WO2023159378A1 - 阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法 - Google Patents

阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法 Download PDF

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WO2023159378A1
WO2023159378A1 PCT/CN2022/077429 CN2022077429W WO2023159378A1 WO 2023159378 A1 WO2023159378 A1 WO 2023159378A1 CN 2022077429 W CN2022077429 W CN 2022077429W WO 2023159378 A1 WO2023159378 A1 WO 2023159378A1
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carbon fiber
semi
flame
composite material
polyamide
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PCT/CN2022/077429
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English (en)
French (fr)
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郭正虹
李娟�
闫红强
王炳涛
杨勇
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浙大宁波理工学院
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Priority to CN202280000287.0A priority Critical patent/CN114729185B/zh
Priority to PCT/CN2022/077429 priority patent/WO2023159378A1/zh
Publication of WO2023159378A1 publication Critical patent/WO2023159378A1/zh

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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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K7/06—Elements
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Definitions

  • the present application relates to the field of composite materials, in particular to a flame-retardant carbon fiber reinforced polyamide composite material, a preparation method thereof, and a preparation method of surface grafted carbon fibers.
  • thermosetting composite materials At present, research on polymer flame-retardant composite materials for aerospace is mainly focused on thermosetting composite materials. Although flame-retardant properties can be improved by adding flame retardants to resins or introducing high-char formation units, the flame-retardant efficiency is not high.
  • CFRTP carbon fiber-reinforced thermoplastic composites
  • the technical problem solved by this application is to provide a flame-retardant carbon fiber reinforced polyamide composite material and its preparation method, and a preparation method of surface grafted carbon fiber, so as to improve the flame retardancy, mechanical properties and heat release performance of the carbon fiber reinforced polyamide composite material.
  • the technical solution of this application provides a flame-retardant carbon fiber reinforced polyamide composite material, which includes: polyamide matrix, 65% to 85%; surface grafted carbon fiber, 10% to 20%,
  • the surface-grafted carbon fiber includes carbon fiber, and the surface of the carbon fiber is grafted with semi-aromatic polyamide, and the semi-aromatic polyamide is a polyamide whose molecular main chain includes aromatic rings and aliphatic chains; flame retardant, 5% ⁇ 15%.
  • the semi-aromatic polyamide is grafted on the surface of the carbon fiber by melt blending.
  • the semi-aromatic polyamide is prepared from aromatic diacids and diamines.
  • the polyamide matrix includes PA6 and/or PA66
  • the semi-aromatic polyamide includes at least one of PA6T, PA9T, and PA12T
  • the carbon fiber has a mass percentage of carbon element higher than 90% inorganic carbon fiber.
  • the flame retardant includes aluminum diethylphosphinate.
  • the technical solution of the present application also provides a method for preparing a flame-retardant carbon fiber-reinforced polyamide composite material, comprising: melt-blending the polyamide matrix, the surface-grafted carbon fiber, and the flame retardant to obtain the flame-retardant Carbon fiber reinforced polyamide composites.
  • the melt blending is carried out in a torque rheometer, and the temperature during the melt blending is 220°C-240°C, the torque is 50rpm-80rpm, and the time is 5min-8min.
  • the technical solution of the present application also provides a method for preparing surface-grafted carbon fibers, comprising: melting and blending carbon fibers and semi-aromatic polyamides to obtain carbon fiber-reinforced semi-aromatic polyamide composite materials; adding into a solvent for heating and dispersing, and taking out the insoluble matter; washing and drying the insoluble matter to obtain surface-grafted semi-aromatic polyamide carbon fiber.
  • the weight ratio of the carbon fiber and the semi-aromatic polyamide during melt blending is (10-20): (80-90); the obtained carbon fiber reinforced semi-aromatic polyamide composite material Among them, the weight percentage of carbon fiber is 10%-20%.
  • melt blending is carried out in a torque rheometer, and the temperature during melt blending is 240°C-260°C, the torque is 50rpm-80rpm, and the time is 5min-8min; heating and dispersing The temperature during drying is 70°C-80°C, and the time is 24h-48h; the temperature during drying is 80°C-110°C, and the time is 24h-48h.
  • the solvent includes m-cresol.
  • FIG. 1 is a schematic flow chart of a method for preparing surface-grafted carbon fibers according to an embodiment of the present application.
