WO2023159379A1 - 阻燃热塑性碳纤维复合材料及其制备方法、隔热碳纤维的制备方法 - Google Patents

阻燃热塑性碳纤维复合材料及其制备方法、隔热碳纤维的制备方法 Download PDF

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WO2023159379A1
WO2023159379A1 PCT/CN2022/077430 CN2022077430W WO2023159379A1 WO 2023159379 A1 WO2023159379 A1 WO 2023159379A1 CN 2022077430 W CN2022077430 W CN 2022077430W WO 2023159379 A1 WO2023159379 A1 WO 2023159379A1
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carbon fiber
rare earth
flame
heat
composite material
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PCT/CN2022/077430
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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 PCT/CN2022/077430 priority Critical patent/WO2023159379A1/zh
Priority to CN202280000292.1A priority patent/CN114729186B/zh
Publication of WO2023159379A1 publication Critical patent/WO2023159379A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—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
    • C08K9/02—Ingredients treated with inorganic 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • 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
    • 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
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present application relates to the field of composite materials, in particular to a flame-retardant thermoplastic carbon fiber composite material, a preparation method thereof, and a preparation method of heat-insulating carbon fibers.
  • Carbon fiber reinforced thermoplastic composites have the advantages of light weight, high strength, designability, impact toughness, short molding cycle, and recyclability, and have become the main trend in the development of aerospace composite materials.
  • the carbon fibers are distributed in the composite matrix, which acts like a candle wick, and acts as a heat concentration point, making the surrounding thermoplastic matrix easier to pyrolyze and ignite.
  • this application provides a flame-retardant thermoplastic carbon fiber composite material, which includes: polyamide, 45%-70%; heat-insulating carbon fiber, 20%-30%, and the heat-insulating carbon fiber It includes carbon fiber and rare earth crystal coating layer on the surface of the carbon fiber; flame retardant, 10%-25%.
  • the rare earth crystal coating layer is formed by performing a hydrothermal synthesis reaction of Ce(NO 3 ) 3 and phenylphosphoric acid, followed by washing and drying.
  • the polyamide includes PA6 and/or PA66
  • the carbon fiber includes polyacrylonitrile-based carbon fiber.
  • the flame retardant includes a halogen-free phosphorus flame retardant.
  • the present application also provides the preparation method of the above-mentioned flame-retardant thermoplastic carbon fiber composite material, comprising: adding the polyamide and the flame retardant from the hopper of the screw extruder to the screw extruder, The heat-insulating carbon fiber is added into the screw extruder through the wire inlet of the exit machine, melted and blended, and then extruded to obtain the flame-retardant thermoplastic carbon fiber composite material.
  • the temperature of the feeding zone of the screw extruder is 150°C-180°C
  • the temperature of the compression zone is 230°C-260°C
  • the temperature of the homogenization zone is 250°C-270°C
  • the screw speed is 120r/min-150r/min
  • the feed rate of the heat-insulating carbon fiber is 1m/min-5m/min.
  • the present application also provides a method for preparing heat-insulating carbon fibers, including: providing a phenyl phosphoric acid solution, a rare earth solution, and carbon fibers; placing the carbon fibers in a sulfuric acid solution, and heating to a first temperature under the protection of an inert gas, so that The surface of the carbon fiber contains hydrogen ions; the protection of the inert gas is removed, and the carbon fiber is cleaned until the pH of the cleaning solution is 6.8 to 7.5, so that the hydrogen ions are oxidized to hydroxyl by oxygen in the air; The carbon fibers are placed in the phenylphosphoric acid solution and heated to a second temperature, and the rare earth solution is added under the protection of an inert gas to form rare earth aggregates on the surface of the carbon fibers; the surface is cleaned and dried to have the rare earth aggregates The carbon fiber of the material forms a rare earth crystal coating layer on the surface of the carbon fiber.
  • the rare earth solution is a saturated aqueous solution of Ce(NO 3 ) 3
  • the phenylphosphoric acid solution is a saturated aqueous solution of phenylphosphoric acid.
  • the first temperature is 50°C-70°C
  • the second temperature is 90°C-110°C.
  • a high-temperature-resistant rare-earth crystal coating layer is formed on the surface of carbon fibers.
  • the rare-earth crystal coating layer can play a role in heat insulation, thereby effectively inhibiting the carbon fiber from being used in the polymer matrix.
  • the "candle wick" triggers the pyrolysis and ignition of the surrounding matrix material, which effectively prolongs the ignition time of the flame-retardant thermoplastic carbon fiber composite material, significantly improves the flame-retardant performance of the flame-retardant thermoplastic carbon fiber composite material, and makes the flame-retardant thermoplastic carbon fiber composite When the material is applied to the fire suit, it can buy precious time for the escape and rescue of people in the fire.
