WO2022227750A1 - 长碳链聚酰胺树脂组合物及连续纤维增强长碳链聚酰胺复合材料 - Google Patents

长碳链聚酰胺树脂组合物及连续纤维增强长碳链聚酰胺复合材料 Download PDF

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WO2022227750A1
WO2022227750A1 PCT/CN2022/074303 CN2022074303W WO2022227750A1 WO 2022227750 A1 WO2022227750 A1 WO 2022227750A1 CN 2022074303 W CN2022074303 W CN 2022074303W WO 2022227750 A1 WO2022227750 A1 WO 2022227750A1
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long carbon
fibers
continuous
carbon chain
parts
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PCT/CN2022/074303
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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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Priority to EP22794231.5A priority Critical patent/EP4332168A4/en
Publication of WO2022227750A1 publication Critical patent/WO2022227750A1/zh
Priority to US18/496,985 priority patent/US20240052115A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids 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
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/012—Additives improving oxygen scavenging properties
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention relates to a long carbon chain polyamide resin composition, a continuous fiber reinforced long carbon chain polyamide 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 long carbon chain polyamide resin composition, a continuous fiber reinforced long carbon chain polyamide composite material and Its preparation method and use.
  • the long carbon chain polyamide resin composition of the present invention has low viscosity, good fluidity and good wettability to fibers in a molten state; the continuous fiber reinforced long carbon chain polyamide prepared based on the long carbon chain polyamide resin composition Composites have high fiber content, good mechanical properties, and are recyclable.
  • a long carbon chain polyamide resin composition comprising the following components in parts by weight: 81.8-99.8 parts of long carbon chain bio-based polyamide 5X resin, 0.2-1.6 parts of antioxidants, and 0 parts of lubricant. -0.8 part, 0-15 part of compatibilizer and 0-0.8 part of coupling agent.
  • the long-carbon-chain bio-based polyamide 5X resin means that the raw material monomers are pentamethylenediamine and/or long-chain dibasic acid prepared by biological fermentation.
  • the long carbon chain dibasic acid is selected from sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid One or more of carbonic acid, heptadecadioic acid, and octadecanedioic acid.
  • the long carbon chain bio-based polyamide 5X resin is selected from one or more of PA510, PA511, PA512, PA513, PA514, PA515, PA516, PA517 and PA518.
  • the PA510 raw material monomers are pentamethylenediamine and sebacic acid prepared by biological fermentation; wherein the PA511 raw material monomers are pentamethylenediamine and undecandioic acid prepared by biological fermentation; wherein PA512 The raw material monomers are pentamethylenediamine and dodecanedioic acid prepared by biological fermentation; the PA513 raw material monomers are pentamethylenediamine and tridecanedioic acid prepared by biological fermentation; the PA514 raw material monomers are Pentamethylenediamine and tetradecanedioic acid prepared by biological fermentation; PA515 raw material monomers are pentamethylenediamine and pentadecanedioic acid prepared by biological fermentation; PA516 raw material monomers are prepared by biological fermentation Pentamethylenediamine and hexadecanedioic acid; PA517 raw material monomers are pentamethylenediamine and heptadecadioic acid prepared by biological fermentation; PA5
  • the long carbon chain bio-based polyamide 5X resin can be purchased from Kasai (Jinxiang) Biomaterials Co., Ltd.
  • the long carbon chain bio-based polyamide 5X resin satisfies the following properties: relative viscosity 1.8-2.7, preferably 2.1-2.6; terminal amino group content 40-60mmol/kg, further 42-60mmol/kg; melting point 170 °C-320°C, preferably 180-230°C; and/or biobased content of 43%-100%.
  • 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.
  • Biobased content was determined by standard method ASTM D6866.
  • the long carbon chain bio-based polyamide 5X resin has a moisture content of less than 2000 ppm, a number average molecular weight of 40-55 kg/mol, and/or a molecular weight distribution of 1.8-2.1.
  • 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: dissolving the sample with trifluoroethanol, titrating with a standard solution of hydrochloric acid and a standard solution of sodium hydroxide, and then obtaining by calculation.
  • the parts in the present invention are all based on parts by weight or parts by mass.
  • the content of the long carbon chain bio-based polyamide 5X resin is preferably 90-95 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 or 0.6 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 content of the compatibilizer is preferably 3-15 parts, further 4-10 parts, such as 4, 5, 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 long carbon chain bio-based polyamide 5X resin.
  • the amount of the coupling agent is preferably 0.1-0.8 part, such as 0.3, 0.4 or 0.5 part.
  • the long carbon-chain polyamide resin composition further comprises 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 long carbon chain polyamide resin composition.
  • the long carbon chain polyamide resin composition further comprises 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 long carbon chain polyamide resin composition comprises the following components in parts by weight: 90-95 parts of long carbon chain bio-based polyamide 5X resin, 0.4-0.6 parts of antioxidant, 0.3 parts of lubricant -0.5 part, 4-8 part of compatibilizer and 0.4-0.5 part of coupling agent.
