An antibacterial modified full-dull polyester fiber and a preparation method thereof

Abstract

The application discloses antibacterial modified full-dull polyester fibers and a preparation method thereof, and belongs to the technical field of polyester fiber processing, and is used for solving the technical problem that mechanical properties and antibacterial properties of full-dull polyester fibers in the prior art need to be further improved, and specifically comprises the following components in parts by weight: polyethylene terephthalate 50-60 parts, activated modified polyester 40-50 parts, epoxy modified polyolefin 25-35 parts, PEG modified titanium 5-7 parts, and auxiliary additives 2-3 parts. The application is characterized in that polyethylene glycol is used to modify zinc modified nano-titanium, and then the polyethylene terephthalate is enhanced by activated modified polyester containing a reactive cross-linking bond and epoxy modified polyolefin. The application not only effectively improves the mechanical strength and ultraviolet aging resistance of the full-dull polyester fibers, but also improves the antibacterial properties and water washing resistance of the full-dull polyester fibers.

Description

Technical Field

[0001] This invention relates to the field of polyester fiber processing technology, specifically to an antibacterial modified fully dull polyester fiber and its preparation method. Background Technology

[0002] Polyester fiber is a fiber material with polyethylene terephthalate as its main component. With its high strength, abrasion resistance, easy washing and quick drying properties, it has become the world's largest synthetic fiber in terms of production volume. It is widely used in clothing, home textiles, medical materials and industrial fabrics. Traditional polyester fibers have a smooth surface that causes strong light reflection and creates a glaring luster. In order to meet the demand of high-end textiles for a matte texture, matting agents are usually added to polyester fiber materials to achieve a fully matte effect.

[0003] In existing technologies, inorganic materials such as titanium dioxide are mainly used as matting agents. However, in traditional processes, titanium dioxide particles are prone to agglomeration, resulting in uneven matting and a decrease in fiber mechanical properties. Furthermore, the hydrophobicity of polyester fibers makes them easily absorb organic matter such as sweat and sebum, providing a breeding ground for bacteria such as Staphylococcus aureus and Escherichia coli. In medical textiles, sportswear, and fabrics used in public places, the growth of microorganisms may cause cross-infection and threaten human health. Although adding inorganic or organic antibacterial agents to polyester materials can effectively improve the antibacterial properties of polyester fibers, the antibacterial components of traditional antibacterial polyester fibers will quickly migrate and be lost after repeated washing, leading to a decrease in the antibacterial properties of polyester fiber materials.

[0004] Therefore, a solution is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide an antibacterial modified fully dull polyester fiber and its preparation method, in order to solve the technical problem that the mechanical properties and antibacterial properties of fully dull polyester fibers in the prior art need to be further improved.

[0006] The objective of this invention can be achieved through the following technical solution: an antibacterial modified fully matte polyester fiber, comprising the following components by weight: 50-60 parts of polyethylene terephthalate, 40-50 parts of activated modified polyester, 25-35 parts of epoxy modified polyolefin, 5-7 parts of PEG modified titanium and 2-3 parts of auxiliary additives.

[0007] The method for preparing the activated modified polyester is as follows: under an inert gas atmosphere, terephthalic acid, adipic acid, 1,4-butanediol and catalyst are mixed and stirred. The temperature of the reaction system is raised to 200-220℃ and kept at this temperature for 2-3 hours. 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol is added to the reaction system and kept at this temperature for 50-60 minutes. 2,2,6,6-tetramethyl-4-piperidinol is added to the reaction system and kept at this temperature for 30-50 minutes. The temperature of the reaction system is raised to 240℃, and a vacuum is drawn until the system pressure drops to 100-180 Pa. Heating is stopped when the system exhibits a climbing effect, and the material is discharged while hot to obtain the activated modified polyester.

[0008] The synthesis reaction mechanism of activated modified polyester is as follows:

[0009]

[0010] In the formula:

[0011]

[0012] During the reaction, the carboxyl groups on terephthalic acid and adipic acid molecules undergo esterification with the hydroxyl groups on the 1,4-butanediol molecule to prepare a polyester prepolymer with carboxyl groups at the end. The ternary hydroxyl groups on the 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol molecule undergo esterification with the carboxyl-terminated polyester prepolymer to increase the degree of crosslinking between molecules. 2,2,6,6-tetramethyl-4-piperidinol is used as the end group to form 2,2,6,6-tetramethyl-4-piperidinol end-capping modification to prepare an activated modified polyester.

[0013] Furthermore, the molar ratio of terephthalic acid, adipic acid, 1,4-butanediol, catalyst, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol and 2,2,6,6-tetramethyl-4-piperidinol is 0.4:0.2:0.4:0.2:0.15:0.1, and the catalyst is tetrabutyl titanate.

