Anti-pilling high-elasticity laminated composite nano polyester fiber and preparation method thereof

Abstract

The invention discloses an anti-pilling high-elasticity laminated composite nano polyester fiber and a preparation method thereof, and relates to the technical field of textile fabrics, the raw materials comprise a polyester raw material, nano ceramic particles, a degradable bio-based polymer and a functional additive; the polyester raw materials comprise polyethylene glycol terephthalate, polybutylene terephthalate and polyethylene naphthalate; the nano ceramic particles comprise nano titanium dioxide, nano zinc oxide and nano zirconium dioxide; the degradable bio-based polymer is prepared from polylactic acid, polyhydroxybutyrate and polycaprolactone; the functional additives comprise an anti-ultraviolet additive, an antibacterial additive, an antistatic additive and an antioxidant. The nano ceramic particles and the degradable bio-based polymer are introduced in the fiber preparation process, and through in-situ polymerization and interface modification reaction, a core-shell-shell three-layer structure of the fiber is achieved, and the problems that traditional fibers are unstable in performance, poor in environmental adaptability and serious in environmental pollution can be solved.

Description

Technical Field

[0001] The invention relates to the technical field of textile fabrics, in particular to an anti-pilling high-elastic laminated composite nano polyester fiber and a preparation method thereof. Background Art

[0002] Traditional polyester fibers have unstable performance, relatively poor environmental adaptability, and are difficult to degrade after being discarded, easily causing environmental pollution. The polyester fibers of the present application can solve the problems of unstable performance, poor environmental adaptability and serious environmental pollution of traditional fibers.

[0003] The defects of existing polyester fibers are: 1. Patent document CN104480565B discloses a negative ion healthy polyester fiber. The document mainly considers how to increase the solubility of air ions produced by polyester fibers, but does not consider how to solve the problems of unstable performance, poor environmental adaptability and serious environmental pollution of traditional fibers; 2. Patent document CN101824666B discloses a method for producing polyester fibers. The document mainly considers how to produce polyester fibers with a dry heat shrinkage rate of more than 50%, but does not consider how to solve the problems of insufficient mechanical properties, short service life and poor reliability of traditional fibers; 3. Patent document CN110438583B discloses a polyester fiber and a preparation method thereof. The document mainly considers how to improve the thermal degradation problem of titanium polyester in the post-processing process, but does not consider how to solve the problems of poor hydrophilicity of the surface of traditional fibers, weak bonding with dyes or finishing agents, poor air permeability and moisture permeability, and poor wearing experience; 4. Patent document CN103572402B discloses a method for preparing multifunctional polyester fiber. The document mainly considers how to reduce production costs, but does not consider how to solve the problems of insufficient performance, poor environmental protection and difficulty in meeting the needs of the modern textile industry of traditional fibers. Summary of the invention

[0004] The object of the present invention is to provide a high-elastic laminated composite nano polyester fiber with anti-pilling properties and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: an anti-pilling high-elastic laminated composite nano polyester fiber, the raw materials of which include: polyester raw material, nano ceramic particles, degradable bio-based polymer and functional additives; The polyester raw material includes polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate in a mass ratio of 5:3:2; The nano-ceramic particles include nano-titanium dioxide, nano-zinc oxide and nano-zirconium dioxide in a mass ratio of 4:3:3; The degradable bio-based polymer includes polylactic acid, polyhydroxybutyrate and polycaprolactone in a mass ratio of 3:2:1; The functional additives include an anti-ultraviolet additive, an antibacterial additive, an antistatic additive and an antioxidant in a mass ratio of 1:1:1:1.

[0006] Preferably, it has a core-shell-shell three-layer structure, wherein the core-shell-shell three-layer structure comprises an inner core layer, an intermediate layer and an outer shell layer; The inner core layer is polyethylene terephthalate containing 4% nano-titanium dioxide by mass; The middle layer is a mixture of lactic acid, polyhydroxybutyrate and polycaprolactone in a mass ratio of 3:2:1; The outer shell layer is polybutylene terephthalate containing 3% by mass of nano zinc oxide.

[0007] Preferably, the method for preparing polyester fiber comprises: Step S1, pre-treating polyester raw materials, nano-ceramic particles, degradable bio-based polymers and additives; Step S2, using microchannel polymerization technology, at a temperature of 240° C. and a pressure of 2 MPa, the pretreated raw material is polymerized to obtain a polyester with a molecular weight distribution of 2.0; Step S3, subjecting the polymerized polyester to multi-stage gradient stretching at different temperatures and stretching ratios; Step S4, using solution spinning technology to obtain inner core layer fibers, middle layer fibers and outer shell layer fibers; Step S5, subjecting the inner core layer fibers, the middle layer fibers and the outer shell layer fibers to an interface modification reaction simultaneously during an in-situ polymerization process; Step S6, performing surface treatment on the fiber, the surface treatment comprising plasma treatment and chemical etching; Step S7: sorting and packaging the prepared fibers.

