CN117343537A

CN117343537A - Preparation method of fiber reinforced polyamide pipe and pipe

Info

Publication number: CN117343537A
Application number: CN202210762488.6A
Authority: CN
Inventors: 王新鑫; 刘修才
Original assignee: Cathay R&D Center Co Ltd; CIBT America Inc
Current assignee: Cathay R&D Center Co Ltd; CIBT America Inc
Priority date: 2022-06-29
Filing date: 2022-06-29
Publication date: 2024-01-05

Abstract

The invention relates to a preparation method of a fiber reinforced polyamide pipe and the pipe. The fiber reinforced polyamide pipe comprises the following components in parts by weight: 30-70 parts of bio-based polyamide resin, 10-30 parts of fiber, 10-20 parts of polyolefin, 5-10 parts of flame retardant and 5-10 parts of antistatic agent; wherein the bio-based polyamide resin is formed of a pentanediamine (a) and a dicarboxylic acid component (B), the sum of (a) and (B) being 100 mol%; the dicarboxylic acid component (B) is composed of (B1) adipic acid in a molar ratio of 10 to 90 and (B2) terephthalic acid in a molar ratio of 10 to 90. The fiber reinforced polyamide pipe has excellent flame-retardant and antistatic properties, has the characteristics of high strength, good heat resistance, low water absorption, high pressure resistance and the like, and can be widely applied to the fields of building gas pipelines, underground gas pipes for coal mines and the like.

Description

Preparation method of fiber reinforced polyamide pipe and pipe

Technical Field

The invention relates to a preparation method of a fiber reinforced polyamide pipe and the pipe.

Background

A large number of industrial pipelines are needed for underground ventilation, drainage, gas drainage and the like of a coal mine, for example, a modern mine is required to be paved with hundreds of kilometers of gas drainage pipelines. The traditional steel pipe has the defects of high rigidity, mature production process, easy corrosion, high dead weight, difficult installation and transportation, high investment cost, short service life and difficult replacement. The glass fiber reinforced plastic pipe has excellent corrosion resistance, higher rigidity and smaller density, but has larger brittleness when used in a coal mine environment, and the brittleness is increased along with the increase of time and is often damaged due to aging, collision and other reasons. Plastic pipes are popular and used in many industries because of their low weight, low cost, corrosion resistance, excellent rigidity and flexibility, wear resistance, long service life, easy installation, etc. However, the underground plastic pipeline for the coal mine has severe conditions, and the gas is mixed negative pressure gas, so that internal explosion is more likely to occur, and special requirements on antistatic and flame retardant properties of the pipeline are met; the drop of the water conveying pipeline is large, the water hammer effect frequently occurs, and the safety coefficient is higher. The performances of the plastic pipes such as polyvinyl chloride, polyethylene and the like which are used at present are not easy to meet the strict technical requirements of the pipes for coal mines, and serious defects and accident potential exist.

The appearance of polyamide has great potential for replacing traditional carbon steel pipes and cement pipes in pipeline transportation. The common polyamide pipe has the characteristics of high water absorption, low strength and poor temperature resistance. Therefore, in order to make polyamide pipes suitable for more complex use occasions, the use temperature is widened, the influence of water absorption is reduced, the strength is improved, the weight is increased, and it is necessary to design and develop a pipe with high strength, high heat deformation temperature, low water absorption and high pressure resistance on the premise of meeting the antistatic and flame retardant properties.

Disclosure of Invention

In order to improve the performance of the existing polyamide pipe and widen the application prospect, the invention provides a preparation method of a fiber reinforced polyamide pipe and the pipe. According to the invention, the fiber reinforced polyamide composite material is prepared by mixing additives such as PA56T, fibers, polyolefin, flame retardant, antistatic agent and the like, and then extruding, cooling and shaping the fiber reinforced polyamide composite material, so that the pipe which can be applied to the fields of building gas pipelines, underground gas pipes for coal mines and the like is prepared, and on the premise of meeting special requirements of the pipe on antistatic property, flame retardant property and the like, the mechanical property and the heat deformation temperature of the pipe are improved, the high pressure resistance is optimized, the water absorption rate of the pipe is reduced, the overall quality is light, and the requirement of the lightweight pipe is met.

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

one of the technical proposal is as follows: the fiber reinforced polyamide pipe comprises the following components in parts by weight: 30-70 parts of bio-based polyamide resin, 10-30 parts of fiber, 10-20 parts of polyolefin, 5-10 parts of flame retardant and 5-10 parts of antistatic agent; wherein,

the bio-based polyamide resin is formed from a pentanediamine (a) and a dicarboxylic acid component (B), the sum of (a) and (B) being 100 mole%; the dicarboxylic acid component (B) is composed of (B1) adipic acid in a molar ratio of 10 to 90 and (B2) terephthalic acid in a molar ratio of 10 to 90.

In some embodiments, the dicarboxylic acid component (B) consists of (B1) 40 to 90 mole ratios of adipic acid, and (B2) 10 to 60 mole ratios of terephthalic acid. I.e. the dicarboxylic acid comprises 40 to 90 mole% adipic acid and 10 to 60 mole% terephthalic acid or derivatives of terephthalic acid, said percentages being mole percentages.

Preferably, the molar ratio of adipic acid to terephthalic acid is 1: (0.1-1.5), for example, may be 1: (0.35-0.55), e.g. 1:0.45;1: (0.55-0.85), e.g. 1:0.72; or 1: (0.85-1.2), e.g., 1:1.05.

