Conductive polyamide elastomer and method for producing the same

Abstract

This invention belongs to the field of conductive elastomer fiber technology, specifically relating to a conductive polyamide elastomer and its preparation method. The raw materials for preparing the conductive polyamide elastomer provided by this invention include a hard-segment polymer, a soft-segment polymer, a conductive component, and additives. The hard-segment polymer is polydodecanoic acid decylamine, with carboxyl groups at the end groups. The soft-segment polymer includes aromatic ether diamines with the structure shown in Formula 1 and terminal amino ether diamines with the structure shown in Formula 2. The conductive component includes conductive fillers and / or conductive conjugated monomers. The conductive fillers include one or more of carbon black, carbon nanotubes, and graphene. The conductive conjugated monomers include one or more of diamino-terminated aniline polymers, ethylenedioxythiophene, aniline, and pyrrole. The conductive polyamide elastomer provided by this invention does not rely on traditional metal conductive fillers and possesses excellent mechanical and electrical properties, making it particularly suitable for flexible electronic devices, smart sensors, conductive elastomers, and thermal management materials.

Description

Technical Field

[0001] This invention belongs to the field of conductive elastomer fiber technology, specifically relating to a conductive polyamide elastomer and its preparation method. Background Technology

[0002] Thermoplastic polyamide elastomers (TPAEs) are polymers that combine elasticity and thermoplasticity, and are widely used in the automotive, electronics, medical device, and packaging industries. The preparation of TPAEs typically involves a combination of polyamide hard segments and polyether soft segments. The polyamide hard segments are usually obtained by reacting diamines with diacids. However, current TPAE materials generally lack electrical conductivity. In smart materials and flexible electronic devices, conductivity is a crucial performance requirement. Existing TPAE materials often rely on other conductive materials (such as metals or conductive coatings) to provide conductivity, but this increases the material's cost and complexity.

[0003] With the increasing miniaturization and functional integration of electronic devices, the demand for conductive polymers is rapidly growing in fields such as smart materials, flexible electronics, sensors, and energy storage. Currently, traditional conductive polymers often require the addition of conductive fillers (such as carbon nanotubes and graphene) to improve their conductivity, but this leads to a decrease in the mechanical properties of the material (such as elasticity), thus failing to achieve a balance between conductivity and elasticity in conductive polymers.

[0004] In summary, designing a polymer that simultaneously possesses conductivity, elasticity, strength, and thermal stability, especially without relying on traditional metal conductive fillers, remains a technological challenge in the field of conductive polymer materials. Summary of the Invention

[0005] The purpose of this invention is to provide a conductive polyamide elastomer and its preparation method. The conductive polyamide elastomer provided by this invention does not rely on traditional metal conductive fillers and has good mechanical and electrical properties, making it particularly suitable for flexible electronic devices, smart sensors, conductive elastomers, and thermal management materials.

[0006] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a conductive polyamide elastomer, the raw materials for which include a hard segment polymer, a soft segment polymer and additives, the additives including conductive components and other additives, the hard segment polymer being polydodecanoic acid decyl diamine, the end group of the hard segment polymer being a carboxyl group, the soft segment polymer including aromatic ether diamine with the structure shown in Formula 1 and terminal amino ether diamine with the structure shown in Formula 2, and the conductive components including conductive fillers and / or conductive conjugated monomers. When the conductive component is a conductive filler, the conductive polyamide elastomer is obtained by reacting the hard segment polymer and the soft segment polymer and then blending them with the additives; When the conductive component is a conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment polymer and the conductive conjugated monomer and then blending them with the other additives; When the conductive component includes conductive filler and conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment polymer and the conductive conjugated monomer and then blending them with the conductive filler and the other additives; Formula 1 Equation 2.

[0007] Preferably, the conductive filler comprises one or more of carbon black, carbon nanotubes, and graphene; the conductive conjugated monomer comprises one or more of diamino-terminated aniline polymers, ethylenedioxythiophene, aniline, and pyrrole; the aniline polymer has the structure shown in Formula 3: Formula 3.

[0008] Preferably, the mass percentage of the aromatic ether diamine with the structure shown in Formula 1 in the soft segment polymer is 10-80%.

[0009] Preferably, the mass of the hard segment polymer accounts for 35-60% of the total mass of the hard segment polymer and the soft segment polymer.

[0010] Preferably, when the conductive component is a conductive filler, the percentage of the conductive filler in the total mass of the hard segment polymer and the soft segment polymer is 1-10%. When the conductive component is a conductive conjugated monomer, the mass percentage of the conductive conjugated monomer to the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is 1-10%. When the conductive component includes conductive filler and conductive conjugated monomer, the mass percentage of the conductive conjugated monomer to the total mass of the hard segment polymer, the soft segment polymer and the conductive conjugated monomer is 1 to 10%, and the percentage of the conductive filler to the total mass of the hard segment polymer, the soft segment polymer and the conductive conjugated monomer is 1 to 10%.

[0011] Preferably, the other additives include antioxidants; when the conductive component includes conductive fillers, the other additives also include dispersants, the dispersants including hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate and silane coupling agents.

[0012] This invention provides a method for preparing the conductive polyamide elastomer described above. When the conductive component is a conductive filler, the method includes the following steps: mixing a hard segment polymer, a soft segment polymer, water, and a catalyst to perform a random block polymerization reaction to obtain an elastomer matrix; and performing a first melt blending of the elastomer matrix, the conductive filler, and the additives to obtain the conductive polyamide elastomer. When the conductive component is a conductive conjugated monomer, the process includes the following steps: mixing and reacting a hard segment polymer, a soft segment polymer, a conductive conjugated monomer, water, and a catalyst to obtain an intermediate; and performing a second melt blending of the intermediate with other additives to obtain the conductive polyamide elastomer. When the conductive component includes conductive filler and conductive conjugated monomer, the process includes the following steps: mixing hard segment polymer, soft segment polymer, conductive conjugated monomer, water and catalyst to react and obtain an intermediate; and performing a third melt blending of the intermediate, conductive filler and other additives to obtain the conductive polyamide elastomer.

