WO2022227751A1 - 聚酰胺56树脂组合物及连续纤维增强聚酰胺56复合材料 - Google Patents

聚酰胺56树脂组合物及连续纤维增强聚酰胺56复合材料 Download PDF

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WO2022227751A1
WO2022227751A1 PCT/CN2022/074304 CN2022074304W WO2022227751A1 WO 2022227751 A1 WO2022227751 A1 WO 2022227751A1 CN 2022074304 W CN2022074304 W CN 2022074304W WO 2022227751 A1 WO2022227751 A1 WO 2022227751A1
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polyamide
fibers
composite material
parts
continuous
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PCT/CN2022/074304
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English (en)
French (fr)
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李园平
官冰
刘修才
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上海凯赛生物技术股份有限公司
Cibt美国公司
凯赛(太原)生物材料有限公司
山西合成生物研究院有限公司
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Publication of WO2022227751A1 publication Critical patent/WO2022227751A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/523—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement in the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/525—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/525—Component parts, details or accessories; Auxiliary operations
    • B29C70/528—Heating or cooling
    • 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
    • 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
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon 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
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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

Definitions

  • the invention relates to a polyamide 56 resin composition, a continuous fiber reinforced polyamide 56 composite material and a preparation method and application thereof.
  • thermoplastic materials do not need to be cross-linked and cured, and can be processed multiple times, and the molding process is more convenient and efficient. Therefore, thermoplastic materials have maintained stable and sustainable development in recent years, especially fiber-reinforced thermoplastic materials.
  • the matrix resin of the fiber-reinforced thermoplastic material can be polypropylene, polyamide, polyester and other thermoplastic materials, and the fiber can be glass fiber, carbon fiber, aramid fiber, etc., among which glass fiber is more commonly used.
  • Fiber reinforced thermoplastic materials are mainly divided into short fiber (2-4mm) reinforced thermoplastic materials, long fiber (12-24mm) reinforced thermoplastic materials, fiber mat reinforced thermoplastic materials, continuous fiber reinforced thermoplastic materials and thermoplastic composite core boards.
  • short fiber reinforced thermoplastic materials cannot meet the performance requirements of structural materials due to their poor strength, so long fiber reinforced thermoplastic materials have been developed; and continuous fibers have better reinforcement effect on thermoplastic materials than short fibers and long fibers, which greatly The mechanical properties and fatigue resistance have been improved, so research has been active in recent years.
  • Continuous fiber reinforced thermoplastic materials mainly focused on aerospace and military applications in the early days, and have been gradually used in automotive materials, sports equipment, construction and other industries since 2003. With the development of automobiles, electronic appliances and other industries, the demand for continuous fiber reinforced thermoplastic materials will also increase, so it is of great significance to accelerate the development and promotion of continuous fiber reinforced thermoplastic materials.
  • Continuous fiber reinforced thermoplastic materials can be stored for a long time, have excellent comprehensive properties, wide molding adaptability, high production efficiency, and products can be repeatedly processed and recycled. Therefore, research has been very active since they were developed in the early 1970s. Domestic research on continuous fiber reinforced thermoplastic materials has also begun in the late 1980s.
  • the preparation technologies of continuous fiber reinforced thermoplastic materials mainly include: (1) solution impregnation technology, (2) melt coating technology, (3) suspension impregnation technology, (4) co-woven fiber, (5) powder impregnation technology and (6) ) melt dipping method. Techniques (1)-(5) limit their wide application in industrial production due to production process, production cost, production efficiency and other reasons.
  • the melt impregnation method is that fiber bundles are impregnated by pulling them out of the molten resin under a certain tension through a designed impregnation die.
  • the method has simple forming process, no environmental pollution, and has the most industrialization prospect.
  • melt impregnation process requires the resin in the molten state to have lower viscosity, higher surface tension, and better wettability with fibers.
  • matrix resin of most thermoplastic materials on the market has high viscosity, poor fluidity and permeability during the molding process, and cannot impregnate and disperse fibers well, resulting in low fiber content and poor mechanical properties of continuous fiber reinforced composites.
  • the present invention provides a polyamide 56 resin composition, a continuous fiber reinforced polyamide 56 composite material and a preparation method thereof and use.
  • the polyamide 56 resin composition of the present invention has low viscosity, good fluidity and good wettability to fibers in a molten state; the continuous fiber reinforced polyamide 56 composite material prepared based on the polyamide 56 resin composition has a high fiber content , Good mechanical properties and recyclability.
  • a polyamide 56 resin composition comprising the following components in parts by weight: 81.8-99.8 parts of bio-based polyamide 56 resin, 0.2-1.6 parts of antioxidants, 0-0.8 parts of lubricants, 0-15 parts of container and 0-0.8 part of coupling agent.
  • the bio-based polyamide 56 resin refers to that the raw material monomer pentamethylene diamine is prepared by biological fermentation.
  • the bio-based polyamide 56 resin satisfies the following properties: relative viscosity 1.9-2.5, content of terminal amino groups 42-60 mmol/kg; melting point 210-260 °C, preferably 253-256 °C; bio-based content 43%-46%, eg 45%.
  • the relative viscosity is measured by the Ubbelohde viscometer concentrated sulfuric acid method.
  • the content of the terminal amino group is obtained by the following method: using trifluoroethanol to dissolve the sample, and titrating with standard hydrochloric acid solution and standard sodium hydroxide solution respectively, and then obtaining by calculation.
  • the biobased content is the content of the corresponding structural units in the polyamide of monomers prepared from biomass-derived feedstocks.
  • Biomass is a variety of organisms formed through photosynthesis.
  • one of the monomers of polyamide 56, pentamethylene diamine can be obtained by decarboxylation of lysine fermented from corn.
  • the moisture content is below 2000 ppm, preferably 800-2000 ppm; and/or the number average molecular weight is 30-45 kg/mol, and the molecular weight distribution is 1.8-2.1.
  • the moisture content was measured by using a Karl Fischer moisture analyzer, wherein the detection temperature was 200° C., and the detection time was 20 min.
  • the number-average molecular weight is determined by gel permeation chromatography (abbreviated as GPC).
  • the bio-based polyamide 56 resin can be purchased from Kasai (Jinxiang) Biomaterials Co., Ltd.
  • the parts in the present invention are all based on parts by weight or parts by mass.
  • the content of the bio-based polyamide 56 resin is preferably 90-95 parts, such as 90.4, 90.5, 92.6 or 93 parts.
  • the antioxidant can be selected from one or more of hindered phenol antioxidants, hindered amine antioxidants and phosphite antioxidants; preferably hindered amine antioxidants and phosphites A combination of antioxidants.
  • the hindered phenolic antioxidant can be conventional in the art, such as antioxidant 1010.
  • the hindered amine antioxidant can be conventional in the art, such as antioxidant 1098 (CAS 23128-74-7).
  • the phosphite antioxidant can be conventional in the art, such as antioxidant 168 (CAS 31570-04-4), antioxidant S9228.
  • the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228. More preferably, the antioxidant is a combination of antioxidant 168 and antioxidant 1098; wherein, the mass ratio of the antioxidant 168 and the antioxidant 1098 is preferably 1:1.
  • the content of the antioxidant is preferably 0.4-0.8 parts, such as 0.4, 0.5, 0.6 or 0.8 parts.
  • the lubricant may include an external lubricant and an internal lubricant; wherein, the mass ratio of the external lubricant to the internal lubricant is preferably 1:1.
  • the external lubricant may be conventional in the art, such as WAXC purchased from Clariant, Germany.
  • the internal lubricant can be conventional in the art, such as WAXE from Clariant, Germany.
  • the content of the lubricant is preferably 0.1-0.8 parts, such as 0.3, 0.4 or 0.5 parts.
