WO2021036614A1 - Glass fiber-reinforced polycarbonate composite material and preparation method and use therefor - Google Patents

Glass fiber-reinforced polycarbonate composite material and preparation method and use therefor Download PDF

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WO2021036614A1
WO2021036614A1 PCT/CN2020/103916 CN2020103916W WO2021036614A1 WO 2021036614 A1 WO2021036614 A1 WO 2021036614A1 CN 2020103916 W CN2020103916 W CN 2020103916W WO 2021036614 A1 WO2021036614 A1 WO 2021036614A1
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composite material
glass fiber
fiber reinforced
reinforced polycarbonate
temperature
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PCT/CN2020/103916
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French (fr)
Chinese (zh)
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岑茵
李明昆
艾军伟
陈勇文
刘贤文
吴俊�
丁超
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金发科技股份有限公司
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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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a glass fiber reinforced polycarbonate composite material and a preparation method and application thereof.
  • Polycarbonate resin PC is a thermoplastic engineering plastic with excellent comprehensive properties.
  • its high transparency, good flame retardancy, heat resistance, electrical insulation and dimensional stability, low water absorption and other characteristics have been widely used in the automotive, electronic and electrical, communication industries, construction industries, etc. field.
  • polycarbonate has higher requirements for its impact strength, flexural modulus, tensile strength, fluidity, dielectric loss and other properties.
  • Simple polycarbonate or ordinary polycarbonate The material still cannot meet the requirements, therefore, the polycarbonate material needs to be modified.
  • glass fiber reinforcement is generally used to improve its processability and modification.
  • the existing glass fiber reinforced polycarbonate composite material has the contradiction of high rigidity but low toughness, and the conventional toughening method is to directly add toughening agents, which will also greatly reduce the fluidity of the composite material, and the composite material
  • the improvement of rigidity and toughness is also very limited, and due to the inherent dielectric loss application characteristics of polycarbonate, which severely limits its application in the automotive, electronic and electrical, communications industry, construction industry and other fields, especially the 5G communications industry .
  • the purpose of the present invention is to provide a glass fiber reinforced polycarbonate composite material with both rigidity and toughness, high fluidity and low dielectric loss.
  • Another object of the present invention is to provide a method for preparing the above-mentioned glass fiber reinforced polycarbonate composite material.
  • Another object of the present invention is to provide the use of the above-mentioned glass fiber reinforced polycarbonate composite material.
  • a glass fiber reinforced polycarbonate composite material in parts by weight, includes the following components:
  • the glass fiber reinforced polycarbonate composite material in parts by weight, includes the following composition:
  • the percentage of siloxane content in the glass fiber reinforced polycarbonate composite material to the total weight of the composite material is 0.8 wt% to 18 wt%, preferably 3.5 wt% to 12.5 wt%.
  • the weight ratio of fluorine element and silicon element in the glass fiber reinforced polycarbonate composite material is 1:(0.1-3), preferably 1:(0.5-2).
  • the polycarbonate is selected from one or more of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, and branched polycarbonate; preferably aromatic polycarbonate .
  • the aromatic polycarbonate is an aromatic polycarbonate with a viscosity average molecular weight of 13,000 to 40,000, preferably an aromatic polycarbonate with a viscosity average molecular weight of 18,000 to 28,000.
  • the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained.
  • the viscosity average molecular weight is calculated by using dichloromethane as a solvent and the solution viscosity at a test temperature of 25°C.
  • the above-mentioned preparation method of polycarbonate can be prepared by interfacial polymerization method and transesterification method, and the content of terminal hydroxyl groups can be controlled in the process.
  • the polysiloxane block copolymer includes a polydimethylsiloxane block and a polycarbonate block of bisphenol A, and has 0.8 wt% to 35 wt% of siloxane based on the weight of component B. content.
  • the siloxane content of the glass fiber reinforced polycarbonate composite can be tested by the near-infrared analysis method. The test method is to weigh a fixed weight of glass fiber reinforced polycarbonate composite pellets. The material is tested after being evenly dissolved into flakes with methane.
  • the fluorine-containing compound can be a fiber-shaped or non-fiber-shaped fluoropolymer, preferably a non-fiber-shaped fluoropolymer.
  • the encapsulated fluoropolymer includes a fluoropolymer with a melting point higher than 320°C, such as polyvinyl fluoride.
  • the preferred encapsulated fluoropolymer is polyethylene encapsulated polytetrafluoroethylene, where PE is 40%, and PTFE Is 60%.
  • the molecular weight of the silicone is 50,000 to 300,000.
