Heat-resistant antistatic polyamide fiber and preparation method thereof

Abstract

The invention discloses a heat-resistant antistatic polyamide fiber and a preparation method thereof, and relates to the technical field of polymer fibers. According to the preparation method, a furan-containing polyamide prepolymer is used as a matrix and is cross-linked with polyether amine and graphene oxide, polymer fibers are prepared through spinning, polyether amine enters an amorphous region of polyamide, graphene oxide and furan groups on polyamide are subjected to a cycloaddition reaction, and the polymer fibers are obtained. A flexible group and a side substituent group are introduced to a rigid polyamide molecule main chain, the hydrophilicity is enhanced, the fiber achieves the antistatic performance, meanwhile, graphene oxide and polyether amine are grafted, the thermal stability of the fiber is greatly improved, then through irradiation treatment, the carbon content and the oxygen content of the fiber are increased, and the anti-static performance of the fiber is improved. The graphene oxide on the surface of the fiber is reduced so as to improve the conductivity and wettability of the surface of the fiber, the graphene oxide on the surface of the fiber is reduced so as to improve the antistatic property, and polyaniline grows on the rough surface of the fiber in situ so as to enhance the stability of the fiber.

Description

Technical Field

[0001] The invention relates to the technical field of polymer fibers, in particular to a heat-resistant and antistatic polyamide fiber and a preparation method thereof. Background Art

[0002] Polyamide fiber has good wear resistance, high breaking strength, good resilience and fatigue resistance, good dyeing performance and other excellent characteristics, so it has a good application in the three major fields of clothing, industry and decorative carpets. However, due to the inherent hydrophobicity and insulation of polyamide fiber, static electricity is serious. The resistivity of ordinary polyamide fiber is as high as 10 14 Ω·cm.

[0003] Recently, some major accidents at home and abroad, such as gas leaks, fires in chemical plants, high dust concentrations in operating workshops, friction in transportation, and oil extraction, are naturally associated with static electricity. Even in ordinary life, static electricity will occur between clothes and the human body. If static electricity is not avoided in time in the above-mentioned production and processing fields, major accidents are likely to occur, causing casualties and endangering the safety of life and property. Static electricity in life can also cause people to be depressed and dizzy, and in the long run, people will be in a sub-healthy state. To put it simply, static electricity makes it difficult for fibers to be bundled and entangled on the machine parts, resulting in difficulties in textile processing. Among them, textiles made of polyamide fibers are easy to stain and absorb dust, making the human body feel uncomfortable when wearing them. These have limited the application of polyamide fibers in many fields. Summary of the invention

[0004] The purpose of the present invention is to provide a heat-resistant and antistatic polyamide fiber and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing heat-resistant and antistatic polyamide fibers, comprising the following preparation steps:

[0006] (1) Under a nitrogen atmosphere, pentaaminoisophthalic acid and methanol are mixed, stirred at 100 rpm until completely dissolved, anhydrous sodium sulfate and acetic acid are added, and during the reaction, furfural is added twice with an interval of 80 to 150 minutes, and then the reaction is continued for 3 to 6 hours, filtered, and the solid is collected to obtain intermediate A;

[0007] (2) Under a nitrogen atmosphere, the intermediate A and methanol are mixed, placed in an ice water bath, sodium borohydride is added four times, each time at an interval of 20 to 60 minutes, and then reacted for 3 to 6 hours. Under a vacuum degree of 50 mbar, rotary evaporation is performed until a solid appears, which is dissolved in deionized water, and the pH of the solution is adjusted to 2 to 4 with dilute hydrochloric acid. The solution is allowed to stand for 1 to 2 hours to precipitate a product, which is washed with deionized water for 3 to 5 times, and dried at 50° C. and a vacuum degree of 0.6 kPa for 4 to 8 hours to obtain a polyamide prepolymer monomer;