[0008] Preferably, step S1 further includes: Step S11: drying under vacuum for 3 hours, with the drying temperature set to 70°C, and preliminarily mixing and stirring the raw materials at a stirring rate of 300-500 rpm for 20-30 minutes; Step S12: using ultrasound-assisted nanoparticle dispersion technology, the ultrasound frequency is 30 kHz, the power is 300 W, the treatment time is 20 minutes, and 1% of polyethylene glycol is added as a dispersant to uniformly disperse the nano-ceramic particles in the polyester matrix. The ultrasound treatment is performed intermittently, with each ultrasound treatment lasting 5 minutes and a pause of 1 minute. Step S13: filtering and removing impurities from the pretreated raw materials, with the filter mesh having an aperture of 112-132 meshes.

[0009] Preferably, step S2 further includes: Step S21: At the beginning of the polymerization reaction, an inert gas is introduced to replace the system 3-5 times to remove impurity gases; Step S22: During the polymerization reaction, the viscosity change of the reaction system is monitored in real time by an online viscometer, and the reaction temperature is adjusted according to the viscosity change, and the temperature adjustment range does not exceed ±3°C; Step S23: When the polymerization reaction lasts for 5-10 min, the pressure is reduced to 0.5-0.9 MPa.

[0010] Preferably, step S3 further includes: Step S31: preliminary stretching, the temperature is 80°C, the stretching ratio is 1.3 times, and the stretching speed is 50-80m / min; Step S32: secondary stretching, the temperature is 130°C, the stretching ratio is 2.5 times, and the stretching speed is 100-150m / min; Step S33: shaping and stretching, the temperature is 100°C, the stretching ratio is 1.1 times, and the stretching speed is 30-60m / min.

[0011] Preferably, step S4 further includes: Step S41: the concentration of the spinning solution is controlled at 20%-30%. When preparing the spinning solution, a gradient heating and stirring is adopted, first stirring at 40-50° C. for 30 minutes, then heating to 60-70° C. and stirring for 60 minutes; Step S42: controlling the relative humidity of the spinning environment to 40%-60% and the temperature to 25-30°C; Step S43: The spinning nozzle is cleaned by ultrasound, with an ultrasound frequency of 40-60 kHz, a power of 200-400 W, a cleaning time of 10-20 minutes, and the nozzle is cleaned once every 2-3 hours of spinning.

[0012] Preferably, step S5 further includes: Step S51: introducing a titanate coupling agent or hydroxyethyl acrylate as a reactive monomer, wherein the mass ratio of the titanate coupling agent to hydroxyethyl acrylate is 1:2; Step S52: reacting at a temperature of 120° C., using magnetic stirring during the reaction, and the stirring speed is 400-600 rpm; Step S53: The reaction time is set to 2 hours. After the reaction is completed, cooling is performed at a cooling rate of 20-30°C / min.

[0013] Preferably, step S6 further includes: Step S61: plasma treatment adopts high frequency discharge technology, the treatment time is 3 minutes, and the discharge power is 300-500W; Step S62: chemical etching uses sodium hydroxide etchant, the processing time is 10 minutes, and the etchant concentration is 5%-10%; Step S63: construct a nanoporous network structure in the middle layer fiber and the outer shell layer fiber by template method, the nanopore size is 100nm, the shape is circular, and the distribution density is 3×10 12 pcs / m²; Step S64: The template is made of biodegradable polymer microspheres, and the template is removed by solvent dissolution after the fiber is formed.

[0014] Preferably, step S7 further includes: Step S71: Conduct mechanical property testing on the fiber, including tensile strength, elongation at break and elastic recovery rate testing, the tensile strength is not less than 5 cN / dtex, the elongation at break is between 35% and 45%, and the elastic recovery rate is not less than 80%; Step S72: Perform functional tests on the fiber, including anti-ultraviolet performance, antibacterial performance and antistatic performance tests. The ultraviolet protection factor (UPF) value is not less than 50, the antibacterial rate against Escherichia coli and Staphylococcus aureus is not less than 90%, and the surface resistance is not higher than 1×10 10 Ω; Step S73: The qualified fibers are packaged and stored. The humidity of the packaging environment does not exceed 30%, and the temperature is 20-25°C. The outer layer of the packaging material is an aluminum foil layer, the middle layer is an antistatic plastic layer, and the inner layer is a fiber material layer.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention realizes the core-shell-shell three-layer structure of the fiber by introducing nano-ceramic particles and degradable bio-based polymers during the fiber preparation process, and through in-situ polymerization and interfacial modification reaction, the nano-titanium dioxide in the inner core layer is evenly dispersed in the polyethylene terephthalate matrix, and its photocatalytic properties can effectively decompose harmful substances such as ultraviolet rays, so that the fiber has excellent anti-ultraviolet performance; the polylactic acid, polyhydroxybutyrate and polycaprolactone mixed in a specific mass ratio in the middle layer provide a stable transition for the overall structure while giving the fiber good biocompatibility and degradability; the nano-zinc oxide in the outer shell layer significantly improves the antibacterial property of the fiber in polybutylene terephthalate, and under the synergistic effect of antistatic additives and antioxidants, the antistatic and antioxidant capabilities of the fiber are comprehensively improved. This structural design enables the fiber to not only have excellent anti-ultraviolet, antibacterial, antistatic and antioxidant properties, but also give the fiber good biocompatibility and degradability. Compared with the existing technology, the fiber's anti-ultraviolet, antibacterial, antistatic and antioxidant properties can be improved, while giving the fiber better biocompatibility and degradability. It can also more effectively solve the problem of performance degradation caused by ultraviolet radiation, microbial erosion, static electricity accumulation and oxidation reaction when the fiber is used outdoors or in harsh environments, including color fading, reduced strength and odor, while reducing pollution to the environment. Therefore, it can solve the problems of unstable performance, poor environmental adaptability and serious environmental pollution of traditional fibers.