  • the compatibilizer can be selected from polyolefin grafted maleic anhydride compatibilizers, polyolefin grafted methacrylic anhydride compatibilizers and rubber elastomer grafted maleic anhydride compatibilizers one or more.
  • the polyolefin-grafted maleic anhydride compatibilizer can be conventional in the field, such as PP-g-MAH (maleic anhydride grafted on polypropylene) or POE-g-MAH (maleic anhydride grafted on polypropylene) on ethylene octene copolymer).
  • the polyolefin-grafted methacrylic compatibilizer can be conventional in the art, such as POE-g-GMA (glycidyl methacrylate grafted on ethylene octene copolymer).
  • the rubber elastomer grafted maleic anhydride compatibilizer can be conventional in the art, such as EPDM-g-MAH (maleic anhydride grafted on ethylene propylene rubber).
  • the compatibilizer can also be polystyrene-maleic anhydride copolymer, polystyrene-glycidyl acrylate copolymer, styrene-glycidyl methacrylate copolymer, polystyrene-maleimide Copolymer, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, etc.; also can be multifunctional epoxy resin, etc.
  • the content of the compatibilizer is preferably 3-15 parts, preferably 6-8 parts, such as 6, 8, 10 or 12 parts.
  • the coupling agent can be selected from one or more of silane coupling agents, carbonate coupling agents and aluminate coupling agents; preferably silane coupling agents, For example, coupling agent KH550, coupling agent KH560 or coupling agent KH570.
  • the coupling agent is generally selected according to the composition and surface structure of the fibers used and the melting point of the bio-based polyamide 56 resin.
  • the amount of the coupling agent is preferably 0.1-0.8 parts, such as 0.2, 0.3, 0.4, 0.5 or 0.6 parts.
  • the polyamide 56 resin composition further includes an end-capped polyamide 5X oligomer.
  • the number average molecular weight of the polyamide 5X oligomer is preferably 500-10000 g/mol, preferably 750-5000 g/mol.
  • the end-capped polyamide 5X oligomer can increase the fluidity of the polyamide 56 resin composition.
  • the polyamide 56 resin composition further includes one or more of a nucleating agent, a mineral salt powder and a flame retardant.
  • the nucleating agent may be, for example, nucleating agent P22 produced by BRUGGOLEN, Germany.
  • the polyamide 56 resin composition comprises the following components in parts by weight: 90.4-93 parts of bio-based polyamide 56 resin (PA56), 0.4-0.8 parts of antioxidant, lubricant 0.4-0.5 part, 6-10 part of compatibilizer and 0.2-0.6 part of coupling agent.
  • the polyamide 56 resin composition comprises the following components in parts by weight: 90.4-93 parts of bio-based polyamide 56 resin (PA56), 1098 parts of antioxidants, 0.2-0.4 parts of antioxidants, 168 0.2-0.4 part, internal lubricant WAXE 0.2-0.3 part, external lubricant WAXC 0.2-0.3 part, compatibilizer 6-8 part and silane coupling agent 0.2-0.6 part.
  • PA56 bio-based polyamide 56 resin
  • the polyamide 56 resin composition can be prepared by a conventional method in the art, and generally all components can be mixed uniformly. Wherein, the mixing can be performed using conventional mixing equipment in the art, such as a high-speed mixer.
  • the second technical solution a continuous fiber reinforced polyamide 56 composite material, comprising the polyamide 56 resin composition and fibers, wherein the fibers account for 40% by mass of the continuous fiber reinforced polyamide 56 composite material %-75%.
  • the mass percentage of the fibers in the continuous fiber-reinforced polyamide 56 composite material is preferably 50-70%, such as 60% or 65%.
  • long fibers refers to fibers having a length greater than 12 mm, eg, about 12-24 mm in length.
  • Continuous fibers and “continuous filaments” are used interchangeably.
  • the type of the fiber can be conventional in the field, such as carbon fiber, glass fiber, basalt fiber or aramid fiber.
  • the fibers are preferably continuous long fibers, preferably, the fibers are continuous long glass fibers.
  • the monofilament diameter of the continuous long glass fiber may be 8-15 ⁇ m, preferably 8-10 ⁇ m.
  • the linear density of the continuous long glass fiber is 1000-3600Tex, preferably 1200Tex, 2400Tex.
  • the continuous long glass fibers are, for example, continuous long glass fibers with a specification of 1200 Tex from Owens Corning (OC), and continuous long glass fibers with a specification of 2400 Tex from Boulder.
  • the fibers are continuous long carbon fibers; the continuous long carbon fibers are preferably polyacrylonitrile carbon fibers; the number of monofilaments of the continuous long carbon fibers may be 20,000-30,000, preferably 12,000 ( 12K), 24000 pieces (24K); the monofilament diameter of the continuous long carbon fiber can be 5-10 ⁇ m.
  • the continuous long carbon fibers are, for example, Toray T700 with a specification of 24K, and Guangwei composite continuous long carbon fiber 700S with a specification of 12K or 24K.
  • the continuous fiber-reinforced polyamide 56 composite material is in the form of a unidirectional prepreg tape.
  • the unidirectional prepreg tape refers to a tape-shaped prepreg made by impregnating resin with continuous fibers parallel to each other.
  • the thickness of the continuous fiber reinforced polyamide 56 composite material is 0.15-0.5 mm.
  • the tensile strength of the continuous fiber reinforced polyamide 56 composite material is 600-1300MPa; the tensile modulus is 20-60GPa; the elongation at break is 2.9- 3.4%.
  • the tensile strength of the continuous fiber reinforced polyamide 56 composite material is 1400-1800MPa; the tensile modulus is 80-140GPa; and the elongation at break is 2.5-3.0 %.
  • the third technical solution a preparation method of continuous fiber reinforced polyamide 56 composite material, which comprises the following steps:
  • the mass percentage of the fibers in the continuous fiber reinforced polyamide 56 composite material is controlled to be 40%-75%.
  • the mass percentage of the fibers in the continuous fiber reinforced polyamide 56 composite material is 50-70%, for example, 60%, 65%.
  • the extrusion can be carried out by a conventional twin-screw extruder or a single-screw extruder, preferably a twin-screw extruder.
  • the length-diameter ratio of the twin-screw extruder is preferably 1:36.
  • the extrusion temperature may be 170-340°C.
  • the twin-screw extruder adopts an eight-zone heating mode, and the temperatures from zone one to zone eight are 205-260°C, 265-305°C, 275-325°C, 275-325°C, 275-325°C, 275-325°C, 275-325°C, 275-325°C, 275-325°C, 275-325°C, 275-325°C.
  • step S1 expressed in terms of the screw speed, the extrusion speed is 200-600 rpm, for example, 300 rpm or 400 rpm.
  • step S1 after the extrusion, the step of filtering is preferably included.
  • the filtration can be performed using melt filters conventional in the art.
  • the temperature of the melt filter is in the range of 0-15°C above and below the temperature of the eight zones of the twin-screw extruder, such as 290°C, 285°C, 295°C, 310°C. °C.
  • the dipping die head can be a conventional die head in the field.
  • the width of the dip die is preferably 100-650 mm.
  • the temperature of the dip die head may be 260-335°C.
  • the temperature of the dipping die is within the range of 0-35°C above and below the temperature of the eight zones of the twin-screw extruder, further within the range of 0-15°C, for example, 250°C. , 290°C, 295°C, 305°C.
  • step S2 when the fiber is a continuous long fiber, the introduction generally includes the following process: the fiber is unwound from the yarn guide frame through the tension controller, passed through the yarn dividing frame, and enters the yarn spreading system, so that each The tow is fully expanded, then enters the drying unit for preheating, and then enters the dipping die.