[0008] (3) 1-methyl-2-pyrrolidone and lithium chloride are mixed, stirred at 100 rpm until completely dissolved, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, and polyetheramine D2000 are added, stirring is continued for 10 to 30 minutes, pyridine and triphenyl phosphite are added, the temperature is raised to 70° C., and stirred in a nitrogen atmosphere for 1 hour, reacted at 130° C. for 2 to 5 hours, and reacted at 230 to 260° C. for 3 to 5 hours, and graphene oxide dispersion is added, stirred at 200 rpm for 30 to 70 minutes, and extruded and granulated to obtain a polymer;

[0009] (4) The polymer is pretreated, melt-spun, and then 60 The polymer fiber is obtained by irradiation treatment with a Co-γ ray source;

[0010] (5) Aniline and formic acid are mixed, stirred at 150 rpm for 1 hour, deionized water, polyvinyl pyrrolidone, and polymer fibers are added in sequence, and stirring is continued for 2 to 6 hours. The temperature is lowered to 0 to -15°C, ammonium persulfate is added, and the reaction is allowed to stand for 2 to 6 hours. The fibers are then taken out, washed with deionized water for 5 to 8 times, and dried at 40 to 60°C to constant weight to obtain heat-resistant and antistatic polyamide fibers.

[0011] Furthermore, in step (1), the mass ratio of pentaaminoisophthalic acid, methanol, anhydrous sodium sulfate, acetic acid and furfural is 5-6:500:20:20:8-15.

[0012] Furthermore, in step (2), the mass ratio of the intermediate A, methanol and sodium borohydride is 5:500:12-20.

[0013] Furthermore, the preparation method of the graphene oxide dispersion in step (3) is as follows: graphene oxide and 1-methyl-2-pyrrolidone are mixed in a mass ratio of 1 to 5:100, and ultrasonicated at 21 kHz for 70 to 130 min to obtain the dispersion.

[0014] Furthermore, in step (3), the mass ratio of 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000, pyridine, triphenyl phosphite, and graphene oxide dispersion is 25:2-4:1:1:0.04-0.1:5-7:6:1-5.

[0015] Furthermore, the temperature of the extrusion granulation in step (3) is 260-300°C.

[0016] Furthermore, the pretreatment step in step (4) is: baking at 110° C. for 24 hours.

[0017] Furthermore, the process parameters of the melt spinning in step (4) are: temperature of 280-330° C., speed of 500-700 m / min, and draft ratio of 2-4.

[0018] Furthermore, the process parameters of the irradiation in step (4) are: a dose of 2 to 10 kGy and a time of 40 to 80 min.

[0019] Furthermore, in step (5), the mass ratio of aniline, formic acid, deionized water, polyvinyl pyrrolidone, polymer fiber and ammonium persulfate is 2:100:100:4-10:1-3:0.8-1.5.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] The fiber of the invention is made by cross-linking and spinning polyamide, polyetheramine and graphene oxide, and growing polyaniline on the surface thereof, so as to achieve the effects of heat resistance and antistatic.

[0022] Firstly, a furan-containing polyamide prepolymer is used as a matrix, and polyetheramine and graphene oxide are added to cross-link it, wherein the polyetheramine enters the amorphous region of the polyamide and then embeds into the flexible segment. The glassy state and semi-crystalline rigid segment microregions of the polyamide act as cross-linking points to form good physical cross-linking. The graphene oxide is covalently bonded to the polymer matrix to form a uniform cross-linked hybrid network, and through its dienophilic properties, it undergoes a cross-linking cycloaddition reaction with the electron-rich furan group to generate a six-membered ring, thereby forming a six-membered ring in the rigid polyamide molecule. Flexible groups and side substituents are introduced into the main chain to enhance its hydrophilicity and spinnability, and are beneficial to the leakage of accumulated charges on the polymer surface, so that the fiber can achieve antistatic properties. At the same time, the oxygen-containing groups of graphene oxide can be grafted with the amide groups of polyetheramine, thereby enhancing the dispersion of graphene oxide in the matrix, hindering the movement of polymer molecular chains, and increasing the thermal decomposition temperature of the matrix. Graphene oxide and polyetheramine both form a continuous heat conduction channel in the matrix, which is beneficial to the dissipation of heat, thereby greatly improving the thermal stability of the fiber. Then, the polymer fiber is obtained by spinning.

