Antistatic polyester fiber and method for producing the same

Abstract

The application discloses an antistatic polyester fiber and a preparation method thereof, and relates to the technical field of polyester fibers. In the preparation of the antistatic polyester fiber, terephthalic acid, isophthalic acid and ethylene glycol are subjected to an esterification reaction, and polyethylene glycol is added to perform a polycondensation reaction to obtain a hydroxyl-terminated polyether ester; an emulsifier, the hydroxyl-terminated polyether ester, graphene oxide, a blocked isocyanate, a smoothing agent, an anti-splashing agent and an antioxidant are mixed to obtain a spinning oil; the polyester fiber is continuously subjected to normal-temperature air plasma treatment, the spinning oil is applied through an oil tank, and then loose bobbin winding is performed; the blocked isocyanate is unblocked and cross-linking reaction occurs through heat treatment; and then microwave irradiation treatment is performed to obtain the antistatic polyester fiber. The antistatic polyester fiber prepared by the application has good antistatic performance and antistatic durability.

Description

Technical Field

[0001] This invention relates to the field of polyester fiber technology, specifically to an antistatic polyester fiber and its preparation method. Background Technology

[0002] Polyester fibers possess advantages such as high strength, abrasion resistance, and good chemical resistance, making them widely used in clothing, home textiles, and industrial textiles. However, polyester fibers have low moisture absorption, and when subjected to friction during spinning, false twisting texturing, weaving, and use, they are prone to generating and accumulating static electricity, which affects the fiber's processing stability and performance.

[0003] Currently, the antistatic properties of polyester fibers are typically improved by adding antistatic components or performing surface antistatic finishing. However, the bonding strength between conventional antistatic components and the polyester fiber surface is limited, and they are prone to migration or detachment during friction, washing, and long-term use. Furthermore, the antistatic properties of some hydrophilic antistatic components are easily affected by environmental humidity. Therefore, developing a polyester fiber with good and durable antistatic properties and its preparation method is of great significance. Summary of the Invention

[0004] The purpose of this invention is to provide an antistatic polyester fiber and its preparation method, so as to improve the antistatic properties and antistatic durability of the polyester fiber.

[0005] This invention provides a method for preparing antistatic polyester fiber, comprising the following steps: S1. Terephthalic acid, isophthalic acid and ethylene glycol are subjected to esterification reaction under the action of a catalyst, and polyethylene glycol is added to carry out polycondensation reaction to obtain hydroxyl-terminated polyether ester. S2. Emulsifier, hydroxyl-terminated polyether ester, graphene oxide, blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant are sequentially added to a preheated reaction vessel and mixed to obtain spinning oil. S3. The polyester fiber is subjected to room temperature air plasma treatment to obtain pretreated polyester fiber. S4. Apply the spinning oil to the pretreated polyester fiber through an oiler, and then perform loose winding to obtain loose polyester fiber coils; S5. The polyester fiber loose tube is heat-treated to obtain a pre-modified polyester fiber loose tube; then the pre-modified polyester fiber loose tube is unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0006] In some preferred embodiments, in step S1, the catalyst is tetrabutyl titanate; the preparation method of the hydroxyl-terminated polyether ester includes: mixing terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate, heating to 175~185℃ under nitrogen protection and stirring, and reacting at a gauge pressure of -0.03~-0.01MPa for 2.5~3.5h; cooling to 155~165℃, adding PEG1000 and PEG1540, and stirring for 30~60min; then heating to 225~240℃, and reducing the absolute pressure of the reaction system to 5~15kPa within 30~60min, and continuing the reaction for 30~60min to obtain the hydroxyl-terminated polyether ester.

[0007] In some further preferred embodiments, the mass ratio of terephthalic acid, isophthalic acid, and ethylene glycol is 1:(0.07~0.11):(0.34~0.40); the amount of tetrabutyl titanate added is 0.03~0.08% of the total mass of terephthalic acid and isophthalic acid; the mass ratio of terephthalic acid, PEG1000, and PEG1540 is 1:(0.75~1.00):(0.35~0.55), and the mass ratio of PEG1000 to PEG1540 is (1.8~2.2):1; the ratio of the total molar number of hydroxyl groups in ethylene glycol, PEG1000, and PEG1540 to the total molar number of carboxyl groups in terephthalic acid and isophthalic acid is (1.02~1.10):1.

[0008] In some preferred embodiments, in step S2, the reactor is preheated to 50-60°C, and emulsifier, hydroxyl-terminated polyether ester and graphene oxide are added sequentially. The mixture is stirred at 700-900 r / min for 10-20 min. Blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant are added, and the mixture is stirred for 20-30 min and then ultrasonically treated for 20 min to obtain the spinning oil.

