CN116925539A

CN116925539A - Continuous fiber reinforced flame-retardant bio-based polyamide composite material and preparation method and application thereof

Info

Publication number: CN116925539A
Application number: CN202210346767.4A
Authority: CN
Inventors: 高莉; 李园平; 刘修才
Original assignee: Kaisai Taiyuan Biomaterials Co ltd; Shanxi Institute Of Synthetic Biology Co ltd; Cathay R&D Center Co Ltd; CIBT America Inc
Current assignee: Kaisai Taiyuan Biomaterials Co ltd; Shanxi Institute Of Synthetic Biology Co ltd; Cathay R&D Center Co Ltd; CIBT America Inc
Priority date: 2022-03-31
Filing date: 2022-03-31
Publication date: 2023-10-24

Abstract

The invention discloses a continuous fiber reinforced flame retardant bio-based polyamide composite material, and a preparation method and application thereof. The continuous fiber reinforced flame-retardant bio-based polyamide composite material comprises a flame-retardant bio-based polyamide resin composition and continuous fibers, wherein the continuous fibers account for 50-90% of the mass of the continuous fiber reinforced flame-retardant bio-based polyamide composite material; the flame-retardant bio-based polyamide resin composition comprises 60-90 parts of bio-based polyamide 5X resin and additives; the additive comprises 8-25 parts of flame retardant, 0.2-1.6 parts of antioxidant and 3-12 parts of compatilizer. The preparation method of the continuous fiber reinforced flame-retardant bio-based polyamide composite material is simple and feasible, low in cost, high in production efficiency and good in impregnation effect, and the prepared continuous fiber reinforced flame-retardant bio-based polyamide composite material is excellent in comprehensive performance, high in flame retardance, good in mechanical property and recyclable.

Description

Continuous fiber reinforced flame-retardant bio-based polyamide composite material and preparation method and application thereof

Technical Field

The invention relates to a continuous fiber reinforced flame retardant bio-based polyamide composite material, and a preparation method and application thereof.

Background

The fiber reinforced thermoplastic resin composite material is prepared from thermoplastic resin and fiber through special forming process, and can be divided into short fiber reinforced thermoplastic resin matrix composite material, long fiber reinforced thermoplastic resin matrix composite material and continuous fiber reinforced thermoplastic resin matrix composite material according to different fiber sizes. Compared with the short and long fiber reinforced thermoplastic resin matrix composite materials, the continuous fiber reinforced thermoplastic resin matrix composite material has more outstanding mechanical properties, heat resistance, warping resistance, dimensional stability and the like, so that products with excellent mechanical properties, such as automobile parts, electronic devices, chemical parts and the like, can be manufactured.

The continuous fiber reinforced flame-retardant polyamide composite material has good comprehensive properties of light weight, high strength, corrosion resistance, impact resistance, heat distortion resistance, nonflammability and the like, and has become one of main research directions for reinforcing and modifying thermoplastic materials, and the reason is that: firstly, the continuous fiber can improve the mechanical property of the composite material, secondly, the flame-retardant polyamide has the characteristics of integral flame retardance, corrosion resistance and the like, and the application range is wide.

The continuous fiber reinforced flame retardant polyamide unidirectional tape is an intermediate material for transition from a raw material to a product of a fiber reinforced thermoplastic resin matrix composite material, is also called a tape-shaped prepreg according to the preparation process of the tape-shaped prepreg, and has different quality, and besides the influence factors of fiber size, the important factors are the composite process of the material, namely the impregnation of fibers. At present, the preparation process for fiber impregnation mainly comprises a melt impregnation method, a solution impregnation method, a powder method and a fiber mixing method, and the melt impregnation method is researched and applied in many ways. However, the melt impregnation method is high in energy consumption, high in cost, poor in impregnation effect and still needs to be further improved in comprehensive performance of the material because the resin is melted into liquid at high temperature and then impregnated on the continuous fibers.

The existing polyamide material has certain flame retardance, but still cannot meet the requirements of modern people living and industrial development on flame retardance, and the flame retardance is often required to be improved by modification. However, excessive amounts of flame retardant affect the mechanical properties of the polyamide.

Accordingly, there is an urgent need in the art for a polyamide composite material having high flame retardancy and good mechanical properties, and a method for preparing the same.

Disclosure of Invention

The invention aims to overcome the defects of high energy consumption and high cost in the preparation process of the continuous fiber reinforced flame retardant polyamide composite material in the prior art, and the comprehensive performance of the material needs to be further improved, thereby providing the continuous fiber reinforced flame retardant bio-based polyamide composite material, and the preparation method and application thereof. The preparation method of the continuous fiber reinforced flame-retardant bio-based polyamide composite material is simple and feasible, low in cost, high in production efficiency and good in impregnation effect, and the prepared continuous fiber reinforced flame-retardant bio-based polyamide composite material is excellent in comprehensive performance, high in flame retardance, good in mechanical property and recyclable.

In order to achieve the above purpose, the present invention adopts the following technical scheme:

the technical scheme is as follows: a flame-retardant bio-based polyamide resin composition, which comprises 60-90 parts by weight of bio-based polyamide 5X resin and additives; the additive comprises 8-25 parts of flame retardant, 0.2-1.6 parts of antioxidant and 3-12 parts of compatilizer.

In the present invention, the bio-based polyamide 5X resin may be selected from one or more of PA56 and long carbon chain bio-based polyamide 5X resins. Wherein the long carbon chain bio-based polyamide 5X resin refers to bio-based polyamide 5X resin with X more than or equal to 10. The long carbon chain bio-based polyamide 5X resin is preferably selected from one or more of PA510, PA511, PA512, PA513, PA514, PA515, PA516, PA517 and PA 518.

In the present invention, preferably, the biobased polyamide 5X resin satisfies the following conditions: the relative viscosity is 1.8-2.7, the content of terminal amino groups is 40-60mmol/kg, the melting point is 170-320 ℃, the water content is below 2000ppm, and the content of biological base is 43-100%. Wherein the relative viscosity is measured by the Ubbelohde viscosimeter concentrated sulfuric acid method. The biobased content is obtained by detection by the standard method for biobased content detection ASTM D6866. The biobased polyamide 5X resin is available from kesai (jinxiang) biomaterial limited.