  • the long carbon chain polyamide resin composition comprises the following components in parts by weight: 90-95 parts of long carbon chain bio-based polyamide 5X resin, 0.4-0.6 parts of antioxidant, 0.3 parts of lubricant -0.5 part, 4-8 parts of compatibilizer and 0.4-0.5 part of coupling agent;
  • the antioxidant is one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228;
  • the The lubricants are WAXC and WAXE;
  • the compatibilizer is selected from polyolefin grafted maleic anhydride compatibilizers, polyolefin grafted methacrylic acid compatibilizers and rubber elastomer grafted maleic anhydride compatibilizers one or more of; and the coupling agent is a silane coupling agent.
  • the long carbon chain polyamide resin composition comprises the following components in parts by weight: PA510 94.5 parts, antioxidant 1098 0.3 parts, antioxidant 168 0.3 parts, internal lubricant WAXE 0.2 parts, 0.2 part of external lubricant WAXC, 4 parts of compatibilizer POE-g-MAH and 0.5 part of coupling agent KH550.
  • the polyamide resin composition comprises the following components in parts by weight: bio-based polyamide resin PA511 94.6 parts, antioxidant 1098 0.25 parts, antioxidant 168 0.25 parts, internal lubricant WAXE 0.2 parts, 0.2 parts of external lubricant WAXC, 4 parts of compatibilizer EPDM-g-MAH and 0.4 parts of coupling agent KH560.
  • the polyamide resin composition comprises the following components in parts by weight: bio-based polyamide resin PA512 92.8 parts, antioxidant 1098 0.25 parts, antioxidant 168 0.25 parts, internal lubricant WAXE 0.15 parts, 0.15 parts of external lubricant WAXC, 6 parts of compatibilizer EPDM-g-MAH and 0.4 part of coupling agent KH550.
  • the long carbon chain polyamide resin composition comprises the following components in parts by weight: PA513 92.5 parts, antioxidant 1098 0.3 parts, antioxidant 168 0.3 parts, internal lubricant WAXE 0.2 parts, 0.2 part of external lubricant WAXC, 6 parts of compatibilizer POE-g-MAH and 0.5 part of coupling agent KH550.
  • the long carbon chain polyamide resin composition comprises the following components in parts by weight: PA514 90.5 parts, antioxidant 1098 0.3 parts, antioxidant 168 0.3 parts, internal lubricant WAXE 0.2 parts, 0.2 part of external lubricant WAXC, 8 parts of compatibilizer POE-g-MAH and 0.5 part of coupling agent KH550.
  • the long carbon chain polyamide resin composition comprises the following components in parts by weight: PA515 94.6 parts, antioxidant 1098 0.2 parts, antioxidant 168 0.2 parts, internal lubricant WAXE 0.2 parts, 0.2 part of external lubricant WAXC, 4 parts of compatibilizer POE-g-MAH and 0.6 part of coupling agent KH550.
  • the long carbon chain polyamide resin composition includes the following components in parts by weight: PA516 92.6 parts, antioxidant 1098 0.3 parts, antioxidant 168 0.3 parts, internal lubricant WAXE 0.2 parts, 0.2 part of external lubricant WAXC, 6 parts of compatibilizer POE-g-MAH and 0.4 part of coupling agent KH550.
  • the long carbon chain polyamide 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 carried out using conventional mixing equipment in the art, such as a high-speed mixer.
  • the second technical solution a continuous fiber reinforced long carbon chain polyamide composite material, comprising the long carbon chain polyamide resin composition and fibers, wherein the fibers account for the continuous fiber reinforced long carbon chain polyamide composite material.
  • the mass percentage of the material is 40%-75%.
  • 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 mass percentage of the fibers in the continuous fiber reinforced long carbon chain polyamide composite material is preferably 50-70%, such as 50%, 55%, 60%, 62%, 65%, 67% %.
  • 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); and/or the monofilament diameter of the continuous long carbon fiber may be 5-10 ⁇ m, preferably 6-8 ⁇ 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 long carbon chain polyamide 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 long carbon chain polyamide composite material is 0.15-0.5 mm.
  • the tensile strength of the continuous fiber reinforced long carbon chain polyamide composite material is 800-1300MPa, preferably 850-1200MPa; the tensile modulus is 30-50GPa , preferably 30-40GPa; and/or the elongation at break is 2.8-3.4%.
  • the continuous fiber reinforced long carbon chain polyamide composite material when the fibers are continuous long carbon fibers, has a tensile strength of 1400-1800 MPa; a tensile modulus of 80-100 GPa; and/or an elongation at break The rate is 2.6-3.1%.
  • the third technical solution a preparation method of a continuous fiber reinforced long carbon chain polyamide composite material, which comprises the following steps:
  • the mass percentage of the continuous fiber in the continuous fiber reinforced polyamide composite material is controlled to be 40%-75%.