[0009] In some preferred embodiments, the spinning oil comprises the following raw materials in parts by weight: 4-6 parts emulsifier, 14-20 parts hydroxyl-terminated polyether ester, 0.3-0.8 parts graphene oxide, 1.5-2.5 parts blocked isocyanate, 69-79 parts smoother, 1-1.5 parts anti-splatter agent, and 0.15-0.3 parts antioxidant.

[0010] In some further preferred embodiments, the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a lateral dimension <500nm and a monolayer ratio ≥99%, purchased from Nanjing Muke Nanotechnology Co., Ltd.; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil, manufactured by Sinopec Jingmen Branch; the antisplatter agent is a polyisobutylene-type antisplatter agent, manufactured by Zhejiang Xinsheng Oils & Fats Technology Co., Ltd.; and the antioxidant is zinc dialkyl dithiophosphate.

[0011] In some preferred embodiments, in step S3, the polyester fiber is a polyester false-twist textured yarn; the polyester fiber reciprocates in the ambient temperature air plasma treatment zone via guide rollers; the ambient temperature air plasma treatment power is 100~150W, the operating speed is 100~300m / min, and the effective treatment time of the polyester fiber in the ambient temperature air plasma treatment zone is 2~4s.

[0012] In some preferred embodiments, in step S4, the winding speed of the loose winding drum is 100~300m / min; and the winding density of the polyester fiber loose drum is 0.32~0.4g / cm³.

[0013] In some preferred embodiments, in step S5, the heat treatment conditions are 120~140℃ for 0.5~1.5h; the continuous microwave irradiation power is 700~900W and the frequency is 2.45GHz; and the effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 50~70s.

[0014] The present invention also provides an antistatic polyester fiber, which is prepared according to the above-described method for preparing antistatic polyester fiber.

[0015] Compared with existing technologies, this invention improves the surface activity of polyester fibers through room temperature air plasma treatment; it uses hydroxyl-terminated polyether ester as the antistatic component, whose polyester segments have good structural similarity and compatibility with polyester fibers, which is conducive to the wetting, penetration and bonding of functional components to the fiber surface, while the polyether segments impart good hydrophilic antistatic properties; during the heat treatment process, the blocked isocyanate is deblocked and reacts with the hydroxyl-terminated polyether ester and the hydroxyl groups on the surface of the polyester fibers, so that the antistatic component forms a stable covalent cross-linked structure on the fiber surface; further, microwave irradiation causes partial reduction of graphene oxide, improving its conductivity, thereby giving the resulting polyester fiber good antistatic properties and antistatic durability. Detailed Implementation

[0016] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0017] This invention uses terephthalic acid, isophthalic acid, and ethylene glycol as raw materials, and performs an esterification reaction under the catalysis of tetrabutyl titanate. Then, PEG1000 and PEG1540 are added for polycondensation to obtain a hydroxyl-terminated polyether ester. The mass ratio of PEG1000 to PEG1540 is (1.8~2.2):1. Polyether segments are introduced into the polyether ester through the compounding of polyethylene glycols with different molecular weights. The polyether segments in the resulting polyether ester have good hydrophilicity, which is beneficial for adsorbing moisture from the environment and promoting charge dissipation. The polyester segments have a similar chemical structure and good compatibility with polyester fibers, which is beneficial for the wetting, penetration, and stable bonding of antistatic components on the polyester fiber surface. Simultaneously, the polyether ester is controlled to have a certain content of terminal hydroxyl groups, providing active sites for subsequent reactions with isocyanates.

[0018] This invention involves compounding polyoxyethylene ether dioleate, hydroxyl-terminated polyether ester, graphene oxide, trifunctional blocked aliphatic polyisocyanate, industrial white oil, polyisobutylene-type antisplatter agent, and zinc dialkyl dithiophosphate to prepare a spinning oil. The amount of hydroxyl-terminated polyether ester added is 14-20 parts by weight, the amount of graphene oxide added is 0.3-0.8 parts by weight, and the amount of blocked isocyanate added is 1.5-2.5 parts by weight. The use of graphene oxide facilitates its dispersion in the spinning oil and the subsequent formation of a more uniform conductive component distribution on the fiber surface. The use of trifunctional blocked aliphatic polyisocyanate maintains low reactivity during the compounding and oiling stages of the spinning oil, while unblocking and exerting a crosslinking effect during subsequent heat treatment.

[0019] This invention pretreats polyester fibers with air plasma before applying spinning oil, with a treatment time of 2-4 seconds and a treatment power of 100-150W. Room temperature air plasma treatment can improve the polarity and reactivity of the polyester fiber surface and form polar groups such as hydroxyl and carboxyl groups on the fiber surface, which is beneficial to the wetting and adhesion of spinning oil, and at the same time provides active sites for the subsequent reaction between isocyanate and fiber surface.