  • the embodiment of this application provides a flame retardant carbon fiber reinforced polymer
  • the amide composite material and its preparation method, and the preparation method of surface grafted carbon fiber are used to comprehensively improve the flame retardancy, mechanical performance and heat release performance of the carbon fiber reinforced polyamide composite material.
  • the flame-retardant carbon fiber-reinforced polyamide composite material of the embodiment of the present application includes, by weight percentage: 65% to 85% of polyamide matrix, 10% to 20% of surface grafted carbon fibers and 5% to 15% of flame retardants.
  • the flame retardant carbon fiber reinforced polyamide composite material has better flame retardancy, mechanical properties and heat release performance, and the comprehensive performance is optimal.
  • the material of the polyamide matrix includes polyamide
  • the polyamide is a polymer containing repeated amide groups (-[NHCO]-) on the molecular backbone, referred to as PA
  • the polyamide matrix can include PA6 (Nylon 6) and PA66 (Nylon 66).
  • the surface-grafted carbon fiber includes carbon fiber, and the surface of the carbon fiber is grafted with semi-aromatic polyamide, and the semi-aromatic polyamide is a polyamide whose molecular main chain includes aromatic rings and aliphatic chains.
  • the semi-aromatic polyamide includes at least one of PA6T, PA9T and PA12T.
  • the method of grafting the semi-aromatic polyamide on the surface of the carbon fiber may be melt blending.
  • the semi-aromatic polyamide is prepared from aromatic diacids and diamines.
  • the carbon fiber is an inorganic carbon fiber whose mass percentage of carbon element is higher than 90%.
  • the inorganic carbon fibers include acrylonitrile-based carbon fibers.
  • the flame retardant includes aluminum diethylphosphinate.
  • the carbon fiber with semi-aromatic polyamide grafted on the surface is introduced. Since the molecular chain of semi-aromatic polyamide has good compatibility in the matrix material, the surface The grafted carbon fiber can be well dispersed in the polyamide matrix, and at the same time, the surface grafted carbon fiber forms a highly adhesive interface with the polyamide matrix, so that the flame-retardant carbon fiber-reinforced polyamide composite material of the embodiment of the present application has better resistance impact performance.
  • the semi-aromatic polyamide molecular chains grafted on the surface can provide low heat release and high mechanical strength, so that the flame-retardant carbon fiber-reinforced polyamide composite material of the embodiment of the present application has both thermal stability and mechanical strength.
  • the preparation method of the surface grafted carbon fiber of the embodiment of the present application comprises:
  • Step S1 Melt blending carbon fiber and semi-aromatic polyamide to obtain a carbon fiber-reinforced semi-aromatic polyamide composite material
  • Step S2 adding the carbon fiber reinforced semi-aromatic polyamide composite material into a solvent for heating and dispersing, and taking out insoluble matter;
  • Step S3 washing and drying the insoluble matter to obtain surface-grafted semi-aromatic polyamide carbon fibers.
  • step S1 since the carbon fiber and the semi-aromatic polyamide are grafted by ⁇ - ⁇ conjugation, but the ⁇ - ⁇ conjugation is relatively weak, the surface grafting rate of the carbon fiber is low. Therefore, the weight ratio of carbon fiber and semi-aromatic polyamide is extremely important.
  • the weight ratio of the carbon fiber and the semi-aromatic polyamide in the melt blending of the embodiment of the present application is (10-20):(80-90)
  • the surface grafting ratio of the carbon fiber can reach a suitable value.
  • the surface grafting rate of the carbon fibers obtained in the examples of the present application should be about 5%, for example, the surface grafting rate of the carbon fibers is 4%-6%.
  • the surface grafting rate the total mass of the semi-aromatic polyamide grafted onto the carbon fiber/the total mass of the carbon fiber ⁇ 100%.
  • the weight percentage of carbon fiber is 10%-20%.
  • melt blending is carried out in a torque rheometer, and the temperature during melt blending is controlled to be 240° C. to 260° C., the torque is 50 rpm to 80 rpm, and the time is 5 min to 8 min.
  • High surface grafting rate provides guarantee.
  • the temperature during melt blending should not be too high. Too high a temperature will cause thermal degradation of the material, and too low a temperature will cause the viscosity of the melt system to be too high.