[0023] Secondly, the polymer fiber is irradiated with γ-rays to increase the carbon and oxygen content of the surface polyamide molecules, thereby improving the conductivity and wettability of the fiber surface, and the roughness is also increased. At the same time, the irradiation causes the water molecules in the fiber and in the air to produce a large number of highly reactive substances, among which the hydrated electrons act on the unstable carbonyl and carboxyl groups in the graphene oxide to reduce them, thereby enhancing the conductivity of the fiber surface and further improving the antistatic property. Then, at a low temperature, polyaniline is in situ grown on the rough surface of the fiber, and in the polymerization medium, the surface energy of the liquid is reduced and a large barrier effect is produced through the amphiphilic substance, thereby wrapping the aniline monomer and the polymer, and causing the polyaniline particles to form spherical particles with smaller size and regular appearance, thereby enhancing the interface bonding force with the fiber, and once again enhancing the antistatic property of the fiber through the improvement of conductivity. The graphene exposed on the fiber surface and the polyaniline interact through π-π, so that the spherical polyaniline is evenly distributed on the fiber surface, thereby enhancing the thermal stability and conductive stability of the fiber. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0025] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the heat-resistant and antistatic polyamide fibers prepared in the following examples are as follows:

[0026] Heat resistance: The embodiment and the comparative example of the same size were subjected to hot air treatment at a test temperature of 150°C for 500 h. The strength retention rate was obtained based on the fiber strength before and after the treatment.

[0027] Antistatic: Take the embodiment and comparative example of the same size and use a fiber specific resistance tester to measure the volume specific resistance of the fiber.

[0028] Example 1; (1) Under a nitrogen atmosphere, pentaaminoisophthalic acid and methanol were mixed, stirred at 100 rpm until completely dissolved, anhydrous sodium sulfate and acetic acid were added, and during the reaction, furfural was added twice with an interval of 80 minutes, and then the reaction was continued for 3 hours, filtered, and the solid was taken to obtain intermediate A; the mass ratio of pentaaminoisophthalic acid, methanol, anhydrous sodium sulfate, acetic acid, and furfural was 5:500:20:20:8;

[0029] (2) Under a nitrogen atmosphere, the intermediate A and methanol are mixed, placed in an ice water bath, sodium borohydride is added four times, each time at an interval of 20 minutes, and then reacted for 3 hours. Under a vacuum degree of 50 mbar, the solid is evaporated until solid appears, dissolved in deionized water, and the solution is adjusted to pH 2 with dilute hydrochloric acid. The solution is allowed to stand for 1 hour to precipitate the product, which is washed three times with deionized water and dried at 50° C. and a vacuum degree of 0.6 kPa for 4 hours to obtain a polyamide prepolymer monomer; the mass ratio of the intermediate A, methanol, and sodium borohydride is 5:500:12;

[0030] (3) Graphene oxide and 1-methyl-2-pyrrolidone were mixed at a mass ratio of 1:100, and ultrasonicated at 21 kHz for 70 min to obtain a graphene oxide dispersion; 1-methyl-2-pyrrolidone and lithium chloride were mixed, stirred at 100 rpm until completely dissolved, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, and polyetheramine D2000 were added, and stirring was continued for 10 min, pyridine and triphenyl phosphite were added, the temperature was raised to 70° C., and the reaction was stirred in a nitrogen atmosphere for 1 h, react at 130° C. for 2 h, react at 230° C. for 3 h, add graphene oxide dispersion, stir at 200 rpm for 30 min, and granulate by extrusion at a temperature of 260° C. to obtain a polymer; the mass ratio of 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000, pyridine, triphenyl phosphite, and graphene oxide dispersion is 25:2:1:1:0.04:5:6:1;

[0031] (4) The polymer was pretreated, dried at 110°C for 24 hours, and then melt-spun. The process parameters were: temperature 280°C, speed 500 m / min, draft multiple 2, and then 60 The irradiation treatment was carried out by using a Co-γ ray source, and the process parameters were as follows: the dose was 2 kGy and the time was 40 min, and the polymer fiber was obtained;

[0032] (5) Aniline and formic acid were mixed, stirred at 150 rpm for 1 hour, deionized water, polyvinyl pyrrolidone, and polymer fiber were added in sequence, and stirring was continued for 2 hours. The temperature was lowered to 0°C, ammonium persulfate was added, and the reaction was allowed to stand for 2 hours. The fiber was then taken out, washed with deionized water for 5 times, and dried at 40°C to constant weight to obtain heat-resistant and antistatic polyamide fiber; the mass ratio of aniline, formic acid, deionized water, polyvinyl pyrrolidone, polymer fiber, and ammonium persulfate was 2:100:100:4:1:0.