[0020] Polyester fibers treated with air plasma at room temperature are wound into loose cans after the spinning oil is applied by an oiler. The resulting loose polyester fiber cans are then heat-treated at 120-140°C for 0.5-1.5 hours to de-encapsulate the blocked isocyanate. The de-encapsulated isocyanate groups react with the hydroxyl groups in the hydroxyl-terminated polyether ester and the hydroxyl groups on the surface of the polyester fiber, causing the hydroxyl-terminated polyether ester to form a cross-linked structure and covalently bond with the surface of the polyester fiber, thereby reducing the migration and shedding of antistatic components during use. Using a loose can form for heat treatment is beneficial for uniform heating of the fiber and for the de-encapsulation and cross-linking reaction to proceed.

[0021] After heat treatment, the material is further irradiated with 700-900W continuous microwave for 50-70s to partially reduce the graphene oxide in the cross-linked structure, remove some oxygen-containing functional groups and restore some sp² conjugated structure, thereby improving its conductivity. The hydrophilic polyether segments in the hydroxyl-terminated polyether ester promote charge dissipation, and the partially reduced graphene oxide provides an electron conduction channel. The two work synergistically to improve the antistatic properties of the polyester fiber. At the same time, the stability of the functional components on the surface of the polyester fiber is improved through the aforementioned cross-linking and interfacial bonding, thereby improving the durability of the antistatic properties.

[0022] Unless otherwise specified, all raw materials used in this invention are commercially available products in the art, and all methods used are conventional methods in the art.

[0023] To further illustrate the technical solution and effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. Example

[0024] A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 175°C under nitrogen protection and stirring. The mixture was reacted for 2.5 h at a gauge pressure of -0.03 MPa. The temperature was then lowered to 155°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 30 min, then heated to 225°C and the absolute pressure of the reaction system was reduced to 5 kPa within 30 min. The reaction was continued for 30 min to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 30 min to obtain hydroxyl-terminated polyether ester. The mass ratio is 1:0.07:0.35, the amount of tetrabutyl titanate added is 0.03% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:0.75:0.35, and the mass ratio of PEG1000 to PEG1540 is 2.14:1; the ratio of the total molar number of hydroxyl groups in ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in terephthalic acid and isophthalic acid is approximately 1.03:1; (2) Preheat the reactor to 50°C, add emulsifier, hydroxyl-terminated polyether ester and graphene oxide in sequence, stir at 700 r / min for 10 min, continue to add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 20 min and then sonicate for 20 min to obtain spinning oil. (3) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 100W, the running speed is 100m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 4s, so as to obtain pretreated polyester fiber. (4) The pretreated polyester fiber is applied the spinning oil through an oiler, and then loosely wound to obtain a loose polyester fiber coil; (5) The polyester fiber loose tube is placed in an oven at 120°C for 0.5 hours to obtain a pre-modified polyester fiber loose tube; then the pre-modified polyester fiber loose tube is unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0025] The spinning oil in step (2) comprises the following raw materials in parts by weight: 4 parts emulsifier, 14 parts hydroxyl-terminated polyether ester, 0.3 parts graphene oxide, 1.5 parts blocked isocyanate, 79 parts smoothing agent, 1 part antisplatter agent, and 0.15 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer ratio ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0026] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0027] In step (4), the winding speed of the loose winding cylinder is 100 m / min; the winding density of the loose polyester fiber cylinder is 0.32 g / cm³.

[0028] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s. Example

[0029] A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 180°C under nitrogen protection and stirring. The mixture was reacted for 3 hours at a gauge pressure of -0.02 MPa. The temperature was then lowered to 160°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 45 minutes, then heated to 230°C and the absolute pressure of the reaction system was reduced to 10 kPa within 45 minutes. The reaction was continued for 45 minutes to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 45 minutes to obtain hydroxyl-terminated polyether ester. The mass ratio of alcohols is 1:0.095:0.37, the amount of tetrabutyl titanate added is 0.05% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:0.9:0.45, and the mass ratio of PEG1000 to PEG1540 is 2:1; the ratio of the total molar number of hydroxyl groups in the ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in the terephthalic acid and isophthalic acid is approximately 1.09:1. (2) Preheat the reactor to 55°C, add emulsifier, hydroxyl-terminated polyether ester and graphene oxide in sequence, stir at 800 r / min for 15 min, continue to add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 25 min and then sonicate for 20 min to obtain spinning oil. (3) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 125W, the running speed is 200m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 3s, so as to obtain pretreated polyester fiber. (4) The pretreated polyester fiber is applied the spinning oil through an oiler, and then loosely wound to obtain a loose polyester fiber coil; (5) The loose polyester fiber tubes are placed in an oven at 130°C for 1 hour to obtain pre-modified polyester fiber tubes; then the pre-modified polyester fiber tubes are unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0030] The spinning oil in step (2) comprises the following raw materials in parts by weight: 5 parts emulsifier, 17 parts hydroxyl-terminated polyether ester, 0.5 parts graphene oxide, 2 parts blocked isocyanate, 74 parts smoothing agent, 1.25 parts antisplatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer ratio ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0031] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0032] In step (4), the winding speed of the loose winding cylinder is 200 m / min; the winding density of the loose polyester fiber cylinder is 0.36 g / cm³.

