Preparation method of polyester fiber fabric

Abstract

The application relates to the technical field of polyester fibers, and discloses a polyester fiber fabric preparation method, which takes N,N'-bis(2-hydroxyethyl)ethylenediamine, N,N'-di-Boc-S-methyl isothiourea and the like as raw materials, and is subjected to esterification polycondensation reaction with dimethyl terephthalate to obtain a waterproof antibacterial copolyester polymer with a similar structure to PET polyester; the waterproof antibacterial copolyester polymer contains quaternary ammonium salt, guanidine and a hydrophobic long-chain structure in the structure, can be uniformly distributed in a polyester fiber matrix, migration of antibacterial groups is avoided, and the antibacterial performance on bacteria is better; the C-F bond energy is high, fluorine atoms are more easily embedded into the polymer, the channel for water molecules to migrate to the inside of the coating is blocked, a stable protective layer can be formed on the surface of the fiber fabric, the fiber is wrapped, water permeation into the fiber is prevented, and thus the waterproof effect is achieved; meanwhile, the hydrophobic layer also has certain durability and can withstand multiple water washes without failure.

Description

[0001] The present application is a divisional application of application number 2024114045976, filed on October 10, 2024, with the title of "A waterproof and antibacterial polyester fiber fabric and its preparation method". TECHNICAL FIELD

[0002] The present application relates to the technical field of polyester fiber, in particular to a preparation method of polyester fiber fabric. BACKGROUND

[0003] Polyester, also known as PET (polyethylene terephthalate) fiber, is obtained by spinning polyester synthesized from organic diacid and dihydric alcohol, and has the advantages of good wrinkle resistance and shape retention, high strength, strong elastic recovery ability, etc., and is durable, wrinkle-resistant, and easy to care for, and can be spun alone or blended with other fibers, so it is widely used in clothing, home textiles, decoration and industry; However, polyester fiber also has some inherent shortcomings, especially in terms of waterproof and antibacterial performance; The growth of microorganisms such as bacteria on polyester fiber due to sweat or moisture provides suitable conditions for the growth of microorganisms, and the attachment of bacteria and other microorganisms on the fabric forms a biofilm that is difficult to remove, which endangers human health; Therefore, it is urgent to develop a polyester fiber fabric with waterproof and antibacterial functions.

[0004] The chemical structure of polyester fiber is stable and not easy to react with chemical reagents such as acid and alkali, and the surface of polyester fiber is smooth and not easy to adsorb antibacterial agents; The antibacterial agents currently applied to fiber products are divided into three categories: inorganic antibacterial agents represented by silver nanoparticles have excellent antibacterial effect, but have the disadvantages of high price, weak adhesion, poor durability, etc., and some inorganic antibacterial agents also pose a safety hazard to the human body due to their own toxicity; Natural antibacterial agents derived from cyclodextrin and chitosan have poor thermal stability, complicated processing process, and are difficult to use for a long time and mass production; Organic synthetic antibacterial agents based on polyethylene imine and alkyl guanidine are limited in practical production and application due to poor heat resistance and complex finishing process.

[0005] The polyester fiber itself does not have waterproof performance, the linear molecules and no large branch in the molecular structure, and the lack of hydrophilic groups make the moisture absorption performance of the polyester fiber poor, and the swelling performance in water is also poor, the structural characteristics determine that the polyester fiber is not easy to form an effective waterproof layer when encountering moisture, thereby being easy to penetrate water; Patent No. CN118087074A discloses an antibacterial polyester fiber and a preparation method thereof, by synthesizing quaternary ammonium salt-ester polymer modified chitosan, the hydrophilicity of the polyester fiber and its fabric can be effectively improved, the moisture absorption and moisture regain are obviously improved, and the quaternary ammonium salt antibacterial group is uniformly distributed in the polyester fiber matrix, which significantly improves the antibacterial performance of the polyester fiber fabric on escherichia coli and staphylococcus aureus, but the waterproof performance of the fiber fabric is not obviously improved, and only contains a single quaternary ammonium salt antibacterial group, and the antibacterial effect is limited; The present application aims to introduce organic fluorine long chain, quaternary ammonium salt and guanidine compound into the diol structure by using the principle that the fluorine atom in organic fluorine is easy to embed into the polymer and block the channel of water molecules migrating to the inside of the coating film, and esterification with dimethyl terephthalate to obtain a polyester fiber fabric after melt spinning, the quaternary ammonium salt and guanidine group are used to synergistically inhibit bacteria, so that the prepared polyester fiber has waterproof and antibacterial properties. SUMMARY