  • the mass percentage of the continuous fibers in the continuous fiber reinforced long carbon chain polyamide composite material is 50-70%, such as 50%, 55%, 60%, 62%, 65%, 67%.
  • the extrusion can be performed by a conventional twin-screw extruder or a single-screw extruder in the art, 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.
  • the temperatures from zone one to zone eight are 195-250°C, 255-300°C, 255-300°C, and 255°C. -300°C, 255-300°C, 255-300°C, 255-300°C, and 275-310°C.
  • step S1 expressed in terms of the screw speed, the extrusion speed is 200-600 rpm, for example, 300 rpm and 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 within the range of 0-35°C above and below the temperature of the eight zones of the twin-screw extruder, further 0-25°C, and further 0-25°C. In the range of 15°C, such as 245°C, 285°C, 290°C or 320°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 260-330°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 0-25°C, and further 0-15°C. °C range, for example 250°C, 290°C, 295°C, 305°C or 330°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 drying device is preferably 70-90°C, such as 80°C, or 85°C; when the fibers are continuous long carbon fibers, the drying The temperature of the yarn device is preferably 70-400°C, such as 80°C, 100°C, 250°C, 300°C, or 350°C.
  • step S2 the continuous 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 field, 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 continuous fiber reinforced long carbon chain polyamide composite material obtained by the preparation method of the continuous fiber reinforced long carbon chain polyamide composite material is preferably in the form of a unidirectional prepreg tape.
  • the thickness of the continuous fiber reinforced long carbon chain polyamide composite material obtained by the preparation method of the continuous fiber reinforced long carbon chain polyamide composite material is 0.15-0.5 mm.
  • the fourth technical solution a molded product comprising the continuous fiber reinforced long carbon chain polyamide composite material.
  • the fifth technical solution a use of the continuous fiber reinforced long carbon chain polyamide composite material in the aerospace field, the military field, automotive materials, sports equipment, building materials or electronic appliances.
  • the reagents and raw materials used in the present invention are all commercially available.
  • the present invention adopts long carbon chain bio-based polyamide 5X resin as raw material:
  • the monomer pentamethylenediamine or long-chain dibasic acid in the raw material is prepared by biological fermentation, and the bio-based content is between 43% and 100%, and the bio-based content is high, which is in line with the concept of sustainable development of material sources;
  • the long carbon chain polyamide resin composition prepared by using the long carbon chain 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 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 long carbon chain polyamide composite material of the present invention can be recycled and reused, and the resource utilization rate is high.
  • the preparation method of the continuous fiber reinforced long carbon chain polyamide composite material of the present invention is simple and feasible.
  • FIG. 1 is a flow chart of the preparation process of the continuous fiber reinforced long carbon chain polyamide composite material in the embodiment of the present invention.
  • long carbon chain bio-based polyamide 5X resins PA510, PA511, PA512, PA513, PA514, PA515 and PA516 were purchased from Kasai (Jinxiang) Biomaterials Co., Ltd.; antioxidants were purchased from BASF, Germany Group; WAXE and WAXC were purchased from Clariant, Germany; compatibilizer was purchased from Shanghai Jiayirong Polymer Co., Ltd.; coupling agent was purchased from Hangzhou Jessica Chemical Co., Ltd.; continuous long glass fibers were purchased from Owens Corning ( OC), the specification is 1200Tex; the continuous long carbon fiber is Toray T700, the specification is 24K.
  • OC Owens Corning
  • FIG. 1 The preparation process of the continuous fiber reinforced long carbon chain polyamide composite material in the following examples and comparative examples is shown in FIG. 1 .
  • the polyamide 510 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA510 melting point 217°C, relative viscosity 2.51, terminal amino group content 54mmol/kg: 94.5 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: 4 part, coupling agent KH550: 0.5 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 510 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 290°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 511 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA511 (melting point 209°C, relative viscosity 2.47, terminal amino group content 52mmol/kg): 94.6 parts,
  • Antioxidant 1098 0.25 part, antioxidant 168: 0.25 part, internal lubricant WAXE: 0.3 part, external lubricant WAXC: 0.2 part, compatibilizer EPDM-g-MAH: 4 part, coupling agent KH550: 0.4 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 511 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, 280°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 290°C; the temperature of the dip die was 290°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 512 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA512 (melting point 210°C, relative viscosity 2.32, terminal amino group content 56mmol/kg): 92.8 parts
  • Antioxidant 1098 0.25 part, antioxidant 168: 0.25 part, internal lubricant WAXE: 0.15 part, external lubricant WAXC: 0.15 part, compatibilizer EPDM-g-MAH: 6 part, coupling agent KH550: 0.4 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 512 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 290°C; the dip die temperature was 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 513 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA513 (melting point 197°C, relative viscosity 2.38, terminal amino group content 41mmol/kg): 92.5 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: 6 part, coupling agent KH550: 0.5 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 513 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 290°C; the dip die temperature was 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 514 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA514 (melting point 205°C, relative viscosity 2.29, terminal amino group content 48mmol/kg): 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 514 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 290°C; the temperature of the dip die was 300°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 515 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA515 (melting point 191°C, relative viscosity 2.25, terminal amino group content 51mmol/kg): 94.6 parts,
  • Antioxidant 1098 0.2 part, antioxidant 168: 0.2 part, internal lubricant WAXE: 0.2 part, external lubricant WAXC: 0.2 part, compatibilizer POE-g-MAH: 4 part, coupling agent KH550: 0.6 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 515 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 290°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 516 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA516 (melting point 192°C, relative viscosity 2.13, terminal amino group content 47mmol/kg): 92.6 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: 6 part, coupling agent KH550: 0.4 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 516 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 290°C; the dip die temperature was 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 510 resin composition is the same as that in Example 1, except that continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 510 composite material:
  • 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 511 resin composition is the same as that in Example 2, except that the continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 511 composite material:
  • 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 512 resin composition adopted in this embodiment includes the following components according to parts by weight:
  • PA512 (melting point 210°C, relative viscosity 2.32, terminal amino group content 56mmol/kg): 92.5 parts,
  • Antioxidant 1098 0.3 part, antioxidant 168: 0.3 part, internal lubricant WAXE: 0.2 part, external lubricant WAXC: 0.2 part, compatibilizer EPDM-g-MAH: 6 part, coupling agent KH550: 0.5 part.