  • the preparation method of heat-insulating carbon fiber uses phenyl phosphoric acid and rare earth solution as raw materials, first uses sulfuric acid solution to treat the surface of carbon fiber, forms hydrogen ion active points on the surface of carbon fiber, and then activates hydrogen ion by oxygen
  • the sites are oxidized to hydroxyl active sites, and the rare earth aggregates generated by the hydrothermal reaction of phenylphosphoric acid and rare earth substances will grow on the hydroxyl active sites. After the reaction is complete, they will be coated on the surface of the carbon fiber to form a rare earth crystal coating layer.
  • the heat-insulating carbon fiber prepared by this method has good insulation ability, and the heat-insulating carbon fiber is used to replace the existing carbon fiber and applied to the carbon fiber composite material, which can greatly improve the fire performance of the carbon fiber composite material.
  • Fig. 1 is the thermogravity test result figure of the rare earth crystal on the surface of the heat-insulating carbon fiber of embodiment 3 under nitrogen atmosphere;
  • Fig. 2 is the thermogravimetric test result figure of the rare earth crystal on the surface of the heat-insulating carbon fiber of embodiment 3 under air atmosphere;
  • Fig. 3 is a scanning electron microscope image of carbon residue after combustion of the carbon fiber composite materials of Example 3 and Comparative Example 3.
  • the embodiment of the present application deposits high-temperature-resistant rare earth crystals on the surface of carbon fibers to form a dense heat-insulating coating on the surface of carbon fibers, thereby preventing carbon fibers from being used as materials.
  • the heat concentration point can alleviate or even suppress the "candle wick effect" to a large extent, so that carbon fiber reinforced thermoplastic composites have excellent fire safety performance.
  • the flame-retardant thermoplastic carbon fiber composite material of the embodiment of the present application includes, by weight percentage: 45% to 70% of polyamide, 20% to 30% of heat insulating carbon fiber and 10% to 25% of flame retardant .
  • the flame-retardant thermoplastic carbon fiber composite material has better flame-retardant performance.
  • the polyamide is a polymer containing repeating amide groups (-[NHCO]-) on the main chain of the molecule, referred to as PA
  • the polyamide can include at least PA6 (nylon 6) and PA66 (nylon 66). A sort of.
  • the carbon fibers may include, for example, polyacrylonitrile-based carbon fibers.
  • the flame retardant includes a halogen-free phosphorus flame retardant, for example, the halogen-free phosphorus flame retardant may include one or more of polyphosphate amine, tricresyl phosphate, aluminum hypophosphite, and the like.
  • the heat-insulating carbon fiber includes carbon fiber and a rare earth crystal coating layer located on the surface of the carbon fiber.
  • the rare earth crystal coating layer can play a role of heat insulation, so that the carbon fiber no longer serves as a heat concentration point, and can effectively suppress the "candle". core effect".
  • the rare earth crystal coating layer is formed by hydrothermal synthesis of Ce(NO 3 ) 3 and phenylphosphoric acid, followed by washing and drying. After the Ce(NO 3 ) 3 and phenyl phosphoric acid react on the surface of the carbon fiber, a rare earth aggregate containing a phenylphosphine structure is formed to cover the surface of the carbon fiber, and the rare earth crystal coating layer is formed after cleaning and drying.
  • the embodiment of the present application also provides a preparation method of the heat-insulating carbon fiber, including:
  • Step S1 providing phenylphosphoric acid solution, rare earth solution and carbon fiber;
  • Step S2 placing the carbon fiber in a sulfuric acid solution, and heating it to a first temperature under the protection of an inert gas, so that the surface of the carbon fiber contains hydrogen ions;
  • Step S3 removing the protection of the inert gas, cleaning the carbon fiber until the pH of the cleaning solution is 6.8-7.5, so that the hydrogen ions are oxidized to hydroxyl by oxygen in the air;
  • Step S4 placing the carbon fibers with hydroxyl groups on the surface in the phenylphosphoric acid solution, heating to a second temperature, adding the rare earth solution under the protection of an inert gas, and forming rare earth aggregates on the surface of the carbon fibers;
  • Step S5 cleaning and drying the carbon fiber with the rare earth aggregates on the surface, forming a rare earth crystal coating layer on the surface of the carbon fiber.
  • the phenyl phosphoric acid solution is used as a raw material for forming rare earth aggregates, and the phenyl phosphoric acid solution is obtained by dissolving phenyl phosphoric acid in water.
  • a saturated aqueous solution of phenylphosphoric acid is selected as the phenylphosphoric acid solution, so that the surface of the carbon fiber can be covered with enough rare earth aggregates.
  • the rare earth solution is a saturated aqueous solution of Ce(NO 3 ) 3 , which is also for increasing the coverage of rare earth aggregates.
  • the method of preparing the rare earth solution is to dissolve Ce(NO 3 ) 3 ⁇ 6H 2 O in deionized water, and keep stirring until completely dissolved.
  • step S2 it is necessary to specifically control the first temperature at a reasonable level. This is because, if the first temperature is too high, the sulfuric acid will volatilize greatly; if the first temperature is too low, the surface of the carbon fiber cannot be well activated.
