WO2022252661A1 - Plaque composite thermoplastique continue renforcée par des fibres longues, son procédé de préparation et son utilisation - Google Patents

Plaque composite thermoplastique continue renforcée par des fibres longues, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2022252661A1
WO2022252661A1 PCT/CN2022/074306 CN2022074306W WO2022252661A1 WO 2022252661 A1 WO2022252661 A1 WO 2022252661A1 CN 2022074306 W CN2022074306 W CN 2022074306W WO 2022252661 A1 WO2022252661 A1 WO 2022252661A1
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continuous long
fiber reinforced
prepreg tape
polyamide resin
prepreg
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PCT/CN2022/074306
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English (en)
Chinese (zh)
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李园平
徐强
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 WO2022252661A1 publication Critical patent/WO2022252661A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • 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
    • 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
    • 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
    • C08K7/14—Glass

Definitions

  • the invention relates to a continuous long fiber reinforced thermoplastic composite board and its preparation method and application.
  • CFRT Continuous long fiber reinforced thermoplastic composite
  • CFRT such as continuous long fiber reinforced thermoplastic composite sheet
  • CFRT is mainly used in automobiles, wind power blades, electronics, home appliances, communications, machinery, chemicals, military industry, sports equipment, medical equipment and other fields, especially in the special plastic market for auto parts
  • PP polypropylene
  • LGF long glass fiber reinforced polypropylene
  • the continuous long fiber reinforced polyamide composite material has high strength, but because polyamide itself contains a certain amount of amide bonds of polar groups, it is easy to form a hydrogen bond structure with water molecules, which will inevitably reduce the hydrogen bond density of the interaction between macromolecular chains , resulting in a decrease in the strength of the material. Therefore, there is an urgent need to prepare a continuous long fiber reinforced thermoplastic composite material that can simultaneously have high mechanical properties and low water absorption.
  • Continuous fiber reinforced thermoplastic prepreg tape is an intermediate used to prepare continuous fiber reinforced thermoplastic composite materials. Its preparation process mainly includes melt impregnation method, solution impregnation method and mixed fiber method.
  • thermoplastic composite materials include injection molding, thermocompression molding, and pultrusion molding.
  • injection molding process is currently the most important molding process for the preparation of thermoplastic composites due to its advantages of high stability, automation, and high efficiency. It is also the most widely used molding process at present, but the glass fiber retention length of this method is short.
  • the thermal compression molding process has the advantages of simple structure, good thermal stability and diversified product shapes, and is one of the more commonly used molding processes for preparing thermoplastic composite materials.
  • the pultrusion molding process is a molding process for preparing continuous long fiber reinforced thermoplastic composites (CFRT) by pulling fiber rovings under external force through impregnation, curing, and cutting processes. After molding, the cross section of the material is fixed and continuous production of materials is realized.
  • CFRT continuous long fiber reinforced thermoplastic composites
  • the present invention provides a continuous long fiber reinforced thermoplastic composite sheet and its preparation method and application.
  • the continuous long fiber reinforced thermoplastic composite board provided by the invention has good mechanical properties and low water absorption, and the preparation method is simple in process and low in cost.
  • a continuous long fiber reinforced thermoplastic composite sheet which includes m layers of prepreg A and n layers of prepreg B, and the outer layer is the prepreg A; wherein, m ⁇ 2, n ⁇ 1, and m and n is an integer;
  • the prepreg tape A is a continuous long fiber reinforced long carbon chain polyamide resin unidirectional prepreg tape, which includes continuous long fibers and long carbon chain polyamide resin;
  • the prepreg tape B is a continuous long fiber reinforced short carbon chain polyamide resin unidirectional prepreg tape, which includes continuous long fiber and short carbon chain polyamide resin.
  • the sum of the values of m and n may be 3-100, such as 4-66 or 20-66.
  • the n can be 1-98, such as 4, 6, 8 or 10.
  • "-" indicates that the prepreg tapes are adjacent, for example, "AB" indicates that a layer of prepreg A is adjacent to a layer of prepreg B.
  • the values of m 1 , m 2 , m 3 , n 1 and n 2 are 1, 0, 1, 3 and 3 respectively, that is, the continuous long fiber reinforced thermoplastic composite sheet includes A-[6B] -A.
  • the values of m1, m2, m3, n1 and n2 are 2, 0, 2, 2 and 2 respectively, that is, the continuous long fiber reinforced thermoplastic composite sheet includes 2A-[4B]-2A.
  • the values of m1, m2, m3, n1 and n2 are 1, 0, 1, 4 and 4 respectively, that is, the continuous long fiber reinforced thermoplastic composite sheet includes A-[8B]-A.
  • the values of m1, m2, m3, n1 and n2 are 2, 0, 2, 3 and 3 respectively, that is, the continuous long fiber reinforced thermoplastic composite sheet includes 2A-[6B]-2A.
  • the prepregs B are each independently selected from the same or different continuous long fiber reinforced short carbon chain polyamide resin unidirectional prepregs
  • the prepregs A are each independently selected from The same or different continuous long fiber reinforced long carbon chain polyamide resin unidirectional prepreg tape.
  • the thickness of the prepreg tape A is preferably 0.15-0.5mm, further 0.21-0.33mm, such as 0.23mm, 0.27mm, 0.28mm, 0.31mm, 0.32mm or 0.33mm.
  • the thickness of the prepreg tape B is preferably 0.15-0.5mm, further 0.21-0.33mm, such as 0.24mm, 0.31mm, 0.32mm or 0.33mm.
