Graphene functionalized reinforced modified polyester fiber and preparation method thereof

Abstract

The invention discloses a graphene functionalized reinforced modified polyester fiber and a preparation method thereof. The method comprises the following steps: 1) polymerizing dimethyl phthalate, ethylene glycol, a catalyst and a multi-component composite modified material as raw materials to obtain functionalized modified polyester master batches; and 2) carrying out melt spinning on the functionalized modified polyester master batch to obtain the graphene functionalized enhanced modified polyester fiber. The functional modified polyester master batch is prepared from the self-made multi-component composite modified material, and then the polyester fiber is prepared, so that a product with excellent mechanical property, flame retardant property, ultraviolet resistance and thermo-oxidative aging resistance can be obtained, and the performance requirements on the polyester fiber in a larger application scene can be better met; the application prospect of the polyester fiber can be widened.

Description

Technical Field

[0001] The present invention relates to the field of polyester fiber materials, and particularly to a graphene-functionalized enhanced modified polyester fiber and a preparation method thereof. Background Art

[0002] Polyester fiber, commonly known as "polyester", is a synthetic fiber made by chemical polycondensation of organic dibasic acids and diols, and it belongs to a kind of high molecular compound. Polyester fiber has excellent wrinkle resistance and shape retention, and the clothes made thereof are not easy to wrinkle during wearing and can maintain the original shape of the clothes. Secondly, polyester fiber has high strength and elastic recovery ability, making the woven fabric strong and durable, and it can quickly return to its original state at the same time. In addition, polyester fiber also has characteristics such as abrasion resistance and non-sticking hair, making the fabric look cleaner.

[0003] In addition to being applied in the textile field, polyester fiber has also been increasingly used in the industrial field, such as being used in the manufacture of key components such as interior parts and seat belts in the automotive industry, being used as a reinforcing material in waterproof coiled materials and heat insulation layers in the construction field, and using polyester fiber fabric as a rubber reinforcing material (such as tire cord, conveyor belt, etc.).

[0004] In order to improve the performance of polyester fiber or expand its functions, using inorganic materials for enhancement and modification is a commonly used method. Graphene is a two-dimensional material composed of a single layer of carbon atoms, and it has excellent thermal, mechanical, electrical and optical properties. The far-infrared polyester fiber prepared by using graphene has excellent far-infrared heat preservation performance, antistatic performance and antibacterial performance, and can also enhance its flame retardancy to a certain extent. For example, a preparation method of a graphene-enhanced polyester fiber disclosed in Patent CN107988650B, a graphene-modified multifunctional polyester fiber and a preparation method thereof and an application in down filling disclosed in CN119102002B, and a multifunctional polyester fiber based on modified graphene and a preparation method thereof disclosed in CN119082920A.

[0005] However, the compatibility between graphene materials and the polyester system is poor, which to a certain extent limits its use. And due to reasons such as the limitation of the addition amount of graphene materials, the improvement of the flame retardancy of polyester fiber is limited. In addition, the ultraviolet aging and thermal-oxidative aging of polyester are inevitable problems. Ultraviolet rays will cause the molecular chains of polyester fiber to break, resulting in aging; polyester fiber will undergo oxidation reaction in a high-temperature environment, which will also cause fiber aging. The aging of polyester fiber will shorten its service life and affect its use effect. Patent CN119102002B solves the problem of poor compatibility between graphene and the polyester fiber system to a certain extent, but does not improve its aging resistance performance. At the same time, further improving the flame retardancy of polyester fiber can improve its use effect and broaden its application fields.

[0006] Therefore, it is necessary to improve the existing technology to provide a more reliable solution. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a graphene-functionalized enhanced modified polyester fiber and a preparation method thereof in view of the deficiencies in the above-mentioned existing technology.

[0008] To solve the above technical problem, the technical solution adopted by the present invention is: a preparation method of a graphene-functionalized enhanced modified polyester fiber, which is characterized by including the following steps:

[0009] 1) Polymerize functionalized modified polyester masterbatch with dimethyl terephthalate, ethylene glycol, catalyst and multi-component composite modification material as raw materials;

[0010] 2) Melt-spin the functionalized modified polyester masterbatch to obtain graphene-functionalized enhanced modified polyester fiber;

[0011] Among them, the multi-component composite modification material is prepared by the following steps:

[0012] S1. Graft Zn-doped carbon dots on graphene by hydrothermal method to obtain graphene-carbon dot composite;

[0013] S2. Deposit rare earth-doped nano-antimony trioxide on the graphene-carbon dot composite to obtain a graphene-based multi-component composite intermediate;

[0014] S3. Graft tung oil-modified phenolic resin on the graphene-based multi-component composite intermediate to obtain a multi-component composite modification material.

[0015] Preferably, the multi-component composite modification material is prepared by the following steps:

[0016] S1. Prepare graphene-carbon dot composite:

[0017] S1-1. Soak graphene in hydrochloric acid, take it out, wash and dry it to obtain pretreated graphene;

[0018] S1-2. Take pretreated graphene and zinc acetate, add them to an ethanol aqueous solution, ultrasonically disperse, then add dopamine hydrochloride, lutein, glucose, 3,5-diaminobenzoic acid, ultrasonically disperse, transfer the obtained mixture to a reaction kettle, and react under heating to obtain a graphene-carbon dot composite;

[0019] S2. Prepare graphene-based multi-component composite intermediate:

[0020] S2-1. Add the graphene-carbon dot composite, antimony chloride, lanthanum nitrate, cerium nitrate, PVP (polyvinylpyrrolidone) to ethanol, and ultrasonically disperse;

[0021] S2-2. While stirring, add alkali to the product of step S2-1 to adjust the pH to obtain a precursor mixture;

[0022] S2-3. Transfer the precursor mixture to a reaction kettle and react under heating to obtain a graphene-based multi-component composite intermediate;

[0023] S3. Graft tung oil-modified phenolic resin onto the graphene-based multi-component composite intermediate:

[0024] S3-1. Take phenol, tung oil, and p-toluenesulfonic acid, mix them evenly, and react under heating and stirring to obtain an intermediate product;

[0025] S3-2. Take the graphene-based multi-component composite intermediate and add it to formaldehyde, ultrasonically disperse it, add the obtained dispersion mixture to the intermediate product, add sodium hydroxide, and react under heating and stirring to obtain a multi-component composite modified material.

[0026] Preferably, step S1 is specifically as follows:

[0027] S1-1. Place graphene in hydrochloric acid with a mass concentration of 5-20%, soak it under ultrasound for 1-4 h, take it out and wash it with deionized water until neutral, and vacuum dry it at 70-100 °C for 4-16 h to obtain pretreated graphene;

[0028] S1-2. Take 1-4 g of pretreated graphene, 0.1375-0.55 g of zinc acetate, add them to 50-200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically disperse for 15-60 min, then add 0.19-0.76 g of dopamine hydrochloride, 0.2845-1.138 g of lutein, 0.36-1.44 g of glucose, 0.152-0.608 g of 3,5-diaminobenzoic acid, ultrasonically disperse for 5-30 min, transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene inner lining, react at 170-210 °C for 4-16 h, cool to room temperature, centrifuge and filter, wash the solid product with deionized water and ethanol in sequence, and vacuum dry it at 70-100 °C for 6-24 h to obtain a graphene-carbon dot composite.