  • the molecular weight of the silicone is too large, and the compatibility with the matrix is not good, which is likely to cause the performance degradation of the composition, and the molecular weight of the silicone is too small, and it is easy to precipitate and cause surface defects.
  • the glass fiber reinforced polycarbonate composite material of the present invention may also include component F: 0-10 parts of other additives; the other additives are selected from stabilizers, One or more of flame retardants, lubricants, mold release agents, plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
  • Suitable stabilizers may include organic phosphites, such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tris-nonylphenyl phosphite, dimethylbenzene Phosphonates, trimethyl phosphate, etc., organic phosphites, alkylated monohydric phenols or polyhydric phenols, alkylation reaction products of polyhydric phenols and dienes, butylation of p-cresol or dicyclopentadiene Reaction products, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones One or more combinations.
  • organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tris-nonyl
  • Suitable flame retardants may include phosphate-based flame retardants or sulfonate flame retardants.
  • Preferred phosphate flame retardants include bisphenol A diphosphate tetraphenyl ester, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, bisphenol A diphosphate tetraphenyl ester, resorcinol tetra( 2,6-Dimethylphenyl ester) and tetramethylbenzylpiperidine amide;
  • sulfonates can also be selected as flame retardants, such as Rimar salt potassium perfluorobutanesulfonate, KSS potassium diphenylsulfone sulfonate, benzenesulfonate Sodium and the like are suitable.
  • the preparation method of the glass fiber reinforced polycarbonate composite material includes the following steps:
  • the length-to-diameter ratio of the twin-screw extruder is 46:1-50:1; the temperature of the twin-screw extruder from the feeding section to the die is as follows: the temperature of the first zone is 120°C-160°C, and the temperature of the twin-screw extruder is 120°C-160°C.
  • Zone temperature 200°C-230°C three zone temperature 200°C-230°C, four zone temperature 200°C-220°C, five zone temperature 200°C-220°C, six zone temperature 200°C-220°C, seven zone temperature 200°C- 220°C, eight zone temperature 200°C-220°C, nine zone temperature 200°C-220°C, ten zone temperature 200°C-220°C, eleven zone temperature 200°C-220°C, machine head temperature 220°C-240°C, host
  • the rotation speed is 350 rpm-700 rpm.
  • the application of the glass fiber reinforced polycarbonate composite material obtained by the above preparation method in the automobile, electronic and electrical, communication industries, and the construction industry is preferably the application in the 5G communication industry.
  • the present invention has the following beneficial effects:
  • the invention chooses to add a specific content of polysiloxane block copolymer, fluorine-containing compound and silicone to the glass fiber reinforced polycarbonate composite material formula, so as to ensure that the prepared composite material has a specific content of siloxane Content and specific weight ratio of fluorine element and silicon element, the prepared composite material not only has excellent high modulus and high toughness characteristics, but also has excellent processing performance.
  • the composite material has both Rigidity and toughness, while having significantly reduced dielectric loss, suitable for automotive, electronic and electrical, communications industry, construction industry and other fields, especially suitable for 5G communications industry.
  • Izod notched impact strength test method according to ASTM D256-2010 standard
  • Tensile strength test method According to ASTM D638-2014 standard, the tensile speed is 10mm/min;
  • test method of flexural modulus is based on ASTM D790-2010 standard, and the bending speed is 2mm/min;
  • Liquidity test method According to ASTM D1238-2013, the melting temperature is 300°C;
  • Dielectric loss test method According to ASTM D150-11 standard.
  • Component A-1 Aromatic polycarbonate with a viscosity average molecular weight of 19,000, Idemitsu, Japan;
  • Component A-2 Aromatic polycarbonate with a viscosity average molecular weight of 28000, Idemitsu, Japan;
  • the polysiloxane block copolymer used in the present invention is a polysiloxane block copolymer used in the present invention:
  • Component B-1 a polysiloxane block copolymer with a siloxane content of 9wt%, Idemitsu, Japan;
  • Component B-2 Polysiloxane block copolymer with a siloxane content of 30% by weight, Idemitsu, Japan;
  • Component C-1 Toyobo;
  • Fluorine-containing compounds used in the present invention are fluorine-containing compounds used in the present invention:
  • Component D-1 non-fiber shaped fluoropolymer, Guangzhou Entropy Energy
  • Component D-2 Polytetrafluoroethylene encapsulated by polyethylene, in which PE is 40%, PTFE is 60%, and Guangzhou Entropy Energy;
  • Component E-1 silicone with a molecular weight of 50,000, Dow Corning;
  • Component E-2 silicone with a molecular weight of 280,000, Dow Corning;
  • Component F-1 Stabilizer: 2112, Adike;
  • Component F-2 Flame retardant: BDP, Adike.

