Far infrared heating fiber based on bio-based polyester and preparation method thereof

Abstract

The application provides a far-infrared heating fiber based on a bio-based polyester and a preparation method thereof, and relates to the technical field of fibers.The application is characterized in that: an azide polycaprolactone is prepared, a cyclization addition reaction is caused between an azide group and a far-infrared material carbon nanotube sidewall, the polycaprolactone is modified on the surface of the carbon nanotube, the dispersibility of the carbon nanotube in a matrix is improved, the terminal hydroxyl group of the polycaprolactone is used together with a hydrophilic chain segment polyethylene glycol to participate in a polycondensation reaction of a bio-based poly 2,5-furandicarboxylic acid-based copolyester, finally, a carbon nanotube / copolyester composite material with good hydrophilic performance and good antistatic performance is prepared, the carbon nanotube / copolyester composite material is introduced into polyester chips for melt spinning, the synergistic effect between the hydrophilic chain segment in the copolyester and the carbon nanotube is utilized, the moisture absorption and antistatic performance of the polyester fiber are improved, and meanwhile, the fiber is endowed with a far-infrared heating function.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fibers, in particular to a far-infrared heating fiber based on bio-based polyester and a preparation method thereof. BACKGROUND

[0002] Polyester is an important variety of synthetic fibers, which is a fiber-forming polymer polyethylene terephthalate made from terephthalic acid or dimethyl terephthalate and ethylene glycol as raw materials through esterification or transesterification and polycondensation. Far-infrared polyester fiber refers to a fiber made by adding an absorber that can absorb external heat and emit far-infrared rays during the processing of polyester fiber. The far-infrared agent can absorb external heat and emit far-infrared rays to the body, thereby achieving the effect of body temperature rise. The current processing method of far-infrared textiles includes coating method, implantation method, spinning method, etc. The preparation method of far-infrared polyester fiber can be divided into three kinds: melt spinning method, blending spinning method and coating method. The selection of far-infrared agent is inorganic material with far-infrared emission performance.

[0003] Although polyester has many excellent properties, such as high strength, good elasticity, excellent heat and wear resistance, etc., the moisture absorption and antistatic properties of polyester fiber are poor, which limits its application. Blending of antistatic agent and hydrophilic material in polyester is one of the effective means to improve the performance of polyester fiber.

[0004] Therefore, in view of the deficiencies of the prior art, it is necessary to design a far-infrared polyester fiber based on hydrophilic bio-based polyester modification to improve the moisture absorption and antistatic properties of far-infrared polyester fiber. SUMMARY

[0005] In order to overcome the deficiencies of the prior art, the present application aims to provide a far-infrared heating fiber based on bio-based polyester and a preparation method thereof. By preparing azido polycaprolactone, using the cycloaddition reaction of azido group with the side wall of far-infrared material carbon nanotube, polycaprolactone is modified on the surface of carbon nanotube to improve the dispersibility of carbon nanotube in the matrix. Then, the terminal hydroxyl group of polycaprolactone is used together with hydrophilic segment polyethylene glycol to participate in the polycondensation reaction of bio-based poly 2,5-furandicarboxylic acid-based copolyester. Finally, a carbon nanotube / copolyester composite material with good hydrophilic performance and good antistatic performance is prepared. The composite material is introduced into polyester chip for melt spinning. By using the synergistic effect between the hydrophilic segment in the copolyester and the carbon nanotube, the moisture absorption and antistatic properties of the polyester fiber are improved, and the fiber is also endowed with far-infrared heating function.

[0006] To achieve the above and other related purposes, the technical solution provided by the present application is as follows:

[0007] A preparation method of a far-infrared heating fiber based on bio-based polyester, comprising the following steps:

[0008] Step (1), 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, stannous octoate are mixed as reactants, toluene is added and mixed uniformly, reacted, after the reaction is completed, purified, to obtain chlorinated modified polycaprolactone;

[0009] Step (2), the chlorinated modified polycaprolactone, sodium azide, N,N-dimethylformamide are mixed, reacted, after the reaction is completed, purified, to obtain azidated polycaprolactone;

[0010] Step (3), the azidated polycaprolactone, N,N-dimethylacetamide L are mixed and dissolved, the N,N-dimethylacetamide mixed solution of multi-walled carbon nanotubes is added, stirred and mixed, reacted, after the reaction is completed, suction filtered, washed, dried, to obtain polycaprolactone modified carbon nanotubes;

[0011] Step (4), 2,5-furandicarboxylic acid dimethyl ester, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, antioxidant 1010 are mixed, melted, reacted, after the reaction is completed, polyethylene glycol and polycaprolactone modified carbon nanotubes are added and mixed uniformly, heated, continued to react, after the reaction is completed, cooled, to obtain carbon nanotube / copolyester composite material;

[0012] Step (5), the carbon nanotube / copolyester composite material, terylene chip are blended, melt spun, cooled and drawn, to obtain far infrared heating fiber based on bio-based polyester.

[0013] Preferably, in step (1), the molar ratio of 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol and stannous octoate is 1.3-1.5:15.8-16.5:0.1-0.15:0.3-0.33; the solid-liquid ratio of the reactants to toluene is 20g:30-50mL.