[0029] Preferably, step S2 is specifically as follows:

[0030] S2-1. Add 0.5-2 g of graphene-carbon dot composite, 0.039-0.156 g of antimony chloride, 0.029-0.116 g of lanthanum nitrate, 0.022-0.086 g of cerium nitrate, and 0.15-0.6 g of PVP to 75-300 mL of ethanol, and ultrasonically disperse for 15-60 min;

[0031] S2-2. While stirring, add a sodium hydroxide solution with a concentration of 0.5 - 2 mol / L to the product of step S2-1, and adjust the pH to 8 - 9 to obtain a precursor mixture;

[0032] S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner container, react at 185 - 230 °C for 6 - 24 h, cool to room temperature, filter, wash the solid product with ethanol, and vacuum dry at 60 - 90 °C to constant weight to obtain a graphene-based multi-component composite intermediate.

[0033] Preferably, step S3 is specifically as follows:

[0034] S3-1. Take 2.575 - 10.3 g of phenol, 0.75 - 3 g of tung oil, and 0.005 - 0.02 g of p-toluenesulfonic acid and mix them in a reaction kettle, stir evenly, stir and react at 100 - 110 °C for 1.5 - 6 h, cool to room temperature to obtain an intermediate product;

[0035] S3-2. Take 1.25 - 5 g of the graphene-based multi-component composite intermediate and add it to 4.3 - 17.2 g of formaldehyde, ultrasonically disperse for 0.5 - 2 h, add the obtained dispersion mixture to the intermediate product while stirring, stir for 15 - 60 min, then add 0.025 - 0.1 g of sodium hydroxide, stir and react at 80 - 100 °C for 2 - 8 h, cool to room temperature, wash and filter the product with ethanol, and vacuum dry at 50 - 80 °C for 6 - 24 h to obtain a multi-component composite modified material.

[0036] Preferably, the multi-component composite modified material is prepared through the following steps:

[0037] S1. Prepare a graphene-carbon dot composite:

[0038] S1-1. Place graphene in hydrochloric acid with a mass concentration of 10%, soak it under ultrasonic for 2 h, take it out and wash it with deionized water until neutral, and vacuum dry at 90 °C for 8 h to obtain pretreated graphene;

[0039] S1-2. Take 2 g of pretreated graphene and 0.275 g of zinc acetate and add them to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically disperse for 30 min, then add 0.38 g of dopamine hydrochloride, 0.569 g of lutein, 0.72 g of glucose, and 0.304 g of 3,5-diaminobenzoic acid, ultrasonically disperse for 15 min, transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene inner lining, react at 190 °C for 8 h, cool to room temperature, centrifuge and filter, wash the solid product with deionized water and ethanol in sequence, and vacuum dry at 80 °C for 12 h to obtain a graphene-carbon dot composite;

[0040] S2. Preparation of graphene-based multi-component composite intermediate: S2-1. Add 1 g of graphene-carbon dot composite, 0.078 g of antimony chloride, 0.058 g of lanthanum nitrate, 0.043 g of cerium nitrate, and 0.3 g of PVP into 150 mL of ethanol, and ultrasonically disperse for 30 min;

[0041] S2-2. Dropwise add 1 mol / L sodium hydroxide solution to the product of step S2-1 under stirring, and adjust the pH to 8 to obtain a precursor mixture;

[0042] S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner container, react at 210 °C for 12 h, cool to room temperature, filter, wash the solid product with ethanol, and vacuum dry at 70 °C to constant weight to obtain a graphene-based multi-component composite intermediate;

[0043] S3. Graft tung oil-modified phenolic resin onto the graphene-based multi-component composite intermediate:

[0044] S3-1. Take 5.15 g of phenol, 1.5 g of tung oil, and 0.01 g of p-toluenesulfonic acid, mix them in a reaction kettle, stir evenly, stir and react at 105 °C for 3 h, and cool to room temperature to obtain an intermediate product;

[0045] S3-2. Take 2.5 g of the graphene-based multi-component composite intermediate and add it to 8.6 g of formaldehyde, ultrasonically disperse for 1 h, add the obtained dispersion mixture to the intermediate product under stirring, add 0.05 g of sodium hydroxide after stirring for 30 min, stir and react at 90 °C for 4 h, cool to room temperature, wash and filter the product with ethanol, and vacuum dry at 60 °C for 12 h to obtain a multi-component composite modified material.

[0046] The main synthesis mechanism of the multi-component composite modified material provided by the present invention is as follows:

[0047] First, pickle graphene, and then in-situ synthesize Zn-doped carbon dots on graphene by a one-pot hydrothermal method. In this process, graphene acid is mixed with zinc acetate, and Zn 2+ is connected to graphene by electrostatic adsorption, coordination and other interactions with functional groups such as hydroxyl groups on the graphene surface. After adding carbon dot raw materials (hydroxytyramine hydrochloride, lutein, glucose, 3,5-diaminobenzoic acid), the carbon dot raw materials can also be combined with Zn 2+ through electrostatic adsorption, coordination and other interactions with functional groups such as hydroxyl groups, amino groups, and carboxyl groups on the surface of Zn 2+ Finally, carbon dots are generated through a hydrothermal reaction, enabling the carbon dots to be uniformly and abundantly loaded on graphene to obtain a graphene-carbon dot composite;

[0048] Then, using the graphene-carbon dot composite as a carrier, using antimony chloride as the antimony source and PVP (polyvinylpyrrolidone) as TableSurfactant La and Ce are rare earth doping components. A hydrothermal reaction is carried out under alkaline conditions at high temperature to deposit rare earth lanthanum cerium oxide-doped nano-antimony trioxide on the graphene-carbon dot composite to obtain an intermediate of the graphene-based multi-component composite.

[0049] Finally, first, a reaction is carried out between phenol and tung oil under the condition of p-toluenesulfonic acid as a catalyst to obtain a tung oil-phenol reaction product. Then, formaldehyde and phenol are in-situ polymerized under the catalysis of an alkaline catalyst sodium hydroxide, and a tung oil-modified phenolic resin is grafted on the intermediate of the graphene-based multi-component composite to obtain the final multi-component composite modified material.

[0050] The multi-component composite modified material prepared by the present invention uses graphene as a basic carrier, on which Zn-doped carbon dots are uniformly loaded. Then, rare earth lanthanum cerium oxide-doped nano-antimony trioxide particles are deposited on the Zn-doped carbon dots and graphene. Finally, a tung oil-modified phenolic resin is grafted to form a multi-effect enhanced structure system of multi-component composite. The main enhanced components in this structure system include: graphene, Zn-doped carbon dots, rare earth lanthanum cerium oxide-doped nano-antimony trioxide particles, and tung oil-modified phenolic resin. The mechanism of action of each component is analyzed and explained below for the understanding of the present invention.

[0051] 1. In the multi-component composite modified material of the present invention, graphene has excellent mechanical, thermal, and electrical properties, and its addition can improve the mechanical strength, flame retardant performance, etc. of the fiber.