[0006] The purpose of the present application is to solve the problems existing in the prior art, and to provide a waterproof and antibacterial polyester fiber fabric and a preparation method thereof, a polyester fiber fabric with good waterproof performance and good antibacterial performance is prepared, and the application range is widened.

[0007] The present application is realized by the following technical scheme:

[0008] A preparation method of a waterproof and antibacterial polyester fiber fabric comprises the following steps:

[0009] Step (1), under a nitrogen atmosphere, dimethyl terephthalate, bisguanidine alcohol quaternary ammonium salt perfluoro intermediate are added to a reaction flask, heated to melt the raw materials, zinc acetate is added, heated to 210-225 DEG C, ester exchange reaction is carried out for 3-6 h, antimony glycol is added, the temperature is raised to 270-290 DEG C, the pressure is reduced to 80-100 Pa, and the reaction is carried out for 1-3 h, and then cooled to room temperature, dried to obtain a waterproof and antibacterial copolyester polymer.

[0010] Step (2), the vacuum dried PET polyester chip and the waterproof and antibacterial copolyester polymer are placed in a double screw extruder for melt blending, extrusion granulation, and then melt spinning is carried out on a high speed composite spinning machine, the spinning speed is 800-1200 m / min, the spinning machine temperature is 260-290 DEG C, after the nascent fiber is balanced, stretching and winding are carried out on a parallel stretching machine to form a waterproof and antibacterial polyester fiber fabric.

[0011] Further, the ratio of dimethyl terephthalate, bisguanidine alcohol quaternary ammonium salt perfluoro intermediate, zinc acetate, and ethylene glycol antimony in step (1) is 1 mol:(0.95-1.1) mol:(0.003-0.005) mol:(0.008-0.012) mol.

[0012] Further, the ratio of PET polyester chip and waterproof antibacterial copolyester polymer in step (2) is 100 g:(5-25) g.

[0013] Further, the screw temperature of the double screw extruder in step (2) is 240-260°C, and the screw rotation speed is set to 25-40 r / min; the heat roller temperature of the drawing machine is 80-90°C, the drawing speed is 300-400 m / min, and the drawing multiple is 5.5-6.5.

[0014] Further, the preparation method of the bisguanidine alcohol quaternary ammonium salt perfluoro intermediate in step (1) comprises the following steps:

[0015] Step S1, under a nitrogen atmosphere, N,N'-bis(2-hydroxyethyl)ethylenediamine and dichloromethane are added to a reaction flask, stirred uniformly, then N,N-diisopropylethylamine and N,N'-bis(2-hydroxyethyl)ethylenediamine are added, stirred and reacted, after the reaction is completed, reduced pressure concentration, column chromatography purification, to obtain a bisguanidine alcohol tertiary amine intermediate. The preparation reaction formula is as follows:

[0016]

[0017] Step S2, under a nitrogen atmosphere, bisguanidine alcohol tertiary amine intermediate and N,N-dimethylformamide are added to a reaction flask, stirred uniformly, then perfluorodecyl ethyl iodine is added, stirred and reacted, after the reaction is completed, reduced pressure concentration, dried to obtain a bisguanidine alcohol quaternary ammonium salt perfluoro intermediate. The preparation reaction formula is as follows:

[0018]

[0019] Further, the ratio of N,N'-bis(2-hydroxyethyl)ethylenediamine, N,N-diisopropylethylamine, and N,N'-di-Boc-S-methyl isothiourea in step S1 is 1 mol:(2.5-3.5) mol:(2.05-2.2) mol.

[0020] Further, the reaction temperature in step S1 is 20-35°C, and the reaction time is 8-16 h.

[0021] Further, the ratio of bisguanidine alcohol tertiary amine intermediate and perfluorodecyl ethyl iodine in step S2 is 1 mol:(2.3-2.8) mol.