  • the above components are added into a high-speed mixer and mixed to obtain a polyamide 512 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 513 resin composition is the same as that in Example 4, except that the continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 513 composite material:
  • 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 514 resin composition is the same as that in Example 5, except that the continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 514 composite material:
  • 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 515 resin composition is the same as that in Example 6, except that continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 515 composite material:
  • 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 516 resin composition is the same as that in Example 7, except that the continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 516 composite material:
  • 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 die) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°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 295°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 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the polyamide 6 resin composition adopted in this comparative example includes the following components according to parts by weight:
  • Polyamide PA6 (purchased from Xinhui Meida, melting point 223°C, relative viscosity 2.46, terminal amino group content 54mmol/kg): 92.5 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 6 part
  • Coupling agent KH550 0.5 part
  • 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 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 6 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • the method for preparing the long carbon chain polyamide 6 resin composition is the same as that of Comparative Example 1, except that the continuous long carbon fibers are used in the preparation of the continuous fiber reinforced polyamide 6 composite material:
  • 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 12 resin composition used in this comparative example includes the following components according to parts by weight:
  • Polyamide PA12 (purchased from Wanhua Chemical, melting point 180°C, relative viscosity 2.17, terminal amino group content 49mmol/kg): 92.5 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 6 part
  • Coupling agent KH550 0.5 part
  • 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 220°C, 280°C, 280°C, 280°C, 280°C, 280°C, 280°C, and 290°C. °C;
  • the screw speed is 400rpm; the length-diameter ratio of the twin-screw extruder is 1:36;
  • the melt filter temperature was 295°C; the dip die temperature was 295°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 12 composite material prepared above is a unidirectional prepreg tape, and the performance parameters are shown in Table 1.
  • Examples 1-7 are different long carbon chain polyamide composite materials containing continuous long glass fibers, the tensile strength is above 850MPa, the tensile modulus is above 30GPa, and the elongation at break is 2.8- 3.4%.
  • Examples 8-14 are polyamide composite materials with different long carbon chains containing continuous long carbon fibers, the tensile strength is above 1400MPa, the tensile modulus is above 80GPa, and the elongation at break is 2.6-3.1%.
  • the PA6 composites with continuous long glass fibers and continuous long carbon fibers, respectively have mechanical properties inferior to those of the corresponding examples with similar fiber content.
  • the mechanical properties of the continuous long glass fiber reinforced polyamide 12 composite obtained in Comparative Example 3 are also inferior to those of the corresponding examples with similar fiber content.
  • the mechanical properties of the embodiments of the present invention are excellent, and the long carbon chain polyamides of the present invention all use pentamethylene diamine derived from bio-based sources, which have high carbon content, effectively reducing the use of fossil raw materials, thereby reducing carbon emission.

