Bacteriostatic antistatic pet slice for fibers and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to a bacteriostatic antistatic pet slice for fibers and a preparation method thereof, and aims to solve the problems that an existing pet slice is easy to accumulate, a large amount of generated charges cannot be released, electrostatic danger is easy to occur, and a pet slice material does not have a bacteriostatic function; according to the preparation method, modified pet is used as a main raw material, metal copper ions complexed on the modified pet enable the modified pet to have excellent antibacterial and bacteriostatic functions, a modified bacteriostatic agent and titanium dioxide are added into the modified pet, and the antibacterial performance of the pet slice material can be remarkably improved; and the modified antistatic agent is added to provide excellent antistatic capability for pet slices, so that the occurrence of electrostatic danger is effectively prevented.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an antibacterial and antistatic PET chip for fibers and its preparation method. Background Technology

[0002] In recent years, with the increasing awareness of health and environmental protection, people have begun to pursue the comfort and hygiene of clothing. Therefore, the fibers and raw materials used in clothing must have corresponding functions. PET fiber is currently the most produced chemical fiber variety at home and abroad. In particular, with the development of new synthetic fibers with new functions, its output and usage have increased dramatically, and its application areas have continued to expand.

[0003] However, because PET chips lack antistatic properties, they are prone to generating static electricity due to friction, stretching, compression, or induction in a dry electric field. This static electricity easily attracts dust, which can then entangle the body, irritate the skin, and severely affect the comfort of wearing them as clothing materials. In scientific research and industrial production in fields such as electronics, petroleum, and defense, static electricity can sometimes cause malfunctions and serious accidents. Furthermore, PET chips lack antibacterial properties, leading to the growth of bacteria and microorganisms, which can easily cause infections. Bacteria can also easily convert odorless human secretions into volatile gases.

[0004] Therefore, it is of great significance to develop a PET chip with antibacterial and antistatic properties for fibers and its preparation method. Summary of the Invention

[0005] To overcome the above-mentioned technical problems, the present invention aims to provide a fiber-grade antibacterial and antistatic PET chip and its preparation method. The method involves mixing a modified antibacterial agent, titanium dioxide, modified PET, and a modified antistatic agent and extruding them in a co-rotating twin-screw extruder. After discharge, slicing, and drying, fiber-grade antibacterial and antistatic PET chips are obtained, which solves the problem that existing fiber-grade PET chips do not have antistatic and antibacterial properties.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A fiber-grade antibacterial and antistatic PET chip comprises the following components by weight:

[0008] 92-94 parts modified PET, 1-2 parts modified antibacterial agent, 1 part titanium dioxide, 3-5 parts modified antistatic agent;

[0009] The modified PET is prepared by the following steps:

[0010] Step a1: Dimethyl terephthalate, ethylene glycol and catalyst are added to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas is introduced for protection. The mixture is reacted in a constant temperature oil bath at 160-200℃ for 3-4 hours. The mixture is washed 2-3 times with deionized water and then placed in a vacuum drying oven at 50℃ for 2 hours to obtain intermediate 1.

[0011] Step a2: Add serine alcohol, ditert-butyl dicarbonate and reaction catalyst to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Dissolve at 25-28℃ for 1 hour, then heat to 40℃ and stir for 2-4 hours. Wash with deionized water 3-4 times, filter, and extract repeatedly with ethyl acetate and sodium chloride solution 1-2 times. Dry the organic layer, filter under reduced pressure, let stand for 12 hours, and then rotary evaporate at 55℃. After that, place in a vacuum drying oven and vacuum dry at 40℃ for 8 hours to obtain intermediate 2.

[0012] Step a3: Dimethyl terephthalate, intermediate 2 and catalyst are added to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas is introduced for protection and the mixture is reacted in a constant temperature oil bath at 140-180℃ for 3-4 hours. The mixture is washed 2-3 times with deionized water and then placed in a vacuum drying oven and dried at 40℃ for 1 hour to obtain intermediate 3.

[0013] Step a4: Add intermediate 1 and intermediate 3 to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube, purge with nitrogen for protection, raise the temperature to 240-260℃, stop purging with nitrogen, start the vacuum pump to control the vacuum degree to 800-1000Pa, react for 1-2 hours, raise the temperature to 250-280℃ and react for 1-2 hours, wash the product with methanol 2-3 times, and then place it in a vacuum drying oven and dry at 60℃ for 2-3 hours to obtain intermediate 4;

[0014] Step a5: Add 2 / 3 of the trifluoroacetic acid solution of intermediate 4 to a reagent dish, stir and react at 25°C for 30 min, add 1 / 2 of the precipitant, filter after 1 h, place in a vacuum drying oven and dry at 40°C for 8 h, add to the remaining 1 / 3 of the trifluoroacetic acid solution and dichloromethane mixture to dissolve, add copper sulfate pentahydrate solution, stir and react in a constant temperature water bath at 40°C for 1 h, add the remaining 1 / 2 of the precipitant, precipitate and filter, wash with deionized water 3-4 times, place in a vacuum drying oven and dry for 8 h to obtain modified PET.

[0015] As a further aspect of the present invention: the ratio of dimethyl terephthalate, ethylene glycol and catalyst in step a1 is 0.5-1 mol: 1-2 mol: 5-10 g; the catalyst is one of manganese acetate and titanate.