[0022] Further, the reaction temperature in step S2 is 110-130 DEG C, and the reaction time is 24-48 hours.

[0023] Compared with the prior art, the application has the following advantages:

[0024] The application firstly utilizes N,N'-bis(2-hydroxyethyl)ethylenediamine to react with N,N'-di-Boc-S-methyl isothiourea under the action of N,N-diisopropylethylamine to obtain a biguanide tertiary amine intermediate, then undergoes quaternary ammonium reaction with perfluorodecyl ethyl iodine to obtain a perfluoro intermediate of quaternary ammonium salt of biguanide tertiary amine, then undergoes esterification and polycondensation reaction with dimethyl terephthalate to obtain a waterproof and antibacterial copolyester polymer, and finally undergoes melt spinning with PET polyester chips to obtain a waterproof and antibacterial polyester fiber fabric.

[0025] The waterproof and antibacterial copolyester polymer contains quaternary ammonium salt, guanidino group and hydrophobic long chain structure, wherein the quaternary ammonium salt is adsorbed on the cell wall through electrostatic force, hydrogen bond force and the like, hinders the action of cell lysozyme, destroys the structure of the cell surface layer, and causes the basic function of the cell membrane to be affected; the guanidino group can destroy the biological activity of phospholipid and the structure of the cell membrane, rapidly adsorb on the negatively charged bacterial cell membrane, and exchange ions with the cations in the cell membrane, thereby increasing the permeability of the cell membrane and causing the substances in the cell to leak out; the hydrophobic long chain is inlaid on the surface of the bacteria and combined with the phospholipid bilayer in the cell membrane, thereby producing a chamber blocking effect and blocking the exchange of substances between the inside and outside of the cell, and finally killing the bacteria.

[0026] The waterproof and antibacterial copolyester polymer has a similar structure to PET polyester, and the two have good compatibility, so that the copolymer containing quaternary ammonium salt and guanidino antibacterial group can be uniformly distributed in the polyester fiber matrix, migration of the antibacterial group is avoided, and the antibacterial performance on bacteria is better; the C-F bond in the waterproof and antibacterial copolyester polymer has high energy, and compared with hydrogen atoms, fluorine atoms are more easily inlaid in the polymer, thereby blocking the channel for water molecules to migrate to the inside of the coating, forming a stable protective layer on the surface of the fiber fabric, wrapping the fiber, preventing water from penetrating into the fiber, and thus playing a waterproof role; in addition, the alkyl long chain provides a hydrophobic group, which can construct a uniform polymer network hydrophobic layer on the surface of the fiber, reduce the surface free energy of the fiber, and limit the diffusion and penetration of water droplets on the fiber fabric; at the same time, the hydrophobic layer also has certain durability and can withstand multiple washes without failure. DETAILED DESCRIPTION

[0027] In order to more clearly understand the above objectives, features and advantages of the present application, the application will be further described in detail below with specific embodiments. It should be noted that the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

[0028] The starting materials and reagents used in this application are commercially available or can be prepared by known methods unless otherwise stated.

[0029] N,N'-bis(2-hydroxyethyl)ethylenediamine, CAS No. 4439-20-7.

[0030] N,N'-di-Boc-S-methylisothiourea, CAS No. 107819-90-9.

[0031] Perfluorodecyl ethyl iodide, CAS No. 2043-54-1.

[0032] Example 1

[0033] (1) Under a nitrogen atmosphere, 85 mmol of N,N'-bis(2-hydroxyethyl)ethylenediamine and 680 mL of dichloromethane were added to a reaction flask, stirred uniformly, then 255 mmol of N,N-diisopropylethylamine and 180.2 mmol of N,N'-di-Boc-S-methylisothiourea were added, reacted at 25°C for 12 h, concentrated under reduced pressure, and purified by column chromatography (volume ratio of n-hexane and ethyl acetate was 2:1) to obtain a biguanide alcohol tertiary amine intermediate.