In some specific embodiments, the molar ratio between the pentanediamine (a) and the dicarboxylic acid component (B) is (1-1.05): 1, for example 1.05:1.

In some specific embodiments, the method of preparing the bio-based polyamide resin comprises the steps of: the preparation method comprises the steps of preparing a polyamide salt solution from pentanediamine, dicarboxylic acid and water, and heating and polymerizing the polyamide salt solution to obtain the bio-based polyamide resin.

Specifically, the preparation method of the bio-based polyamide resin comprises the following steps: (1) Mixing water, pentanediamine and terephthalic acid or derivatives of terephthalic acid and adipic acid under nitrogen or inert gas atmosphere to prepare polyamide salt water solution with the concentration of 30-75wt%; (2) Transferring the aqueous solution of the polyamide salt into a polymerization device (such as a polymerization kettle), heating under nitrogen or inert gas atmosphere, raising the temperature in a reaction system to 230-310 ℃, raising the pressure to 0.7-2.5MPa, and keeping for 60-180 minutes; then exhausting and reducing the pressure to normal pressure within 30-120 minutes, and simultaneously raising the temperature to 260-340 ℃; vacuumizing to reduce the pressure to- (0.02-0.08) MPa, and maintaining for 30-120 minutes to obtain a melt; (3) And (3) carrying out bracing and granulating on the melt to obtain the bio-based polyamide resin PA56T.

In some embodiments, the bio-based polyamide resin has a melting point of 260 to 330 ℃, preferably 270 to 300 ℃.

In some specific embodiments, the biobased polyamide resin has a relative viscosity of 2.0 to 3.2. The relative viscosity was determined by the Ubbelohde viscometer method with concentrated sulfuric acid (96% concentration).

In some specific embodiments, the bio-based polyamide resin has a number average molecular weight of 2 to 7 tens of thousands, further 3 to 6 tens of thousands.

In some specific embodiments, the biobased polyamide resin has a water content of 500 to 2000ppm. The water content can be reduced by drying.

In some specific embodiments, the biobased polyamide resin is present in an amount of 30 to 50 parts, for example 35 parts, 40, 45 parts, 50 parts.

In some embodiments, the type of fiber is carbon fiber, glass fiber, basalt fiber, or aramid fiber.

In some embodiments, the fibers are glass fibers; glass fibers are conventional in the art, preferably having a filament diameter of 5-15um and a length of 0.5-5mm, such as ECS10-4.5-T435N available from Taishan glass fibers, and a fiber filament diameter of 10um and a length of 4.5mm.

In some embodiments, the fibers are carbon fibers; carbon fibers are conventional in the art, preferably having a filament diameter of 5-10 μm and a length of 0.5-6mm, such as DSC-4mm available from Kaben Van composite, germany, with a fiber filament diameter of 8 μm and a length of 4mm.

In some embodiments, the fibers are preferably present in an amount of 15 to 30 parts, for example 20 parts, 25 parts, 30 parts.

In some embodiments, the polyolefin is selected from one or more of polyethylene, polypropylene, polybutylene. The polyethylene is conventional in the art, for example polyethylene PE100S available from giline petrochemicals. The polypropylene may be conventional in the art, for example polypropylene PP212E available from northern european chemical industry.

In some embodiments, the flame retardant comprises one or a combination of several of nitrogen-based organic flame retardants, phosphorus-based organic flame retardants, halogen-based organic flame retardants, and inorganic flame retardants.

In some specific embodiments, the nitrogen-based organic flame retardant includes one or more of melamine cyanurate, melamine polyphosphate, melamine pyrophosphate, melamine phosphate, dimelamine pyrophosphate, melam polyphosphate, and melem polyphosphate.

In some embodiments, the phosphorus-based organic flame retardant is 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.

In some embodiments, the halogenated organic flame retardant includes, but is not limited to, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, and combinations of bromine-based flame retardants and antimony trioxide.

In some specific embodiments, the inorganic flame retardant comprises one or more of aluminum hydroxide, magnesium hydroxide, zinc borate, red phosphorus, ammonium phosphate salts, and ammonium polyphosphate.

According to a preferred embodiment of the present invention, the flame retardant is at least one selected from the group consisting of aluminum methylethylphosphinate, aluminum diethylphosphinate, brominated polyphenylene oxide, red phosphorus.

In some embodiments, the antistatic agent comprises one or a combination of several of conductive carbon black, carbon nanotubes, carbon fibers, anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents.

In some specific embodiments, the anionic antistatic agent includes, but is not limited to, at least one of alkyl sulfonates, alkyl sulfates, alkyl phosphates, alkylphenol ethoxylate sulfates.

In some specific embodiments, the cationic antistatic agent includes, but is not limited to: at least one of (lauramidopropyl trimethyl ammonium) methyl sulfate, N-bis (2-hydroxyethyl) -N- (3 '-dodecyloxy-2' -hydroxypropyl) methyl ammonium methyl sulfate, tris hydroxyethyl methyl quaternary ammonium methyl sulfate, and N, N-hexadecylethyl morpholine ethyl sulfate.

In some specific embodiments, the nonionic antistatic agent includes, but is not limited to, at least one of polyoxyethylene sorbitan monostearate, polyethylene glycol esters, polyol fatty acid esters, fatty acid alkanolamides, fatty amine ethoxy ethers.