[0014] Furthermore, the preparation method of epoxy-modified polyolefin is as follows: Ethyl methacrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, methacryloyloxyethyltrimethylammonium chloride, and toluene are mixed and stirred. The temperature of the reaction system is raised to 75-85℃. An initiator solution is added to the reaction system. After the addition is complete, the reaction is kept at the temperature for 5-7 hours. The epoxy-modified polyolefin is then obtained after post-treatment.

[0015] The synthesis reaction mechanism of epoxy-modified polyolefins is as follows:

[0016]

[0017] During the reaction, the olefin double bonds on the molecules of ethyl methacrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, and methacryloyloxyethyltrimethylammonium chloride undergo free radical polymerization under the action of an initiator to form epoxy-modified polyolefins with hydroxyl and quaternary ammonium salt modifications.

[0018] Furthermore, the ratio of ethyl methacrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, methacryloyloxyethyltrimethylammonium chloride, toluene, and the initiator solution is 7-8g:2-3g:3-4g:2-3g:80mL:7mL. The initiator solution is composed of azobisisobutyronitrile and toluene at a ratio of 1g:20mL. The post-treatment includes: after the reaction is complete, maintaining the temperature of the reaction system at 75-85℃, drawing a negative pressure to 0.1MPa, and removing low-boiling-point substances under reduced pressure to obtain epoxy-modified polyolefin.

[0019] Furthermore, PEG-modified titanium is obtained through the following steps:

[0020] A1. Under an inert gas atmosphere, polyethylene glycol and tetrahydrofuran are mixed and stirred. The temperature of the reaction system is raised to 50-60℃. Propyltriethoxysilane isocyanate is added to the reaction system and the reaction is kept at the temperature for 60-80 min to obtain PEG modified solution.

[0021] A2. Mix zinc-modified nano-titanium and PEG-modified liquid, ultrasonically disperse for 40-60 min, raise the temperature of the reaction system to 50-60℃, add sodium hydroxide solution to the reaction system, keep the reaction at the temperature for 80-100 min, and then perform post-treatment to obtain PEG-modified titanium.

[0022] The synthesis reaction mechanism of PEG-modified titanium is as follows:

[0023]

[0024] During the reaction, the hydroxyl groups on polyethylene glycol condense with the isocyanate groups on propyltriethoxysilane molecules to form triethoxysilane end-capping modification. Under alkaline conditions, triethoxysilane hydrolyzes to form silanol, which condenses with the active functional groups on the surface of zinc-modified titanium nanoparticles. PEG is then modified on the surface of zinc-modified titanium nanoparticles to prepare PEG-modified titanium.

[0025] Furthermore, in step A1, the ratio of polyethylene glycol to tetrahydrofuran is 1g:20mL, the polyethylene glycol is PEG-1000, and the molar ratio of propyltriethoxysilane isocyanate to polyethylene glycol is 2:1.

[0026] Further, in step A2, the ratio of zinc-modified nano-titanium, PEG-modified solution, and sodium hydroxide solution is 5g:30mL:7mL, and the concentration of sodium hydroxide solution is 2-3mol / L. The post-treatment includes: after the reaction is complete, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral, dried, and the filter cake is transferred to a drying oven at a temperature of 70-80℃ and dried to constant weight to obtain PEG-modified titanium.

[0027] Furthermore, the preparation method of zinc-modified nano-titanium is as follows: nano-titanium dioxide and zinc chloride solution are mixed and ultrasonically dispersed for 30-50 min. Sodium hydroxide solution is added to the reaction system to adjust the pH of the system to 8. The system is stirred and dispersed for 20-30 min. After post-treatment, zinc-modified nano-titanium is obtained.

[0028] The synthesis reaction mechanism of zinc-modified nano-titanium is as follows:

[0029] During the reaction, the surface of nano-titanium dioxide is rich in hydroxyl groups. Under weak alkaline conditions, the surface is negatively charged. When nano-titanium dioxide is mixed with zinc chloride solution, zinc ions are attached to the surface of nano-titanium dioxide by electrostatic adsorption. At the same time, zinc ions generate zinc hydroxide under alkaline conditions, which is coated on the surface of nano-titanium dioxide in the form of solid matter. In the subsequent high-temperature treatment, zinc hydroxide decomposes to generate zinc oxide, thus preparing zinc-modified nano-titanium.

[0030] Furthermore, the ratio of nano-titanium dioxide to zinc chloride solution is 5-7g:50mL. The zinc chloride solution is composed of zinc chloride, purified water, and sodium dodecyl sulfate in a ratio of 1g:30mL:0.2g. The post-treatment includes: after the reaction is complete, the reaction system temperature is lowered to room temperature, filtered, the filter cake is washed three times with purified water and then dried, the filter cake is transferred to a tube furnace, the temperature of the tube furnace is raised to 80-90℃ in an air atmosphere, dried to constant weight, the temperature of the tube furnace is raised to 500℃, and kept at this temperature for 120-150min, then cooled and discharged to obtain zinc-modified nano-titanium.