  • the total thickness of the continuous long fiber reinforced thermoplastic composite sheet is preferably >0.5mm, such as 10mm, and the thickness can be molded and composited according to specific products.
  • the layering method between layers in the continuous long fiber reinforced thermoplastic composite sheet may be parallel layering or cross layering.
  • the parallel layup means that the layers are laid in the same direction; the cross layup means that the layers are cross laid at a certain angle.
  • the crossing manner of the cross-laminated layer may be 0°-90° crossing, for example, 45° crossing, 90° crossing.
  • the crossing manner of the cross-laminated layers may be greater than 0° to less than or equal to 90° crossing.
  • the long carbon chain polyamide resin generally refers to the polyamide obtained by the polymerization of a dibasic acid with a methylene group between two carboxyl groups having 10 or more carbon atoms (mainly referring to pentamethylene diamine).
  • amides The short carbon chain polyamide resin generally refers to a polyamide obtained by polymerizing dibasic amine (mainly pentamethylenediamine) and a dibasic acid whose methylene group between two carboxyl groups has less than 10 carbon atoms.
  • the short carbon chain polyamide resin may be commercially available short carbon chain polyamide resin in the field, preferably purchased from Cathay (Jinxiang) Biomaterials Co., Ltd.
  • the short carbon chain polyamide resin is preferably a short carbon chain bio-based polyamide resin.
  • bio-based polyamide resins generally refer to polyamide resins obtained by using renewable resources such as corn and castor as raw materials, preparing diamines through microbial methods, and then polymerizing with dibasic acids.
  • the dibasic acid is also prepared by microbial methods.
  • the short carbon chain polyamide resin is preferably polyamide 56, referred to as PA56.
  • the PA56 preferably has the following characteristics:
  • the relative viscosity is 1.9-2.7, such as 2.29;
  • the content of terminal amino group is 42-60mmol/kg, such as 55mmol/kg;
  • the raw material monomers are pentamethylenediamine and adipic acid, and the bio-based content is 43%-46%.
  • the long carbon chain polyamide resin may be commercially available long carbon chain polyamide resin in the field, preferably purchased from Cathay (Jinxiang) Biomaterials Co., Ltd.
  • the long carbon chain polyamide resin is preferably a long carbon chain bio-based polyamide resin.
  • the long carbon chain polyamide resin is preferably 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 undecanedioic acid prepared by biological fermentation; wherein PA512 The raw material monomers are pentanediamine and dodecanedioic acid prepared by biological fermentation; the raw material monomers of PA513 are pentanediamine and tridecanedioic acid prepared by biological fermentation; the raw material monomers of PA514 are Pentylenediamine and tetradecanedioic acid prepared by biological fermentation; among them, PA515 raw material monomers are pentanediamine and pentadecanedioic acid prepared by biological fermentation; among them, PA516 raw material monomers are prepared by biological fermentation pentanediamine and hexadecandioic acid; PA517 raw material monomers are pentanediamine and heptadecandioic acid prepared by biological fermentation; among them, PA
  • the long carbon chain polyamide resin preferably has the following characteristics:
  • Relative viscosity 1.8-2.7, preferably 2.1-2.6, such as 2.25, 2.32, 2.38, 2.46 or 2.51;
  • the content of terminal amino group is 40-60mmol/kg, further 42-60mmol/kg;
  • Melting point 170°C-320°C preferably 180-230°C, for example 191, 197, 210 or 217°C;
  • the biobased content is between 29% and 100%, for example 29.6, 32.3, 33.8 or 45%.
  • the bio-based content is the content of the corresponding structural units of monomers prepared from raw materials derived from biomass in polyamides. Biomass is a variety of organisms formed through photosynthesis. As one of the monomers of polyamide 56, pentamethylenediamine can be obtained by decarboxylation of lysine fermented from corn. Obtained by ASTM D6866, the standard method for detection of biobased content.
  • the relative viscosity is measured by Ubbelohde viscometer concentrated sulfuric acid method.
  • the terminal amino content is determined by the following method: after dissolving the sample with trifluoroethanol, titrate with hydrochloric acid standard solution and sodium hydroxide standard solution respectively, and calculate.
  • the continuous long fibers may be conventional and commercially available continuous long fibers in this field.
  • the type of the continuous long fiber can be conventional in the field, such as carbon fiber, glass fiber, basalt fiber or aramid fiber.
  • the continuous long fiber is a continuous long glass fiber, and the diameter of a single filament may be 8-15 ⁇ m, preferably 8-10 ⁇ m.
  • the linear density of the continuous long glass fibers may be 1000-3600Tex, preferably 1200Tex, 2400Tex.
  • the continuous long glass fiber is, for example, a continuous long glass fiber with a specification of 1200 Tex purchased from Owens Corning (OC) or a continuous long glass fiber with a specification of 2400 Tex purchased from Jushi.
  • the continuous long 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 fiber can be 20000-30000, preferably 12000 (12K), 24000 (24K).
  • the monofilament diameter of the continuous long carbon fiber may be 5-10 ⁇ m, preferably 6-8 ⁇ m.
  • the continuous long carbon fiber is, for example, Toray T700 with a specification of 24K, or Guangwei composite continuous long carbon fiber 700S with a specification of 12K or 24K.
  • the mass percentage of the continuous long fibers is preferably 40-80wt%, more preferably 60-70wt%, such as 50.1wt%, 60.5wt%, 62.1wt% %, 62.8wt% or 51.3wt%, the mass percentage means that the mass of the continuous long fiber accounts for the mass of the prepreg tape A.