[0034] (2) Under a nitrogen atmosphere, 80 mmol of the biguanide alcohol tertiary amine intermediate and 1200 mL of N,N-dimethylformamide were added to a reaction flask, stirred uniformly, then 200 mmol of perfluorodecyl ethyl iodide was added, reacted at 120°C for 32 h, concentrated under reduced pressure, and dried to obtain a biguanide alcohol quaternary ammonium salt perfluoro intermediate.

[0035] (3) Under a nitrogen atmosphere, 10 mmol of dimethyl terephthalate and 9.5 mol of the biguanide alcohol quaternary ammonium salt perfluoro intermediate were added to a reaction flask, heated to melt the raw material, 0.04 mmol of zinc acetate was added, heated to 215°C, and transesterification was carried out for 5 h, 0.09 mmol of ethylene glycol antimony was added, the temperature was raised to 280°C, and the pressure was reduced to 90 Pa for 2 h, cooled to room temperature, and dried to obtain a waterproof antibacterial copolyester polymer.

[0036] (4) 100 g of PET polyester chips and 5 g of the waterproof antibacterial copolyester polymer after vacuum drying were melt blended in a twin-screw extruder, extruded and granulated, the screw temperature of the twin-screw extruder was 250°C, and the screw rotation speed was set to 30 r / min, then melt spinning was carried out on a high-speed composite spinning machine, the spinning speed was 1000 m / min, the spinning machine temperature was 280°C, after the nascent fiber was balanced, drawing and winding were carried out on a parallel drawing machine, the hot roller temperature of the drawing machine was 85°C, the drawing speed was 350 m / min, and the drawing multiple was 6, to obtain a waterproof antibacterial polyester fiber fabric.

[0037] Example 2

[0038] (1) Under nitrogen atmosphere, 120 mmol of N,N'-bis(2-hydroxyethyl)ethylenediamine and 600 mL of dichloromethane were added to a reaction flask, stirred uniformly, 300 mmol of N,N-diisopropylethylamine and 246 mmol of N,N'-di-Boc-S-methyl isothiourea were added, reacted at 35°C for 8 h, concentrated under reduced pressure, and purified by column chromatography (volume ratio of n-hexane and ethyl acetate was 2:1) to obtain a biguanide alcohol tertiary amine intermediate.

[0039] (2) Under nitrogen atmosphere, 110 mmol of biguanide alcohol tertiary amine intermediate and 1320 mL of N,N-dimethylformamide were added to a reaction flask, stirred uniformly, 253 mmol of perfluorodecyl ethyl iodine was added, reacted at 130°C for 24 h, concentrated under reduced pressure, and dried to obtain a biguanide alcohol quaternary ammonium salt perfluoro intermediate.

[0040] (3) Under nitrogen atmosphere, 10 mmol of dimethyl terephthalate and 10 mol of biguanide alcohol quaternary ammonium salt perfluoro intermediate were added to a reaction flask, heated to melt the raw material, 0.03 mmol of zinc acetate was added, and ester exchange reaction was carried out at 225°C for 3 h, 0.08 mmol of ethylene glycol antimony was added, and the temperature was increased to 270°C and reacted under reduced pressure of 100 Pa for 1 h, and then cooled to room temperature, and dried to obtain a waterproof antibacterial copolyester polymer.

[0041] (4) 100 g of PET polyester chips and 10 g of waterproof antibacterial copolyester polymer after vacuum drying were melt blended in a twin-screw extruder, extruded and granulated, the screw temperature of the twin-screw extruder was 260°C, and the screw rotation speed was set to 40 r / min, then melt spinning was carried out on a high-speed composite spinning machine, the spinning speed was 1200 m / min, the spinning machine temperature was 290°C, after the nascent fiber was balanced, drawing and winding were carried out on a parallel drawing machine, the hot roller temperature of the drawing machine was 90°C, the drawing speed was 400 m / min, and the drawing multiple was 6.5, to obtain a waterproof antibacterial polyester fiber fabric.

[0042] Example 3

[0043] (1) Under nitrogen atmosphere, 60 mmol of N,N'-bis(2-hydroxyethyl)ethylenediamine and 600 mL of dichloromethane were added to a reaction flask, stirred uniformly, 210 mmol of N,N-diisopropylethylamine and 132 mmol of N,N'-di-Boc-S-methyl isothiourea were added, reacted at 20°C for 16 h, concentrated under reduced pressure, and purified by column chromatography (volume ratio of n-hexane and ethyl acetate was 2:1) to obtain a biguanide alcohol tertiary amine intermediate.