[0033] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s. Example

[0034] A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 185°C under nitrogen protection and stirring. The mixture was reacted for 3.5 h at a gauge pressure of -0.01 MPa. The temperature was then lowered to 165°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 60 min, then heated to 240°C and the absolute pressure of the reaction system was reduced to 15 kPa within 60 min. The reaction was continued for another 60 min to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 60 min to obtain hydroxyl-terminated polyether ester. The mass ratio of alcohols is 1:0.11:0.37, the amount of tetrabutyl titanate added is 0.08% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:1.00:0.55, and the mass ratio of PEG1000 to PEG1540 is 1.82:1; the ratio of the total molar number of hydroxyl groups in the ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in the terephthalic acid and isophthalic acid is approximately 1.1:1. (2) Preheat the reactor to 60°C, add emulsifier, hydroxyl-terminated polyether ester and graphene oxide in sequence, stir at 900 r / min for 20 min, add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 30 min and then sonicate for 20 min to obtain spinning oil. (3) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 150W, the running speed is 300m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 2s, so as to obtain pretreated polyester fiber. (4) The pretreated polyester fiber is applied the spinning oil through an oiler, and then loosely wound to obtain a loose polyester fiber coil; (5) The loose polyester fiber tubes are placed in an oven at 140°C for 1.5 hours to obtain pre-modified polyester fiber tubes; then the pre-modified polyester fiber tubes are unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0035] The spinning oil in step (2) comprises the following raw materials in parts by weight: 6 parts emulsifier, 20 parts hydroxyl-terminated polyether ester, 0.8 parts graphene oxide, 2.5 parts blocked isocyanate, 69 parts smoothing agent, 1.5 parts anti-splatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer ratio ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the anti-splatter agent is a polyisobutylene-type anti-splatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0036] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0037] In step (4), the winding speed of the loose winding cylinder is 300 m / min; the winding density of the loose polyester fiber cylinder is 0.4 g / cm³.

[0038] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s.

[0039] Comparative Example 1: This comparative example provides a method for preparing antistatic polyester fiber, which differs from Example 2 only in that the continuous microwave irradiation power in step (5) is adjusted to 500W.

[0040] Comparative Example 2: This comparative example provides a method for preparing antistatic polyester fiber, which differs from Example 2 only in that the continuous microwave irradiation power in step (5) is adjusted to 600W.

[0041] Comparative Example 3: This comparative example provides a method for preparing antistatic polyester fiber, which differs from Example 2 only in that the continuous microwave irradiation power in step (5) is adjusted to 700W.

[0042] Comparative Example 4: This comparative example provides a method for preparing antistatic polyester fiber, which differs from Example 2 only in that the continuous microwave irradiation power in step (5) is adjusted to 900W.

[0043] Comparative Example 5: This comparative example provides a method for preparing antistatic polyester fiber, which differs from Example 2 only in that the continuous microwave irradiation power in step (5) is adjusted to 1000W.

[0044] Comparative Example 6: This comparative example provides a method for preparing antistatic polyester fiber. The only difference from Example 2 is that the effective residence time of the pre-modified polyester fiber after unwinding in step (5) in the microwave treatment zone is adjusted to 30s.

[0045] Comparative Example 7: This comparative example provides a method for preparing antistatic polyester fiber. The only difference from Example 2 is that the effective residence time of the pre-modified polyester fiber after unwinding in step (5) in the microwave treatment zone is adjusted to 90s.

[0046] Comparative Example 8: A method for preparing antistatic polyester fiber includes the following steps: (1) Preheat the reactor to 55°C, add emulsifier, PEG6000, PEG8000 and graphene oxide in sequence, stir at 800 r / min for 15 min, add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 25 min and then sonicate for 20 min to obtain spinning oil. (2) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 125W, the running speed is 200m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 3s, so as to obtain pretreated polyester fiber. (3) The pretreated polyester fiber is applied to the spinning oil through a roller, and then loosely wound to obtain a loose polyester fiber coil; (4) The loose polyester fiber tubes are placed in an oven at 130°C for 1 hour to obtain pre-modified polyester fiber tubes; then the pre-modified polyester fiber tubes are unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0047] The spinning oil in step (1) comprises the following raw materials in parts by weight: 5 parts emulsifier, 8.5 parts PEG6000, 8.5 parts PEG8000, 0.5 parts graphene oxide, 2 parts blocked isocyanate, 74 parts smoothing agent, 1.25 parts antisplatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer rate ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0048] The polyester fiber mentioned in step (2) is a polyester false twist textured yarn.