  • the mass percentage of the continuous long fibers in the prepreg tape B is preferably 40-80%, more preferably 60-70%, such as 50.4wt% or 61.3wt%.
  • the percentage means that the mass of the continuous long fibers accounts for the mass of the prepreg B.
  • the water content of the prepreg tape A is lower than 2000ppm, more preferably lower than 1200ppm, such as 100-1200ppm, or 500-1000ppm.
  • the water content of the prepreg tape B is lower than 2000ppm, more preferably lower than 1200ppm, such as 100-1200ppm, or 500-1000ppm.
  • the method of measuring the water content is as follows: Take 1g of the prepreg sample and measure it with a Karl Fischer moisture analyzer. The detection temperature is 200°C and the detection time is 20 minutes.
  • the short carbon chain polyamide resin is PA56
  • the long carbon chain polyamide resin is any one or more of PA510, PA511, PA512, PA513, PA514, PA515 and PA516.
  • the prepreg A includes continuous long glass fiber and long carbon chain polyamide resin
  • the long carbon chain polyamide resin is PA510, PA511, PA512, PA513, PA514, PA515 and PA516 Any one or more of them, more preferably, the prepreg tape A is a continuous long glass fiber reinforced long carbon chain polyamide thermoplastic unidirectional prepreg tape.
  • the prepreg tape A includes continuous long carbon fiber and long carbon chain polyamide resin
  • the long carbon chain polyamide resin is PA510, PA511, PA512, PA513, PA514, PA515 and PA516 Any one or more, more preferably the prepreg tape A is continuous long carbon fiber reinforced long carbon chain polyamide thermoplastic unidirectional prepreg tape.
  • the prepreg B includes continuous long glass fibers and PA56, more preferably the prepreg B is a continuous long glass fiber reinforced PA56 unidirectional prepreg.
  • the prepreg B includes continuous long carbon fibers and PA56, more preferably the prepreg B is a continuous long carbon fiber reinforced PA56 unidirectional prepreg.
  • the prepreg tape A is a continuous long glass fiber reinforced long carbon chain polyamide unidirectional prepreg tape
  • the prepreg tape B is continuous long glass fiber reinforced PA56 unidirectional prepreg tape.
  • the prepreg tape A is a continuous long glass fiber reinforced PA513 unidirectional prepreg tape
  • the prepreg tape B is a continuous long glass fiber reinforced PA56 unidirectional prepreg tape .
  • the prepreg tape A is a continuous long glass fiber reinforced PA510 unidirectional prepreg tape
  • the prepreg tape B is a continuous long glass fiber reinforced PA56 unidirectional prepreg tape .
  • the prepreg tape A is a continuous long glass fiber reinforced PA512 unidirectional prepreg tape
  • the prepreg tape B is a continuous long glass fiber reinforced PA56 unidirectional prepreg tape .
  • the prepreg tape A is a continuous long glass fiber reinforced PA515 unidirectional prepreg tape
  • the prepreg tape B is a continuous long glass fiber reinforced PA56 unidirectional prepreg tape .
  • the prepreg tape A is a continuous long carbon fiber reinforced long carbon chain polyamide unidirectional prepreg tape
  • the prepreg tape B It is a continuous long carbon fiber reinforced PA56 unidirectional prepreg tape.
  • the prepreg tape A is a continuous long carbon fiber reinforced PA510 unidirectional prepreg tape
  • the prepreg tape B is a continuous long carbon fiber reinforced PA56 unidirectional prepreg tape.
  • the present invention also provides a method for preparing the aforementioned continuous long fiber reinforced thermoplastic composite sheet, which includes the following steps: laminating the prepreg tape B and the prepreg tape A, and compression molding to obtain the composite sheet.
  • the layering method can be a conventional layering method in the field, such as cross-layering or parallel layering.
  • the angle of the cross-laminated layers may be 0° and 90°, or 45°.
  • the drying operation may be a conventional drying operation in the art, such as vacuum drying.
  • the drying temperature is preferably 85-120°C, such as 105°C.
  • the drying time is preferably 4-25 hours, further 15-24 hours, such as 15 hours, 20 hours or 24 hours.
  • the equipment used for the compression molding can be the equipment conventionally used in the field for molding, such as a molding machine, and the molding machine can be a double-steel belt molding compound machine.
  • the compression molding temperature is preferably 5-10°C higher than the melting point of the short carbon chain polyamide resin, preferably 190-310°C, more preferably 250-310°C, for example 260°C or 278°C.
  • the compression molding pressure is preferably 1-5 MPa, such as 2-3 MPa.
  • the compression molding method may be a conventional compression molding method in the art, such as continuous compression molding or direct compression molding.
  • the step of continuous automatic layer laying can be included according to the conventional practice in the field.
  • the direct compression molding may include the steps of preheating, degassing, pressure maintaining and/or cooling according to the routine in the art.
  • the preheating time is preferably 3-8 minutes, such as 5 minutes.
  • the number of exhaust gas is preferably 3-6 times, for example 3 times.
  • the time for maintaining the pressure is preferably 5-10 minutes, such as 8 minutes.
  • the cooling rate is preferably 5-20°C/min, such as 15°C/min.
  • the temperature after cooling is preferably room temperature.
  • the room temperature generally refers to 20 ⁇ 5°C.
  • the prepreg tape A and the prepreg tape B are preferably prepared by a melt impregnation method.
  • melt impregnation method may be a conventional melt impregnation method in the art.