[0016] 2. The present invention realizes the high molecular weight distribution of polyester and the multi-stage stretching of fiber by adopting microchannel polymerization technology and gradient stretching process. In the microchannel polymerization technology, temperature and pressure control, as well as inert gas replacement, viscosity monitoring and pressure reduction at the end of the reaction, ensure the high efficiency and stability of the polymerization reaction, obtain polyester with a molecular weight distribution of 2.0, and provide a good molecular basis for the fiber. The multi-stage gradient stretching process, from preliminary stretching to secondary stretching and then to final stretching, makes the fiber molecular chain gradually arranged in an orderly manner, which can not only improve the mechanical properties of the fiber, make the tensile strength not less than 5cN / dtex, but also control the elongation at break between 35%-45%, the elastic recovery rate is not less than 80%, and form a more uniform structure during the stretching process, thereby enhancing its durability and fatigue resistance. Compared with the prior art, it can more effectively solve the problem of fiber being easy to break, deform and fatigue due to insufficient mechanical properties during use, including maintaining good performance in application scenarios of frequent stretching, bending or friction, and improving the service life and reliability of the fiber, so it can solve the problems of insufficient mechanical properties, short service life and poor reliability of traditional fibers.

[0017] 3. The present invention adopts surface treatment technologies such as plasma treatment, chemical etching and template method to prepare nanoporous network structure, which not only improves the surface performance and functional characteristics of the fiber, but also gives the fiber better air permeability and hygroscopicity. Plasma treatment bombards the fiber surface with high-energy particles and introduces active groups, which effectively improves the surface wettability and adhesion of the fiber and enhances the bonding ability of the fiber with other materials; chemical etching accurately removes defects and impurities on the fiber surface, making the fiber surface smoother and reducing stress concentration points; a nanoporous network structure is constructed in the middle layer fiber and the outer shell layer fiber. The introduction of the nanoporous network structure makes the fiber surface rougher and increases the contact area between the fiber and the surrounding environment, thereby improving the adsorption capacity and reaction activity of the fiber, and significantly improving the air permeability and moisture permeability. Compared with the existing technology, this surface treatment technology can more effectively solve the problems of poor fiber surface performance and insufficient functional performance, including poor hydrophilicity of the fiber surface, weak bonding with dyes or finishing agents, poor air and moisture permeability leading to uncomfortable wearing, etc., while improving the comfort and usage experience of the fiber. Therefore, it can solve the problems of poor hydrophilicity of traditional fiber surface, weak bonding with dyes or finishing agents, poor air and moisture permeability and poor wearing experience.