[0044] (2) Under nitrogen atmosphere, 50 mmol of the diguanidol tertiary amine intermediate and 1000 mL of N,N-dimethylformamide were added into a reaction flask, after stirring uniformly, 140 mmol of perfluorodecyl ethyl iodine was added, and the reaction was carried out at 110°C for 48 h, and then concentrated under reduced pressure, and dried to obtain the diguanidol quaternary ammonium salt perfluoro intermediate.

[0045] (3) Under nitrogen atmosphere, 40 mmol of dimethyl terephthalate, 42 mol of the diguanidol quaternary ammonium salt perfluoro intermediate were added into a reaction flask, and heated to melt the raw material, 0.2 mmol of zinc acetate was added, and the ester exchange reaction was carried out at 210°C for 6 h, 0.48 mmol of ethylene glycol antimony was added, and the reaction was carried out at 270°C under 8 Pa for 3 h, and then cooled to room temperature, and dried to obtain the waterproof antibacterial copolyester polymer.

[0046] (4) 100 g of PET polyester chips and 15 g of waterproof antibacterial copolyester polymer after vacuum drying were placed in a twin-screw extruder for melt blending, and then extruded and granulated, the screw temperature of the twin-screw extruder was 240°C, and the screw rotation speed was set to 25 r / min, and then melt spinning was carried out on a high-speed composite spinning machine, the spinning speed was 800 m / min, the spinning machine temperature was 260°C, after the nascent fiber was balanced, drawing and winding were carried out on a parallel drawing machine, the hot roller temperature of the drawing machine was 80°C, the drawing speed was 300 m / min, and the drawing multiple was 5.5, to obtain the waterproof antibacterial polyester fiber fabric.

[0047] Example 4

[0048] (1) Under nitrogen atmosphere, 35 mmol of N,N'-bis(2-hydroxyethyl)ethylenediamine and 220 mL of dichloromethane were added into a reaction flask, after stirring uniformly, 110 mmol of N,N-diisopropylethylamine and 76.3 mmol of N,N'-di-Boc-S-methyl isothiourea were added, and the reaction was carried out at 30°C for 15 h, and then concentrated under reduced pressure, and purified by column chromatography (the volume ratio of n-hexane to ethyl acetate was 2:1) to obtain the diguanidol tertiary amine intermediate.

[0049] (2) Under nitrogen atmosphere, 28 mmol of the diguanidol tertiary amine intermediate and 460 mL of N,N-dimethylformamide were added into a reaction flask, after stirring uniformly, 74.2 mmol of perfluorodecyl ethyl iodine was added, and the reaction was carried out at 125°C for 32 h, and then concentrated under reduced pressure, and dried to obtain the diguanidol quaternary ammonium salt perfluoro intermediate.

[0050] (3) Under nitrogen atmosphere, 10 mmol of dimethyl terephthalate, 10.8 mmol of the bis-guanidinium quaternary ammonium salt perfluoro intermediate were added into a reaction flask, heated to melt the raw materials, 0.035 mmol of zinc acetate was added, heated to 215°C for ester exchange reaction for 4h, 0.1 mmol of ethylene glycol antimony was added, heated to 275°C, and reduced to 95 Pa for 3h, cooled to room temperature, and dried to obtain a waterproof antibacterial copolyester polymer.

[0051] (4) 100g of PET polyester chips and 20g of waterproof antibacterial copolyester polymer after vacuum drying were placed in a twin-screw extruder for melt blending, extrusion granulation, the screw temperature of the twin-screw extruder was 245°C, and the screw rotation speed was set to 35r / min, then melt spinning was carried out on a high-speed composite spinning machine, the spinning speed was 1100m / min, the spinning machine temperature was 280°C, after the nascent fiber was balanced, drawing and winding were carried out on a parallel drawing machine, the hot roller temperature of the drawing machine was 90°C, the drawing speed was 360m / min, and the drawing multiple was 5.8, to obtain a waterproof antibacterial polyester fiber fabric.