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Abstract

本发明公开了一种长碳链聚酰胺树脂组合物及连续纤维增强长碳链聚酰胺复合材料。所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：长碳链生物基聚酰胺5X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。基于所述长碳链聚酰胺树脂组合物制得的连续纤维增强长碳链聚酰胺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

长碳链聚酰胺树脂组合物及连续纤维增强长碳链聚酰胺复合材料 技术领域
本发明涉及一种长碳链聚酰胺树脂组合物、连续纤维增强长碳链聚酰胺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，从而提供了一种长碳链聚酰胺树脂组合物、连续纤维增强长碳链聚酰胺复合材料及其制备方法和用途。本发明的长碳链聚酰胺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；基于该长碳链聚酰胺树脂组合物制得的连续纤维增强长碳链聚酰胺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：
技术方案之一：一种长碳链聚酰胺树脂组合物，其包括以下重量份数的组分：长碳链生物基聚酰胺5X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。
所述长碳链生物基聚酰胺5X树脂是指原料单体为通过生物发酵制备而来的戊二胺和/或长链二元酸。
较佳地，所述长碳链二元酸选自癸二酸、十一碳二酸、十二碳二酸、十三碳二酸、十四碳二酸、十五碳二酸、十六碳二酸、十七碳二酸和十八碳二酸中的一种或多种。
较佳地，所述长碳链生物基聚酰胺5X树脂选自PA510、PA511、PA512、 PA513、PA514、PA515、PA516、PA517和PA518中的一种或多种。
较佳地，其中PA510原料单体为通过生物发酵制备而来的戊二胺和癸二酸；其中PA511原料单体为通过生物发酵制备而来的戊二胺和十一碳二酸；其中PA512原料单体为通过生物发酵制备而来的戊二胺和十二碳二酸；其中PA513原料单体为通过生物发酵制备而来的戊二胺和十三碳二酸；其中PA514原料单体为通过生物发酵制备而来的戊二胺和十四碳二酸；其中PA515原料单体为通过生物发酵制备而来的戊二胺和十五碳二酸；其中PA516原料单体为通过生物发酵制备而来的戊二胺和十六碳二酸；其中PA517原料单体为通过生物发酵制备而来的戊二胺和十七碳二酸；其中PA518原料单体为通过生物发酵制备而来的戊二胺和十八碳二酸。
本发明中，所述长碳链生物基聚酰胺5X树脂可以购自凯赛(金乡)生物材料有限公司。
较佳地，所述长碳链生物基聚酰胺5X树脂满足以下性能：相对粘度1.8-2.7，优选为2.1-2.6；端氨基含量40-60mmol/kg，进一步为42-60mmol/kg；熔点170℃-320℃，优选180-230℃；和/或生物基含量为43％-100％。
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。生物基含量通过标准方法ASTM D6866检测获得。
较佳地，所述长碳链生物基聚酰胺5X树脂的含水率为2000ppm以下，数均分子量为40-55kg/mol，和/或分子量分布为1.8-2.1。
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。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，所述长碳链生物基聚酰胺5X树脂的含量较佳地为90-95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或0.6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)。
本发明中，所述相容剂的含量较佳地为3-15份，进而为4-10份，例如 4、5、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长碳链生物基聚酰胺5X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0.3、0.4或0.5份。
本发明中，可选地，所述长碳链聚酰胺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寡聚物可增加所述长碳链聚酰胺树脂组合物的流动性。
本发明中，可选地，所述长碳链聚酰胺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。
在某些实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：长碳链生物基聚酰胺5X树脂90-95份、抗氧化剂0.4-0.6份、润滑剂0.3-0.5份、相容剂4-8份和偶联剂0.4-0.5份。
在某些实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：长碳链生物基聚酰胺5X树脂90-95份、抗氧化剂0.4-0.6份、润滑剂0.3-0.5份、相容剂4-8份和偶联剂0.4-0.5份；所述抗氧化剂为抗氧化剂168、抗氧化剂1098、抗氧化剂1010和抗氧化剂S9228中的一种或多种；所述润滑剂为WAXC和WAXE；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；以及所述偶联剂为硅烷类偶联剂。
在一具体的实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：PA510 94.5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 4份和 偶联剂KH550 0.5份。
在一具体的实施方案中，所述聚酰胺树脂组合物包括以下重量份数的组分：生物基聚酰胺树脂PA511 94.6份、抗氧化剂1098 0.25份、抗氧化剂168 0.25份、内润滑剂WAXE 0.2份、外润滑剂WAXC 0.2份、相容剂EPDM-g-MAH 4份和偶联剂KH560 0.4份。
在一具体的实施方案中，所述聚酰胺树脂组合物包括以下重量份数的组分：生物基聚酰胺树脂PA512 92.8份、抗氧化剂1098 0.25份、抗氧化剂168 0.25份、内润滑剂WAXE 0.15份、外润滑剂WAXC 0.15份、相容剂EPDM-g-MAH 6份和偶联剂KH550 0.4份。
在一具体的实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：PA513 92.5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 6份和偶联剂KH550 0.5份。
在一具体的实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：PA514 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份和偶联剂KH550 0.5份。
在一具体的实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：PA515 94.6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 4份和偶联剂KH550 0.6份。
在一具体的实施方案中，所述长碳链聚酰胺树脂组合物包括以下重量份数的组分：PA516 92.6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 6份和偶联剂KH550 0.4份。
本发明中，所述长碳链聚酰胺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长碳链聚酰胺复合材料，其包括所述长碳链聚酰胺树脂组合物和纤维，其中，所述纤维占所述连续纤维增强长碳链聚酰胺复合材料的质量百分比为40％-75％。
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，所述纤维占所述连续纤维增强长碳链聚酰胺复合材料的质量百分比为较佳地为50-70％，例如50％、55％、60％、62％、65％、67％。
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)；和/或所述连续长碳纤维的单丝直径可为5-10μm，较佳地为6-8μm。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，所述连续纤维增强长碳链聚酰胺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，所述连续纤维增强长碳链聚酰胺复合材料的厚度为0.15-0.5mm。
本发明中，当所述纤维为连续长玻璃纤维时，所述连续纤维增强长碳链聚酰胺复合材料的拉伸强度为800-1300MPa，优选为850-1200MPa；拉伸模量为30-50GPa，优选为30-40GPa；和/或断裂伸长率为2.8-3.4％。