[0013] Preferably, when the conductive polyamide elastomer is a conductive polyamide elastomer fiber, the process after the first melt blending, the second melt blending, or the third melt blending further includes: sequentially performing pre-stretching, hot stretching, and heat setting to obtain the conductive polyamide elastomer fiber.

[0014] Preferably, the first melt blending, the second melt blending, or the third melt blending is carried out in a screw extruder, which is divided into a long conveying zone for material storage, a high-temperature melting zone, a high-shear mixing zone, a melt conveying zone, and a die head discharge zone; the temperature of the long conveying zone for material storage is 50~60℃, the temperature of the high-temperature melting zone is 250~280℃, the temperature of the high-shear mixing zone is 230~280℃, the temperature of the melt conveying zone is 230~280℃, and the temperature of the die head discharge zone is 250~280℃.

[0015] Preferably, the pre-drawing is performed by drawing through a spinneret, and then undrawn yarn is obtained on a take-up hot roller; the draw ratio of the pre-drawing is 20 to 50 times, the temperature of the take-up hot roller is 110 to 120°C, and the rotation speed is 200 to 300 m / min; The hot drawing process includes sequentially performing a first-stage drawing and a second-stage drawing. The temperature of the first-stage drawing is 100~120℃, and the drawing ratio is 3~3.2 times. The temperature of the second-stage drawing is 150~180℃, and the drawing ratio is 1.2~1.5 times. The heat setting temperature is 230~250℃.

[0016] This invention provides a conductive polyamide elastomer, prepared from raw materials including a hard segment polymer, a soft segment polymer, and additives. The additives include a conductive component and other additives. The hard segment polymer is polydodecanoic acid decylamine, with carboxyl groups at the end groups. The soft segment polymer includes an aromatic ether diamine with the structure shown in Formula 1 and a terminal amino ether diamine with the structure shown in Formula 2. The conductive component includes a conductive filler and / or a conductive conjugated monomer. When the conductive component is a conductive filler, the conductive polyamide elastomer is obtained by reacting the hard segment polymer and the soft segment polymer, followed by blending with the additives. When the conductive component is a conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer, followed by blending with the other additives. When the conductive component includes both a conductive filler and a conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer, followed by blending with the conductive filler and the other additives. Compared with the prior art, this invention has the following beneficial effects: This invention successfully solves the balance problem between conductivity and elasticity in traditional TPAEs by introducing PA1012 hard segments and two types of soft segments (aromatic ether diamine with the structure shown in Formula 1 and terminal amino ether diamine with the structure shown in Formula 2), and by introducing conductive fillers and / or conductive conjugated monomers. By optimizing the types of hard and soft segments and conductive components, this invention can impart conductivity to the polymer while ensuring its elasticity and thermal stability. This makes the conductive polyamide elastomer fibers of this invention have broader application prospects in fields such as smart materials, flexible electronics, and conductive elastomers.

[0017] This invention employs a soft segment combining an aromatic ether diamine of Formula 1 and a terminal amino ether diamine of Formula 2, replacing traditional polyether or polyester soft segments. The soft segment used in this invention not only provides better elasticity to the polyamide elastomer, but its amino-terminated structure also offers greater functionalization potential. Compared to existing polyether soft segments, the soft segment designed in this invention provides superior thermal and structural stability, as well as better chemical resistance and compatibility. Traditional conductive polymers often suffer from the negative impact of conductive fillers on mechanical properties; that is, the addition of conductive fillers leads to increased brittleness or decreased elasticity. This invention, through the optimization of the hard segment polymer, soft segment polymer, and conductive component of the conductive polyamide elastomer, not only significantly improves the conductivity of the material but also ensures that the polymer maintains high mechanical strength and good elasticity while maintaining high conductivity, avoiding excessive damage to mechanical properties caused by the addition of conductive fillers. The conductive polyamide elastomer provided by this invention is highly innovative in the field of polyamide elastomers, breaking through the performance bottlenecks of traditional conductive polymers.

[0018] Furthermore, in this invention, the mass percentage of the hard segment polymer to the total mass of the hard segment polymer and the soft segment polymer is 35-60%. When the conductive component is a conductive filler, the conductive filler accounts for 1-10% of the total mass of the hard segment polymer and the soft segment polymer; when the conductive component is a conductive conjugated monomer, the conductive conjugated monomer accounts for 1-10% of the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer; when the conductive component includes both conductive filler and conductive conjugated monomer, the conductive conjugated monomer accounts for 1-10% of the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer, and the conductive filler accounts for 1-10% of the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer. By optimizing the mass ratio of the hard segment polymer, the soft segment polymer, and the conductive component, this invention can further improve the conductivity of the conductive polyamide elastomer while ensuring the elasticity and thermal stability of the polymer. This makes the conductive polyamide elastomer fiber of this invention have broader application prospects in the fields of smart materials, flexible electronics, and conductive elastomers.

[0019] Furthermore, in this invention, the conductive agent is a conductive conjugated monomer, which is a diamino-terminated aniline polymer, specifically a diamino-terminated aniline trimer with the structure shown in Formula 3. This invention uses the diamino-terminated aniline trimer with the structure shown in Formula 3 as the conductive component, providing a conjugated structure on the polyamide elastomer backbone, allowing electrons to move throughout the entire polyamide elastomer backbone, resulting in a smaller band gap and higher conductivity. The conductive polyamide elastomer obtained by using the diamino-terminated aniline trimer with the structure shown in Formula 3 as the conductive component has a band structure similar to that of an inorganic semiconductor, significantly increasing the carrier concentration and significantly improving the conductivity of the polyamide elastomer. Detailed Implementation

[0020] This invention provides a conductive polyamide elastomer, the raw materials for which include a hard segment polymer, a soft segment polymer and additives, the additives including conductive components and other additives, the hard segment polymer being polydodecanoic acid decyl diamine, the end group of the hard segment polymer being a carboxyl group, the soft segment polymer including aromatic ether diamine with the structure shown in Formula 1 and terminal amino ether diamine with the structure shown in Formula 2, and the conductive components including conductive fillers and / or conductive conjugated monomers. When the conductive component is a conductive filler, the conductive polyamide elastomer is obtained by reacting the hard segment polymer and the soft segment polymer and then blending them with the additives; When the conductive component is a conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment polymer and the conductive conjugated monomer and then blending them with the other additives; When the conductive component includes conductive filler and conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment polymer and the conductive conjugated monomer and then blending them with the conductive filler and the other additives; Formula 1 Equation 2.