[0014] Preferably, in step (1), the reaction conditions are: polymerization reaction under argon atmosphere at 60-70℃ for 48-56h.

[0015] Preferably, in step (1), the purification operation includes: chloroform is added for dissolution, ethanol is added for precipitation, filtration, and the operation of dissolution, precipitation and filtration is repeated once, and the precipitate is dried.

[0016] Preferably, in step (2), the solid-liquid ratio of chlorinated modified polycaprolactone, sodium azide and N,N-dimethylformamide is 10g:6-8g:30-50mL; the reaction conditions are: stirring reaction at room temperature for 24-28h.

[0017] Preferably, in the step (2), the purification operation comprises: removing the solvent by distillation under reduced pressure, adding chloroform, washing with water, separating the liquid, taking the organic phase, adding anhydrous magnesium sulfate, standing and drying, and removing the solvent by rotary evaporation.

[0018] Preferably, in the step (3), the mass ratio of the azide poly-caprolactone and the multi-walled carbon nanotube is 10:0.5-1.5, and the reaction condition is that the reaction is carried out at a temperature of 155-165 DEG C for 2.5-4h.

[0019] Preferably, in the step (4), the molar ratio of the dimethyl 2,5-furandicarboxylate and the ethylene glycol is 1:1-1.3, the catalyst ethylene glycol antimony, the catalyst zinc acetate, the thermal stabilizer trimethyl phosphate, and the antioxidant 1010 are added in an amount of 0.1-0.3% of the mass of the dimethyl 2,5-furandicarboxylate, and the mass ratio of the dimethyl 2,5-furandicarboxylate, the polyethylene glycol, and the poly-caprolactone modified carbon nanotube is 36:11-15:5-6, and the reaction condition is that the reaction is carried out in a nitrogen atmosphere, at a pressure of 400-700pa and a temperature of 90-100 DEG C, the temperature is raised to 180-190 DEG C, and the reaction is carried out for 3-4h, and the continuous reaction condition is that the reaction is continuously carried out in a nitrogen atmosphere, at a pressure of 80-100pa and a temperature of 230-240 DEG C for 4-5h.

[0020] Preferably, in the step (5), the mass ratio of the carbon nanotube / copolyester composite material and the terylene chip is 16-20:80-84, the melt spinning condition is that the melt spinning is carried out at a temperature of 275-285 DEG C in a first zone to a second zone, 285-290 DEG C in a third zone to a fifth zone, and a spinning speed of 1500-2500m / min, and the draft ratio is 3-3.8 times.

[0021] Preferably, the bio-based polyester-based far infrared heating fiber is prepared by the preparation method of the bio-based polyester-based far infrared heating fiber.

[0022] Due to the use of the above technical scheme, the application has the beneficial effects of:

[0023] The application improves the dispersibility of the carbon nanotube in the matrix by preparing the azide poly-caprolactone, utilizing the cyclization addition reaction of the azide group and the far infrared material carbon nanotube sidewall, modifying the poly-caprolactone on the surface of the carbon nanotube, and utilizing the end hydroxyl group of the poly-caprolactone and the hydrophilic segment polyethylene glycol to participate in the polycondensation reaction of the bio-based poly-2,5-furandicarboxylic acid-based copolyester, finally preparing the carbon nanotube / copolyester composite material with good hydrophilic performance and good antistatic performance, introducing the carbon nanotube / copolyester composite material into the terylene chip for melt spinning, utilizing the synergistic effect between the hydrophilic segment in the copolyester and the carbon nanotube to improve the moisture absorption and antistatic performance of the terylene fiber, and simultaneously endowing the fiber with the far infrared heating function.

[0024] The application utilizes 2-chloro-epsilon-caprolactone, 6-caprolactone as caprolactone monomers, neopentyl glycol as an initiator, and stannous octoate as a catalyst to prepare chlorinated modified poly-caprolactone containing terminal hydroxyl and chlorine groups through ring-opening copolymerization, and then utilizes nucleophilic substitution reaction to convert the chlorinated modified poly-caprolactone into azide-modified poly-caprolactone through sodium azide, and finally utilizes the ring-opening addition reaction of the azide group with the sidewall of carbon nanotubes to modify the poly-caprolactone on the surface of the carbon nanotubes without damaging the structure of the carbon nanotubes, which not only improves the dispersibility and compatibility of the carbon nanotubes in the matrix, but also introduces active groups of hydroxyl groups through the poly-caprolactone, so that further reactions can occur.

[0025] The application introduces the bio-based poly-2,5-furandicarboxylic acid-based copolyester into the material through ester exchange reaction of 2,5-furandicarboxylic acid dimethyl ester and ethylene glycol, and then through polycondensation reaction of polyethylene glycol and poly-caprolactone modified carbon nanotubes, which on one hand improves the antistatic property of the material through the hydrophilic segment of the polyethylene glycol and the conductivity of the carbon nanotubes, and on the other hand further improves the dispersibility and compatibility of the carbon nanotubes in the polyester chip. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The moisture regain column chart of the bio-based polyester-based far infrared heating fiber prepared in the examples and comparative examples in the performance test;

[0027] Figure 2 The electrostatic voltage half-life fold line chart of samples 1-7 prepared in the examples and comparative examples in the performance test. DETAILED DESCRIPTION

[0028] The embodiments of the application are illustrated by specific specific examples below, and those skilled in the art can easily understand other advantages and effects of the application from the contents disclosed in the specification.