  • the first temperature is strictly controlled at 50° C. to 70° C., so as to ensure that the surface of the carbon fiber is fully activated without causing the sulfuric acid to volatilize significantly.
  • the "activation of the surface of the carbon fiber” mentioned in the embodiment of the present application refers to treating the surface of the carbon fiber to form hydrogen ions or hydroxyl groups on the surface of the carbon fiber. Immerse carbon fiber in phosphoric acid solution at 50°C to 70°C for 15min to 20min to fully activate the surface of carbon fiber.
  • step S3 deionized water can be used as a cleaning solution to clean the carbon fibers until the cleaning solution is weakly acidic to weakly alkaline, so that the acidification points (that is, hydrogen ions) on the surface of the carbon fibers are oxidized to hydroxyl by oxygen in the air (OH), the hydroxyl group serves as the active point for the subsequent modification of the carbon fiber.
  • the acidification points that is, hydrogen ions
  • the carbon fibers with hydroxyl groups on the surface are immersed in the phenylphosphoric acid solution, and heated to a second temperature .
  • a hydrothermal synthesis reaction occurs.
  • the second temperature is controlled to be 90° C. to 110° C.
  • adding the rare earth solution it needs to be carried out under the protection of an inert gas to ensure that the Ce element of Ce(NO 3 ) 3 is positive trivalent.
  • adding the rare earth solution it may be gradually added dropwise until the surface of the carbon fiber is completely covered by milky white flocs, which are rare earth aggregates.
  • the surface-activated carbon fiber is placed in a phenyl phosphoric acid solution, and then the rare earth solution is added into it, so that a hydrothermal synthesis reaction can occur on the surface of the carbon fiber, thus growing on each activation point on the surface of the carbon fiber.
  • Rare earth aggregates with phosphorus structure (CeP n Arm ), since the growth of rare earth aggregates does not need to be random, the values of n and m in the rare earth aggregates grown on different activation points are different, but the final result is The rare earth aggregate is covered on the surface of the carbon fiber.
  • the rare earth aggregates may be allowed to stand at the second temperature for at least 24 hours to allow the rare earth aggregates to grow completely.
  • the carbon fibers covered with rare earth aggregates on the surface were taken out of the phenyl phosphoric acid solution, washed repeatedly with deionized water and dried, finally forming a brownish-yellow rare earth crystal coating. This is because when the trivalent Ce element contacts the air, it will be oxidized to the positive tetravalent Ce element, making the color change from milky white to brownish yellow.
  • the embodiment of the present application also provides the preparation method of the aforementioned flame-retardant thermoplastic carbon fiber composite material, including: adding the polyamide and the flame retardant from the hopper of the screw extruder to the screw extruder, and adding the polyamide and the flame retardant from the screw extruder
  • the fiber inlet of the extruder is used to add the heat-insulating carbon fiber into the screw extruder, melt and blend, and extrude to obtain the flame-retardant thermoplastic carbon fiber composite material.
  • the polyamide and the flame retardant may be dried in an oven at 110-130°C for 6h-12h before feeding.
  • the processing parameters of the screw extruder also have a great influence on the performance of the flame-retardant thermoplastic carbon fiber composite material.
  • the temperature of the feeding zone of the screw extruder is 150°C-180°C
  • the temperature of the compression zone is 230°C-260°C
  • the temperature of the homogenization zone is 250°C-270°C
  • the screw speed is 120r/min ⁇ 150r/min
  • the feeding speed of the heat insulating carbon fiber is 1m/min ⁇ 5m/min.
  • Ce(NO 3 ) 3 ⁇ 6H 2 O was dissolved in deionized water at 90°C, and stirred continuously until it was completely dissolved, and Ce(NO 3 ) 3 ⁇ 6H 2 O was saturated in deionized water to obtain Ce(NO 3 ) 3 ⁇ 6H 2 O 3 ) the saturated aqueous solution of 3 , standby;
  • the carbon fiber was taken out from the saturated aqueous solution of phenylphosphoric acid, washed repeatedly with deionized water, and then vacuum-dried at 80° C. for more than 8 hours to constant weight to obtain a heat-insulating carbon fiber with a brown-yellow surface.
  • Table 1 for the formulations of Examples 2 to 6, please refer to Table 2 for the extrusion molding process parameters, and refer to Example 1 for the description of the method steps.
  • FIG. 1 is a diagram of the thermogravimetric test results in a nitrogen atmosphere
  • FIG. 2 is a diagram of the thermogravimetric test results in an air atmosphere. It can be seen from Figures 1 and 2 that the rare earth crystals deposited and grown on the surface of carbon fibers begin to thermally degrade when the temperature rises to 425°C under a nitrogen atmosphere.