[0021] The conductive polyamide elastomer provided by this invention can be a conductive polyamide elastomer fiber.

[0022] The conductive polyamide elastomer provided by this invention comprises a hard segment polymer as a raw material. The hard segment polymer is polydodecanoic acid decylamine (PA1012), and the end groups of the hard segment polymer are carboxyl groups. The hard segment polymer is a dicarboxyl-terminated PA1012 prepolymer. The PA1012 can be bio-based PA1012. The PA1012 is prepared using an excess of diacid monomer compared to the diamine monomer. The excess diacid during the polymerization of the hard segment polymer leads to dicarboxyl-termined ends; the preferred molar ratio of diacid monomer to diamine monomer during the polymerization of the hard segment polymer is 3:1.

[0023] The raw materials for preparing the conductive polyamide elastomer provided by this invention include a soft-segment polymer. The soft-segment polymer includes an aromatic ether diamine with the structure shown in Formula 1 and a terminal amino ether diamine with the structure shown in Formula 2. The mass percentage of the aromatic ether diamine with the structure shown in Formula 1 in the soft-segment polymer is preferably 10-80%, preferably 30-50%, and in some examples, it can be 70%. The mass percentage of the terminal amino ether diamine with the structure shown in Formula 2 in the soft-segment polymer is preferably 20-90%, preferably 50-70%, and in some examples, it can be 30%.

[0024] In this invention, the mass percentage of the hard segment polymer to the total mass of the hard segment polymer and the soft segment polymer is preferably 35-60%, more preferably 40-45%, and in the embodiments it can be 40% or 44.4%. The mass percentage of the soft segment polymer to the total mass of the hard segment polymer and the soft segment polymer is preferably 40-65%, more preferably 55-60%, and in the embodiments it can be 60% or 55.6%.

[0025] The raw materials for preparing the conductive polyamide elastomer provided by this invention include additives. These additives include conductive components and other additives.

[0026] In this invention, the conductive component includes conductive filler and / or conductive conjugated monomer. The conductive filler preferably includes one or more of carbon black, carbon nanotubes, and graphene. The conductive conjugated monomer preferably includes one or more of diamino-terminated aniline polymers, ethylenedioxythiophene, aniline, and pyrrole. The conductive component preferably includes one or more of diamino-terminated aniline polymers, aniline, pyrrole, ethylenedioxythiophene, carbon black, carbon nanotubes, and graphene, more preferably one or more of diamino-terminated aniline polymers, carbon black, carbon nanotubes, aniline, and pyrrole. In specific embodiments of this invention, the conductive component can be a mixture of carbon black, carbon nanotubes, aniline, and pyrrole, a diamino-terminated aniline polymer, or a mixture of diamino-terminated aniline polymer and carbon black. When the conductive component is a mixture of aniline and pyrrole, the mass ratio of aniline to pyrrole is 1:1.

[0027] In this invention, the aniline polymer has the structure shown in Formula 3: Formula 3.

[0028] In this invention, the conductive component achieves the conductivity of the conductive polyamide elastomer through in-situ polymerization and / or doping.

[0029] In this invention, when the conductive component is a conductive filler, the percentage of the conductive filler in the total mass of the hard segment polymer and the soft segment polymer is preferably 1-10%. In this invention, when the conductive component is a conductive conjugated monomer, the mass percentage of the conductive conjugated monomer to the total mass of the hard segment polymer, the soft segment polymer and the conductive conjugated monomer is 1 to 10%, and in the embodiment it can be 10%.

[0030] In this invention, when the conductive component includes conductive filler and conductive conjugated monomer, the mass percentage of the conductive conjugated monomer to the total mass of the hard segment polymer, the soft segment polymer and the conductive conjugated monomer is 1 to 10%, which can be 10% in the embodiment; the percentage of the conductive filler to the total mass of the hard segment polymer, the soft segment polymer and the conductive conjugated monomer is 1 to 10%, which can be 10% in the embodiment.

[0031] In this invention, by controlling the mass fraction of the conductive component, the conductive polyamide elastomer can have excellent conductivity, making it suitable for high-end applications such as flexible electronics and smart sensors. In this invention, the other additives preferably include antioxidants. In the examples, the antioxidant may be antioxidant 1098. When the conductive component includes conductive fillers, the other additives preferably also include dispersants. In this invention, the dispersant preferably includes hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, and a silane coupling agent, and the mass ratio of hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, and the silane coupling agent is preferably 1~2:1~2:2~3, and in the examples, it can be 1:1:2. In a specific embodiment of this invention, the silane coupling agent may be KH-550.

[0032] In this invention, when the conductive component is a conductive filler, the percentage of the antioxidant in the total mass of the hard segment polymer and the soft segment polymer is preferably 0.05~0.15%, and in the embodiment it can be 0.1%; the percentage of the dispersant in the total mass of the hard segment polymer and the soft segment polymer is preferably 0.5~1.5%, and in the embodiment it can be 1%.

[0033] In this invention, when the conductive component is a conductive conjugated monomer, the percentage of the antioxidant by mass of the total mass of the hard segment polymer, the soft segment polymer and the conductive conjugated monomer is preferably 0.05 to 0.15%, and in the embodiments it can be 0.1%.