  • the melt impregnation method comprises the steps of:
  • the polyamide resin composition includes the long carbon chain polyamide resin or the short carbon chain polyamide resin;
  • the mass percentage of the continuous long fiber in the prepreg tape is controlled.
  • the polyamide resin composition further includes additives.
  • the additives preferably include one or more of antioxidants, lubricants, compatibilizers and coupling agents.
  • the antioxidant is preferably selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228.
  • the lubricant preferably includes the external lubricant WAXC and the internal lubricant WAXE.
  • the compatibilizer can be selected from PP-g-MAH (maleic anhydride grafted on polypropylene), POE-g-MAH (maleic anhydride grafted on ethylene octene copolymer), POE-g - one or more of GMA (glycidyl methacrylate grafted on ethylene octene copolymer) and EPDM-g-MAH (maleic anhydride grafted on ethylene propylene diene rubber).
  • the coupling agent can be selected from one or more of coupling agent KH550, coupling agent KH560 and coupling agent KH570.
  • the parts in the present invention are based on parts by weight or parts by mass.
  • the polyamide resin composition includes the following components in parts by weight: 81.8-99.8 parts of the long carbon chain polyamide resin or the short carbon chain polyamide resin, 0.2-1.6 parts of antioxidant parts, lubricant 0-0.8 parts, compatibilizer 0-15 parts and coupling agent 0-0.8 parts.
  • the polyamide resin composition includes the following components in parts by weight: 90-95 parts of the long carbon chain polyamide resin, 0.4-0.6 parts of antioxidant, 0.3-0.5 parts of lubricant, 4-8 parts of compatibilizer and 0.4-0.5 parts of coupling agent.
  • the polyamide resin composition includes the following components in parts by weight: the long carbon chain polyamide resin: 94.5 parts, antioxidant 1098: 0.3 parts, antioxidant 168: 0.3 parts, internal lubricant WAXE: 0.2 parts parts, external lubricant WAXC: 0.2 parts, compatibilizer POE-g-MAH: 4 parts, coupling agent KH550: 0.5 parts.
  • the polyamide resin composition includes the following components in parts by weight: 90.5-93 parts of the short carbon chain polyamide resin, 10980.2-0.4 parts of antioxidants, 1680.2-0.4 parts of antioxidants, 0.2-0.3 parts of internal lubricant WAXE, 0.2-0.3 parts of external lubricant WAXC, 6-8 parts of compatibilizer and 0.3-0.6 parts of silane coupling agent.
  • the polyamide resin composition raw material includes the following components in parts by weight: PA56: 90.5 parts, antioxidant 1098: 0.4 parts, antioxidant 168: 0.4 parts, internal lubricant WAXE: 0.2 parts, external lubricant WAXC : 0.2 parts, compatibilizer POE-g-MAH: 8 parts, coupling agent KH560: 0.3 parts.
  • the polyamide resin composition raw material includes the following components in parts by weight: PA56: 90.5 parts, antioxidant 1098: 0.3 parts, antioxidant 168: 0.3 parts, internal lubricant WAXE: 0.2 parts, external lubricant WAXC: 0.2 parts, compatibilizer POE-g-MAH: 8 parts, coupling agent KH560: 0.5 parts.
  • step S1 before extruding the polyamide resin composition, preferably, the following step is further included: mixing the polyamide resin composition.
  • the mixing can be stirring and mixing; the equipment for stirring and mixing can be a high-speed mixer.
  • step S1 the extruding can be carried out using a conventional twin-screw extruder or single-screw extruder in the art, preferably a twin-screw extruder.
  • the aspect 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 the first zone to the eighth zone are 195-260°C, 255- 305°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C, 255-325°C.
  • the temperatures in Zone 1 to Zone 8 are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, 300°C, 300°C.
  • the temperatures in Zone 1 to Zone 8 are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, and 280°C.
  • step S1 expressed by the screw speed, the extrusion speed is 200-600 rpm, such as 400 rpm.
  • step S1 the step of filtering is preferably further included after the extrusion.
  • the filtration can be performed by using a conventional melt filter in the art.
  • the temperature of the melt filter is within the range of 0-15° C. above and below the eight-zone temperature of the twin-screw extruder.
  • the dipping die head can be a conventional die head in the field.
  • the width of the dipping die is preferably 100-650mm.
  • the temperature of the dipping die may be 240-335°C, such as 295 or 300°C.
  • the temperature of the dipping die is within the range of 0-15°C above and below the eight-zone temperature of the twin-screw extruder.
  • the introduction preferably includes the following process: the continuous long fiber is unwound from the yarn guide frame through the tension controller, passes through the yarn dividing frame, and enters the yarn spreading system, so that the continuous long fiber Each tow is fully unfolded, then enters the yarn drying device for preheating, and then enters the impregnation die to impregnate the continuous long fibers with the melt.
  • the temperature of the yarn drying device is preferably 70-400°C.
  • step S3 the molding and cooling can be carried out using conventional roller presses in the field, preferably four-rollers.
  • the temperature of the internal circulating water of the four-roll machine may be 60-90°C.
  • the traction can be carried out using a conventional traction device in the field, in which further cooling and edge trimming are performed.
  • the traction speed of the traction can be 5-15m/min.
  • the winding can be carried out using a conventional winding device in the field, preferably an automatic winding machine.
  • the present invention also provides the use of the aforementioned continuous long fiber reinforced thermoplastic composite plate in plastic products.
  • the plastic products preferably include plastic products in auto parts.