  • the maximum thermal degradation occurs at 527.1°C, and the amount of residual carbon at 800°C is 74.0%; in the air atmosphere, the thermal degradation begins when the temperature rises to 419.6 °C, the maximum thermal degradation occurs at 512.5 °C, and the carbon residue remains at 74.0% at 800 °C. It can be seen that the rare earth crystals deposited and grown on the surface of carbon fibers have excellent thermal stability, can resist high temperature erosion during combustion, and have a high amount of residual carbon, which can completely cover carbon fibers, thus effectively Suppresses the "candle wick effect" of carbon fiber in the polymer matrix.
  • Figure A is a scanning electron microscope image of carbon residue after combustion of the carbon fiber composite material in Comparative Example 3. In the carbon residue after combustion of the carbon fiber composite material of Comparative Example 3, the carbon fibers are completely exposed, and the surface of the carbon fibers is smooth without attachments.
  • Figure B is a scanning electron microscope image of carbon residue after combustion of the carbon fiber composite material of Example 3. In the carbon residue after combustion of the carbon fiber composite material of Example 3, the carbon fibers are almost completely covered under the continuous and dense carbon layer.
  • Figure B The local part (the position of the arrow pointing to the end of the arrow in the picture B pointing to the picture C) is enlarged as shown in the picture C, and the structure of the carbon fiber itself can hardly be seen. Even if the very small amount of exposed carbon fibers in Figure B (the dotted line box in Figure B) is enlarged and observed, as shown in Figure D, it will be found that the surface of the carbon fibers is no longer smooth, but a large amount of carbon layer substances are closely attached.
  • the rare earth crystals deposited and grown on the surface of carbon fibers form a high-temperature heat insulation layer on the surface of carbon fibers due to their excellent thermal stability and high char formation, which can effectively inhibit the "candle wick effect" of carbon fibers, and then can
  • the reinforced thermoplastic composite material has excellent flame retardant properties.
