Graphene modified polyester fiber and preparation method thereof

Abstract

This invention relates to the field of fiber manufacturing technology, specifically to a graphene-modified polyester fiber and its preparation method. The method includes the following steps: S1: (1) reacting diethylenetriamine and salicylic acid to obtain an intermediate; (2) modifying graphene oxide using the intermediate, and then modifying it with n-octyl chloride to obtain modified graphene; S2: mixing terephthalic acid, ethylene glycol, and modified graphene, followed by esterification and polycondensation reactions to obtain modified graphene polyester masterbatch; S3: mixing the modified graphene polyester masterbatch, polyester chips, and modified wool fibers, melt spinning, stretching, and winding to obtain graphene-modified polyester fiber. Beneficial effects: The obtained modified graphene can improve the interfacial compatibility of graphene in polyester, and simultaneously introduce related functional groups, enhancing the performance and strength of the polyester fiber.

Description

Technical Field

[0001] This invention relates to the field of fiber manufacturing technology, specifically to a graphene-modified polyester fiber and its preparation method. Background Technology

[0002] Polyester fiber, also known as polyester fiber, is a synthetic fiber with the chemical name polyethylene terephthalate (PET). Since its invention in 1941, polyester fiber has become an important variety of synthetic fiber, widely used in clothing, home textiles, and other industrial fields due to its excellent physical and chemical properties. However, polyester fiber also has some limitations. Due to its hydrophobicity, its moisture absorption is not as good as that of natural fibers, which may make it feel less breathable when worn; polyester fiber has poor electrical conductivity and is prone to generating static electricity when rubbed; chemical reagents are added during the production process of polyester fiber, which may cause allergies in some people; although the dyeing performance of polyester fiber can be improved through certain chemical treatments, its dyeing performance is still relatively poor compared with natural fibers, which may limit the application of polyester fiber in certain color and pattern designs. Therefore, in order to solve the above problems, a graphene-modified polyester fiber was prepared. Summary of the Invention

[0003] The purpose of this invention is to provide a graphene-modified polyester fiber and its preparation method to solve the problems mentioned in the background art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0005] A method for preparing graphene-modified polyester fiber includes the following steps:

[0006] S1: (1) Diethylenetriamine and salicylic acid are reacted to obtain an intermediate; (2) Graphene oxide is modified using the intermediate and then modified with n-octyl chloride to obtain modified graphene.

[0007] S2: Terephthalic acid, ethylene glycol, and modified graphene are mixed, and esterification and polycondensation reactions are carried out to obtain modified graphene polyester masterbatch.

[0008] S3: Mix modified graphene polyester masterbatch, polyester chips, and modified wool fibers, melt spin, stretch and wind to obtain graphene modified polyester fibers.

[0009] In a more optimized manner, the modified graphene polyester masterbatch comprises the following substances: by weight, 1-2 parts terephthalic acid, 1-2.5 parts ethylene glycol, and 0.5-1 parts modified graphene.

[0010] In a more optimized manner, the graphene-modified polyester fiber comprises the following components: by weight, 2-5 parts modified graphene polyester masterbatch, 1-3 parts polyester chips, and 0.5-1 parts modified wool fiber.

[0011] In a more optimized manner, the process parameters for the esterification reaction are: temperature 180-200℃, stirring speed 90-100r / min, nitrogen gas is used as a protective gas throughout the process, and the nitrogen pressure is 0.4-0.5MPa; the process parameters for the polycondensation reaction are: introduction of catalyst Sb2O3, the amount added is 10wt% of terephthalic acid, temperature 260-300℃, and time 1.5-2h.

[0012] In a more optimized manner: the specific process of melt spinning is as follows: under the protection of nitrogen, the fibers are melted at 270-300℃, fed into the spinning box by a screw, and ejected from the spinneret to obtain fine filaments; the specific process of stretching and winding is as follows: the fine filaments are passed through a hot stretching device, the temperature of the heating cylinder is set to 110-150℃, and under the action of the stretching roller, the fibers are stretched 3-5 times, and finally wound on the winding roller at a winding speed of 150-200 r / min, ultimately obtaining graphene-modified polyester fibers.