[0052] Example 5

[0053] (1) Under nitrogen atmosphere, 25 mmol of N,N'-bis(2-hydroxyethyl)ethylenediamine and 200 mL of dichloromethane were added into a reaction flask, stirred uniformly, then 80 mmol of N,N-diisopropylethylamine and 54 mmol of N,N'-di-Boc-S-methyl isothiourea were added, reacted at 35°C for 12h, reduced pressure concentration, column chromatography purification (volume ratio of n-hexane to ethyl acetate was 2:1), to obtain a bis-guanidinium tertiary amine intermediate.

[0054] (2) Under nitrogen atmosphere, 20 mmol of the bis-guanidinium tertiary amine intermediate and 350 mL of N,N-dimethylformamide were added into a reaction flask, stirred uniformly, then 56 mmol of perfluorodecyl ethyl iodine was added, reacted at 125°C for 48h, reduced pressure concentration, and dried to obtain a bis-guanidinium quaternary ammonium salt perfluoro intermediate.

[0055] (3) Under nitrogen atmosphere, 10 mmol of dimethyl terephthalate, 10.8 mmol of the bis-guanidinium quaternary ammonium salt perfluoro intermediate were added into a reaction flask, heated to melt the raw materials, 0.035 mmol of zinc acetate was added, heated to 215°C for ester exchange reaction for 4h, 0.1 mmol of ethylene glycol antimony was added, heated to 275°C, and reduced to 95 Pa for 3h, cooled to room temperature, and dried to obtain a waterproof antibacterial copolyester polymer.

[0056] (4) 100 g of the PET polyester chips and 25 g of the waterproof antibacterial copolyester polymer dried in vacuum were melt blended in a twin-screw extruder, extruded and granulated, the screw temperature of the twin-screw extruder was 255℃, the screw rotation speed was set to 30 r / min, then melt spinning was performed on a high-speed composite spinning machine, the spinning speed was 950 m / min, the spinning machine temperature was 275℃, after the nascent fiber was balanced, drawing and winding were performed on a parallel drawing machine, the hot roller temperature of the drawing machine was 90℃, the drawing speed was 350 m / min, the drawing multiple was 6, and a waterproof antibacterial polyester fiber fabric was obtained.

[0057] Comparative Example 1

[0058] (1) 10 mmol of dimethyl terephthalate and 9.5 mol of the bis-guanidinyl alcohol tertiary amine intermediate (prepared by Example 1) were added to a reaction flask under nitrogen atmosphere, heated to melt the raw materials, 0.04 mmol of zinc acetate was added, heated to 215℃, and ester exchange reaction was performed for 5 h, 0.09 mmol of ethylene glycol antimony was added, heated to 280℃, and reaction was performed under reduced pressure to 90 Pa for 2 h, cooled to room temperature, and dried to obtain a copolyester polymer.

[0059] (2) 100 g of the PET polyester chips and 5 g of the copolyester polymer dried in vacuum were melt blended in a twin-screw extruder, extruded and granulated, the screw temperature of the twin-screw extruder was 250℃, the screw rotation speed was set to 30 r / min, then melt spinning was performed on a high-speed composite spinning machine, the spinning speed was 1000 m / min, the spinning machine temperature was 280℃, after the nascent fiber was balanced, drawing and winding were performed on a parallel drawing machine, the hot roller temperature of the drawing machine was 85℃, the drawing speed was 350 m / min, the drawing multiple was 6, and a polyester fiber fabric was obtained.

[0060] Comparative Example 2

[0061] (1) 10 mmol of dimethyl terephthalate and 9.5 mol of N,N'-bis(2-hydroxyethyl)ethylenediamine were added to a reaction flask under nitrogen atmosphere, heated to melt the raw materials, 0.04 mmol of zinc acetate was added, heated to 215℃, and ester exchange reaction was performed for 5 h, 0.09 mmol of ethylene glycol antimony was added, heated to 280℃, and reaction was performed under reduced pressure to 90 Pa for 2 h, cooled to room temperature, and dried to obtain a copolyester polymer.

