Nylon 66 in-situ nano composite resin and melt gradient spinning method thereof

Abstract

The invention relates to a nylon 66 in-situ nano composite resin and a melt gradient spinning method thereof, belongs to the technical field of high polymer materials, and solves the problem that the traditional modification method of nylon 66 is difficult to consider high strength and high cohesiveness at the same time. The composite resin comprises the following components in parts by weight: 80-100 parts of nylon 66 salt; the diheterocyclic comonomer comprises the following components in parts by weight: 5-10 parts of pyridine ring-containing binary acid and 3-8 parts of triazine ring diamine; the surface modification nano material comprises the following components in percentage by weight: 1 to 3 percent of aminated carbon nano tube and 0.5 to 1 percent of aramid nano fiber; and 0.3-1 part of a copper bromide heat stabilizer. Compared with domestic conventional nylon 66 fibers, the nano composite resin provided by the invention has the advantage that the performance is obviously improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a nylon 66 in-situ nanocomposite resin and a melt gradient spinning method thereof. Background Art

[0002] Polyamide (nylon) has excellent mechanical properties and durability, making it widely used in industrial fibers such as tire cord and carpet fibers, as well as in the manufacture of molded products. Polyhexamethylene adipamide (nylon 66) is a representative polyamide, and its applications include industrial fibers, carpet fibers, and clothing fibers, as well as molded products.

[0003] Nylon 66 industrial yarn is widely used in aircraft tire cord due to its high strength and excellent heat resistance. However, existing nylon 66 yarns lack sufficient strength. For example, domestically produced nylon 66 industrial yarns have a breaking strength of 8.4–8.9 cN / dtex. Traditional modification methods (such as copolymerization and surface treatment) struggle to achieve both high strength and high adhesion. Therefore, there is an urgent need to develop a comprehensive technology that integrates nano-reinforcement, interface optimization, and gradient spinning. Summary of the Invention

[0004] In view of the above analysis, the embodiments of the present invention aim to provide a nylon 66 in-situ nanocomposite resin and a melt gradient spinning method thereof, so as to solve the problem that traditional modification methods of nylon 66 are difficult to achieve both high strength and high adhesion.

[0005] In one aspect, an embodiment of the present invention provides a nylon 66 in-situ nanocomposite resin, comprising: 80–100 parts of nylon 66 salt; Bis-heterocyclic comonomer: containing 5–10 parts of pyridine ring dibasic acid and 3–8 parts of triazine ring diamine; Surface modified nanomaterials: 1-3 wt% amino carbon nanotubes and 0.5-1 wt% aramid nanofibers; Copper bromide heat stabilizer 0.3-1 part; Among them, the general formula of the resin structure is: Wherein Py is a pyridine ring, Tri is a triazine ring, a+b+c=100-120, b+c=8-15.

[0006] Further, including: 100 parts of nylon 66 salt; Bis-heterocyclic comonomer: containing 3.5 parts of pyridine ring dibasic acid and 5 parts of triazine ring diamine; Surface modified nanomaterials: 2 wt% amino carbon nanotubes and 0.8 wt% aramid nanofibers; Copper bromide heat stabilizer (0.6 parts).

[0007] Furthermore, the bicyclic heterocyclic comonomer is 2,6-pyridinedicarboxylic acid and 2,4,6-triaminotriazine.

[0008] Furthermore, the plasma grafting rate of the amino-treated carbon nanotubes is 12%.

[0009] Furthermore, the molecular weight of the nylon 66 in-situ nanocomposite resin is 24,000 g / mol, and the heterocyclic unit accounts for 8.5%.

[0010] On the one hand, an embodiment of the present invention provides a melt gradient spinning method for preparing the nylon 66 in-situ nanocomposite resin as described above, characterized in that it comprises: S1: Preparation of nanocomposite resin by in situ polymerization; S2: Pre-dispersed nanoparticles in solid phase thickening tower; S3: The melt is conveyed to the spinning box under pressure after three-stage filtration; S4: A ring heater is set below the spinneret for gradient cooling; S5: Six-roller drafting, shaping and winding.