[0049] In step (3), the winding speed of the loose winding cylinder is 200 m / min; the winding density of the loose polyester fiber cylinder is 0.36 g / cm³.

[0050] Step (4) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s.

[0051] Comparative Example 9: A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 180°C under nitrogen protection and stirring. The mixture was reacted for 3 hours at a gauge pressure of -0.02 MPa. The temperature was then lowered to 160°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 45 minutes, then heated to 230°C and the absolute pressure of the reaction system was reduced to 10 kPa within 45 minutes. The reaction was continued for 45 minutes to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 45 minutes to obtain hydroxyl-terminated polyether ester. The mass ratio of alcohols is 1:0.095:0.37, the amount of tetrabutyl titanate added is 0.05% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:0.9:0.45, and the mass ratio of PEG1000 to PEG1540 is 2:1; the ratio of the total molar number of hydroxyl groups in the ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in the terephthalic acid and isophthalic acid is approximately 1.09:1. (2) Preheat the reactor to 55°C, add emulsifier, hydroxyl-terminated polyether ester and graphene oxide in sequence, stir at 800 r / min for 15 min, add smoothing agent, anti-splatter agent and antioxidant, stir for 25 min and then sonicate for 20 min to obtain spinning oil. (3) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 125W, the running speed is 200m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 3s, so as to obtain pretreated polyester fiber. (4) The pretreated polyester fiber is applied the spinning oil through an oiler, and then loosely wound to obtain a loose polyester fiber coil; (5) The loose polyester fiber tubes are placed in an oven at 130°C for 1 hour to obtain pre-modified polyester fiber tubes; then the pre-modified polyester fiber tubes are unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0052] The spinning oil in step (2) comprises the following raw materials in parts by weight: 5 parts emulsifier, 17 parts hydroxyl-terminated polyether ester, 0.5 parts graphene oxide, 76 parts smoothing agent, 1.25 parts anti-splatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer rate ≥99%; the smoothing agent is 10# industrial white oil; the anti-splatter agent is a polyisobutylene-type anti-splatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0053] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0054] In step (4), the winding speed of the loose winding cylinder is 200 m / min; the winding density of the loose polyester fiber cylinder is 0.36 g / cm³.

[0055] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s.

[0056] Comparative Example 10: A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 180°C under nitrogen protection and stirring. The mixture was reacted for 3 hours at a gauge pressure of -0.02 MPa. The temperature was then lowered to 160°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 45 minutes, then heated to 230°C and the absolute pressure of the reaction system was reduced to 10 kPa within 45 minutes. The reaction was continued for 45 minutes to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 45 minutes to obtain hydroxyl-terminated polyether ester. The mass ratio of alcohols is 1:0.095:0.37, the amount of tetrabutyl titanate added is 0.05% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:0.9:0.45, and the mass ratio of PEG1000 to PEG1540 is 2:1; the ratio of the total molar number of hydroxyl groups in the ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in the terephthalic acid and isophthalic acid is approximately 1.09:1. (2) Preheat the reactor to 55°C, add emulsifier and hydroxyl-terminated polyether ester in sequence, stir at 800 r / min for 15 min, continue to add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 25 min and then sonicate for 20 min to obtain spinning oil. (3) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 125W, the running speed is 200m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 3s, so as to obtain pretreated polyester fiber. (4) The pretreated polyester fiber is applied the spinning oil through an oiler, and then loosely wound to obtain a loose polyester fiber coil; (5) The loose polyester fiber tubes are placed in an oven at 130°C for 1 hour to obtain pre-modified polyester fiber tubes; then the pre-modified polyester fiber tubes are unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0057] The spinning oil in step (2) comprises the following raw materials in parts by weight: 5 parts emulsifier, 17 parts hydroxyl-terminated polyether ester, 2 parts blocked isocyanate, 74.5 parts smoothing agent, 1.25 parts antisplatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0058] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0059] In step (4), the winding speed of the loose winding cylinder is 200 m / min; the winding density of the loose polyester fiber cylinder is 0.36 g / cm³.

[0060] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s.