  • the positive progress effect of the present invention is: the present invention uses the continuous long fiber reinforced polyamide prepreg tape as a molded interlayer, fully utilizes the performance characteristics of bio-based polyamide, and polyamide is used as a resin matrix to connect the continuous long fibers with excellent performance. Together, a continuous long fiber reinforced thermoplastic composite sheet with low water absorption, excellent mechanical properties, smooth appearance, reliable performance and practicality is prepared.
  • the preparation method of the invention adopts a mold pressing composite process, which has the advantages of simple process, short time consumption, high production efficiency and low cost.
  • the present invention can also prepare unidirectional prepreg tape by melt impregnation method, so that each monofilament in the continuous long fiber can be impregnated by resin, and the effect of impregnation is uniform; a unidirectional prepreg tape with a thickness of 0.15-0.5mm can be prepared. Dip tape can be molded or wound, allowing more freedom in production design.
  • the present invention can also change the orientation of the long fibers in the composite board by adjusting the different placement directions of the prepreg tape, improve the impact resistance of the composite board against forces in different directions, and adjust the number of layers of the prepreg tape to adjust the composite board. thickness to suit different applications.
  • Figure 1 is a schematic structural view of the continuous long fiber reinforced thermoplastic composite sheet 2A-[4B]-2A prepared in Example 2.
  • Fig. 2 is a schematic structural view of the continuous long fiber reinforced thermoplastic composite sheet A-[6B]-A prepared in Example 4.
  • A is continuous long glass fiber reinforced PA513 unidirectional prepreg tape
  • B is continuous long glass fiber reinforced PA56 unidirectional prepreg tape
  • A is continuous long glass fiber reinforced PA512 unidirectional prepreg tape
  • B is continuous long glass fiber reinforced PA56 unidirectional prepreg tape.
  • the raw materials were purchased from the following sources: bio-based polyamide resins PA56, PA510, PA512, PA513 and PA515 were purchased from Cathay (Jinxiang) Biomaterials Co., Ltd. PA6 was purchased from Guangzhou Xinhui Meida Nylon Co., Ltd. The continuous long glass fiber was purchased from Owens Corning (OC), and the specification was 1200Tex. Continuous carbon fiber was purchased from Toray Group T700 with a specification of 24K.
  • bio-based polyamide resins PA56, PA510, PA512, PA513 and PA515 were purchased from Cathay (Jinxiang) Biomaterials Co., Ltd.
  • PA6 was purchased from Guangzhou Xinhui Meida Nylon Co., Ltd.
  • the continuous long glass fiber was purchased from Owens Corning (OC), and the specification was 1200Tex.
  • Continuous carbon fiber was purchased from Toray Group T700 with a specification of 24K.
  • each polyamide resin is as follows:
  • the relative viscosity of PA56 is 2.29, the terminal amino group content is 55mmol/kg, the melting point is 253°C, and the bio-based content is 45%;
  • the relative viscosity of PA510 is 2.51, the terminal amino group content is 54mmol/kg, the melting point is 217°C, and the bio-based content is 100%;
  • the relative viscosity of PA512 is 2.32, the terminal amino group content is 56mmol/kg, the melting point is 210°C, and the bio-based content is 33.8%;
  • the relative viscosity of PA513 is 2.38, the terminal amino group content is 41mmol/kg, the melting point is 197°C, and the bio-based content is 32.3%;
  • the relative viscosity of PA515 is 2.25, the terminal amino group content is 51mmol/kg, the melting point is 191°C, and the bio-based content is 29.6%;
  • the relative viscosity of PA6 is 2.46, the terminal amino group content is 54mmol/kg, the melting point is 223°C, and it does not contain bio-based.
  • the relative viscosity is measured by Ubbelohde viscometer concentrated sulfuric acid method.
  • the biobased content is measured by carbon 14, for example, obtained by ASTM D6866, a standard method for detection of biobased content.
  • Release paper was purchased from Shandong Shenghe Paper Plastic Packaging Co., Ltd.; release cloth was purchased from Taiwei New Composite Materials Co., Ltd.
  • the unidirectional prepreg tapes in the following examples and comparative examples are all prepared by the melt impregnation method, and the preparation methods refer to the following preparation examples 1-4.
  • the raw materials of the polyamide 56 resin composition include the following components in parts by weight: PA56: 90.5 parts, antioxidant 1098: 0.4 parts, antioxidant 168: 0.4 parts, internal lubricant WAXE: 0.2 parts, external lubricant WAXC: 0.2 parts , compatibilizer POE-g-MAH: 8 parts, coupling agent KH560: 0.3 parts, add the above components into a high-speed mixer and mix to obtain a polyamide 56 resin composition;
  • the twin-screw extruder adopts an eight-zone heating mode, and the temperatures from zone one to zone eight (along the direction of feeding to the machine head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, 300°C °C;
  • the screw speed is 400rpm; the aspect ratio of the twin-screw extruder is 1:36;
  • the temperature of the melt filter was 300°C; the temperature of the dipping die was 300°C.
  • the impregnated continuous long glass fiber is shaped and cooled by a four-roller machine, wherein the temperature of the circulating water in the four-roller machine is set to 80°C;
  • the traction speed is 8m/min
  • the screw speed of the twin-screw extruder and the winding speed of the automatic winder are controlled to ensure that the weight fraction ratio of the continuous long glass fiber and polyamide 56 resin composition is 65:35, and the continuous long glass fiber reinforced PA56 unidirectional prepreg tape.
  • Prepreg tape treatment place the prepreg tape obtained in step 3 in a vacuum drying oven at 105°C for 15 hours to vacuum dry to reduce the moisture content of the prepreg tape to 500ppm.