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Abstract

A glass fiber-reinforced polycarbonate composite material and a preparation method and a use therefor, comprising the following components: component A: 40 parts - 90 parts of a polycarbonate; component B: 5 parts - 60 parts of a polysiloxane block copolymer; component C: 5 parts - 30 parts of a glass fiber; component D: 2 parts - 40 parts of a fluorine-containing compound; and component E: 1 part - 30 parts of silicone. Adding a specific amount of a polysiloxane block copolymer, a fluorine-containing compound, and silicone to the formula of the glass fiber-reinforced polycarbonate composite material is able to ensure that the composite material ultimately produced has a certain siloxane content and a certain mass ratio of fluorine and silicon, causing the composite material produced to have an excellent high modulus of elasticity and high toughness, and also have excellent processability. Unlike conventional reinforcement modification means, the present composite material is provided with both rigidity and toughness, and at the same time, is provided with high fluidity and markedly reduced dielectric loss, and is particularly suited for the 5G communications industry.

Description

一种玻纤增强聚碳酸酯复合材料及其制备方法与应用Glass fiber reinforced polycarbonate composite material and preparation method and application thereof 技术领域Technical field
本发明涉及工程塑料技术领域，特别涉及一种玻纤增强聚碳酸酯复合材料及其制备方法与应用。The invention relates to the technical field of engineering plastics, in particular to a glass fiber reinforced polycarbonate composite material and a preparation method and application thereof.
背景技术Background technique
聚碳酸酯树脂PC是一种综合性能优良的热塑性工程塑料。近年来，其较高的透明度，良好的阻燃性、耐热性、电绝缘性和尺寸稳定性，较低的吸水率等特点而被广泛应用于汽车、电子电气、通讯行业、建筑行业等领域。随着其应用领域的扩展，聚碳酸酯的冲击强度、弯曲模量、拉伸强度、流动性、介电损耗等性能都有了较高的要求，单纯的聚碳酸酯或普通的聚碳酸酯材料仍无法满足要求，因此，需要对聚碳酸酯材料进行改性处理。为了提升材料性能和档次，满足最终部件和客户的需求，一般通过玻璃纤维增强来改进其加工性和改性。Polycarbonate resin PC is a thermoplastic engineering plastic with excellent comprehensive properties. In recent years, its high transparency, good flame retardancy, heat resistance, electrical insulation and dimensional stability, low water absorption and other characteristics have been widely used in the automotive, electronic and electrical, communication industries, construction industries, etc. field. With the expansion of its application fields, polycarbonate has higher requirements for its impact strength, flexural modulus, tensile strength, fluidity, dielectric loss and other properties. Simple polycarbonate or ordinary polycarbonate The material still cannot meet the requirements, therefore, the polycarbonate material needs to be modified. In order to improve the performance and grade of materials and meet the needs of final parts and customers, glass fiber reinforcement is generally used to improve its processability and modification.
但是，现有玻纤增强聚碳酸酯复合材料存在高刚性但是低韧性的矛盾，而常规的增韧方法是直接添加增韧剂，这同样会大幅度降低复合材料的流动性，且复合材料的刚性和韧性的提高也非常有限，且由于聚碳酸酯固有的介电损耗应用特性，从而严重限制了其在汽车、电子电气、通讯行业、建筑行业等领域中，特别是5G通讯行业中的应用。However, the existing glass fiber reinforced polycarbonate composite material has the contradiction of high rigidity but low toughness, and the conventional toughening method is to directly add toughening agents, which will also greatly reduce the fluidity of the composite material, and the composite material The improvement of rigidity and toughness is also very limited, and due to the inherent dielectric loss application characteristics of polycarbonate, which severely limits its application in the automotive, electronic and electrical, communications industry, construction industry and other fields, especially the 5G communications industry .
发明内容Summary of the invention
为了克服现有技术的缺点与不足，本发明的目的在于提供一种兼具刚性和韧性、且高流动性和低介电损耗的玻纤增强聚碳酸酯复合材料。In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a glass fiber reinforced polycarbonate composite material with both rigidity and toughness, high fluidity and low dielectric loss.
本发明的另一目的是提供上述玻纤增强聚碳酸酯复合材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned glass fiber reinforced polycarbonate composite material.
本发明的再一目的是提供上述玻纤增强聚碳酸酯复合材料的用途。Another object of the present invention is to provide the use of the above-mentioned glass fiber reinforced polycarbonate composite material.