[0031] This invention also proposes a method for preparing antibacterial modified fully dull polyester fiber, comprising the following steps:

[0032] S1. Polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, and PEG modified titanium are added to an oven at 150-160℃ and dried for 20-25 hours to obtain dried material.

[0033] S2. After mixing the drying oven and auxiliary additives, add the mixture to a twin-screw extruder and melt mix for 3-5 minutes. Then, extrude the mixture into a spinning machine, melt spin it, and then heat stretch it to obtain fully dull polyester fiber.

[0034] Furthermore, the auxiliary additives are composed of plasticizer, dispersant, antioxidant, and antistatic agent in a weight ratio of 5:4:2:2. The plasticizer is phthalate, the dispersant is stearate, the antioxidant is any one of antioxidant 1010, antioxidant 1076, and antioxidant 1035, and the antistatic agent is antistatic agent SN. The temperature of the six temperature zones of the twin-screw extruder from the feed end to the discharge end is sequentially set to 260°C. The temperatures are 270℃, 270℃, 275℃, 275℃, and 280℃. The spindle speed of the twin-screw extruder is 15 r / min. The spinning temperature of the melt spinning machine is 290℃. The number of holes in the spinneret of the melt spinning machine is 36, the hole diameter is 0.2 mm, the spinning pressure is 6-8 MPa, air-cooled curing is adopted, the air-cooled air supply temperature is 15℃, the blowing speed is 0.6 m / s, the hot stretching temperature is 85℃, and the stretching ratio is 4-5 times.

[0035] The present invention has the following beneficial effects:

[0036] 1. This invention utilizes a mixed diacid system of terephthalic acid and adipic acid, combined with 1,4-butanediol to synthesize a basic polyester chain. The introduced adipic acid provides flexible aliphatic segments, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol promotes cross-linking between molecular chains, and 2,2,6,6-tetramethyl-4-piperidinol acts as a capping agent to effectively terminate chain cross-linking. Furthermore, the steric hindrance effect of the hindered amine groups inhibits molecular chain entanglement, which is beneficial for orientation crystallization during spinning. This allows the polyester to maintain strength while improving toughness. During the preparation of epoxy-modified polyolefins, glycidyl methacrylate provides epoxy groups. During melt blending, the epoxy groups undergo in-situ compatibilization reactions with the active reaction sites on the polyester chain. The polyethylene glycol coated on PEG-modified titanium effectively enhances its compatibility and interfacial bonding with the polyester matrix, improves the dispersion of inorganic particles in the polyester matrix, reduces stress concentration, and improves the mechanical strength and matte properties of the material, meeting the demand for matte texture in high-end textiles.

[0037] 2. This invention utilizes zinc-modified nano-titanium, modifying zinc oxide on the surface of nano-titanium dioxide to enhance its antibacterial effect through the synergistic effect between zinc oxide and titanium oxide. During the synthesis of epoxy-modified polyolefin, quaternary ammonium salt is modified on its molecular chain through methacryloyloxyethyltrimethylammonium chloride. The cationic groups of the quaternary ammonium salt disrupt the bacterial cell membrane potential balance through electrostatic adsorption, further improving the antibacterial effect of the fiber material. PEG-modified titanium forms an organic coating layer for zinc ions by branching propyltriethoxysilane onto polyethylene glycol long links. During melt spinning, the PEG-modified titanium is encapsulated in the cross-linked polyester matrix, with only surface particles participating in initial antibacterial activity, while internal particles are slowly released during use. The quaternary ammonium salt is chemically bonded to the polyester, thereby improving the wash resistance of the fiber material.

[0038] 3. This invention modifies the surface of nano-titanium oxide with zinc oxide. Zinc ions have UV catalytic inertness and can quench excited singlet oxygen, reducing photosensitive oxidation. Compared with silver ion antibacterial agents, which are easily reduced and blackened under UV light, the zinc-based system is more suitable for outdoor light environments. Zinc oxide and titanium oxide work synergistically to achieve full-band protection. PEG modification gives nano-titanium excellent dispersibility, allowing it to form a continuous protective layer on the fiber surface. The 2,2,6,6-tetramethyl-4-piperidinol introduced into the activated modified polyester quenches free radicals through a recycling mechanism, improving the UV aging resistance of the polyester fiber material. The activated modified polyester and epoxy modified polyolefin form a chemical cross-linking network in the polyester fiber material, forming cross-linking points in the polyester fiber, thereby inhibiting the photolytic chain breakage of the main chain. Even after some molecular chains break due to UV attack, the material still maintains its integrity and avoids a sharp drop in mechanical properties. Detailed Implementation

[0039] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] In this invention, the nano-titanium dioxide has a particle size of 30-50 nm and a purity of 99.9%.

