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.

Claims (9)

1. The low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material is characterized by being prepared from the following components in percentage by mass: 43-82% of siloxane copolycarbonate resin, 9.8-25% of chopped low-dielectric glass fiber, 5-15% of modified hollow glass beads, 1-10% of polyphosphate flame retardant, 1-4% of polyphenyl siloxane flame retardant, 0.1-1% of silane coupling agent, 1-5% of organosilicon toughening agent and 0.1-2% of auxiliary agent.
2. The low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material according to claim 1, wherein the low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material is prepared from the following components in percentage by mass: 55.4% of siloxane copolycarbonate resin, 20% of chopped low-dielectric glass fiber, 10% of modified hollow glass beads, 7% of polyphosphate flame retardant, 3% of polyphenyl siloxane flame retardant, 0.3% of silane coupling agent, 3% of organosilicon toughening agent and 1.3% of auxiliary agent.
3. The low dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material according to claim 1, wherein the siloxane copolycarbonate resin is a polycarbonate resin copolymerized by bisphenol a and siloxane, the relative molecular weight is 25000-32000, and the siloxane content is 5-20%;
the chopped low dielectric glass fiber, siO 2 The mass percentage of the dielectric constant is more than or equal to 90 percent, the dielectric constant is 4.2-4.6, and the dielectric loss is 0.0020-0.0030.
4. The low dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material according to claim 1, wherein the particle size of the modified hollow glass microspheres is 15-20 μm, and the density is 0.125-0.60g/cm 3 The strength is 82MPa-124MPa, the dielectric constant is 1.2-2.0, and the dielectric loss is 0.001-0.002;
the relative molecular weight of the polyphosphate flame retardant is 40000-50000.
5. The low dielectric halogen-free flame retardant weatherable reinforced polycarbonate material of claim 1, wherein the polyphenylsiloxane flame retardant is octaphenylcyclotetrasiloxane;
the silane coupling agent is at least one selected from gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane or gamma-glycidoxypropyl triethoxy silane.
6. The low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material according to claim 1, wherein the organosilicon toughening agent is a core-shell graft copolymer with a silicone rubber-acrylic ester as a core and polymethyl methacrylate as a shell, and the silicon content is 70-80%;
the auxiliary agent is prepared from an antioxidant, a light stabilizer, a processing aid and toner.
7. The low dielectric halogen-free flame retardant weatherable reinforced polycarbonate material of claim 6, wherein the antioxidant is at least one of phosphite antioxidant 168, S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098, hindered phenol antioxidant 1076;
the light stabilizer is cyanoacrylate ultraviolet absorber;
the processing aid is at least one selected from polyethylene wax, oxidized polyethylene wax and pentaerythritol stearate;
the toner is mainly composed of pigment and lubricant EBS, wherein the pigment is phthalocyanine blue, phthalocyanine green, BR red, HG yellow or 3R blue.
8. A method for preparing the low dielectric halogen-free flame retardant weatherable reinforced polycarbonate material according to any one of claims 1 to 7, comprising the steps of:
adding a silane coupling agent into the siloxane copolycarbonate resin, and mixing in a high-speed mixer; adding the polyphosphate flame retardant, the polyphenyl siloxane flame retardant, the organosilicon toughening agent and the auxiliary agent into a high-speed mixer, mixing at a high speed for 6-8 minutes, uniformly mixing, and then feeding the mixture into a double-screw extruder through a main feeder; the chopped low dielectric glass fiber and the modified hollow glass beads are fed into a double-screw extruder from the side feeding of the 4 th section and the 5 th section of the extruder respectively, and are granulated after melt blending; the low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material is obtained.
9. The method for preparing the low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material according to claim 8, wherein, the temperature of the 11 region of the twin-screw extruder is respectively set to 250 ℃, 260 ℃, 270 DEG C270 ℃, 260 ℃ and 260 DEG C260 ℃, 260 ℃; the obtained pellets were dried at 120℃for 4 hours and then injection molded into standard bars at 280-290 ℃.
CN202211680142.8A 2022-12-27 2022-12-27 Low-dielectric halogen-free flame-retardant weather-resistant reinforced polycarbonate material and preparation method thereof Pending CN116478520A (en)

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