[0029] Example 1

[0030] The embodiment discloses a preparation method of a bio-based polyester-based far infrared heating fiber, comprising the following steps:

[0031] Step (1), 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol and stannous octoate are mixed as reactants, toluene is added and mixed uniformly in an argon atmosphere, and the temperature is raised to 70 DEG C for polymerization reaction for 48 h, after the reaction is completed, chloroform is added for dissolution, ethanol is added for precipitation, filtration is performed, and the operation of dissolution, precipitation and filtration is repeated once, and the precipitate is dried at a temperature of 40 DEG C for 12 h to obtain chlorinated modified poly-caprolactone;

[0032] The molar ratio of 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol, stannous octoate is 1.3:16.5:0.1:0.3; the solid-liquid ratio of the reactants and toluene is 20g:30mL;

[0033] Step (2), the chlorinated modified polycaprolactone, sodium azide, N,N-dimethylformamide are mixed in a solid-liquid ratio of 10g:7g:30mL, stirred at room temperature for 24h, after the reaction is completed, the solvent is removed by reduced pressure distillation, chloroform is added, washed with water, separated, take the organic phase, add anhydrous magnesium sulfate and dry, remove the solvent by rotary evaporation, dry at 45℃ for 12h, to obtain azidation polycaprolactone;

[0034] Step (3), the azidation polycaprolactone, N,N-dimethylacetamide are mixed and dissolved in a solid-liquid ratio of 1g:10mL, a multi-walled carbon nanotube N,N-dimethylacetamide mixture is added, stirred and mixed for 10min, reacted at 160℃ for 3h, after the reaction is completed, filtered, take the filter cake, washed with acetone for 3 times, dry at 60℃ for 24h, to obtain polycaprolactone modified carbon nanotubes;

[0035] The mass ratio of azidation polycaprolactone and multi-walled carbon nanotubes is 10:1; the multi-walled carbon nanotube N,N-dimethylacetamide mixture is prepared by mixing multi-walled carbon nanotubes and N,N-dimethylacetamide in a solid-liquid ratio of 1:500 and ultrasonic dispersion for 30min;

[0036] Step (4), 2,5-furandicarboxylic acid dimethyl ester, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, antioxidant 1010 are mixed, melted in a nitrogen atmosphere, pressure 500pa, temperature 90℃, heated to 190℃ and reacted for 3-4h, after the reaction is completed, polyethylene glycol and polycaprolactone modified carbon nanotubes are added and mixed uniformly, heated, reacted in a nitrogen atmosphere, pressure 80-100pa, temperature 235℃ for 4h, after the reaction is completed, cooled, to obtain carbon nanotube / copolyester composite material;

[0037] The molar ratio of 2,5-furandicarboxylic acid dimethyl ester and ethylene glycol is 1:1.3; the added mass of catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate and antioxidant 1010 is 0.15% of the added mass of 2,5-furandicarboxylic acid dimethyl ester; the mass ratio of 2,5-furandicarboxylic acid dimethyl ester, polyethylene glycol and polycaprolactone modified carbon nanotubes is 36:11:5;

[0038] Step (5), the carbon nanotube / copolyester composite material and terylene chip are blended in a mass ratio of 16:84 at a temperature of 250℃, melt spun, cooled and drawn, to obtain a far infrared heating fiber based on a bio-based polyester;

[0039] wherein the melt spinning conditions are: melt spinning at a temperature of 280°C in zone 1 to zone 2, 290°C in zone 3 to zone 5, and a spinning speed of 2000 m / min; and the draw ratio is 3.8 times.

[0040] Example 2

[0041] The present embodiment discloses a preparation method of a far infrared heating fiber based on a bio-based polyester, comprising the following steps:

[0042] Step (1), 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol, stannous octoate are mixed as reactants, toluene is added and mixed uniformly in an argon atmosphere, the temperature is raised to 70°C, and the polymerization reaction is carried out for 48 h. After the reaction is completed, chloroform is added for dissolution, ethanol is added for precipitation, filtration is carried out, and the operation of dissolution, precipitation and filtration is repeated once. The precipitate is dried at a temperature of 40°C for 12 h to obtain chlorinated modified poly caprolactone;

[0043] wherein the molar ratio of 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol and stannous octoate is 1.35:16:0.1:0.3; and the solid-liquid ratio of the reactants to toluene is 20 g:30 mL;

[0044] Step (2), chlorinated modified poly caprolactone, sodium azide and N,N-dimethylformamide are mixed in a solid-liquid ratio of 10 g:7 g:30 mL, and stirred at room temperature for 24 h. After the reaction is completed, the solvent is removed by reduced pressure distillation, chloroform is added, washed with water, separated, and the organic phase is taken. Anhydrous magnesium sulfate is added and dried, the solvent is removed by rotary evaporation, and dried at a temperature of 45°C for 12 h to obtain azidated poly caprolactone;

[0045] Step (3), azidated poly caprolactone and N,N-dimethylacetamide are mixed and dissolved in a solid-liquid ratio of 1 g:10 mL, and a multi-walled carbon nanotube N,N-dimethylacetamide mixture is added. After stirring and mixing for 10 min, the reaction is carried out at a temperature of 160°C for 3 h. After the reaction is completed, the filter cake is taken, washed with acetone for 3 times, and dried at a temperature of 60°C for 24 h to obtain poly caprolactone modified carbon nanotubes.