  • the torque at the time of melt blending is within the above range, the carbon fiber and the semi-aromatic polyamide can be blended uniformly while preventing the carbon fiber from being damaged by shearing force.
  • step S2 m-cresol is used as a solvent for dispersion, the insoluble matter taken out is the carbon fiber with semi-aromatic polyamide grafted on the surface, and the dissolved part is semi-aromatic polyamide that has not been successfully grafted.
  • the temperature during heating and dispersing is 70°C to 80°C, and the time is 24h to 48h.
  • step S3 washing the insoluble matter until the washing solution is in a clear state without turbid matter, and then the washing can be stopped.
  • the temperature is controlled at 80°C to 110°C, and the time is 24h to 48h, so as to ensure that the structure of the surface-grafted semi-aromatic polyamide carbon fiber is not damaged.
  • the preparation method of the flame-retardant carbon fiber-reinforced polyamide composite material in the embodiment of the present application includes: melt-blending the polyamide matrix, the surface-grafted semi-aromatic polyamide carbon fiber and the flame retardant to obtain the flame-retardant Carbon fiber reinforced polyamide composites.
  • the preparation method is simple and easy for industrial production.
  • melt blending is carried out in a torque rheometer, and at the same time, the temperature during melt blending needs to be controlled at 220° C. to 240° C., the torque is 50 rpm to 80 rpm, and the time is 5 min to 8 min.
  • the carbon fiber reinforced semi-aromatic polyamide composite material was ground into powder in a pulverizer, added to m-cresol, heated to 70°C, dispersed by ultrasonic for 48 hours, and the insoluble matter was taken out.
  • Aromatic polyamide, the insoluble matter is the carbon fiber after the surface is grafted with semi-aromatic polyamide;