In some specific embodiments, the amphoteric antistatic agent includes, but is not limited to, at least one of an inner quaternary ammonium carboxylate, an imidazolinium metal salt.

According to a preferred embodiment of the present invention, the antistatic agent is selected from at least one of carbon fiber, conductive carbon black, carbon nanotube, methyl quaternary ammonium tris-hydroxyethyl methyl sulfate salt, methyl sulfate salt of (lauramidopropyl trimethyl ammonium).

In some embodiments, the fiber reinforced polyamide tubing further comprises other additives selected from at least one of antioxidants, compatibilizers, mold release agents, color concentrates, coupling agents, and anti-falling agents.

In some embodiments, the antioxidant may be selected from one or more of hindered phenolic antioxidants, hindered aminic antioxidants, and phosphite antioxidants. Wherein the hindered phenolic antioxidant may be conventional in the art, such as antioxidant 1010. The hindered amine antioxidant may be conventional in the art, such as antioxidant 1098 (CAS 23128-74-7). The phosphite antioxidants may be conventional in the art, such as antioxidant 168 (CAS 31570-04-4), antioxidant S9228.

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

In the present invention, the content of the antioxidant is preferably 0.1 to 1 part, further 0.2 to 1 part, still further 0.2 to 0.5 part, for example 0.2 part.

In some embodiments, 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 compatibilizing agent, and a rubber elastomer grafted maleic anhydride-based compatibilizing agent. Wherein the polyolefin grafted maleic anhydride-based compatibilizer may be conventional in the art, such as PP-g-MAH or POE-g-MAH. The polyolefin grafted methyl ester acrylic compatibilizer may be conventional in the art, such as POE-g-GMA. The rubber elastomer grafted maleic anhydride-based compatibilizer may be conventional in the art, such as EPDM-g-MAH. For example, the compatibilizing agent may also be a polystyrene-maleic anhydride copolymer, a polystyrene glycidyl acrylate copolymer, a styrene and glycidyl methacrylate copolymer, a polystyrene-maleimide copolymer, a hydrogenated styrene-isoprene copolymer grafted maleic anhydride, or the like; and may be a polyfunctional epoxy resin or the like.

In the present invention, the content of the compatibilizing agent is preferably 5 to 10 parts, further 5 to 8 parts, for example 5 parts.

In some embodiments, the mold release agent may be selected from one or more of oleamide, erucamide.

In the present invention, the content of the release agent is preferably 0.2 to 1 part, further 0.2 to 0.8 part, for example 0.2 part.

In some embodiments, the color master batch is selected from one of a black master batch and a yellow master batch. The masterbatch is conventional in the art, for example, a PA3785 black masterbatch available from cabot.

In the present invention, the content of the masterbatch is preferably 0 to 5 parts, further 1 to 3 parts, for example 2 parts.

In some specific embodiments, the coupling agent is selected from one or more of a silane-based coupling agent, a carbonate-based coupling agent, and an aluminate-based coupling agent; preferably a silane-based coupling agent, such as coupling agent KH550, KH560 or KH570 available from Nanjing Nandina chemical Co., ltd.

In the present invention, the content of the coupling agent is preferably 0.1 to 1 part, further 0.2 to 0.8 part, for example, 0.6 part.

In some specific embodiments, the anti-drip agent is selected from polytetrafluoroethylene anti-drip agents. The anti-drip agent is conventional in the art, for example, flntech FT-1-10 anti-drip agent available from New Material technology Co., ltd.

In the present invention, the content of the anti-dripping agent is preferably 1 to 5 parts, further 1 to 3 parts, for example 2 parts.

In some embodiments, the fiber reinforced polyamide tubing comprises glass fibers having a flexural strength of 180 to 300MPa, preferably 200 to 280MPa, a; the Heat Distortion Temperature (HDT) is 180-280 ℃, preferably 200-260 ℃; the longitudinal retraction rate is 0.1-0.4%, preferably 0.1-0.3%; the water absorption is 0.3-0.8%, preferably 0.3-0.6%; an oxygen index of 28 to 35, preferably 30 to 34; surface resistance of 10 ⁶ -10 ⁸ Ω。

In some embodiments, the fiber reinforced polyamide tubing comprises carbon fibers having a flexural strength of 200 to 300MPa, preferably 250 to 300MPa; the Heat Distortion Temperature (HDT) is 200-300 ℃, preferably 230-280 ℃; the longitudinal retraction rate is 0.1-0.3%, preferably 0.1-0.2%; the water absorption is 0.3-0.6%, preferably 0.3-0.45%; an oxygen index of 30 to 35, preferably 32 to 34; surface resistance of 10 ⁶ -10 ⁸ Ω。

The second technical scheme is as follows: a method for preparing a fiber reinforced polyamide tubing, the method comprising the steps of:

s1, mixing a bio-based polyamide resin, polyolefin, a flame retardant, an antistatic agent and other additives to obtain a premix;

S2, carrying out melt extrusion, cooling and granulating on the premix and the fibers to obtain a fiber reinforced polyamide composite material;

and S3, extruding the fiber reinforced polyamide composite material, cooling and shaping, and cutting the pipe according to a preset size.

In some specific embodiments, in step S2, the melt extrusion may be performed using a twin screw extruder or a single screw extruder, preferably a twin screw extruder.