  • the temperature of the yarn drying device is preferably 70-90°C, such as 80°C or 85°C; when the fibers are continuous long carbon fibers, the drying yarn The temperature of the device is preferably 70-400°C, such as 80°C, 100°C, 200°C, 250°C or 300°C, 350°C.
  • step S2 the fibers are as described above.
  • step S3 the molding and cooling can be performed by a conventional roller press in the art, preferably a four-roller.
  • the temperature of the inner circulating water of the four-roll machine may be 60-90°C, such as 70°C and 80°C.
  • step S3 the pulling can be performed using a conventional pulling device in the art, and further cooling and edge trimming are performed in the pulling device.
  • the pulling speed of the pulling may be 5-15 m/min, eg 8 m/min.
  • step S3 the winding can be performed by a conventional winding device in the art, preferably an automatic winder.
  • the fiber-reinforced polyamide 56 composite material obtained by the preparation method of the fiber-reinforced polyamide 56 composite material is preferably in the form of a unidirectional prepreg tape.
  • the thickness of the fiber-reinforced polyamide 56 composite material obtained by the preparation method of the fiber-reinforced polyamide 56 composite material is 0.15-0.5 mm.
  • the fourth technical solution a molded product comprising the fiber-reinforced polyamide 56 composite material.
  • the fifth technical solution a use of the fiber-reinforced polyamide 56 composite material in the aerospace field, the military field, automobile materials, sports equipment, building materials or electronic appliances.
  • the present invention adopts bio-based polyamide as raw material:
  • the monomer pentamethylene diamine in the raw material is prepared by biological fermentation, and the bio-based content is high, which is in line with the concept of sustainable development of material sources;
  • the polyamide 56 resin composition prepared by using the bio-based polyamide of the present invention as a raw material has low viscosity, good fluidity and good wettability to fibers in a molten state.
  • the fiber content is high, within the mass percentage range of 40%-75%;
  • the thickness of the composite material can be set between 0.15-0.5mm according to the needs, which can provide more design freedom for the product;
  • the final molded product comprising the continuous fiber-reinforced polyamide 56 composite material of the present invention can be recycled and reused, and the resource utilization rate is high.
  • FIG. 1 is a flow chart of the preparation process of the continuous fiber reinforced polyamide 56 composite material in the embodiment of the present invention.
  • bio-based polyamide 56 (referred to as PA56, with a relative viscosity of 2.29, a terminal amino group content of 55 mmol/kg, a melting point of 253° C., and a bio-based content of 45%) was purchased from Kasai (Jinxiang) Biological Materials Co., Ltd.; antioxidants were purchased from BASF Group, Germany; WAXE and WAXC were purchased from Clariant, Germany; compatibilizers were purchased from Shanghai Jiayirong Polymer Co., Ltd.; coupling agents were purchased from Hangzhou Jessica Chemical Co., Ltd.; continuous Long glass fibers were purchased from Owens Corning (OC) with a specification of 1200Tex; continuous long carbon fibers were Toray T700 with a specification of 24K.
  • PA56 bio-based polyamide 56
  • the polyamide 56 resin composition used in this example includes the following components in parts by weight: PA56: 90.4 parts, antioxidant 1098: 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubrication Agent WAXC: 0.2 part, compatibilizer EPDM-g-MAH: 8 parts, coupling agent KH550: 0.6 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 56 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, and 300°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 310°C; the dip die temperature was 305°C.
  • the impregnated continuous long glass fibers are molded and cooled through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the continuous long glass fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 56 resin composition used in this example includes the following components in parts by weight: PA56: 90.5 parts, antioxidant 1098: 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubrication Agent WAXC: 0.2 part, compatibilizer POE-g-MAH: 8 parts, coupling agent KH560: 0.5 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 56 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, and 300°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 310°C; the dip die temperature was 305°C.
  • the impregnated continuous long glass fibers are molded and cooled through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the continuous long glass fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 56 resin composition used in this example includes the following components in parts by weight: PA56: 92.6 parts, antioxidant 1098: 0.2 part, antioxidant 168: 0.2 part, internal lubricant WAXE: 0.2 part, external lubrication Agent WAXC: 0.2 part, compatibilizer POE-g-MAH: 6.2 part, coupling agent KH560: 0.4 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 56 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, and 300°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 310°C; the dip die temperature was 305°C.
  • the impregnated continuous long glass fibers are molded and cooled through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the continuous long glass fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 56 resin composition used in this example includes the following components in parts by weight: PA56: 90.5 parts, antioxidant 1098: 0.4 part, antioxidant 168: 0.4 part, internal lubricant WAXE: 0.2 part, external lubrication Agent WAXC: 0.2 part, compatibilizer EPDM-g-MAH: 8 parts, coupling agent KH560: 0.3 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 56 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, and 300°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 310°C; the dip die temperature was 305°C.
  • the impregnated continuous long glass fibers are molded and cooled through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the continuous long glass fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 56 resin composition used in this example includes the following components in parts by weight: PA56: 93 parts, antioxidant 1098: 0.2 part, antioxidant 168: 0.2 part, internal lubricant WAXE: 0.2 part, external lubrication Agent WAXC: 0.2 part, compatibilizer POE-g-MAH: 6 parts, coupling agent KH550: 0.2 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 56 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, and 300°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 310°C; the dip die temperature was 305°C.
  • the impregnated continuous long glass fibers are molded and cooled through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the continuous long glass fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 56 resin composition used in this example includes the following components in parts by weight: PA56: 90.5 parts, antioxidant 1098: 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubrication Agent WAXC: 0.2 part, compatibilizer POE-g-MAH: 8 parts, coupling agent KH560: 0.5 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 56 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (along the direction of feeding to the die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, 270°C °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 285°C; the dip die temperature was 290°C.
  • the impregnated continuous long carbon fibers are molded and cooled through a four-roll machine, wherein the temperature of the circulating water in the four-roll machine is set to 80°C;
  • the continuous long carbon fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the preparation method of the continuous fiber reinforced polyamide 56 composite material is the same as that in Example 6, the difference is: in the preparation process, the screw speed of the twin-screw extruder and the winding speed of the automatic winder are controlled to ensure continuous long carbon fiber and polyamide 56.
  • the weight fraction ratio of the amide 56 resin composition was 60:40.
  • the continuous long carbon fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the preparation method of the continuous fiber reinforced polyamide 56 composite material is the same as that in Example 6, the difference is: in the preparation process, the screw speed of the twin-screw extruder and the winding speed of the automatic winder are controlled to ensure continuous long carbon fiber and polyamide 56.
  • the weight fraction ratio of the amide 56 resin composition was 65:35.
  • the continuous long carbon fiber reinforced polyamide 56 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 6 resin composition used in this comparative example includes the following components in parts by weight: polyamide PA6 (purchased from Xinhui Meida Co., Ltd., the relative viscosity is 2.3, the content of terminal amino groups is 54 mmol/kg, and the melting point is 223° C. ): 90.5 parts, antioxidant 1098: 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubricant WAXC: 0.2 part, compatibilizer POE-g-MAH: 8 parts, coupling agent KH550: 0.5 servings.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 6 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 200°C, 220°C, 245°C, 245°C, 245°C, 245°C, 245°C, 245°C °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the temperature of the melt filter was 250°C; the temperature of the dip die was 250°C.
  • the continuous long glass fiber after dipping is subjected to molding and cooling through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80 ° C;
  • the continuous long glass fiber reinforced polyamide 6 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 6 resin composition used in this comparative example includes the following components in parts by weight: polyamide PA6 (purchased from Xinhui Meida Co., Ltd., the relative viscosity is 2.3, the content of terminal amino groups is 54 mmol/kg, and the melting point is 223° C. ): 90.5 parts, antioxidant 1098: 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubricant WAXC: 0.2 part, compatibilizer POE-g-MAH: 8 parts, coupling agent KH550: 0.5 servings.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 6 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 200°C, 220°C, 245°C, 245°C, 245°C, 245°C, 245°C, 245°C °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 245°C; the dip die temperature was 250°C.