[0018] 4. The present invention adopts polyester raw materials, nano-ceramic particles, degradable bio-based polymers and functional additives. The polyester raw materials include polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, the nano-ceramic particles include nano-titanium dioxide, nano-zinc oxide and nano-zirconium dioxide, the degradable bio-based polymers include polylactic acid, polyhydroxybutyrate and polycaprolactone, and the functional additives include anti-ultraviolet additives, antibacterial additives, antistatic additives and antioxidants to achieve the preparation of a high-elastic laminated composite nano-polyester fiber with anti-pilling. At the raw material level, multiple components work synergistically to lay the foundation for the fiber performance from the molecular structure. In terms of preparation technology, a series of precisely controlled process steps from vacuum drying, ultrasonic dispersion and filtration and impurity removal in the pretreatment stage to polymerization reaction, stretching, spinning, lamination and post-treatment ensure the high-quality molding of the fiber. The composite nano polyester fiber not only has excellent anti-pilling properties, but also its core-shell-shell structure and reasonable combination of various components effectively reduce the friction and entanglement on the fiber surface, thereby reducing the pilling phenomenon. It also has high elasticity and a high elastic recovery rate, which allows it to quickly return to its original shape after stretching. It is durable and can maintain stable performance under long-term use and complex environments. It also has good environmental performance. The degradable bio-based polymer can be naturally decomposed after the fiber is discarded, reducing the burden on the environment. Compared with the existing technology, the composite nano polyester fiber can more effectively solve the problems of traditional polyester fibers being easy to pill, poor elasticity, not durable, and not environmentally friendly, and meet the needs of the modern textile industry for high-performance and environmentally friendly fibers, including applications in high-end sportswear, outdoor equipment, and environmentally friendly textiles. Therefore, it can solve the problems of insufficient performance, poor environmental protection, and difficulty in meeting the needs of the modern textile industry. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] Embodiment 1: An anti-pilling high-elastic laminated composite nano polyester fiber and a preparation method thereof, the preparation method of the polyester fiber comprising: Step S1, pre-treating polyester raw materials, nano-ceramic particles, degradable bio-based polymers and additives; Step S1 also includes: Step S11: drying under vacuum for 3 hours, with the drying temperature set to 70°C, and preliminarily mixing and stirring the raw materials at a stirring rate of 350 rpm for 28 minutes; Step S12: using ultrasound-assisted nanoparticle dispersion technology, the ultrasound frequency is 30 kHz, the power is 300 W, the treatment time is 20 minutes, and 1% of polyethylene glycol is added as a dispersant to uniformly disperse the nano-ceramic particles in the polyester matrix. The ultrasound treatment is performed intermittently, with each ultrasound treatment lasting 5 minutes and a pause of 1 minute. Step S13: filtering and removing impurities from the pretreated raw materials, with the filter mesh having an aperture of 125 meshes.

[0021] Step S2, using microchannel polymerization technology, at a temperature of 240° C. and a pressure of 2 MPa, the pretreated raw material is polymerized to obtain a polyester with a molecular weight distribution of 2.0; Step S2 also includes: Step S21: At the beginning of the polymerization reaction, an inert gas is introduced to replace the system 4 times to remove impurity gases; Step S22: During the polymerization reaction, the viscosity change of the reaction system is monitored in real time by an online viscometer, and the reaction temperature is adjusted according to the viscosity change, and the temperature adjustment range does not exceed ±3°C; Step S23: When the polymerization reaction lasts for 7 minutes, the pressure is reduced to 0.7 MPa.

[0022] Step S3, subjecting the polymerized polyester to multi-stage gradient stretching at different temperatures and stretching ratios; Step S3 also includes: Step S31: preliminary stretching, the temperature is 80°C, the stretching ratio is 1.3 times, and the stretching speed is 65m / min; Step S32: secondary stretching, the temperature is 130°C, the stretching ratio is 2.5 times, and the stretching speed is 130m / min; Step S33: shaping and stretching, the temperature is 100°C, the stretching ratio is 1.1 times, and the stretching speed is 45m / min.

[0023] Step S4, using solution spinning technology to obtain inner core layer fibers, middle layer fibers and outer shell layer fibers; Step S4 also includes: Step S41: The concentration of the spinning solution is controlled at 23%. When preparing the spinning solution, a gradient heating and stirring is adopted, first stirring at 43° C. for 30 minutes, then heating to 63° C. and stirring for 60 minutes; Step S42: controlling the relative humidity of the spinning environment to 48% and the temperature to 27°C; Step S43: The spinning nozzle is cleaned by ultrasound, with an ultrasonic frequency of 48 kHz, a power of 280 W, a cleaning time of 16 minutes, and the nozzle is cleaned once every 2.5 hours of spinning.

[0024] Step S5, subjecting the inner core layer fibers, the middle layer fibers and the outer shell layer fibers to an interface modification reaction simultaneously during an in-situ polymerization process; Step S5 also includes: Step S51: introducing a titanate coupling agent or hydroxyethyl acrylate as a reactive monomer, wherein the mass ratio of the titanate coupling agent to hydroxyethyl acrylate is 1:2; Step S52: reacting at a temperature of 120° C., using magnetic stirring during the reaction, and the stirring speed is 520 rpm; Step S53: The reaction time is set to 2 hours. After the reaction is completed, the mixture is cooled at a cooling rate of 23°C / min.

[0025] Step S6, performing surface treatment on the fiber, the surface treatment comprising plasma treatment and chemical etching; Step S6 also includes: Step S61: plasma treatment adopts high frequency discharge technology, the treatment time is 3 minutes, and the discharge power is 420W; Step S62: chemical etching uses sodium hydroxide etchant, the processing time is 10 minutes, and the etchant concentration is 7%; Step S63: construct a nanoporous network structure in the middle layer fiber and the outer shell layer fiber by template method, the nanopore size is 100nm, the shape is circular, and the distribution density is 3×10 12 pcs / m²; Step S64: The template is made of biodegradable polymer microspheres, and the template is removed by solvent dissolution after the fiber is formed.

[0026] Step S7: sorting and packaging the prepared fibers.