[0052] 2. The carbon dots in the multi-component composite modified material of the present invention are prepared from hydrochloric acid dopamine, lutein, glucose, and 3,5-diaminobenzoic acid as the main raw materials. It well inherits the reducing properties of lutein and 3,5-diaminobenzoic acid and can provide good antioxidant performance for the system. This antioxidant performance can play the following roles: (1) During the synthesis process of PET (polyethylene terephthalate), it can help reduce side reactions caused by thermal degradation or oxidation, reduce product impurities, and this effect can cooperate with the effect of Sb2O3 on PET synthesis; (2) During the subsequent application process, the carbon dots with antioxidant performance can capture free radicals with strong oxidation effects in the system, prevent their damage to the polymer system, slow down the degradation or oxidation of the polymer, and improve the aging resistance of PET.

[0053] At the same time, the carbon dots can efficiently absorb ultraviolet light, endowing the system with excellent ultraviolet resistance; on the other hand, the grafting of carbon dots on graphene can also increase the specific surface area, provide more loading sites for the deposition of rare earth lanthanum cerium oxide-doped nano-antimony trioxide particles, and promote the uniform dispersion of rare earth lanthanum cerium oxide-doped nano-antimony trioxide particles.

[0054] The doped Zn in the carbon dots is mainly ZnO nanoparticles, which can play the following roles:

[0055] (1) ZnO itself is a natural ultraviolet absorber, which can further enhance the ultraviolet resistance and provide the post - resistance of the polymer in the system; ZnO can absorb or react to scavenge free radicals and improve the thermal stability, and this effect can complement the antioxidant performance of the carbon dots;

[0056] (2) Zinc doping can passivate the surface defects of carbon dots, reduce non - radiative recombination centers, and at the same time inhibit the aggregation of carbon dots through electrostatic repulsion, maintaining a high specific surface area (Yang Mingxi. Study on the preparation, structure and properties of metal - ion - doped carbon dots based on gluconate [D]. Jilin University [2025 - 04 - 25]); The doping of Zn can also increase the electron cloud density and provide the electron transfer rate, thereby enhancing the reducibility of carbon dots;

[0057] (3) During the subsequent in - situ grafting of tung oil - modified phenolic resin, during the polymerization process of phenolic resin, the hydroxymethyl phenols form methylene bridges (-CH2-) or ether bonds (-O-) through dehydration condensation. Zinc oxide may activate the hydroxyl groups in hydroxymethyl and accelerate the progress of the polycondensation reaction, thus playing a catalytic effect on the polymerization of phenolic resin. Since the ZnO nanoparticles can be uniformly dispersed in the system of the multi - component composite modified material, this can enhance the above - mentioned effects of ZnO.

[0058] 3. In the multi - component composite modified material of the present invention, one of the functions of Sb2O3 is to act as a catalyst for PET synthesis in the preparation stage. In the system of the present invention, due to the nano - sized structure and uniform dispersion of Sb2O3, it can contact the reactants more fully, which is beneficial to improving its catalytic efficiency; on the other hand, in the application stage of polyester fiber, Sb2O3 plays the role of a flame - retardant filler. Loading Sb2O3 into the multi - component composite modified material system can achieve its uniform dispersion. This uniform dispersion characteristic can improve the catalytic efficiency in the polyester preparation stage, better play its flame - retardant performance in the subsequent use stage, and at the same time reduce its adverse impact on the mechanical properties of the polyester fiber system.

[0059] And the doped lanthanum - cerium rare - earth elements can at least play the following roles:

[0060] (1)For Sb2O3, the doping and compounding of rare earth elements can reduce the activation energy of the polycondensation reaction, enabling the reaction to achieve high-efficiency catalytic effects at lower temperatures. The outer electron energy levels of rare earth elements are rich and have variable valence states. They can form coordination bonds or electron transfer channels with Sb³⁺ in antimony trioxide, enhancing the redox activity of Sb³⁺, thereby improving the catalytic activity of Sb2O3. Rare earth oxides have a high specific surface area and abundant lattice oxygen defects, which can promote the dispersion of antimony trioxide particles and increase the density of active sites in the catalytic system. At the same time, the basic sites provided by rare earths help neutralize the acidic by-products generated in the reaction and inhibit side reactions.

[0061] (2)For carbon dots, some of the doped rare earth elements are in-situ attached to the surface of the carbon dots. The rare earth elements are anchored on the surface of the carbon dots in a monodispersed form, forming a highly active metal-carbon interface. The π-conjugated system of rare earths and carbon dots enhances the electron delocalization through energy transfer, increasing the electron migration rate and enhancing the reducibility of the carbon dots. At the same time, rare earth elements can also stabilize the oxygen vacancies in the carbon dot lattice, further enhancing the reduction activity of the carbon dots.

[0062] (3)For ZnO, doping rare earth elements can increase the density of surface hydroxyl groups of ZnO and improve its adsorption capacity for ultraviolet light. At the same time, rare earth oxides themselves also have strong ultraviolet resistance (Sun Haiyun. Ultraviolet Absorbents and Their Applications in Leather Chemicals [J]. Leather and Chemicals, 2014, 31(5):7. DOI: 10.3969 / j.issn.1674-0939.2014.05.003.). Therefore, the combination of rare earths and ZnO can improve the ultraviolet resistance of the system.

[0063] (4)Rare earth oxides have a high melting point, which can improve the high-temperature stability, slow down the degradation rate of materials, and achieve a certain flame retardant synergistic effect.

[0064] 4. In the multi-component composite modified material of the present invention, the tung oil-modified phenolic resin in-situ grafted on the graphene-based multi-component composite intermediate can improve the compatibility of the graphene-based multi-component composite intermediate with the organic system, promote its uniform dispersion in the polyester fiber system, thereby simultaneously solving the defect that inorganic components such as graphene, Zn-doped carbon dots, and nano-antimony trioxide particles doped with lanthanum and cerium oxides are difficult to disperse in the polyester organic system;

[0065] The uniform loading of Zn-doped carbon dots and nano-antimony trioxide particles doped with lanthanum and cerium oxides on graphene can mechanically drag the two-dimensional structure of graphene, promote the spreading of graphene, and reduce its curling and winding phenomenon, thereby promoting the exertion of its enhanced performance.

[0066] Meanwhile, the molecular structure of phenolic resin contains benzene rings and phenolic hydroxyl groups, endowing it with high thermal stability and oxygen index. When phenolic resin decomposes at high temperatures, acidic substances are produced, and further decomposition generates incombustible gases such as carbon dioxide and water vapor, making it have certain flame retardant properties. Therefore, the addition of tung oil modified phenolic resin can improve the heat resistance and flame retardant properties of polyester.

[0067] Furthermore, the modification of tung oil can improve toughness, adhesion, and flame retardancy. When the prepared PET fibers are used as rubber reinforcing materials (such as tire cords, conveyor belts, etc.), the addition of tung oil modified phenolic resin in the PET system can improve the adhesion performance between the prepared polyester fibers and the rubber interface (Lu Qinwei. Synthesis of Phenolic Resin and Its Influence on the Interface Performance of PET Reinforced Composites [D]. Anhui Polytechnic University, 2016.), which is beneficial to enhancing the application effect of polyester fibers in different usage scenarios.