  • the impregnated continuous long carbon fibers are molded and cooled through a four-roll machine, wherein the temperature of the circulating water in the four-roll machine is set to 80°C;
  • the continuous long carbon fiber reinforced polyamide 6 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 66 resin composition used in this comparative example includes the following components in parts by weight: polyamide PA66 (purchased from DuPont, the relative viscosity is 2.6, the content of terminal amino groups is 48mmol/kg, and the melting point is 255°C): 90.5 parts , antioxidant 1098: 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubricant WAXC: 0.2 part, compatibilizer POE-g-MAH: 8 part, coupling agent KH550: 0.5 part .
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 6 resin composition.
  • the twin-screw extruder is an eight-zone heating mode, and the temperatures from zone one to zone eight (in the direction of feeding to the head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, and 300°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 315°C; the dip die temperature was 310°C.
  • the impregnated continuous long glass fibers are molded and cooled through a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the continuous long glass fiber reinforced polyamide 66 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the continuous fiber reinforced polyamide composite material unidirectional prepreg tapes of Examples 1-8 and Comparative Examples 1-3 were tested for performance according to the following test methods: (1) areal density: ASTM 792-98; (2) fiber content: ASTM D5630; (3) Tensile strength: ASTM D3039; (4) Tensile modulus: ASTM D3039; (5) Elongation at break: ASTM D3039. The results are shown in Table 1.
  • Examples 1-5 are polyamide 56 composite materials containing continuous long glass fibers, and the tensile strengths are all above 600 MPa, and Example 5 is as high as 1127 MPa; the tensile modulus also increases with the increase of fiber content, Example 5 was up to 47 Gpa.
  • Examples 6-8 are polyamide 56 composites containing continuous long carbon fibers, which achieve higher mechanical properties even with lower fiber content.
  • the contents of continuous long glass fibers in Example 4, Comparative Example 1 and Comparative Example 3 are similar, but the mechanical properties of the PA56 composite material obtained in Example 4 are significantly higher than those of the Comparative Example 1PA6 composite material and the Comparative Example 3PA66 composite material.
  • Example 8 the content of continuous long carbon fibers in Example 8 and Comparative Example 2 are similar, and the mechanical strength of the PA56 composite obtained in Example 8 is also significantly higher than that in Comparative Example 2.
  • the embodiments of the present invention have excellent mechanical properties, and the PA56 bio-based content of the present invention is high, which effectively reduces the use of fossil raw materials, thereby reducing carbon emissions.

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Abstract

本发明公开了一种聚酰胺56树脂组合物、连续纤维增强聚酰胺56复合材料及其制备方法和用途。所述聚酰胺56树脂组合物包括以下重量份数的组分：生物基聚酰胺56树脂81.8-99.8份、抗氧化剂0.2-1.6份、润滑剂0-0.8份、相容剂0-15份和偶联剂0-0.8份。所述连续纤维增强聚酰胺56复合材料包括所述聚酰胺56树脂组合物和纤维，其中，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为40％-75％。本发明的连续纤维增强聚酰胺56复合材料的纤维含量高、力学性能好，且具有可回收性，可适用于航空航天领域、军事领域、汽车材料、运动器材、建筑材料、电子电器等领域。

Description

聚酰胺56树脂组合物及连续纤维增强聚酰胺56复合材料 技术领域
本发明涉及一种聚酰胺56树脂组合物、连续纤维增强聚酰胺56复合材料及其制备方法和用途。
背景技术
相比于热固性材料，热塑性材料不需要经过交联和固化，可以多次加工成型，且成型工艺更为便捷高效，所以热塑性材料近年来一直保持稳定持续发展，尤其是纤维增强热塑性材料。纤维增强热塑性材料的基体树脂可采用聚丙烯、聚酰胺、聚酯等热塑性材料，纤维可采用玻璃纤维、碳纤维、芳纶纤维等，其中又以玻璃纤维较为常用。
纤维增强热塑性材料主要分为短纤(2-4mm)增强热塑性材料、长纤(12-24mm)增强热塑性材料、纤维毡增强热塑性材料、连续纤维增强热塑性材料和热塑性复合材料芯板。其中，短纤增强热塑性材料因其强度较差，不能满足结构材料的性能要求，所以发展出了长纤增强热塑性材料；而连续纤维对热塑性材料的增强效果比短纤和长纤更好，大幅提升了机械性能和耐疲劳性能，所以近年来研究活跃。连续纤维增强热塑性材料早期主要着重于航天和军事的应用，从2003年开始逐步应用于汽车材料、运动器材、建筑等行业。随着汽车、电子电器等行业的发展，连续纤维增强热塑性材料的需求也会越来越大，因此加快连续纤维增强热塑性材料的研制和推广具有重要意义。