[0034] In this invention, when the conductive component comprises conductive filler and conductive conjugated monomer, the percentage of the antioxidant by mass of the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is preferably 0.05-0.15%, and in the embodiments it can be 0.1%. The percentage of the dispersant by mass of the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is preferably 0.5-1.5%, and in the embodiments it can be 1%.

[0035] The conductive polyamide elastomer fiber provided by the present invention preferably has a tensile strength of 30 MPa to 40 MPa; the conductive elastomer fiber preferably has an electrical conductivity of 10. -4 ~10 -1 S / cm.

[0036] This invention provides a method for preparing the conductive polyamide elastomer described above. When the conductive component is a conductive filler, the method includes the following steps: mixing a hard segment polymer, a soft segment polymer, water, and a catalyst to perform a random block polymerization reaction to obtain an elastomer matrix; and performing a first melt blending of the elastomer matrix, the conductive filler, and the additives to obtain the conductive polyamide elastomer. When the conductive component is a conductive conjugated monomer, the process includes the following steps: mixing and reacting a hard segment polymer, a soft segment polymer, a conductive conjugated monomer, water, and a catalyst to obtain an intermediate; and performing a second melt blending of the intermediate with other additives to obtain the conductive polyamide elastomer. When the conductive component includes conductive filler and conductive conjugated monomer, the process includes the following steps: mixing hard segment polymer, soft segment polymer, conductive conjugated monomer, water and catalyst to react and obtain an intermediate; and performing a third melt blending of the intermediate, conductive filler and other additives to obtain the conductive polyamide elastomer.

[0037] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0038] In this invention, the preparation method of the hard segment polymer preferably includes: mixing dodecanoic acid, decanediamine, and water to obtain an aqueous slurry; mixing the aqueous slurry with a catalyst and reacting to obtain the hard segment polymer. In this invention, the water is preferably deionized water. The catalyst is preferably sodium hypophosphite. The molar ratio of the dodecanoic acid and decanediamine is preferably 3:1. The mass ratio of the total mass of the dodecanoic acid and decanediamine to the mass of water in the aqueous slurry is preferably 1:1. The mass percentage of the catalyst to the total mass of the dodecanoic acid and decanediamine is preferably 0.03~0.05%. The reaction is carried out in a protective gas atmosphere, which can be nitrogen. The reaction includes a salt-forming reaction and a polymerization reaction performed sequentially. The temperature of the salt-forming reaction is preferably 100~150℃, the time is preferably 3~4h, and the pressure of the salt-forming reaction is preferably atmospheric pressure. The salt-forming reaction is carried out under stirring conditions, and the stirring speed is preferably 100~150rpm. The heating rate from room temperature to the temperature of the salt-forming reaction is preferably 1~10℃ / min. After the salt-forming reaction is completed, a salt-forming reaction solution is obtained. Preferably, the polymerization reaction is carried out by heating the salt-forming reaction solution. The heating rate from the salt-forming reaction temperature to the polymerization reaction temperature is preferably 1~5℃ / min. The polymerization reaction is carried out in a protective gas atmosphere, which can be nitrogen. The polymerization reaction includes a first-stage reaction and a second-stage reaction sequentially. The temperature of the first-stage reaction is preferably 200~230℃, the time is preferably 1~1.5h, and the pressure is preferably 1.5~2MPa. The temperature of the second-stage reaction is preferably 250~260℃, the time is preferably 1~1.5h, and the pressure is preferably 1.5~2MPa. In this invention, the second-stage reaction ends when the amount of water discharged reaches 25~30wt% of the total feed amount, and the material is discharged. The total feed amount is the total mass of dodecanoic acid, decanediamine, and water. The pressure is released instantaneously during discharge. After the reaction is completed, the discharged material is sequentially dried and pulverized to obtain the hard segment polymer.

[0039] In this invention, when the conductive component is a conductive filler, the hard segment polymer, soft segment polymer, water, and catalyst are mixed and subjected to random block polymerization to obtain an elastomer matrix. After obtaining the elastomer matrix, the elastomer matrix and the additives are subjected to a first melt blending to obtain the conductive polyamide elastomer. In this invention, the water can be deionized water. The catalyst preferably includes sodium hypophosphite and benzoic acid, and the mass ratio of sodium hypophosphite to benzoic acid is preferably 3:7. The mass percentage of water in the total mass of the hard segment polymer and soft segment polymer is preferably 10-20%, and in the example, it can be 15%. The mass percentage of the catalyst in the total mass of the hard segment polymer and soft segment polymer is preferably 0.05-0.15%, and in the example, it can be 0.1%. The random block polymerization reaction is carried out in a protective gas atmosphere, and the protective gas can be nitrogen. The random block polymerization reaction includes a first stage reaction and a second stage reaction in sequence. The temperature of the first stage reaction is preferably 200-230°C, the time is preferably 1-3 hours, and the pressure is preferably atmospheric pressure. The preferred temperature for the second stage reaction is 250-280℃, and the preferred time is 1-4 hours. The second stage is carried out under vacuum conditions. The random block polymerization reaction is carried out under stirring conditions. After the second stage reaction is completed, the discharge valve is opened to discharge the material under a protective gas atmosphere, which can be nitrogen. The discharged melt is water-cooled and then pelletized to obtain granules of the elastomer matrix.

[0040] In this invention, when the conductive component is a conductive conjugated monomer, the hard-segment polymer, soft-segment polymer, conductive conjugated monomer, water, and catalyst are mixed and reacted to obtain an intermediate. After obtaining the intermediate, the intermediate is melt-blended with other additives to obtain the conductive polyamide elastomer. In this invention, the water can be deionized water. The catalyst preferably includes sodium hypophosphite and benzoic acid, and the mass ratio of sodium hypophosphite to benzoic acid is preferably 3:7. The mass percentage of water in the total mass of the hard-segment polymer, soft-segment polymer, and conductive conjugated monomer is preferably 10-20%, and in the examples, it can be 15%. The mass percentage of the catalyst in the total mass of the hard-segment polymer, soft-segment polymer, and conductive conjugated monomer is preferably 0.05-0.15%, and in the examples, it can be 0.1%. The reaction conditions are the same as those for the random block polymerization reaction when the conductive component is a conductive filler, and will not be repeated here.