[0027] Step S7 also includes: Step S71: Conduct mechanical property testing on the fiber, including tensile strength, elongation at break and elastic recovery rate testing, the tensile strength is not less than 5 cN / dtex, the elongation at break is between 35% and 45%, and the elastic recovery rate is not less than 80%; Step S72: Perform functional tests on the fiber, including anti-ultraviolet performance, antibacterial performance and antistatic performance tests. The ultraviolet protection factor (UPF) value is not less than 50, the antibacterial rate against Escherichia coli and Staphylococcus aureus is not less than 90%, and the surface resistance is not higher than 1×10 11 Ω; Step S73: The qualified fibers are packaged and stored. The humidity of the packaging environment does not exceed 30%, and the temperature is 20-25°C. The outer layer of the packaging material is an aluminum foil layer, the middle layer is an antistatic plastic layer, and the inner layer is a fiber material layer.

[0028] Embodiment 2: An anti-pilling high-elastic laminated composite nano polyester fiber and a preparation method thereof, the preparation method of the polyester fiber comprising: Step S1, pre-treating polyester raw materials, nano-ceramic particles, degradable bio-based polymers and additives; Step S1 also includes: Step S11: drying under vacuum for 3 hours, with the drying temperature set to 70°C, and preliminarily mixing and stirring the raw materials at a stirring rate of 420 rpm for 23 minutes; Step S12: using ultrasound-assisted nanoparticle dispersion technology, the ultrasound frequency is 30 kHz, the power is 300 W, the treatment time is 20 minutes, and 1% of polyethylene glycol is added as a dispersant to uniformly disperse the nano-ceramic particles in the polyester matrix. The ultrasound treatment is performed intermittently, with each ultrasound treatment lasting 5 minutes and a pause of 1 minute. Step S13: filtering and removing impurities from the pretreated raw materials, with the filter mesh having an aperture of 118 meshes.

[0029] Step S2, using microchannel polymerization technology, at a temperature of 240° C. and a pressure of 2 MPa, the pretreated raw material is polymerized to obtain a polyester with a molecular weight distribution of 2.0; Step S2 also includes: Step S21: At the beginning of the polymerization reaction, an inert gas is introduced to replace the system three times to remove impurity gases; Step S22: During the polymerization reaction, the viscosity change of the reaction system is monitored in real time by an online viscometer, and the reaction temperature is adjusted according to the viscosity change, and the temperature adjustment range does not exceed ±3°C; Step S23: When the polymerization reaction lasts for 9 minutes, the pressure is reduced to 0.6 MPa.

[0030] Step S3, subjecting the polymerized polyester to multi-stage gradient stretching at different temperatures and stretching ratios; Step S3 also includes: Step S31: preliminary stretching, the temperature is 80°C, the stretching ratio is 1.3 times, and the stretching speed is 58m / min; Step S32: secondary stretching, the temperature is 130°C, the stretching ratio is 2.5 times, and the stretching speed is 140m / min; Step S33: shaping and stretching, the temperature is 100°C, the stretching ratio is 1.1 times, and the stretching speed is 38m / min.

[0031] Step S4, using solution spinning technology to obtain inner core layer fibers, middle layer fibers and outer shell layer fibers; Step S4 also includes: Step S41: The concentration of the spinning solution is controlled at 27%. When preparing the spinning solution, a gradient heating and stirring is adopted, first stirring at 47° C. for 30 minutes, then heating to 67° C. and stirring for 60 minutes; Step S42: controlling the relative humidity of the spinning environment to 53% and the temperature to 29°C; Step S43: The spinning nozzle is cleaned by ultrasound, with an ultrasonic frequency of 53 kHz, a power of 330 W, a cleaning time of 13 minutes, and the nozzle is cleaned once every 2.8 hours of spinning.

[0032] Step S5, subjecting the inner core layer fibers, the middle layer fibers and the outer shell layer fibers to an interface modification reaction simultaneously during an in-situ polymerization process; Step S5 also includes: Step S51: introducing a titanate coupling agent or hydroxyethyl acrylate as a reactive monomer, wherein the mass ratio of the titanate coupling agent to hydroxyethyl acrylate is 1:2; Step S52: reacting at a temperature of 120° C., using magnetic stirring during the reaction, and the stirring speed is 580 rpm; Step S53: The reaction time is set to 2 hours. After the reaction is completed, the mixture is cooled at a cooling rate of 27°C / min.

[0033] Step S6, performing surface treatment on the fiber, the surface treatment comprising plasma treatment and chemical etching; Step S6 also includes: Step S61: plasma treatment adopts high frequency discharge technology, the treatment time is 3 minutes, and the discharge power is 480W; Step S62: chemical etching uses sodium hydroxide etchant, the processing time is 10 minutes, and the etchant concentration is 9%; Step S63: construct a nanoporous network structure in the middle layer fiber and the outer shell layer fiber by template method, the nanopore size is 100nm, the shape is circular, and the distribution density is 3×10 12 pcs / m²; Step S64: The template is made of biodegradable polymer microspheres, and the template is removed by solvent dissolution after the fiber is formed.

[0034] Step S7: sorting and packaging the prepared fibers.