连续纤维增强热塑性材料可以长期保存，综合性能优异，成型适应性广，生产效率高，制品可重复加工再生利用，所以在20世纪70年代初开发出来以后研究就十分活跃。国内从20世纪80年代后期也开始了连续纤维增强热塑性材料的研究。连续纤维增强热塑性材料的制备技术主要包括：(1)溶液浸渍技术，(2)熔体涂覆技术，(3)悬浮浸渍技术，(4)共织纤维，(5)粉 末浸渍技术和(6)熔融浸渍法。技术(1)-(5)由于生产工艺、生产成本、生产效率等原因限制了其在工业生产中的广泛应用。熔融浸渍法是纤维束通过设计的浸渍模具，在一定的张力作用下从在熔融状态下的树脂中拉出而被浸渍。该方法成型工艺简单，无环境污染，最具工业化前景。
然而，熔融浸渍法工艺要求在熔融状态下的树脂具有较低的粘度、较高的表面张力，并与纤维有较好的浸润性。但是市场上大部分热塑性材料的基体树脂粘度较高，在成型过程中流动性和渗透性差，不能很好地浸渍和分散纤维，使得连续纤维增强复合材料的纤维含量低，力学性能差，从而限制了基体树脂在连续纤维增强复合材料中的应用。
发明内容
本发明为了解决现有技术中连续纤维增强复合材料存在的纤维含量低、力学性能差的缺陷，从而提供了一种聚酰胺56树脂组合物、连续纤维增强聚酰胺56复合材料及其制备方法和用途。本发明的聚酰胺56树脂组合物在熔融状态下粘度低、流动性好，对纤维的浸润性好；基于该聚酰胺56树脂组合物制得的连续纤维增强聚酰胺56复合材料的纤维含量高、力学性能好，且具有可回收性。
为了实现上述目的，本发明采用以下技术方案：
技术方案之一：一种聚酰胺56树脂组合物，其包括以下重量份数的组分：生物基聚酰胺56树脂81.8-99.8份、抗氧化剂0.2-1.6份、润滑剂0-0.8份、相容剂0-15份和偶联剂0-0.8份。
所述生物基聚酰胺56树脂是指原料单体戊二胺为通过生物发酵制备而来。
较佳地，所述生物基聚酰胺56树脂满足以下性能：相对粘度1.9-2.5，端氨基含量42-60mmol/kg；熔点210℃-260℃，较佳为253℃-256℃；生物基含量为43％-46％，例如45％。其中，所述相对粘度通过乌氏粘度计浓硫酸法测定。所述端氨基含量通过如下方法获得：采用三氟乙醇溶解样品，并 分别采用盐酸标准溶液和氢氧化钠标准溶液滴定，然后经计算获得。生物基含量是由来源于生物质的原料制备的单体在聚酰胺中对应的结构单元的含量。生物质是通过光合作用而形成的各种有机体。如聚酰胺56的单体之一戊二胺可以由玉米发酵的赖氨酸脱羧后得到。生物基含量检测标准方法ASTM D6866检测获得。
较佳的，含水率2000ppm以下，较佳的为800-2000ppm；和/或数均分子量为30-45kg/mol，分子量分布为1.8-2.1。含水率通过采用卡尔费休水分测定仪测得，其中检测温度为200℃，并且检测时间为20min。数均分子量通过凝胶渗透色谱(简称为GPC)测试得到。
所述生物基聚酰胺56树脂可以购自凯赛(金乡)生物材料有限公司。
除非另有说明，本发明中的份数均基于重量份或质量份。本发明中，所述生物基聚酰胺56树脂的含量较佳地为90-95份，例如90.4、90.5、92.6或93份。
本发明中，所述抗氧化剂可选自受阻酚类抗氧化剂、受阻胺类抗氧化剂和亚磷酸酯类抗氧化剂中的一种或多种；较佳地为受阻胺类抗氧化剂和亚磷酸酯类抗氧化剂的组合。其中，所述受阻酚类抗氧化剂可为本领域常规，例如抗氧化剂1010。所述受阻胺类抗氧化剂可为本领域常规，例如抗氧化剂1098(CAS 23128-74-7)。所述亚磷酸酯类抗氧化剂可为本领域常规，例如抗氧化剂168(CAS 31570-04-4)、抗氧化剂S9228。
较佳地，所述抗氧化剂选自抗氧化剂168、抗氧化剂1098、抗氧化剂1010和抗氧化剂S9228中的一种或多种。更佳地，所述抗氧化剂为抗氧化剂168和抗氧化剂1098的组合；其中，所述抗氧化剂168和所述抗氧化剂1098的质量比优选为1:1。
本发明中，所述抗氧化剂的含量较佳地为0.4-0.8份，例如0.4、0.5、0.6或0.8份。
本发明中，所述润滑剂可包括外润滑剂和内润滑剂；其中，所述外润滑剂和所述内润滑剂的质量比优选为1:1。
其中，所述外润滑剂可为本领域常规，例如为购自德国科莱恩公司的WAXC。所述内润滑剂可为本领域常规，例如为购自德国科莱恩公司的WAXE。
本发明中，所述润滑剂的含量较佳地为0.1-0.8份，例如0.3、0.4或0.5份。
本发明中，所述相容剂可选自聚烯烃接枝马来酸酐类相容剂、聚烯烃接枝甲基丙烯酸类相容剂和橡胶弹性体接枝马来酸酐类相容剂中的一种或多种。其中，所述聚烯烃接枝马来酸酐类相容剂可为本领域常规，例如PP-g-MAH(马来酸酐接枝于聚丙烯上)或POE-g-MAH(马来酸酐接枝于乙烯辛烯共聚物上)。所述聚烯烃接枝甲基丙烯酸类相容剂可为本领域常规，例如POE-g-GMA(甲基丙烯酸缩水甘油酯接枝于乙烯辛烯共聚物上)。所述橡胶弹性体接枝马来酸酐类相容剂可为本领域常规，例如EPDM-g-MAH(马来酸酐接枝于三元乙丙橡胶上)。所述相容剂也可以是聚苯乙烯-马来酸酐共聚物、聚苯乙烯-丙烯酸缩水甘油酯共聚物、苯乙烯-甲基丙烯酸缩水甘油酯共聚物、聚苯乙烯-马来酰亚胺共聚物、氢化苯乙烯-异戊二烯共聚物接枝马来酸酐等；也可以是多官能度的环氧树脂等。
本发明中，所述相容剂的含量较佳地为3-15份，较佳的为6-8份，例如6、8、10或12份。
本发明中，所述偶联剂可选自硅烷类偶联剂、碳酸酯类偶联剂和铝酸酯类偶联剂中的一种或多种；较佳地为硅烷类偶联剂，例如偶联剂KH550、偶联剂KH560或偶联剂KH570。所述偶联剂一般根据所使用的纤维的组成和表面结构以及所述生物基聚酰胺56树脂的熔点而选择。
本发明中，所述偶联剂的用量较佳地为0.1-0.8份，例如0.2、0.3、0.4、0.5或0.6份。
本发明中，可选地，所述聚酰胺56树脂组合物还包括封端的聚酰胺5X寡聚物。聚酰胺5X寡聚物的数均分子量优选为500-10000g/mol，优选为750-5000g/mol。所述封端的聚酰胺5X寡聚物可增加所述聚酰胺56树脂组 合物的流动性。
本发明中，可选地，所述聚酰胺56树脂组合物还包括成核剂、矿物盐粉末和阻燃剂中的一种或多种。其中，所述成核剂例如可为由德国布吕格曼BRUGGOLEN生产的成核剂P22。
在某些较佳的实施方案中，所述聚酰胺56树脂组合物包括以下重量份数的组分：生物基聚酰胺56树脂(PA56)90.4-93份、抗氧化剂0.4-0.8份、润滑剂0.4-0.5份、相容剂6-10份和偶联剂0.2-0.6份。
在一较佳的实施方案中，所述聚酰胺56树脂组合物包括以下重量份数的组分：生物基聚酰胺56树脂(PA56)90.4-93份、抗氧化剂1098 0.2-0.4份、抗氧化剂168 0.2-0.4份、内润滑剂WAXE0.2-0.3份、外润滑剂WAXC 0.2-0.3份、相容剂6-8份和硅烷类偶联剂0.2-0.6份。
本发明中，所述聚酰胺56树脂组合物可采用本领域常规的方法制备，一般将各组分混合均匀即可。其中，所述混合可采用本领域常规的混合设备进行，例如高速搅拌机。
技术方案之二：一种连续纤维增强聚酰胺56复合材料，其包括所述聚酰胺56树脂组合物和纤维，其中，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为40％-75％。
本发明中，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为较佳地为50～70％，例如60％或65％。
在本文中，“长纤维”指的是长度大于12mm，例如长度大约为12-24mm的纤维。“连续纤维”、以及“连续长纤维”可互换使用。本发明中，所述纤维的种类可为本领域常规，例如碳纤维、玻璃纤维、玄武岩纤维或芳纶纤维。所述纤维优选为连续长纤维，较佳地，所述纤维为连续长玻璃纤维。所述连续长玻璃纤维的单丝直径可为8-15μm，较佳地为8-10μm。所述连续长玻璃纤维的线密度为1000-3600Tex，较佳地为1200Tex、2400Tex。所述连续长玻璃纤维例如为购自欧文斯科宁(OC)的规格为1200Tex的连续长玻璃纤维、购自巨石的规格为2400Tex的连续长玻璃纤维。
较佳地，所述纤维为连续长碳纤维；所述连续长碳纤维较佳地为聚丙烯腈类碳纤维；所述连续长碳纤维的单丝数量可为20000-30000根，较佳地为12000根(12K)、24000根(24K)；所述连续长碳纤维的单丝直径可为5-10μm。所述连续长碳纤维例如为规格为24K的东丽T700、规格为12K或24K的光威复材连续长碳纤维700S。
本发明中，较佳地，所述连续纤维增强聚酰胺56复合材料为单向预浸带的形式。所述单向预浸带是指由相互平行的连续纤维浸渍树脂后制成的一种带状预浸料。