In some specific embodiments, the twin screw extruder employs a five zone heating mode, preferably, a first zone temperature of 220-270 ℃, a second zone temperature of 240-290 ℃, a third zone temperature of 280-310 ℃, a fourth zone temperature of 290-320 ℃, and a fifth zone temperature of 290-320 ℃; for example, the processing temperatures from zone 1 to zone 5 are 250 ℃, 280 ℃, 300 ℃, 310 ℃ in this order.

In some embodiments, the twin screw extruder has a head temperature of 270-315 ℃.

In some embodiments, the twin screw extruder has a screw speed of 300 to 500r/min.

In the invention, the premix is fed into the twin-screw extruder through the main feeding port, and the fibers are fed into the twin-screw extruder through the side feeding port. The invention adjusts the feeding rate to adjust the adding amount of the fiber.

In some embodiments, the twin screw extruder has a main feed speed of 10 to 100r/min; the side feeding rotating speed of the double-screw extruder is 1-100r/min.

In some specific embodiments, the twin screw extruder has an aspect ratio of (30-50): 1, preferably 36:1.

in some embodiments, the cooling uses water cooling, with the water temperature being controlled to be 10-40 ℃.

In some embodiments, the pelletizer may be a pelletizer commonly used in the art.

In some specific embodiments, in step S2, the fiber-reinforced polyamide composite material is in the form of particles having a length of 3-5mm, for example 4mm; the particle diameter is 0.5-1mm, for example 1mm.

The invention also comprises the steps of drying the prepared composite material and then sealing and preserving. The drying step may be a drying operation conventional in the art, such as vacuum drying. The drying temperature is preferably 100-120 ℃. The drying time is preferably 10 to 15 hours.

In some specific embodiments, in step S3, the extrusion molding may employ a pipe extruder.

In some specific embodiments, in step S3, the processing temperature is 270-300 ℃ and the die temperature is 260-290 ℃; vacuum setting is adopted, and the vacuum degree is between-0.02 and-0.05 MPa.

In some specific embodiments, in step S3, the cooling is performed using water, and the water temperature is controlled to be 10-40 ℃.

On the basis of conforming to the common knowledge in the field, the above 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.

Compared with the prior art, the invention has the positive progress effects that:

1. the fiber reinforced polyamide pipe adopts the bio-based polyamide as the raw material, and the monomer pentanediamine in the raw material is prepared by biological fermentation, so that the bio-based content is high, the concept of sustainable development of material sources is met, the use of fossil raw materials is effectively reduced, and the carbon emission is reduced.

2. According to the fiber reinforced polyamide pipe, the PA56T, the glass fiber, the polyolefin, the flame retardant, the antistatic agent and other additives are mixed, and the pipe prepared by the synergistic effect of the components further improves the mechanical property and the heat deformation temperature of the pipe on the premise of improving the antistatic and flame retardant properties, reduces the water absorption rate of the pipe, and can be widely applied to the fields of building gas pipelines, underground gas pipes for coal mines and the like.

3. The invention adopts cheap fiber to modify, on one hand, the cost can be reduced, on the other hand, the mechanical strength of nylon can be enhanced, and the water absorption of nylon can be reduced, so that the nylon can be developed and applied in the light-weight field.

4. The fiber reinforced polyamide pipe provided by the invention adopts an extrusion process, can be continuously produced, and has the characteristics of rapid molding and high efficiency.

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 which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.

In the following examples and comparative examples: ECS10-4.5-T435N of glass fiber purchased from Taishan glass fiber, and having a diameter of 10um and a length of 4.5mm; carbon fiber was purchased from Kaben Van composite Co., ltd. DSC-4mm, with a diameter of 8 μm and a length of 4mm; flame retardants are available from Lanyan chemical Co., ltd; the antistatic agent is purchased from Zibolxin; the coupling agent is purchased from Nanjing LongTian latitude chemical industry Co., ltd; anti-drip agents were purchased from Huangshan Australian New Material technologies Co., ltd; polyethylene PE100S was purchased from giline petrochemical; polypropylene PP212E was purchased from Nordic chemical industry; antioxidants were purchased from basf group, germany; the compatibilizing agent is available from Shanghai good compatible polymers limited; mold release agents were purchased from acksu corporation, usa; color master batches were purchased from cabot corporation. Other raw materials are commercially available unless otherwise specified.

Biobased polyamide a: the preparation method comprises the following steps: (1) Mixing water, pentanediamine and dicarboxylic acid (adipic acid and terephthalic acid in a molar ratio of 1:0.45) under nitrogen atmosphere to obtain a polyamide salt aqueous solution with a concentration of 65 wt%; the molar ratio of the pentanediamine to the dicarboxylic acid is 1.05:1, a step of; (2) Transferring the aqueous solution of the polyamide salt into a polymerization kettle, heating the aqueous solution of the polyamide salt in a nitrogen atmosphere, raising the temperature in the kettle to 290 ℃, raising the pressure in a polymerization device to 1.6MPa, and keeping the temperature for 110 minutes; then exhausting and reducing the pressure to normal pressure within 85 minutes, and simultaneously raising the temperature in the polymerization device to 300 ℃; vacuum pumping to reduce the pressure to-0.05 MPa, maintaining for 60 min to obtain melt, and strand granulating to obtain bio-based polyamide resin PA56T-A (relative viscosity 2.45, number average molecular weight 6 ten thousand, melting point 270 ℃, and water content 800ppm after drying).