[0035] Step S7 also includes: Step S71: Conduct mechanical property testing on the fiber, including tensile strength, elongation at break and elastic recovery rate testing, the tensile strength is not less than 5 cN / dtex, the elongation at break is between 35% and 45%, and the elastic recovery rate is not less than 80%; Step S72: Perform functional tests on the fiber, including anti-ultraviolet performance, antibacterial performance and antistatic performance tests. The ultraviolet protection factor (UPF) value is not less than 50, the antibacterial rate against Escherichia coli and Staphylococcus aureus is not less than 90%, and the surface resistance is not higher than 1×10 11 Ω; Step S73: The qualified fibers are packaged and stored. The humidity of the packaging environment does not exceed 30%, and the temperature is 20-25°C. The outer layer of the packaging material is an aluminum foil layer, the middle layer is an antistatic plastic layer, and the inner layer is a fiber material layer.

[0036] Embodiment three: An anti-pilling high-elastic laminated composite nano polyester fiber and a preparation method thereof, the preparation method of the polyester fiber comprising: Step S1, pre-treating polyester raw materials, nano-ceramic particles, degradable bio-based polymers and additives; Step S1 also includes: Step S11: drying under vacuum for 3 hours, with the drying temperature set to 70°C, and preliminarily mixing and stirring the raw materials at a stirring rate of 380 rpm for 26 minutes; Step S12: using ultrasound-assisted nanoparticle dispersion technology, the ultrasound frequency is 30 kHz, the power is 300 W, the treatment time is 20 minutes, and 1% of polyethylene glycol is added as a dispersant to uniformly disperse the nano-ceramic particles in the polyester matrix. The ultrasound treatment is performed intermittently, with each ultrasound treatment lasting 5 minutes and a pause of 1 minute. Step S13: filtering and removing impurities from the pretreated raw materials, with the filter mesh having an aperture of 130 meshes.

[0037] Step S2, using microchannel polymerization technology, at a temperature of 240° C. and a pressure of 2 MPa, the pretreated raw material is polymerized to obtain a polyester with a molecular weight distribution of 2.0; Step S2 also includes: Step S21: At the beginning of the polymerization reaction, an inert gas is introduced to replace the system 5 times to remove impurity gases; Step S22: During the polymerization reaction, the viscosity change of the reaction system is monitored in real time by an online viscometer, and the reaction temperature is adjusted according to the viscosity change, and the temperature adjustment range does not exceed ±3°C; Step S23: When the polymerization reaction lasts for 6 minutes, the pressure is reduced to 0.8 MPa.

[0038] Step S3, subjecting the polymerized polyester to multi-stage gradient stretching at different temperatures and stretching ratios; Step S3 also includes: Step S31: preliminary stretching, the temperature is 80°C, the stretching ratio is 1.3 times, and the stretching speed is 72m / min; Step S32: secondary stretching, the temperature is 130°C, the stretching ratio is 2.5 times, and the stretching speed is 110m / min; Step S33: shaping and stretching, the temperature is 100°C, the stretching ratio is 1.1 times, and the stretching speed is 52m / min.

[0039] Step S4, using solution spinning technology to obtain inner core layer fibers, middle layer fibers and outer shell layer fibers; Step S4 also includes: Step S41: The concentration of the spinning solution is controlled at 21%. When preparing the spinning solution, a gradient heating and stirring is adopted, first stirring at 41° C. for 30 minutes, then heating to 61° C. and stirring for 60 minutes; Step S42: controlling the relative humidity of the spinning environment to 43% and the temperature to 26°C; Step S43: The spinning nozzle is cleaned by ultrasound, with an ultrasonic frequency of 43 kHz, a power of 230 W, a cleaning time of 19 minutes, and the nozzle is cleaned once every 2.2 hours of spinning.

[0040] Step S5, subjecting the inner core layer fibers, the middle layer fibers and the outer shell layer fibers to an interface modification reaction simultaneously during an in-situ polymerization process; Step S5 also includes: Step S51: introducing a titanate coupling agent or hydroxyethyl acrylate as a reactive monomer, wherein the mass ratio of the titanate coupling agent to hydroxyethyl acrylate is 1:2; Step S52: reacting at a temperature of 120° C., using magnetic stirring during the reaction, and the stirring speed is 470 rpm; Step S53: The reaction time is set to 2 hours. After the reaction is completed, the mixture is cooled at a cooling rate of 21°C / min.

[0041] Step S6, performing surface treatment on the fiber, the surface treatment comprising plasma treatment and chemical etching; Step S6 also includes: Step S61: plasma treatment adopts high frequency discharge technology, the treatment time is 3 minutes, and the discharge power is 380W; Step S62: chemical etching using sodium hydroxide etchant, the processing time is 10 minutes, and the etchant concentration is 6%; Step S63: construct a nanoporous network structure in the middle layer fiber and the outer shell layer fiber by template method, the nanopore size is 100nm, the shape is circular, and the distribution density is 3×10 12 pcs / m²; Step S64: The template is made of biodegradable polymer microspheres, and the template is removed by solvent dissolution after the fiber is formed.