[0013] In a more optimized way: This patent effectively improves the antibacterial, UV-resistant, and hydrophilic properties of polyester fibers by introducing modified graphene. The synthesis of the modified graphene is as follows:

[0014] Step 1: Preparation of graphene oxide: Add graphite powder to concentrated sulfuric acid, and while stirring, add phosphorus pentoxide and potassium permanganate in sequence. Place at 80-90℃ and react for 4-5 hours. Dry to obtain graphene oxide.

[0015] Step 2: Preparation of intermediate: Diethylenetriamine, salicylic acid and cyclohexane are mixed evenly, 4-N,N-dimethylpyridine is added, and the mixture is reacted at 75-80℃ for 4-5 hours to obtain the intermediate;

[0016] Step 3: Preparation of modified graphene: Graphene oxide, intermediate, 4-N,N-dimethylpyridine, and cyclohexane were placed in a dry round-bottom flask. After the reaction was completed, the mixture was purified by rotary evaporation. The obtained product was placed in a round-bottom flask, and n-octyl chloride and deionized water were added. The mixture was stirred and reacted. The solvent was removed by vacuum distillation of the mixture after the reaction. The mixture was washed and dried to obtain modified graphene.

[0017] More preferably, the raw materials for the graphene oxide include the following substances: by weight, 1-2 parts graphite powder, 1-2 parts, 2-4 parts phosphorus pentoxide, and 2.3-3 parts potassium permanganate; the intermediate raw materials include the following components: by weight, 1-3 parts diethylenetriamine, 1-2 parts salicylic acid, 3-4 parts cyclohexane, and 1-2 parts 4-N,N-dimethylpyridine.

[0018] A more optimized approach is as follows: 1-2 parts graphene oxide, 1-1.5 parts intermediate, 0.5-1 parts 4-N,N-dimethylpyridine, and 3-4 parts cyclohexane are placed in a dry round-bottom flask and refluxed at 80-90℃ for 5-6 hours. After the reaction, some solvent is removed by rotary evaporation, and the product is purified by column chromatography. The obtained product is placed in a round-bottom flask equipped with a stirrer, and 3-4 parts n-octyl chloride and 3-5 parts deionized water are added. The mixture is stirred at 50-60℃ for 3-4 hours. The resulting mixture is dissolved in chloroform and the water is absorbed by anhydrous sodium sulfate. The solvent is then removed by vacuum distillation. The obtained product is washed three times with a mixture of ethyl acetate and acetone. The precipitate is dried in an oven at 60-70℃ for 5-6 hours to obtain the modified graphene.

[0019] A more optimized preparation process for the modified wool fiber is as follows: By weight, 1-2 parts of trypsin solution, 0.5-1 parts of hydrogen peroxide solution, and 5-6 parts of wool fiber are mixed and stirred until homogeneous to obtain oxidized wool fiber. The concentration of trypsin is 58-60 g / L, and 83-92 ml of hydrogen peroxide solution is added to each liter of trypsin solution. 1-1.5 parts of 2.3-2.6% keratinase, 1-1.3 parts of 5.1-5.8% alkaline protease, and 2-2.3 parts of deionized water are stirred and dissolved. 1-2 parts of 0.1-0.2 mol / L sodium bicarbonate solution are added to obtain a composite enzymatic hydrolysate. The oxidized wool fiber is added to the composite enzymatic hydrolysate, mixed and stirred, and reacted at room temperature for 16-17 hours to obtain the modified wool fiber.