[0011] Furthermore, the temperature compensation rate of the slow cooling zone of the gradient cooling is 5-10°C / cm, and the drawing and setting includes three stages: preheating at 30-55°C, stretching at 5.0-5.5 times, and heat setting at 180-220°C.

[0012] Further, including: S101: 5 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added; S102: polycondensation at 265°C, vacuum devolatilization, and obtaining a nanocomposite resin; S2: at 160°C, nitrogen countercurrent, nitrogen flow rate 20 L / min, pre-disperse nanoparticles in a solid phase thickening tower to a viscosity of 3.4; S3: The melt is conveyed under pressure after three-stage filtration; S4: Slow cooling with a ring heater, gradient cooling conditions: 280°C → 230°C / 6cm; S5: online plasma treatment, six-roller drafting and winding; The winding speed is 3500 m / min.

[0013] Furthermore, the online plasma treatment includes: using argon as the process gas and inputting a plasma energy of 100 W power.

[0014] Furthermore, the six-roller drawing and shaping conditions include: preheating at 45°C, stretching at 5.3 times, and shaping at 210°C.

[0015] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects: The nylon 66 in-situ nanocomposite resin and its melt gradient spinning method provided by the present invention achieve a breaking strength of ≥9.1 cN / dtex, an H extraction force ≥210 N / cm, a peel strength of 25 N / mm, and a strength retention rate of ≥90% at 180°C×4h of the finished product through the "heterocyclic-nano" two-phase synergy of pyridine ring adsorption glue and triazine ring cross-linked rubber, and amino carbon nanotubes to enhance the interfacial bonding force, and gradient slow cooling of an annular heater to reduce molecular chain entanglement, thereby significantly improving the performance of the finished product compared with domestic conventional nylon 66 fibers. DETAILED DESCRIPTION

[0016] The preferred embodiments of the present invention are described in detail below, wherein the embodiments of the present invention are used to illustrate the principles of the present invention but are not used to limit the scope of the present invention.

[0017] The present invention provides a nylon 66 in-situ nanocomposite resin, comprising: 80–100 parts of nylon 66 salt; Bis-heterocyclic comonomer: Contains 5–10 parts of pyridine ring dibasic acid and 3–8 parts of triazine ring diamine. The bis-heterocyclic comonomer is used to form a rigid network skeleton to improve heat resistance. The pyridine ring absorbs acidic adhesive, and the triazine ring cross-links with rubber sulfide to improve H extraction performance. Surface-modified nanomaterials: 1-3 wt% amino-modified carbon nanotubes and 0.5-1 wt% aramid nanofibers. The amino-modified carbon nanotubes are obtained by plasma grafting modification of carbon nanotubes to introduce amino groups on the surface. These amino groups react with the carboxyl groups at the ends of nylon 66 to enhance interfacial bonding. Copper bromide heat stabilizer 0.3-1 part; Among them, the general formula of the resin structure is: Wherein Py is a pyridine ring, Tri is a triazine ring, a+b+c=100-120, b+c=8-15; wherein, a+b+c=100-120, i.e. the resin molecular weight is controlled at 17000-24000 g / mol; b + c = 8-15, and the heterocyclic unit accounts for 8%-15% of the total units.

[0018] In one possible embodiment, the bicyclic comonomer is 2,6-pyridinedicarboxylic acid and 2,4,6-triaminotriazine.

[0019] In one possible embodiment, the pyridine ring is , the triazine ring is .

[0020] In one possible embodiment, the plasma grafting rate of the aminated carbon nanotubes is 12%, wherein the method for aminated carbon nanotubes comprises: ultrasonically cleaning the carbon nanotubes in acetone for 30 minutes, centrifugally separating and vacuum drying at 80°C for 3.5 hours, placing the carbon nanotubes in a reaction chamber, evacuating the chamber to 0.1 kPa, introducing NH3 / Ar (95:5) to a pressure of 3 kPa, starting a radio frequency power supply (150 W), and treating the chamber for 30 minutes while monitoring the uniformity of the plasma glow. After the treatment, introducing N2 to replace the reaction chamber gas to avoid amino oxidation.