  • the insoluble matter was washed with deionized water for more than 10 times, and placed in a vacuum oven, and dried at 80° C. for 48 hours to obtain a surface-grafted semi-aromatic polyamide carbon fiber with a grafting rate of 5%.
  • Table 1 for the formulations of Examples 2 to 6, please refer to Table 2 for the melt blending process parameters, and refer to Example 1 for the description of the method steps.
  • Flame retardant test refer to the FAR 25.853 international aviation standard, measure the vertical burning time, vertical burning length, and horizontal burning average rate of the composite material samples, measure 10 splines for each group of samples, and take the average value. The results are shown in Table 3.
  • Heat release test refer to the FAR 25.853 international aviation standard, measure the total heat release of the composite material sample within the first 2 minutes, the maximum average heat release rate within 5 minutes, measure 10 splines for each group of samples, and take the average value. The results are shown in Table 3 .

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Abstract

本申请提供一种阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法，所述阻燃碳纤维增强聚酰胺复合材料，以重量百分比计，包括：聚酰胺基体，65％～85％；表面接枝碳纤维，10％～20％，所述表面接枝碳纤维包括碳纤维，且所述碳纤维的表面接枝有半芳香聚酰胺，所述半芳香聚酰胺为分子主链包括芳环和脂肪链的聚酰胺；阻燃剂，5％～15％。本申请技术方案可以提高碳纤维增强聚酰胺复合材料的阻燃性能、力学性能及热释放性能。

Description

阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法 技术领域
本申请涉及复合材料领域，尤其涉及一种阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法。
背景技术
目前，航空航天用高分子阻燃复合材料的研究主要集中在热固性复合材料，通过在树脂中添加阻燃剂或引入高成炭单元，虽能提升阻燃性能，但阻燃效率不高。
与碳纤维增强热固性复合材料相比，碳纤维增强热塑性复合材料(CFRTP)因质轻高强、抗冲击、成型周期短、可循环利用等优点，成为航空复材发展的主流趋势。而且，由于CFRTP还具有流动加工性、低成本以及易回收等特性，特别适合制造航空复杂结构零部件。
发明内容
本申请解决的技术问题是提供一种阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法，提高碳纤维增强聚酰 胺复合材料的阻燃性能、力学性能及热释放性能。
未解决上述技术问题，本申请技术方案提供一种阻燃碳纤维增强聚酰胺复合材料，以重量百分比计，包括：聚酰胺基体，65％～85％；表面接枝碳纤维，10％～20％，所述表面接枝碳纤维包括碳纤维，且所述碳纤维的表面接枝有半芳香聚酰胺，所述半芳香聚酰胺为分子主链包括芳环和脂肪链的聚酰胺；阻燃剂，5％～15％。
在本申请的一些实施例中，通过熔融共混的方法在所述碳纤维的表面接枝所述半芳香聚酰胺。
在本申请的一些实施例中，所述半芳香聚酰胺由芳香族二酸和二胺制备获得。