[0068] The main principle of tung oil improving flame retardant performance is as follows: Unsaturated fatty acids such as α - eleostearic acid contained in tung oil form a dense carbon layer through pyrolysis, which can effectively isolate oxygen from contacting the substrate and slow down heat transfer; Epoxidation and ring - opening reactions cause the molecular chains of tung oil to form a cross - linked structure, improving the thermal stability of the material and delaying the thermal decomposition process.

[0069] Through the analysis of the action mechanisms of the main components in the multi - component composite modified material of the present invention, it can be seen that the present invention constructs a composite system with a special structure through graphene, Zn - doped carbon dots, lanthanum - cerium oxide - doped nano - antimony trioxide particles, and tung oil modified phenolic resin, etc. While fully exerting the self - enhancing effects of each component, it can also rely on the mutual cooperation and complementary enhancement among the components to achieve a synergistic enhancement effect in improving the flame retardant performance, antioxidant performance, ultraviolet resistance performance, etc. of the prepared polyester fibers.

[0070] Preferably, the preparation method of the graphene functionalized and enhanced modified polyester fiber comprises the following steps:

[0071] 1) Mix dimethyl terephthalate, ethylene glycol, and a catalyst, carry out transesterification reaction under heating, then add the multi - component composite modified material, stir evenly, raise the temperature for polycondensation reaction, discharge the material after the reaction, cool it, and pelletize it to obtain the functionalized modified polyester masterbatch;

[0072] 2) Dry the functionalized modified polyester masterbatch, and then carry out melt spinning, winding, and stretching in a melt spinning machine to obtain the graphene functionalized and enhanced modified polyester fiber.

[0073] Preferably, the catalyst is one or both of zinc acetate and manganese acetate.

[0074] Preferably, the preparation method of the graphene-functionalized enhanced modified polyester fiber comprises the following steps:

[0075] 1) Take 50 - 200 g of dimethyl terephthalate, 34 - 136 g of ethylene glycol, and 0.09 - 0.36 g of zinc acetate and add them to a reaction kettle. Conduct transesterification reaction at 200 - 250 °C for 1 - 4 h, then add 0.25 - 9.0 g of a multi-component composite modification material, stir evenly, heat to 255 - 290 °C, and conduct polycondensation for 1 - 4 h. After the reaction ends, discharge under nitrogen pressure, cool, and pelletize to obtain a functionalized modified polyester masterbatch;

[0076] 2) Dry the functionalized modified polyester masterbatch at 80 - 110 °C for 2 - 8 h, then conduct melt spinning, winding, and stretching in a melt spinning machine to obtain graphene-functionalized enhanced modified polyester fiber; wherein, the spinning temperature is 270 - 300 °C, the winding speed is 600 - 2400 m / min, the stretching ratio is 1 - 3 times, and the stretching speed is 350 - 1400 m / min.

[0077] The present invention also provides a graphene-functionalized enhanced modified polyester fiber, which is prepared by the method as described above.

[0078] The beneficial effects of the present invention are:

[0079] The present invention provides a graphene-functionalized enhanced modified polyester fiber and its preparation method. By using a self-made multi-component composite modification material to prepare a functionalized modified polyester masterbatch and then preparing polyester fiber, a product with excellent mechanical properties, flame retardancy, ultraviolet resistance, and thermal oxygen aging resistance can be obtained, which can better meet the performance requirements of polyester fiber in a larger application scenario and broaden the application prospects of polyester fiber;

[0080] Based on graphene as the basic carrier, Zn-doped carbon dots are uniformly loaded thereon, and then rare earth lanthanum cerium oxide-doped nano-antimony trioxide particles are deposited on the Zn-doped carbon dots and graphene, and finally tung oil-modified phenolic resin is grafted to form a multi-component composite multi-effect enhancement system with a special structure. The multi-components: graphene, Zn-doped carbon dots, lanthanum cerium oxide-doped nano-antimony trioxide particles, and tung oil-modified phenolic resin can not only give full play to the self-enhancing effects of each component, but also cooperate and complement each other to enhance, resulting in a synergistic enhancement effect in improving the flame retardancy, antioxidant performance, ultraviolet resistance, etc. of the prepared polyester fiber, thereby significantly improving the comprehensive performance of the prepared polyester fiber. Description of the Drawings

[0081] Figure 1 It is the infrared absorption spectrum of the graphene-based multi-component composite intermediate prepared in Example 1;

[0082] Figure 2 The ultraviolet-visible light absorption spectra of the multi-component composite modified materials prepared in Example 1, Comparative Example 3, and Comparative Example 4;

[0083] Figure 3 The test results of the antioxidant properties of the multi-component composite modified materials prepared in Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4;

[0084] Figure 4 The test results of the intrinsic viscosity of the functionalized modified polyester masterbatch prepared in the examples and comparative examples;

[0085] Figure 5 The test results of the end carboxyl group value of the functionalized modified polyester masterbatch prepared in the examples and comparative examples;

[0086] Figure 6 The test results of the breaking strength of the polyester fibers prepared in the examples and comparative examples;

[0087] Figure 7 The test results of the limiting oxygen index of the polyester fibers prepared in the examples and comparative examples;

[0088] Figure 8 The test results of the anti-ultraviolet performance of the polyester fibers prepared in the examples and comparative examples;

[0089] Figure 9 The test results of the thermal-oxidative aging performance of the polyester fibers prepared in the examples and comparative examples. Detailed implementation manners

[0090] The following further describes the present invention in detail with reference to examples, so that those skilled in the art can implement it according to the description in the specification.

[0091] It should be understood that the terms such as "having", "comprising", and "including" used herein do not exclude the presence or addition of one or more other elements or their combinations.

[0092] Unless otherwise specified, the test methods used in the following examples are all conventional methods. The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified. For those not specified in the following examples, they are carried out under conventional conditions or the conditions recommended by the manufacturer. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be purchased commercially.

[0093] The sources of some raw materials involved in the following examples and comparative examples are as follows:

[0094] Dimethyl terephthalate, brand: SK of South Korea, purchased from Shanghai Fengrui Chemical Co., Ltd.;

[0095] Graphene, with an average particle size of 20 μm, was purchased from Shanghai Fengguang Plasticization Technology Co., Ltd.;

[0096] Antimony trioxide, with an average particle size of 200 nm, was purchased from Shanghai Naiou Nano Technology Co., Ltd.;

[0097] Tung oil, industrial grade (content > 99%), was purchased from Shandong Jibei New Materials Co., Ltd.;

[0098] Phenol, from Shanghai Hengxinde Chemical Co., Ltd.

[0099] Example 1

[0100] A preparation method of graphene-functionalized enhanced modified polyester fiber, comprising the following steps:

[0101] 1) Take 100 g of dimethyl terephthalate, 68 g of ethylene glycol, and 0.18 g of zinc acetate and add them to a reaction kettle. Conduct transesterification reaction at 225 °C for 2 h, then add 4.5 g of multi-component composite modification material, stir evenly, heat to 270 °C, and carry out polycondensation for 2 h. After the reaction is completed, discharge under nitrogen pressure, cool, and pelletize to obtain functionalized modified polyester masterbatch;

[0102] 2) Dry the functionalized modified polyester masterbatch at 100 °C for 4 h, and then carry out melt spinning, winding, and stretching in a melt spinning machine to obtain graphene-functionalized enhanced modified polyester fiber; among them, the spinning temperature is 290 °C, the winding speed is 1200 m / min, the stretching ratio is 2 times, and the stretching speed is 700 m / min.