本发明中，当所述纤维为连续长碳纤维时，所述连续纤维增强长碳链聚酰胺复合材料的拉伸强度为1400-1800MPa；拉伸模量为80-100GPa；和/或断裂伸长率为2.6-3.1％。
技术方案之三：一种连续纤维增强长碳链聚酰胺复合材料的制备方法，其包括以下步骤：
S1、将所述长碳链聚酰胺树脂组合物挤出，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，控制所述连续纤维占所述连续纤维增强聚酰胺复合材料的质量百分比为40％-75％。
本发明中，较佳地，所述连续纤维占所述连续纤维增强长碳链聚酰胺复合材料的质量百分比为50～70％，例如50％、55％、60％、62％、65％、67％。
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℃。
当采用双螺杆挤出机时，所述双螺杆挤出机采用八区加热模式，较佳地，一区至八区温度依次为195-250℃、255-300℃、255-300℃、255-300℃、255-300℃、255-300℃、255-300℃、和275-310℃。
步骤S1中，以螺杆转速表示，所述挤出的速度为200-600rpm，例如300rpm、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0-35℃范围内，进一步为0-25℃，进一步为0-15℃范围内，例如245℃、285℃、290℃或320℃。
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260-330℃。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0-25℃，进一步为0-15℃范围内，例如250℃、290℃、295℃、305℃或330℃。
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℃、250℃、300℃、或350℃。
步骤S2中，所述连续纤维如前所述。
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，所述连续纤维增强长碳链聚酰胺复合材料的制备方法制得的连续纤维增强长碳链聚酰胺复合材料较佳地为单向预浸带的形式。
本发明中，较佳地，所述连续纤维增强长碳链聚酰胺复合材料的制备方法制得的连续纤维增强长碳链聚酰胺复合材料的厚度为0.15-0.5mm。
技术方案之四：一种成型品，其包含所述连续纤维增强长碳链聚酰胺复合材料。
技术方案之五：一种所述连续纤维增强长碳链聚酰胺复合材料在航天领 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、本发明采用长碳链生物基聚酰胺5X树脂为原料：
(1)原料中的单体戊二胺或长链二元酸通过生物发酵制备而来，生物基含量在43％-100％之间，生物基含量高，符合材料来源可持续发展的理念；
(2)采用本发明所述的长碳链生物基聚酰胺为原料制备出的长碳链聚酰胺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；
(3)扩大了选材范围，降低了成本。
2、本发明所述的连续纤维增强长碳链聚酰胺复合材料：
(1)纤维含量高，在40％-75％的范围内；
(2)具有优异的力学性能；
(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长碳链聚酰胺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长碳链聚酰胺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长碳链聚酰胺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：长碳链生物基聚酰胺5X树脂PA510，PA511，PA512，PA513，PA514，PA515以及PA516均购自凯赛(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长碳链聚酰胺复合材料的制备工艺如图1所示。
实施例1
1、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺510树脂组合物按照重量份数包括以下组分：
PA510(熔点217℃，相对粘度2.51，端氨基含量54mmol/kg)：94.5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：4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510树脂组合物。
2、制备连续纤维增强聚酰胺510复合材料
S1、利用双螺杆挤出机对上述聚酰胺510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℃、280℃；
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290℃；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510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、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺511树脂组合物按照重量份数包括以下组分：
PA511(熔点209℃，相对粘度2.47，端氨基含量52mmol/kg)：94.6份，
抗氧化剂1098：0.25份，抗氧化剂168：0.25份，内润滑剂WAXE：0.3份，外润滑剂WAXC：0.2份，相容剂EPDM-g-MAH：4份，偶联剂KH550：0.4份。将上述组分加入高速搅拌机中混合，得到聚酰胺511树脂组合物。
2、制备连续纤维增强聚酰胺511复合材料
S1、利用双螺杆挤出机对上述聚酰胺511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℃、280℃；
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290℃；浸渍模头温度为290℃。
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511树脂组合物的重量分数比为62：38。上述制备得到的连续长玻璃纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表1。
实施例3
1、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺512树脂组合物按照重量份数包括以下组分：
PA512(熔点210℃，相对粘度2.32，端氨基含量56mmol/kg)：92.8份，
抗氧化剂1098：0.25份，抗氧化剂168：0.25份，内润滑剂WAXE：0.15份，外润滑剂WAXC：0.15份，相容剂EPDM-g-MAH：6份，偶联剂KH550：0.4份。将上述组分加入高速搅拌机中混合，得到聚酰胺512树脂组合物。
2、制备连续纤维增强聚酰胺512复合材料
S1、利用双螺杆挤出机对上述聚酰胺512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℃、280℃；
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290℃；浸渍模头温度为295℃。
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512树脂组合物的重量分数比为67：33。上述制备得到的连续长玻璃纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表1。
实施例4
1、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺513树脂组合物按照重量份数包括以下组分：
PA513(熔点197℃，相对粘度2.38，端氨基含量41mmol/kg)：92.5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：6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513树脂组合物。
2、制备连续纤维增强聚酰胺513复合材料
S1、利用双螺杆挤出机对上述聚酰胺513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℃、280℃；
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290℃；浸渍模头温度为295℃。
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513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、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺514树脂组合物按照重量份数包括以下组分：
PA514(熔点205℃，相对粘度2.29，端氨基含量48mmol/kg)：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514树脂组合物。