在本申请的一些实施例中，所述聚酰胺基体包括PA6和/或PA66，所述半芳香聚酰胺包括PA6T、PA9T、PA12T中的至少一种，所述碳纤维为碳元素的质量百分比高于90％的无机碳纤维。
在本申请的一些实施例中，所述阻燃剂包括二乙基次膦酸铝。
本申请技术方案还提供一种阻燃碳纤维增强聚酰胺复合材料的制备方法，包括：将所述聚酰胺基体、所述表面接枝碳纤维及所述阻燃剂进行熔融共混，获得所述阻燃碳纤维增强聚酰胺复合材料。
在本申请的一些实施例中，在转矩流变仪中进行熔融共混，且熔融共混时的温度为220℃～240℃、转矩为50rpm～80rpm，时间为5min～8min。
本申请技术方案还提供一种表面接枝碳纤维的制备方法，包括：使碳纤维和半芳香聚酰胺熔融共混，获得碳纤维增强半芳香聚酰胺复合材料；将所述碳纤维增强半芳香聚酰胺复合材料加入溶剂中进行加热分散，并取出不溶物；清洗并干燥所述不溶物，获得表面接枝半芳香聚酰胺碳纤维。
在本申请的一些实施例中，所述碳纤维和所述半芳香聚酰胺熔融共混时的重量比为(10～20)∶(80～90)；在获得的碳纤维增强半芳香聚酰胺复合材料中，碳纤维的重量百分比为10％～20％。
在本申请的一些实施例中，在转矩流变仪中进行熔融共混，且熔融共混时的温度为240℃～260℃，转矩为50rpm～80rpm，时间为5min～8min；加热分散时的温度为70℃～80℃，时间为24h～48h；干燥时的温度为80℃～110℃，时间为24h～48h。
在本申请的一些实施例中，所述溶剂包括间甲苯酚。
与现有技术相比，本申请技术方案具有如下有益效果：
利用碳纤维分子中整齐排列的碳-碳六元环的大π共轭结构，与半芳香族聚酰胺中的苯环之间的π-π共轭效应，仅通过简单的熔融共混便可将半芳香族聚酰胺分子链接枝到碳纤维表面，不需要对碳纤维表面进行化学处理，不会破坏碳纤维分子结构，最大程度的保持了碳纤维优异的力学性能和热性能。
表面接枝碳纤维分子结构中有半芳香聚酰胺分子链，与聚酰胺基 体材料具有良好的相容性，使其可以在基体材料中良好分散并与基体形成粘附性很强的界面，从而使复合材料具有突出的抗冲击性能。
引入低热释放、高机械强度的半芳香聚酰胺，可以有效改善碳纤维增强聚酰胺复合材料的热稳定性和力学强度。
附图说明
图1为本申请实施例的表面接枝碳纤维的制备方法的流程示意图。
具体实施方式
以下描述提供了本申请的特定应用场景和要求，目的是使本领域技术人员能够制造和使用本申请中的内容。对于本领域技术人员来说，对所公开的实施例的各种局部修改是显而易见的，并且在不脱离本申请的精神和范围的情况下，可以将这里定义的一般原理应用于其他实施例和应用。因此，本申请不限于所示的实施例，而是与权利要求一致的最宽范围。
基于目前热固性复合材料存在的通过在树脂中添加阻燃剂或引入高成碳单元，以提升阻燃性能，但阻燃效率不高的问题，本申请实施例提供了一种阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法，以综合提高碳纤维增强聚酰胺复合材料的阻燃性能、力学性能及热释放性能。
具体地，本申请实施例的阻燃碳纤维增强聚酰胺复合材料，以重量百分比计，包括：65％～85％的聚酰胺基体、10％～20％的表面接枝碳纤维以及5％～15％的阻燃剂。当聚酰胺基体、表面接枝碳纤维和阻燃剂的重量比在上述范围中时，阻燃碳纤维增强聚酰胺复合材料的阻燃性能、力学性能及热释放性能较好，综合性能最优。
其中所述聚酰胺基体的材料包括聚酰胺，且所述聚酰胺是分子主链上含有重复酰胺基团(-[NHCO]-)的聚合物，简称PA，例如所述聚酰胺基体可以包括PA6(尼龙6)和PA66(尼龙66)中的至少一种。
所述表面接枝碳纤维包括碳纤维，且所述碳纤维的表面接枝有半芳香聚酰胺，所述半芳香聚酰胺为分子主链包括芳环和脂肪链的聚酰胺。所述半芳香聚酰胺包括PA6T、PA9T、PA12T中的至少一种。在所述碳纤维的表面接枝所述半芳香聚酰胺的方法可以是熔融共混。在一些实施例中，所述半芳香聚酰胺由芳香族二酸和二胺制备获得。在本申请实施例中，所述碳纤维为碳元素的质量百分比高于90％的无机碳纤维。所述无机碳纤维包括丙烯腈基碳纤维。所述阻燃剂包括二乙基次膦酸铝。
在本申请实施例的阻燃碳纤维增强聚酰胺复合材料中，引入了采用表面接枝有半芳香聚酰胺的碳纤维，由于半芳香聚酰胺分子链在基体材料中具有良好的相容性，使得表面接枝碳纤维可以在聚酰胺基体中分散良好，同时表面接枝碳纤维与聚酰胺基体形成粘附性很强的界面，进而 使得本申请实施例的阻燃碳纤维增强聚酰胺复合材料具有较好的抗冲击性能。此外，表面接枝的半芳香聚酰胺分子链可以提供低热释放、高机械强度，使本申请实施例的阻燃碳纤维增强聚酰胺复合材料兼备热稳定性和力学强度。