[0046] wherein the mass ratio of azidated poly caprolactone to multi-walled carbon nanotubes is 10:1; and the multi-walled carbon nanotube N,N-dimethylacetamide mixture is prepared by mixing multi-walled carbon nanotubes and N,N-dimethylacetamide in a solid-liquid ratio of 1:500 and ultrasonic dispersion for 30 min;

[0047] Step (4), mix dimethyl 2,5-furandicarboxylate, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, thermal stabilizer trimethyl phosphate, antioxidant 1010, melt under nitrogen atmosphere, pressure 500 pa, temperature 90℃, heat to 190℃, react for 3-4h, after the reaction, add polyethylene glycol and polycaprolactone modified carbon nanotubes, heat, react under nitrogen atmosphere, pressure 80-100 pa, temperature 235℃ for 4h, after the reaction, cool, obtain carbon nanotube / copolyester composite material;

[0048] The molar ratio of dimethyl 2,5-furandicarboxylate and ethylene glycol is 1:1.3; the added mass of catalyst ethylene glycol antimony, catalyst zinc acetate, thermal stabilizer trimethyl phosphate and antioxidant 1010 is 0.15% of the added mass of dimethyl 2,5-furandicarboxylate; the mass ratio of dimethyl 2,5-furandicarboxylate, polyethylene glycol and polycaprolactone modified carbon nanotubes is 36:12:5.3;

[0049] Step (5), blend carbon nanotube / copolyester composite material and terylene chip at a mass ratio of 17:83 at a temperature of 250℃, melt and spin, and cool and draw to obtain a far infrared heating fiber based on a bio-based polyester;

[0050] The melt spinning conditions are: melt spinning under the conditions of a temperature of 280℃ in the first zone to the second zone, 290℃ in the third zone to the fifth zone, and a spinning speed of 2000 m / min; and the draw ratio is 3.8 times.

[0051] Embodiment 3

[0052] The embodiment discloses a preparation method of a far infrared heating fiber based on a bio-based polyester, comprising the following steps:

[0053] Step (1), mix 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol and stannous octoate as reactants, add toluene and mix uniformly under argon atmosphere, heat to 70℃, and polymerize for 48h, after the reaction, dissolve in chloroform, precipitate in ethanol, filter, repeat the operation of dissolving, precipitating and filtering once, and dry the precipitate at a temperature of 40℃ for 12h to obtain chlorinated modified polycaprolactone;

[0054] The molar ratio of 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol and stannous octoate is 1.4:16.1:0.1:0.3; and the solid-liquid ratio of the reactants to toluene is 20g:30mL;

[0055] Step (2), chlorinated modified polycaprolactone, sodium azide, N, N-dimethylformamide were mixed at a solid-liquid ratio of 10 g:7 g:30 mL, stirred at room temperature for 24 h, after the reaction was completed, the solvent was removed by reduced pressure distillation, chloroform was added, washed with water, separated, took the organic phase, added anhydrous magnesium sulfate and dried, removed the solvent by rotary evaporation, dried at 45℃ for 12 h, to obtain azidation polycaprolactone;

[0056] Step (3), azidation polycaprolactone, N, N-dimethylacetamide were mixed and dissolved at a solid-liquid ratio of 1 g:10 mL, N, N-dimethylacetamide mixed solution of multi-walled carbon nanotubes was added, stirred and mixed for 10 min, reacted at 160℃ for 3 h, after the reaction was completed, filtered, took the filter cake, washed with acetone for 3 times, dried at 60℃ for 24 h, to obtain polycaprolactone modified carbon nanotubes;

[0057] Wherein, the mass ratio of azidation polycaprolactone and multi-walled carbon nanotubes is 10:1; the N, N-dimethylacetamide mixed solution of multi-walled carbon nanotubes is prepared by mixing multi-walled carbon nanotubes and N, N-dimethylacetamide at a solid-liquid ratio of 1:500, ultrasonic dispersion for 30 min;

[0058] Step (4), 2, 5-furan dimethyl acid, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, antioxidant 1010 were mixed, melted at 90℃ under nitrogen atmosphere and 500pa pressure, heated to 190℃ and reacted for 3-4 h, after the reaction was completed, polyethylene glycol and polycaprolactone modified carbon nanotubes were added and mixed uniformly, heated, reacted at 235℃ under nitrogen atmosphere and 80-100pa pressure for 4 h, after the reaction was completed, cooled, to obtain carbon nanotube / copolyester composite material;

[0059] Wherein, the molar ratio of 2, 5-furan dimethyl acid and ethylene glycol is 1:1.3; the added mass of catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate and antioxidant 1010 is 0.15% of the added mass of 2, 5-furan dimethyl acid; the mass ratio of 2, 5-furan dimethyl acid, polyethylene glycol and polycaprolactone modified carbon nanotubes is 36:13:5.5;

[0060] Step (5), carbon nanotube / copolyester composite material and polyester chip were blended at a mass ratio of 18:82 at 250℃, melt spun, cooled and drawn, to obtain far infrared heating fiber based on bio-based polyester;

[0061] Wherein, the melt spinning conditions are: melt spinning under the conditions of temperature zone 1 to zone 2 280℃, zone 3 to zone 5 290℃, and spinning speed 2000m / min; the draw ratio is 3.8 times.