[0016] As a further aspect of the present invention: the ratio of serine alcohol, di-tert-butyl dicarbonate, and reaction catalyst in step a2 is 36.4g:95.9g:2.1g; the reaction catalyst is aminosulfonic acid; and the mass fraction of the sodium chloride solution is 15%.

[0017] As a further aspect of the present invention: the ratio of dimethyl terephthalate, intermediate 2 and catalyst in step a3 is 0.4-0.6 mol: 0.8-1.2 mol: 4-8 g; the catalyst is one of manganese acetate and titanate.

[0018] As a further aspect of the present invention: the ratio of intermediate 1 to intermediate 3 in step a4 is 75-100g: 5-25g.

[0019] As a further aspect of the present invention: the ratio of intermediate 4, trifluoroacetic acid solution, precipitant, dichloromethane, and copper sulfate pentahydrate solution in step a5 is 20-25g:150mL:100mL:100-150mL:20-30mL; the mass fraction of the trifluoroacetic acid solution is 20%; the mass fraction of the copper phosphate pentahydrate solution is 1mg / mL; and the precipitant is methanol.

[0020] As a further embodiment of the present invention, the modified antibacterial agent is prepared by the following steps:

[0021] Step b1: Add carbon microspheres and deionized water to a beaker, place it in an ultrasonic disperser, ultrasonically disperse for 30 min, wash and dry, then add it to a three-necked flask containing silver nitrate solution, adjust the pH to 8 with ammonia, stir for 30 min, keep warm at 50℃ for 3-7 h, cool naturally to 25℃, centrifuge, wash the precipitate 1-2 times with deionized water, and dry in a constant temperature drying oven at 120℃ for 4 h to obtain silver-loaded antibacterial agent;

[0022] Step b2: Add the coupling agent and deionized water to a beaker, adjust the pH to 4-5 with glacial acetic acid, add anhydrous ethanol and silver-loaded antibacterial agent, and place it in an ultrasonic disperser. After ultrasonic dispersion for 30 minutes, transfer it to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, and magnetically stir at 65°C for 2 hours. Cool to 25°C, centrifuge, wash the precipitate 1-2 times with deionized water, and dry at 120°C for 4 hours to obtain the modified antibacterial agent.

[0023] As a further aspect of the present invention: the ratio of carbon microspheres, deionized water and silver nitrate solution used in step b1 is 5-10g:100-150mL:200mL; the mass fraction of the silver nitrate solution is 0.2mol / L; and the carbon microspheres are TOB-HPC disordered mesoporous microspheres.

[0024] As a further aspect of the present invention: the ratio of the coupling agent, deionized water, anhydrous ethanol and silver-loaded antibacterial agent used in step b2 is 2-5 mL: 150-200 mL: 50 mL: 5-10 g; the coupling agent is silane coupling agent KH-560.

[0025] As a further embodiment of the present invention, the modified antistatic agent is prepared by the following steps:

[0026] Step c1: Add adipic acid and zinc oxide to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, react at 80-100℃ for 1 hour, add polyethylene glycol and esterification catalyst, heat to 150-180℃, purge with nitrogen for protection, stir and react for 3-4 hours to obtain intermediate 5.

[0027] Step c2: Diethylene terephthalate particles, polycondensation catalyst, trimethyl phosphate and antioxidant are added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser. The temperature is raised to 140°C and stirred for 1-2 hours. When the temperature is raised to 200°C, intermediate 5 is added. When the temperature rises to 250°C, a low vacuum is drawn and the pressure is reduced to 66.5 Pa. High vacuum polycondensation is carried out for 1-2 hours. After cooling to 25°C with deionized water, the modified antistatic agent is obtained.

[0028] As a further aspect of the present invention: the ratio of adipic acid, zinc oxide, polyethylene glycol and esterification catalyst in step c1 is 2-3 mol: 25-30 g: 2 mol: 0.05-0.1 mol; the polyethylene glycol is polyethylene glycol PEG-4000; and the esterification catalyst is p-toluenesulfonic acid.

[0029] As a further aspect of the present invention: the ratio of the diethylene terephthalate particles, polycondensation catalyst, trimethyl phosphate, antioxidant, and intermediate 5 in step c2 is 30g:15g:5g:5g:43g; the polycondensation catalyst is antimony trioxide; and the antioxidant is antioxidant 1010.

[0030] As a further aspect of the present invention: a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0031] Step 1: Weigh out 92-94 parts of modified PET, 1-2 parts of modified antibacterial agent, 1 part of titanium dioxide, and 3-5 parts of modified antistatic agent according to the weight ratio, and set aside.

[0032] Step 2: Add the modified antibacterial agent and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with modified PET and modified antistatic agent and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, antibacterial and antistatic PET chips for fiber are obtained.

[0033] The beneficial effects of this invention are:

[0034] This invention discloses a method for preparing antibacterial and antistatic PET chips for fiber use. The method involves ball milling a modified antibacterial agent and titanium dioxide in a ball mill, then mixing the mixture with modified PET and a modified antistatic agent, and extruding the mixture in a co-rotating twin-screw extruder. The resulting material is discharged, sliced, and dried to obtain the antibacterial and antistatic PET chips for fiber use. This preparation method uses modified PET as the main raw material. The modified PET has a large number of benzene rings, giving it excellent thermal stability and heat resistance. Copper ions have good antibacterial and bacteriostatic effects. By adding a modified antibacterial agent and titanium dioxide, the silver in the modified antibacterial agent and the titanium dioxide significantly improve the antibacterial and bacteriostatic functions of the material. The addition of a modified antistatic agent enhances the antistatic ability of the PET chips.