参考图1，本申请实施例的表面接枝碳纤维的制备方法，包括：
步骤S1：使碳纤维和半芳香聚酰胺熔融共混，获得碳纤维增强半芳香聚酰胺复合材料；
步骤S2：将所述碳纤维增强半芳香聚酰胺复合材料加入溶剂中进行加热分散，并取出不溶物；
步骤S3：清洗并干燥所述不溶物，获得表面接枝半芳香聚酰胺碳纤维。
在步骤S1中，由于碳纤维和半芳香聚酰胺依靠π-π共轭作用进行接枝，但是该π-π共轭作用比较弱，导致所述碳纤维的表面接枝率较低。因此，碳纤维和半芳香聚酰胺的重量比极为重要。本申请实施例的碳纤维和半芳香聚酰胺熔融共混时的重量比在(10～20)∶(80～90)时，可以使所述碳纤维的表面接枝率达到合适值。本申请实施例得到的碳纤维的表面接枝率应在5％左右适宜，例如碳纤维的表面接枝率在4％～6％。所述表面接枝率＝接枝到碳纤维上的半芳香聚酰胺的总质量/碳纤维总质量×100％。
在获得的碳纤维增强半芳香聚酰胺复合材料中，碳纤维的重量百分比为10％～20％。通过在熔融共混时，对碳纤维和半芳香聚酰胺的重量比进行控制，可以保证在表面接枝有半芳香聚酰胺的碳纤维中，碳纤维的重量百分比在上述范围内。
在一些实施例中，在转矩流变仪中进行熔融共混，且控制熔融共混时的温度为240℃～260℃，转矩为50rpm～80rpm，时间为5min～8min，为碳纤维具有较高的表面接枝率提供保障。具体地，熔融共混时的温度不宜过高，温度太高时会导致材料的热降解，而温度太低时又会使熔融体系的黏度过大。熔融共混时的转矩在上述的范围时，可以使碳纤维不被剪切力破坏的同时，使得碳纤维和半芳香聚酰胺共混均匀。熔融共混时的时间若太长，会导致材料长时间受热和剪切力的作用，导致接枝产物发生热降解或剪切降解，而时间过短又会造成接枝不充分，使得表面接枝率较低。因此，熔融共混时的温度、转矩及时间需要相互匹配，调整其中任何一个参数，都会影响表面接枝率。
在步骤S2中，采用间甲苯酚作为溶剂进行分散，取出的不溶物为表面接枝有半芳香聚酰胺的碳纤维，溶解的部分为未接枝成功的半芳香聚酰胺。加热分散时的温度为70℃～80℃，时间为24h～48h。通过控制上述参数，以保证未接枝成功的半芳香聚酰胺充分溶解，提高产物的纯度。而未接枝成功的半芳香聚酰胺还可以进行回收利用，作为下一次接枝的原料。
进行步骤S3，清洗所述不溶物至清洗液为澄清状态、无浑浊物，即可停止清洗。干燥清洗后的不溶物时，控制温度为80℃～110℃，时间为24h～48h，以保证表面接枝半芳香聚酰胺碳纤维的结构不受破坏。
本申请实施例的阻燃碳纤维增强聚酰胺复合材料的制备方法包括：将所述聚酰胺基体、所述表面接枝半芳香聚酰胺碳纤维及所述阻燃剂进行熔融共混，获得所述阻燃碳纤维增强聚酰胺复合材料。该制备方法简单、易于工业化生产。在本申请实施例中，在转矩流变仪中进行熔融共混，同时需控制熔融共混时的温度为220℃～240℃、转矩为50rpm～80rpm，时间为5min～8min。这是由于温度在上述范围时，避免了温度过高造成的材料热降解问题，也不会存在因熔体黏度过大，产生的表面接枝碳纤维不容易分散的问题。而转矩在上述范围时，可以较好的避免因转矩过大使得表面接枝碳纤维受到过大剪切力导致的接枝结构被破坏的问题，最终导致表面接枝碳纤维无法发挥应有的作用。而当转矩较小时，剪切力较小，导致表面接枝碳纤维、聚酰胺基体及阻燃剂混合不均，也会影响最终阻燃碳纤维增强聚酰胺复合材料的综合性能。当熔融共混时的时间太长时，会导致材料长时间受热和剪切作用，容易发生热降解或剪切降解。当熔融共混时的时间过短时，又影响混合和分散的效果。
实施例1
(1)表面接枝碳纤维的制备
将10g碳纤维和40g半芳香聚酰胺(PA6T)混合加入哈克转矩流变仪中，在220℃、50rpm的条件下，熔融共混8min，获得碳纤维增强半芳香聚酰胺复合材料；
将碳纤维增强半芳香聚酰胺复合材料在粉碎机中磨制成粉末状，并加入间甲苯酚中，加热至70℃，采用超声分散48h，取出不溶物，其中溶解的为未参与接枝的半芳香聚酰胺，不溶物为表面接枝半芳香聚酰胺后的碳纤维；
采用去离子水清洗不溶物达10遍以上，并放于真空烘箱中，在80℃下干燥48h，制得接枝率为5％的表面接枝半芳香聚酰胺碳纤维。
(2)阻燃碳纤维增强聚酰胺复合材料的制备
将重量百分比为65％的PA6和重量百分比为20％的前述制备的表面接枝碳纤维以及重量百分比为15％的二乙基次膦酸铝加入哈克转矩流变仪中，在220℃，50rpm的条件下，熔融共混5min，获得阻燃碳纤维增强聚酰胺复合材料。
实施例2～实施例6
实施例2～实施例6的配方请参考表1，熔融共混工艺参数请参考表2，且方法步骤的描述可参考实施例1。
对比例1～对比例6