In some preferred embodiments of the invention, the biobased polyamide 5X resin is PA56, the PA56 satisfying the following properties: a relative viscosity of 1.9 to 2.5, for example 2.29; the terminal amino group content is 40-60mmol/kg, for example 55mmol/kg; melting point 210-260 deg.c, preferably 253-256 deg.c; the biobased content is 43% -46%, such as 45%; the water content is less than 2000ppm, preferably 800-1500 ppm.

In some preferred embodiments of the present invention, the biobased polyamide 5X resin is a long carbon chain biobased polyamide 5X resin that meets the following properties: relative viscosities of 2.1-2.6, e.g. 2.13, 2.25, 2.29, 2.32, 2.38, 2.51, 2.47; the terminal amino group content is 40-60mmol/kg, for example 41mmol/kg, 42mmol/kg, 47mmol/kg, 48mmol/kg, 51mmol/kg, 52mmol/kg, 54mmol/kg, 56mmol/kg; melting point 180-230deg.C, such as 191 deg.C, 192 deg.C, 205 deg.C, 209 deg.C, 210 deg.C, 217 deg.C; the content of the biological base is 43% -100%; the water content is less than 2000 ppm.

In the present invention, the content of the bio-based polyamide 5X resin is preferably 78 to 88 parts, for example 80.9 parts, 81.5 parts, 82.8 parts, 83 parts, 85 parts.

In the present invention, the flame retardant may include one or more of a nitrogen-based organic flame retardant, a phosphorus-based organic flame retardant, and an inorganic flame retardant. The flame retardant gives the material a flame retardant effect, so that the material is not easy to burn in the air.

Wherein the nitrogen-based organic flame retardant preferably comprises one or more of melamine cyanurate, melamine polyphosphate, melamine pyrophosphate, melamine phosphate, dimelamine pyrophosphate, melam polyphosphate and melem polyphosphate.

Wherein the phosphorus-based organic flame retardant preferably comprises an organic phosphinate flame retardant. Wherein the organic phosphinate flame retardant is preferably an organic phosphinate containing an alkyl group having 1 to 4 carbon atoms, more preferably an organic phosphinate containing a methyl group and/or an ethyl group, still more preferably one or more of aluminum methylethyl phosphinate, aluminum diethyl phosphinate, zinc methylethyl phosphinate and zinc diethyl phosphinate.

Wherein the inorganic flame retardant may include one or more of aluminum hydroxide, magnesium hydroxide, zinc borate, red phosphorus, ammonium phosphate salt, and ammonium polyphosphate.

In the present invention, the content of the flame retardant is preferably 10 to 15 parts, for example, 13 parts, 14 parts.

In the invention, the antioxidant ensures that the material is not easy to age and denature in a common environment, and the service life is prolonged. The antioxidant may be selected from one or more of hindered phenolic antioxidants, hindered aminic antioxidants and phosphite antioxidants.

Preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228.

In the present invention, the antioxidant is contained in an amount of 0.3 to 0.6 parts, for example, 0.3, 0.4, 0.5 or 0.6 parts.

In the present invention, the compatibilizing agent may be selected from one or more of a polyolefin grafted maleic anhydride-based compatibilizing agent, a polyolefin grafted methyl ester acrylic-based compatibilizing agent, and a rubber elastomer grafted maleic anhydride-based compatibilizing agent. Wherein, the polyolefin grafted maleic anhydride compatilizer is preferably PP-g-MAH or POE-g-MAH; the polyolefin grafted methyl ester acrylic compatilizer is preferably POE-g-GMA; the rubber elastomer grafted maleic anhydride-based compatibilizer is preferably EPDM-g-MAH.

In the present invention, the content of the compatibilizing agent is preferably 4 to 10 parts, for example, 4, 4.2, 5, 6, 6.5, 8 or 10 parts.

In the present invention, preferably, the flame retardant bio-based polyamide resin composition further comprises a lubricant.

Wherein the lubricant may comprise an outer lubricant and/or an inner lubricant. Wherein the outer lubricant is, for example, WAXC and the inner lubricant is, for example, WAXE.

Preferably, the lubricant is present in an amount of 0.1 to 0.8 parts, for example 0.3, 0.4 or 0.5 parts.

In the present invention, preferably, the flame retardant bio-based polyamide resin composition further comprises a coupling agent.

Wherein the coupling agent can be selected from one or more of silane coupling agents, carbonate coupling agents and aluminate coupling agents; preferably a silane-based coupling agent, such as coupling agent KH550, coupling agent KH560 or coupling agent KH570.

Preferably, the coupling agent is used in an amount of 0.1 to 0.8 parts, for example 0.3, 0.4 or 0.5 parts.

The flame retardant bio-based polyamide resin composition can be prepared by a method conventional in the art, and generally comprises the steps of adding the components into a high-speed stirrer for mixing.

The second technical scheme is as follows: the continuous fiber reinforced flame-retardant bio-based polyamide composite material comprises the flame-retardant bio-based polyamide resin composition and continuous fibers, wherein the mass percentage of the continuous fibers in the continuous fiber reinforced flame-retardant bio-based polyamide composite material is 50% -90%.

In the present invention, the mass percentage of the continuous fiber-reinforced flame retardant bio-based polyamide composite material is preferably 60% -90%, for example 65%,69%,70%,75%,80%, 82%, 83% or 85%.

In the present invention, the continuous fiber may be one or more of carbon fiber, glass fiber, basalt fiber and aramid fiber.

In the present invention, the continuous fibers are preferably continuous long fibers.

Preferably, the continuous fibers are continuous long glass fibers. The continuous long glass fibers may have a filament diameter of 8-15 μm, preferably 8-10 μm. The continuous long glass fibers have a linear density of 1000-3600 Tex, preferably 1200Tex, 2400Tex. The continuous long glass fibers are, for example, 1200Tex continuous long glass fibers from euclidean (OC) and 2400Tex continuous long glass fibers from boulder.