本发明是通过以下技术方案实现的：The present invention is realized through the following technical solutions:
一种玻纤增强聚碳酸酯复合材料，按重量份计，包括以下组成：A glass fiber reinforced polycarbonate composite material, in parts by weight, includes the following components:
Figure PCTCN2020103916-appb-000001
Figure PCTCN2020103916-appb-000001
优选地，所述的玻纤增强聚碳酸酯复合材料，按重量份计，包括以下组成：Preferably, the glass fiber reinforced polycarbonate composite material, in parts by weight, includes the following composition:
Figure PCTCN2020103916-appb-000002
Figure PCTCN2020103916-appb-000002
其中，所述玻纤增强聚碳酸酯复合材料中硅氧烷含量占复合材料总重量的百分比 为0.8wt％-18wt％，优选为3.5wt％-12.5wt％。Wherein, the percentage of siloxane content in the glass fiber reinforced polycarbonate composite material to the total weight of the composite material is 0.8 wt% to 18 wt%, preferably 3.5 wt% to 12.5 wt%.
其中，所述玻纤增强聚碳酸酯复合材料中氟元素和硅元素的重量比为1：(0.1-3)，优选为1：(0.5-2)。Wherein, the weight ratio of fluorine element and silicon element in the glass fiber reinforced polycarbonate composite material is 1:(0.1-3), preferably 1:(0.5-2).
其中，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯。Wherein, the polycarbonate is selected from one or more of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, and branched polycarbonate; preferably aromatic polycarbonate .
优选地，所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，优选为粘均分子量18000-28000的芳香族聚碳酸酯。当粘均分子量在上述范围内，机械强度良好并且能保持优异的成型性。其中，粘均分子量是通过使用二氯甲烷作为溶剂在测试温度为25℃的溶液粘度计算出来的。Preferably, the aromatic polycarbonate is an aromatic polycarbonate with a viscosity average molecular weight of 13,000 to 40,000, preferably an aromatic polycarbonate with a viscosity average molecular weight of 18,000 to 28,000. When the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained. Among them, the viscosity average molecular weight is calculated by using dichloromethane as a solvent and the solution viscosity at a test temperature of 25°C.
上述聚碳酸酯的制备方法可以通过界面聚合法和酯交换法制得，并且可以在过程中控制端羟基的含量。The above-mentioned preparation method of polycarbonate can be prepared by interfacial polymerization method and transesterification method, and the content of terminal hydroxyl groups can be controlled in the process.
优选地，所述聚硅氧烷嵌段共聚物包括聚二甲基硅氧烷嵌段和双酚A的聚碳酸酯嵌段，具有基于组分B重量0.8wt％-35wt％的硅氧烷含量。加入硅氧烷嵌段共聚物后，可以通过近红外分析法对玻纤增强聚碳酸酯复合材料的硅氧烷含量进行测试，测试方法是称量固定重量的玻纤增强聚碳酸酯复合材料粒料用甲烷均匀溶解成片状后进行检测。Preferably, the polysiloxane block copolymer includes a polydimethylsiloxane block and a polycarbonate block of bisphenol A, and has 0.8 wt% to 35 wt% of siloxane based on the weight of component B. content. After adding the siloxane block copolymer, the siloxane content of the glass fiber reinforced polycarbonate composite can be tested by the near-infrared analysis method. The test method is to weigh a fixed weight of glass fiber reinforced polycarbonate composite pellets. The material is tested after being evenly dissolved into flakes with methane.
优选地，所述含氟化合物可以为纤维成型或者非纤维成型的含氟聚合物，优选为非纤维成型的含氟聚合物，在某些实施方案中，优选使用包囊含氟聚合物，可以和第二聚物，尤其是聚烯烃类进行预先共混，以形成附聚材料。包囊含氟聚合物中包括熔点高于320℃的含氟聚合物，如聚氟乙烯，优选的包囊含氟聚合物是聚乙烯包囊的聚四氟乙烯，其中PE为40％，PTFE为60％。Preferably, the fluorine-containing compound can be a fiber-shaped or non-fiber-shaped fluoropolymer, preferably a non-fiber-shaped fluoropolymer. In some embodiments, it is preferable to use an encapsulated fluoropolymer. Pre-blended with the second polymer, especially polyolefins, to form an agglomerated material. The encapsulated fluoropolymer includes a fluoropolymer with a melting point higher than 320°C, such as polyvinyl fluoride. The preferred encapsulated fluoropolymer is polyethylene encapsulated polytetrafluoroethylene, where PE is 40%, and PTFE Is 60%.