[0020] The modified graphene obtained is grafted with organic molecular chains through chemical bonding, forming an organic layer on its surface. This significantly improves the interfacial compatibility of graphene with polyester. Simultaneously, salicylic acid groups are introduced, which contain intrinsic hydrogen bonds. These hydrogen bonds undergo molecular rearrangement under ultraviolet irradiation, forming a benzophenone structure with stronger ultraviolet absorption. After absorbing ultraviolet light, salicylic acid esters release the absorbed energy as heat or other harmless forms through molecular vibrations, preventing damage from ultraviolet light. The introduced amino and other hydrophilic groups absorb and retain moisture, using water as charge carriers to neutralize surface static charge, improving the material's antistatic ability and hydrophilicity. The introduced quaternary ammonium salt groups can disrupt bacterial cell membranes, inhibiting bacteria and viruses, achieving an antibacterial effect. Furthermore, the modified wool fiber surface contains a large number of anions, which, through electrostatic interactions with the prepared modified graphene polyester fiber, form a tighter surface bond, further improving the performance of the blended fiber. Attached Figure Description

[0021] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0022] Figure 1 This is a schematic diagram of the synthesis reaction of the intermediate;

[0023] Figure 2 This is a schematic diagram of the synthesis reaction of modified graphene. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] In this embodiment, it should be noted that the following parts are by weight. There are no special restrictions on the manufacturers from which the raw materials involved in this invention are purchased. Exemplarily, they include: graphene with serial number XF001H and a sheet diameter of 0.5-0.6 μm; salicylic acid with CAS number 69-72-7 and a purity of 99%; diethylenetriamine with CAS number 111-40-0 and a purity of 99%; terephthalic acid with CAS number 100-21-0; ethylene glycol with CAS number 107-21-1 and a purity of 99%; and n-octyl chloride with CAS number 111. -85-3, purity 99%; trypsin CAS 9002-07-7, enzyme activity retention rate 99%, manufacturer: Yuanye Biotechnology; keratinase product number: GDG-2021, enzyme activity retention rate 99%, brand: Xiasheng; alkaline protease product number: SDG-2439, active ingredient content 92%, brand: Xiasheng; wool fiber product number: YG-3150, purity 100%, manufacturer: Qinghe County Yuguan Wool Products Co., Ltd.; polyester chips product number: CZ-318, manufacturer: Jiangyin Xingye.

[0026] Reference Figure 1 and Figure 2 The preparation method of modified graphene is as follows:

[0027] Step 1: Preparation of graphene oxide: Add 1 part graphite powder to a 250 mL flask containing concentrated sulfuric acid. While stirring, add 2 parts phosphorus pentoxide and 2.3 parts potassium permanganate to the flask sequentially. Place the flask in a water bath at 80°C and react for 4 hours. Filter and dry to obtain graphene oxide.

[0028] Step 2: Preparation of intermediate: Place 1 part diethylenetriamine, 1 part salicylic acid, and 3 parts cyclohexane into a dry round-bottom flask, and add 2.5 parts 4-N,N-dimethylpyridine while shaking. Reflux at 75°C for 4 hours. When the reaction solution cools to room temperature, centrifuge and wash 5 times to obtain the intermediate.

[0029] Step 3: Preparation of modified graphene: 1 part graphene oxide, 1 part intermediate, 0.5 parts 4-N,N-dimethylpyridine, and 3 parts cyclohexane were placed in a dry round-bottom flask and refluxed at 80°C for 5 hours. After the reaction, some solvent was removed by rotary evaporation, and then purified by column chromatography. The obtained product was placed in a round-bottom flask equipped with a stirrer, and 3 parts n-octyl chloride and 3 parts deionized water were added. The mixture was stirred at 50°C for 3 hours. The resulting mixture was dissolved in chloroform and the water was absorbed by anhydrous sodium sulfate. The solvent was then removed by vacuum distillation. The obtained product was washed three times with a mixture of ethyl acetate and acetone. The precipitate was dried in an oven at 60°C for 5 hours to obtain modified graphene.

[0030] The modified wool fiber is prepared as follows: 2 parts trypsin solution, 1 part hydrogen peroxide solution, and 6 parts wool fiber are mixed and stirred evenly to obtain oxidized wool fiber. The concentration of trypsin is 60 g / L, and 92 ml of hydrogen peroxide solution is added to each liter of trypsin solution. 1.5 parts of 2.6% keratinase, 1.3 parts of 5.8% alkaline protease, and 2.3 parts of deionized water are stirred and dissolved. 2 parts of 0.2 mol / L sodium bicarbonate solution are added to obtain a composite enzymatic hydrolysate. The oxidized wool fiber is added to the composite enzymatic hydrolysate, mixed and stirred, and reacted at room temperature for 17 h to obtain modified wool fiber.