[0062] Example 4

[0063] The present embodiment discloses a preparation method of far infrared heating fiber based on bio-based polyester, comprising the following steps:

[0064] Step (1), 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, stannous octoate are mixed as reactants, toluene is added and mixed uniformly in an argon atmosphere, and the temperature is raised to 70 DEG C for polymerization reaction for 48 h. After the reaction is completed, chloroform is added for dissolution, ethanol is added for precipitation, filtration is performed, and the operation of dissolution, precipitation and filtration is repeated once. The precipitate is dried at a temperature of 40 DEG C for 12 h to obtain chlorinated modified polycaprolactone;

[0065] In the formula, the molar ratio of 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, stannous octoate is 1.4:5:16.3:0.1:0.3; and the solid-liquid ratio of the reactants to toluene is 20 g:30 mL;

[0066] Step (2), chlorinated modified polycaprolactone, sodium azide and N,N-dimethylformamide are mixed in a solid-liquid ratio of 10 g:7 g:30 mL, and stirred at room temperature for 24 h. After the reaction is completed, the solvent is removed by distillation under reduced pressure, chloroform is added, washed with water, separated, and the organic phase is taken. Anhydrous magnesium sulfate is added and dried, and the solvent is removed by rotary evaporation. The mixture is dried at a temperature of 45 DEG C for 12 h to obtain azidated polycaprolactone;

[0067] Step (3), azidated polycaprolactone and N,N-dimethylacetamide are mixed and dissolved in a solid-liquid ratio of 1 g:10 mL, and a multi-walled carbon nanotube N,N-dimethylacetamide mixture is added. The mixture is stirred for 10 min, and reacted at a temperature of 160 DEG C for 3 h. After the reaction is completed, the filter cake is taken, washed with acetone for 3 times, and dried at a temperature of 60 DEG C for 24 h to obtain polycaprolactone modified carbon nanotubes;

[0068] In the formula, the mass ratio of azidated polycaprolactone to multi-walled carbon nanotube is 10:1; and the multi-walled carbon nanotube N,N-dimethylacetamide mixture is prepared by mixing multi-walled carbon nanotubes and N,N-dimethylacetamide in a solid-liquid ratio of 1:500 and ultrasonic dispersion for 30 min;

[0069] Step (4), 2,5-furandicarboxylic acid dimethyl ester, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, and antioxidant 1010 are mixed, melted in a nitrogen atmosphere, at a pressure of 500 pa and a temperature of 90 DEG C, the temperature is raised to 190 DEG C, and reacted for 3-4 h. After the reaction is completed, polyethylene glycol and polycaprolactone modified carbon nanotubes are added and mixed uniformly, the temperature is raised, and the mixture is reacted in a nitrogen atmosphere, at a pressure of 80-100 pa and a temperature of 235 DEG C for 4 h. After the reaction is completed, the mixture is cooled to obtain carbon nanotube / copolyester composite material;

[0070] The molar ratio of dimethyl 2,5-furan dicarboxylate and ethylene glycol is 1:1.3; the added mass of the catalyst ethylene glycol antimony, the catalyst zinc acetate, the thermal stabilizer trimethyl phosphate, and the antioxidant 1010 is 0.15% of the added mass of dimethyl 2,5-furan dicarboxylate; the mass ratio of dimethyl 2,5-furan dicarboxylate, polyethylene glycol, and poly-caprolactone modified carbon nanotubes is 36:14:5.8;

[0071] Step (5), blending the carbon nanotube / copolyester composite material and the terylene chip at a mass ratio of 19:81 at a temperature of 250 DEG C, melt spinning, cooling and drawing to obtain the far infrared heating fiber based on the bio-based polyester;

[0072] The melt spinning conditions are as follows: melt spinning under the conditions that the temperature is 280 DEG C in the first zone to the second zone, 290 DEG C in the third zone to the fifth zone, and the spinning speed is 2000 m / min; and the draw ratio is 3.8 times.