[0035] In the preparation of antibacterial and antistatic PET chips for fiber use, a modified PET was first prepared. Firstly, using dimethyl terephthalate and ethylene glycol as raw materials, the ester group of dimethyl terephthalate underwent an exchange reaction with the hydroxyl group of ethylene glycol to obtain intermediate 1. Then, using serine and di-tert-butyl dicarbonate as raw materials, the amino group on serine underwent a nucleophilic substitution reaction with the carbonyl oxygen group, and the tert-butyloxycarbonyl group acted as a protecting group to protect the amino group on serine while simultaneously introducing a tert-butyloxycarbonyl group, to obtain intermediate 2. Intermediate 2 was then exchanged with dimethyl terephthalate under a catalyst, with the ester group and hydroxyl group undergoing an exchange reaction to introduce a hydroxyl group and an amino group protected by the tert-butyloxycarbonyl group, to obtain intermediate 3. Intermediate 1 and intermediate 3 were then mixed and melt-polymerized. The hydroxyl group at one end of intermediate 1 underwent an exchange reaction with the ester group of intermediate 3, connecting them to a main chain. One end of the ester group is hydrolyzed to form a carboxyl group, which undergoes a polycondensation reaction with the hydroxyl group of the next intermediate 1. At the same time, the other end of the hydroxyl group of intermediate 3 undergoes a polycondensation reaction with the carboxyl group formed by the hydrolysis of the ester group of the next intermediate 3 to obtain intermediate 4. Intermediate 4 is mixed with trifluoroacetic acid to remove the amino protecting group, and copper sulfate pentahydrate is added. The carboxyl and amino groups with strong coordination ability undergo a complexation reaction with copper ions to obtain modified PET. The molecular structure of modified PET contains a large number of benzene rings and tert-butyloxycarbonyl groups, which endow it with excellent thermal stability and significantly improves its heat resistance. The larger the mass ratio of tert-butyloxycarbonyl groups, the more amino groups are on the copolyester. During the preparation of the complex, more metal ions can be captured, increasing the antibacterial properties. The carboxyl and amino groups complex with copper ions to introduce copper ions. Copper ions exert a bactericidal effect by destroying the bacterial cell wall and interfering with the metabolic process.

[0036] In the preparation of antibacterial and antistatic PET chips for fibers, a modified antibacterial agent was first prepared. Carbon microspheres were mixed with silver nitrate solution, and silver or silver oxide was adsorbed onto the surface of the carbon microspheres using an adsorption method, resulting in a silver-loaded antibacterial agent. The silver-loaded antibacterial agent was then modified using the silane coupling agent KH-560, which was grafted onto the surface of the silver-loaded antibacterial agent to obtain the modified antibacterial agent. The carbon microspheres have hydroxyl and carboxyl groups on their surface, which can improve the interfacial interaction between the antibacterial agent and the matrix material, and also enhance its dispersibility. The silver can bind to the cell membranes, cell walls, and intracellular proteins, enzymes, and other biomolecules of bacteria, fungi, and other microorganisms, interfering with their normal physiological functions, thereby playing an antibacterial and bacteriostatic role. The silane coupling agent KH-560 can improve the dispersibility and compatibility of the material, thereby improving its mechanical properties.

[0037] In the preparation of antibacterial and antistatic PET chips for fiber, a modified antistatic agent was first prepared. Adipic acid, zinc oxide, and polyethylene glycol were mixed and subjected to an esterification reaction to obtain polyethylene glycol adipate containing metal elements in the main chain. Then, it was mixed with diethylene glycol terephthalate particles and subjected to an ester exchange reaction to generate polyester ether, thus obtaining the modified antistatic agent. Zinc oxide migrated to the material surface to form a hydrophilic conductive network structure to reduce surface impedance. In the modified antistatic agent, the metal elements and macromolecules are combined by chemical bonds. The metal elements can increase the anisopolarity of the fiber raw material polymer and improve the antistatic performance. Due to the poor water solubility of polyester ether, the washability of the fiber can be improved. Detailed Implementation

[0038] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0039] Example 1:

[0040] This embodiment describes a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0041] Step S1: Add 0.5 mol of dimethyl terephthalate, 1 mol of ethylene glycol and 5 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and react at 160°C for 3 h in a constant temperature oil bath. Wash twice with deionized water and then place in a vacuum drying oven and dry at 50°C for 2 h to obtain intermediate 1.

[0042] Step S2: 36.4g serine alcohol, 95.9g ditert-butyl dicarbonate and 2.1g aminosulfonic acid were added to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was dissolved at 25°C for 1 hour, then heated to 40°C and stirred for 2 hours. The mixture was washed three times with deionized water, filtered, extracted with ethyl acetate and 15% sodium chloride solution, dried, filtered under reduced pressure, allowed to stand for 12 hours, rotary evaporated at 55°C, and then placed in a vacuum drying oven and vacuum dried at 40°C for 8 hours to obtain intermediate 2.

[0043] Step S3: Add 0.4 mol of dimethyl terephthalate, 0.8 mol of intermediate 2 and 4 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen and react in a constant temperature oil bath at 140°C for 3 h. Wash twice with deionized water and then place in a vacuum drying oven and dry at 40°C for 1 h to obtain intermediate 3.