对比例1～对比例6的配方请参考表1，熔融共混工艺参数请参考表2，且方法步骤的描述可参考实施例1。
表1实施例和对比例的配方
Figure PCTCN2022077429-appb-000001
表2实施例与对比例的熔融共混工艺参数
Figure PCTCN2022077429-appb-000002
对实施例1～6和对比例1～6制备的复合材料的阻燃性能、力学性能及热性能进行如下测试：
阻燃测试：参照FAR 25.853国际航空标准，测量复合材料样品的垂直燃烧时间、垂直烧焦长度、水平燃烧平均速率，每组样品测10个样条，取均值，结果如表3。
力学测试：参照FAR 25.853国际航空标准，测量复合材料样品的拉伸强度、弯曲强度、层间剪切强度、冲击后压缩强度，每组样品测10个样条， 取均值，结果如表3。
热释放测试：参照FAR 25.853国际航空标准，测量复合材料样品的初始2分钟内总热释放量、5分钟内最大平均热释放速率，每组样品测10个样条，取均值，结果如表3。
从表3中可以看出，采用共混熔融工艺对碳纤维进行半芳香聚酰胺的表面接枝后，由于半芳香聚酰胺与聚酰胺基体具有良好的相容性，从而使碳纤维在聚酰胺基体中分散良好，且碳纤维与聚酰胺基体之间的界面粘接力提高，而且引入具有高耐热、高抗冲、低热释放的半芳香聚酰胺，显著提高了复合材料的阻燃性能、力学性能及热释放性能，均可满足FAR 25.853国际航空标准，使得本申请实施例的阻燃碳纤维增强聚酰胺复合材料可作为客机中结构零部件的制备材料。
Figure PCTCN2022077429-appb-000003
最后，应理解，本文公开的申请的实施方案是对本申请的实施方案的原理的说明。其他修改后的实施例也在本申请的范围内。因此，本申请披露的实施例仅仅作为示例而非限制。本领域技术人员可以根据本申请中的 实施例采取替代配置来实现本申请中的申请。因此，本申请的实施例不限于申请中被精确地描述过的那些实施例。

Claims (11)

  1. 一种阻燃碳纤维增强聚酰胺复合材料，以重量百分比计，包括：
    聚酰胺基体，65％～85％；
    表面接枝碳纤维，10％～20％，所述表面接枝碳纤维包括碳纤维，且所述碳纤维的表面接枝有半芳香聚酰胺，所述半芳香聚酰胺为分子主链包括芳环和脂肪链的聚酰胺；
    阻燃剂，5％～15％。
  2. 根据权利要求1所述的阻燃碳纤维增强聚酰胺复合材料，其特征在于，通过熔融共混的方法在所述碳纤维的表面接枝所述半芳香聚酰胺。
  3. 根据权利要求2所述的阻燃碳纤维增强聚酰胺复合材料，其特征在于，所述半芳香聚酰胺由芳香族二酸和二胺制备获得。
  4. 根据权利要求1所述的阻燃碳纤维增强聚酰胺复合材料，其特征在于，所述聚酰胺基体包括PA6和/或PA66，所述半芳香聚酰胺包括PA6T、PA9T、PA12T中的至少一种，所述碳纤维为碳元素的质量百分比高于90％的无机碳纤维。
  5. 根据权利要求1所述的阻燃碳纤维增强聚酰胺复合材料，其特征在于，所述阻燃剂包括二乙基次膦酸铝。
  6. 一种权利要求1至5任一项所述的阻燃碳纤维增强聚酰胺复合材料的制备方法，其特征在于，包括：将所述聚酰胺基体、所述表面接枝碳纤维及所述阻燃剂进行熔融共混，获得所述阻燃碳纤维增强聚酰胺复合材料。
  7. 根据权利要求6所述的阻燃碳纤维增强聚酰胺复合材料的制备方法，其特征在于，在转矩流变仪中进行熔融共混，且熔融共混时的温度为220℃～240℃、转矩为50rpm～80rpm，时间为5min～8min。
  8. 一种表面接枝碳纤维的制备方法，其特征在于，包括：
    使碳纤维和半芳香聚酰胺熔融共混，获得碳纤维增强半芳香聚酰胺复合材料；
    将所述碳纤维增强半芳香聚酰胺复合材料加入溶剂中进行加热分散，并取出不溶物；
    清洗并干燥所述不溶物，获得表面接枝半芳香聚酰胺碳纤维。
  9. 根据权利要求8所述的表面接枝碳纤维的制备方法，其特征在于，所述碳纤维和所述半芳香聚酰胺熔融共混时的重量比为(10～20)∶(80～90)；在获得的碳纤维增强半芳香聚酰胺复合材料中，碳纤维的重量百分比为10％～20％。
  10. 根据权利要求8所述的表面接枝碳纤维的制备方法，其特征在于，在转矩流变仪中进行熔融共混，且熔融共混时的温度为240℃～260℃，转矩为50rpm～80rpm，时间为5min～8min；加热分散时的温度为70℃～80℃，时间为24h～48h；干燥时的温度为80℃～110℃，时间为24h～48h。
  11. 根据权利要求8所述的表面接枝碳纤维的制备方法，其特征在于，所述溶剂包括间甲苯酚。
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