Preferably, the continuous fibers are continuous long carbon fibers; the continuous long carbon fibers are preferably polyacrylonitrile-based carbon fibers; the number of monofilaments of the continuous long carbon fiber can be 20000-30000, preferably 12000 (12K) and 24000 (24K); the continuous long carbon fibers may have a monofilament diameter of 5-10 μm. The continuous long carbon fiber is, for example, dongli T700 with the specification of 24K, or Guangwei composite continuous long carbon fiber 700S with the specification of 12K or 24K.

In the present invention, the continuous fiber reinforced flame retardant bio-based polyamide composite material is preferably in the form of a unidirectional tape, which may be referred to as a continuous fiber reinforced flame retardant bio-based polyamide unidirectional tape. The unidirectional tape refers to a tape-like prepreg made by impregnating resin with continuous fibers parallel to each other.

Preferably, the continuous fiber reinforced flame retardant biobased polyamide unidirectional tape has a thickness of 0.15 to 0.5mm, more preferably 0.21 to 0.33mm, for example 0.23mm,0.27mm,0.28mm,0.31mm, 0.32mm or 0.33mm.

In the invention, when the continuous fiber is a continuous long glass fiber, the tensile strength of the continuous fiber reinforced flame retardant bio-based polyamide composite material is 800-2000MPa; the water absorption rate for 24 hours can be 0.4-1.2%; the Heat Distortion Temperature (HDT) may be 210-240 ℃; the oxygen index may be 29-33%.

In the invention, when the continuous fibers are continuous long carbon fibers, the tensile strength of the continuous fiber reinforced flame retardant bio-based polyamide composite material can be 1000-2400MPa; the water absorption rate for 24 hours can be 0.5-1.4%; the HDT may be 220-240℃and the oxygen index may be 31-36%.

The technical scheme is as follows: a method for preparing a continuous fiber reinforced flame retardant bio-based polyamide composite material, which comprises the following steps:

s1, extruding and granulating the flame-retardant bio-based polyamide resin composition to obtain resin slices, and dissolving the resin slices in a solvent to obtain a resin solution;

s2, impregnating the continuous fibers through a resin solution under traction, and removing solvent, heating, rolling and winding the impregnated continuous fibers to obtain the continuous fiber reinforced flame-retardant bio-based polyamide composite material; wherein the mass percentage of the continuous fiber accounting for the continuous fiber reinforced flame retardant bio-based polyamide composite material is 50-90%.

In step S1, the extrusion may be performed using a twin screw extruder or a single screw extruder, which are conventional in the art, preferably a twin screw extruder. Wherein the aspect ratio of the twin-screw extruder is preferably 1:36.

In step S1, the extrusion temperature may be 170-340 ℃.

When a twin-screw extruder is used, the twin-screw extruder adopts an eight-zone heating mode, and preferably, the temperatures from one zone to eight zones are 195 to 250 ℃, 200 to 300 ℃, 225 to 310 ℃ in order.

In step S1, the extrusion speed is 200-600r/min, such as 300r/min and 400r/min, expressed in terms of screw speed.

In step S1, the concentration of the resin solution is preferably 15 to 35%, for example, 20%, 24%, 28%, 29%, 30%, 33%, the percentage being the mass percentage of the resin chips to the resin solution.

In step S1, the solvent may be formic acid, concentrated sulfuric acid or m-cresol, preferably formic acid.

In step S1, the components of the flame retardant bio-based polyamide resin composition are uniformly mixed before the flame retardant bio-based polyamide resin composition is extruded. Wherein said mixing may be carried out by conventional means, preferably magnetic stirring; the mixing time is preferably 8-12 hours.

In step S2, before the continuous fibers are drawn, the continuous fibers are subjected to the following operations: the continuous fibers are unreeled from the creel through the tension controller and enter the yarn spreading system through the yarn dividing frame, so that each tow is fully spread.

Wherein the creel preferably adopts an externally-placed creel, and each spindle independently controls tension.

In step S2, the speed of the traction is preferably 20-30mm/S, for example 24mm/S, 25mm/S, 26mm/S. The traction is performed by a traction device.

In step S2, the temperature of the impregnation may be room temperature, preferably 25 ℃. The temperature of the impregnation refers to the temperature of the resin solution when the continuous fibers are impregnated with the resin solution under traction.

In step S2, the solvent removal may be performed in a solvent removal channel, and the solvent is evaporated by heating in the solvent removal channel. The temperature of the solvent removal channel is preferably 90-110 ℃, e.g. 102 ℃, 105 ℃. The time for the desolvation is preferably 50 to 75s, for example 55s, 60s, 65s or 70s.

In step S2, the heating may be performed in a heating channel, the heating temperature of which is preferably 200-290 ℃, such as 230 ℃, 240 ℃, 248 ℃, 250 ℃ or 278 ℃. The heating time is preferably 60 to 150s, for example 70s, 75s, 85s, 90s or 100s.

In step S2, the rolling is preferably a passive impregnation roller. The passive impregnation roller automatically adjusts the rotating speed according to the viscosity of the resin solution and interacts with the continuous fibers to promote the resin solution to generate shearing motion so as to impregnate the continuous fibers. The passive impregnation rollers may have a roller spacing of 0.1 to 0.3mm, for example 0.15mm, 0.18mm, 0.2mm, 0.22mm, 0.25mm. The solution impregnation method adopts a mode that the viscosity of continuous fibers and resin solution drives a passive impregnation roller to rotate, so that the resin matrix is sheared to improve the impregnation effect, the porosity of the prepared unidirectional tape is low, and continuous fiber traction fracture is avoided.

In step S2, the winding may be a double-station winding. The speed of the winding is the same as the speed of the pulling, preferably 20-30mm/s, e.g. 24mm/s, 25mm/s, 26mm/s.

Preferably, in step S2, drying and forming are further included after the winding. Wherein the drying temperature may be 100-150 ℃, preferably 100-120 ℃. The drying means is preferably vacuum drying. The drying time may be 8 to 15 hours, preferably 10 to 12 hours.

In the invention, the mass percentage of the continuous fibers in the continuous fiber reinforced polyamide composite material is controlled and realized by controlling the concentration of the resin solution and the traction speed.

In the above preparation method, the continuous fibers are as described above.