[0041] In this invention, when the conductive component includes conductive filler and conductive conjugated monomer, the process includes the following steps: mixing and reacting a hard segment polymer, a soft segment polymer, a conductive conjugated monomer, water, and a catalyst to obtain an intermediate; and performing a third melt blending of the intermediate, the conductive filler, and other additives to obtain the conductive polyamide elastomer. In this invention, the water can be deionized water. The catalyst preferably includes sodium hypophosphite and benzoic acid, with a preferred mass ratio of 3:7. The mass percentage of water relative to the total mass of the hard segment polymer, soft segment polymer, and conductive conjugated monomer is preferably 10-20%, and in some examples, it can be 15%. The mass percentage of the catalyst relative to the total mass of the hard segment polymer, soft segment polymer, and conductive conjugated monomer is preferably 0.05-0.15%, and in some examples, it can be 0.1%. The preparation method of the intermediate is the same as when the conductive component is a conductive conjugated monomer, and will not be repeated here.

[0042] In this invention, when the conductive component is a conductive filler, the additives used in the first melt blending preferably include antioxidants and dispersants. The percentage of the conductive filler in the total mass of the hard segment polymer and the soft segment polymer during the first melt blending is preferably 1-10%; the percentage of the antioxidant in the total mass of the hard segment polymer and the soft segment polymer is preferably 0.05-0.15%, and in some examples it can be 0.1%; the percentage of the dispersant in the total mass of the hard segment polymer and the soft segment polymer is preferably 0.5-1.5%, and in some examples it can be 1%.

[0043] In this invention, when the conductive component is a conductive conjugated monomer, the additive used in the second melt blending is preferably an antioxidant, and the percentage of the antioxidant's mass in the third melt blending relative to the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is preferably 0.05~0.15%, and in the examples it can be 0.1%.

[0044] In this invention, when the conductive component is a conductive filler and a conductive conjugated monomer, the additives used in the second melt blending preferably include an antioxidant and a dispersant. In the third melt blending, the percentage of the conductive filler in the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is preferably 1-10%; the percentage of the antioxidant in the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is preferably 0.05-0.15%, and in some examples, it can be 0.1%. The percentage of the dispersant in the total mass of the hard segment polymer, the soft segment polymer, and the conductive conjugated monomer is preferably 0.5-1.5%, and in some examples, it can be 1%.

[0045] In this invention, the first melt blending, second melt blending, or third melt blending is preferably carried out in a screw extruder, preferably a twin-screw extruder. The screw extruder is divided into a long conveying zone, a high-temperature melting zone, a high-shear mixing zone, a melt conveying zone, and a die-head discharge zone. The temperature of the long conveying zone is preferably 50-60°C, but can be 50°C in this embodiment; the temperature of the high-temperature melting zone is preferably 250-280°C, but can be 260°C in this embodiment; the temperature of the high-shear mixing zone is preferably 230-280°C, but can be 270°C in this embodiment; the temperature of the melt conveying zone is preferably 230-280°C, but can be 260°C in this embodiment; and the temperature of the die-head discharge zone is preferably 250-280°C, but can be 260°C in this embodiment.

[0046] In this invention, nascent fibers are obtained after the first melt blending, the second melt blending, or the third melt blending.

[0047] In this invention, the conductive polyamide elastomer is preferably conductive polyamide elastomer fiber. After the first melt blending, second melt blending, or third melt blending, the invention preferably further includes: sequentially performing pre-drawing, hot drawing, and heat setting to obtain the conductive polyamide elastomer fiber. In this invention, the raw material for pre-drawing is nascent fiber. Pre-drawing is preferably performed through a spinneret, and then undrawn yarn is obtained on a hot take-up roller. The draw ratio of the pre-drawing is preferably 20 to 50 times, and in this embodiment it can be 30 times. The temperature of the hot take-up roller is preferably 110 to 120°C, and in this embodiment it can be 120°C. The rotation speed is preferably 200 to 300 m / min, and in this embodiment it can be 300 m / min.

[0048] After obtaining the undrawn yarn, the present invention sequentially draws and heat-sets the undrawn yarn to obtain the conductive polyamide elastomer fiber. The drawing includes sequential primary and secondary drawing. The temperature of the primary drawing is preferably 100-120°C, and in this embodiment it can be 110°C; the draw ratio is preferably 3-3.2 times, and in this embodiment it can be 3.2 times. The temperature of the secondary drawing is preferably 150-180°C, and in this embodiment it can be 160°C; the draw ratio is preferably 1.2-1.5 times, and in this embodiment it can be 1.5 times. The heat-setting temperature is preferably 230-250°C, and in this embodiment it can be 230°C.

[0049] The preparation method provided by this invention, by adjusting the composition and structure of the raw materials, yields conductive polyamide elastomer fibers that not only meet the requirements of high-performance conductive materials, but also achieve multifunctional integration in smart materials, wearable devices and other high-tech fields.

[0050] To further illustrate the present invention, the technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention. The dispersants used in the following embodiments are hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, and KH-550, and the mass ratio of hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, and KH-550 is 1:1:2.