[0042] Step S7: sorting and packaging the prepared fibers.

[0043] Step S7 also includes: Step S71: Conduct mechanical property testing on the fiber, including tensile strength, elongation at break and elastic recovery rate testing, the tensile strength is not less than 5 cN / dtex, the elongation at break is between 35% and 45%, and the elastic recovery rate is not less than 80%; Step S72: Perform functional tests on the fiber, including anti-ultraviolet performance, antibacterial performance and antistatic performance tests. The ultraviolet protection factor (UPF) value is not less than 50, the antibacterial rate against Escherichia coli and Staphylococcus aureus is not less than 90%, and the surface resistance is not higher than 1×10 11 Ω; Step S73: The qualified fibers are packaged and stored. The humidity of the packaging environment does not exceed 30%, and the temperature is 20-25°C. The outer layer of the packaging material is an aluminum foil layer, the middle layer is an antistatic plastic layer, and the inner layer is a fiber material layer.

[0044] Embodiment 4: Step S1: using single polyethylene terephthalate as polyester raw material, without adding nano ceramic particles, adding only a small amount of polylactic acid as the degradable bio-based polymer, and using antistatic agent as the functional additive, drying for 2 hours without ultrasonic dispersion treatment.

[0045] Step S2: The polymerization reaction was carried out at a temperature of 260° C. and a pressure of 1.2 MPa using a kettle polymerization technique, and viscosity monitoring was not performed.

[0046] Step S3: single-stage stretching is performed, the stretching temperature is 120°C, the stretching ratio is 1.8 times, and the stretching speed is 120m / min.

[0047] Step S4: using solution spinning technology, the concentration of the spinning solution is controlled at 35%, no gradient heating and stirring is performed, and the spinning nozzle is not ultrasonically cleaned to obtain fibers.

[0048] Step S5: water washing treatment is performed, plasma treatment and chemical etching are not performed, and a nanoporous network structure is not constructed.

[0049] Step S6: sorting and packaging the prepared fibers.

[0050] Embodiment five: Example 4 was used as a control group, and mechanical properties and functional tests were performed on the polyester fibers prepared in Example 1, Example 2, Example 3 and Example 4. The test results are as follows:

[0051] The test results show that the tensile strength, elongation at break, elastic recovery, UV resistance, antibacterial performance and antistatic performance of Examples 1, 2 and 3 are significantly better than those of Example 4.

[0052] The polyester raw materials used in Examples 1, 2, and 3 are pretreated with nano-ceramic particles, degradable bio-based polymers, and additives, microchannel polymerization technology combined with online viscosity monitoring, multi-stage gradient stretching, gradient heating stirring during solution spinning, and ultrasonic cleaning of the nozzle, as well as subsequent interface modification, plasma and chemical etching treatment, and construction of a nanoporous network structure, effectively improving the comprehensive performance of the fiber. In contrast, Example 4 has poor performance in various performance indicators due to its single raw material composition and simplified process. Examples 1, 2, and 3 effectively improve the mechanical properties, UV resistance, antibacterial properties, and antistatic properties of polyester fibers by adopting advanced processes and technologies. These fibers have broad market prospects in outdoor clothing, sunscreen products, and application fields that require high antibacterial and antistatic properties.

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

Claims

1. An anti-pilling high-elastic laminated composite nano polyester fiber, characterized in that: Raw materials include: Polyester raw materials, nano-ceramic particles, biodegradable bio-based polymers and functional additives; The polyester raw material includes polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate in a mass ratio of 5:3:2; The nano-ceramic particles include nano-titanium dioxide, nano-zinc oxide and nano-zirconium dioxide in a mass ratio of 4:3:3; The degradable bio-based polymer includes polylactic acid, polyhydroxybutyrate and polycaprolactone in a mass ratio of 3:2:1; The functional additives include an anti-ultraviolet additive, an antibacterial additive, an antistatic additive and an antioxidant in a mass ratio of 1:1:1:

1.

2. The anti-pilling high-elastic laminated composite nano polyester fiber according to claim 1, characterized in that: It has a core-shell-shell three-layer structure, which includes an inner core layer, an intermediate layer and an outer shell layer; The inner core layer is polyethylene terephthalate containing 4% by mass of nano-titanium dioxide; The middle layer is a mixture of lactic acid, polyhydroxybutyrate and polycaprolactone in a mass ratio of 3:2:1; The outer shell layer is polybutylene terephthalate containing 3% by mass of nano zinc oxide.