The fourth technical scheme is as follows: a continuous fiber reinforced flame retardant bio-based polyamide composite material, which is prepared according to the preparation method of the continuous fiber reinforced flame retardant bio-based polyamide composite material.

Fifth technical scheme: the use of a continuous fiber reinforced flame retardant biobased polyamide composite material as described above in the aerospace field, the military field, automotive materials, sports equipment, construction materials or electronic appliances.

On the basis of conforming to the common knowledge in the field, the preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.

The reagents and materials used in the present invention are commercially available.

The invention has the positive progress effects that:

1. the invention adopts bio-based polyamide resin as raw material:

(1) The monomer pentanediamine or the dibasic acid in the raw material of the bio-based polyamide resin is prepared by biological fermentation, the bio-based content is between 43 and 100 percent, the bio-based content is high, and the concept of sustainable development of material sources is met;

(2) The flame-retardant bio-based polyamide resin composition prepared by adopting the bio-based polyamide resin as a raw material has good fiber wettability;

(3) The material selection range is enlarged, and the cost is reduced.

2. The continuous fiber reinforced flame retardant bio-based polyamide composite material has excellent comprehensive performance, and specifically:

(1) The fiber content is high, and in the range of 50-90%, the material has excellent mechanical properties (such as high tensile strength and the like) under the high fiber content;

(2) The flame retardant has excellent flame retardance and higher oxygen index;

(3) Good heat resistance and high Heat Distortion Temperature (HDT);

(4) The moisture resistance is good, and the water absorption is low;

(5) The fibers are uniformly distributed, no fibers are exposed, and the processing is easy;

(6) The thickness of the composite material can be set between 0.15 and 0.5mm according to the requirement, so that more design freedom degrees can be provided for the product;

(7) The product containing the continuous fiber reinforced flame retardant bio-based polyamide composite material can be recovered and reused, and the resource utilization rate is high.

3. The invention researches and uses the solution impregnation method to prepare the continuous fiber reinforced flame retardant bio-based polyamide composite material, and the preparation method is simple and feasible, and has low energy consumption, low cost and high production efficiency. And a plurality of technological parameters in the preparation process are further optimized to improve the impregnation effect of the fiber.

Detailed Description

The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods in the following examples, for which specific conditions are not noted, were selected according to conventional methods and conditions, or according to the commercial specifications.

In the following examples and comparative examples:

bio-based polyamide 5X resins PA56, PA510, PA511, PA512, PA513, PA514, PA515, and PA516 were all purchased from kesai (jinxiang) biomaterial limited;

polyamide 6 (PA 6 for short, viscosity of 2.46, amino end content of 54mmol/kg, melting point of 223 ℃ C., no bio-based) was purchased from Xinhuida chinlon Co., guangzhou;

polyamide 66 (PA 66 for short, viscosity of 2.6, amino end content of 48mmol/kg, melting point of 255 ℃) was purchased from DuPont;

antioxidants were purchased from basf group, germany;

lubricants and flame retardants are available from the company clariant, germany;

the compatibilizing agent is available from Shanghai good compatible polymers limited; coupling agent was purchased from jercard chemical company, hangzhou;

solvents were purchased from national pharmaceutical group chemical company, inc;

continuous long glass fibers were purchased from eurvescening (OC) in a specification of 1200Tex;

the continuous long carbon fiber is Toli T700 with the specification of 24K.

Example 1

1. Preparation of biobased Polyamide 56 resin composition

Weighing the following components in parts by weight: 80.9 parts of PA56 particles (relative viscosity of 2.29, amino end content of 55mmol/kg, melting point of 253 ℃ C., water content of 900 ppm), 10 parts of aluminium diethylphosphinate flame retardant, 0.5 part of antioxidant 1098, 0.4 part of external lubricant WAXC, 8 parts of compatilizer PP-g-MAH and 0.3 part of coupling agent KH560. The above components were added to a high-speed mixer and mixed to obtain a biobased polyamide 56 resin composition.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 56 composite material

S1, extruding and granulating the bio-based polyamide 56 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 8 hours to obtain a resin solution with the concentration of 33%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 240 ℃, 290 ℃, 300 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each fiber bundle, dipping the spread fiber bundles through resin solution under traction, wherein the dipping temperature is 25 ℃, the resin solution is coated on the fiber bundles by viscosity, and the traction speed is 26mm/S;

Then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 55s; the temperature of the heating channel is controlled to be 278 ℃, and the heating time is controlled to be 70s, so that the resin solution and the continuous fibers are fully infiltrated; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the continuous fibers to promote the resin solution to generate shearing motion so as to realize calendaring impregnation, wherein the roller spacing of the passive impregnation roller is 0.1mm; controlling the winding speed to be 26mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the prepared continuous long glass fiber reinforced flame-retardant bio-based polyamide 56 composite material is 65 percent; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 2

1. Preparation of biobased Polyamide 510 resin composition

Weighing the following components in parts by weight: 83 parts of PA510 particles (relative viscosity of 2.51, amino end content of 54mmol/kg, melting point of 217 ℃ C., water content of 900 ppm), 10 parts of aluminium diethylphosphinate flame retardant, 0.4 part of antioxidant 168, 0.3 part of external lubricant WAXC, 6 parts of compatilizer PP-g-MAH and 0.3 part of coupling agent KH560. The above components are added into a high-speed stirrer to be mixed, and the bio-based polyamide 510 resin composition is obtained.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 510 composite material

S1, extruding and granulating the bio-based polyamide 510 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 8 hours to obtain a resin solution with the concentration of 29%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 210 ℃, 260 ℃ and 240 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each fiber bundle, dipping the spread fiber bundles through resin solution under traction, wherein the dipping temperature is 25 ℃, the resin solution is coated on the fiber bundles by viscosity, and the traction speed is 24mm/S;

then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 65s; the temperature of the heating channel is controlled to be 240 ℃ and the heating time is controlled to be 90 seconds, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize casting impregnation, wherein the roller spacing of the passive impregnation roller is 0.2mm; controlling the winding speed to be 24mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the prepared continuous long glass fiber reinforced flame-retardant bio-based polyamide 510 composite material is 65%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 3