[0051] Example 1 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min. Under normal pressure, stir continuously at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at this temperature and pressure for 1 hour. Then the temperature was increased to 260℃ and maintained at 2MPa pressure for 1 hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0052] (2) Weigh 400g of PA1012 prepolymer, 420g of aromatic ether diamine with the structure shown in Formula 1, 180g of terminal amino ether diamine with the structure shown in Formula 2, 15wt% of deionized water (based on the total mass of PA1012 prepolymer, aromatic ether diamine and terminal amino ether diamine), and 0.1wt% of sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite to benzoic acid is 3:7) (based on the total mass of PA1012 prepolymer, aromatic ether diamine and terminal amino ether diamine). Add them sequentially to the polymerization reactor, replace the atmosphere inside the reactor with nitrogen, heat to 200℃ and stir for 3h under normal pressure, turn on the vacuum pump to draw a vacuum, continue to heat to 280℃ and continue stirring for 4h, stop stirring, open the discharge valve and use nitrogen to assist in discharge, and cut the melt into pellets after cooling in a water tank to obtain polyamide elastomer.

[0053] (3) The obtained polyamide elastomer, carbon black accounting for 10 wt% of the mass of the polyamide elastomer, dispersant accounting for 1 wt% of the mass of the polyamide elastomer, and antioxidant 1098 accounting for 0.1 wt% of the mass of the polyamide elastomer are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine with the structure shown in Formula 1, and terminal amino ether diamine with the structure shown in Formula 2. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone, and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C, and the temperature of the die head discharge zone is 260°C.

[0054] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0055] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0056] Example 2 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min, and continue stirring at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at this temperature and pressure for 1 hour. Then the temperature was increased to 260℃ and maintained at 2MPa pressure for 1 hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0057] (2) Weigh 400g of PA1012 prepolymer, 420g of aromatic ether diamine with the structure shown in Formula 1, 180g of terminal amino ether diamine with the structure shown in Formula 2, 15wt% of deionized water (based on the total mass of PA1012 prepolymer, aromatic ether diamine and terminal amino ether diamine), and 0.1wt% of sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite to benzoic acid is 3:7) (based on the total mass of PA1012 prepolymer, aromatic ether diamine and terminal amino ether diamine). Add them sequentially to the polymerization reactor, replace the atmosphere inside the reactor with nitrogen, heat to 200℃ and stir for 3h under normal pressure, turn on the vacuum pump to draw a vacuum, continue to heat to 280℃ and continue stirring for 4h, stop stirring, open the discharge valve and use nitrogen to assist in discharge, and cut the melt into pellets after cooling in a water tank to obtain polyamide elastomer.

[0058] (3) The obtained polyamide elastomer, carbon nanotubes accounting for 10 wt% of the mass of the polyamide elastomer, dispersant accounting for 1 wt% of the mass of the polyamide elastomer, and antioxidant 1098 accounting for 0.1 wt% of the mass of the polyamide elastomer are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine with the structure shown in Formula 1, and terminal amino ether diamine with the structure shown in Formula 2. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone, and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C, and the temperature of the die head discharge zone is 260°C.

[0059] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0060] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0061] Example 3 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min, and continue stirring at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at 2MPa for 1 hour. The temperature was then increased to 260℃ and maintained at 2MPa for 1 hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0062] (2) Weigh 400g of PA1012 prepolymer, 350g of aromatic ether diamine with the structure shown in Formula 1, 150g of terminal amino ether diamine with the structure shown in Formula 2, 50g of aniline, 50g of pyrrole, 15wt% of deionized water (based on the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, aniline and pyrrole), and 0.1wt% of sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite to benzoic acid is 3:7) (based on the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, aniline and pyrrole) and add them sequentially to the polymerization reactor. Use nitrogen to replace the atmosphere inside the reactor, heat to 200℃ and stir for 3h under normal pressure, then turn on the vacuum pump to draw a vacuum, continue to heat to 280℃ and continue stirring for 4h, then stop stirring, open the discharge valve and use nitrogen to assist in discharge, and cut the melt into pellets after cooling in a water tank to obtain polyamide elastomer.

[0063] (3) The obtained polyamide elastomer and antioxidant 1098, which accounts for 0.1 wt% of the mass of the polyamide elastomer, are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, aniline and pyrrole. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C, and the temperature of the die head discharge zone is 260°C.

[0064] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0065] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0066] Example 4 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min, and continue stirring at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at 2MPa for 1 hour. Then the temperature was increased to 260℃ and maintained for another hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0067] (2) Weigh 400g of PA1012 prepolymer, 350g of aromatic ether diamine with the structure shown in Formula 1, 150g of terminal amino ether diamine with the structure shown in Formula 2, 100g of diamino-terminated aniline trimer with the structure shown in Formula 3, and 15wt% of deionized water (based on the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, and diamino-terminated aniline trimer with the structure shown in Formula 3). Amine, sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite to benzoic acid is 3:7) of 0.1 wt% of the total mass of the diamino-terminated aniline trimer of Formula 3 were added sequentially to the polymerization reactor. The atmosphere inside the reactor was replaced with nitrogen. After stirring at 200°C for 3 hours under normal pressure, the vacuum pump was turned on to draw a vacuum. The temperature was then raised to 280°C and stirring was continued for 4 hours. After stirring was stopped, the discharge valve was opened and nitrogen was used to assist in the discharge. The melt was cooled in a water bath and then pelletized to obtain polyamide elastomer.

[0068] (3) The obtained polyamide elastomer and antioxidant 1098, which accounts for 0.1 wt% of the mass of the polyamide elastomer, are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, and the double amino end-capped structure shown in Formula 3. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone, and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C, and the temperature of the die head discharge zone is 260°C.

[0069] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0070] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0071] Example 5 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min, and continue stirring at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at 2MPa for 1 hour. Then the temperature was increased to 260℃ and maintained for another hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0072] (2) Weigh 400g of PA1012 prepolymer, 350g of aromatic ether diamine, 150g of terminal amino ether diamine, 100g of diamino-terminated aniline trimer with the structure shown in Formula 3, 15wt% of deionized water (based on the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, and diamino-terminated aniline trimer with the structure shown in Formula 3), and 15wt% of deionized water (based on the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine, and diamino-terminated aniline trimer with the structure shown in Formula 3). 0.1 wt% of sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite to benzoic acid is 3:7) of the total mass of the diamino-terminated aniline trimer were added sequentially to the polymerization reactor. The atmosphere inside the reactor was replaced with nitrogen. After stirring at 200°C under normal pressure for 3 hours, the vacuum pump was turned on to create a vacuum. The temperature was then raised to 280°C and stirring was continued for 4 hours. After stirring was stopped, the discharge valve was opened and nitrogen was used to assist in the discharge. The melt was cooled in a water bath and then pelletized to obtain polyamide elastomer.