  • Limiting oxygen index test measure the limiting oxygen index value of the carbon fiber composite material sample with reference to the international standard ISO-4598, the sample size is 130mm ⁇ 6.5mm ⁇ 3mm, measure 5 splines for each group of samples, and take the average value to obtain the limiting oxygen index (LOI, %), the test results are shown in Table 3;
  • the limiting oxygen index of the carbon fiber composite material prepared from the heat insulating carbon fiber is significantly improved when the rare earth crystals are deposited and grown on the surface of the carbon fiber to form the heat insulating carbon fiber, and the first ignition time and the second ignition time of the carbon fiber composite material are both It is obviously shortened, and at the same time, no high-temperature flammable dripping substances will be produced during combustion, and it can reach the UL94 V0 level of vertical combustion. The ignition of the composite material becomes difficult, which improves the fire safety performance of the carbon fiber composite material.

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Abstract

本申请提供一种阻燃热塑性碳纤维复合材料及其制备方法、隔热碳纤维的制备方法，其中所述阻燃热塑性碳纤维复合材料以重量百分比计，包括：聚酰胺，45％～70％；隔热碳纤维，20％～30％，且所述隔热碳纤维包括碳纤维以及位于所述碳纤维的表面的稀土晶体包覆层；阻燃剂，10％～25％。本申请技术方案的阻燃热塑性碳纤维复合材料及其制备方法、隔热碳纤维的制备方法可以解决碳纤维在复合材料燃烧时出现的"烛芯效应"。

Description

阻燃热塑性碳纤维复合材料及其制备方法、隔热碳纤维的制备方法 技术领域
本申请涉及复合材料领域，尤其涉及一种阻燃热塑性碳纤维复合材料及其制备方法、隔热碳纤维的制备方法。
背景技术
碳纤维增强热塑性复合材料具有轻质高强、可设计、抗冲击韧性、成型周期短、可循环利用等优点，已成为航空复合材料发展的主要趋势。碳纤维分布在复合材料基体中，起到类似蜡烛烛芯的作用，会作为热量集中点使其周边的热塑性基体更容易热解和点燃。
这种碳纤维在复合材料燃烧时出现的“烛芯效应”已成为限制其安全使用的技术瓶颈，严重制约了碳纤维增强热塑性复合材料在航空领域的规模化应用。
发明内容
本申请解决的技术问题是碳纤维在复合材料燃烧时出现的“烛芯效应”。
为解决上述技术问题，本申请提供一种阻燃热塑性碳纤维复合材料， 以重量百分比计，包括：聚酰胺，45％～70％；隔热碳纤维，20％～30％，且所述隔热碳纤维包括碳纤维以及位于所述碳纤维的表面的稀土晶体包覆层；阻燃剂，10％～25％。
在本申请的一些实施例中，所述稀土晶体包覆层通过Ce(NO 3) 3和苯基磷酸进行水热合成反应并清洗干燥形成。
在本申请的一些实施例中，所述聚酰胺包括PA6和/或PA66，所述碳纤维包括聚丙烯腈基碳纤维。
在本申请的一些实施例中，所述阻燃剂包括无卤磷系阻燃剂。
本申请还提供上述的阻燃热塑性碳纤维复合材料的制备方法，包括：自螺杆挤出机的料斗向所述螺杆挤出机中加入所述聚酰胺和所述阻燃剂，自所述螺杆挤出机的进丝口向所述螺杆挤出机中加入所述隔热碳纤维，熔融共混后挤出成型获得所述阻燃热塑性碳纤维复合材料。
在本申请的一些实施例中，所述螺杆挤出机的加料区温度为150℃～180℃，压缩区温度为230℃～260℃，均化区温度为250℃～270℃，螺杆转速为120r/min～150r/min，所述隔热碳纤维的进丝速率为1米/min～5米/min。