[0062] (2) 100 g of PET polyester chips and 5 g of the waterproof antibacterial copolyester polymer after vacuum drying were melt blended in a twin-screw extruder, extruded and granulated, the screw temperature of the twin-screw extruder was 250°C, and the screw rotation speed was set to 30 r / min, then melt spinning was performed on a high-speed composite spinning machine, the spinning speed was 1000 m / min, the spinning machine temperature was 280°C, after the nascent fiber was balanced, drawing and winding were performed on a parallel drawing machine, the hot roller temperature of the drawing machine was 85°C, the drawing speed was 350 m / min, and the drawing multiple was 6, to obtain a polyester fiber fabric.

[0063] Antibacterial performance test: The antibacterial rates of the polyester fiber fabrics prepared in the examples and the comparative examples on E. coli and S. aureus were tested according to the standard GB / T 20944.3-2008 “Evaluation of antibacterial properties of textiles Part 3: Shake flask method”.

[0064] Table 1: Antibacterial rate test

[0065]

[0066] From the above test results, it can be seen that as the content of the waterproof antibacterial copolyester polymer increases, the antibacterial performance of the polyester fiber fabric gradually increases, among which the antibacterial rate on E. coli in Example 4 reaches 99.9%, and the antibacterial rate on S. aureus reaches 98.2%, because on the one hand, the waterproof antibacterial copolyester polymer contains quaternary ammonium salt, guanidine group and hydrophobic long chain structure, among which the quaternary ammonium salt is adsorbed on the cell wall through electrostatic force, hydrogen bond force and other ways, hinders the action of cell lysozyme, destroys the structure of the cell surface layer, and affects the basic function of the cell membrane; the guanidine group can destroy the biological activity of phospholipids and the structure of the cell membrane, rapidly adsorb to the negatively charged bacterial cell membrane, and exchange ions with the cations in the cell membrane, leading to an increase in the permeability of the cell membrane, causing the leakage of substances inside the cell; the hydrophobic long chain is embedded on the surface of the bacteria, combined with the phospholipid bilayer in the cell membrane, and produces a room blocking effect, blocking the exchange of substances inside and outside the cell, and ultimately killing the bacteria. Comparative Example 1 contains only guanidine antibacterial groups, and the antibacterial effect is limited; Comparative Example 2 does not contain any antibacterial groups and has no antibacterial effect.

[0067] Antibacterial durability test: The prepared polyester fiber fabric was cut into a size of 5 cm x 5 cm, placed in a beaker with a diameter of 50 cm, washed with 50 mL of a 2% sodium dodecyl sulfate aqueous solution, stirred at 300 rpm and 25°C, and each 10 minutes was a washing cycle, then washed with deionized water, dried, and then the washed sample was tested for antibacterial durability according to the standard GB / T 20944.3-2008 “Evaluation of antibacterial properties of textiles Part 3: Shake flask method”.

[0068] Table 2 Antimicrobial durability test

[0069]

[0070] From the above table test results, with the increase of the content of waterproof antibacterial copolyester polymer, the antimicrobial durability of polyester fiber fabric gradually enhanced, after 50 times washing, polyester fiber fabric still had high inhibition rate on escherichia coli and staphylococcus aureus, because waterproof antibacterial copolyester polymer had similar structure with PET polyester, and the two had good compatibility, the copolymer containing quaternary ammonium salt and guanidine antibacterial group could be uniformly distributed in the polyester fiber matrix, avoiding the migration of antibacterial group, and better playing the antibacterial performance on bacteria.

[0071] Water absorption rate test: the prepared polyester fiber fabric was cut into 5cm x 5cm size, put into a beaker with deionized water with a diameter of 200cm, soaked for 30min, then the weight difference was calculated to calculate the water absorption rate, measured 3 times and took the average value, water absorption rate= (W2-W1) / W1 x 100%, wherein W1 and W2 were the weight of the fiber fabric before and after soaking respectively.

[0072] Contact angle test: the contact angle tester was used to measure the water contact angle of the fiber fabric at 25℃ and standard atmospheric pressure, using deionized water (3μL), measured 3 times and took the average value.