[0073] (3) The obtained polyamide elastomer, 10 wt% carbon black, 1 wt% dispersant and 0.1 wt% antioxidant 1098 are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine, terminal amino ether diamine and the double amino end-capped structure shown in Formula 3. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C and the temperature of the die head discharge zone is 260°C.

[0074] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0075] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0076] Comparative Example 1 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min, and continue stirring at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at this temperature and pressure for 1 hour. Then the temperature was increased to 260℃ and maintained at 2MPa pressure for 1 hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0077] (2) Weigh 400g of PA1012 prepolymer, 180g of aromatic ether diamine with the structure shown in Formula 1, 420g of terminal amino ether diamine with the structure shown in Formula 2, 15wt% of deionized water (total mass of PA1012 prepolymer, aromatic ether diamine and terminal amino ether diamine), and 0.1wt% of sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite and benzoic acid is 3:7) and add them sequentially to the polymerization reactor. Use nitrogen to replace the atmosphere inside the reactor, heat to 200℃ and stir for 3h under normal pressure, then turn on the vacuum pump to draw a vacuum, continue to heat to 280℃ and continue stirring for 4h, then stop stirring, open the discharge valve and use nitrogen to assist in discharge, and cut the melt into pellets after cooling in a water tank to obtain polyamide elastomer.

[0078] (3) The obtained polyamide elastomer and antioxidant 1098, which accounts for 0.1 wt% of the mass of the polyamide elastomer, are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine with the structure shown in Formula 1 and terminal amino ether diamine with the structure shown in Formula 2. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C, and the temperature of the die head discharge zone is 260°C.

[0079] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0080] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0081] Comparative Example 2 (1) The mass and proportion of each raw material are as follows: Weigh 6 mol of dodecanoic acid and 2 mol of decacarbonylamine, add 50 wt% of deionized water (total mass of diacid and diamine), and heat and stir in a stirring device to form a water slurry. Add the above water slurry and sodium hypophosphite catalyst (0.05 wt% of total mass of diacid and diamine) to the polymerization reactor. After replacing the gas in the reactor with nitrogen, continue to heat to 150°C at a heating rate of 10°C / min, and continue stirring at a stirring speed of 100 rpm for 3 hours to promote the salt formation of diacid and diamine monomers in the solution. The temperature was then increased to 200℃ at a rate of 5℃ / min, and the pressure was increased to 2MPa. The pressure was kept stable and maintained at this temperature and pressure for 1 hour. Then the temperature was increased to 260℃ and maintained at 2MPa pressure for 1 hour. When the water output reached 30wt% of the total feed (total mass of diacid, diamine and water), the pressure was released instantaneously and the material was discharged. After drying, it was pulverized to obtain PA1012 prepolymer.

[0082] (2) Weigh 400g of PA1012 prepolymer, 420g of aromatic ether diamine with the structure shown in Formula 1, 180g of terminal amino ether diamine with the structure shown in Formula 2, 15wt% of deionized water (total mass of PA1012 prepolymer, aromatic ether diamine and terminal amino ether diamine), and 0.1wt% of sodium hypophosphite and benzoic acid (mass ratio of sodium hypophosphite and benzoic acid is 3:7) and add them sequentially to the polymerization reactor. Use nitrogen to replace the atmosphere inside the reactor, heat to 200℃ and stir for 3h under normal pressure, turn on the vacuum pump to draw a vacuum, continue to heat to 280℃ and continue stirring for 4h, stop stirring, open the discharge valve and use nitrogen to assist in discharge, and cut the melt into pellets after cooling in a water tank to obtain polyamide elastomer.

[0083] (3) The obtained polyamide elastomer and antioxidant 1098, which accounts for 0.1 wt% of the mass of the polyamide elastomer, are melt-blended in a twin-screw extruder with strong shear capacity and then drawn to obtain nascent fibers. The mass of the polyamide elastomer is the total mass of PA1012 prepolymer, aromatic ether diamine with the structure shown in Formula 1 and terminal amino ether diamine with the structure shown in Formula 2. The extruder area is divided into a storage long conveying zone, a high temperature melting zone, a strong shear mixing zone, a melt conveying zone and a die head discharge zone. The temperature of the storage long conveying zone is 50°C, the temperature of the high temperature melting zone is 260°C, the temperature of the strong shear mixing zone is 270°C, the temperature of the melt conveying zone is 260°C, and the temperature of the die head discharge zone is 260°C.

[0084] (4) The nascent fiber is drawn by the spinneret after passing through the first winding hot roller. The spinneret draw ratio is 30 times. The temperature of the first winding hot roller is 120℃ and the rotation speed is 300m / min. After the spinneret is drawn, the undrawn fiber is obtained.

[0085] (5) The undrawn yarn obtained in step (4) is subjected to a drawing process. The drawing process is to perform first-stage drawing and second-stage drawing in sequence. The temperature of the first-stage drawing is 110°C and the drawing ratio is 3.2 times. The temperature of the second-stage drawing is 160°C and the drawing ratio is 1.5 times. The heat setting temperature before and after the second stage is 230°C to obtain conductive polyamide elastomer fiber.

[0086] Test case The conductive polyamide elastomer fibers prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests, and the test results are shown in Table 1.