2、制备连续纤维增强聚酰胺514复合材料
S1、利用双螺杆挤出机对上述聚酰胺514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℃、280℃；
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290℃；浸渍模头温度为300℃。
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514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、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺515树脂组合物按照重量份数包括以下组分：
PA515(熔点191℃，相对粘度2.25，端氨基含量51mmol/kg)：94.6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：4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515树脂组合物。
2、制备连续纤维增强聚酰胺515复合材料
S1、利用双螺杆挤出机对上述聚酰胺515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℃、280℃；
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290℃；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515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复合材料为单向预浸带，性能参数参见表1。
实施例7
1、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺516树脂组合物按照重量份数包括以下组分：
PA516(熔点192℃，相对粘度2.13，端氨基含量47mmol/kg)：92.6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：6份，偶联剂KH550：0.4份。将上述组分加入高速搅拌机中混合，得到聚酰胺516树脂组合物。
2、制备连续纤维增强聚酰胺516复合材料
S1、利用双螺杆挤出机对上述聚酰胺516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℃、280℃；
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290℃；浸渍模头温度为295℃。
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516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复合材料为单向预浸带，性能参数参见表1。
实施例8
制备长碳链聚酰胺510树脂组合物的方法与实施例1相同，区别在于，制备连续纤维增强聚酰胺510复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺510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℃、280℃；
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295℃。
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350℃，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510树脂组合物的重量分数比为56：44。上述制备得到的连续长碳纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表1。
实施例9
制备长碳链聚酰胺511树脂组合物的方法与实施例2相同，区别在于，制备连续纤维增强聚酰胺511复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺511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℃、280℃；
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295℃。
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玻璃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511树脂组合物的重量分数比为52：48。上述制备得到的连续长碳纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表 1。
实施例10
1、制备长碳链聚酰胺树脂组合物
本实施例所采用的聚酰胺512树脂组合物按照重量份数包括以下组分：
PA512(熔点210℃，相对粘度2.32，端氨基含量56mmol/kg)：92.5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EPDM-g-MAH：6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512树脂组合物。
2、制备连续纤维增强聚酰胺512复合材料
S1、利用双螺杆挤出机对聚酰胺512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℃、280℃；
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295℃。
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玻璃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512树脂组合物的重量分数比为55：45。上述制备得到的连续长碳纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表 1。
实施例11
制备长碳链聚酰胺513树脂组合物的方法与实施例4相同，区别在于，制备连续纤维增强聚酰胺513复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺513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℃、280℃；
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295℃。
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350℃，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513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复合材料为单向预浸带，性能参数参见表1。
实施例12
制备长碳链聚酰胺514树脂组合物的方法与实施例5相同，区别在于，制备连续纤维增强聚酰胺514复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺514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℃、280℃；
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295℃。
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玻璃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514树脂组合物的重量分数比为59：41。上述制备得到的连续长碳纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表1。
实施例13
制备长碳链聚酰胺515树脂组合物的方法与实施例6相同，区别在于，制备连续纤维增强聚酰胺515复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺515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℃、280℃；
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295℃。
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玻璃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515树脂组合物的重量分数比为63：37。上述制备得到的连续长碳纤维增强聚酰胺复合材料为单向预浸带，性能参数参见表1。
实施例14
制备长碳链聚酰胺516树脂组合物的方法与实施例7相同，区别在于，制备连续纤维增强聚酰胺516复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺516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℃、280℃；