本发明中，较佳地，所述连续纤维增强聚酰胺56复合材料的厚度为0.15-0.5mm。
本发明中，当所述纤维为连续长玻璃纤维时，所述连续纤维增强聚酰胺56复合材料的拉伸强度为600-1300MPa；拉伸模量为20-60GPa；断裂伸长率为2.9-3.4％。
本发明中，当所述纤维为连续长碳纤维时，所述连续纤维增强聚酰胺56复合材料的拉伸强度为1400-1800MPa；拉伸模量为80-140GPa；断裂伸长率为2.5-3.0％。
技术方案之三：一种连续纤维增强聚酰胺56复合材料的制备方法，其包括以下步骤：
S1、将所述聚酰胺56树脂组合物挤出，并使挤出的熔体进入浸渍模头；
S2、将所述纤维导入所述浸渍模头，使所述熔体和所述纤维发生浸渍；
S3、将浸渍后的纤维进行模压、冷却、牵引和卷绕，由此得到连续纤维增强长碳链聚酰胺复合材料；
其中，通过调节所述挤出的速度和所述卷绕的速度，控制所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为40％-75％。
本发明中，较佳地，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为50～70％，例如60％、65％。
步骤S1中，所述挤出可采用本领域常规的双螺杆挤出机或者单螺杆挤 出机进行，较佳地为双螺杆挤出机。其中，所述双螺杆挤出机的长径比较佳地为1:36。
步骤S1中，所述挤出的温度可为170-340℃。
较佳地，所述双螺杆挤出机采用八区加热模式，一区至八区温度依次为205-260℃、265-305℃、275-325℃、275-325℃、275-325℃、275-325℃、275-325℃、275-325℃。
步骤S1中，以螺杆转速表示，所述挤出的速度为200-600rpm，例如300rpm或400rpm。
步骤S1中，所述挤出后较佳地还包括过滤的步骤。所述过滤可采用本领域常规的熔体过滤器进行。较佳地，当采用双螺杆挤出机时，所述熔体过滤器的温度在双螺杆挤出机的八区温度上下0-15℃范围内，例如290℃、285℃、295℃、310℃。
步骤S1中，所述浸渍模头可采用本领域常规的模头。所述浸渍模头的幅宽较佳地为100-650mm。
其中，所述浸渍模头的温度可为260-335℃。较佳地，当采用双螺杆挤出机时，所述浸渍模头的温度在双螺杆挤出机的八区温度上下0-35℃范围内，进一步为0-15℃范围内，例如250℃、290℃、295℃、305℃。
步骤S2中，当所述纤维为连续长纤维时，所述导入一般包括以下过程：所述纤维经过张力控制器从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，接着进入烘纱装置进行预热，然后进入浸渍模头。
其中，当所述纤维为连续长玻璃纤维时，所述烘纱装置的温度较佳地为70-90℃，例如80℃或85℃；当所述纤维为连续长碳纤维时，所述烘纱装置的温度较佳地为70-400℃，例如80℃、100℃、200℃、250℃或300℃、350℃。
步骤S2中，所述纤维如前所述。
步骤S3中，所述模压、冷却可采用本领域常规的压辊机进行，较佳地为四辊机。所述四辊机的内循环水的温度可为60-90℃，例如70℃、80℃。
步骤S3中，所述牵引可采用本领域常规的牵引装置进行，在牵引装置 中进行进一步冷却和切边。所述牵引的牵引速度可为5-15m/min，例如8m/min。
步骤S3中，所述卷绕可采用本领域常规的卷绕装置进行，较佳地为自动收卷机。
本发明中，所述纤维增强聚酰胺56复合材料的制备方法制得的纤维增强聚酰胺56复合材料较佳地为单向预浸带的形式。
本发明中，较佳地，所述纤维增强聚酰胺56复合材料的制备方法制得的纤维增强聚酰胺56复合材料的厚度为0.15-0.5mm。
技术方案之四：一种成型品，其包含所述纤维增强聚酰胺56复合材料。
技术方案之五：一种所述纤维增强聚酰胺56复合材料在航空航天领域、军事领域、汽车材料、运动器材、建筑材料或电子电器中的用途。
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：
1、本发明采用生物基聚酰胺为原料：
(1)原料中的单体戊二胺通过生物发酵制备而来，生物基含量高，符合材料来源可持续发展的理念；
(2)采用本发明所述的生物基聚酰胺为原料制备出的聚酰胺56树脂组合物在熔融状态下粘度低、流动性好，对纤维的浸润性好。
2、本发明所述的连续纤维增强聚酰胺56复合材料：
(1)纤维含量高，在40％-75％的质量百分比范围内；
(2)具有优异的力学性能，具体地，拉伸强度均在600MPa以上，拉伸模量在20GPa以上；
(3)纤维分布均匀，无纤维外露，易加工；
(4)可以根据需要将复合材料的厚度设置在0.15-0.5mm之间，能够为产品提供更多的设计自由度；
(5)包含本发明所述的连续纤维增强聚酰胺56复合材料的最终成型品 可回收和重复使用，资源利用率高。
3、本发明的连续纤维增强聚酰胺56复合材料的制备方法简单可行。
附图说明
图1为本发明实施例中连续纤维增强聚酰胺56复合材料的制备工艺流程图。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
以下实施例和对比例中：生物基聚酰胺56(简称PA56，相对粘度为2.29、端氨基含量为55mmol/kg、熔点为253℃、生物基含量45％)购自凯赛(金乡)生物材料有限公司；抗氧化剂购自德国巴斯夫集团；WAXE和WAXC购自德国科莱恩公司；相容剂购自上海佳易容聚合物有限公司；偶联剂购自杭州杰西卡化工有限公司；连续长玻璃纤维购自欧文斯科宁(OC)，规格为1200Tex；连续长碳纤维为东丽T700，规格为24K。
以下实施例和对比例中连续纤维增强聚酰胺56复合材料的制备工艺如图1所示。
实施例1
1、制备聚酰胺56树脂组合物
本实施例所采用的聚酰胺56树脂组合物按照重量份数包括以下组分：PA56：90.4份，抗氧化剂1098：0.3份，抗氧化剂168：0.3份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂EPDM-g-MAH：8份，偶联剂KH550：0.6份。
将上述组分加入高速搅拌机中混合，得到聚酰胺56树脂组合物。
2、制备连续纤维增强聚酰胺56复合材料
S1、利用双螺杆挤出机对上述聚酰胺56树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为240℃、290℃、300℃、300℃、300℃、300℃、300℃、300℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为310℃；浸渍模头温度为305℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺56树脂组合物的重量分数比为40：60。上述制备得到的连续长玻璃纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例2
1、制备聚酰胺56树脂组合物
本实施例所采用的聚酰胺56树脂组合物按照重量份数包括以下组分：PA56：90.5份，抗氧化剂1098：0.3份，抗氧化剂168：0.3份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：8份，偶联剂KH560：0.5份。
将上述组分加入高速搅拌机中混合，得到聚酰胺56树脂组合物。
2、制备连续纤维增强聚酰胺56复合材料
S1、利用双螺杆挤出机对上述聚酰胺56树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为240℃、290℃、300℃、300℃、300℃、300℃、300℃、300℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为310℃；浸渍模头温度为305℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺56树脂组合物的重量分数比为50：50。上述制备得到的连续长玻璃纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例3
1、制备聚酰胺56树脂组合物
本实施例所采用的聚酰胺56树脂组合物按照重量份数包括以下组分：PA56：92.6份，抗氧化剂1098：0.2份，抗氧化剂168：0.2份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：6.2份，偶联剂KH560：0.4份。
将上述组分加入高速搅拌机中混合，得到聚酰胺56树脂组合物。
2、制备连续纤维增强聚酰胺56复合材料