1. Preparation of biobased Polyamide 511 resin composition

Weighing the following components in parts by weight: 81.5 parts of PA511 particles (relative viscosity of 2.47, amino end content of 52mmol/kg, melting point of 209 ℃ C., water content of 900 ppm), 13 parts of aluminium diethylphosphinate flame retardant, 0.6 part of antioxidant 1098, 0.4 part of external lubricant WAXC, 4 parts of compatilizer PP-g-MAH and 0.5 part of coupling agent KH560. The above components were mixed in a high-speed mixer to obtain a bio-based polyamide 511 resin composition.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 511 composite material

S1, extruding and granulating the bio-based polyamide 511 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 9 hours to obtain a resin solution with the concentration of 30%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 220 ℃, 260 ℃ and 240 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 102 ℃, and the solvent is heated and evaporated for 70 seconds; the temperature of the heating channel is controlled to be 240 ℃, and the heating time is controlled to be 85 seconds, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize casting impregnation, wherein the roller spacing of the passive impregnation roller is 0.18mm; controlling the winding speed to be 24mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the continuous long glass fiber reinforced flame-retardant bio-based polyamide 511 composite material is 69%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 4

1. Preparation of biobased Polyamide 512 resin composition

Weighing the following components in parts by weight: 82.8 parts of PA512 particles (relative viscosity 2.32, amino end content 56mmol/kg, melting point 210 ℃ C., water content 900 ppm), 10 parts of melamine pyrophosphate flame retardant, 0.5 part of antioxidant 168, 0.3 part of external lubricant WAXC, 6 parts of compatilizer POE-g-MAH and 0.4 part of coupling agent KH560. The components are added into a high-speed stirrer to be mixed, and the bio-based polyamide 512 resin composition is obtained.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 512 composite material

S1, extruding and granulating the bio-based polyamide 512 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 9 hours to obtain a resin solution with the concentration of 30%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 220 ℃, 260 ℃ and 260 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each fiber bundle, dipping the spread fiber bundles through resin solution under traction, wherein the dipping temperature is 25 ℃, the resin solution is coated on the fiber bundles by viscosity, and the traction speed is 20mm/S;

Then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 70 seconds; the temperature of the heating channel is controlled to 248 ℃, and the heating time is controlled to 85s, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize casting impregnation, wherein the roller spacing of the passive impregnation roller is 0.22mm; controlling the winding speed to be 20mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the prepared continuous long glass fiber reinforced flame-retardant bio-based polyamide 512 composite material is 70 percent; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 5

1. Preparation of biobased Polyamide 513 resin composition

Weighing the following components in parts by weight: 78 parts of PA513 particles (relative viscosity of 2.38, amino end content of 41mmol/kg, melting point of 197 ℃ C., water content of 900 ppm), 14 parts of melamine pyrophosphate flame retardant, 0.5 part of antioxidant 1098, 0.5 part of internal lubricant WAXE, 6.5 parts of compatilizer POE-g-MAH and 0.5 part of coupling agent KH560. The above components were mixed in a high-speed mixer to obtain a bio-based polyamide 513 resin composition.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 513 composite material

S1, extruding and granulating the bio-based polyamide 513 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 8.5 hours to obtain a resin solution with the concentration of 28%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 210 ℃, 240 ℃ and 230 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each fiber bundle, dipping the spread fiber bundles through resin solution under traction, wherein the dipping temperature is 25 ℃, the resin solution is coated on the fiber bundles by viscosity, and the traction speed is 25mm/S;

then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 60 seconds; the temperature of the heating channel is controlled to be 230 ℃ and the heating time is controlled to be 75 seconds, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize casting impregnation, wherein the roller spacing of the passive impregnation roller is 0.15mm; controlling the winding speed to be 25mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the continuous long glass fiber reinforced flame-retardant bio-based polyamide 513 composite material prepared by the method is 75 percent; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 6

1. Preparation of biobased Polyamide 514 resin composition

Weighing the following components in parts by weight: 85 parts of PA514 particles (with a relative viscosity of 2.29, an amino end content of 48mmol/kg, a melting point of 205 ℃ C., a water content of 900 ppm), 10 parts of aluminium diethylphosphinate flame retardant, 0.3 part of antioxidant 1010, 0.2 part of internal lubricant WAXE, 4.2 parts of compatilizer POE-g-MAH and 0.3 part of coupling agent KH560. The above components are added into a high-speed stirrer to be mixed, and the bio-based polyamide 514 resin composition is obtained.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 514 composite material

S1, extruding and granulating the bio-based polyamide 514 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 9.5 hours to obtain a resin solution with the concentration of 25%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 230 ℃, 260 ℃ and 260 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 75 seconds; the temperature of the heating channel is controlled to be 250 ℃ and the heating time is controlled to be 90s, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize casting impregnation, wherein the roller spacing of the passive impregnation roller is 0.22mm; controlling the winding speed to be 20mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the continuous long glass fiber reinforced flame-retardant bio-based flame-retardant polyamide 514 composite material is 83%; the composite material is in the form of unidirectional tapes, the thickness of which is shown in table 1.

Example 7

1. Preparation of biobased Polyamide resin 515 composition

Weighing the following components in parts by weight: 80.9 parts of PA515 particles (relative viscosity of 2.25, amino end content of 51mmol/kg, melting point of 191 ℃ C., water content of 900 ppm), 10 parts of melamine aluminium phosphate flame retardant, 0.5 part of antioxidant 168, 0.3 part of internal lubricant WAXE, 8 parts of compatilizer POE-g-MAH and 0.3 part of coupling agent KH560. The above components are added to a high speed mixer to mix, resulting in a bio-based polyamide resin 515 composition.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 515 composite material

S1, extruding and granulating the bio-based polyamide resin 515 composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 10 hours to obtain a resin solution with the concentration of 24%;

Then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 70 seconds; the temperature of the heating channel is controlled to be 240 ℃, and the heating time is controlled to be 100s, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize calendaring impregnation, wherein the roller spacing of the passive impregnation roller is 0.25mm; controlling the winding speed to be 20mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the continuous long glass fiber reinforced flame-retardant bio-based polyamide 515 composite material is 80 percent; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 8

1. Preparation of biobased Polyamide 516 resin composition

Weighing the following components in parts by weight: 81.5 parts of PA516 particles (relative viscosity 2.13, amino end content 47mmol/kg, melting point 192 ℃ C., water content 900 ppm), 13 parts of melamine aluminium phosphate flame retardant, 0.6 part of antioxidant 1098, 0.4 part of internal lubricant WAXE, 4 parts of compatibiliser POE-g-MAH and 0.5 part of coupling agent KH560. The above components are added into a high-speed stirrer to be mixed, and the bio-based polyamide 516 resin composition is obtained.