Biobased copolyamide B: the preparation method comprises the following steps: (1) Mixing water, pentanediamine and dicarboxylic acid (adipic acid and terephthalic acid in a molar ratio of 1:0.72) under nitrogen atmosphere to obtain a polyamide salt aqueous solution with a concentration of 65 wt%; the molar ratio of the pentanediamine to the dicarboxylic acid is 1.05:1, a step of; (2) Transferring the aqueous solution of the polyamide salt into a polymerization kettle, heating the aqueous solution of the polyamide salt in a nitrogen atmosphere, raising the temperature in the kettle to 290 ℃, raising the pressure in a polymerization device to 1.6MPa, and keeping the temperature for 110 minutes; then exhausting and reducing the pressure to normal pressure within 85 minutes, and simultaneously raising the temperature in the polymerization device to 300 ℃; vacuum pumping to reduce the pressure to-0.05 MPa, maintaining for 60 min to obtain melt, and strand granulating to obtain bio-based polyamide resin PA56T-B (relative viscosity 2.31, number average molecular weight 4 ten thousand, melting point 290 deg.C, and water content 800ppm after drying).

Biobased copolyamide C: the preparation method comprises the following steps: (1) Mixing water, pentanediamine and dicarboxylic acid (adipic acid and terephthalic acid in a molar ratio of 1:1.05) under nitrogen atmosphere to obtain a polyamide salt aqueous solution with a concentration of 65 wt%; the molar ratio of the pentanediamine to the dicarboxylic acid is 1.05:1, a step of; (2) Transferring the aqueous solution of the polyamide salt into a polymerization kettle, heating the aqueous solution of the polyamide salt in a nitrogen atmosphere, raising the temperature in the kettle to 290 ℃, raising the pressure in a polymerization device to 1.6MPa, and keeping the temperature for 110 minutes; then exhausting and reducing the pressure to normal pressure within 85 minutes, and simultaneously raising the temperature in the polymerization device to 300 ℃; vacuum pumping to reduce the pressure to-0.05 MPa, maintaining for 60 min to obtain melt, and strand granulating to obtain bio-based polyamide resin PA56T-C (relative viscosity 2.24, number average molecular weight 3 ten thousand, melting point 300 deg.C, and water content 800ppm after drying).

Example 1

S1, mixing 45 parts of bio-based polyamide resin PA56T-A, 5 parts of flame retardant melamine cyanurate, 5 parts of antistatic agent polyethylene glycol ester, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant S9228 to obtain a premix.

S2, putting the premix into a double-screw extruder through a main feeding port, simultaneously adding 15 parts of glass fibers into the double-screw extruder through a side feeding port, and obtaining fiber reinforced polyamide particles with the length of 4mm through melt extrusion, cooling and granulating.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 305 ℃, 310 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 30r/min; the rotation speed of the side feeding is 10r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 40 ℃.

And drying the obtained fiber reinforced polyamide particles in a vacuum drying oven at 110 ℃ for 15 hours, and then sealing and preserving.

S3, adding the fiber reinforced polyamide particles into a pipe extruder for extrusion molding, wherein the processing temperature is 300 ℃, the die temperature is 290 ℃, the pipe is obtained after water cooling shaping, the water temperature is controlled to be 30 ℃, and the vacuum shaping is adopted, so that the vacuum degree is-0.05 MPa.

Example 2

S1, mixing 45 parts of bio-based polyamide resin PA56T-B, 5 parts of flame retardant melamine cyanurate, 5 parts of antistatic agent polyethylene glycol ester, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant S9228 to obtain a premix.

S3 procedure is as in example 1.

Example 3

S1, mixing 45 parts of bio-based polyamide resin PA56T-C, 5 parts of flame retardant melamine cyanurate, 5 parts of antistatic agent polyethylene glycol ester, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant S9228 to obtain a premix.

S3 procedure is as in example 1.

Example 4

S1, mixing 40 parts of bio-based polyamide resin PA56T-C, 10 parts of flame retardant brominated epoxy resin, 5 parts of antistatic agent alkylphenol ethoxylate sulfate, 0.6 part of coupling agent KH550, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant S9228 to obtain a premix;

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 280 ℃, 295 ℃, 305 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 450r/min; the main feeding rotating speed is 45r/min; the rotation speed of the side feeding is 15r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Example 5

S1, mixing 40 parts of bio-based polyamide resin PA56T-C, 5 parts of flame retardant brominated polystyrene, 10 parts of antistatic agent conductive carbon black HG1B, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polyethylene PE100S, 10 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 1098 to obtain a premix.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 280 ℃, 300 ℃, 305 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 350r/min; the main feeding rotating speed is 35r/min; the rotation speed of the side feeding is 12r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Example 6

S1, mixing 40 parts of bio-based polyamide resin PA56T-C, 10 parts of flame retardant red phosphorus, 10 parts of antistatic agent N, N-hexadecyl ethyl morpholine ethyl sulfate salt, 0.6 part of coupling agent KH550, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polypropylene PP212E, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 9228 to obtain a premix.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 300 ℃, 310 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 300r/min; the main feeding rotating speed is 30r/min; the rotation speed of the side feeding is 9r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Example 7

S1, mixing 40 parts of bio-based polyamide resin PA56T-C, 10 parts of flame retardant diethyl phosphinate aluminum, 5 parts of antistatic agent (lauramidopropyl trimethyl ammonium) methyl sulfate, 0.6 part of coupling agent KH550, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polypropylene PP212E, 5 parts of compatilizer PP-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 9228 to obtain a premix;