S1、利用双螺杆挤出机对上述聚酰胺56树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为240℃、290℃、300℃、300℃、300℃、300℃、300℃、300℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为310℃；浸渍模头温度为305℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺56树脂组合物的重量分数比为60：40。上述制备得到的连续长玻璃纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例4
1、制备聚酰胺56树脂组合物
本实施例所采用的聚酰胺56树脂组合物按照重量份数包括以下组分：PA56：90.5份，抗氧化剂1098：0.4份，抗氧化剂168：0.4份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂EPDM-g-MAH：8份，偶联剂KH560：0.3份。
将上述组分加入高速搅拌机中混合，得到聚酰胺56树脂组合物。
2、制备连续纤维增强聚酰胺56复合材料
S1、利用双螺杆挤出机对上述聚酰胺56树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为240℃、290℃、300℃、300℃、300℃、300℃、300℃、300℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为310℃；浸渍模头温度为305℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺56树脂组合物的重量分数比为65：35。上述制备得到的连续长玻璃纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例5
1、制备聚酰胺56树脂组合物
本实施例所采用的聚酰胺56树脂组合物按照重量份数包括以下组分：PA56：93份，抗氧化剂1098：0.2份，抗氧化剂168：0.2份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：6份，偶联剂KH550：0.2份。
将上述组分加入高速搅拌机中混合，得到聚酰胺56树脂组合物。
2、制备连续纤维增强聚酰胺56复合材料
S1、利用双螺杆挤出机对上述聚酰胺56树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为240℃、290℃、300℃、300℃、300℃、300℃、300℃、300℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为310℃；浸渍模头温度为305℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺56树脂组合物的重量分数比为70：30。上述制备得到的连续长玻璃纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例6
1、制备聚酰胺56树脂组合物
本实施例所采用的聚酰胺56树脂组合物按照重量份数包括以下组分：PA56：90.5份，抗氧化剂1098：0.3份，抗氧化剂168：0.3份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：8份，偶联剂KH560：0.5份。
将上述组分加入高速搅拌机中混合，得到聚酰胺56树脂组合物。
2、制备连续纤维增强聚酰胺56复合材料
S1、利用双螺杆挤出机对上述聚酰胺56树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为210℃、270℃、270℃、270℃、270℃、270℃、270℃、270℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为285℃；浸渍模头温度为290℃。
S2、将连续长碳纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为250℃，然后进入浸渍模头，在浸渍模头中连续长碳纤维与熔体发生浸渍；
S3、将浸渍后的连续长碳纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长碳纤维和聚酰胺56树脂组合物的重量分数比为50：50。上述制备得到的连续长碳纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例7
与实施例6制备连续纤维增强聚酰胺56复合材料的制备方法相同，区别在于：制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长碳纤维和聚酰胺56树脂组合物的重量分数比为60：40。上述制备得到的连续长碳纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
实施例8
与实施例6制备连续纤维增强聚酰胺56复合材料的制备方法相同，区别在于：制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长碳纤维和聚酰胺56树脂组合物的重量分数比为65：35。上述制备得到的连续长碳纤维增强聚酰胺56复合材料为单向预浸带，性能参数参见表1。
对比例1：
1、制备聚酰胺6树脂组合物
本对比例所采用的聚酰胺6树脂组合物按照重量份数包括以下组分：聚酰胺PA6(购自新会美达公司、相对粘度为2.3、端氨基含量为54mmol/kg、熔点为223℃)：90.5份，抗氧化剂1098：0.3份，抗氧化剂168：0.3份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：8份，偶联剂KH550：0.5份。
将上述组分加入高速搅拌机中混合，得到聚酰胺6树脂组合物。
2、制备连续纤维增强聚酰胺复合材料
S1、利用双螺杆挤出机对上述聚酰胺6树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为200℃、220℃、245℃、245℃、245℃、245℃、245℃、245℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为250℃；浸渍模头温度为250℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中， 四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺6树脂组合物的重量分数比为65：35。上述制备得到的连续长玻璃纤维增强聚酰胺6复合材料为单向预浸带，性能参数参见表1。
对比例2
1、制备聚酰胺6树脂组合物
本对比例所采用的聚酰胺6树脂组合物按照重量份数包括以下组分：聚酰胺PA6(购自新会美达公司、相对粘度为2.3、端氨基含量为54mmol/kg、熔点为223℃)：90.5份，抗氧化剂1098：0.3份，抗氧化剂168：0.3份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：8份，偶联剂KH550：0.5份。
将上述组分加入高速搅拌机中混合，得到聚酰胺6树脂组合物。
2、制备连续纤维增强聚酰胺复合材料
S1、利用双螺杆挤出机对上述聚酰胺6树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为200℃、220℃、245℃、245℃、245℃、245℃、245℃、245℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为245℃；浸渍模头温度为250℃。
S2、将连续长碳纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为300℃，然后进入浸渍模头，在浸渍模头中连续长碳纤维与熔体发生浸渍；
S3、将浸渍后的连续长碳纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长碳纤维和聚酰胺6树脂组合物的重量分数比为65：35。上述制备得到的连续长碳纤维增强聚酰胺6复合材料为单向预浸带，性能参数参见表1。
对比例3
1、制备聚酰胺66树脂组合物
本对比例所采用的聚酰胺66树脂组合物按照重量份数包括以下组分：聚酰胺PA66(购自杜邦、相对粘度为2.6、端氨基含量为48mmol/kg、熔点为255℃)：90.5份，抗氧化剂1098：0.3份，抗氧化剂168：0.3份，内润滑剂WAXE：0.2份，外润滑剂WAXC：0.2份，相容剂POE-g-MAH：8份，偶联剂KH550：0.5份。
将上述组分加入高速搅拌机中混合，得到聚酰胺6树脂组合物。
2、制备连续纤维增强聚酰胺复合材料
S1、利用双螺杆挤出机对上述聚酰胺66树脂组合物进行挤出，挤出的熔体经过熔体过滤器的过滤，进入浸渍模头；其中：