[0021] In one possible embodiment, the molecular weight of the nylon 66 in-situ nanocomposite resin is 24,000 g / mol, and the heterocyclic unit accounts for 8.5%.

[0022] In one aspect, the present invention provides a melt gradient spinning method for preparing the nylon 66 in-situ nanocomposite resin as described above, comprising: S1: Preparation of nanocomposite resin by in situ polymerization; S2: Pre-dispersed nanoparticles in solid phase thickening tower; S3: The melt is conveyed to the spinning box under pressure after three-stage filtration; S4: A ring heater is set below the spinneret for gradient cooling; S5: Six-roller drafting, shaping and winding.

[0023] Among them, the temperature compensation rate of the slow cooling zone of the gradient cooling is 5-10℃ / cm, and the drawing and setting includes three stages: preheating at 30-55℃, stretching at 5.0-5.5 times, and heat setting at 180-220℃.

[0024] In one possible embodiment, the melt gradient spinning method includes: S101: 5 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 8 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino carbon nanotubes, 1 wt% aramid nanofiber, 0.6 parts of copper bromide heat stabilizer; wherein, 2,4,6-triaminotriazine and adipic acid are added to water in a molar ratio of 1:1, stirred at 80°C for 1 hour to react with salt, cooled to room temperature, and allowed to stand in an ice-water bath for 1 hour to complete crystallization, the solid is collected by filtration, washed with cold ethanol 3 times to remove residual acid, and vacuum dried (60°C, 24 hours) to obtain a white crystalline salt; wherein, 2,6-pyridinedicarboxylic acid and hexamethylenediamine are added in a molar ratio of 1:1, specifically, 2,6-pyridinedicarboxylic acid is dissolved in hot ethanol (50-60°C), stirred to dissolve, hexamethylenediamine is added dropwise, the temperature is maintained at <60°C, stirred for reaction for 1 hour to generate a white precipitate, then cooled to 0-5°C (ice bath), aged for 30 minutes, filtered, washed with cold ethanol to remove unreacted matter, and vacuum dried (40°C, 12 hours) to obtain a white powdery salt; S102: polycondensing at 265°C and devolatilizing in vacuum to obtain a nanocomposite resin; S2: at 160°C, under nitrogen protection, nitrogen flow rate 20 L / min, pre-disperse the nanoparticles in a solid phase thickening tower to a viscosity of 3.4; S3: The melt is conveyed under pressure after three-stage filtration, wherein the three-stage filtration includes: suction filtration, sand layer, filter screen, and then conveyed to the spinning box after filtration. The mesh range of the suction filtration screen is 20-40 mesh, the particle size of the sand layer is 0.5-1.2mm, and the mesh of the filter screen is 100-200 mesh; S4: Slow cooling with a ring heater, the gradient cooling conditions are: 280℃→230℃ / 6cm, where the starting temperature is 280℃, the end temperature is 230℃, the temperature difference is ΔT = 280℃ - 230℃ = 50℃, the spatial distance is 6 cm = 0.06 m, and the temperature gradient is: gradient = ΔT / distance, that is, the temperature drops by about 8.33℃ for every 1 cm movement in a specific direction; the ring heater is placed under the spinneret to delay the crystallization time and realize gradient cooling, where the temperature compensation rate in the slow cooling zone is 5–10℃ / cm, and the heater adopts a resistive ring heater, that is, a ceramic or metal matrix is ​​embedded with a resistance wire, surrounding the outer ring of the spinneret, and its diameter is 2-3cm larger than the spinneret, or other conventional heaters that can realize the heating function.