[0061] Comparative Example 11: A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 180°C under nitrogen protection and stirring. The mixture was reacted for 3 hours at a gauge pressure of -0.02 MPa. The temperature was then lowered to 160°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 45 minutes, then heated to 230°C and the absolute pressure of the reaction system was reduced to 10 kPa within 45 minutes. The reaction was continued for 45 minutes to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 45 minutes to obtain hydroxyl-terminated polyether ester. The mass ratio of alcohols is 1:0.095:0.37, the amount of tetrabutyl titanate added is 0.05% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:0.9:0.45, and the mass ratio of PEG1000 to PEG1540 is 2:1; the ratio of the total molar number of hydroxyl groups in the ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in the terephthalic acid and isophthalic acid is approximately 1.09:1. (2) Preheat the reactor to 55°C, add emulsifier, hydroxyl-terminated polyether ester and graphene oxide in sequence, stir at 800 r / min for 15 min, continue to add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 25 min and then sonicate for 20 min to obtain spinning oil. (3) The polyester fiber is continuously passed through the room temperature air plasma treatment zone under traction. The treatment power is 125W, the running speed is 200m / min, and the effective treatment time of the polyester fiber in the room temperature air plasma treatment zone is 3s, so as to obtain pretreated polyester fiber. (4) The pretreated polyester fiber is applied the spinning oil through an oiler, and then loosely wound to obtain a loose polyester fiber coil; (5) The loose polyester fiber tubes were placed in an oven at 130°C for 1 hour to obtain antistatic polyester fiber.

[0062] The spinning oil in step (2) comprises the following raw materials in parts by weight: 5 parts emulsifier, 17 parts hydroxyl-terminated polyether ester, 0.5 parts graphene oxide, 2 parts blocked isocyanate, 74 parts smoothing agent, 1.25 parts antisplatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer ratio ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0063] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0064] In step (4), the winding speed of the loose winding cylinder is 200 m / min; the winding density of the loose polyester fiber cylinder is 0.36 g / cm³.

[0065] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s.

[0066] Comparative Example 12: A method for preparing antistatic polyester fiber includes the following steps: (1) Terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate were mixed and heated to 180°C under nitrogen protection and stirring. The mixture was reacted for 3 hours at a gauge pressure of -0.02 MPa. The temperature was then lowered to 160°C, and PEG1000 and PEG1540 were added. The mixture was stirred for 45 minutes, then heated to 230°C and the absolute pressure of the reaction system was reduced to 10 kPa within 45 minutes. The reaction was continued for 45 minutes to obtain hydroxyl-terminated polyether ester. The terephthalic acid, isophthalic acid and ethylene glycol were mixed and stirred for 45 minutes to obtain hydroxyl-terminated polyether ester. The mass ratio of alcohols is 1:0.095:0.37, the amount of tetrabutyl titanate added is 0.05% of the total mass of terephthalic acid and isophthalic acid, the mass ratio of terephthalic acid to PEG1000 and PEG1540 is 1:0.9:0.45, and the mass ratio of PEG1000 to PEG1540 is 2:1; the ratio of the total molar number of hydroxyl groups in the ethylene glycol, PEG1000 and PEG1540 to the total molar number of carboxyl groups in the terephthalic acid and isophthalic acid is approximately 1.09:1. (2) Preheat the reactor to 55°C, add emulsifier, hydroxyl-terminated polyether ester and graphene oxide in sequence, stir at 800 r / min for 15 min, continue to add blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant, stir for 25 min and then sonicate for 20 min to obtain spinning oil. (3) Apply the spinning oil to the polyester fiber through an oiler, and then perform loose winding to obtain a loose polyester fiber coil; (4) The polyester fiber loose tube is placed in an oven at 130°C for 1 hour to obtain a pre-modified polyester fiber loose tube; then the pre-modified polyester fiber loose tube is unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

[0067] The spinning oil in step (2) comprises the following raw materials in parts by weight: 5 parts emulsifier, 17 parts hydroxyl-terminated polyether ester, 0.5 parts graphene oxide, 2 parts blocked isocyanate, 74 parts smoothing agent, 1.25 parts antisplatter agent, and 0.2 parts antioxidant; the emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a transverse dimension <500nm and a monolayer ratio ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

[0068] The polyester fiber mentioned in step (3) is a polyester false twist textured yarn.

[0069] In step (4), the winding speed of the loose winding cylinder is 200 m / min; the winding density of the loose polyester fiber cylinder is 0.36 g / cm³.

[0070] Step (5) The continuous microwave irradiation power is 800W and the frequency is 2.45GHz. The effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 60s.

[0071] The antistatic polyester fibers prepared in each embodiment and comparative example were tested for antistatic properties and antistatic durability. The test methods and results are as follows.

[0072] Antistatic properties: The antistatic properties of antistatic polyester fibers were tested using a ZC36 high insulation resistance meter. Before testing, the fibers were prepared into sample cakes with a thickness of approximately 1 mm and a diameter of approximately 100 mm. The sample cakes were placed in a constant temperature and humidity incubator at 20℃ and 55% relative humidity for 48 hours to equilibrate, and then removed for antistatic property testing.

[0073] Antistatic durability: Antistatic polyester fibers were subjected to 20 washes according to GB / T8629-2017 standard. Each wash was first performed at 40℃ with a 2g / L detergent solution for 3 minutes, followed by rinsing with clean water 3 times at room temperature for 2 minutes each time. After dehydration and drying, the fibers were equilibrated at 20℃ and 55%RH for 48 hours before the antistatic performance test was conducted.