优选地，所述硅酮的分子量为50000-300000。其中，硅酮分子量过大，和基体的相容性不好，容易造成组合物的性能衰减，硅酮分子量太小，其容易析出造成表面缺陷。Preferably, the molecular weight of the silicone is 50,000 to 300,000. Among them, the molecular weight of the silicone is too large, and the compatibility with the matrix is not good, which is likely to cause the performance degradation of the composition, and the molecular weight of the silicone is too small, and it is easy to precipitate and cause surface defects.
本发明所述的玻纤增强聚碳酸酯复合材料，基于玻纤增强聚碳酸酯复合材料重量，还可以包括组分F：其它助剂0-10份；所述其它助剂选自稳定剂、阻燃剂、润滑剂、脱模剂、增塑剂、填料、抗静电剂、抗菌剂、着色剂中的一种或几种。The glass fiber reinforced polycarbonate composite material of the present invention, based on the weight of the glass fiber reinforced polycarbonate composite material, may also include component F: 0-10 parts of other additives; the other additives are selected from stabilizers, One or more of flame retardants, lubricants, mold release agents, plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
合适的稳定剂，可以包括有机亚磷酸酯，如亚磷酸三苯酯，亚磷酸三-(2,6-二甲基苯基)酯，亚磷酸三-壬基苯基酯，二甲基苯膦酸酯，磷酸三甲酯等，有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类，苯并三唑类，二苯甲酮类的一种或者多种组合。Suitable stabilizers may include organic phosphites, such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tris-nonylphenyl phosphite, dimethylbenzene Phosphonates, trimethyl phosphate, etc., organic phosphites, alkylated monohydric phenols or polyhydric phenols, alkylation reaction products of polyhydric phenols and dienes, butylation of p-cresol or dicyclopentadiene Reaction products, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones One or more combinations.
合适的阻燃剂，可以包括基于磷酸酯的阻燃剂或者磺酸盐阻燃剂。较好的磷酸酯阻燃剂包括双酚A二磷酸四苯酯，磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯基二苯酯、双酚A二磷酸四甲苯酯、间苯二酚四(2,6-二甲基苯酯)和四甲苄基哌啶酰胺；也可以阻燃剂选择磺酸盐，如Rimar盐全氟丁基磺酸钾、KSS二苯砜磺酸钾、苯磺酸钠等均为合适。Suitable flame retardants may include phosphate-based flame retardants or sulfonate flame retardants. Preferred phosphate flame retardants include bisphenol A diphosphate tetraphenyl ester, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, bisphenol A diphosphate tetraphenyl ester, resorcinol tetra( 2,6-Dimethylphenyl ester) and tetramethylbenzylpiperidine amide; sulfonates can also be selected as flame retardants, such as Rimar salt potassium perfluorobutanesulfonate, KSS potassium diphenylsulfone sulfonate, benzenesulfonate Sodium and the like are suitable.
上述玻纤增强聚碳酸酯复合材料的制备方法，包括如下步骤：The preparation method of the glass fiber reinforced polycarbonate composite material includes the following steps:
1)按照配比称取聚碳酸酯、聚硅氧烷嵌段共聚物、含氟化合物、硅酮、其它助剂在高混机中搅拌共混1-3min，得到预混料；1) Weigh polycarbonate, polysiloxane block copolymer, fluorine-containing compound, silicone, and other additives according to the ratio, stir and blend for 1-3 minutes in a high-mixer to obtain a premix;
2)将得到的预混料置于双螺杆挤出机的主喂料口中，在侧喂料口加入玻纤进行熔融挤出，造粒干燥，即得。2) Place the obtained premix in the main feed port of the twin-screw extruder, add glass fiber to the side feed port for melt extrusion, pelletize and dry, and get ready.
其中，所述双螺杆挤出机长径比为46：1-50：1；所述双螺杆挤出机的温度从喂料段到机头依次为：一区温度120℃-160℃，二区温度200℃-230℃，三区温度200℃-230℃，四区温度200℃-220℃，五区温度200℃-220℃，六区温度200℃-220℃，七区温度200℃-220℃，八区温度200℃-220℃，九区温度200℃-220℃，十区温度200℃-220℃，十一区温度200℃-220℃，机头温度220℃-240℃，主机转速350转/分钟-700转/分钟。Wherein, the length-to-diameter ratio of the twin-screw extruder is 46:1-50:1; the temperature of the twin-screw extruder from the feeding section to the die is as follows: the temperature of the first zone is 120℃-160℃, and the temperature of the twin-screw extruder is 120℃-160℃. Zone temperature 200℃-230℃, three zone temperature 200℃-230℃, four zone temperature 200℃-220℃, five zone temperature 200℃-220℃, six zone temperature 200℃-220℃, seven zone temperature 200℃- 220℃, eight zone temperature 200℃-220℃, nine zone temperature 200℃-220℃, ten zone temperature 200℃-220℃, eleven zone temperature 200℃-220℃, machine head temperature 220℃-240℃, host The rotation speed is 350 rpm-700 rpm.