[0031] Example 1: A method for preparing graphene-modified polyester fiber, comprising the following steps:

[0032] S1: Preparation of modified graphene polyester masterbatch: Mix 1 part terephthalic acid, 1 part ethylene glycol, and 0.5 parts modified graphene evenly and place them in a dry reaction vessel. Heat to 180℃ for esterification reaction. Use nitrogen as protective gas throughout the process. The nitrogen pressure is 0.4MPa and the stirring speed is 90r / min. When the amount of water evaporated reaches 90% of the theoretical value, release the pressure to atmospheric pressure. The esterification reaction is completed. Add 2 parts of catalyst Sb2O3, heat to 260℃, and vacuum. Polycondense for 1.5h. After the reaction is completed, put the obtained polyester into an extruder and extrude and granulate to obtain modified graphene polyester masterbatch.

[0033] S2: Melt spinning: Weigh 2 parts of modified graphene polyester masterbatch, 1 part of polyester chips, and 0.5 parts of modified wool fiber and mix them. Under nitrogen protection, melt the mixture at 270°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 110°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 150 r / min to obtain graphene modified polyester fiber.

[0034] Example 2: A method for preparing graphene-modified polyester fiber, comprising the following steps:

[0035] S1: Preparation of modified graphene polyester masterbatch: Mix 2 parts terephthalic acid, 2.5 parts ethylene glycol, and 1 part modified graphene evenly and place them in a dry reaction vessel. Heat to 200℃ for esterification reaction. Nitrogen is used as the protective gas throughout the process. The nitrogen pressure is 0.5MPa and the stirring speed is 100r / min. When the amount of water evaporated reaches 90% of the theoretical value, the pressure is released to atmospheric pressure, and the esterification reaction ends. Add 2 parts of catalyst Sb2O3, heat to 300℃, vacuum, and polycondense for 2 hours. After the reaction is completed, put the obtained polyester into an extruder and extrude and granulate to obtain modified graphene polyester masterbatch.

[0036] S2: Melt spinning: Weigh 5 parts of modified graphene polyester masterbatch, 3 parts of polyester chips, and 1 part of modified wool fiber and mix them. Under nitrogen protection, melt the mixture at 300°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 150°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 200 r / min to obtain graphene modified polyester fiber.

[0037] Example 3: A method for preparing graphene-modified polyester fiber, comprising the following steps:

[0038] S1: Preparation of modified graphene polyester masterbatch: 1.5 parts terephthalic acid, 1.5 parts ethylene glycol, and 0.6 parts modified graphene were mixed evenly and placed in a dry reaction vessel. The mixture was heated to 190℃ for esterification reaction. Nitrogen was used as the protective gas throughout the process, with a nitrogen pressure of 0.45 MPa and a stirring speed of 95 r / min. When the amount of water evaporated reached 90% of the theoretical value, the pressure was released to atmospheric pressure, and the esterification reaction was completed. 2 parts of catalyst Sb2O3 were added, the temperature was raised to 280℃, and a vacuum was drawn for condensation for 1.6 h. After the reaction was completed, the obtained polyester was put into an extruder and extruded and granulated to obtain modified graphene polyester masterbatch.

[0039] S2: Melt spinning: Weigh 3 parts of modified graphene polyester masterbatch, 2 parts of polyester chips, and 0.8 parts of modified wool fiber and mix them. Under nitrogen protection, melt the mixture at 280°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 140°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 180 r / min to obtain graphene modified polyester fiber.