  • the parts by weight of the raw materials of the polyamide 56 resin composition include the following components: PA56: 90.5 parts, antioxidant 1098: 0.3 parts, antioxidant 168: 0.3 parts, internal lubricant WAXE: 0.2 parts, external lubricant WAXC: 0.2 parts , Compatibilizer POE-g-MAH: 8 parts, coupling agent KH560: 0.5 parts. Add the above components into a high-speed mixer and mix to obtain a polyamide 56 resin composition;
  • the twin-screw extruder adopts an eight-zone heating mode, and the temperatures from zone one to zone eight (along the direction of feeding to the machine head) are 240°C, 290°C, 300°C, 300°C, 300°C, 300°C, 300°C, 300°C °C;
  • the screw speed is 400r/min; the aspect ratio of the twin-screw extruder is 1:36;
  • the temperature of the melt filter is 300°C; the temperature of the die is 300°C.
  • the continuous long carbon fiber passes through the tension controller, unwinds from the yarn guide frame, passes through the yarn dividing frame, and enters the yarn spreading system to fully expand each tow, and then enters the yarn drying device for preheating, and the yarn drying device Set the temperature to 250°C, and then enter the impregnation die, where the continuous long carbon fiber is impregnated with the melt;
  • the traction speed is 8m/min
  • the screw speed of the twin-screw extruder and the winding speed of the automatic winder were controlled to ensure that the weight fraction ratio of the continuous long carbon fiber and the polyamide 56 resin composition was 65:35, and the continuous long carbon fiber reinforced PA56 sheet was obtained. to the prepreg tape.
  • Prepreg tape treatment place the prepreg tape obtained in step 3 in a vacuum drying oven at 105°C for 15 hours to vacuum dry to reduce the moisture content of the prepreg tape to 500ppm.
  • the long carbon chain bio-based polyamide includes PA513, PA510, PA512 or PA515.
  • the parts by weight of the long carbon chain bio-based polyamide composition raw materials include the following components: long carbon chain bio-based polyamide: 94.5 parts, antioxidant 1098: 0.3 parts, antioxidant 168: 0.3 parts, internal lubricant WAXE: 0.2 parts, external lubricant WAXC: 0.2 parts, compatibilizer POE-g-MAH: 4 parts, coupling agent KH550: 0.5 parts. adding the above components into a high-speed mixer and mixing to obtain a long carbon chain bio-based polyamide composition;
  • the twin-screw extruder adopts eight-zone heating mode, and the temperatures from zone one to zone eight (along the direction of feeding to the head) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, 280°C °C;
  • the screw speed is 400rpm; the aspect ratio of the twin-screw extruder is 1:36;
  • the temperature of the melt filter was 290°C; the temperature of the die was 295°C.
  • the traction speed is 8m/min
  • the screw speed of the twin-screw extruder and the winding speed of the automatic winder are controlled to ensure that the weight fraction ratio of the continuous long glass fiber and the long carbon chain bio-based polyamide resin composition is 65:35, and continuous Long glass fiber reinforced long carbon chain bio-based polyamide unidirectional prepreg tape.
  • Prepreg tape treatment place the prepreg tape obtained in step 3 in a vacuum drying oven at 105°C for 15 hours to vacuum dry to reduce the moisture content of the prepreg tape to 500ppm.
  • the long carbon chain bio-based polyamide includes PA513, PA510, PA512 or PA515.
  • the parts by weight of raw materials of the long carbon chain bio-based polyamide resin composition include the following components: long carbon chain bio-based polyamide: 94.5 parts, antioxidant 1098: 0.3 parts, antioxidant 168: 0.3 parts, internal lubricant WAXE: 0.2 parts, external lubricant WAXC: 0.2 parts, compatibilizer POE-g-MAH: 4 parts, coupling agent KH560: 0.5 parts. Adding the above components into a high-speed mixer and mixing to obtain a long carbon chain bio-based polyamide resin composition;
  • the twin-screw extruder adopts eight-zone heating mode, and the temperatures from zone one to zone eight (along the direction of feeding to the head) are 210°C, 270°C, 270°C, 270°C, 270°C, 270°C, 280°C °C;
  • the screw speed is 400rpm; the aspect ratio of the twin-screw extruder is 1:36;
  • the temperature of the melt filter was 290°C; the temperature of the die was 295°C.
  • the continuous long carbon fiber passes through the tension controller, unwinds from the yarn guide frame, passes through the yarn dividing frame, and enters the yarn spreading system to fully expand each tow, and then enters the yarn drying device for preheating, and the yarn drying device Set the temperature to 250°C, and then enter the impregnation die, where the continuous long carbon fiber is impregnated with the melt;
  • the traction speed is 8m/min
  • the screw speed of the twin-screw extruder and the winding speed of the automatic winder are controlled to ensure that the weight fraction ratio of the continuous long carbon fiber and the long carbon chain bio-based polyamide resin composition is 65:35, and the continuous long carbon fiber is obtained.
  • Carbon fiber reinforced long carbon chain bio-based polyamide unidirectional prepreg tape is controlled to ensure that the weight fraction ratio of the continuous long carbon fiber and the long carbon chain bio-based polyamide resin composition is 65:35, and the continuous long carbon fiber is obtained.
  • Prepreg tape treatment place the prepreg tape obtained in step 3 in a vacuum drying oven at 105°C for 15 hours to vacuum dry to reduce the moisture content of the prepreg tape to 500ppm.