[0025] S5: Online plasma treatment, six-roller drafting, setting, and winding. The online plasma treatment includes: using argon as the process gas and a plasma energy input of 100 W; the six-roller drafting conditions include: preheating at 45°C, stretching 5.3 times, and setting at 210°C; and the winding speed is 3500 m / min.

[0026] Compared with the existing technology, the nylon 66 in-situ nanocomposite resin and its melt gradient spinning method provided by the present invention achieve a breaking strength of ≥9.1 cN / dtex, H extraction force ≥210 N / cm, peel strength of 25 N / mm, and strength retention rate of ≥90% at 180℃×4h of the finished product through the "heterocyclic-nano" two-phase synergy of pyridine ring adsorption glue and triazine ring cross-linked rubber, amino carbon nanotubes to enhance the interface bonding force, and gradient slow cooling of the annular heater to reduce molecular chain entanglement, which significantly improves the performance of the finished product compared with domestic conventional nylon 66 fibers.

[0027] Example 1 The invention discloses a nylon 66 in-situ nanocomposite resin prepared by a melt gradient spinning method, comprising: S101: 5 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added; S102: polycondensation at 265°C, vacuum devolatilization, and obtaining a nanocomposite resin; S2: at 160°C, nitrogen countercurrent, nitrogen flow rate 20 L / min, pre-disperse nanoparticles in a solid phase thickening tower to a viscosity of 3.4; S3: The melt is conveyed under pressure after three-stage filtration; S4: Slow cooling with a ring heater, gradient cooling conditions: 280°C → 230°C / 6cm; S5: online plasma treatment, six-roller drafting and winding; wherein, 2,4,6-triaminotriazine and adipic acid are added to water in a molar ratio of 1:1, stirred at 80°C for 1 hour to carry out a salt-forming reaction, cooled to room temperature, and allowed to stand in an ice-water bath for 1 hour to complete crystallization, the solid is collected by filtration, washed with cold ethanol 3 times to remove residual acid, and vacuum dried (60°C, 24 hours) to obtain a white crystalline salt; wherein, 2,6-pyridinedicarboxylic acid and hexamethylenediamine are added in a molar ratio of 1:1. Specifically, 2,6-pyridinedicarboxylic acid is dissolved in hot ethanol (50-60°C), stirred to dissolve, and hexamethylenediamine is added dropwise, maintaining the temperature <60°C, stirring and reacting for 1 hour to generate a white precipitate, then cooled to 0-5°C (ice bath), aged for 30 minutes, filtered, washed with cold ethanol to remove unreacted matter, and vacuum dried (40°C, 12 hours) to obtain a white powdery salt; Among them, the three-stage filtration includes: suction filtration, sand layer, filter screen, and after filtration, it is transported to the spinning box. Among them, the mesh range of the suction filtration screen is 30 mesh, the particle size of the sand layer is 0.5-1.2mm, and the mesh of the filter screen is 150 mesh; Among them, the winding speed is 3500 m / min; The online plasma treatment includes: using argon as process gas and a plasma energy input of 100 W power; Among them, the six-roller drafting setting conditions include: preheating at 45°C, stretching 5.3 times, and setting at 210°C; Among them, the temperature compensation rate of the slow cooling zone of gradient cooling is 5–10°C / cm.

[0028] Example 2 The difference from Example 1 is: S101: 3 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added.

[0029] Example 3 The difference from Example 1 is: S101: 8 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added.

[0030] Example 4 The difference from Example 1 is: S101: 1 part of 2,4,6-triaminotriazine is reacted with adipic acid to form a salt, and 8 parts of 2,6-pyridinedicarboxylic acid is reacted with hexamethylenediamine to form a salt, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added.

[0031] Example 5 The difference from Example 1 is: S101: 5 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 0.8 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added.

[0032] Comparative Example 1 The difference from Example 1 is: S101: 5 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added.

[0033] Comparative Example 2 The difference from Example 1 is: S101: 3 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, and 0.6 parts of copper bromide heat stabilizer are added.