[0044] Step S4: Add 75g of intermediate 1 and 5g of intermediate 3 to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection, raise the temperature to 240℃, stop purging with nitrogen, start the vacuum pump to control the vacuum degree to 800Pa, react for 1 hour, raise the temperature to 250℃ and react for 1 hour. Wash the product twice with methanol, then place it in a vacuum drying oven and dry it at 60℃ for 2 hours to obtain intermediate 4.

[0045] Step S5: Add 20g of intermediate 4 and 100mL of trifluoroacetic acid solution to a reagent dish, stir and react at 25℃ for 30min, add 50mL of methanol, filter after 1h, place in a vacuum drying oven and dry at 40℃ for 8h, add to a solution of 50mL of trifluoroacetic acid solution and 100mL of dichloromethane to dissolve, add 20mL of copper sulfate pentahydrate solution with a mass fraction of 1mg / mL, stir and react in a constant temperature water bath at 40℃ for 1h, add 50mL of methanol, precipitate and filter, wash 3 times with deionized water, place in a vacuum drying oven and dry for 8h to obtain modified PET, the mass fraction of trifluoroacetic acid solution is 20%;

[0046] Step S6: Add 5g of TOB-HPC disordered mesoporous microspheres and 100mL of deionized water to a beaker, place it in an ultrasonic disperser, and ultrasonically disperse for 30min. Wash and dry, then add it to a three-necked flask containing 200mL of 0.2mol / L silver nitrate solution. Adjust the pH to 8 with ammonia water, stir for 30min, keep warm at 50℃ for 3h, cool naturally to 25℃, centrifuge, wash the precipitate with deionized water, and dry in a constant temperature drying oven at 120℃ for 4h to obtain the silver-loaded antibacterial agent.

[0047] Step S7: Add 2 mL of silane coupling agent KH-560 and 150 mL of deionized water to a beaker, adjust the pH to 4 with glacial acetic acid, add 50 mL of anhydrous ethanol and 5 g of silver-loaded antibacterial agent, and place it in an ultrasonic disperser. After ultrasonic dispersion for 30 min, transfer it to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, and magnetically stir at 65 °C for 2 h. Cool to 25 °C, centrifuge, wash the precipitate with deionized water 1-2 times, and dry at 120 °C for 4 h to obtain the modified antibacterial agent.

[0048] Step S8: Add 2 mol adipic acid and 25 g zinc oxide to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, react at 80 °C for 1 h, add 2 mol polyethylene glycol PEG-4000 and 0.05 mol p-toluenesulfonic acid, heat to 150 °C, purge with nitrogen for protection, stir and react for 3 h to obtain intermediate 5;

[0049] Step S9: Add 30g of diethylene terephthalate granules, 15g of antimony trioxide, 5g of trimethyl phosphate and 5g of antioxidant 1010 to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser. When the temperature is raised to 140℃, stir for 1 hour. When the temperature is raised to 200℃, add 43g of intermediate 5. When the temperature is raised to 250℃, draw a low vacuum and reduce the pressure to 66.5Pa. Perform high vacuum polycondensation for 1 hour. After cooling to 25℃ with deionized water, the modified antistatic agent is obtained.

[0050] Step S10: Weigh out 92 parts of modified PET, 1 part of modified antibacterial agent, 1 part of titanium dioxide, and 3 parts of modified antistatic agent according to the weight ratio, and set aside.

[0051] Step S11: Add the modified antibacterial agent and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with the modified PET and modified antistatic agent and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, obtain antibacterial and antistatic PET chips for fiber.

[0052] Example 2:

[0053] This embodiment describes a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0054] Step S1: Add 0.8 mol of dimethyl terephthalate, 2 mol of ethylene glycol and 8 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and react at 180°C for 4 h in a constant temperature oil bath. Wash three times with deionized water and then place in a vacuum drying oven and dry at 50°C for 2 h to obtain intermediate 1.

[0055] Step S2: 36.4g serine alcohol, 95.9g ditert-butyl dicarbonate and 2.1g aminosulfonic acid were added to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was dissolved at 27°C for 1 hour, then heated to 40°C and stirred for 3 hours. The mixture was washed 4 times with deionized water, filtered, and extracted twice with ethyl acetate and 15% sodium chloride solution. The organic layer was dried, filtered under reduced pressure, and allowed to stand for 12 hours. The mixture was then rotary evaporated at 55°C and then placed in a vacuum drying oven and dried under vacuum at 40°C for 8 hours to obtain intermediate 2.

[0056] Step S3: Add 0.5 mol of dimethyl terephthalate, 1 mol of intermediate 2 and 6 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen and react in a constant temperature oil bath at 160°C for 4 h. Wash with deionized water 3 times and then place in a vacuum drying oven and dry at 40°C for 1 h to obtain intermediate 3.

[0057] Step S4: Add 85g of intermediate 1 and 15g of intermediate 3 to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection, raise the temperature to 250°C, stop purging with nitrogen, start the vacuum pump to control the vacuum degree to 900Pa, react for 2 hours, raise the temperature to 265°C and react for 2 hours. Wash the product three times with methanol, then place it in a vacuum drying oven and dry it at 60°C for 3 hours to obtain intermediate 4.