S2, putting the premix into a double-screw extruder through a main feeding port, simultaneously adding 20 parts of glass fibers into the double-screw extruder through a side feeding port, and obtaining fiber reinforced polyamide particles with the length of 4mm through melt extrusion, cooling and granulating.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 305 ℃, 310 ℃ and 315 ℃ in sequence; the temperature of the machine head is 305 ℃; the rotating speed of the screw is 450r/min; the main feeding rotating speed is 45r/min; the rotation speed of the side feeding is 16r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Example 8

S1, mixing 35 parts of bio-based polyamide resin PA56T-C, 5 parts of flame retardant methyl ethyl phosphinate aluminum, 10 parts of antistatic agent carbon nano tube, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polypropylene PP212E, 5 parts of compatilizer PP-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 9228 to obtain a premix.

S2, putting the premix into a double-screw extruder through a main feeding port, simultaneously adding 25 parts of glass fibers into the double-screw extruder through a side feeding port, and obtaining fiber reinforced polyamide particles with the length of 4mm through melt extrusion, cooling and granulating.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 295 ℃, 305 ℃ and 300 ℃ in sequence; the temperature of the machine head is 290 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 40r/min; the rotation speed of the side feeding is 17r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

And (3) preparing the fiber reinforced polyamide particles obtained in the above way, drying the fiber reinforced polyamide particles in a vacuum drying oven at 110 ℃ for 15 hours, and then sealing and preserving the fiber reinforced polyamide particles.

S3 procedure is as in example 1.

Example 9

S1, 45 parts of bio-based polyamide resin PA56T-C, 10 parts of flame retardant methyl ethyl phosphinate aluminum, 5 parts of antistatic agent alkylphenol ethoxylate sulfate, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polypropylene PP212E, 5 parts of compatilizer PP-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 9228 are mixed to obtain a premix.

S2, putting the premix into a double-screw extruder through a main feeding port, simultaneously adding 15 parts of carbon fibers into the double-screw extruder through a side feeding port, and obtaining fiber reinforced polyamide particles with the length of 4mm through melt extrusion, cooling and granulating.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 290 ℃, 300 ℃ and 305 ℃ in sequence; the temperature of the machine head is 290 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 40r/min; the rotation speed of the side feeding is 17r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Example 10

S1, mixing 35 parts of bio-based polyamide resin PA56T-C, 10 parts of flame retardant methyl ethyl phosphinate aluminum, 5 parts of antistatic agent alkylphenol ethoxylate sulfate, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polypropylene PP212E, 5 parts of compatilizer PP-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 9228 to obtain a premix.

S2, putting the premix into a double-screw extruder through a main feeding port, simultaneously adding 25 parts of carbon fibers into the double-screw extruder through a side feeding port, and obtaining fiber reinforced polyamide particles with the length of 4mm through melt extrusion, cooling and granulating.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 290 ℃, 300 ℃ and 305 ℃ in sequence; the temperature of the machine head is 290 ℃; the rotating speed of the screw rod is 370r/min; the main feeding rotating speed is 35r/min; the rotation speed of the side feeding is 17r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Comparative example 1

S1, 55 parts of bio-based polyamide resin PA56T-C, 0.6 part of coupling agent KH560, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant S9228 are mixed to obtain a premix.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 to the machine head is 250 ℃, 285 ℃, 305 ℃, 310 ℃ and 315 ℃ in sequence; the temperature of the machine head is 305 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 30r/min; the rotation speed of the side feeding is 12r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Comparative example 2

S1, 45 parts of bio-based polyamide resin PA56T-C, 10 parts of flame retardant diethyl phosphinate aluminum, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 15 parts of polyethylene PE100S, 10 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 1098 are mixed to obtain a premix.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 295 ℃, 310 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 30r/min; the rotation speed of the side feeding is 10r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Comparative example 3

S1, mixing 45 parts of bio-based polyamide resin PA56T-C, 0.6 part of coupling agent KH560, 10 parts of antistatic agent conductive carbon black HG1B, 15 parts of polyethylene PE100S, 10 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant 1098 to obtain a premix;

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 285 ℃, 290 ℃, 305 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 35r/min; the rotation speed of the side feeding is 13r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Comparative example 4

S1, 45 parts of polyamide PA6 (from Sanchida, viscosity 2.3, terminal amino content 54mmol/kg, melting point 223 ℃), 5 parts of melamine cyanurate, 5 parts of antistatic polyethylene glycol ester, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 parts of erucamide and 0.2 part of antioxidant S9228 are mixed to obtain a premix.

In the step S2, a double-screw extruder can be adopted for melt extrusion, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 230 ℃, 245 ℃, 260 ℃, 270 ℃ and 275 ℃ in sequence; the temperature of the machine head is 250 ℃; the rotating speed of the screw is 300r/min; the main feeding rotating speed is 30r/min; the rotation speed of the side feeding is 8r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Comparative example 5

S1, 45 parts of polyamide PA66 (from DuPont, viscosity 2.6, terminal amino content 48mmol/kg, melting point 255 ℃), 5 parts of melamine cyanurate as flame retardant, 5 parts of antistatic polyethylene glycol ester, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 parts of erucamide and 0.2 part of antioxidant S9228 are mixed to obtain a premix.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature of the zones 1 to 5 is 240 ℃, 275 ℃, 285 ℃, 290 ℃ and 290 ℃ in sequence; the temperature of the machine head is 270 ℃; the rotating speed of the screw is 400r/min; the main feeding rotating speed is 40r/min; the rotation speed of the side feeding is 10r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 30 ℃.