[0040] Comparative Example 1: The modified graphene was replaced with graphene oxide, and the rest was the same as in Example 3, as follows:

[0041] S1: Preparation of graphene oxide polyester masterbatch: 1.5 parts terephthalic acid, 1.5 parts ethylene glycol, and 0.6 parts graphene oxide were mixed evenly and placed in a dry reaction vessel. The mixture was heated to 190℃ for esterification reaction. Nitrogen was used as the protective gas throughout the process at a pressure of 0.45 MPa. The stirring speed was 95 r / min. When the amount of water evaporated reached 90% of the theoretical value, the pressure was released to atmospheric pressure, and the esterification reaction was completed. 2 parts of catalyst Sb2O3 were added, the temperature was raised to 280℃, and a vacuum was drawn for condensation for 1.6 h. After the reaction was completed, the obtained polyester was put into an extruder and extruded and granulated to obtain graphene oxide polyester masterbatch.

[0042] S2: Melt spinning: Weigh 3 parts of graphene oxide polyester masterbatch, 2 parts of polyester chips, and 0.8 parts of modified wool fiber and mix them. Under nitrogen protection, melt the mixture at 280°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 140°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 180 r / min to obtain graphene oxide polyester fiber.

[0043] Comparative Example 2: Graphene modified with a silane coupling agent was used to replace the original graphene. The rest of the process was the same as in Example 3, as detailed below:

[0044] Pre-preparation: Preparation of modified graphene: 1 part graphene oxide and 80 parts 70wt% ethanol were ultrasonically dispersed for 1 hour, KH550 silane coupling agent was added, and the mixture was stirred at 60℃ for 4 hours. After washing and drying, modified graphene was obtained.

[0045] S1: Preparation of modified graphene polyester masterbatch: 1.5 parts terephthalic acid, 1.5 parts ethylene glycol, and 0.6 parts modified graphene were mixed evenly and placed in a dry reaction vessel. The mixture was heated to 190℃ for esterification reaction. Nitrogen was used as the protective gas throughout the process, with a nitrogen pressure of 0.45 MPa and a stirring speed of 95 r / min. When the amount of water evaporated reached 90% of the theoretical value, the pressure was released to atmospheric pressure, and the esterification reaction was completed. 2 parts of catalyst Sb2O3 were added, the temperature was raised to 280℃, and a vacuum was drawn for condensation for 1.6 h. After the reaction was completed, the obtained polyester was put into an extruder and extruded and granulated to obtain modified graphene polyester masterbatch.

[0046] S2: Melt spinning: Weigh 3 parts of modified graphene polyester masterbatch, 2 parts of polyester chips, and 0.8 parts of modified wool fiber and mix them. Under nitrogen protection, melt the mixture at 280°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 140°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 180 r / min to obtain graphene modified polyester fiber.

[0047] Comparative Example 3: Blended without the addition of modified wool fibers, otherwise the process is the same as in Example 3, as detailed below:

[0048] S1: Preparation of modified graphene polyester masterbatch: 1.5 parts terephthalic acid, 1.5 parts ethylene glycol, and 10 parts modified graphene were mixed evenly and placed in a dry reaction vessel. The mixture was heated to 190℃ for esterification reaction. Nitrogen was used as the protective gas throughout the process, with a nitrogen pressure of 0.45 MPa and a stirring speed of 95 r / min. When the amount of water evaporated reached 90% of the theoretical value, the pressure was released to atmospheric pressure, and the esterification reaction was completed. 2 parts of catalyst Sb2O3 were added, the temperature was raised to 280℃, and a vacuum was drawn for condensation for 1.6 h. After the reaction was completed, the obtained polyester was put into an extruder and extruded and granulated to obtain modified graphene polyester masterbatch.

[0049] S2: Melt spinning: Weigh 3 parts of modified graphene polyester masterbatch and 2 parts of polyester chips. Under nitrogen protection, melt them at 280°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes on the spinneret are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 140°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 180 r / min to obtain graphene modified polyester fiber.