[0041] In this invention, the polyethylene glycol is PEG-1000, and the content of the active ingredient is 99%.

[0042] In this invention, the effective component content of polyethylene terephthalate is 99%, the density is 1.68 g / mL, and the melting point is 250-255℃.

[0043] Example 1

[0044] This embodiment provides a method for preparing antibacterial modified fully dull polyester fiber, including the following steps:

[0045] S1. Preparation of activated modified polyester

[0046] Weigh out 332.3g of terephthalic acid, 146.1g of adipic acid, 180.2g of 1,4-butanediol, and 340.3g of tetrabutyl titanate and add them to an argon-protected reaction flask. Stir the mixture and raise the temperature of the reaction flask to 200℃. Maintain the temperature for 2 hours. Add 101.4g of 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol to the reaction flask and maintain the temperature for 50 minutes. Add 78.6g of 2,2,6,6-tetramethyl-4-piperidinol to the reaction flask and maintain the temperature for 30 minutes. Raise the temperature of the reaction flask to 240℃ and evacuate the system until the pressure drops to 180 Pa. Stop heating when the system exhibits a climbing effect. Discharge the material while it is still hot to obtain the activated modified polyester.

[0047] S2, Preparation of epoxy-modified polyolefins

[0048] Azobisisobutyronitrile and toluene were mixed evenly at a ratio of 1g:20mL to obtain an initiator solution;

[0049] Weigh out 350g of ethyl methacrylate, 100g of 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, 150g of glycidyl methacrylate, 100g of methacryloyloxyethyltrimethylammonium chloride, and 4000mL of toluene and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 75℃. Add 350mL of initiator solution to the reaction flask. After the addition is complete, keep the reaction at this temperature for 5 hours. Maintain the temperature of the reaction flask at 75℃ and apply a negative pressure of 0.1MPa to remove low-boiling-point substances by vacuum distillation to obtain epoxy-modified polyolefin.

[0050] S3. Preparation of zinc-modified nano-titanium

[0051] Weigh out zinc chloride, purified water, and sodium dodecyl sulfate and mix them evenly at a ratio of 1g:30mL:0.2g to obtain a zinc chloride solution;

[0052] Weigh out 50g of nano-titanium dioxide and 500mL of zinc chloride solution and add them to a reaction flask. Mix and ultrasonically disperse for 30min. Fix the reaction flask on an iron stand with a mechanical stirrer and stir. Add 2mol / L sodium hydroxide solution to the reaction flask to adjust the pH of the system to 8. Stir and disperse for 20min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake three times with purified water and dry it. Transfer the filter cake to a tube furnace. Under an air atmosphere, raise the temperature of the tube furnace to 80℃ and dry it to constant weight. Then raise the temperature of the tube furnace to 500℃ and keep it at that temperature for 120min. Cool down and discharge the material to obtain zinc-modified nano-titanium.

[0053] S4. Preparation of PEG-modified titanium

[0054] Weigh out 100g of polyethylene glycol and 2000mL of tetrahydrofuran and add them to an argon-protected reaction flask. Stir the mixture and raise the temperature of the reaction flask to 50°C. Then add the mixture according to n... 聚乙二醇-OH :n 异氰酸丙基三乙氧基硅烷 =1:2, add the calculated amount of propyltriethoxysilane isocyanate to the reaction system, keep the reaction at the temperature for 60 min, and obtain the PEG modified solution;

[0055] Weigh out 50g of zinc-modified nano-titanium and 300mL of PEG-modified solution and add them to a reaction flask. Mix and ultrasonically disperse for 40min. Fix the reaction flask on an iron stand with mechanical stirring and stir. Raise the temperature of the reaction flask to 50℃ and add 70mL of 2mol / L sodium hydroxide solution to the reaction flask. Keep the reaction at this temperature for 80min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight to obtain PEG-modified titanium.

[0056] S5. Preparation of fully matte polyester fibers

[0057] Dimethyl phthalate, sodium stearate, antioxidant 1010 and antistatic agent SN were mixed evenly in a weight ratio of 5:4:2:2 to obtain the auxiliary additive.

[0058] Weigh out the following by weight: 50 parts polyethylene terephthalate, 40 parts activated modified polyester, 25 parts epoxy modified polyolefin, 5 parts PEG modified titanium and 2 parts auxiliary additives, and set aside.

[0059] Polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, and PEG modified titanium were added to an oven at 150°C and dried for 20 hours to obtain the dried material.