[0087] Table 1. Comparison of performance indicators of Examples 1-5 and Comparative Examples 1-2

[0088] As can be seen from the above embodiments, the conductive polyamide elastomer provided by the present invention is composed of PA1012 polyamide hard segments, soft segments combining aromatic ether diamine and terminal amino ether diamine, and conductive components. The hard segments provide rigidity and strength to the conductive polyamide elastomer fiber, while the soft segments impart elasticity and flexibility, and improve the thermal and chemical stability of the conductive polyamide elastomer fiber. The conductive components enhance the conductivity of the conductive polyamide elastomer fiber through conjugation or doping effects. The resulting conductive polyamide elastomer fiber exhibits excellent mechanical properties, with a tensile strength of 30 MPa to 40 MPa, and also possesses good electrical conductivity, with a conductivity range of 10. -4 ~10 -1 The S / cm ratio meets the application requirements of conductive elastomer materials. The conductive polyamide elastomer fiber provided by this invention has broad application prospects, especially suitable for flexible electronic devices, smart sensors, conductive elastomers, and thermal management materials.

[0089] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A conductive polyamide elastomer, characterized in that, The raw materials for preparation include a hard segment polymer, a soft segment, and additives. The additives include conductive components and other additives. The hard segment polymer is polydodecanoic acid diamine, and the end group of the hard segment polymer is a carboxyl group. The soft segment includes an aromatic ether diamine with the structure shown in Formula 1 and a terminal amino ether diamine with the structure shown in Formula 2. The mass percentage of the aromatic ether diamine with the structure shown in Formula 1 in the soft segment is 10-80%. The mass percentage of the hard segment polymer in the total mass of the hard segment polymer and the soft segment is 35-60%. The conductive component includes conductive fillers and / or conductive conjugated monomers. The conductive fillers include one or more of carbon black, carbon nanotubes, and graphene. The conductive conjugated monomers include one or more of diamino-terminated aniline polymers, ethylenedioxythiophene, aniline, and pyrrole. The diamino-terminated aniline polymer has the structure shown in Formula 3. When the conductive component is a conductive filler, the conductive polyamide elastomer is obtained by reacting the hard segment polymer and the soft segment and then blending them with the additives; When the conductive component is a conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment and the conductive conjugated monomer and then blending them with the other additives; When the conductive component includes conductive filler and conductive conjugated monomer, the conductive polyamide elastomer is obtained by reacting the hard segment polymer, the soft segment and the conductive conjugated monomer and then blending it with the conductive filler and the other additives. Formula 1 Formula 2 Formula 3.

2. The conductive polyamide elastomer according to claim 1, characterized in that, When the conductive component is a conductive filler, the percentage of the conductive filler in the total mass of the hard segment polymer and the soft segment is 1-10%. When the conductive component is a conductive conjugated monomer, the mass percentage of the conductive conjugated monomer to the total mass of the hard segment polymer, the soft segment, and the conductive conjugated monomer is 1-10%. When the conductive component includes conductive filler and conductive conjugated monomer, the mass percentage of the conductive conjugated monomer to the total mass of the hard segment polymer, the soft segment and the conductive conjugated monomer is 1 to 10%, and the percentage of the conductive filler to the total mass of the hard segment polymer, the soft segment and the conductive conjugated monomer is 1 to 10%.

3. The conductive polyamide elastomer according to claim 1, characterized in that, The other additives include antioxidants; when the conductive component includes conductive fillers, the other additives also include dispersants, which include hexadecyltrimethylammonium chloride, sodium dodecylbenzenesulfonate, and silane coupling agents.

4. The method for preparing the conductive polyamide elastomer according to any one of claims 1 to 3, characterized in that, When the conductive component is a conductive filler, the process includes the following steps: mixing a hard segment polymer, a soft segment polymer, water, and a catalyst to carry out a random block polymerization reaction to obtain an elastomer matrix; and performing a first melt blending of the elastomer matrix and an additive to obtain the conductive polyamide elastomer. When the conductive component is a conductive conjugated monomer, the process includes the following steps: mixing and reacting a hard segment polymer, a soft segment, a conductive conjugated monomer, water, and a catalyst to obtain an intermediate; and performing a second melt blending of the intermediate with other additives to obtain the conductive polyamide elastomer. When the conductive component includes conductive filler and conductive conjugated monomer, the process includes the following steps: mixing hard segment polymer, soft segment, conductive conjugated monomer, water and catalyst to react and obtain an intermediate; and performing a third melt blending of the intermediate, conductive filler and other additives to obtain the conductive polyamide elastomer.

5. The preparation method according to claim 4, characterized in that, The conductive polyamide elastomer is a conductive polyamide elastomer fiber. After the first melt blending, the second melt blending, or the third melt blending, the process further includes: pre-stretching, hot stretching, and heat setting in sequence to obtain the conductive polyamide elastomer fiber.

6. The preparation method according to claim 4, characterized in that, The first melt blending, the second melt blending, or the third melt blending is carried out in a screw extruder, which is divided into a long conveying zone for material storage, a high-temperature melting zone, a high-shear mixing zone, a melt conveying zone, and a die head discharge zone. The temperature of the long conveying zone for material storage is 50~60℃, the temperature of the high-temperature melting zone is 250~280℃, the temperature of the high-shear mixing zone is 230~280℃, the temperature of the melt conveying zone is 230~280℃, and the temperature of the die head discharge zone is 250~280℃.

7. The preparation method according to claim 5, characterized in that, The pre-drawing is achieved by drawing through a spinneret, and then obtaining undrawn yarn on a take-up hot roller; the draw ratio of the pre-drawing is 20 to 50 times, the temperature of the take-up hot roller is 110 to 120°C, and the rotation speed is 200 to 300 m / min; The hot drawing process includes sequentially performing a first-stage drawing and a second-stage drawing. The temperature of the first-stage drawing is 100~120℃, and the drawing ratio is 3~3.2 times. The temperature of the second-stage drawing is 150~180℃, and the drawing ratio is 1.2~1.5 times. The heat setting temperature is 230~250℃.

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