  • Prepreg A Continuous long glass fiber reinforced PA513 unidirectional prepreg, prepared as in Preparation Example 3, with a thickness of 0.28mm and a fiber content of 60.5wt%;
  • Prepreg tape B continuous long glass fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in Preparation Example 1, the thickness is 0.32mm, and the fiber content is 61.3wt%;
  • the temperature of the molding machine is set at 260°C, and 6 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is laid on the top and bottom of the adjacent prepreg B at 90°.
  • Prepreg A Continuous long glass fiber reinforced PA513 unidirectional prepreg, prepared as in Preparation Example 3, with a thickness of 0.28mm and a fiber content of 60.5wt%;
  • Prepreg tape B continuous long glass fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in Preparation Example 1, the thickness is 0.32mm, and the fiber content is 61.3wt%;
  • the temperature of the molding machine is set at 260°C, 4 layers of prepreg B are cross-laid at 0° and 90°, and two layers of prepreg A are cross-laid at 0° and 90° on the upper and lower sides respectively, and the pressure of the molding machine is controlled at 3MPa.
  • Prepreg A Continuous long glass fiber reinforced PA510 unidirectional prepreg, prepared as in Preparation Example 3, with a thickness of 0.31mm and a fiber content of 62.8wt%;
  • Prepreg tape B continuous long glass fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in Preparation Example 1, the thickness is 0.32mm, and the fiber content is 61.3wt%;
  • the temperature of the molding machine is set at 260°C, 4 layers of prepreg B are cross-laid at 0° and 90°, and two layers of prepreg A are cross-laid at 0° and 90° on the upper and lower sides respectively, and the pressure of the molding machine is controlled at 3MPa. Preheat for 5 minutes, exhaust 3 times, hold pressure for 8 minutes, and then move to the cooling layer to cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet 2A-[4B]-2A with a thickness of 2.39mm .
  • Prepreg A Continuous long glass fiber reinforced PA512 unidirectional prepreg, prepared as in Preparation Example 3, with a thickness of 0.28mm and a fiber content of 62.1wt%;
  • Prepreg tape B continuous long glass fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in Preparation Example 1, the thickness is 0.32mm, and the fiber content is 61.3wt%;
  • the temperature of the molding machine is set to 260°C, 6 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is cross-laid at 90° relative to the adjacent prepreg B, and the pressure of the molding machine is Controlled at 3MPa, preheat for 5 minutes, exhaust 3 times, hold pressure for 8 minutes, then move to the cooling layer to cool at a cooling rate of 15°C/min, and prepare a continuous long fiber reinforced thermoplastic composite sheet A-[ 6B]-A, its structural diagram is shown in Figure 2, 3 in Figure 2 represents A, A is continuous long glass fiber reinforced PA512 unidirectional prepreg tape, 4 in Figure 2 represents 6B, and B is continuous long glass fiber reinforced PA56 Unidirectional prepreg tape.
  • Prepreg A Continuous long glass fiber reinforced PA515 unidirectional prepreg, prepared as in Preparation Example 3, with a thickness of 0.27mm and a fiber content of 62.8wt%;
  • Prepreg tape B continuous long glass fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in Preparation Example 1, the thickness is 0.32mm, and the fiber content is 61.3wt%;
  • the temperature of the molding machine is set at 260°C, and 6 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is laid on the top and bottom of the adjacent prepreg B at 90°.
  • Prepreg tape A continuous long carbon fiber reinforced PA513 unidirectional prepreg tape, the preparation method is as in preparation example 4, the thickness is 0.21mm, and the fiber content is 51.3wt%;
  • Prepreg tape B continuous long carbon fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in preparation example 2, the thickness is 0.24mm, and the fiber content is 50.4wt%;
  • the temperature of the molding machine is set at 260°C, and 8 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is cross-laid at 90° with respect to the adjacent prepreg B, and the pressure of the molding machine is Controlled at 3MPa, preheat for 5 minutes, exhaust 3 times, hold pressure for 8 minutes, then move to the cooling layer and cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet A-[ 8B]-A.
  • Prepreg tape A continuous long carbon fiber reinforced PA513 unidirectional prepreg tape, the preparation method is as in Preparation Example 4, the thickness is 0.21mm, and the fiber content is 51.3wt%;
  • Prepreg tape B continuous long carbon fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in preparation example 2, the thickness is 0.24mm, and the fiber content is 50.4wt%;
  • the temperature of the molding machine is set at 260°C, 6 layers of prepreg B are cross-laid at 0° and 90°, and two layers of prepreg A are cross-laid at 0° and 90° on the upper and lower sides respectively, and the pressure of the molding machine is controlled at 3MPa. Preheat for 5 minutes, exhaust 3 times, hold the pressure for 8 minutes, then move to the cooling layer and cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet 2A-[6B]-2A with a thickness of 2.25mm .
  • Prepreg tape A continuous long carbon fiber reinforced PA510 unidirectional prepreg tape, the preparation method is as in Preparation Example 4, the thickness is 0.23mm, and the fiber content is 50.1wt%;
  • Prepreg tape B continuous long carbon fiber reinforced PA56 unidirectional prepreg tape, the preparation method is as in preparation example 2, the thickness is 0.24mm, and the fiber content is 50.4wt%;
  • the temperature of the molding machine is set at 260°C, and 8 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is cross-laid at 90° with respect to the adjacent prepreg B, and the pressure of the molding machine is Controlled at 3MPa, preheat for 5 minutes, exhaust 3 times, hold pressure for 8 minutes, then move to the cooling layer and cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet A-[ 8B]-A.