[0060] The drying oven and auxiliary additives are mixed and then added to a twin-screw extruder. The temperatures of the six temperature zones of the twin-screw extruder from the feed end to the discharge end are set sequentially to 260℃, 270℃, 270℃, 275℃, 275℃, and 280℃. The spindle speed of the twin-screw extruder is 15 r / min. The melt mixing is carried out for 3 minutes, and the melt extrusion is then sent to a spinning machine. The spinning temperature is set to 290℃. The spinneret of the melt spinning machine has 36 holes with a diameter of 0.2 mm. The spinning pressure is 6 MPa. Air-cooled curing is used with an air supply temperature of 15℃ and a blowing speed of 0.6 m / s. The hot stretching temperature is 85℃, and the stretching ratio is 4 times, resulting in fully dull polyester fiber.

[0061] Example 2

[0062] This embodiment provides a method for preparing antibacterial modified fully dull polyester fiber, including the following steps:

[0063] S1. Preparation of activated modified polyester

[0064] Weigh out 332.3g of terephthalic acid, 146.1g of adipic acid, 180.2g of 1,4-butanediol, and 340.3g of tetrabutyl titanate and add them to an argon-protected reaction flask. Stir the mixture and raise the temperature of the reaction flask to 210℃. Maintain the temperature for 2.5h. Add 101.4g of 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol to the reaction flask and maintain the temperature for 55min. Add 78.6g of 2,2,6,6-tetramethyl-4-piperidinol to the reaction flask and maintain the temperature for 40min. Raise the temperature of the reaction flask to 240℃ and evacuate the system until the pressure drops to 140pa. Stop heating when the system exhibits a climbing effect and discharge the material while it is still hot to obtain the activated modified polyester.

[0065] S2, Preparation of epoxy-modified polyolefins

[0066] Azobisisobutyronitrile and toluene were mixed evenly at a ratio of 1g:20mL to obtain an initiator solution;

[0067] Weigh out 375g of ethyl methacrylate, 125g of 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, 175g of glycidyl methacrylate, 125g of methacryloyloxyethyltrimethylammonium chloride, and 4000mL of toluene and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 80℃. Add 350mL of initiator solution to the reaction flask. After the addition is complete, keep the reaction at this temperature for 6 hours. Maintain the temperature of the reaction flask at 80℃ and apply a negative pressure of 0.1MPa to remove low-boiling-point substances by vacuum distillation to obtain epoxy-modified polyolefin.

[0068] S3. Preparation of zinc-modified nano-titanium

[0069] Weigh out zinc chloride, purified water, and sodium dodecyl sulfate and mix them evenly at a ratio of 1g:30mL:0.2g to obtain a zinc chloride solution;

[0070] Weigh out 60g of nano-titanium dioxide and 500mL of zinc chloride solution and add them to a reaction flask. Mix and ultrasonically disperse for 40min. Fix the reaction flask on an iron stand with a mechanical stirrer and stir. Add 2.5mol / L sodium hydroxide solution to the reaction flask to adjust the pH of the system to 8. Stir and disperse for 25min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake three times with purified water and dry it. Transfer the filter cake to a tube furnace. Under an air atmosphere, raise the temperature of the tube furnace to 85℃ and dry it to constant weight. Then raise the temperature of the tube furnace to 500℃ and keep it at that temperature for 135min. Cool down and discharge the material to obtain zinc-modified nano-titanium.

[0071] S4. Preparation of PEG-modified titanium

[0072] Weigh out 100g of polyethylene glycol and 2000mL of tetrahydrofuran and add them to an argon-protected reaction flask. Stir the mixture and raise the temperature of the reaction flask to 55℃. Then add the mixture according to n... 聚乙二醇-OH :n 异氰酸丙基三乙氧基硅烷 =1:2, add the calculated amount of propyltriethoxysilane isocyanate to the reaction system, keep the reaction at the temperature for 70 min, and obtain PEG modified solution;

[0073] Weigh out 50g of zinc-modified nano-titanium and 300mL of PEG-modified solution and add them to a reaction flask. Mix and ultrasonically disperse for 50min. Fix the reaction flask on an iron stand with a mechanical stirrer and stir. Raise the temperature of the reaction flask to 55℃ and add 70mL of 2.5mol / L sodium hydroxide solution to the reaction flask. Keep the reaction at this temperature for 90min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 75℃ and dry it to constant weight to obtain PEG-modified titanium.

[0074] S5. Preparation of fully matte polyester fibers

[0075] Diisobutyl phthalate, calcium stearate, antioxidant 1076 and antistatic agent SN were mixed evenly in a weight ratio of 5:4:2:2 to obtain the auxiliary additive.

[0076] Weigh out the following components by weight: 55 parts polyethylene terephthalate, 45 parts activated modified polyester, 30 parts epoxy modified polyolefin, 6 parts PEG modified titanium, and 2.5 parts auxiliary additives, and set aside.

[0077] Polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, and PEG modified titanium were added to an oven at 155°C and dried for 23 hours to obtain the dried material.