2. Preparation of continuous long glass fiber reinforced flame retardant bio-based polyamide 516 composite material

S1, extruding and granulating the bio-based polyamide 516 resin composition by using a double-screw extruder to obtain resin slices, pouring the resin slices into formic acid, and magnetically stirring for 10 hours to obtain a resin solution with the concentration of 20%;

the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 210 ℃, 240 ℃ and 240 ℃ in sequence; the rotating speed of the screw is 400r/min; the aspect ratio of the twin screw extruder was 1:36.

then, sequentially passing the immersed fiber through a solvent removal channel, a heating channel and a rolling system, finally winding, drying, molding and sealing for storage; wherein the temperature of the solvent removal channel is controlled to be 105 ℃, and the solvent is heated and evaporated for 75 seconds; the temperature of the heating channel is controlled to be 230 ℃ and the heating time is controlled to be 120s, so that the resin solution and the continuous fibers are fully soaked; in the rolling system, the rotation speed of the passive impregnation roller is automatically adjusted according to the viscosity of the resin solution, and the passive impregnation roller interacts with the fiber bundles to promote the resin matrix to generate shearing motion so as to realize calendaring impregnation, wherein the roller spacing of the passive impregnation roller is 0.26mm; controlling the winding speed to be 20mm/s; the drying and molding operation is to dry for 10 hours in a vacuum oven at 150 ℃.

The mass percentage of the continuous long glass fiber in the continuous long glass fiber reinforced flame-retardant bio-based polyamide 515 composite material is 85%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 9

The procedure was carried out in the same manner as in example 1, except that: continuous long carbon fibers are used in the preparation of the continuous fiber reinforced flame retardant bio-based polyamide 56 composite material.

The mass percentage of the continuous long carbon fiber in the prepared continuous long carbon fiber reinforced flame-retardant bio-based polyamide 56 composite material is 65%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 10

The procedure was carried out in the same manner as in example 2, except that: continuous long carbon fibers are used in the preparation of the continuous fiber reinforced flame retardant bio-based polyamide 510 composite material.

The mass percentage of the continuous long carbon fiber in the prepared continuous long carbon fiber reinforced flame-retardant bio-based polyamide 510 composite material is 65%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 11

The procedure was carried out in the same manner as in example 4, except that: continuous long carbon fibers are used in the preparation of the continuous fiber reinforced flame retardant bio-based polyamide 512 composite material.

The mass percentage of the continuous long carbon fiber in the prepared continuous long carbon fiber reinforced flame-retardant bio-based polyamide 512 composite material is 70%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Example 12

The procedure was carried out in the same manner as in example 5, except that: continuous long carbon fibers are used in the preparation of the continuous fiber reinforced flame retardant bio-based polyamide 513 composite material.

The mass percentage of the continuous long carbon fiber in the continuous long carbon fiber reinforced flame-retardant bio-based polyamide 513 composite material prepared by the method is 75%; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Comparative example 1

The procedure was carried out in the same manner as in example 1, except that:

weighing the following components in parts by weight: 80.9 parts of PA6 particles (relative viscosity of 2.46, amino end content of 54mmol/kg, melting point of 223 ℃ C., no biobased), 10 parts of aluminium diethylphosphinate flame retardant, 0.5 part of antioxidant 1098, 0.4 part of external lubricant WAXC, 8 parts of compatilizer PP-g-MAH and 0.3 part of coupling agent KH560. The above components were mixed in a high-speed mixer to obtain a polyamide 6 resin composition.

The mass percentage of the continuous long glass fiber in the prepared continuous long glass fiber reinforced flame-retardant polyamide 6 composite material is 65 percent; the composite material is in the form of a unidirectional tape, the thickness of which is shown in table 1.

Comparative example 2

The procedure was carried out in the same manner as in comparative example 1, except that: continuous long carbon fibers are used in the preparation of the continuous fiber reinforced flame retardant polyamide 6 composite material.

Comparative example 3

The procedure was carried out in the same manner as in example 1, except that:

weighing the following components in parts by weight: 80.9 parts of PA66 particles (relative viscosity 2.65, amino end content 36mmol/kg, melting point 260 ℃ C. Free of biogroups), 10 parts of aluminium diethylphosphinate flame retardant, 0.5 part of antioxidant 1098, 0.4 part of internal lubricant WAXE, 8 parts of compatibiliser PP-g-MAH and 0.3 part of coupling agent KH560. The components are added into a high-speed stirrer to be mixed, and the polyamide 66 resin composition is obtained.

The mass percentage of the continuous long glass fiber in the prepared continuous long glass fiber reinforced flame-retardant polyamide 66 composite material is 65%; the composite material is in the form of a unidirectional tape, and the thickness of the unidirectional tape is shown in table 1.

Comparative example 4

The procedure was carried out in the same manner as in comparative example 3, except that: continuous long carbon fibers are used in the preparation of the continuous fiber reinforced flame retardant polyamide 66 composite material.

Effect examples

The continuous fiber reinforced polyamide composite unidirectional tapes of examples 1-12 and comparative examples 1-4 were tested for performance according to the following test methods:

(2) Water absorption rate: firstly preparing a sample with the length of 60mm, the width of 60mm and the thickness of 2mm according to the standard ASTM-D570-2005, and testing for 24 hours according to a test method of the water absorption of plastics;

(2) Tensile strength: preparing sample bars with the sample size of 250mm long, 15mm wide and 1mm thick according to GB/T1040.5-2008 standard requirements for a stretching experiment;

(3) HDT test: referring to national standard GB/T1634.2-2004, a sample bar with a sample size of 120mm long, 10mm wide and 4mm thick was prepared first, and a bending stress of 1.8MPa was applied for HDT experiments.