上述制备方法得到的玻纤增强聚碳酸酯复合材料在汽车、电子电气、通讯行业、建筑行业中的应用，优选在5G通讯行业中的应用。The application of the glass fiber reinforced polycarbonate composite material obtained by the above preparation method in the automobile, electronic and electrical, communication industries, and the construction industry is preferably the application in the 5G communication industry.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明选用在玻纤增强聚碳酸酯复合材料配方中添加特定含量的聚硅氧烷嵌段共聚物、含氟化合物和硅酮，从而能够保证制备得到的复合材料中具有特定含量的硅氧烷含量和特定的氟元素和硅元素的重量比，制备得到的复合材料既具有优异的高模量高韧性特性，又具有优异的加工性能，与常规增强改性手段相比，该复合材料兼具刚性和韧性，同时具有显著降低的介电损耗，适用于汽车、电子电气、通讯行业、建筑行业等领域，特别适用于5G通讯行业。The invention chooses to add a specific content of polysiloxane block copolymer, fluorine-containing compound and silicone to the glass fiber reinforced polycarbonate composite material formula, so as to ensure that the prepared composite material has a specific content of siloxane Content and specific weight ratio of fluorine element and silicon element, the prepared composite material not only has excellent high modulus and high toughness characteristics, but also has excellent processing performance. Compared with conventional reinforcement modification methods, the composite material has both Rigidity and toughness, while having significantly reduced dielectric loss, suitable for automotive, electronic and electrical, communications industry, construction industry and other fields, especially suitable for 5G communications industry.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。The present invention will be further explained by specific embodiments below. The following examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples.
各性能的测试标准或方法：Test standards or methods for each performance:
Izod缺口冲击强度的测试方法：根据ASTM D256-2010标准；Izod notched impact strength test method: according to ASTM D256-2010 standard;
Izod无缺口冲击强度的测试方式：根据ASTM D256-2010标准；Izod unnotched impact strength test method: according to ASTM D256-2010 standard;
拉伸强度的测试方式：根据ASTM D638-2014标准，拉伸速度为10mm/min；Tensile strength test method: According to ASTM D638-2014 standard, the tensile speed is 10mm/min;
弯曲模量的测试方式根据ASTM D790-2010标准，弯曲速度为2mm/min；The test method of flexural modulus is based on ASTM D790-2010 standard, and the bending speed is 2mm/min;
流动性的测试方式：根据ASTM D1238-2013标准，熔融温度为300℃；Liquidity test method: According to ASTM D1238-2013, the melting temperature is 300℃;
介电损耗的测试方式：根据ASTM D150-11标准。Dielectric loss test method: According to ASTM D150-11 standard.
本发明中使用的聚碳酸酯：Polycarbonate used in the present invention:
组分A-1：粘均分子量为19000的芳香族聚碳酸酯，日本出光；Component A-1: Aromatic polycarbonate with a viscosity average molecular weight of 19,000, Idemitsu, Japan;
组分A-2：粘均分子量为28000的芳香族聚碳酸酯，日本出光；Component A-2: Aromatic polycarbonate with a viscosity average molecular weight of 28000, Idemitsu, Japan;
本发明中使用的聚硅氧烷嵌段共聚物：The polysiloxane block copolymer used in the present invention:
组分B-1：硅氧烷含量为9wt％的聚硅氧烷嵌段共聚物，日本出光；Component B-1: a polysiloxane block copolymer with a siloxane content of 9wt%, Idemitsu, Japan;
组分B-2：硅氧烷含量为30wt％的聚硅氧烷嵌段共聚物，日本出光；Component B-2: Polysiloxane block copolymer with a siloxane content of 30% by weight, Idemitsu, Japan;
本发明中使用的玻纤：Glass fiber used in the present invention:
组分C-1：日本东洋纺；Component C-1: Toyobo;
本发明中使用的含氟化合物：Fluorine-containing compounds used in the present invention:
组分D-1：非纤维成型的含氟聚合物，广州熵能；Component D-1: non-fiber shaped fluoropolymer, Guangzhou Entropy Energy;
组分D-2：聚乙烯包囊的聚四氟乙烯，其中PE为40％，PTFE为60％，广州熵能；Component D-2: Polytetrafluoroethylene encapsulated by polyethylene, in which PE is 40%, PTFE is 60%, and Guangzhou Entropy Energy;
本发明中使用的硅酮：Silicone used in the present invention:
组分E-1：分子量为50000的硅酮，道康宁；Component E-1: silicone with a molecular weight of 50,000, Dow Corning;
组分E-2：分子量为280000的硅酮，道康宁；Component E-2: silicone with a molecular weight of 280,000, Dow Corning;
本发明中使用的其它助剂：Other additives used in the present invention:
组分F-1：稳定剂：2112，艾迪科；Component F-1: Stabilizer: 2112, Adike;
组分F-2：阻燃剂：BDP，艾迪科。Component F-2: Flame retardant: BDP, Adike.