S3 procedure is as in example 1.

Comparative example 6

S1, 60 parts of bio-based polyamide resin PA56T-C, 3 parts of flame retardant melamine cyanurate, 2 parts of antistatic agent polyethylene glycol ester, 0.6 part of coupling agent KH560, 2 parts of anti-dripping agent Flntech FT-1-10, 20 parts of polyethylene PE100S, 5 parts of compatilizer POE-g-MAH, 2 parts of black master batch (PA 3785), 0.2 part of erucamide and 0.2 part of antioxidant S9228 are mixed to obtain a premix.

S2, putting the premix into a double-screw extruder through a main feeding port, simultaneously adding 5 parts of glass fibers into the double-screw extruder through a side feeding port, and obtaining fiber reinforced polyamide particles with the length of 4mm through melt extrusion, cooling and granulating.

In the step S2, a double-screw extruder can be adopted, the double-screw extruder adopts a five-zone heating mode, and the processing temperature from zone 1 to zone 5 is 250 ℃, 280 ℃, 300 ℃, 310 ℃ and 310 ℃ in sequence; the temperature of the machine head is 300 ℃; the rotating speed of the screw is 450r/min; the main feeding rotating speed is 30r/min; the rotation speed of the side feeding is 10r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the cooling was performed using water cooling, the water temperature being controlled at 40 ℃.

And drying the obtained fiber reinforced polyamide particles in a vacuum drying oven at 110 ℃ for 17 hours, and then sealing and preserving.

S3 procedure is as in example 1.

The pipes prepared in examples 1 to 10 and comparative examples 1 to 6 were subjected to performance test according to the following test methods, and the results are shown in Table 1:

(1) Preparing sample bars with the sample size of 80mm long, 10mm wide and 4mm thick according to the GB/T2406.1-2008 standard requirements and measuring oxygen indexes;

(2) Preparing a sheet with a sample size of 100mm long, 100mm wide and 2mm thick according to the GB/T31838.3-2019 standard requirements and testing the surface resistance;

(3) Injection molding is carried out according to the ISO-178-2010 standard to obtain sample bars with the sample size of 80mm long, 10mm wide and 4mm thick, and the sample bars are used for bending experiments;

(4) Referring to national standard GB/T1634.2-2004, firstly preparing a spline with the sample size of 80mm long, 10mm wide and 4mm thick, and applying a bending stress of 1.8MPa for HDT experiments;

(5) Preparing a composite board with the thickness of 0.2mm by injection molding, preparing a water absorbing board with the length of 60mm, the width of 60mm and the thickness of 2mm by referring to a standard ASTM-D570-2005, and testing according to a test method of the water absorption rate of plastics, wherein the test time is 24 hours;

(6) Intercepting a 200mm pipe section according to the GB/T6671-2001 standard requirement for measuring the longitudinal retraction rate;

(7) And measuring the high-temperature internal pressure resistance according to the GB/T6111-2018 standard.

TABLE 1

As shown in Table 1, the fiber reinforced polyamide tubing of the invention has better flame retardant and antistatic properties, and simultaneously has obviously improved mechanical properties, high temperature resistance, water absorption, high temperature internal pressure resistance and the like compared with the corresponding properties of the fiber reinforced polyamide tubing obtained based on PA6 or PA 66.

The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.

Claims

1. The fiber reinforced polyamide pipe is characterized by comprising the following components in parts by weight: 30-70 parts of bio-based polyamide resin, 10-30 parts of fiber, 10-20 parts of polyolefin, 5-10 parts of flame retardant and 5-10 parts of antistatic agent; wherein,

2. The fiber reinforced polyamide tubing of claim 1 wherein said dicarboxylic acid component (B) consists of (B1) 40 to 90 mole ratio of adipic acid, and (B2) 10 to 60 mole ratio of terephthalic acid;

preferably, the molar ratio of adipic acid to terephthalic acid is 1: (0.1-1.5);

and/or the molar ratio between the pentanediamine (a) and the dicarboxylic acid component (B) is (1-1.05): 1.

3. fiber reinforced polyamide tubing according to claim 1 or 2, characterized in that the bio-based polyamide resin has a melting point of 260-330 ℃, preferably 270-300 ℃; and/or

The relative viscosity of the bio-based polyamide resin is 2.0-3.2; and/or

The number average molecular weight of the bio-based polyamide resin is 2-7 ten thousand, and further 3-6 ten thousand; and/or

The water content of the bio-based polyamide resin is 500-2000 ppm; and/or

The content of the bio-based polyamide resin is 30-50 parts.

4. A fibre reinforced polyamide tubing as claimed in any one of claims 1-3, wherein the type of fibres is carbon fibres, glass fibres, basalt fibres or aramid fibres;

preferably, the fibers are glass fibers; the diameter of the monofilament of the glass fiber is 5-15um, and the length is 0.5-5mm;

Preferably, the fiber is a carbon fiber, and the diameter of a monofilament of the carbon fiber is 5-10 mu m, and the length of the monofilament is 0.5-6mm;

and/or the content of the fiber is preferably 15-30 parts;

and/or the polyolefin is selected from one or more of polyethylene, polypropylene and polybutylene.