双螺杆挤出机为八区加热模式，一区至八区(沿喂料至机头方向)温度依次为240℃、290℃、300℃、300℃、300℃、300℃、300℃、300℃；
螺杆转速为400rpm；双螺杆挤出机的长径比为1:36；
熔体过滤器的温度为315℃；浸渍模头温度为310℃。
S2、将连续长玻璃纤维经过张力控制器，从导纱架上退绕下来，经过分纱框，进入展纱系统，使每根丝束充分展开，然后进入烘纱装置进行预热，烘纱装置设置温度为85℃，然后进入浸渍模头，在浸渍模头中连续长玻璃纤 维与熔体发生浸渍；
S3、将浸渍后的连续长玻璃纤维经过四辊机进行模压和冷却定型，其中，四辊机内循环水的温度设置为80℃；
然后进入牵引装置进行进一步冷却和切边，牵引速度为8m/min；
最后进入自动收卷机中卷绕成卷，卷绕速度为8m/min。
制备过程中，控制双螺杆挤出机的螺杆转速和自动收卷机的卷绕速度，保证连续长玻璃纤维和聚酰胺66树脂组合物的重量分数比为65：35。上述制备得到的连续长玻璃纤维增强聚酰胺66复合材料为单向预浸带，性能参数参见表1。
将实施例1-8和对比例1-3的连续纤维增强聚酰胺复合材料单向预浸带按照如下测试方法进行性能测试：(1)面密度：ASTM 792-98；(2)纤维含量：ASTM D5630；(3)拉伸强度：ASTM D3039；(4)拉伸模量：ASTM D3039；(5)断裂伸长率：ASTM D3039。结果如表1所示。
表1
Figure PCTCN2022074304-appb-000001
由表1可见，实施例1-5系含有连续长玻璃纤维的聚酰胺56复合材料，拉伸强度均在600MPa以上，实施例5高达1127MPa；拉伸模量也随着纤维含量增加而增加，实施例5高达47Gpa。实施例6-8系含有连续长碳纤维的聚酰胺56复合材料，即使纤维含量较低也获得了较高的力学性能。实施例4、 对比例1和对比例3中连续长玻璃纤维含量相近，但是实施例4获得的PA56复合材料的力学性能明显高于对比例1PA6复合材料以及对比例3PA66复合材料的力学性能。类似的，实施例8和对比例2中连续长碳纤维含量相近，实施例8获得的PA56复合材料力学强度也明显高于对比例2。综合来看，本发明的实施例的力学性能优异，而且本发明PA56生物基含量高，有效地减少了化石原料的使用，从而减少了碳排放。

Claims (10)

  1. 一种聚酰胺56树脂组合物，其包括以下重量份数的组分：生物基聚酰胺56树脂81.8-99.8份、抗氧化剂0.2-1.6份、润滑剂0-0.8份、相容剂0-15份和偶联剂0-0.8份；
    所述生物基聚酰胺56树脂的相对粘度1.9-2.5，端氨基含量42-60mmol/kg，熔点210℃-260℃，和/或生物基含量为43％-46％。
  2. 根据权利要求1所述的聚酰胺56树脂组合物，其特征在于，所述生物基聚酰胺56树脂的含量为90-95份。
  3. 根据权利要求1所述的聚酰胺56树脂组合物，其特征在于，所述抗氧化剂选自受阻酚类抗氧化剂、受阻胺类抗氧化剂和亚磷酸酯类抗氧化剂中的一种或多种；较佳地为受阻胺类抗氧化剂和亚磷酸酯类抗氧化剂的组合；
    较佳地，所述抗氧化剂选自抗氧化剂168、抗氧化剂1098、抗氧化剂1010和抗氧化剂S9228中的一种或多种；更佳地，所述抗氧化剂为抗氧化剂168和抗氧化剂1098的组合；其中，所述抗氧化剂168和所述抗氧化剂1098的质量比优选为1:1；
    和/或，所述抗氧化剂的含量为0.4-0.8份，例如0.4、0.5、0.6或0.8份；
    和/或，所述润滑剂包括外润滑剂和内润滑剂；其中，所述外润滑剂和所述内润滑剂的质量比优选为1:1；其中，所述外润滑剂例如为WAXC，所述内润滑剂例如为WAXE；
    和/或，所述润滑剂的含量为0.1-0.8份，例如0.3、0.4或0.5份；
    和/或，所述相容剂选自聚烯烃接枝马来酸酐类相容剂、聚烯烃接枝甲基丙烯酸类相容剂和橡胶弹性体接枝马来酸酐类相容剂中的一种或多种；其中，所述聚烯烃接枝马来酸酐类相容剂较佳地为PP-g-MAH或POE-g-MAH；所述聚烯烃接枝甲基丙烯酸类相容剂较佳地为POE-g-GMA；和/或所述橡胶弹性体接枝马来酸酐类相容剂较佳地为EPDM-g-MAH；
    和/或，所述相容剂的含量为3-15份，例如6、8、10或12份；
    和/或，所述偶联剂选自硅烷类偶联剂、碳酸酯类偶联剂和铝酸酯类偶联剂中的一种或多种；较佳地为硅烷类偶联剂，例如偶联剂KH550、偶联剂 KH560或偶联剂KH570；
    和/或，所述偶联剂的用量为0.1-0.8份，例如0.2、0.3、0.4、0.5或0.6份。
  4. 一种连续纤维增强聚酰胺56复合材料，其包括权利要求1-3中任一项所述聚酰胺56树脂组合物和纤维，其中，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为40％-75％。
  5. 根据权利要求4所述的连续纤维增强聚酰胺56复合材料，其特征在于，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为50～70％；
    和/或，所述纤维的种类为碳纤维、玻璃纤维、玄武岩纤维或芳纶纤维；
    和/或，所述纤维为连续长纤维；
    较佳地，所述纤维为连续长玻璃纤维；所述连续长玻璃纤维的单丝直径可为8-15μm；和/或所述连续长玻璃纤维的线密度为1000～3600Tex；
    较佳地，所述纤维为连续长碳纤维；所述连续长碳纤维较佳地为聚丙烯腈类碳纤维；所述连续长碳纤维的单丝数量可为20000-30000根；所述连续长碳纤维的单丝直径可为5-10μm；
    和/或，所述连续纤维增强聚酰胺56复合材料为单向预浸带的形式；
    和/或，所述连续纤维增强聚酰胺56复合材料的厚度为0.15-0.5mm；
    和/或，当所述纤维为连续长玻璃纤维时，所述连续纤维增强聚酰胺56复合材料的拉伸强度为600-1300MPa；拉伸模量为20-60GPa；断裂伸长率为2.9-3.4％；
    和/或，当所述纤维为连续长碳纤维时，所述连续纤维增强聚酰胺56复合材料的拉伸强度为1400-1800MPa；拉伸模量为80-140GPa；和/或断裂伸长率为2.5-3.0％。
  6. 一种权利要求4或5所述的连续纤维增强聚酰胺56复合材料的制备方法，其包括以下步骤：
    S1、将所述聚酰胺56树脂组合物挤出，并使挤出的熔体进入浸渍模头；
    S2、将所述纤维导入所述浸渍模头，使所述熔体和纤维发生浸渍；
    S3、将浸渍后的纤维进行模压、冷却、牵引和卷绕，由此得到所述连续纤维增强聚酰胺56复合材料；
    其中，通过调节所述挤出的速度和所述卷绕的速度，控制所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为40％-75％。
  7. 根据权利要求6所述的连续纤维增强聚酰胺56复合材料的制备方法，其特征在于，所述纤维占所述连续纤维增强聚酰胺56复合材料的质量百分比为50～70％；
    和/或，步骤S1中，所述挤出采用双螺杆挤出机或者单螺杆挤出机进行，较佳地为双螺杆挤出机；其中，所述双螺杆挤出机的长径比较佳地为1:36；
    和/或，步骤S1中，所述挤出的温度为170-340℃；
    和/或，步骤S1中，以螺杆转速表示，所述挤出的速度为200-600rpm；
    和/或，步骤S1中，所述挤出后还包括过滤的步骤，所述过滤采用熔体过滤器进行；
    和/或，步骤S1中，所述浸渍模头的幅宽为100-650mm；
    和/或，步骤S1中，所述浸渍模头的温度为260-335℃。
  8. 根据权利要求6所述的连续纤维增强聚酰胺56复合材料的制备方法，其特征在于，步骤S2中，当所述纤维为连续长纤维时，所述导入包括以下过程：所述纤维经过张力控制器从导纱架上退绕下来，经过分纱框，进入展纱系统，使所述纤维的每根丝束充分展开，接着进入烘纱装置进行预热，然后进入浸渍模头；
    和/或，步骤S3中，所述模压、冷却采用压辊机进行，较佳地为四辊机；所述四辊机的内循环水的温度较佳地为60-90℃；
    和/或，步骤S3中，所述牵引采用牵引装置进行，在牵引装置中进行进一步冷却和切边；所述牵引的牵引速度较佳地为5-15m/min；
    和/或，步骤S3中，所述卷绕采用卷绕装置进行，较佳地为自动收卷机。
  9. 一种成型品，其包含权利要求4或5所述连续纤维增强聚酰胺56复合材料。
  10. 一种权利要求4或5所述所述连续纤维增强聚酰胺56复合材料在航空航天领域、军事领域、汽车材料、运动器材、建筑材料或电子电器中的用途。
PCT/CN2022/074304 2021-04-30 2022-01-27 聚酰胺56树脂组合物及连续纤维增强聚酰胺56复合材料 WO2022227751A1 (zh)

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