3. A method for preparing anti-pilling high-elastic laminated composite nano polyester fiber, characterized in that: The preparation method of polyester fiber comprises: Step S1, pre-treating polyester raw materials, nano-ceramic particles, degradable bio-based polymers and additives; Step S2, using microchannel polymerization technology, at a temperature of 240° C. and a pressure of 2 MPa, the pretreated raw material is polymerized to obtain a polyester with a molecular weight distribution of 2.0; Step S3, subjecting the polymerized polyester to multi-stage gradient stretching at different temperatures and stretching ratios; Step S4, using solution spinning technology to obtain inner core layer fibers, middle layer fibers and outer shell layer fibers; Step S5, simultaneously subjecting the inner core layer fibers, the middle layer fibers and the outer shell layer fibers to an interface modification reaction during an in-situ polymerization process; Step S6, performing surface treatment on the fiber, the surface treatment comprising plasma treatment and chemical etching; Step S7: sorting and packaging the prepared fibers.

4. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S1 also includes: Step S11: drying under vacuum for 3 hours, with the drying temperature set to 70°C, and preliminarily mixing and stirring the raw materials at a stirring rate of 300-500 rpm for 20-30 minutes; Step S12: using ultrasound-assisted nanoparticle dispersion technology, the ultrasound frequency is 30 kHz, the power is 300 W, the treatment time is 20 minutes, and 1% of polyethylene glycol is added as a dispersant to uniformly disperse the nano-ceramic particles in the polyester matrix. The ultrasound treatment is performed intermittently, with each ultrasound treatment lasting 5 minutes and a pause of 1 minute. Step S13: filtering and removing impurities from the pretreated raw materials, with the filter mesh having an aperture of 112-132 meshes.

5. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S2 also includes: Step S21: At the beginning of the polymerization reaction, an inert gas is introduced to replace the system 3-5 times to remove impurity gases; Step S22: During the polymerization reaction, the viscosity change of the reaction system is monitored in real time by an online viscometer, and the reaction temperature is adjusted according to the viscosity change, and the temperature adjustment range does not exceed ±3°C; Step S23: When the polymerization reaction lasts for 5-10 min, the pressure is reduced to 0.5-0.9 MPa.

6. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S3 also includes: Step S31: preliminary stretching, the temperature is 80°C, the stretching ratio is 1.3 times, and the stretching speed is 50-80m / min; Step S32: secondary stretching, the temperature is 130°C, the stretching ratio is 2.5 times, and the stretching speed is 100-150m / min; Step S33: shaping and stretching, the temperature is 100°C, the stretching ratio is 1.1 times, and the stretching speed is 30-60m / min.

7. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S4 also includes: Step S41: the concentration of the spinning solution is controlled at 20%-30%. When preparing the spinning solution, a gradient heating and stirring is adopted, first stirring at 40-50° C. for 30 minutes, then heating to 60-70° C. and stirring for 60 minutes; Step S42: controlling the relative humidity of the spinning environment to 40%-60% and the temperature to 25-30°C; Step S43: The spinning nozzle is cleaned by ultrasonic method, the ultrasonic frequency is 40-60kHz, the power is 200-400W, the cleaning time is 10-20 minutes, and the nozzle is cleaned once every 2-3 hours of spinning.

8. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S5 also includes: Step S51: introducing a titanate coupling agent or hydroxyethyl acrylate as a reactive monomer, wherein the mass ratio of the titanate coupling agent to hydroxyethyl acrylate is 1:2; Step S52: reacting at a temperature of 120° C., using magnetic stirring during the reaction, and the stirring speed is 400-600 rpm; Step S53: The reaction time is set to 2 hours. After the reaction is completed, cooling is performed at a cooling rate of 20-30°C / min.

9. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S6 also includes: Step S61: plasma treatment adopts high frequency discharge technology, the treatment time is 3 minutes, and the discharge power is 300-500W; Step S62: chemical etching uses sodium hydroxide etchant, the processing time is 10 minutes, and the etchant concentration is 5%-10%; Step S63: construct a nanoporous network structure in the middle layer fiber and the outer shell layer fiber by template method, the nanopore size is 100nm, the shape is circular, and the distribution density is 3×10 12 pcs / m²; Step S64: The template is made of biodegradable polymer microspheres, and the template is removed by solvent dissolution after the fiber is formed.

10. The method for preparing the anti-pilling high-elastic laminated composite nano polyester fiber according to claim 3, characterized in that: Step S7 also includes: Step S71: Conduct mechanical property tests on the fiber, including tensile strength, elongation at break and elastic recovery rate tests, with the tensile strength being no less than 5 cN / dtex, the elongation at break being between 35% and 45%, and the elastic recovery rate being no less than 80%; Step S72: Perform functional tests on the fiber, including anti-ultraviolet performance, antibacterial performance and antistatic performance tests. The ultraviolet protection factor (UPF) value is not less than 50, the antibacterial rate against Escherichia coli and Staphylococcus aureus is not less than 90%, and the surface resistance is not higher than 1×10 10 Ω; Step S73: The qualified fibers are packaged and stored. The humidity of the packaging environment does not exceed 30%, and the temperature is 20-25°C. The outer layer of the packaging material is an aluminum foil layer, the middle layer is an antistatic plastic layer, and the inner layer is a fiber material layer.

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