[0033] Example 2; (1) Under a nitrogen atmosphere, pentaaminoisophthalic acid and methanol were mixed, stirred at 100 rpm until completely dissolved, anhydrous sodium sulfate and acetic acid were added, and during the reaction, furfural was added twice with an interval of 120 min, and then the reaction was continued for 4.5 h, filtered, and the solid was taken to obtain intermediate A; the mass ratio of pentaaminoisophthalic acid, methanol, anhydrous sodium sulfate, acetic acid, and furfural was 5.6:500:20:20:12;

[0034] (2) Under a nitrogen atmosphere, the intermediate A and methanol were mixed, placed in an ice water bath, sodium borohydride was added four times, each time with an interval of 40 minutes, and then reacted for 4 hours. Under a vacuum degree of 50 mbar, the solid was evaporated until solid appeared, dissolved in deionized water, and the solution pH was adjusted to 3 with dilute hydrochloric acid. The solution was allowed to stand for 1.5 hours to precipitate the product, which was washed with deionized water for 4 times and dried at 50° C. and a vacuum degree of 0.6 kPa for 6 hours to obtain a polyamide prepolymer monomer; the mass ratio of the intermediate A, methanol, and sodium borohydride was 5:500:16;

[0035] (3) Graphene oxide and 1-methyl-2-pyrrolidone were mixed in a mass ratio of 3:100, and ultrasonicated at 21 kHz for 100 min to obtain a graphene oxide dispersion; 1-methyl-2-pyrrolidone and lithium chloride were mixed, stirred at 100 rpm until completely dissolved, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, and polyetheramine D2000 were added, and stirring was continued for 20 min, pyridine and triphenyl phosphite were added, the temperature was raised to 70° C., and the reaction was stirred in a nitrogen atmosphere for 1 hour. h, react at 130° C. for 3.5 h, react at 245° C. for 4 h, add graphene oxide dispersion, stir at 200 rpm for 50 min, and granulate by extrusion at a temperature of 280° C. to obtain a polymer; the mass ratio of 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000, pyridine, triphenyl phosphite, and graphene oxide dispersion is 25:3:1:1:0.07:6:6:3;

[0036] (4) The polymer was pretreated, dried at 110°C for 24 hours, and then melt-spun. The process parameters were: temperature of 305°C, speed of 600 m / min, and draft ratio of 3. 60 The irradiation treatment was carried out by using a Co-γ ray source, and the process parameters were as follows: the dose was 6 kGy and the time was 60 min, and the polymer fiber was obtained;

[0037] (5) Aniline and formic acid were mixed, stirred at 150 rpm for 1 hour, deionized water, polyvinyl pyrrolidone, and polymer fiber were added in sequence, and stirring was continued for 4 hours. The temperature was lowered to -10°C, ammonium persulfate was added, and the reaction was allowed to stand for 4 hours. The fiber was then taken out, washed with deionized water for 7 times, and dried at 50°C to constant weight to obtain heat-resistant and antistatic polyamide fiber; the mass ratio of aniline, formic acid, deionized water, polyvinyl pyrrolidone, polymer fiber, and ammonium persulfate was 2:100:100:7:2:1.2.