本申请还提供一种隔热碳纤维的制备方法，包括：提供苯基磷酸溶液、稀土溶液及碳纤维；将所述碳纤维置于硫酸溶液中，并在惰性气体的保护下加热至第一温度，使所述碳纤维的表面包括氢离子；去除所述惰性气体的保护，清洗所述碳纤维直至清洗液的pH在6.8～7.5，使所述氢离子被空气中的 氧气氧化为羟基；将表面包括羟基的碳纤维置于所述苯基磷酸溶液中，并加热至第二温度，在惰性气体的保护下加入所述稀土溶液，在所述碳纤维的表面形成稀土聚集物；清洗并干燥表面具有所述稀土聚集物的碳纤维，在所述碳纤维表面形成稀土晶体包覆层。
在本申请的一些实施例中，所述稀土溶液为Ce(NO 3) 3的饱和水溶液，所述苯基磷酸溶液为苯基磷酸的饱和水溶液。
在本申请的一些实施例中，所述第一温度为50℃～70℃，所述第二温度为90℃～110℃。
在本申请的一些实施例中，形成所述稀土聚集物后，还包括在所述第二温度下静置至少24小时，使稀土聚集物生长完全。
与现有技术相比，本申请技术方案具有如下有益效果：
通过在碳纤维表面沉积生长稀土聚集物，从而在碳纤维表面形成耐高温的稀土晶体包覆层，稀土晶体包覆层可以起到隔热的作用，从而可以有效地抑制碳纤维在高分子基体中作为″烛芯″引发其周围基体材料的热解和点燃，进而有效地延长了阻燃热塑性碳纤维复合材料被点燃的时间，显著提高了阻燃热塑性碳纤维复合材料的阻燃性能，将阻燃热塑性碳纤维复合材料应用于火灾服时，可以为火灾中人员逃生与救援争取宝贵的时间。
本申请技术方案的隔热碳纤维的制备方法，以苯基磷酸和稀土溶液为原料，先采用硫酸溶液对碳纤维的表面进行处理，在碳纤维表面形成氢离子活性点，然后再通过氧气将氢离子活性点氧化为羟基活性点，苯基磷酸和稀土 物质反应经水热化反应生成的稀土聚集物会生长在羟基活性点上，待反应完全后，会在碳纤维表面包覆形成稀土晶体包覆层，通过该方法制备的隔热碳纤维具有较好的隔离能力，采用隔热碳纤维取代现有的碳纤维并应用于碳纤维复合材料中，可以大幅提高碳纤维复合材料的火性能。
附图说明
以下附图详细描述了本申请中披露的示例性实施例。其中相同的附图标记在附图的若干视图中表示类似的结构。本领域的一般技术人员将理解这些实施例是非限制性的、示例性的实施例，附图仅用于说明和描述的目的，并不旨在限制本申请的范围，其他方式的实施例也可能同样的完成本申请中的发明意图。应当理解，附图未按比例绘制。其中：
图1为实施例3的隔热碳纤维表面的稀土晶体在氮气气氛下的热失重测试结果图；
图2为实施例3的隔热碳纤维表面的稀土晶体在空气气氛下的热失重测试结果图；
图3为实施例3和对比例3的碳纤维复合材料燃烧后残炭的扫描电镜图。
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。
基于目前碳纤维增强热塑性复合材料中存在的“烛心效应”，本申请实施例在碳纤维表面沉积了耐高温的稀土晶体，在碳纤维表面形成致密的隔热包覆层，从而阻止了碳纤维作为材料中的热量集中点，很大程度上缓解甚至抑制了“烛芯效应”，进而使碳纤维增强热塑性复合材料具有了优异的火安全性能。
具体地，本申请实施例的阻燃热塑性碳纤维复合材料，以重量百分比计，包括：45％～70％的聚酰胺、20％～30％的隔热碳纤维和10％～25％的阻燃剂。当聚酰胺、隔热碳纤维和阻燃剂的比例在上述范围中时，阻燃热塑性碳纤维复合材料具有较好的阻燃性能。其中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，例如所述聚酰胺可以包括PA6(尼龙6)和PA66(尼龙66)中的至少一种。所述碳纤维例如可以包括聚丙烯腈基碳纤维。所述阻燃剂包括无卤磷系阻燃剂，例如所述无卤磷系阻燃剂可以包括聚磷酸胺、磷酸三甲苯酯、次磷酸铝等其中的一种或几种。
所述隔热碳纤维包括碳纤维以及位于所述碳纤维的表面的稀土晶体包覆层，所述稀土晶体包覆层可以起到隔热的作用，使得碳纤维不再作为热量集中点，可以有效抑制“烛芯效应”。在本申请实施例中，所述稀土晶体包覆层通过Ce(NO 3) 3和苯基磷酸进行水热合成反应并清洗干燥形成。所述Ce(NO 3) 3 和苯基磷酸在碳纤维表面发生反应后，生成含有苯基膦结构的稀土聚集物覆盖在碳纤维表面，再经清洗并干燥后形成所述稀土晶体包覆层。
本申请实施例还提供所述隔热碳纤维的制备方法，包括：
步骤S1：提供苯基磷酸溶液、稀土溶液及碳纤维；
步骤S2：将所述碳纤维置于硫酸溶液中，并在惰性气体的保护下加热至第一温度，使所述碳纤维的表面包括氢离子；
步骤S3：去除所述惰性气体的保护，清洗所述碳纤维直至清洗液的pH在6.8～7.5，使所述氢离子被空气中的氧气氧化为羟基；
步骤S4：将表面包括羟基的碳纤维置于所述苯基磷酸溶液中，并加热至第二温度，在惰性气体的保护下加入所述稀土溶液，在所述碳纤维的表面形成稀土聚集物；
步骤S5：清洗并干燥表面具有所述稀土聚集物的碳纤维，在所述碳纤维表面形成稀土晶体包覆层。
在步骤S1中，所述苯基磷酸溶液作为形成稀土聚集物的原料，所述苯基磷酸溶液通过苯基磷酸溶于水获得。优选地，选择苯基磷酸的饱和水溶液作为苯基磷酸溶液，以使碳纤维表面可以覆盖足够多的稀土聚集物。在本申请实施例中，所述稀土溶液为Ce(NO 3) 3的饱和水溶液，同理也是为了提高稀土聚集物的覆盖量。配置稀土溶液的方法是将Ce(NO 3) 3·6H 2O溶解在去离子水中，并不断搅拌至完全溶解。