[0078] The drying oven and auxiliary additives were mixed and then added to a twin-screw extruder. The temperatures of the six temperature zones of the twin-screw extruder from the feed end to the discharge end were set sequentially to 260℃, 270℃, 270℃, 275℃, 275℃, and 280℃. The spindle speed of the twin-screw extruder was 15 r / min. The melt mixing was carried out for 4 minutes, and the melt extrusion was then sent to a spinning machine. The spinning temperature was set to 290℃. The spinneret of the melt spinning machine had 36 holes with a diameter of 0.2 mm. The spinning pressure was 7 MPa. Air-cooled curing was used with an air supply temperature of 15℃ and a blowing speed of 0.6 m / s. The hot stretching temperature was 85℃, and the stretching ratio was 4.5 times, resulting in fully dull polyester fiber.

[0079] Example 3

[0080] This embodiment provides a method for preparing antibacterial modified fully dull polyester fiber, including the following steps:

[0081] S1. Preparation of activated modified polyester

[0082] Weigh out 332.3g of terephthalic acid, 146.1g of adipic acid, 180.2g of 1,4-butanediol, and 340.3g of tetrabutyl titanate and add them to an argon-protected reaction flask. Stir the mixture and raise the temperature of the reaction flask to 220℃. Maintain the temperature for 3 hours. Add 101.4g of 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol to the reaction flask and maintain the temperature for 60 minutes. Add 78.6g of 2,2,6,6-tetramethyl-4-piperidinol to the reaction flask and maintain the temperature for 50 minutes. Raise the temperature of the reaction flask to 240℃ and evacuate the system until the pressure drops to 100 Pa. Stop heating when the system exhibits a climbing effect. Discharge the material while it is still hot to obtain the activated modified polyester.

[0083] S2, Preparation of epoxy-modified polyolefins

[0084] Azobisisobutyronitrile and toluene were mixed evenly at a ratio of 1g:20mL to obtain an initiator solution;

[0085] Weigh out 400g of ethyl methacrylate, 150g of 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, 200g of glycidyl methacrylate, 150g of methacryloyloxyethyltrimethylammonium chloride, and 4000mL of toluene and add them to a reaction flask. Stir the mixture and raise the temperature of the reaction flask to 85℃. Add 350mL of initiator solution to the reaction flask. After the addition is complete, keep the reaction at this temperature for 7 hours. Maintain the temperature of the reaction flask at 85℃ and apply a negative pressure of 0.1MPa to remove low-boiling-point substances by vacuum distillation to obtain epoxy-modified polyolefin.

[0086] S3. Preparation of zinc-modified nano-titanium

[0087] Weigh out zinc chloride, purified water, and sodium dodecyl sulfate and mix them evenly at a ratio of 1g:30mL:0.2g to obtain a zinc chloride solution;

[0088] Weigh out 70g of nano-titanium dioxide and 500mL of zinc chloride solution and add them to a reaction flask. Mix and ultrasonically disperse for 50min. Fix the reaction flask on an iron stand with a mechanical stirrer and stir. Add 3mol / L sodium hydroxide solution to the reaction flask to adjust the pH of the system to 8. Stir and disperse for 30min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake three times with purified water and dry it. Transfer the filter cake to a tube furnace. Under an air atmosphere, raise the temperature of the tube furnace to 90℃ and dry it to constant weight. Then raise the temperature of the tube furnace to 500℃ and keep it at that temperature for 150min. Cool down and discharge the material to obtain zinc-modified nano-titanium.

[0089] S4. Preparation of PEG-modified titanium

[0090] Weigh out 100g of polyethylene glycol and 2000mL of tetrahydrofuran and add them to an argon-protected reaction flask. Stir the mixture and raise the temperature of the reaction flask to 60℃. Then add the mixture according to n... 聚乙二醇-OH :n 异氰酸丙基三乙氧基硅烷 =1:2, add the calculated amount of propyltriethoxysilane isocyanate to the reaction system, keep the reaction at the temperature for 80 min, and obtain PEG modified solution;

[0091] Weigh out 50g of zinc-modified nano-titanium and 300mL of PEG-modified solution and add them to a reaction flask. Mix and ultrasonically disperse for 60min. Fix the reaction flask on an iron stand with a mechanical stirrer and stir. Raise the temperature of the reaction flask to 60℃ and add 70mL of 3mol / L sodium hydroxide solution to the reaction flask. Keep the reaction at this temperature for 100min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 80℃ and dry it to constant weight to obtain PEG-modified titanium.

[0092] S5. Preparation of fully matte polyester fibers

[0093] Dioctyl phthalate, zinc stearate, antioxidant 1035 and antistatic agent SN were mixed evenly in a weight ratio of 5:4:2:2 to obtain the auxiliary additive.