[0073] Embodiment 5

[0074] The embodiment discloses a preparation method of a far infrared heating fiber based on bio-based polyester, comprising the following steps:

[0075] Step (1), mixing 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, and stannous octoate as reactants, adding toluene, mixing uniformly in an argon atmosphere, heating to 70 DEG C, and polymerizing for 48 h; after the reaction is completed, dissolving in chloroform, precipitating in ethanol, filtering, repeating the operation of dissolving, precipitating, and filtering once, and drying the precipitate at a temperature of 40 DEG C for 12 h to obtain chlorinated modified poly-caprolactone;

[0076] The molar ratio of 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, and stannous octoate is 1.5:15.8:0.1:0.3; and the solid-liquid ratio of the reactants to toluene is 20 g:30 mL;

[0077] Step (2), mixing chlorinated modified poly-caprolactone, sodium azide, and N,N-dimethylformamide at a solid-liquid ratio of 10 g:7 g:30 mL, stirring at room temperature for 24 h, removing the solvent by distillation under reduced pressure after the reaction is completed, washing with chloroform, separating the liquid, taking the organic phase, adding anhydrous magnesium sulfate, standing and drying, removing the solvent by rotary evaporation, and drying at a temperature of 45 DEG C for 12 h to obtain azidated poly-caprolactone;

[0078] Step (3), the azidation polycaprolactone, N, N-dimethylacetamide is mixed and dissolved with a solid-liquid ratio of 1 g:10 mL, the multi-walled carbon nanotube N, N-dimethylacetamide mixed solution is added, stirring and mixing for 10 min, reacting at a temperature of 160 DEG C for 3 h, after the reaction is completed, suction filtration is performed, the filter cake is taken, washed with acetone for 3 times, and dried at a temperature of 60 DEG C for 24 h to obtain polycaprolactone modified carbon nanotubes;

[0079] The mass ratio of the azidation polycaprolactone and the multi-walled carbon nanotube is 10:1; the multi-walled carbon nanotube N, N-dimethylacetamide mixed solution is prepared by mixing the multi-walled carbon nanotube with N, N-dimethylacetamide at a solid-liquid ratio of 1:500 and ultrasonic dispersion for 30 min;

[0080] Step (4), 2, 5-furan dimethyl acid, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, antioxidant 1010 are mixed, melted in a nitrogen atmosphere, a pressure of 500 pa, and a temperature of 90 DEG C, heated to 190 DEG C and reacted for 3-4 h, after the reaction is completed, polyethylene glycol and polycaprolactone modified carbon nanotube are added and uniformly mixed, heated, reacted in a nitrogen atmosphere, a pressure of 80-100 pa, and a temperature of 235 DEG C for 4 h, after the reaction is completed, cooled, and a carbon nanotube / copolyester composite material is obtained;

[0081] The molar ratio of 2, 5-furan dimethyl acid and ethylene glycol is 1:1.3; the added mass of catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, and antioxidant 1010 is 0.15% of the added mass of 2, 5-furan dimethyl acid; the mass ratio of 2, 5-furan dimethyl acid, polyethylene glycol, and polycaprolactone modified carbon nanotube is 36:15:6;

[0082] Step (5), the carbon nanotube / copolyester composite material and terylene chip are blended at a mass ratio of 20:80 at a temperature of 250 DEG C, melt spun, and cooled and drawn to obtain a far infrared heating fiber based on a bio-based polyester;

[0083] The melt spinning conditions are: melt spinning under the conditions of a temperature of 280 DEG C in a first zone to a second zone, 290 DEG C in a third zone to a fifth zone, and a spinning speed of 2000 m / min; and the draw ratio is 3.8 times.

[0084] Comparative Example 1

[0085] The comparative example discloses a preparation method of a far infrared heating fiber based on a bio-based polyester, comprising the following steps:

[0086] Step (1), 6-caprolactone, neopentyl glycol, stannous octoate were mixed as reactants, toluene was added and mixed uniformly under argon atmosphere, and the polymerization reaction was carried out at 70℃ for 48h. After the reaction was completed, chloroform was added for dissolution, ethanol was added for precipitation, and filtration was carried out. The operation of dissolution, precipitation and filtration was repeated once. The precipitate was dried at 40℃ for 12h, and poly-caprolactone was obtained.

[0087] The molar ratio of 6-caprolactone, neopentyl glycol and stannous octoate was 17.8:0.1:0.3, and the solid-liquid ratio of the reactants to toluene was 20g:30mL.

[0088] Step (2), poly-caprolactone and multi-walled carbon nanotubes were mixed uniformly at a mass ratio of 10:1 to obtain a poly-caprolactone / carbon nanotube mixture.

[0089] Step (3), dimethyl 2,5-furandicarboxylate, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate, antioxidant 1010 were mixed, and the mixture was melted under nitrogen atmosphere at a pressure of 500pa and a temperature of 90℃. The temperature was raised to 190℃, and the reaction was carried out for 3-4h. After the reaction was completed, polyethylene glycol and the poly-caprolactone / carbon nanotube mixture were mixed uniformly, and the reaction was carried out under nitrogen atmosphere at a pressure of 80-100pa and a temperature of 235℃ for 4h. After the reaction was completed, cooling was carried out to obtain a carbon nanotube / copolyester composite material.

[0090] The molar ratio of dimethyl 2,5-furandicarboxylate and ethylene glycol was 1:1.3. The addition amount of catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate and antioxidant 1010 was 0.15% of the addition amount of dimethyl 2,5-furandicarboxylate. The mass ratio of dimethyl 2,5-furandicarboxylate, polyethylene glycol and poly-caprolactone / carbon nanotube mixture was 36:11:5.

[0091] Step (4), the carbon nanotube / copolyester composite material and polyester chip were blended at a mass ratio of 16:84 at a temperature of 250℃, and melt spinning was carried out. Cooling and drawing were carried out to obtain a far infrared heating fiber based on bio-based polyester.