[0074] The test results are shown in Table 1.

[0075] Table 1 Example 1 <![CDATA[1.6×10 9 ]]> <![CDATA[3.1×10 8 ]]> <![CDATA[5.1×10 9 ]]> <![CDATA[9.8×10 8 ]]> Example 2 <![CDATA[6.8×10 8 ]]> <![CDATA[1.3×10 8 ]]> <![CDATA[2.4×10 9 ]]> <![CDATA[4.6×10 8 ]]> Example 3 <![CDATA[5.2×10 8 ]]> <![CDATA[1.0×10 8 ]]> <![CDATA[2.7×10 9 ]]> <![CDATA[5.3×10 8 ]]> Comparative Example 1 <![CDATA[2.4×10 10 ]]> <![CDATA[4.6×10 9 ]]> <![CDATA[4.2×10 10 ]]> <![CDATA[7.9×10 9 ]]> Comparative Example 2 <![CDATA[8.5×10 9 ]]> <![CDATA[1.6×10 9 ]]> <![CDATA[1.7×10 10 ]]> <![CDATA[3.2×10 9 ]]> Comparative Example 3 <![CDATA[1.8×10 9 ]]> <![CDATA[3.5×10 8 ]]> <![CDATA[5.8×10 9 ]]> <![CDATA[1.1×10 9 ]]> Comparative Example 4 <![CDATA[5.8×10 8 ]]> <![CDATA[1.1×10 8 ]]> <![CDATA[2.3×10 9 ]]> <![CDATA[4.4×10 8 ]]> Comparative Example 5 <![CDATA[5.5×10 8 ]]> <![CDATA[1.0×10 8 ]]> <![CDATA[2.2×10 9 ]]> <![CDATA[4.2×10 8 ]]> Comparative Example 6 <![CDATA[3.6×10 9 ]]> <![CDATA[7.1×10 8 ]]> <![CDATA[9.6×10 9 ]]> <![CDATA[1.9×10 9 ]]> Comparative Example 7 <![CDATA[5.7×10 8 ]]> <![CDATA[1.1×10 8 ]]> <![CDATA[2.3×10 9 ]]> <![CDATA[4.3×10 9 ]]> Comparative Example 8 <![CDATA[7.5×10 8 ]]> <![CDATA[1.5×10 8 ]]> <![CDATA[2.3×10 10 ]]> <![CDATA[4.4×10 9 <!-- 10 -->]]> Comparative Example 9 <![CDATA[9.2×10 8 ]]> <![CDATA[1.8×10 8 ]]> <![CDATA[3.5×10 10 ]]> <![CDATA[6.7×10 9 ]]> Comparative Example 10 <![CDATA[3.2×10 10 ]]> <![CDATA[6.1×10 9 ]]> <![CDATA[5.1×10 10 ]]> <![CDATA[9.7×10 9 ]]> Comparative Example 11 <![CDATA[7.6×10 9 ]]> <![CDATA[1.5×10 9 ]]> <![CDATA[1.4×10 10 ]]> <![CDATA[2.7×10 9 ]]> Comparative Example 12 <![CDATA[1.1×10 9 ]]> <![CDATA[2.1×10 8 ]]> <![CDATA[1.5×10 10 ]]> <![CDATA[2.9×10 9 ]]> As shown in Table 1, the antistatic polyester fibers prepared in Examples 1 to 3 all have low surface resistivity and volume resistivity, and still maintain good antistatic properties after 20 water washes, indicating that the polyester fibers prepared by the present invention have good antistatic properties and antistatic durability.

[0076] Comparative Examples 2 and 1-7 show that appropriate microwave irradiation power and time are beneficial to the partial reduction of graphene oxide, thereby improving the antistatic properties of polyester fibers. Comparative Examples 2 and 8-12 show that the combination of hydroxyl-terminated polyether ester, blocked isocyanate, graphene oxide, and room temperature air plasma treatment is beneficial to the formation of a stable antistatic structure on the surface of polyester fibers, improving the antistatic properties and antistatic durability of polyester fibers. Among them, hydroxyl-terminated polyether ester has good compatibility with polyester fibers, blocked isocyanate participates in crosslinking after heat treatment, and microwave irradiation partially reduces graphene oxide, thus achieving both antistatic properties and washability.

[0077] It will be apparent to those skilled in the art that the present 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 characteristics of the invention. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended technical solutions rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the technical solutions are intended to be included within the present invention.