[0094] Weigh out the following components by weight: 60 parts polyethylene terephthalate, 50 parts activated modified polyester, 35 parts epoxy modified polyolefin, 7 parts PEG modified titanium and 3 parts auxiliary additives, and set aside.

[0095] Polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, and PEG modified titanium were added to an oven at 160°C and dried for 25 hours to obtain the dried material.

[0096] The drying oven and auxiliary additives were mixed and then added to a twin-screw extruder. The temperatures of the six temperature zones of the twin-screw extruder from the feed end to the discharge end were set sequentially to 260℃, 270℃, 270℃, 275℃, 275℃, and 280℃. The spindle speed of the twin-screw extruder was 15 r / min. The melt mixing was carried out for 5 minutes, and the melt extrusion was then sent to a spinning machine. The spinning temperature was set to 290℃. The spinneret of the melt spinning machine had 36 holes with a diameter of 0.2 mm. The spinning pressure was 8 MPa. Air-cooled curing was used with an air supply temperature of 15℃ and a blowing speed of 0.6 m / s. The hot stretching temperature was 85℃, and the stretching ratio was 5 times, resulting in fully dull polyester fiber.

[0097] Comparative Example 1

[0098] The difference between this comparative example and Example 3 is that in step S1, the amount of 1,4-butanediol added is calculated according to the ratio of 1,4-butanediol:2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol = 1.5 mol: 1 mol, and the calculated amount of 1,4-butanediol is used to replace 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol.

[0099] Comparative Example 2

[0100] The difference between this comparative example and Example 3 is that glycidyl methacrylate was not added in step S2.

[0101] Comparative Example 3

[0102] The difference between this comparative example and Example 3 is that step S3 is omitted, and the zinc-modified nano-titanium in step S4 is replaced by nano-titanium dioxide in step S3.

[0103] Comparative Example 4

[0104] The difference between this comparative example and Example 3 is that step S4 is omitted, and the zinc-modified nano-titanium prepared in step S3 is used to replace the PEG-modified titanium in step S5 in an equal amount.

[0105] Performance testing:

[0106] The breaking strength, breaking elongation and antibacterial rate of the fully dull polyester fiber samples prepared in Examples 1-3 and Comparative Examples 1-4 were determined in accordance with the standard FZ / T 52035-2014 "Antibacterial Polyester Staple Fiber".

[0107] The fully matte polyester fiber samples prepared in Examples 1-3 and Comparative Examples 1-4 were placed at a temperature of 65°C and an irradiation intensity of 1.2 W / m². 2 The samples were exposed to fluorescent ultraviolet light for 100 hours, and the fracture strength and elongation at break were measured after aging.

[0108] The fully dull polyester fiber samples prepared in Examples 1-3 and Comparative Examples 1-4 were washed with water and then dried. After being washed 200 times with water, the antibacterial rate of the samples was determined according to the standard. The specific test data are shown in Table 1-2 below.

[0109] Table 1 - Mechanical properties and aging resistance test data of the samples

[0110]

[0111] Table 2 - Test data on antibacterial properties and water resistance of the samples

[0112]

[0113] Data Analysis:

[0114] Comparative analysis of the data in Table 1 shows that the fully matte polyester fiber prepared by this invention has a tensile strength of 6.55 cN / dtex and a tensile elongation of 39%. After UV aging, the tensile strength of the fully matte polyester fiber reaches 5.96 cN / dtex and the tensile elongation of 36%. The antibacterial rate against Staphylococcus aureus reaches 99.7%, and the antibacterial rate against Escherichia coli reaches 99.6%. After 200 washes, the antibacterial rate against Staphylococcus aureus reaches 95.4%, and the antibacterial rate against Escherichia coli reaches 95.6%. All performance test data are superior to the comparative example. This indicates that the present invention, by modifying zinc-modified nano-titanium with polyethylene glycol and reinforcing it with reactive cross-linked activated modified polyester and epoxy-modified polyolefin to polyethylene terephthalate, not only effectively improves the mechanical strength and UV aging resistance of the fully matte polyester fiber, but also improves its antibacterial and wash resistance.