实施例1-8及对比例1-6：玻纤增强聚碳酸酯复合材料的制备Examples 1-8 and Comparative Examples 1-6: Preparation of glass fiber reinforced polycarbonate composite materials
按照配比称取聚碳酸酯、聚硅氧烷嵌段共聚物、含氟化合物、硅酮、其它助剂在高混机中搅拌共混1-3min，得到预混料；将得到的预混料置于双螺杆挤出机的主喂料口中，在侧喂料口加入玻纤进行熔融挤出，造粒干燥，即得玻纤增强聚碳酸酯复合材料。对上述玻纤增强聚碳酸酯复合材料的Izod缺口冲击强度、Izod无缺口冲击强度、拉伸强度、弯曲模量、流动性、介电损耗进行测试，测试得到的数据如表1所示。Weigh the polycarbonate, polysiloxane block copolymer, fluorine-containing compound, silicone, and other additives according to the ratio, stir and blend for 1-3 minutes in a high-mixer to obtain a premix; combine the obtained premix The material is placed in the main feed port of the twin-screw extruder, glass fiber is added to the side feed port for melt extrusion, granulated and dried, and the glass fiber reinforced polycarbonate composite material is obtained. The Izod notched impact strength, Izod unnotched impact strength, tensile strength, flexural modulus, fluidity, and dielectric loss of the above-mentioned glass fiber reinforced polycarbonate composite materials were tested.
表1实施例1-8及对比例1-6的具体配比(重量份)及其测试性能结果Table 1 Specific proportions (parts by weight) of Examples 1-8 and Comparative Examples 1-6 and their test performance results
Figure PCTCN2020103916-appb-000003
Figure PCTCN2020103916-appb-000003
续表1Continued Table 1
Figure PCTCN2020103916-appb-000004
Figure PCTCN2020103916-appb-000004
注：表1中所述“-”表示完全不能测试。Note: The "-" in Table 1 means that the test cannot be performed at all.

Claims (12)

  1. 一种玻纤增强聚碳酸酯复合材料，按重量份计，包括以下组成：A glass fiber reinforced polycarbonate composite material, in parts by weight, includes the following components:
    Figure PCTCN2020103916-appb-100001
    Figure PCTCN2020103916-appb-100001
  2. 根据权利要求1所述的玻纤增强聚碳酸酯复合材料，按重量份计，包括以下组成：The glass fiber reinforced polycarbonate composite material according to claim 1, in parts by weight, comprising the following components:
    Figure PCTCN2020103916-appb-100002
    Figure PCTCN2020103916-appb-100002
  3. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，所述玻纤增强聚碳酸酯复合材料中硅氧烷含量占复合材料总重量的百分比为0.8wt％-18wt％，优选为3.5wt％-12.5wt％。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the siloxane content in the glass fiber reinforced polycarbonate composite material accounts for 0.8 wt% to 18 wt% of the total weight of the composite material. %, preferably 3.5wt%-12.5wt%.
  4. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，所述玻纤增强聚碳酸酯复合材料中氟元素和硅元素的重量比为1：(0.1-3)，优选为1：(0.5-2)。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the weight ratio of fluorine element and silicon element in the glass fiber reinforced polycarbonate composite material is 1: (0.1-3), Preferably it is 1: (0.5-2).
  5. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯；所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，优选为粘均分子量18000-28000的芳香族聚碳酸酯。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the polycarbonate is selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, One or more of branched polycarbonates; preferably aromatic polycarbonate; the aromatic polycarbonate is an aromatic polycarbonate with a viscosity average molecular weight of 13,000-40000, preferably a viscosity average molecular weight of 18,000-28,000 Of aromatic polycarbonate.