[0034] Comparative Example 3 The difference from Example 1 is: S101: 8 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 8 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added.

[0035] Comparative Example 4 The difference from Example 1 is that step S4 is not included, that is, the ring heater gradient cooling method is not adopted, and the spindle is directly cooled to 230° C. after being spun out.

[0036] Test 1: Breaking Strength Test Test standard: GB / T 14344-2022 Test method for tensile properties of chemical fiber filaments Testing equipment: electronic universal material testing machine (Instron 5967), pneumatic clamping fixture (to prevent slippage).

[0037] Sample preparation: Take 50 cm long fiber, pre-tension 0.05 cN / dtex; clamping distance 250 mm, pre-stretch to eliminate curl.

[0038] Test conditions: tensile speed: 250 mm / min; temperature: 23±1°C, humidity: 65±5% RH; 30 samples were tested in each group and the average value was taken.

[0039] Result calculation: Breaking strength (cN / dtex) = maximum breaking force (cN) / linear density (dtex) The breaking strength test was performed on Examples 1-5 and Comparative Examples 1-4. The test results are shown in Table 1 below.

[0040] Test 2: H extraction force test Test standard: GB / T 33331-2016 Technical conditions and evaluation methods for nylon 66 dipped cord fabric Testing equipment: H extraction force testing machine (U-CAN UT-2060), rubber vulcanization mold.

[0041] Sample preparation: The cord was embedded in rubber (natural rubber / carbon black = 100 / 50) to a depth of 10 mm. Vulcanization conditions: 150°C × 20 min, pressure 15 MPa.

[0042] Test conditions: tensile speed: 100 mm / min; temperature: 23±1°C; 10 samples were tested in each group, and data with deviation >10% were excluded.

[0043] Result calculation: H extraction force (N / cm) = maximum extraction force (N) / embedded width (cm) The H extraction force test was performed on Examples 1-5 and Comparative Examples 1-4. The test results are shown in Table 1 below: Test 3: Peel strength test Test standard: ASTM D413 Standard Test Method for Bond Strength between Rubber and Rigid Materials Test equipment: Electronic peel tester (Thwing-Alpha T-Peel), T-peel fixture.

[0044] Sample preparation: The cord was composited with a rubber sheet (2 mm thick) with an overlap length of 25 mm. Curing conditions were: 150°C for 20 min and a pressure of 10 MPa.

[0045] Test conditions: Peel angle: 180°; Peel speed: 50 mm / min; Temperature range: -55°C (low temperature chamber) to 200°C (high temperature chamber).

[0046] Result calculation: Peel strength (N / mm) = average peel force (N) / sample width (mm) The peel strength test was performed on Examples 1-5 and Comparative Examples 1-4. The test results are shown in Table 1 below: Test 4: Extreme heat resistance test: 180°C x 4h strength retention Test standard: ISO 188 Rubber, vulcanized or thermoplastic, heat aging tests Testing equipment: hot air circulation aging chamber (BINDER FD-115), electronic universal testing machine.

[0047] Sample preparation: Standard tensile specimens (length 250 mm) were prepared from the same batch of fibers and pre-humidified (105°C × 1 h).

[0048] Aging conditions: temperature: 180±1℃; time: 4 h; wind speed: 0.5 m / s (avoid local overheating).

[0049] Testing process: 1. Test the original fiber breaking strength (S0); 2. After aging, cool to 23°C for 24 h; 3. Test the breaking strength after aging (S1).