[0058] Step S5: Add 23g of intermediate 4 and 100mL of trifluoroacetic acid solution to a reagent dish, stir and react at 25℃ for 30min, add 50mL of methanol, filter after 1h, place in a vacuum drying oven and dry at 40℃ for 8h, add to a solution of 50mL of trifluoroacetic acid solution and 125mL of dichloromethane to dissolve, add 25mL of copper sulfate pentahydrate solution with a mass fraction of 1mg / mL, stir and react in a constant temperature water bath at 40℃ for 1h, add 50mL of methanol, precipitate and filter, wash 4 times with deionized water, place in a vacuum drying oven and dry for 8h to obtain modified PET, the mass fraction of trifluoroacetic acid solution is 20%;

[0059] Step S6: Add 8g of TOB-HPC disordered mesoporous microspheres and 125mL of deionized water to a beaker, place it in an ultrasonic disperser, and ultrasonically disperse for 30min. Wash and dry, then add it to a three-necked flask containing 200mL of 0.2mol / L silver nitrate solution. Adjust the pH to 8 with ammonia water, stir for 30min, keep warm at 50℃ for 5h, cool naturally to 25℃, centrifuge, wash the precipitate twice with deionized water, and dry in a constant temperature drying oven at 120℃ for 4h to obtain the silver-loaded antibacterial agent.

[0060] Step S7: Add 4 mL of silane coupling agent KH-560 and 175 mL of deionized water to a beaker, adjust the pH to 5 with glacial acetic acid, add 50 mL of anhydrous ethanol and 8 g of silver-loaded antibacterial agent, and place it in an ultrasonic disperser. After ultrasonic dispersion for 30 min, transfer it to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, and magnetically stir at 65 °C for 2 h. Cool to 25 °C, centrifuge, wash the precipitate twice with deionized water, and dry at 120 °C for 4 h to obtain the modified antibacterial agent.

[0061] Step S8: Add 3 mol adipic acid and 28 g zinc oxide to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, react at 90 °C for 1 h, add 2 mol polyethylene glycol PEG-4000 and 0.08 mol p-toluenesulfonic acid, raise the temperature to 165 °C, purge with nitrogen for protection, stir and react for 4 h to obtain intermediate 5;

[0062] Step S9: Add 30g of diethylene terephthalate granules, 15g of antimony trioxide, 5g of trimethyl phosphate and 5g of antioxidant 1010 to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser. When the temperature is raised to 140℃, stir for 2 hours. When the temperature is raised to 200℃, add 43g of intermediate 5. When the temperature is raised to 250℃, draw a low vacuum and reduce the pressure to 66.5Pa. Perform high vacuum polycondensation for 2 hours. After cooling to 25℃ with deionized water, the modified antistatic agent is obtained.

[0063] Step S10: Weigh out 93 parts of modified PET, 2 parts of modified antibacterial agent, 1 part of titanium dioxide, and 4 parts of modified antistatic agent according to the weight ratio, and set aside for later use;

[0064] Step S11: Add the modified antibacterial agent and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with the modified PET and modified antistatic agent and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, obtain antibacterial and antistatic PET chips for fiber.

[0065] Example 3:

[0066] This embodiment describes a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0067] Step S1: Add 1 mol of dimethyl terephthalate, 2 mol of ethylene glycol and 10 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and react at 200°C for 4 h in a constant temperature oil bath. Wash three times with deionized water and then place in a vacuum drying oven and dry at 50°C for 2 h to obtain intermediate 1.

[0068] Step S2: 36.4g serine, 95.9g ditert-butyl dicarbonate and 2.1g aminosulfonic acid were added to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was dissolved at 28°C for 1 hour, then heated to 40°C and stirred for 4 hours. The mixture was washed four times with deionized water, filtered, extracted twice with ethyl acetate and 15% sodium chloride solution, dried the organic layer, filtered under reduced pressure, allowed to stand for 12 hours, and then rotary evaporated at 55°C. After that, it was placed in a vacuum drying oven and vacuum dried at 40°C for 8 hours to obtain intermediate 2.

[0069] Step S3: Add 0.6 mol of dimethyl terephthalate, 1.2 mol of intermediate 2 and 8 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen and react in a constant temperature oil bath at 180°C for 4 h. Wash with deionized water 3 times and then place in a vacuum drying oven and dry at 40°C for 1 h to obtain intermediate 3.

[0070] Step S4: Add 100g of intermediate 1 and 25g of intermediate 3 to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection, raise the temperature to 260°C, stop purging with nitrogen, start the vacuum pump to control the vacuum degree to 1000Pa, react for 2 hours, raise the temperature to 280°C and react for 2 hours. Wash the product three times with methanol, then place it in a vacuum drying oven and dry it at 60°C for 3 hours to obtain intermediate 4.

[0071] Step S5: Add 25g of intermediate 4 and 100mL of trifluoroacetic acid solution to a reagent dish, stir and react at 25℃ for 30min, add 50mL of methanol, filter after 1h, place in a vacuum drying oven and dry at 40℃ for 8h, add to a solution of 50mL of trifluoroacetic acid solution and 150mL of dichloromethane to dissolve, add 30mL of copper sulfate pentahydrate solution with a mass fraction of 1mg / mL, stir and react in a constant temperature water bath at 40℃ for 1h, add 50mL of methanol, precipitate and filter, wash 4 times with deionized water, place in a vacuum drying oven and dry for 8h to obtain modified PET, the mass fraction of trifluoroacetic acid solution is 20%;

[0072] Step S6: Add 10g of TOB-HPC disordered mesoporous microspheres and 150mL of deionized water to a beaker, place it in an ultrasonic disperser, and ultrasonically disperse for 30min. Wash and dry, then add it to a three-necked flask containing 200mL of 0.2mol / L silver nitrate solution. Adjust the pH to 8 with ammonia water, stir for 30min, keep warm at 50℃ for 7h, cool naturally to 25℃, centrifuge, wash the precipitate twice with deionized water, and dry in a constant temperature drying oven at 120℃ for 4h to obtain the silver-loaded antibacterial agent.