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295℃。
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玻璃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516树脂组合物的重量分数比为57：43。上述制备得到的连续长碳纤维增强聚酰胺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，熔点223℃，相对粘度2.46，端氨基含量54mmol/kg)：92.5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：6份，偶联剂KH550：0.5份，将上述组分加入高速搅拌机中混合，得到聚酰胺树脂6组合物。
2、制备连续纤维增强聚酰胺6复合材料
S1、利用双螺杆挤出机对上述聚酰胺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树脂6组合物的重量分数比为64：36。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
制备长碳链聚酰胺6树脂组合物的方法与对比例1相同，区别在于，制备连续纤维增强聚酰胺6复合材料时使用的是连续长碳纤维：
S1、利用双螺杆挤出机对聚酰胺树脂6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350℃，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树脂6组合物的重量分数比为51：49。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、制备聚酰胺树脂组合物
本对比例所采用的聚酰胺12树脂组合物按照重量份数包括以下组分：
聚酰胺PA12(购自万华化学，熔点180℃，相对粘度2.17，端氨基含量49mmol/kg)：92.5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：6份，偶联剂KH550：0.5份，将上述组分加入高速搅拌机中混合，得到聚酰胺树脂12组合物。
2、制备连续纤维增强聚酰胺12复合材料
S1、利用双螺杆挤出机对上述聚酰胺树脂12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220℃、280℃、280℃、280℃、280℃、280℃、280℃、290℃；
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295℃；浸渍模头温度为295℃。
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树脂12组合物的重量分数比为61：39。上述制备得到的连续长玻璃纤维增强聚酰胺12复合材料为单向预浸带，性能参数参见表1。
将实施例1-14和对比例1-3的连续纤维增强长碳链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 PCTCN2022074303-appb-000001
由表1可见，实施例1-7系含有连续长玻璃纤维的不同长碳链聚酰胺复 合材料，拉伸强度均在850MPa以上，拉伸模量均在30GPa以上，断裂伸长率为2.8-3.4％。实施例8-14系含有连续长碳纤维的不同长碳链聚酰胺复合材料，拉伸强度均在1400MPa以上，拉伸模量均在80GPa以上，断裂伸长率为2.6-3.1％。对比例1和对比例2中分别为复合连续长玻璃纤维和连续长碳纤维的PA6复合材料，其力学性能均劣于与其纤维含量相近的对应实施例。类似的，对比例3获得的连续长玻璃纤维增强聚酰胺12复合材料的力学性能也劣于与其纤维含量相近的对应实施例。综合来看，本发明的实施例的力学性能优异，而且本发明长碳链聚酰胺均使用了生物基来源的戊二胺，碳含量高，有效地减少了化石原料的使用，从而减少了碳排放。

Claims (10)

  1. 一种长碳链聚酰胺树脂组合物，其包括以下重量份数的组分：长碳链生物基聚酰胺5X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。
  2. 根据权利要求1所述的长碳链聚酰胺树脂组合物，其特征在于，所述长碳链生物基聚酰胺5X树脂选自PA510、PA511、PA512、PA513、PA514、PA515、PA516、PA517和PA518中的一种或多种；
    和/或，所述长碳链生物基聚酰胺5X树脂的相对粘度1.8-2.7，端氨基含量42-60mmol/kg，熔点170℃-320℃，和/或生物基含量为43％-100％；
    和/或，所述长碳链生物基聚酰胺5X树脂的含量为90-95份。
  3. 根据权利要求1所述的长碳链聚酰胺树脂组合物，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或0.6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；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4、5、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0.3、0.4或0.5份。
  4. 一种连续纤维增强长碳链聚酰胺复合材料，其包括权利要求1-3中任一项所述长碳链聚酰胺树脂组合物和纤维，其中，所述纤维占所述连续纤维增强长碳链聚酰胺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长碳链聚酰胺复合材料，其特征在于，所述纤维占所述连续纤维增强长碳链聚酰胺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较佳地为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；和/或所述连续长碳纤维的单丝直径可为5-10μm；
    和/或，所述连续纤维增强长碳链聚酰胺复合材料为单向预浸带的形式；
    和/或，所述连续纤维增强长碳链聚酰胺复合材料的厚度为0.15-0.5mm；
    和/或，当所述纤维为连续长玻璃纤维时，所述连续纤维增强长碳链聚酰胺复合材料的拉伸强度为800-1300MPa，优选为850-1200MPa；拉伸模量为30-50GPa，优选为30-40GPa；断裂伸长率为2.8-3.4％；
    和/或，当所述纤维为连续长碳纤维时，所述连续纤维增强长碳链聚酰胺复合材料的拉伸强度为1400-1800MPa；拉伸模量为80-100GPa；和/或断裂伸长率为2.6-3.1％。
  6. 一种权利要求4或5所述的连续纤维增强长碳链聚酰胺复合材料的制备方法，其包括以下步骤：
    S1、将所述长碳链聚酰胺树脂组合物挤出，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，由此得到所述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长碳链聚酰胺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长碳链聚酰胺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长碳链聚酰胺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℃；
    较佳地，当采用双螺杆挤出机时，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195-250℃、255-300℃、255-300℃、255-300℃、255-300℃、255-300℃、255-300℃、和275-310℃；
    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；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；
    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260-330℃；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0-15℃范围内。
  8. 根据权利要求6所述的连续纤维增强长碳链聚酰胺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℃、250℃、300℃、或350℃；
    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所述连续纤维增强长碳链聚酰胺复合材料。
  10. 一种权利要求4或5所述连续纤维增强长碳链聚酰胺复合材料在航天领域、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。
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