[0038] Example 3; (1) Under a nitrogen atmosphere, pentaaminoisophthalic acid and methanol were mixed, stirred at 100 rpm until completely dissolved, anhydrous sodium sulfate and acetic acid were added, and during the reaction, furfural was added twice with an interval of 150 min, and then the reaction was continued for 6 h, filtered, and the solid was taken to obtain intermediate A; the mass ratio of pentaaminoisophthalic acid, methanol, anhydrous sodium sulfate, acetic acid, and furfural was 6:500:20:20:15;

[0039] (2) Under a nitrogen atmosphere, the intermediate A and methanol are mixed, placed in an ice water bath, sodium borohydride is added four times, each time at an interval of 60 minutes, and then reacted for 6 hours. Under a vacuum degree of 50 mbar, the solid is evaporated until solid appears, dissolved in deionized water, and the solution is adjusted to pH 4 with dilute hydrochloric acid. The solution is allowed to stand for 2 hours to precipitate the product, which is washed with deionized water 5 times and dried at 50° C. and a vacuum degree of 0.6 kPa for 8 hours to obtain a polyamide prepolymer monomer; the mass ratio of the intermediate A, methanol, and sodium borohydride is 5:500:20;

[0040] (3) Graphene oxide and 1-methyl-2-pyrrolidone were mixed in a mass ratio of 5:100, and ultrasonicated at 21kHz for 130min to obtain a graphene oxide dispersion; 1-methyl-2-pyrrolidone and lithium chloride were mixed, stirred at 100rpm until completely dissolved, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, and polyetheramine D2000 were added, and stirring was continued for 30min, pyridine and triphenyl phosphite were added, the temperature was raised to 70°C, and the reaction was stirred in a nitrogen atmosphere. 1h, react at 130°C for 5h, react at 260°C for 5h, add graphene oxide dispersion, stir at 200rpm for 70min, and granulate by extrusion at a temperature of 300°C to obtain a polymer; the mass ratio of 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000, pyridine, triphenyl phosphite, and graphene oxide dispersion is 25:4:1:1:0.1:7:6:5;

[0041] (4) The polymer was pretreated, dried at 110°C for 24 hours, and then melt-spun with the following process parameters: temperature of 330°C, speed of 700 m / min, and draft ratio of 4. 60The irradiation treatment was carried out by using a Co-γ ray source, and the process parameters were as follows: the dose was 10 kGy and the time was 80 min, and the polymer fiber was obtained;

[0042] (5) Aniline and formic acid were mixed, stirred at 150 rpm for 1 hour, deionized water, polyvinyl pyrrolidone, and polymer fiber were added in sequence, and stirring was continued for 6 hours. The temperature was lowered to -15°C, ammonium persulfate was added, and the reaction was allowed to stand for 6 hours. The fiber was then taken out, washed with deionized water for 8 times, and dried at 60°C to constant weight to obtain heat-resistant and antistatic polyamide fiber; the mass ratio of the aniline, formic acid, deionized water, polyvinyl pyrrolidone, polymer fiber, and ammonium persulfate was 2:100:100:10:3:1.5.

[0043] Comparative Example 1; The difference between Comparative Example 1 and Example 2 is that step (3) is different, and step (3) is changed to: graphene oxide and 1-methyl-2-pyrrolidone are mixed in a mass ratio of 3:100, and ultrasonicated at 21kHz for 100min to obtain a graphene oxide dispersion; 1-methyl-2-pyrrolidone and lithium chloride are mixed, stirred at 100rpm until completely dissolved, polyamide prepolymer monomer and 4,4'-diaminodiphenyl ether are added, stirring is continued for 20min, pyridine and triphenyl phosphite are added, and the temperature is raised to 7 0°C, react with stirring in a nitrogen atmosphere for 1h, react at 130°C for 3.5h, react at 245°C for 4h, add graphene oxide dispersion, stir at 200rpm for 50min, and granulate by extrusion at a temperature of 280°C to obtain a polymer; the mass ratio of 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, pyridine, triphenyl phosphite, and graphene oxide dispersion is 25:3:1:1:6:6:3; the remaining steps are the same as in Example 2.

[0044] Comparative Example 2; The difference between Comparative Example 2 and Example 2 is that step (3) is different, and step (3) is changed to: 1-methyl-2-pyrrolidone and lithium chloride are mixed, stirred at 100rpm until completely dissolved, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000 are added, stirring is continued for 20min, pyridine and triphenyl phosphite are added, the temperature is raised to 70°C, stirred and reacted in a nitrogen atmosphere for 1h, reacted at 130°C for 3.5h, reacted at 245°C for 4h, and granulated by extrusion at a temperature of 280°C to obtain a polymer; the mass ratio of 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000, pyridine and triphenyl phosphite is 25:3:1:1:0.07:6:6; the remaining steps are the same as in Example 2.