[0073] Step S7: Add 5 mL of silane coupling agent KH-560 and 200 mL of deionized water to a beaker, adjust the pH to 5 with glacial acetic acid, add 50 mL of anhydrous ethanol and 10 g of silver-loaded antibacterial agent, and place it in an ultrasonic disperser. After ultrasonic dispersion for 30 min, transfer it to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, and magnetically stir at 65 °C for 2 h. Cool to 25 °C, centrifuge, wash the precipitate twice with deionized water, and dry at 120 °C for 4 h to obtain the modified antibacterial agent.

[0074] Step S8: Add 3 mol adipic acid and 30 g zinc oxide to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, react at 100℃ for 1 h, add 2 mol polyethylene glycol PEG-4000 and 0.1 mol p-toluenesulfonic acid, heat to 180℃, purge with nitrogen for protection, stir and react for 3-4 h to obtain intermediate 5;

[0075] Step S9: Add 30g of diethylene terephthalate granules, 15g of antimony trioxide, 5g of trimethyl phosphate and 5g of antioxidant 1010 to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser. When the temperature is raised to 140℃, stir for 2 hours. When the temperature is raised to 200℃, add 43g of intermediate 5. When the temperature is raised to 250℃, draw a low vacuum and reduce the pressure to 66.5Pa. Perform high vacuum polycondensation for 2 hours. After cooling to 25℃ with deionized water, the modified antistatic agent is obtained.

[0076] Step S10: Weigh out 94 parts of modified PET, 2 parts of modified antibacterial agent, 1 part of titanium dioxide, and 5 parts of modified antistatic agent according to the weight ratio, and set aside.

[0077] Step S11: Add the modified antibacterial agent and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with the modified PET and modified antistatic agent and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, obtain antibacterial and antistatic PET chips for fiber.

[0078] Comparative Example 1:

[0079] This comparative example illustrates a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0080] Step S1: Weigh out 3 parts of PET RE150229, 2 parts of antibacterial agent AEM5700-A2, 1 part of titanium dioxide, and 4 parts of antistatic agent JL-AS-55 according to the weight ratio, and set aside.

[0081] Step S2: Add antibacterial agent AEM5700-A2 and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with PET RE15022 and antistatic agent JL-AS-55 and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, antibacterial and antistatic PET chips for fiber are obtained.

[0082] Comparative Example 2:

[0083] This comparative example illustrates a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0084] Step S1: Add 0.8 mol of dimethyl terephthalate, 2 mol of ethylene glycol and 8 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and react at 180°C for 4 h in a constant temperature oil bath. Wash three times with deionized water and then place in a vacuum drying oven and dry at 50°C for 2 h to obtain intermediate 1.

[0085] Step S2: 36.4g serine alcohol, 95.9g ditert-butyl dicarbonate and 2.1g aminosulfonic acid were added to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. The mixture was dissolved at 27°C for 1 hour, then heated to 40°C and stirred for 3 hours. The mixture was washed 4 times with deionized water, filtered, and extracted twice with ethyl acetate and 15% sodium chloride solution. The organic layer was dried, filtered under reduced pressure, and allowed to stand for 12 hours. The mixture was then rotary evaporated at 55°C and then placed in a vacuum drying oven and dried under vacuum at 40°C for 8 hours to obtain intermediate 2.

[0086] Step S3: Add 0.5 mol of dimethyl terephthalate, 1 mol of intermediate 2 and 6 g of manganese acetate to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen and react in a constant temperature oil bath at 160°C for 4 h. Wash with deionized water 3 times and then place in a vacuum drying oven and dry at 40°C for 1 h to obtain intermediate 3.

[0087] Step S4: Add 85g of intermediate 1 and 15g of intermediate 3 to a four-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection, raise the temperature to 250°C, stop purging with nitrogen, start the vacuum pump to control the vacuum degree to 900Pa, react for 2 hours, raise the temperature to 265°C and react for 2 hours. Wash the product three times with methanol, then place it in a vacuum drying oven and dry it at 60°C for 3 hours to obtain intermediate 4.

[0088] Step S5: Add 23g of intermediate 4 and 100mL of trifluoroacetic acid solution to a reagent dish, stir and react at 25℃ for 30min, add 50mL of methanol, filter after 1h, place in a vacuum drying oven and dry at 40℃ for 8h, add to a solution of 50mL of trifluoroacetic acid solution and 125mL of dichloromethane to dissolve, add 25mL of copper sulfate pentahydrate solution with a mass fraction of 1mg / mL, stir and react in a constant temperature water bath at 40℃ for 1h, add 50mL of methanol, precipitate and filter, wash 4 times with deionized water, place in a vacuum drying oven and dry for 8h to obtain modified PET, the mass fraction of trifluoroacetic acid solution is 20%;

[0089] Step S6: Add 8g of TOB-HPC disordered mesoporous microspheres and 125mL of deionized water to a beaker, place it in an ultrasonic disperser, and ultrasonically disperse for 30min. Wash and dry, then add it to a three-necked flask containing 200mL of 0.2mol / L silver nitrate solution. Adjust the pH to 8 with ammonia water, stir for 30min, keep warm at 50℃ for 5h, cool naturally to 25℃, centrifuge, wash the precipitate twice with deionized water, and dry in a constant temperature drying oven at 120℃ for 4h to obtain the silver-loaded antibacterial agent.