[0050] Comparative Example 4: Blending without adding polyester chips, otherwise the process is the same as in Example 3, as detailed below:

[0051] S1: Preparation of modified graphene polyester masterbatch: 1.5 parts terephthalic acid, 1.5 parts ethylene glycol, and 10 parts modified graphene were mixed evenly and placed in a dry reaction vessel. The mixture was heated to 190℃ for esterification reaction. Nitrogen was used as the protective gas throughout the process, with a nitrogen pressure of 0.45 MPa and a stirring speed of 95 r / min. When the amount of water evaporated reached 90% of the theoretical value, the pressure was released to atmospheric pressure, and the esterification reaction was completed. 2 parts of catalyst Sb2O3 were added, the temperature was raised to 280℃, and a vacuum was drawn for condensation for 1.6 h. After the reaction was completed, the obtained polyester was put into an extruder and extruded and granulated to obtain modified graphene polyester masterbatch.

[0052] S2: Melt spinning: Weigh 3 parts of modified graphene polyester masterbatch and 0.8 parts of modified wool fiber. Under nitrogen protection, melt them at 280°C. The resulting melt is fed into the spinning box by a screw driven by an electric motor and ejected from the spinneret. The spinneret holes on the spinneret are arranged in a matrix. Then, the filaments are passed through a hot stretching device. The temperature of the heating cylinder is set to 140°C. Under the action of the stretching roller, the fiber is stretched 4 times. Finally, it is wound on the winding roller at a winding speed of 180 r / min to obtain graphene modified polyester fiber.

[0053] Testing experiments: The obtained graphene-modified polyester fibers were dried, and the water absorption rate of the fabric was determined according to national standard GB / T21655.1-2008; the antibacterial rate was tested according to national standard GB / T20944.2-2007; the UV protection performance of the fabric was determined according to national standard GB / T18830-2009; and the surface charge density of the fabric was determined according to national standard GB / T12703.2-2009. The obtained fibers were made into graphene polyester staple fibers with a specification of 0.17tex×51mm, and their tensile strength was tested. The results are shown in Table 1.

[0054] Table 1 Test Results

[0055]

[0056] Conclusion: The above data shows that the polyester fibers prepared in Examples 1-3, by introducing modified graphene, exhibit improved antibacterial, UV-resistant, antistatic, hydrophilic, and strength properties. This is because the introduction of salicylic acid groups creates intrinsic hydrogen bonds within the molecule. These hydrogen bonds undergo molecular rearrangement under UV irradiation, forming a benzophenone structure with enhanced UV absorption. After absorbing UV light, salicylic ester compounds release the absorbed energy as heat or other harmless forms through molecular vibrations, preventing UV damage to the material. The introduced amino and other hydrophilic groups absorb and retain moisture, using water as charge carriers to neutralize surface static charges, thus improving the material's antistatic and hydrophilic properties. The introduced quaternary ammonium salt groups can disrupt bacterial cell membranes, inhibiting bacteria and viruses and achieving an antibacterial effect. In Comparative Example 1, graphene oxide was used to replace modified graphene, resulting in a decrease in performance compared to Example 3. In Comparative Example 2, silane coupling agent was used to modify graphene, which was used to replace the modified graphene, resulting in a decrease in performance compared to Example 3. In Comparative Example 3, no modified wool fiber was added during blending, resulting in a decrease in performance compared to Example 3. In Comparative Example 4, no polyester chips were added during blending, resulting in a decrease in performance compared to Example 3.