(4) Oxygen index: according to GB/T8924-2005, a sample bar 120mm long, 6.5mm wide and 3mm thick was prepared for testing the oxygen index to evaluate flame retardant properties.

The test results are shown in Table 1.

TABLE 1

As can be seen from Table 1, example 1 is a polyamide 56 composite material containing continuous long glass fibers, having a 24-hour water absorption of 1.2% or less, a tensile strength of 850MPa or more, an HDT of 210 ℃ or more, and an oxygen index of 29% or more; example 9 polyamide 56 composite material containing continuous long carbon fiber, water absorption of 24 hours is 1.4% or less, tensile strength is 1000MPa or more, heat distortion temperature is 220 ℃ or more, and oxygen index is 31% or more.

Examples 2-8 are polyamide composites of different long carbon chains containing continuous long glass fibers, having a 24-hour water absorption of less than 0.9%, a tensile strength of greater than 850MPa, a heat distortion temperature of greater than 210 ℃, and an oxygen index of greater than 30%; examples 10 to 12 are polyamide composite materials having different long carbon chains and containing continuous long carbon fibers, wherein the water absorption rate for 24 hours is less than 0.9%, the tensile strength is more than 1000MPa, the heat distortion temperature is more than 220 ℃, and the oxygen index is more than 30%.

The PA6 composite materials of comparative example 1 and comparative example 2, which are composite continuous long glass fibers and continuous long carbon fibers, respectively, are inferior in mechanical properties to the corresponding examples having similar fiber contents.

Similarly, the PA66 composite materials of comparative examples 3 and 4, which are composite continuous long glass fibers and continuous long carbon fibers, respectively, are inferior in mechanical properties to the corresponding examples having similar fiber contents.

In the comprehensive view, the polyamide provided by the embodiment of the invention has excellent mechanical properties and good flame retardance, and the polyamide provided by the invention uses the bio-based pentylene diamine, so that the carbon content is high, and the use of fossil raw materials is effectively reduced, thereby reducing the carbon emission.

Claims

1. The flame-retardant bio-based polyamide resin composition is characterized by comprising 60-90 parts by weight of bio-based polyamide 5X resin and additives; the additive comprises 8-25 parts of flame retardant, 0.2-1.6 parts of antioxidant and 3-12 parts of compatilizer.

2. The flame retardant biobased polyamide resin composition according to claim 1, wherein said biobased polyamide 5X resin is selected from one or more of PA56 and long carbon chain biobased polyamide 5X resin, wherein said long carbon chain biobased polyamide 5X resin is a biobased polyamide 5X resin having x.gtoreq.10; the long carbon chain bio-based polyamide 5X resin is preferably selected from one or more of PA510, PA511, PA512, PA513, PA514, PA515, PA516, PA517 and PA 518;

and/or, the biobased polyamide 5X resin satisfies the following conditions: the relative viscosity is 1.8-2.7, the amino end content is 40-60mmol/kg, the melting point is 170-320 ℃, the water content is below 2000ppm, and the biobased content is 43-100%;

preferably, the biobased polyamide 5X resin is PA56, the PA56 satisfying the following properties: a relative viscosity of 1.9 to 2.5, for example 2.29; terminal amino content 42-60mmol/kg, e.g. 55mmol/kg; melting point 210-260 deg.c, preferably 253-256 deg.c; biobased content is 43% -46%, such as 45%; the water content is below 2000ppm, preferably 800-1500ppm;

preferably, the biobased polyamide 5X resin is a long carbon chain biobased polyamide 5X resin, which satisfies the following properties: relative viscosities of 2.1-2.6, e.g. 2.13, 2.25, 2.29, 2.32, 2.38, 2.51, 2.47; the terminal amino group content is 40-60mmol/kg, for example 41mmol/kg, 42mmol/kg, 47mmol/kg, 48mmol/kg, 51mmol/kg, 52mmol/kg, 54mmol/kg, 56mmol/kg; melting point 180-230deg.C, such as 191 deg.C, 192 deg.C, 205 deg.C, 209 deg.C, 210 deg.C, 217 deg.C; the content of the biological base is 43% -100%; the water content is below 2000 ppm;

And/or the biobased polyamide 5X resin is contained in an amount of 78 to 88 parts, for example 80.9 parts, 81.5 parts, 82.8 parts, 83 parts, 85 parts.

3. The flame retardant biobased polyamide resin composition according to claim 1, wherein said flame retardant comprises one or more of nitrogen-based organic flame retardant, phosphorus-based organic flame retardant and inorganic flame retardant; wherein the nitrogen-based organic flame retardant preferably comprises one or more of melamine cyanurate, melamine polyphosphate, melamine pyrophosphate, melamine phosphate, dimelamine pyrophosphate, melam polyphosphate and melem polyphosphate; the phosphorus-based organic flame retardant preferably includes an organic phosphinate flame retardant; wherein the organic phosphinate flame retardant is preferably an organic phosphinate containing an alkyl group having 1 to 4 carbon atoms, more preferably an organic phosphinate containing a methyl group and/or an ethyl group, still more preferably one or more of aluminum methylethylphosphinate, aluminum diethylphosphinate, zinc methylethylphosphinate and zinc diethylphosphinate; the inorganic flame retardant preferably includes one or more of aluminum hydroxide, magnesium hydroxide, zinc borate, red phosphorus, ammonium phosphate salts, and ammonium polyphosphate;

And/or the content of the flame retardant is 10-15 parts, for example 13 parts, 14 parts;

and/or the antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants and phosphite antioxidants; preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228;

and/or the antioxidant is present in an amount of 0.3 to 0.6 parts, for example 0.3, 0.4, 0.5 or 0.6 parts;

and/or the compatilizer is selected from one or more of polyolefin grafted maleic anhydride compatilizer, polyolefin grafted methyl ester acrylic compatilizer and rubber elastomer grafted maleic anhydride compatilizer; wherein, the polyolefin grafted maleic anhydride compatilizer is preferably PP-g-MAH or POE-g-MAH; the polyolefin grafted methyl ester acrylic compatilizer is preferably POE-g-GMA; the rubber elastomer grafted maleic anhydride type compatibilizer is preferably EPDM-g-MAH;

and/or the compatibilizing agent is present in an amount of 4-10 parts, e.g., 4, 4.2, 5, 6, 6.5, 8, or 10 parts;

and/or, the flame retardant bio-based polyamide resin composition further comprises a lubricant; wherein the lubricant preferably comprises an outer lubricant, such as WAXC, and/or an inner lubricant, such as WAXE; preferably, the lubricant is present in an amount of 0.1 to 0.8 parts, for example 0.3, 0.4 or 0.5 parts;