[0103] Among them, the multi-component composite modification material is prepared through the following steps:

[0104] S1. Prepare graphene-carbon dot composite:

[0105] S1-1. Place graphene in hydrochloric acid with a mass concentration of 10%, soak it under ultrasonic wave for 2 h, take it out and wash it with deionized water until neutral, and vacuum dry it at 90 °C for 8 h to obtain pretreated graphene;

[0106] S1-2. Take 2 g of pretreated graphene and 0.275 g of zinc acetate and add them to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1. Ultrasonically disperse for 30 min, then add 0.38 g of dopamine hydrochloride, 0.569 g of lutein, 0.72 g of glucose, and 0.304 g of 3,5-diaminobenzoic acid, ultrasonically disperse for 15 min, transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene inner lining, react at 190 °C for 8 h, cool to room temperature, centrifuge and filter, wash the solid product with deionized water and ethanol in sequence, and vacuum dry it at 80 °C for 12 h to obtain graphene-carbon dot composite;

[0107] S2. Preparation of graphene-based multi-component composite intermediate:

[0108] S2-1. Add 1 g of graphene-carbon dot composite, 0.078 g of antimony chloride, 0.058 g of lanthanum nitrate, 0.043 g of cerium nitrate, and 0.3 g of PVP into 150 mL of ethanol, and ultrasonically disperse for 30 min;

[0109] S2-2. Dropwise add 1 mol / L sodium hydroxide solution to the product of step S2-1 under stirring, and adjust the pH to 8 to obtain a precursor mixture;

[0110] S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner container, react at 210 °C for 12 h, cool to room temperature, filter, wash the solid product with ethanol, and vacuum dry at 70 °C to constant weight to obtain a graphene-based multi-component composite intermediate;

[0111] S3. Graft tung oil-modified phenolic resin onto the graphene-based multi-component composite intermediate:

[0112] S3-1. Take 5.15 g of phenol, 1.5 g of tung oil, and 0.01 g of p-toluenesulfonic acid, mix them in a reaction kettle, stir evenly, stir and react at 105 °C for 3 h, and cool to room temperature to obtain an intermediate product;

[0113] S3-2. Take 2.5 g of the graphene-based multi-component composite intermediate and add it to 8.6 g of formaldehyde, ultrasonically disperse for 1 h, add the obtained dispersion mixture to the intermediate product under stirring, add 0.05 g of sodium hydroxide after stirring for 30 min, stir and react at 90 °C for 4 h, cool to room temperature, wash and filter the product with ethanol, and vacuum dry at 60 °C for 12 h to obtain a multi-component composite modified material.

[0114] Example 2

[0115] A preparation method of graphene-functionalized enhanced modified polyester fiber, comprising the following steps:

[0116] 1) Take 100 g of dimethyl terephthalate, 68 g of ethylene glycol, and 0.18 g of zinc acetate and add them to a reaction kettle, carry out transesterification reaction at 225 °C for 2 h, then add 4.0 g of the multi-component composite modified material, stir evenly, heat to 275 °C, carry out polycondensation for 2 h, after the reaction is completed, discharge under nitrogen pressure, cool, and pelletize to obtain a functionalized modified polyester masterbatch;

[0117] 2) Dry the functionalized modified polyester masterbatch at 100 °C for 4 h, and then carry out melt spinning, winding, and stretching in a melt spinning machine to obtain graphene-functionalized enhanced modified polyester fiber; wherein, the spinning temperature is 290 °C, the winding speed is 1200 m / min, the stretching ratio is 2 times, and the stretching speed is 700 m / min.

[0118] Among them, the multi-component composite modified material is prepared through the following steps:

[0119] S1. Prepare graphene-carbon dot composite:

[0120] S1-1. Place graphene in hydrochloric acid with a mass concentration of 10%, soak it under ultrasonic wave for 2 h, take it out, wash it with deionized water until neutral, and vacuum dry it at 90 °C for 8 h to obtain pretreated graphene;

[0121] S1-2. Take 2 g of pretreated graphene and 0.25 g of zinc acetate, add them into 100 mL of an ethanol aqueous solution composed of ethanol and deionized water according to a volume ratio of 1:1, ultrasonically disperse for 30 min, then add 0.38 g of dopamine hydrochloride, 0.569 g of lutein, 0.72 g of glucose, and 0.304 g of 3,5-diaminobenzoic acid, ultrasonically disperse for 15 min, transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene inner lining, react at 190 °C for 8 h, cool to room temperature, centrifuge and filter, wash the solid product with deionized water and ethanol in sequence, and vacuum dry it at 80 °C for 12 h to obtain graphene-carbon dot composite;

[0122] S2. Prepare graphene-based multi-component composite intermediate:

[0123] S2-1. Add 1.2 g of graphene-carbon dot composite, 0.078 g of antimony chloride, 0.058 g of lanthanum nitrate, 0.043 g of cerium nitrate, and 0.3 g of PVP into 150 mL of ethanol, and ultrasonically disperse for 30 min;

[0124] S2-2. While stirring, dropwise add 1 mol / L sodium hydroxide solution to the product of step S2-1 to adjust the pH to 8 to obtain a precursor mixture;

[0125] S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner lining, react at 210 °C for 12 h, cool to room temperature, filter, wash the solid product with ethanol, and vacuum dry it at 70 °C to constant weight to obtain graphene-based multi-component composite intermediate;

[0126] S3. Graft tung oil modified phenolic resin onto the graphene-based multi-component composite intermediate:

[0127] S3-1. Take 5.15 g of phenol, 1.5 g of tung oil, and 0.01 g of p-toluenesulfonic acid, mix them in a reaction kettle, stir evenly, stir and react at 105 °C for 3 h, cool to room temperature to obtain an intermediate product;

[0128] S3-2. Take 2.5 g of the graphene-based multi-component composite intermediate and add it to 8.6 g of formaldehyde. Ultrasonically disperse for 1 h. Add the resulting dispersion mixture to the intermediate product under stirring. After stirring for 30 min, add 0.05 g of sodium hydroxide. Stir and react at 90 °C for 4 h. Cool to room temperature. Wash the product with ethanol and filter. Dry it under vacuum at 60 °C for 12 h to obtain the multi-component composite modified material.

[0129] Example 3

[0130] A preparation method of graphene-functionalized enhanced modified polyester fiber, comprising the following steps:

[0131] 1) Take 100 g of dimethyl terephthalate, 68 g of ethylene glycol, and 0.16 g of zinc acetate and add them to a reaction kettle. Conduct an ester exchange reaction at 210 °C for 2.5 h. Then add 4.5 g of the multi-component composite modified material, stir evenly, heat to 275 °C, and conduct polycondensation for 2 h. After the reaction ends, discharge under nitrogen pressure, cool, and pelletize to obtain the functionalized modified polyester masterbatch;

[0132] 2) Dry the functionalized modified polyester masterbatch at 100 °C for 4 h, and then conduct melt spinning, winding, and stretching in a melt spinning machine to obtain graphene-functionalized enhanced modified polyester fiber; wherein, the spinning temperature is 290 °C, the winding speed is 1000 m / min, the stretching ratio is 2 times, and the stretching speed is 800 m / min.