[0092] The melt spinning conditions were as follows: melt spinning was carried out under the conditions of a temperature of 280℃ in the first and second zones, 290℃ in the third to fifth zones, and a spinning speed of 2000m / min; and the drawing ratio was 3.8 times.

[0093] Comparative Example 2

[0094] The present comparative example discloses a preparation method of a far infrared heating fiber based on bio-based polyester, which comprises the following steps:

[0095] Step (1), 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol, stannous octoate were mixed as reactants, toluene was added and mixed uniformly under argon atmosphere, and the mixture was polymerized at 70℃ for 48h. After the reaction was completed, chloroform was added for dissolution, and ethanol was added for precipitation. After filtration, the operation of dissolution, precipitation and filtration was repeated once. The precipitate was dried at 40℃ for 12h to obtain chlorinated modified poly caprolactone;

[0096] The molar ratio of 2-chloro-ε-caprolactone, 6-caprolactone, neopentyl glycol and stannous octoate was 1.3:16.5:0.1:0.3, and the solid-liquid ratio of the reactants to toluene was 20g:30mL;

[0097] Step (2), chlorinated modified poly caprolactone, sodium azide and N,N-dimethylformamide were mixed in a solid-liquid ratio of 10g:7g:30mL, and stirred at room temperature for 24h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, chloroform was added, washed with water, separated, and the organic phase was taken. Anhydrous magnesium sulfate was added and dried, the solvent was removed by rotary evaporation, and the mixture was dried at 45℃ for 12h to obtain azidated poly caprolactone;

[0098] Step (3), azidated poly caprolactone and N,N-dimethylacetamide were mixed and dissolved in a solid-liquid ratio of 1g:10mL. Multi-walled carbon nanotube N,N-dimethylacetamide mixed solution was added, stirred and mixed for 10min, and reacted at 160℃ for 3h. After the reaction was completed, the filter cake was taken, washed with acetone for 3 times, and dried at 60℃ for 24h to obtain poly caprolactone modified carbon nanotubes;

[0099] The mass ratio of azidated poly caprolactone to multi-walled carbon nanotubes was 10:1. The multi-walled carbon nanotube N,N-dimethylacetamide mixed solution was prepared by mixing multi-walled carbon nanotubes and N,N-dimethylacetamide in a solid-liquid ratio of 1:500 and ultrasonic dispersion for 30min;

[0100] Step (4), 2,5-furandicarboxylic acid dimethyl ester, ethylene glycol, catalyst ethylene glycol antimony, catalyst zinc acetate, heat stabilizer trimethyl phosphate and antioxidant 1010 were mixed, melted under nitrogen atmosphere at a pressure of 500pa and a temperature of 90℃, and then heated to 190℃ for reaction for 3-4h. After the reaction was completed, poly caprolactone modified carbon nanotubes were added and mixed uniformly, heated, and reacted under nitrogen atmosphere at a pressure of 80-100pa and a temperature of 235℃ for 4h. After the reaction was completed, the mixture was cooled to obtain carbon nanotube / copolyester composite material;

[0101] The molar ratio of dimethyl 2,5-furan dicarboxylate and ethylene glycol is 1:1.3; the added mass of the catalyst ethylene glycol antimony, the catalyst zinc acetate, the thermal stabilizer trimethyl phosphate, and the antioxidant 1010 is 0.15% of the added mass of dimethyl 2,5-furan dicarboxylate; the mass ratio of dimethyl 2,5-furan dicarboxylate and polycaprolactone modified carbon nanotubes is 47:5;

[0102] Step (5), blending the carbon nanotube / copolyester composite material and the terylene chip at a mass ratio of 16:84 at a temperature of 250 DEG C, melt spinning, cooling and drawing to obtain a far infrared heating fiber based on a bio-based polyester;

[0103] The melt spinning conditions are as follows: melt spinning at a temperature of 280 DEG C in a first zone to a second zone, 290 DEG C in a third zone to a fifth zone, and a spinning speed of 2000 m / min; and the draw ratio is 3.8 times.

[0104] In the above examples and comparative examples, the specifications of the multi-walled carbon nanotubes are as follows: a diameter of 10-20 nm and a length of 0.5-500 μm; the polyethylene glycol is polyethylene glycol 2000; and the terylene chip is a fiber grade PET chip with a characteristic viscosity of 0.69 dl / g.

[0105] Test Example

[0106] The fibers prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to moisture absorption performance testing. The fibers prepared in Examples 1-5 and Comparative Examples 1-2 were made into fabrics with a grammage of 150 g / m2, denoted as samples 1-7, and the samples 1-7 were subjected to far infrared heating performance and antistatic performance testing, and the specific test results are shown in Tables 1 and 2:

[0107] Table 1

[0108]

[0109] Table 2

[0110]

[0111] The detection of each index in Tables 1 and 2 is respectively based on the following standards: the moisture regain is tested in accordance with GB / T6503-2008 "Chemical Fiber Moisture Regain Test Method"; the far infrared heating performance is represented by the temperature difference, and the test method is as follows: the samples 1-7 are placed on a glass substrate and fixed, an infrared heating lamp with a power of 500 W is used to heat the fabric, the distance is 30 cm, and the heating time is 5 min, and the surface temperature difference of the fabric before and after heating is tested; the static voltage half-life period is determined in accordance with GB / T12703 "Evaluation of Textile Static Performance".