And/or, the flame retardant bio-based polyamide resin composition further comprises a coupling agent; wherein the coupling agent is preferably selected from one or more of silane coupling agents, carbonate coupling agents and aluminate coupling agents; more preferably a silane-based coupling agent, such as coupling agent KH550, coupling agent KH560 or coupling agent KH570; preferably, the coupling agent is used in an amount of 0.1 to 0.8 parts, for example 0.3, 0.4 or 0.5 parts.

4. A continuous fiber reinforced flame retardant bio-based polyamide composite material, characterized in that it comprises the flame retardant bio-based polyamide resin composition according to any one of claims 1 to 3 and continuous fibers, wherein the mass percentage of the continuous fibers in the continuous fiber reinforced flame retardant bio-based polyamide composite material is 50% to 90%.

5. The continuous fiber reinforced flame retardant biobased polyamide composite material of claim 4, wherein said continuous fibers comprise 60% to 90%, such as 65%,69%,70%,75%,80%,82%, 83% or 85% by mass of said continuous fiber reinforced flame retardant biobased polyamide composite material;

and/or the continuous fibers are one or more of carbon fibers, glass fibers, basalt fibers and aramid fibers;

And/or, the continuous fibers are continuous long fibers; preferably, the continuous fibers are continuous long glass fibers or continuous long carbon fibers;

and/or, the continuous fiber reinforced flame retardant bio-based polyamide composite material is in the form of a unidirectional tape;

preferably, the continuous fiber reinforced flame retardant biobased polyamide unidirectional tape has a thickness of 0.15 to 0.5mm, more preferably 0.21 to 0.36mm, for example 0.23mm,0.27mm,0.28mm,0.31mm,0.32mm, 0.33mm, 0.35mm or 0.36mm.

6. A method for preparing a continuous fiber reinforced flame retardant bio-based polyamide composite material, which comprises the following steps:

s1, extruding and granulating the flame-retardant bio-based polyamide resin composition according to any one of claims 1-3 to obtain resin slices, and dissolving the resin slices in a solvent to obtain a resin solution;

7. The method for producing a continuous fiber reinforced flame retardant biobased polyamide composite material according to claim 6, wherein in step S1, the extrusion is performed using a twin screw extruder or a single screw extruder, preferably a twin screw extruder; wherein the aspect ratio of the twin-screw extruder is preferably 1:36;

and/or, in the step S1, the extrusion temperature is 170-340 ℃;

preferably, the extrusion adopts a double-screw extruder, the double-screw extruder adopts an eight-zone heating mode, and the temperatures from one zone to eight zones are 195-250 ℃, 200-300 ℃ and 225-310 ℃ in sequence;

and/or, in step S1, the extrusion speed is 200-600r/min, such as 300r/min, 400rmin, expressed as screw speed;

and/or, in step S1, the concentration of the resin solution is 15-35%, for example 20%, 24%, 28%, 29%, 30%, 33%, the percentage being the mass percentage of the resin slice in the resin solution;

and/or in step S1, the solvent is formic acid, concentrated sulfuric acid or m-cresol, preferably formic acid;

and/or, in step S1, before the flame retardant bio-based polyamide resin composition is extruded, uniformly mixing the components of the flame retardant bio-based polyamide resin composition; wherein the mixing is preferably magnetic stirring; the mixing time is preferably 8-12 hours.

8. The method for preparing a continuous fiber reinforced flame retardant bio-based polyamide composite material according to claim 6, wherein in step S2, before the continuous fiber is drawn, the continuous fiber is subjected to the following operations: the continuous fibers are unreeled from the creel through the tension controller and enter the yarn spreading system through the yarn dividing frame, so that each silk bundle is fully spread; wherein the creel preferably adopts an externally-placed creel, and each spindle independently controls tension;

and/or, in step S2, the speed of the traction is 20-30mm/S, such as 24mm/S, 25mm/S, 26mm/S;

and/or, in step S2, the temperature of the impregnation is room temperature, preferably 25 ℃;

and/or, in step S2, the solvent removal is performed in a solvent removal channel, and the solvent is evaporated by heating in the solvent removal channel; the temperature of the solvent removal channel is preferably 90-110 ℃, e.g. 102 ℃, 105 ℃; the time for the desolvation is preferably 50 to 75s, for example 55s, 60s, 65s or 70s;

and/or, in step S2, the heating is performed in a heating channel, the heating temperature of which is preferably 200-290 ℃, such as 230 ℃, 240 ℃, 248 ℃, 250 ℃ or 278 ℃; the heating time is preferably 60 to 150s, for example 70s, 75s, 85s, 90s or 100s;

And/or, in the step S2, the rolling adopts a passive dipping roller; the roll spacing of the passive impregnation roll is preferably 0.1-0.3mm, for example 0.15mm, 0.18mm, 0.2mm, 0.22mm, 0.25mm;

and/or, in step S2, the winding is a double-station winding; the speed of the winding is the same as the speed of the pulling, preferably 20-30mm/s, for example 24mm/s, 25mm/s, 26mm/s;

and/or, in step S2, drying and forming are further included after the winding; wherein the drying temperature may be 100-150 ℃, preferably 100-120 ℃; the drying mode is preferably vacuum drying; the drying time may be 8 to 15 hours, preferably 10 to 12 hours.

9. Continuous fiber reinforced flame retardant bio-based polyamide composite material, characterized in that it is produced according to the method for producing a continuous fiber reinforced flame retardant bio-based polyamide composite material according to any one of claims 6-8.

10. Use of the continuous fiber reinforced flame retardant biobased polyamide composite material of any one of claims 4, 5 and 9 in the aerospace field, military field, automotive material, sports equipment, construction material or electronic appliances.