[0090] Step S7: Add 4 mL of silane coupling agent KH-560 and 175 mL of deionized water to a beaker, adjust the pH to 5 with glacial acetic acid, add 50 mL of anhydrous ethanol and 8 g of silver-loaded antibacterial agent, and place it in an ultrasonic disperser. After ultrasonic dispersion for 30 min, transfer it to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, and magnetically stir at 65 °C for 2 h. Cool to 25 °C, centrifuge, wash the precipitate twice with deionized water, and dry at 120 °C for 4 h to obtain the modified antibacterial agent.

[0091] Step S8: Weigh out 93 parts of modified PET, 2 parts of modified antibacterial agent, 1 part of titanium dioxide, and 4 parts of antistatic agent JL-AS-55 according to the weight ratio, and set aside.

[0092] Step S9: Add the modified antibacterial agent and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with modified PET and antistatic agent JL-AS-55 and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, obtain antibacterial and antistatic PET chips for fiber.

[0093] Comparative Example 3:

[0094] This comparative example illustrates a method for preparing antibacterial and antistatic PET chips for fibers, comprising the following steps:

[0095] Step S1: Add 3 mol adipic acid and 28 g zinc oxide to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, react at 90 °C for 1 h, add 2 mol polyethylene glycol PEG-4000 and 0.08 mol p-toluenesulfonic acid, raise the temperature to 165 °C, purge with nitrogen for protection, stir and react for 4 h to obtain intermediate 5;

[0096] Step S2: Add 30g of diethylene terephthalate granules, 15g of antimony trioxide, 5g of trimethyl phosphate and 5g of antioxidant 1010 to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser. When the temperature is raised to 140℃, stir for 2 hours. When the temperature is raised to 200℃, add 43g of intermediate 5. When the temperature is raised to 250℃, draw a low vacuum and reduce the pressure to 66.5Pa. Perform high vacuum polycondensation for 2 hours. After cooling to 25℃ with deionized water, the modified antistatic agent is obtained.

[0097] Step S3: Weigh out 3 parts of PET RE150229, 2 parts of antibacterial agent AEM5700-A2, 1 part of titanium dioxide, and 4 parts of modified antistatic agent according to the weight ratio, and set aside.

[0098] Step S4: Add the antibacterial agent AEM5700-A2 and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with PET RE15022 and modified antistatic agent and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, obtain antibacterial and antistatic PET chips for fiber.

[0099] The antibacterial and antistatic properties of the fibers from Examples 1-3 and Comparative Examples 1-3 were tested using antibacterial and antistatic PET slices according to GB / T31402-2023 standard. A surface resistivity meter was used to measure the electrostatic impedance value, and an electrostatic voltage meter was used to detect the surface voltage generated by friction. The test results are shown in the table below:

[0100]

[0101] Referring to the table above, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the antibacterial performance of the materials with modified PET and modified antibacterial agents is significantly improved, and the electrostatic resistance and surface voltage of the materials with modified antistatic agents are significantly lower, indicating excellent antistatic performance.

[0102] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0103] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A type of antibacterial and antistatic PET chip for fibers, characterized in that, Includes the following components by weight: 92-94 parts modified PET, 1-2 parts modified antibacterial agent, 1 part titanium dioxide, 3-5 parts modified antistatic agent; The modified PET is prepared by the following steps: Step a1: Dimethyl terephthalate, ethylene glycol and catalyst were added to a four-necked flask, nitrogen gas was introduced for protection, and the mixture was reacted in a constant temperature oil bath. After washing, it was placed in a vacuum drying oven and dried to obtain intermediate 1. Step a2: Add serine alcohol, ditert-butyl dicarbonate and reaction catalyst to a four-necked flask, dissolve, stir and react, wash, filter, extract with ethyl acetate and sodium chloride solution respectively, dry the organic layer, filter under reduced pressure, let stand, rotary evaporate, and then place in a vacuum drying oven to dry under vacuum to obtain intermediate 2. Step a3: Dimethyl terephthalate, intermediate 2 and catalyst are added to a four-necked flask, nitrogen gas is introduced for protection, and the mixture is reacted in a constant temperature oil bath. After washing, it is placed in a vacuum drying oven to dry, and intermediate 3 is obtained. Step a4: Add intermediate 1 and intermediate 3 to a four-necked flask, purge with nitrogen for protection, raise the temperature to 240-260℃, stop purging with nitrogen, start the vacuum pump to react, raise the temperature to 250-280℃ and react, wash, and then place in a vacuum drying oven to dry to obtain intermediate 4. Step a5: Add 2 / 3 of the trifluoroacetic acid solution of intermediate 4 to a reagent dish, stir to react, add 1 / 2 of the precipitant, filter and place in a vacuum drying oven to dry, add to the remaining 1 / 3 of the trifluoroacetic acid solution and dichloromethane solution to dissolve, add copper sulfate pentahydrate solution, stir to react in a constant temperature water bath, add the remaining 1 / 2 of the precipitant, precipitate and filter, wash with deionized water, and place in a vacuum drying oven to dry to obtain modified PET.