[0057] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0058] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing graphene-modified polyester fiber, characterized in that: Includes the following steps: S1: (1) Diethylenetriamine and salicylic acid are reacted to obtain an intermediate; (2) Graphene oxide is modified using the intermediate and then modified with n-octyl chloride to obtain modified graphene. S2: Terephthalic acid, ethylene glycol, and modified graphene are mixed, and esterification and polycondensation reactions are carried out to obtain modified graphene polyester masterbatch. S3: Mix modified graphene polyester masterbatch, polyester chips, and modified wool fibers, melt spin, stretch and wind to obtain graphene modified polyester fibers. The graphene-modified polyester fiber comprises the following components: by weight, 2-5 parts modified graphene polyester masterbatch, 1-3 parts polyester chips, and 0.5-1 parts modified wool fiber. The method for preparing the modified graphene is as follows: Step 1: Preparation of graphene oxide: Add graphite powder to concentrated sulfuric acid, and while stirring, add phosphorus pentoxide and potassium permanganate in sequence. Place at 80-90℃ and react for 4-5 hours. Dry to obtain graphene oxide. Step 2: Preparation of intermediate: Diethylenetriamine, salicylic acid and cyclohexane are mixed evenly, 4-N,N-dimethylpyridine is added, and the mixture is reacted at 75-80℃ for 4-5 hours to obtain the intermediate; Step 3: Preparation of modified graphene: Graphene oxide, intermediate, 4-N,N-dimethylpyridine, and cyclohexane were placed in a dry round-bottom flask. After the reaction was completed, the mixture was purified by rotary evaporation. The obtained product was placed in a round-bottom flask, and n-octyl chloride and deionized water were added. The mixture was stirred and the solvent was removed by vacuum distillation. The mixture was washed and dried to obtain modified graphene. The preparation process of the modified wool fiber is as follows: 1-2 parts by weight of trypsin solution, 0.5-1 parts by weight of hydrogen peroxide solution, and 5-6 parts by weight of wool fiber are mixed and stirred evenly to obtain oxidized wool fiber; 1-1.5 parts by weight of keratinase, 1-1.3 parts by weight of alkaline protease, and 2-2.3 parts by weight of deionized water are stirred and dissolved, and 1-2 parts by weight of sodium bicarbonate solution are added to obtain a composite enzymatic hydrolysate; the oxidized wool fiber is added to the composite enzymatic hydrolysate, mixed and stirred, and reacted at room temperature for 16-17 hours to obtain the modified wool fiber; The specific process of melt spinning is as follows: under the protection of nitrogen, the fibers are melted at 270-300℃, fed into the spinning box by a screw, and ejected from the spinneret to obtain fine filaments; the specific process of stretching and winding is as follows: the fine filaments are passed through a hot stretching device, the temperature of the heating cylinder is set to 110-150℃, and under the action of the stretching roller, the fibers are stretched 3-5 times, and finally wound on the winding roller at a winding speed of 150-200 r / min, ultimately obtaining graphene-modified polyester fibers.

2. The method for preparing graphene-modified polyester fiber according to claim 1, characterized in that: The modified graphene polyester masterbatch comprises the following components: by weight, 1-2 parts terephthalic acid, 1-2.5 parts ethylene glycol, and 0.5-1 parts modified graphene.

3. The method for preparing graphene-modified polyester fiber according to claim 1, characterized in that: The raw materials for the graphene oxide include the following components: by weight, 1-2 parts graphite powder, 1-2 parts concentrated sulfuric acid, 2-4 parts phosphorus pentoxide, and 2.3-3 parts potassium permanganate; the intermediate raw materials include the following components: by weight, 1-3 parts diethylenetriamine, 1-2 parts salicylic acid, 3-4 parts cyclohexane, and 1-2 parts 4-N,N-dimethylpyridine.

4. The method for preparing graphene-modified polyester fiber according to claim 1, characterized in that: The specific process for preparing the modified graphene is as follows: by weight, 1-2 parts of graphene oxide, 1-1.5 parts of intermediate, 0.5-1 parts of 4-N,N-dimethylpyridine, and 3-4 parts of cyclohexane are mixed and reacted at 80-90℃ for 5-6 hours. The cyclohexane is removed by rotary evaporation. At room temperature, 3-5 parts of deionized water and 3-4 parts of n-octyl chloride are added and stirred at 50-60℃ for 3-4 hours. After post-treatment, the modified graphene is obtained.

5. The method for preparing graphene-modified polyester fiber according to claim 1, characterized in that: The process parameters for esterification reaction are: temperature 180-200℃, stirring speed 90-100r / min, nitrogen gas is used as a protective gas throughout the process, and the nitrogen pressure is 0.4-0.5MPa; the process parameters for polycondensation reaction are: introducing catalyst Sb2O3, the amount added is 10wt% of terephthalic acid, temperature 260-300℃, and time 1.5-2h.

6. The graphene-modified polyester fiber obtained by any one of the preparation methods of graphene-modified polyester fiber according to any one of claims 1-5.

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