  6. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，所述聚硅氧烷嵌段共聚物包括聚二甲基硅氧烷嵌段和双酚A的聚碳酸酯嵌段，具有基于组分B重量0.8wt％-35wt％的硅氧烷含量。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the polysiloxane block copolymer comprises polydimethylsiloxane block and bisphenol A polycarbonate The block has a siloxane content of 0.8 wt% to 35 wt% based on the weight of component B.
  7. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，所述含氟化合物选自纤维成型、非纤维成型的含氟聚合物、包囊含氟聚合物中的一种或几种；所述包囊含氟聚合物优选为聚乙烯包囊的聚四氟乙烯，其中PE为35wt％-45wt％，PTFE为55wt％-65wt％。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the fluorine-containing compound is selected from one of fiber forming, non-fiber forming fluoropolymer, and encapsulated fluoropolymer. One or more; the encapsulated fluoropolymer is preferably polyethylene encapsulated polytetrafluoroethylene, wherein PE is 35 wt% to 45 wt%, and PTFE is 55 wt% to 65 wt%.
  8. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，所述硅酮的分子量为50000-300000。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the molecular weight of the silicone is 50,000 to 300,000.
  9. 根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料，其特征在于，基于玻纤增强聚碳酸酯复合材料重量，还包括组分F：其它助剂0-10份；所述其它助剂选自稳定剂、阻燃剂、润滑剂、脱模剂、增塑剂、填料、抗静电剂、抗菌剂、着色剂中的一种或几种。The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, characterized in that, based on the weight of the glass fiber reinforced polycarbonate composite material, further comprising component F: 0-10 parts of other additives; The auxiliary agent is selected from one or more of stabilizers, flame retardants, lubricants, mold release agents, plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
  10. 一种如权利要求1-9任一项所述的玻纤增强聚碳酸酯复合材料的制备方法，其特征在于，包括如下步骤：A method for preparing glass fiber reinforced polycarbonate composite material according to any one of claims 1-9, characterized in that it comprises the following steps:
    1)按照配比称取聚碳酸酯、聚硅氧烷嵌段共聚物、含氟化合物、硅酮、其它助剂在高混机中搅拌共混1-3min，得到预混料；1) Weigh polycarbonate, polysiloxane block copolymer, fluorine-containing compound, silicone, and other additives according to the ratio, stir and blend for 1-3 minutes in a high-mixer to obtain a premix;
    2)将得到的预混料置于双螺杆挤出机的主喂料口中，在侧喂料口加入玻纤进行熔融挤出，造粒干燥，即得。2) Place the obtained premix in the main feed port of the twin-screw extruder, add glass fiber to the side feed port for melt extrusion, pelletize and dry, and get ready.
  11. 根据权利要求10所述的玻纤增强聚碳酸酯复合材料的制备方法，其特征在于，所述 双螺杆挤出机长径比为46：1-52：1；所述双螺杆挤出机的温度从喂料段到机头依次为：一区温度120℃-160℃，二区温度200℃-230℃，三区温度200℃-230℃，四区温度200℃-220℃，五区温度200℃-220℃，六区温度200℃-220℃，七区温度200℃-220℃，八区温度200℃-220℃，九区温度200℃-220℃，十区温度200℃-220℃，十一区温度200℃-220℃，机头温度220℃-240℃，主机转速350转/分钟-700转/分钟。The method for preparing glass fiber reinforced polycarbonate composite material according to claim 10, wherein the length to diameter ratio of the twin-screw extruder is 46:1-52:1; The temperature from the feeding section to the machine head is as follows: the temperature in the first zone is 120℃-160℃, the temperature in the second zone is 200℃-230℃, the temperature in the third zone is 200℃-230℃, the temperature in the fourth zone is 200℃-220℃, and the temperature in the fifth zone 200℃-220℃, six zone temperature 200℃-220℃, seven zone temperature 200℃-220℃, eight zone temperature 200℃-220℃, nine zone temperature 200℃-220℃, ten zone temperature 200℃-220℃ , The temperature of the eleven zone is 200℃-220℃, the temperature of the machine head is 220℃-240℃, and the main engine speed is 350rpm-700rpm.
  12. 如权利要求10所述的制备方法得到的玻纤增强聚碳酸酯复合材料在汽车、电子电气、通讯行业、建筑行业中的应用，优选在5G通讯行业中的应用。The application of the glass fiber-reinforced polycarbonate composite material obtained by the preparation method of claim 10 in the automobile, electronic and electrical, communication industries, and construction industries, preferably in the 5G communication industry.
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