2. The antibacterial and antistatic PET chip for fibers according to claim 1, characterized in that, In step a1, the ratio of dimethyl terephthalate, ethylene glycol, and catalyst is 0.5-1 mol: 1-2 mol: 5-10 g; the catalyst is one of manganese acetate and titanate. In step a2, the ratio of serinel, di-tert-butyl dicarbonate, and reaction catalyst is 36.4 g: 95.9 g: 2.1 g; the reaction catalyst is aminosulfonic acid; and the mass fraction of the sodium chloride solution is 15%.

3. The antibacterial and antistatic PET chip for fibers according to claim 1, characterized in that, In step a3, the ratio of dimethyl terephthalate, intermediate 2, and catalyst is 0.4-0.6 mol: 0.8-1.2 mol: 4-8 g; the catalyst is one of manganese acetate and titanate. In step a4, the ratio of intermediate 1 and intermediate 3 is 75-100 g: 5-25 g. In step a5, the ratio of intermediate 4, trifluoroacetic acid solution, precipitant, dichloromethane, and copper sulfate pentahydrate solution is 20-25 g: 150 mL: 100 mL: 100-150 mL: 20-30 mL; the mass fraction of the trifluoroacetic acid solution is 20%; the mass fraction of the copper phosphate pentahydrate solution is 1 mg / mL; the precipitant is methanol.

4. The antibacterial and antistatic PET chip for fibers according to claim 1, characterized in that, The modified antibacterial agent is prepared by the following steps: Step b1: Add carbon microspheres and deionized water to a beaker, place it in an ultrasonic disperser, ultrasonically disperse for 30 min, wash and dry, then add it to a three-necked flask containing silver nitrate solution, adjust the pH to 8 with ammonia, stir for 30 min, keep warm at 50℃ for 3-7 h, cool naturally to 25℃, centrifuge, wash the precipitate 1-2 times with deionized water, and dry in a constant temperature drying oven at 120℃ for 4 h to obtain silver-loaded antibacterial agent; Step b2: Add the coupling agent and deionized water to a beaker, adjust the pH to 4-5 with glacial acetic acid, add anhydrous ethanol and silver-loaded antibacterial agent, and place it in an ultrasonic disperser. After ultrasonic dispersion for 30 minutes, transfer it to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, and magnetically stir at 65°C for 2 hours. Cool to 25°C, centrifuge, wash the precipitate 1-2 times with deionized water, and dry at 120°C for 4 hours to obtain the modified antibacterial agent.

5. The antibacterial and antistatic PET chip for fibers according to claim 4, characterized in that, In step b1, the ratio of carbon microspheres, deionized water, and silver nitrate solution is 5-10g:100-150mL:200mL; the mass fraction of the silver nitrate solution is 0.2mol / L; the carbon microspheres are TOB-HPC disordered mesoporous microspheres. In step b2, the ratio of coupling agent, deionized water, anhydrous ethanol, and silver-loaded antibacterial agent is 2-5mL:150-200mL:50mL:5-10g; the coupling agent is silane coupling agent KH-560.

6. The antibacterial and antistatic PET chip for fibers according to claim 1, characterized in that, The modified antistatic agent is prepared by the following steps: Step c1: Add adipic acid and zinc oxide to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser, react at 80-100℃ for 1 hour, add polyethylene glycol and esterification catalyst, heat to 150-180℃, purge with nitrogen for protection, stir and react for 3-4 hours to obtain intermediate 5. Step c2: Diethylene terephthalate particles, polycondensation catalyst, trimethyl phosphate and antioxidant are added to a three-necked flask equipped with a stirrer, thermometer, gas delivery tube and reflux condenser. The temperature is raised to 140°C and stirred for 1-2 hours. When the temperature is raised to 200°C, intermediate 5 is added. When the temperature rises to 250°C, a low vacuum is drawn and the pressure is reduced to 66.5 Pa. High vacuum polycondensation is carried out for 1-2 hours. After cooling to 25°C with deionized water, the modified antistatic agent is obtained.

7. The antibacterial and antistatic PET chip for fibers according to claim 6, characterized in that, In step c1, the ratio of adipic acid, zinc oxide, polyethylene glycol, and esterification catalyst is 2-3 mol: 25-30 g: 2 mol: 0.05-0.1 mol; the polyethylene glycol is polyethylene glycol PEG-4000; and the esterification catalyst is p-toluenesulfonic acid.

8. The antibacterial and antistatic PET chip for fibers according to claim 6, characterized in that, In step c2, the ratio of diethylene terephthalate particles, polycondensation catalyst, trimethyl phosphate, antioxidant, and intermediate 5 is 30g:15g:5g:5g:43g; the polycondensation catalyst is antimony trioxide; and the antioxidant is antioxidant 1010.

9. A method for preparing an antibacterial and antistatic PET chip for fibers as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Weigh out 92-94 parts of modified PET, 1-2 parts of modified antibacterial agent, 1 part of titanium dioxide, and 3-5 parts of modified antistatic agent according to the weight ratio, and set aside. Step 2: Add the modified antibacterial agent and titanium dioxide to a ball mill and ball mill at 2000 r / min for 30 min. Mix with modified PET and modified antistatic agent and add to a co-rotating twin-screw extruder for extrusion. After discharge, slicing and drying, antibacterial and antistatic PET chips for fiber are obtained.

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