[0133] Among them, the preparation method of the multi-component composite modified material is the same as that in Example 1.

[0134] Comparative Example 1

[0135] A preparation method of modified polyester fiber, comprising the following steps:

[0136] 1) Take 100 g of dimethyl terephthalate, 68 g of ethylene glycol, and 0.18 g of zinc acetate and add them to a reaction kettle. Conduct an ester exchange reaction at 225 °C for 2 h. Then add 0.2 g of antimony trioxide and 2 g of graphene, stir evenly, heat to 270 °C, and conduct polycondensation for 2 h. After the reaction ends, discharge under nitrogen pressure, cool, and pelletize to obtain the functionalized modified polyester masterbatch;

[0137] 2) Dry the functionalized modified polyester masterbatch at 100 °C for 4 h, and then conduct melt spinning, winding, and stretching in a melt spinning machine to obtain graphene-functionalized enhanced modified polyester fiber; wherein, the spinning temperature is 290 °C, the winding speed is 1200 m / min, the stretching ratio is 2 times, and the stretching speed is 700 m / min.

[0138] Comparative Example 2

[0139] The difference between this example and Example 1 is only that:

[0140] The multi-component composite modified material in this example is prepared through the following steps:

[0141] S1. Place graphene in hydrochloric acid with a mass concentration of 10%, soak it under ultrasonic waves for 2 h, take it out and wash it with deionized water until neutral, and vacuum dry it at 90 °C for 8 h to obtain pretreated graphene;

[0142] S2. Prepare a graphene-based multi-component composite intermediate:

[0143] S2-1. Add 1 g of pretreated graphene, 0.078 g of antimony chloride, 0.058 g of lanthanum nitrate, 0.043 g of cerium nitrate, and 0.3 g of PVP to 150 mL of ethanol, and ultrasonically disperse for 30 min;

[0144] S2-2. While stirring, dropwise add 1 mol / L sodium hydroxide solution to the product of step S2-1, and adjust the pH to 8 to obtain a precursor mixture;

[0145] S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner container, react at 210 °C for 12 h, cool to room temperature, filter, wash the solid product with ethanol, and vacuum dry it at 70 °C to constant weight to obtain a graphene-based multi-component composite intermediate;

[0146] S3. Graft tung oil-modified phenolic resin onto the graphene-based multi-component composite intermediate, and the steps are the same as in Example 1.

[0147] Comparative Example 3

[0148] The difference between this example and Example 1 is only that:

[0149] The multi-component composite modified material in this example is prepared through the following steps:

[0150] S1. Prepare a graphene-carbon dot composite:

[0151] S1-1. Place graphene in hydrochloric acid with a mass concentration of 10%, soak it under ultrasonic waves for 2 h, take it out and wash it with deionized water until neutral, and vacuum dry it at 90 °C for 8 h to obtain pretreated graphene;

[0152] S1-2. Take 2 g of pretreated graphene and add it to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1. Ultrasonically disperse for 30 min, then add 0.38 g of dopamine hydrochloride, 0.569 g of lutein, 0.72 g of glucose, and 0.304 g of 3,5-diaminobenzoic acid, and ultrasonically disperse for 15 min. Transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene inner liner, react at 190 °C for 8 h, cool to room temperature, centrifuge and filter. Wash the solid product successively with deionized water and ethanol, and vacuum dry at 80 °C for 12 h to obtain a graphene-carbon dot composite;

[0153] S2. Prepare an intermediate of a graphene-based multi-component composite, and the steps are the same as those in Example 1;

[0154] S3. Graft tung oil-modified phenolic resin onto the intermediate of the graphene-based multi-component composite, and the steps are the same as those in Example 1.

[0155] Comparative Example 4

[0156] The difference between this example and Example 1 is only that:

[0157] The multi-component composite modified material in this example is prepared through the following steps:

[0158] S1. Prepare a graphene-carbon dot composite, and the steps are the same as those in Example 1;

[0159] S2. Prepare an intermediate of a graphene-based multi-component composite:

[0160] S2-1. Add 1 g of graphene-carbon dot composite, 0.078 g of antimony chloride, and 0.3 g of PVP to 150 mL of ethanol, and ultrasonically disperse for 30 min;

[0161] S2-2. While stirring, add a 1 mol / L sodium hydroxide solution to the product of step S2-1 to adjust the pH to 8 to obtain a precursor mixture;

[0162] S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner liner, react at 210 °C for 12 h, cool to room temperature, filter, wash the solid product with ethanol, and vacuum dry at 70 °C to constant weight to obtain an intermediate of a graphene-based multi-component composite;

[0163] S3. Graft tung oil-modified phenolic resin onto the intermediate of the graphene-based multi-component composite, and the steps are the same as those in Example 1.

[0164] Comparative Example 5

[0165] The difference between this example and Example 1 is only that: This example uses the intermediate of the graphene-based multi-component composite prepared in Example 1 as the multi-component composite modified material

[0166] Comparative Example 6

[0167] The multi-component composite modified material in this example was prepared through the following steps:

[0168] S1. Prepare the graphene-carbon dot composite, and the steps are the same as those in Example 1;

[0169] S2. Prepare the graphene-based multi-component composite intermediate, and the steps are the same as those in Example 1;

[0170] S3. Graft phenolic resin onto the graphene-based multi-component composite intermediate:

[0171] Take 2.5 g of the graphene-based multi-component composite intermediate and add it to 8.6 g of formaldehyde, ultrasonically disperse for 1 h, add the obtained dispersion mixture to 5.15 g of phenol under stirring, add 0.05 g of sodium hydroxide after stirring for 30 min, stir and react at 90 °C for 4 h, cool to room temperature, wash the product with ethanol and filter, and vacuum dry at 60 °C for 12 h to obtain the multi-component composite modified material.

[0172] I. Performance Characterization

[0173] 1. Refer to Figure 1 , which is the infrared absorption spectrum of the graphene-based multi-component composite intermediate prepared in Example 1. The characteristic peaks near 1585 cm- 1 and 1040 cm- 1 come from the C-C bonds of sp2 and sp3 hybridization types in graphene; the characteristic peaks of amino group, carboxyl group, hydroxyl group, benzene ring, etc. come from the functional groups on the carbon dots, indicating the successful synthesis of carbon dots; the appearance of the Zn-O characteristic peak indicates the successful doping of Zn, and the appearance of the characteristic peaks of Sb-O, Ce-O, and La-O indicates the successful deposition of rare earth lanthanum cerium oxide-doped nano-antimony trioxide; in summary, it shows that the graphene-based multi-component composite intermediate was successfully prepared.

[0174] 2. Ultraviolet absorption spectrum

[0175] Refer to Figure 2 , which is the ultraviolet-visible light absorption spectrum of the multi-component composite modified materials prepared in Example 1, Comparative Example 3, and Comparative Example 4. It can be seen that the ultraviolet absorption ability of Example 1 is stronger than that of Comparative Example 3 and Comparative Example 4.