  • Prepreg tape continuous long glass fiber reinforced PA6 unidirectional prepreg tape
  • the process preparation method refers to Preparation Example 3 (only the raw material long carbon chain bio-based polyamide of the resin composition is replaced by PA6), the thickness is 0.31mm, the fiber content 61.8wt%;
  • the temperature of the molding machine is set at 228°C, and 8 layers of the above-mentioned prepreg tapes are cross-laid at 0° and 90°.
  • the pressure of the molding machine is controlled at 3MPa. First, preheat for 5 minutes, exhaust 3 times, hold the pressure for 8 minutes, and then move to the cooling layer Cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet with a thickness of 2.24mm.
  • Prepreg tape continuous long carbon fiber reinforced PA6 unidirectional prepreg tape
  • the process preparation method refers to Preparation Example 4 (only the raw material long carbon chain bio-based polyamide of the resin composition is replaced by PA6), the thickness is 0.23mm, and the fiber content is 50.9 wt%;
  • the temperature of the molding machine is set at 228°C, and the above prepreg tapes are cross-laid at 0° and 90° for 10 layers.
  • the pressure of the molding machine is controlled at 3MPa. First, preheat for 5 minutes, exhaust 3 times, hold the pressure for 8 minutes, and then move to the cooling layer Cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet with a thickness of 2.12mm.
  • Prepreg A Continuous long glass fiber reinforced PA513 unidirectional prepreg, prepared as in Preparation Example 3, with a thickness of 0.28mm and a fiber content of 60.5wt%;
  • Prepreg B continuous long glass fiber reinforced PA6 unidirectional prepreg
  • the process preparation method refers to Preparation Example 3 (only the raw material long carbon chain bio-based polyamide of the resin composition is replaced by PA6), the thickness is 0.31mm, the fiber The content is 61.8wt%;
  • the temperature of the molding machine is set at 228°C, and 6 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is cross-laid at 90° with respect to the adjacent prepreg B, and the pressure of the molding machine is Controlled at 3MPa, preheated for 5 minutes, exhausted 3 times, held for 8 minutes, then moved to the cooling layer and cooled at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet 1A-[ 6B]-1A.
  • Prepreg tape A continuous long carbon fiber reinforced PA513 unidirectional prepreg tape, the preparation method is as in preparation example 4, the thickness is 0.21mm, and the fiber content is 51.3wt%;
  • Prepreg tape B continuous long carbon fiber reinforced PA6 unidirectional prepreg tape
  • the process preparation method refers to Preparation Example 4 (only the raw material long carbon chain bio-based polyamide of the resin composition is replaced by PA6), the thickness is 0.23mm, the fiber content is 50.9wt%;
  • the temperature of the molding machine is set at 228°C, and 8 layers of prepreg B are cross-laid at 0° and 90°, and a layer of prepreg A is cross-laid at 90° relative to the adjacent prepreg B respectively. Controlled at 3MPa, preheat for 5 minutes, exhaust 3 times, hold pressure for 8 minutes, then move to the cooling layer and cool at a cooling rate of 15°C/min to prepare a continuous long fiber reinforced thermoplastic composite sheet A-[ 8B]-A.
  • Bending test (bending strength, bending modulus): According to the requirements of the ISO 14125 standard, cut out a sample with a sample size of 80 mm long, 10 mm wide, and 2 mm thick for the bending test.
  • the test refers to the standard ASTM-D570-2005, and a 60mm long, 60mm wide, and 2mm thick composite plate is prepared as a water absorbent plate. According to the test method of plastic water absorption, the test time is 24h.
  • Tensile test (tensile strength, tensile modulus, Poisson's ratio): According to the requirements of ASTM D3039 standard, the sample size is 80mm long, 10mm wide, and 2mm thick.
  • the strength and modulus of the continuous long glass fiber reinforced bio-based polyamide composite sheet are significantly improved compared with the corresponding performance of the continuous long glass fiber reinforced PA6 composite sheet, and the heat resistance is also significantly better.
  • the water absorption performance is lower than that of continuous long glass fiber reinforced PA6 composite sheet;

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Abstract

Plaque composite thermoplastique continue renforcée par des fibres longues, son procédé de préparation et son application. La plaque composite thermoplastique continue renforcée par des fibres longues comprend m couches de bandes préimprégnées A et n couches de bandes préimprégnées B, et les bandes préimprégnées A sont disposées sur la couche externe, m ≥ 2, n ≥ 1, et m et n étant des nombres entiers ; les bandes préimprégnées A sont des bandes préimprégnées unidirectionnelles de résine de polyamide à longue chaîne renforcée par des fibres longues continues qui comprennent des fibres longues continues et des résines de polyamide à longue chaîne de carbone ; et les bandes préimprégnées B sont des bandes préimprégnées unidirectionnelles de résine de polyamide à chaîne courte renforcée par des fibres longues qui comprennent des fibres longues continues et des résines de polyamide à chaîne de carbone courte. La plaque composite présente les avantages d'avoir une faible absorption de l'eau, d'excellentes propriétés mécaniques, un aspect lisse, des performances fiables et d'être pratique ; de plus, le procédé de préparation est simple, le temps nécessaire est court, l'efficacité de production est élevée, et le coût est faible.
PCT/CN2022/074306 2021-05-31 2022-01-27 Plaque composite thermoplastique continue renforcée par des fibres longues, son procédé de préparation et son utilisation WO2022252661A1 (fr)

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CN202110604722.8A CN113232384A (zh) 2021-05-31 2021-05-31 连续长纤维增强热塑性复合板材及其制备方法、应用
CN202110604722.8 2021-05-31

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