在步骤S2中，需要特别控制所述第一温度在合理的大小。这是因为，若所述第一温度过大，会造成硫酸大幅挥发；若所述第一温度过小时，又不能较好的活化碳纤维的表面。本申请实施例将所述第一温度严格控制在50℃～70℃，在不会造成硫酸大幅挥发的情况下，还能保证碳纤维表面被充分活化。本申请实施例所述的“活化碳纤维的表面”是指，处理所述碳纤维的表面，在碳纤维表面形成氢离子或羟基。将碳纤维浸入磷酸溶液中，在50℃～70℃下，浸渍15min～20min可以充分活化碳纤维表面。
在步骤S3中，可以采用去离子水作为清洗液清洗所述碳纤维直至清洗液呈弱酸性～弱碱性即可，使得碳纤维表面的酸化点(也即氢离子)被空气中的氧气氧化成羟基(OH)，所述羟基作为后续对碳纤维改性的活性点。
然后，将表面包括羟基的碳纤维浸渍在苯基磷酸溶液中，并加热至第二温度，所述第二温度也需控制在适宜的大小，以满足苯基磷酸和Ce(NO 3) 3能够正常发生水热合成反应。本申请实施例控制所述第二温度为90℃～110℃。在加入所述稀土溶液时，需要在惰性气体的保护下进行，保证Ce(NO 3) 3的Ce元素为正三价。加入所述稀土溶液时可以采用逐渐滴加的方式，直至碳纤维表面完全被乳白色絮状物覆盖，所述乳白色絮状物即为稀土聚集物。
本申请实施例将表面活化后的碳纤维放置在苯基磷酸溶液中，然后将稀土溶液加入进去，这样可以在碳纤维表面发生水热合成反应，因而在碳纤维表面的各个活化点上生长出含有苯基磷结构的稀土聚集物 (CeP nAr m)，由于稀土聚集物的生长是无需随机的，不同活化点上生长出来的稀土聚集物中n和m的值是不一样的，但最终的结果是在碳纤维表面覆盖所述稀土聚集物。
形成稀土聚集物之后，可以在所述第二温度下静置至少24小时，使稀土聚集物生长完全。
将表面覆盖有稀土聚集物的碳纤维从苯基磷酸溶液中取出，用去离子水反复洗涤并进行干燥，最终形成棕黄色的稀土晶体包覆层。这是因为当三价的Ce元素接触到空气后，会被氧化为正四价的Ce元素，使得颜色从乳白色变成棕黄色。
本申请实施例还提供前述阻燃热塑性碳纤维复合材料的制备方法，包括：自螺杆挤出机的料斗向所述螺杆挤出机中加入所述聚酰胺和所述阻燃剂，自所述螺杆挤出机的进丝口向所述螺杆挤出机中加入所述隔热碳纤维，熔融共混后挤出成型获得所述阻燃热塑性碳纤维复合材料。所述聚酰胺和所述阻燃剂在进料前，可以在110～130℃的烘箱中干燥6h～12h。
所述螺杆挤出机的加工参数对于阻燃热塑性碳纤维复合材料的性能也具有很大影响。本申请实施例中，所述螺杆挤出机的加料区温度为150℃～180℃，压缩区温度为230℃～260℃，均化区温度为250℃～270℃，螺杆转速为120r/min～150r/min，所述隔热碳纤维的进丝速率为1米/min～5米/min。
实施例1
(1)隔热碳纤维的制备
将苯基磷酸(PPOA)溶解于去离子水中，并不断搅拌至完全溶解，保持PPOA在去离子水中达到饱和状态，得到苯基磷酸饱和水溶液，备用；
将Ce(NO 3) 3·6H 2O溶解在90℃的去离子水中，并不断搅拌至完全溶解，保持Ce(NO 3) 3·6H 2O在去离子水中达到饱和状态，得到Ce(NO 3) 3的饱和水溶液，备用；
将碳纤维浸入浓硫酸中，并在氩气保护下升温至50℃，浸渍15min～20min后，碳纤维表面达到酸化处理的目的，碳纤维表面上出现大量氢离子；然后去除氩气保护，用去离子水不断清洗碳纤维，直至清洗液的pH值大约为7，碳纤维表面的氢离子被空气中的氧气氧化，形成羟基基团；
将表面经过羟基处理的碳纤维浸渍在苯基磷酸饱和水溶液中，加热至90℃，并逐渐滴加Ce(NO 3) 3的饱和水溶液，直至碳纤维表面完全被乳白色絮状物覆盖，并在90℃下静置24小时以上，保证稀土晶体生长完全；
最后将碳纤维从苯基磷酸饱和水溶液中取出，用去离子水反复洗涤后，在80℃下真空干燥8小时以上至恒重，获得表面呈棕黄色的隔热碳纤维。
(2)阻燃热塑性碳纤维复合材料的制备
将重量百分比为60％的PA6和重量百分比为10％的聚磷酸胺分别在120℃的烘箱中干燥10h；自螺杆挤出机的料斗向所述螺杆挤出机中加入干燥后的PA6和聚磷酸胺，自所述螺杆挤出机的进丝口向所述螺杆挤出机中加入上述制备的隔热碳纤维，熔融共混后挤出成型获得阻燃热塑性碳纤维复合材 料，其中隔热碳纤维的重量百分比为30％，所述螺杆挤出机的加料区温度为150℃，压缩区温度为230℃，均化区温度为255℃，螺杆转速为125r/min，隔热碳纤维的进丝速率为5米/min。
实施例2～实施例6
实施例2～实施例6的配方请参考表1，挤出成型工艺参数请参考表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，挤出成型工艺参数请参考表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 PCTCN2022077430-appb-000001
表2实施例与对比例的挤出成型工艺参数
Figure PCTCN2022077430-appb-000002
对实施例3的隔热碳纤维表面的稀土晶体进行热失重分析测试，图1为氮气气氛下的热失重测试结果图，图2为空气气氛下的热失重测试结果图。由图1和图2可以看出，沉积生长在碳纤维表面的稀土晶体在氮气气氛下，升温至425℃时才开始热降解，最大程度的热降解发生在527.1℃，800℃时残炭量为74.0％；在空气气氛下，升温至419.6℃时才开始热降解，最大程度的热降解发生在512.5℃，800℃时残炭量仍维持在74.0％。由此可见，沉积生长在碳纤维表面的稀土晶体具有非常优异的热稳定性，可以抵御燃烧过程中的高温侵蚀，并具有很高的残炭量，可以较完整的包覆住碳纤维，从而可以有效抑制碳纤维在高分子基体中的“烛芯效应”。