[0045] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that step (4) is different. Step (4) is changed to: the polymer is first pretreated, baked at 110°C for 24 hours, and then melt-spun. The process parameters are: temperature of 305°C, speed of 600m / min, and stretching multiple of 3 to obtain polymer fibers; the remaining steps are the same as Example 2.

[0046] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that step (5) is different. Step (5) is changed to: aniline and formic acid are mixed, stirred at 150 rpm for 1 hour, deionized water and polymer fiber are added in sequence, stirring is continued for 4 hours, the temperature is lowered to -10°C, ammonium persulfate is added, and the reaction is allowed to stand for 4 hours. Then the fiber is taken out, washed with deionized water 7 times, and dried at 50°C to constant weight to obtain heat-resistant and antistatic polyamide fiber; the mass ratio of aniline, formic acid, deionized water, polymer fiber and ammonium persulfate is 2:100:100:2:1.2; the remaining steps are the same as Example 2.

[0047] Comparative Example 5; The difference between Comparative Example 5 and Example 2 is that there is no step (5); the remaining steps are the same as Example 2.

[0048] Effect example

[0049] Table 1 below shows the performance analysis results of the heat-resistant and antistatic polyamide fibers of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0050] Table 1

[0051] Retention rate (%) Volume resistivity (Ω·cm) Example 1 92.4 <![CDATA[8.7×10 4 ]]> Example 2 93.8 <![CDATA[1.5×10 4 ]]> Example 3 93.3 <![CDATA[4.1×10 4 ]]> Comparative Example 1 90.1 <![CDATA[2.6×10 5 ]]> Comparative Example 2 83.2 <![CDATA[7.8×10 6 ]]> Comparative Example 3 87.7 <![CDATA[8.9×10 5 ]]> Comparative Example 4 90.6 <![CDATA[1.9×10 5 ]]> Comparative Example 5 89.9 <![CDATA[6.2×10 7 ]]>

[0052] From the comparison of the experimental data of the embodiment and the comparative example in Table 1, it can be found that the present invention uses a furan-containing polyamide prepolymer as a matrix, and cross-links it with polyetheramine and graphene oxide, wherein the polyetheramine enters the amorphous region of the polyamide and then embeds the flexible chain segment to form a good physical cross-linking, wherein the graphene oxide forms a uniform cross-linked hybrid network with the polymer matrix, and through its dienophilic properties, undergoes a cross-linked cycloaddition reaction with the furan group to generate a six-membered ring, thereby enhancing its hydrophilicity, and is beneficial to the leakage of the accumulated charge on the polymer surface, so that the fiber achieves antistatic properties, and at the same time, the oxygen-containing group of the graphene oxide can be grafted with the amide group of the polyetheramine, thereby enhancing the dispersibility of the graphene oxide in the matrix, hindering the movement of the polymer molecular chain, and increasing the thermal decomposition temperature of the matrix, and the graphene oxide and the polyetheramine form a continuous heat conduction channel in the matrix. , which is conducive to the dissipation of heat, thereby greatly improving the thermal stability of the fiber. Then, the polymer fiber is obtained by spinning and irradiated. The carbon content and oxygen content of the surface polyamide molecules are increased by γ-rays, thereby improving the conductivity and wettability of the fiber surface, and the roughness is also increased. At the same time, the irradiation also acts on the graphene oxide to reduce it, further improving the antistatic property. Then, at a low temperature, polyaniline is in situ grown on the rough surface of the fiber, and in the polymerization medium, through amphiphilic substances, the polyaniline particles are prompted to form spherical particles with smaller size and regular appearance, thereby enhancing the interfacial bonding force with the fiber and once again enhancing the antistatic property of the fiber. The graphene exposed on the fiber surface interacts with the polyaniline through π-π, so that the spherical polyaniline is evenly distributed on the fiber surface, thereby enhancing the thermal stability and conductive stability of the fiber.