5. The fiber reinforced polyamide tubing of any of claims 1-4, wherein the flame retardant comprises one or a combination of several of a nitrogen-based organic flame retardant, a phosphorus-based organic flame retardant, a halogen-based organic flame retardant, and an inorganic flame retardant;

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

preferably, the phosphorus-based organic flame retardant is 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;

preferably, the halogen-based organic flame retardant includes, but is not limited to, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, and a combination of a bromine-based flame retardant and antimony trioxide;

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

6. The fiber reinforced polyamide tubing of any of claims 1-5, wherein the antistatic agent comprises one or a combination of several of conductive carbon black, carbon nanotubes, carbon fibers, anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents;

preferably, the anionic antistatic agent comprises at least one of alkyl sulfonate, alkyl sulfate, alkyl phosphate and alkylphenol polyoxyethylene sulfate;

preferably, the cationic antistatic agent includes, but is not limited to: at least one of methyl (lauramidopropyl trimethylammonium) sulfate, methyl (N, N-bis (2-hydroxyethyl) -N- (3 '-dodecyloxy-2' -hydroxypropyl) methylammonium sulfate, methyl (tri) hydroxyethyl methyl quaternary ammonium sulfate, ethyl (N, N-hexadecylethyl) morpholine sulfate;

preferably, the nonionic antistatic agent comprises at least one of polyoxyethylene sorbitan monostearate, polyethylene glycol ester, polyol fatty acid ester, fatty acid alkanolamide and fatty amine ethoxy ether;

Preferably, the amphoteric antistatic agent includes, but is not limited to, at least one of quaternary ammonium carboxylic acid inner salts, imidazoline metal salts.

7. The fiber reinforced polyamide tubing of any one of claims 1-6, further comprising other additives selected from at least one of antioxidants, compatibilizers, mold release agents, color concentrates, coupling agents, and anti-falling agents;

further, 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;

and/or the antioxidant content is preferably 0.1 to 1 part, further 0.2 to 1 part, still further 0.2 to 0.5 part;

and/or the compatilizer can be selected from one or more of polyolefin grafted maleic anhydride compatilizer, polyolefin grafted methyl ester acrylic compatilizer and rubber elastomer grafted maleic anhydride compatilizer;

and/or the content of the compatilizer is preferably 5-10 parts, and further 5-8 parts;

And/or the release agent can be selected from one or more of oleamide and erucamide;

and/or the content of the release agent is preferably 0.2 to 1 part, further 0.2 to 0.8 part;

and/or the color master batch is selected from one of black master batch and yellow master batch;

and/or the content of the color master batch is preferably 0-5 parts, and further 1-3 parts;

and/or the coupling agent is 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;

and/or the content of the coupling agent is preferably 0.1 to 1 part, further 0.2 to 0.8 part;

and/or the anti-drip agent is selected from polytetrafluoroethylene anti-drip agents;

and/or the content of the anti-dripping agent is preferably 1 to 5 parts, further 1 to 3 parts.

8. Fiber reinforcement according to any of claims 1-7Polyamide tubing, characterized in that the fiber reinforced polyamide tubing comprises glass fibers with a flexural strength of 180-300MPa, preferably 200-280MPa; the Heat Distortion Temperature (HDT) is 180-280 ℃, preferably 200-260 ℃; the longitudinal retraction rate is 0.1-0.4%, preferably 0.1-0.3%; the water absorption is 0.3-0.8%, preferably 0.3-0.6%; an oxygen index of 28 to 35, preferably 30 to 34; surface resistance of 10 ⁶ -10 ⁸ Ω；

And/or the fiber reinforced polyamide tubing comprises carbon fibers with a flexural strength of 200-300MPa, preferably 250-300MPa; the Heat Distortion Temperature (HDT) is 200-300 ℃, preferably 230-280 ℃; the longitudinal retraction rate is 0.1-0.3%, preferably 0.1-0.2%; the water absorption is 0.3-0.6%, preferably 0.3-0.45%; an oxygen index of 30 to 35, preferably 32 to 34; surface resistance of 10 ⁶ -10 ⁸ Ω。

9. A method for preparing a fiber reinforced polyamide tubing, the method comprising the steps of:

s1 mixing a biobased polyamide resin as defined in any one of claims 1 to 8, a polyolefin, a flame retardant, an antistatic agent and other additives to obtain a premix;

10. The method for producing a fiber reinforced polyamide tubing according to claim 9, wherein in step S2, the melt extrusion is performed using a twin screw extruder or a single screw extruder, preferably a twin screw extruder, and/or,

The twin-screw extruder adopts a five-zone heating mode, preferably, the temperature of the first zone is 220-270 ℃, the temperature of the second zone is 240-290 ℃, the temperature of the third zone is 280-310 ℃, the temperature of the fourth zone is 290-320 ℃, and the temperature of the fifth zone is 290-320 ℃;

and/or the temperature of the head of the double-screw extruder is 270-315 ℃;

and/or the screw speed of the double-screw extruder is 300-500r/min;

and/or the length-diameter ratio of the double screw extruder is (30-50): 1, preferably 36:1, a step of;

and/or cooling by using water, wherein the temperature of the water is controlled to be 10-40 ℃;

and/or, the pelletizer may be used as is commonly used in the art;

and/or, in step S2, the glass fiber reinforced polyamide composite material is in the shape of particles, and the particle length is 3-5mm, for example 4mm; the particle diameter is 0.5-1mm, for example 1mm.