[0176] 3. Antioxidant performance

[0177] The antioxidant performance of the multi-component composite modified materials prepared in Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 was tested, and the test method is as follows:

[0178] The prepared multi-component composite modified material was added to ethanol and ultrasonically dispersed to prepare a dispersion with a concentration of 1 mg / mL. The DPPH free radical scavenging ability test kit (Cat. No. LE-1-168, Hefei Lyle Biotechnology Co., Ltd.) was used to detect the antioxidant properties of the dispersion within a certain period of time.

[0179] Determination principle: DPPH free radical has a single electron, its alcohol solution is purple, and has strong absorption at 515nm. When antioxidants are present, DPPH free radicals are scavenged, the solution color becomes lighter, and the absorbance at 515nm decreases. Within a certain range, the change in its absorbance is proportional to the degree of free radical scavenging. Specifically, the lower the absorbance at 515nm, the stronger the antioxidant performance.

[0180] Test results such as Figure 3 As shown, it can be seen from the test results that the antioxidant performance of the multi-component composite modified material of Example 1 is stronger than that of Comparative Example 2, Comparative Example 3, and Comparative Example 4, and Comparative Example 2 has basically no antioxidant performance, indicating that the antioxidant performance mainly comes from the carbon dots.

[0181] 2. Performance Test

[0182] 1. Intrinsic viscosity and terminal carboxyl value of functional modified polyester masterbatch

[0183] The intrinsic viscosity and terminal carboxyl value of the functionalized modified polyester masterbatch prepared in the examples and comparative examples were tested with reference to the standard "GB / T 14190-2008 Test method for fiber-grade polyester chips (PET)". The test results are shown in Tables 1 and Figure 4 - Figure 5 As shown:

[0184] Table 1

[0185] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Intrinsic viscosity dL / g 1.19 1.15 1.18 0.64 0.95 0.87 0.82 0.69 1.06 Terminal carboxyl value mol / t 21.04 20.35 20.95 11.32 18.27 15.38 14.50 13.02 19.22

[0186] It can be seen from the test results that the intrinsic viscosity and terminal carboxyl value of the functionalized modified polyester masterbatch prepared in Comparative Examples 1-6 decreased to varying degrees compared with the examples.

[0187] 2. Properties of polyester fiber

[0188] (1) Mechanical properties

[0189] The breaking strength of the polyester fibers prepared in the examples and comparative examples was measured with reference to the standard “GB / T 14344-2022 Test method for tensile properties of chemical fiber filaments”.

[0190] (2) Flame retardant properties

[0191] The limiting oxygen index LOI (%) of the polyester fibers prepared in the examples and comparative examples was measured by an oxygen index tester.

[0192] (3)UV resistance

[0193] Measure the UV resistance of the polyester fibers prepared in the examples and comparative examples: irradiate with an ultraviolet lamp, with a distance of 20 cm between the ultraviolet lamp and the sample, a power of 30 W, and an ultraviolet light treatment for 48 h; then refer to the standard "GB / T 14344-2022 Test Method for Tensile Properties of Chemical Fibers - Filament Yarns" to measure the breaking strength after ultraviolet irradiation treatment, and calculate the retention rate of breaking strength.

[0194] (4)Thermal-oxidative aging resistance

[0195] Measure the thermal-oxidative aging resistance of the polyester fibers prepared in the examples and comparative examples: place the samples in an air atmosphere at 150 °C for thermal-oxidative aging treatment for 120 h, then refer to the standard "GB / T 14344-2022 Test Method for Tensile Properties of Chemical Fibers - Filament Yarns" to measure the breaking strength after thermal-oxidative aging treatment, and calculate the retention rate of breaking strength.

[0196] The test results are shown in Table 2 below and Figure 6 - Figure 9 as follows:

[0197] Table 2

[0198] Breaking strength (cN / detx) LOI(%) Retention rate of breaking strength after UV irradiation (%) Retention rate of breaking strength after thermal - oxidative aging (%) Example 1 4.9 35.3 96.2 95.5 Example 2 4.6 34.2 95.4 94.9 Example 3 4.8 35 96.1 95.2 Comparative Example 1 2.7 23.4 62.7 64.1 Comparative Example 2 4.1 31.5 81.4 80.2 Comparative Example 3 3.5 33.7 85.6 87.0 Comparative Example 4 3.4 29 84.2 85.5 Comparative Example 5 2.9 26.3 89.5 89.9 Comparative Example 6 4.5 30.8 94.4 92.3

[0199] It can be seen from the test results that the polyester fibers prepared in Examples 1-3 have excellent mechanical properties and flame retardancy, and at the same time also have good UV resistance and thermal-oxidative aging resistance, while the comprehensive properties of the polyester fibers prepared in each comparative example have decreased to varying degrees.

[0200] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those skilled in the art, additional modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalent scope, the present invention is not limited to specific details.

Claims

1. A preparation method of graphene-functionalized enhanced modified polyester fiber, characterized in that, It includes the following steps: 1) Polymerize using dimethyl terephthalate, ethylene glycol, a catalyst, and a multi-component composite modifier as raw materials to obtain a functionalized modified polyester masterbatch; 2) Melt-spin the functionalized modified polyester masterbatch to obtain graphene-functionalized reinforced modified polyester fibers; Among them, the multi-component composite modifier is prepared through the following steps: S1. Graft Zn-doped carbon dots onto graphene by a hydrothermal method to obtain a graphene-carbon dot composite; S2. Deposit rare earth-doped antimony trioxide on the graphene-carbon dot composite to obtain an intermediate of a graphene-based multi-component composite; S3. Graft tung oil-modified phenolic resin onto the intermediate of the graphene-based multi-component composite to obtain a multi-component composite modifier.

2. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 1, characterized in that, The multi-component composite modifier is prepared through the following steps: S1. Prepare a graphene-carbon dot composite: S1-1. Immerse graphene in hydrochloric acid, take it out, wash and dry it to obtain pretreated graphene; S1-2. Take the pretreated graphene and zinc acetate, add them to an ethanol aqueous solution, ultrasonically disperse, then add dopamine hydrochloride, lutein, glucose, 3,5-diaminobenzoic acid, ultrasonically disperse, transfer the obtained mixture to a reaction kettle, and react under heating to obtain a graphene-carbon dot composite; S2. Prepare an intermediate of a graphene-based multi-component composite: S2-1. Add the graphene-carbon dot composite, antimony chloride, lanthanum nitrate, cerium nitrate, and PVP to ethanol, and ultrasonically disperse; S2-2. Add an alkali to adjust the pH to the product of step S2-1 under stirring to obtain a precursor mixture; S2-3. Transfer the precursor mixture to a reaction kettle and react under heating to obtain an intermediate of a graphene-based multi-component composite; S3. Graft tung oil-modified phenolic resin onto the intermediate of the graphene-based multi-component composite: S3-1. Take phenol, tung oil, and p-toluenesulfonic acid, mix them evenly, and react under heating and stirring to obtain an intermediate product; S3-2. Take the intermediate of the graphene-based multi-component composite, add it to formaldehyde, ultrasonically disperse, add the obtained dispersion mixture to the intermediate product, add sodium hydroxide, and react under heating and stirring to obtain a multi-component composite modifier.

3. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 2, characterized in that, Step S1 is specifically: S1-1. Place graphene in hydrochloric acid with a mass concentration of 5-20%, ultrasonically soak for 1-4 h, take it out, wash it with deionized water until neutral, and vacuum dry at 70-100 °C for 4-16 h to obtain pretreated graphene; S1-2. Take 1-4 g of pretreated graphene and 0.1375-0.55 g of zinc acetate and add them to 50-200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:

1. Ultrasonically disperse for 15-60 min, then add 0.19-0.76 g of dopamine hydrochloride, 0.2845-1.138 g of lutein, 0.36-1.44 g of glucose, and 0.152-0.608 g of 3,5-diaminobenzoic acid. Ultrasonically disperse for 5-30 min. Transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene lining and react at 170-210 °C for 4-16 h. Cool to room temperature, centrifuge and filter. Wash the solid product with deionized water and ethanol in sequence, and vacuum dry at 70-100 °C for 6-24 h to obtain a graphene-carbon dot composite.

4. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 2, wherein, Step S2 is specifically as follows: S2-1. Add 0.5-2 g of the graphene-carbon dot composite, 0.039-0.156 g of antimony chloride, 0.029-0.116 g of lanthanum nitrate, 0.022-0.086 g of cerium nitrate, and 0.15-0.6 g of PVP to 75-300 mL of ethanol. Ultrasonically disperse for 15-60 min; S2-2. While stirring, add a sodium hydroxide solution with a concentration of 0.5-2 mol / L to the product of step S2-1 and adjust the pH to 8-9 to obtain a precursor mixture; S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner container and react at 185-230 °C for 6-24 h. Cool to room temperature, filter. Wash the solid product with ethanol and vacuum dry at 60-90 °C to constant weight to obtain an intermediate of a graphene-based multi-component composite.

5. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 2, wherein, Step S3 is specifically as follows: S3-1. Take 2.575-10.3 g of phenol, 0.75-3 g of tung oil, and 0.005-0.02 g of p-toluenesulfonic acid and mix them in a reaction kettle. Stir evenly and stir and react at 100-110 °C for 1.5-6 h. Cool to room temperature to obtain an intermediate product; S3-2. Take 1.25-5 g of the intermediate of the graphene-based multi-component composite and add it to 4.3-17.2 g of formaldehyde. Ultrasonically disperse for 0.5-2 h. Add the obtained dispersed mixture to the intermediate product while stirring. After stirring for 15-60 min, add 0.025-0.1 g of sodium hydroxide and stir and react at 80-100 °C for 2-8 h. Cool to room temperature. Wash and filter the product with ethanol and vacuum dry at 50-80 °C for 6-24 h to obtain a multi-component composite modified material.

6. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 2, wherein, The multi-component composite modified material is prepared through the following steps: S1. Prepare a graphene-carbon dot composite: S1-1. Place graphene in hydrochloric acid with a mass concentration of 10%, soak it under ultrasonic for 2 h, take it out and wash it with deionized water until neutral, and vacuum dry at 90 °C for 8 h to obtain pretreated graphene; S1-2. Take 2 g of pretreated graphene and 0.275 g of zinc acetate, add them to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically disperse for 30 min, then add 0.38 g of dopamine hydrochloride, 0.569 g of lutein, 0.72 g of glucose, and 0.304 g of 3,5-diaminobenzoic acid, ultrasonically disperse for 15 min. Transfer the obtained mixture to a reaction kettle with a polytetrafluoroethylene lining, react at 190 °C for 8 h, cool to room temperature, centrifuge and filter. Wash the solid product with deionized water and ethanol in sequence, and vacuum dry at 80 °C for 12 h to obtain a graphene-carbon dot composite; S2. Prepare an intermediate of a graphene-based multi-component composite: S2-1. Add 1 g of the graphene-carbon dot composite, 0.078 g of antimony chloride, 0.058 g of lanthanum nitrate, 0.043 g of cerium nitrate, and 0.3 g of PVP to 150 mL of ethanol, and ultrasonically disperse for 30 min; S2-2. While stirring, add a 1 mol / L sodium hydroxide solution to the product of step S2-1 to adjust the pH to 8 to obtain a precursor mixture; S2-3. Transfer the precursor mixture to a reaction kettle with a polytetrafluoroethylene inner container, react at 210 °C for 12 h, cool to room temperature, filter. Wash the solid product with ethanol, and vacuum dry at 70 °C to constant weight to obtain an intermediate of the graphene-based multi-component composite; S3. Graft tung oil-modified phenolic resin onto the intermediate of the graphene-based multi-component composite: S3-1. Take 5.15 g of phenol, 1.5 g of tung oil, and 0.01 g of p-toluenesulfonic acid, mix them in a reaction kettle, stir evenly, and stir and react at 105 °C for 3 h. Cool to room temperature to obtain an intermediate product; S3-2. Take 2.5 g of the intermediate of the graphene-based multi-component composite and add it to 8.6 g of formaldehyde, ultrasonically disperse for 1 h. Add the obtained dispersion mixture to the intermediate product while stirring, stir for 30 min, then add 0.05 g of sodium hydroxide, and stir and react at 90 °C for 4 h. Cool to room temperature, wash and filter the product with ethanol, and vacuum dry at 60 °C for 12 h to obtain a multi-component composite modified material.

7. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 1, characterized in that, It includes the following steps: 1) Mix dimethyl terephthalate, ethylene glycol, and a catalyst, carry out a transesterification reaction under heating, then add the multi-component composite modified material, stir evenly, raise the temperature to carry out a polycondensation reaction. After the reaction ends, discharge the material, cool, and pelletize to obtain a functionalized modified polyester masterbatch; 2) Dry the functionalized modified polyester masterbatch, and then carry out melt spinning, winding, and stretching in a melt spinning machine to obtain graphene-functionalized reinforced modified polyester fibers.

8. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 7, characterized in that, The catalyst is one or both of zinc acetate and manganese acetate.

9. The preparation method of the graphene-functionalized enhanced modified polyester fiber according to claim 8, characterized in that, It includes the following steps: 1) Take 50 - 200 g of dimethyl terephthalate, 34 - 136 g of ethylene glycol, and 0.09 - 0.36 g of zinc acetate, add them to a reaction kettle, carry out a transesterification reaction at 200 - 250 °C for 1 - 4 h, then add 0.25 - 9.0 g of the multi-component composite modified material, stir evenly, heat to 255 - 290 °C, and carry out polycondensation for 1 - 4 h. After the reaction ends, discharge the material under nitrogen pressure, cool, and pelletize to obtain a functionalized modified polyester masterbatch; 2) Dry the functionalized modified polyester masterbatch at 80 - 110 °C for 2 - 8 h, and then carry out melt spinning, winding, and drawing in a melt spinning machine to obtain graphene-functionalized enhanced modified polyester fiber; wherein, the spinning temperature is 270 - 300 °C, the winding speed is 600 - 2400 m / min, the draw ratio is 1 - 3 times, and the drawing speed is 350 - 1400 m / min.

10. A graphene-functionalized enhanced modified polyester fiber, characterized in that, It is prepared by the method described in any one of claims 1 - 9.

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