[0050] Result calculation: Strength retention (%) = S1 / S0×100 Examples 1-5 and Comparative Examples 1-4 were subjected to extreme heat resistance tests. The test results are shown in Table 1 below: Table 1 Breaking strength (cN / dtex) H extraction force Peel strength 180℃×4h Strength retention (%) Example 1 9.2 215 25 93 Example 2 9.0 205 23 91 Example 3 9.0 215 24 90 Example 4 9.0 195 22 88 Example 5 9.1 208 20 92 Comparative Example 1 9.0 200 18 85 Comparative Example 2 9.0 198 15 91 Comparative Example 3 8.9 203 21 90 Comparative Example 4 8.7 204 22 91 The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. A nylon 66 in-situ nanocomposite resin, characterized in that: Include: 80–100 parts of nylon 66 salt; Bis-heterocyclic comonomer: containing 5–10 parts of pyridine ring dibasic acid and 3–8 parts of triazine ring diamine; Surface modified nanomaterials: 1-3 wt% amino carbon nanotubes and 0.5-1 wt% aramid nanofibers; Copper bromide heat stabilizer 0.3-1 part; Among them, the general formula of the resin structure is: Wherein Py is a pyridine ring, Tri is a triazine ring, a+b+c=100-120, b+c=8-15.

2. The nylon 66 in-situ nanocomposite resin according to claim 1, characterized in that Include: 100 parts of nylon 66 salt; Bis-heterocyclic comonomer: containing 3.5 parts of pyridine ring dibasic acid and 5 parts of triazine ring diamine; Surface modified nanomaterials: 2 wt% amino carbon nanotubes and 0.8 wt% aramid nanofibers; Copper bromide heat stabilizer (0.6 parts).

3. The nylon 66 in-situ nanocomposite resin according to claim 1 or 2, characterized in that: The bicyclic comonomers are 2,6-pyridinedicarboxylic acid and 2,4,6-triaminotriazine.

4. The nylon 66 in-situ nanocomposite resin according to any one of claims 1 to 3, characterized in that The plasma grafting rate of the amino-treated carbon nanotubes was 12%.

5. The nylon 66 in-situ nanocomposite resin according to any one of claims 1 to 4, characterized in that: The molecular weight of the nylon 66 in-situ nanocomposite resin is 24,000 g / mol, and the heterocyclic unit accounts for 8.5%.

6. A melt gradient spinning method for preparing the nylon 66 in-situ nanocomposite resin according to claims 1-5, characterized in that: include: S1: Preparation of nanocomposite resin by in situ polymerization; S2: Pre-dispersed nanoparticles in solid phase thickening tower; S3: The melt is conveyed to the spinning box under pressure after three-stage filtration; S4: A ring heater is set below the spinneret for gradient cooling; S5: Six-roller drafting, shaping and winding.

7. The method according to claim 6, characterized in that: The temperature compensation rate of the slow cooling zone of the gradient cooling is 5-10℃ / cm, and the drawing and setting includes three stages: preheating at 30-55℃, stretching at 5.0-5.5 times, and heat setting at 180-220℃.

8. The method according to claim 6 or 7, characterized in that include: S101: 5 parts of 2,4,6-triaminotriazine and adipic acid are salified, and 3.5 parts of 2,6-pyridinedicarboxylic acid and hexamethylenediamine are salified, and then 100 parts of nylon 66 salt, 2 wt% of amino-treated carbon nanotubes, 1 wt% of aramid nanofibers, and 0.6 parts of copper bromide heat stabilizer are added; S102: polycondensation at 265°C, vacuum devolatilization, and obtaining a nanocomposite resin; S2: at 160°C, nitrogen countercurrent, nitrogen flow rate 20 L / min, pre-disperse nanoparticles in a solid phase thickening tower to a viscosity of 3.4; S3: The melt is conveyed under pressure after three-stage filtration; S4: Slow cooling with a ring heater, gradient cooling conditions: 280°C → 230°C / 6cm; S5: online plasma treatment, six-roller drafting and winding; The winding speed is 3500 m / min.

9. The method according to any one of claims 6 to 8, characterized in that The online plasma treatment includes: using argon as a process gas and inputting a plasma energy of 100 W power.

10. The method according to any one of claims 6 to 9, characterized in that The six-roller drafting and setting conditions include: preheating at 45°C, stretching at 5.3 times, and setting at 210°C.

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