[0053] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing heat-resistant and antistatic polyamide fiber, characterized in that: The method comprises the following preparation steps: (1) Under a nitrogen atmosphere, pentaaminoisophthalic acid and methanol are mixed, stirred at 100 rpm until completely dissolved, anhydrous sodium sulfate and acetic acid are added, and during the reaction, furfural is added twice with an interval of 80 to 150 minutes, and then the reaction is continued for 3 to 6 hours, filtered, and the solid is collected to obtain intermediate A; (2) Under a nitrogen atmosphere, the intermediate A and methanol are mixed, placed in an ice water bath, sodium borohydride is added four times, each time at an interval of 20 to 60 minutes, and then reacted for 3 to 6 hours. Under a vacuum degree of 50 mbar, rotary evaporation is performed until a solid appears, which is dissolved in deionized water, and the pH of the solution is adjusted to 2 to 4 with dilute hydrochloric acid. The solution is allowed to stand for 1 to 2 hours to precipitate a product, which is washed with deionized water for 3 to 5 times, and dried at 50° C. and a vacuum degree of 0.6 kPa for 4 to 8 hours to obtain a polyamide prepolymer monomer; (3) 1-methyl-2-pyrrolidone and lithium chloride are mixed, stirred at 100 rpm until completely dissolved, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, and polyetheramine D2000 are added, stirring is continued for 10 to 30 minutes, pyridine and triphenyl phosphite are added, the temperature is raised to 70° C., and stirred in a nitrogen atmosphere for 1 hour, reacted at 130° C. for 2 to 5 hours, and reacted at 230 to 260° C. for 3 to 5 hours, and graphene oxide dispersion is added, stirred at 200 rpm for 30 to 70 minutes, and extruded and granulated to obtain a polymer; (4) The polymer is pretreated, melt-spun, and then 60 The polymer fiber is obtained by irradiation treatment with a Co-γ ray source; (5) Aniline and formic acid are mixed, stirred at 150 rpm for 1 hour, deionized water, polyvinyl pyrrolidone, and polymer fibers are added in sequence, and stirring is continued for 2 to 6 hours. The temperature is lowered to 0 to -15°C, ammonium persulfate is added, and the reaction is allowed to stand for 2 to 6 hours. The fibers are then taken out, washed with deionized water for 5 to 8 times, and dried at 40 to 60°C to constant weight to obtain heat-resistant and antistatic polyamide fibers.

2. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The mass ratio of pentaaminoisophthalic acid, methanol, anhydrous sodium sulfate, acetic acid and furfural in step (1) is 5-6:500:20:20:8-15.

3. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The mass ratio of the intermediate A, methanol and sodium borohydride in step (2) is 5:500:12-20.

4. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The preparation method of the graphene oxide dispersion in step (3) is as follows: graphene oxide and 1-methyl-2-pyrrolidone are mixed in a mass ratio of 1 to 5:100, and ultrasonicated at 21 kHz for 70 to 130 min to obtain the dispersion.

5. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The mass ratio of the 1-methyl-2-pyrrolidone, lithium chloride, polyamide prepolymer monomer, 4,4'-diaminodiphenyl ether, polyetheramine D2000, pyridine, triphenyl phosphite, and graphene oxide dispersion in step (3) is 25:2-4:1:1:0.04-0.1:5-7:6:1-5.

6. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The temperature of the extrusion granulation in step (3) is 260-300°C.

7. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The pretreatment step in step (4) is: baking at 110° C. for 24 hours.

8. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The process parameters of the melt spinning in step (4) are: temperature of 280-330° C., speed of 500-700 m / min, and drafting multiple of 2-4.

9. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The process parameters of the irradiation in step (4) are: a dose of 2 to 10 kGy and a time of 40 to 80 min.

10. The method for preparing heat-resistant and antistatic polyamide fiber according to claim 1, characterized in that: The mass ratio of aniline, formic acid, deionized water, polyvinyl pyrrolidone, polymer fiber and ammonium persulfate in step (5) is 2:100:100:4-10:1-3:0.8-1.5.