Claims

1. A method for preparing antistatic polyester fiber, characterized in that, Includes the following steps: S1. Terephthalic acid, isophthalic acid and ethylene glycol are subjected to esterification reaction under the action of a catalyst, and polyethylene glycol is added to carry out polycondensation reaction to obtain hydroxyl-terminated polyether ester. S2. Emulsifier, hydroxyl-terminated polyether ester, graphene oxide, blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant are sequentially added to a preheated reaction vessel and mixed to obtain spinning oil. S3. The polyester fiber is subjected to room temperature air plasma treatment to obtain pretreated polyester fiber. S4. Apply the spinning oil to the pretreated polyester fiber through an oiler, and then perform loose winding to obtain loose polyester fiber coils; S5. The polyester fiber loose tube is heat-treated to obtain a pre-modified polyester fiber loose tube; then the pre-modified polyester fiber loose tube is unwound and continuously passed through a microwave zone for microwave irradiation treatment to obtain antistatic polyester fiber.

2. The method for preparing antistatic polyester fiber according to claim 1, characterized in that, In step S1, the catalyst is tetrabutyl titanate; the preparation method of the hydroxyl-terminated polyether ester includes: mixing terephthalic acid, isophthalic acid, ethylene glycol and tetrabutyl titanate, heating to 175~185℃ under nitrogen protection and stirring, and reacting at a gauge pressure of -0.03~-0.01MPa for 2.5~3.5h; cooling to 155~165℃, adding PEG1000 and PEG1540, and stirring for 30~60min; then heating to 225~240℃, and reducing the absolute pressure of the reaction system to 5~15kPa within 30~60min, and continuing the reaction for 30~60min to obtain the hydroxyl-terminated polyether ester.

3. The method for preparing antistatic polyester fiber according to claim 2, characterized in that, The mass ratio of terephthalic acid, isophthalic acid, and ethylene glycol is 1:(0.07~0.11):(0.34~0.40); the amount of tetrabutyl titanate added is 0.03~0.08% of the total mass of terephthalic acid and isophthalic acid; the mass ratio of terephthalic acid, PEG1000, and PEG1540 is 1:(0.75~1.00):(0.35~0.55), and the mass ratio of PEG1000 to PEG1540 is (1.8~2.2):1; the ratio of the total molar number of hydroxyl groups in ethylene glycol, PEG1000, and PEG1540 to the total molar number of carboxyl groups in terephthalic acid and isophthalic acid is (1.02~1.10):

1.

4. The method for preparing antistatic polyester fiber according to claim 1, characterized in that, In step S2, the reactor is preheated to 50-60°C, and emulsifier, hydroxyl-terminated polyether ester and graphene oxide are added sequentially. The mixture is stirred at 700-900 r / min for 10-20 min. Blocked isocyanate, smoothing agent, anti-splatter agent and antioxidant are added. The mixture is stirred for 20-30 min and then ultrasonically treated for 20 min to obtain the spinning oil.

5. The method for preparing antistatic polyester fiber according to claim 4, characterized in that, The spinning oil comprises the following raw materials in parts by weight: 4-6 parts emulsifier, 14-20 parts hydroxyl-terminated polyether ester, 0.3-0.8 parts graphene oxide, 1.5-2.5 parts blocked isocyanate, 69-79 parts smoother, 1-1.5 parts anti-splatter agent, and 0.15-0.3 parts antioxidant.

6. The method for preparing antistatic polyester fiber according to claim 5, characterized in that, The emulsifier is polyoxyethylene ether dioleate; the graphene oxide is a dry powder with a lateral dimension <500nm and a monolayer ratio ≥99%; the blocked isocyanate is a trifunctional blocked aliphatic polyisocyanate, model Hafotex®HF-4401; the smoothing agent is 10# industrial white oil; the antisplatter agent is a polyisobutylene-type antisplatter agent; and the antioxidant is zinc dialkyl dithiophosphate.

7. The method for preparing antistatic polyester fiber according to claim 1, characterized in that, In step S3, the polyester fiber is a false-twist textured polyester yarn; the polyester fiber reciprocates in the ambient temperature air plasma treatment zone via guide rollers; the ambient temperature air plasma treatment power is 100~150W, the operating speed is 100~300m / min, and the effective treatment time of the polyester fiber in the ambient temperature air plasma treatment zone is 2~4s.

8. The method for preparing antistatic polyester fiber according to claim 1, characterized in that, In step S4, the winding speed of the loose winding drum is 100~300m / min; the winding density of the polyester fiber loose drum is 0.32~0.4g / cm³.

9. The method for preparing antistatic polyester fiber according to claim 1, characterized in that, In step S5, the heat treatment conditions are 120~140℃ for 0.5~1.5h; the continuous microwave irradiation power is 700~900W and the frequency is 2.45GHz; and the effective residence time of the unwound pre-modified polyester fiber in the microwave treatment zone is 50~70s.

10. An antistatic polyester fiber, characterized in that, The antistatic polyester fiber was prepared according to the preparation method of any one of claims 1 to 9.