[0115] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. An antibacterial modified fully dull polyester fiber, characterized in that, It comprises the following components by weight: 50-60 parts polyethylene terephthalate, 40-50 parts activated modified polyester, 25-35 parts epoxy modified polyolefin, 5-7 parts PEG modified titanium and 2-3 parts auxiliary additives. The method for preparing the activated modified polyester is as follows: under an inert gas atmosphere, terephthalic acid, adipic acid, 1,4-butanediol and catalyst are mixed and stirred. The temperature of the reaction system is raised to 200-220℃ and kept at this temperature for 2-3 hours. 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol is added to the reaction system and kept at this temperature for 50-60 minutes. 2,2,6,6-tetramethyl-4-piperidinol is added to the reaction system and kept at this temperature for 30-50 minutes. The temperature of the reaction system is raised to 240℃. Vacuum is applied until the system pressure drops to 100-180 Pa. Heating is stopped when the system exhibits a climbing effect. The material is discharged while hot to obtain the activated modified polyester. The preparation method of epoxy-modified polyolefin is as follows: Ethyl methacrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, methacryloyloxyethyltrimethylammonium chloride, and toluene are mixed and stirred. The temperature of the reaction system is raised to 75-85℃. An initiator solution is added to the reaction system. After the addition is complete, the reaction is kept at the temperature for 5-7 hours. The epoxy-modified polyolefin is then obtained after post-treatment. PEG-modified titanium is obtained through the following steps: A1. Under an inert gas atmosphere, polyethylene glycol and tetrahydrofuran are mixed and stirred. The temperature of the reaction system is raised to 50-60℃. Propyltriethoxysilane isocyanate is added to the reaction system and the reaction is kept at the temperature for 60-80 min to obtain PEG modified solution. A2. Mix zinc-modified nano-titanium and PEG-modified liquid, ultrasonically disperse for 40-60 min, raise the temperature of the reaction system to 50-60℃, add sodium hydroxide solution to the reaction system, keep the reaction at the temperature for 80-100 min, and then perform post-treatment to obtain PEG-modified titanium. The preparation method of zinc-modified nano-titanium is as follows: nano-titanium dioxide and zinc chloride solution are mixed and ultrasonically dispersed for 30-50 min. Sodium hydroxide solution is added to the reaction system to adjust the pH of the system to 8. The system is stirred and dispersed for 20-30 min. After post-treatment, zinc-modified nano-titanium is obtained.

2. The antibacterial modified fully dull polyester fiber according to claim 1, characterized in that, The molar ratio of terephthalic acid, adipic acid, 1,4-butanediol, catalyst, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol and 2,2,6,6-tetramethyl-4-piperidinol is 0.4:0.2:0.4:0.2:0.15:0.1, and the catalyst is tetrabutyl titanate.

3. The antibacterial modified fully dull polyester fiber according to claim 1, characterized in that, The ratio of ethyl methacrylate, 2-methyl-2-acrylate-2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, methacryloyloxyethyltrimethylammonium chloride, toluene, and the initiator solution is 7-8g:2-3g:3-4g:2-3g:80mL:7mL, and the initiator solution is composed of azobisisobutyronitrile and toluene at a ratio of 1g:20mL.

4. The antibacterial modified fully dull polyester fiber according to claim 1, characterized in that, In step A1, the ratio of polyethylene glycol to tetrahydrofuran is 1g:20mL, the polyethylene glycol is PEG-1000, and the molar ratio of propyltriethoxysilane isocyanate to polyethylene glycol is 2:1; in step A2, the ratio of zinc-modified nano-titanium, PEG-modified solution, and sodium hydroxide solution is 5g:30mL:7mL, and the concentration of sodium hydroxide solution is 2-3mol / L.

5. The antibacterial modified fully dull polyester fiber according to claim 1, characterized in that, The ratio of nano-titanium dioxide to zinc chloride solution is 5-7g:50mL. The zinc chloride solution is composed of zinc chloride, purified water, and sodium dodecyl sulfate in a ratio of 1g:30mL:0.2g.

6. A method for preparing an antibacterial modified fully dull polyester fiber as described in any one of claims 1-5, characterized in that, Includes the following steps: S1. Polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, and PEG modified titanium are added to an oven at 150-160℃ and dried for 20-25 hours to obtain dried material. S2. After mixing the drying oven and auxiliary additives, add the mixture to a twin-screw extruder and melt mix for 3-5 minutes. Then, extrude the mixture into a spinning machine, melt spin it, and then heat stretch it to obtain fully dull polyester fiber.

7. The method for preparing an antibacterial modified fully dull polyester fiber according to claim 6, characterized in that, The auxiliary additives are composed of plasticizer, dispersant, antioxidant, and antistatic agent in a weight ratio of 5:4:2:

2. The plasticizer is phthalate, the dispersant is stearate, the antioxidant is any one of antioxidant 1010, antioxidant 1076, and antioxidant 1035, and the antistatic agent is antistatic agent SN. The temperature of the six temperature zones of the twin-screw extruder from the feed end to the discharge end is sequentially set to 260°C. The spindle speed of the twin-screw extruder is 15 r / min, the spinning temperature of the melt spinning machine is 290℃, the spinneret of the melt spinning machine has 36 holes with a diameter of 0.2 mm, the spinning pressure is 6-8 MPa, the curing is done by air cooling, the air cooling air supply temperature is 15℃, the blowing speed is 0.6 m / s, the hot stretching temperature is 85℃, and the stretching ratio is 4-5 times.

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