[0112] From the test results of Table 1 and Table 2, it can be seen that the fiber prepared by the present application has far infrared heating performance, and the moisture absorption performance and the anti-static performance are improved, which is because the carbon nanotube / copolyester composite material with good hydrophilic performance and good anti-static performance is prepared, introduced into the polyester chip for melt spinning, the synergistic effect between the hydrophilic segment in the copolyester and the carbon nanotube is utilized, the moisture absorption and anti-static performance of the polyester fiber is improved, and the fiber is endowed with far infrared heating function.

[0113] In the comparative example 1, the polycaprolactone is not used to modify the carbon nanotube, and the dispersibility of the carbon nanotube in the polyester matrix is poor, and the carbon nanotube is easy to agglomerate, thereby affecting the anti-static performance of the fiber. In the comparative example 2, the carbon nanotube / copolyester composite material is prepared without adding polyethylene glycol for polycondensation reaction, and the effect of the polyethylene glycol hydrophilic segment on improving the moisture absorption and anti-static performance of the material is lacking, so the moisture absorption performance and the anti-static performance of the comparative example 2 are not as good as those of the examples.

[0114] The above examples only illustrate the principles and effects of the present application, and are not used to limit the present application. Any person skilled in the art can modify or change the above examples without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those skilled in the art without departing from the spirit and technical thought disclosed by the present application should be covered by the claims of the present application.

Claims

1. A method for preparing a far-infrared heating fiber based on a bio-based polyester, comprising the following steps: Step (1), mixing and dissolving azidation polycaprolactone and N, N-dimethylacetamide, adding a multi-walled carbon nanotube N, N-dimethylacetamide mixture, stirring and mixing, reacting at a temperature of 155-165 ℃ for 2.5-4 h, after the reaction is completed, performing suction filtration, washing, and drying to obtain polycaprolactone modified carbon nanotubes; wherein the mass ratio of azidation polycaprolactone to multi-walled carbon nanotubes is 10:0.5-1.5; The azidation polycaprolactone is prepared by the following steps: S1, mixing 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, and stannous octoate as reactants, uniformly mixing with toluene, polymerizing at a temperature of 60-70 ℃ for 48-56 h in an argon atmosphere, after the reaction is completed, purifying to obtain chlorinated modified polycaprolactone; S2, mixing chlorinated modified polycaprolactone, sodium azide, and N, N-dimethylformamide at a solid-liquid ratio of 10 g:6-8 g:30-50 mL, stirring and reacting at room temperature for 24-28 h, after the reaction is completed, purifying to obtain azidation polycaprolactone; Step (2), mixing 2, 5-dimethyl furan dicarboxylate, ethylene glycol, a catalyst, a thermal stabilizer, and an antioxidant, melting under a nitrogen atmosphere at a pressure of 400-700 pa and a temperature of 90-100 ℃, heating to 180-190 ℃ and reacting for 3-4 h, after the reaction is completed, adding polyethylene glycol and polycaprolactone modified carbon nanotubes and uniformly mixing, continuing to react under a nitrogen atmosphere at a pressure of 80-100 pa and a temperature of 230-240 ℃ for 4-5 h, after the reaction is completed, cooling to obtain a carbon nanotube / copolyester composite material; wherein the molar ratio of 2, 5-dimethyl furan dicarboxylate to ethylene glycol is 1:1-1.3; the added mass of the catalyst ethylene glycol antimony, the catalyst zinc acetate, the thermal stabilizer trimethyl phosphate, and the antioxidant 1010 is 0.1-0.3% of the added mass of 2, 5-dimethyl furan dicarboxylate; the mass ratio of 2, 5-dimethyl furan dicarboxylate, polyethylene glycol, and polycaprolactone modified carbon nanotubes is 36:11-15:5-6; Step (3), blending the carbon nanotube / copolyester composite material and terylene chips, melt spinning, and cooling and drawing to obtain a far-infrared heating fiber based on a bio-based polyester.

2. The method for preparing far-infrared heating fiber based on bio-based polyester according to claim 1, characterized in that, In the preparation of azidation polycaprolactone in step (1), in S1, the molar ratio of 2-chloro-epsilon-caprolactone, 6-caprolactone, neopentyl glycol, and stannous octoate is 1.3-1.5:15.8-16.5:0.1-0.15:0.3-0.33; the solid-liquid ratio of the reactants to toluene is 20 g:30-50 mL.

3. The method for preparing far-infrared heating fiber based on bio-based polyester according to claim 1, characterized in that, In step (3), the mass ratio of the carbon nanotube / copolyester composite material to terylene chips is 16-20:80-84; the melt spinning conditions are as follows: melt spinning under the conditions of a temperature of 275-285 ℃ in zone one to zone two, 285-290 ℃ in zone three to zone five, and a spinning speed of 1500-2500 m / min; the draw ratio is 3-3.8 times.

4. A bio-based polyester-based far infrared heating fiber prepared by the method according to any one of claims 1 to 3.

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