分别对实施例3和对比例3的碳纤维复合材料燃烧后的残炭进行扫描电镜测试，结果如图3所示。其中A图为对比例3的碳纤维复合材料燃烧后残炭的扫描电镜图，在对比例3的碳纤维复合材料燃烧后的残炭中，碳纤维完全暴露出来，碳纤维表面光滑没有附着物。B图为实施例3的碳纤维复合材料燃烧后残炭的扫描电镜图，在实施例3的碳纤维复合材料燃烧后的残炭中，碳纤维几乎完全被覆盖在连续致密的炭层下面，将B图的局部(B图指向C图的箭头末端所在位置)进行放大如C图所示，几乎看不到碳纤维本身的结构。即使对B图中极少量暴露出来的碳纤维(B图中虚线框处)放大观察，如D图所示，也会发现碳纤维表面已经不再是光滑的，而是紧密附着有大量炭层物质。由此可见，沉积生长在碳纤维表面的稀土晶体，由于其优异的热稳定性和高成炭作用，在碳纤维表面形成了高温隔热层，从而可以有效抑制碳纤维的“烛芯效应”，进而可以使其增强的热塑性复合材料具有十分优异的阻燃性能。
进一步，对实施例1～6和对比例1～6的碳纤维复合材料的阻燃性能进行如下测试：
极限氧指数测试：参照国际标准ISO-4598测量碳纤维复合材料样品的极限氧指数值，试样尺寸130mm×6.5mm×3mm，每组样品测5个样条，取均值获得极限氧指数(LOI，％)，测试结果如表3；
垂直燃烧测试：参照IEC 60695-11-10标准测量碳纤维复合材料样品的垂直燃烧等级，试样尺寸127mm×12.7mm×3mm，每组样品测5个样条，取均 值获得UL94垂直燃烧测试级别、一次点燃后持续燃烧时间(t1，s)、二次点燃后持续燃烧时间(t2，s)、滴落情况和引燃下方脱脂棉情况，测试结果如表3。
表3实施例与对比例的碳纤维复合材料的阻燃性能测试结果
Figure PCTCN2022077430-appb-000003
由表3可知，在碳纤维表面沉积生长稀土晶体形成隔热碳纤维，由隔热碳纤维制备的碳纤维复合材料的极限氧指数显著提高，且碳纤维复合材料的第一次点燃时间和第二次点燃时间都明显缩短，同时燃烧时不会再产生高温可燃的滴落物质，都可以达到垂直燃烧UL94 V0级，这主要归功于沉积在碳纤维表面的稀土晶体具有优异的耐高温性能和成炭作用，使得碳纤维复合材料的引燃变得困难，提高了碳纤维复合材料的火安全性能。
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 (10)

  1. 一种阻燃热塑性碳纤维复合材料，以重量百分比计，包括：
    聚酰胺，45％～70％；
    隔热碳纤维，20％～30％，且所述隔热碳纤维包括碳纤维以及位于所述碳纤维的表面的稀土晶体包覆层；
    阻燃剂，10％～25％。
  2. 根据权利要求1所述的阻燃热塑性碳纤维复合材料，其特征在于，所述稀土晶体包覆层通过Ce(NO 3) 3和苯基磷酸进行水热合成反应并清洗干燥形成。
  3. 根据权利要求1所述的阻燃热塑性碳纤维复合材料，其特征在于，所述聚酰胺包括PA6和/或PA66，所述碳纤维包括聚丙烯腈基碳纤维。
  4. 根据权利要求1所述的阻燃热塑性碳纤维复合材料，其特征在于，所述阻燃剂包括无卤磷系阻燃剂。
  5. 一种如权利要求1至4任一项所述的阻燃热塑性碳纤维复合材料的制备方法，其特征在于，包括：自螺杆挤出机的料斗向所述螺杆挤出机中加入所述聚酰胺和所述阻燃剂，自所述螺杆挤出机的进丝口向所述螺杆挤出机中加入所述隔热碳纤维，熔融共混后挤出成型获得所述阻燃热塑性碳纤维复合材料。
  6. 根据权利要求5所述的阻燃热塑性碳纤维复合材料的制备方法，其特 征在于，所述螺杆挤出机的加料区温度为150℃～180℃，压缩区温度为230℃～260℃，均化区温度为250℃～270℃，螺杆转速为120r/min～150r/min，所述隔热碳纤维的进丝速率为1米/min～5米/min。
  7. 一种隔热碳纤维的制备方法，其特征在于，包括：
    提供苯基磷酸溶液、稀土溶液及碳纤维；
    将所述碳纤维置于硫酸溶液中，并在惰性气体的保护下加热至第一温度，使所述碳纤维的表面包括氢离子；
    去除所述惰性气体的保护，清洗所述碳纤维直至清洗液的pH在6.8～7.5，使所述氢离子被空气中的氧气氧化为羟基；
    将表面包括羟基的碳纤维置于所述苯基磷酸溶液中，并加热至第二温度，在惰性气体的保护下加入所述稀土溶液，在所述碳纤维的表面形成稀土聚集物；
    清洗并干燥表面具有所述稀土聚集物的碳纤维，在所述碳纤维表面形成稀土晶体包覆层。
  8. 根据权利要求7所述的隔热碳纤维的制备方法，其特征在于，所述稀土溶液为Ce(NO 3) 3的饱和水溶液，所述苯基磷酸溶液为苯基磷酸的饱和水溶液。
  9. 根据权利要求7所述的隔热碳纤维的制备方法，其特征在于，所述第一温度为50℃～70℃，所述第二温度为90℃～110℃。
  10. 根据权利要求7所述的隔热碳纤维的制备方法，其特征在于，形成所述稀土聚集物后，还包括在所述第二温度下静置至少24小时，使稀土聚集物生长完全。
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