[0073] Table 3 Waterproof performance test

[0074] Water absorption (%) Contact angle (°) Example 1 8.29 112.2 Example 2 5.01 125.3 Example 3 3.87 139.4 Example 4 1.32 153.0 Example 5 0.16 155.1 Comparative Example 1 15.32 80.7 Comparative Example 2 16.55 78.4

[0075] From the above table test results, with the increase of the content of waterproof antibacterial copolyester polymer, the waterproof performance of polyester fiber fabric gradually enhanced, because the waterproof antibacterial copolyester polymer contained organic fluorine, the C-F bond energy was high, compared with hydrogen atom, fluorine atom was more easily embedded into the polymer, blocking the channel of water molecules migrating to the inside of the coating, a layer of stable protective layer could be formed on the surface of the fiber fabric, wrapping the fiber, preventing water from penetrating into the fiber, thereby playing a waterproof effect; in addition, the long chain alkyl provided hydrophobic group, which could construct uniform polymer network hydrophobic layer on the fiber surface, reducing the surface free energy of the fiber, limiting the diffusion and penetration of water droplets on the fiber fabric; at the same time, this layer of hydrophobic layer also had certain durability, could withstand multiple washing without failure.

[0076] The above merely describes preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art, without departing from the technical solution of the present application, can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, as long as it does not deviate from the technical solution of the present application, still belongs to the scope of the technical solution of the present application.

Claims

1. A method for preparing a terylene fiber fabric, characterized by, The preparation method comprises the following steps: Step (1), under a nitrogen atmosphere, dimethyl terephthalate, bisguanidine alcohol quaternary ammonium salt perfluoro intermediate, zinc acetate are added to a reaction flask, heated to melt the raw materials, ester exchange reaction is carried out at 210-225 DEG C for 3-6 h, antimony glycol is added, the temperature is raised to 270-290 DEG C, the pressure is reduced to 80-100 Pa, and reaction is carried out for 1-3 h, and after cooling to room temperature, the waterproof antibacterial copolyester polymer is obtained after drying; The ratio of dimethyl terephthalate, bisguanidine alcohol quaternary ammonium salt perfluoro intermediate, zinc acetate and antimony glycol in step (1) is 1 mol: (0.95-1.1) mol: (0.003-0.005) mol: (0.008-0.012) mol; Step (2), the vacuum dried PET polyester chip and the waterproof antibacterial copolyester polymer are placed in a twin screw extruder for melt blending, extruded and granulated, and then melt spun on a high speed composite spinning machine, the spinning speed is 800-1200 m / min, the spinning machine temperature is 260-290 DEG C, after the nascent fiber is balanced, the fiber is drawn and wound into a shape on a parallel drawing machine, and a waterproof antibacterial polyester fiber fabric is obtained; The preparation method of the bisguanidine alcohol quaternary ammonium salt perfluoro intermediate in step (1) comprises the following steps: Step S1, under a nitrogen atmosphere, N,N'-bis(2-hydroxyethyl)ethylenediamine and dichloromethane are added to a reaction flask, after stirring uniformly, N,N-diisopropylethylamine and N,N'-di-Boc-S-methyl isothiourea are added, stirring reaction is carried out, after the reaction is completed, vacuum concentration is carried out, column chromatography purification is carried out, and the bisguanidine alcohol tertiary amine intermediate is obtained; Step S2, under a nitrogen atmosphere, the bisguanidine alcohol tertiary amine intermediate and N,N-dimethylformamide are added to a reaction flask, after stirring uniformly, perfluorodecyl ethyl iodine is added, stirring reaction is carried out, after the reaction is completed, vacuum concentration is carried out, and the bisguanidine alcohol quaternary ammonium salt perfluoro intermediate is obtained after drying.

2. The method for preparing polyester fiber fabric according to claim 1, characterized in that, The ratio of PET polyester chip and waterproof antibacterial copolyester polymer is 100 g: (5-25) g; the screw temperature of the twin screw extruder is 240-260 DEG C, and the screw rotation speed is set to 25-40 r / min; the hot roller temperature of the drawing machine is 80-90 DEG C, the drawing speed is 300-400 m / min, and the drawing multiple is 5.5-6.

5.

3. The method for preparing polyester fiber fabric according to claim 2, characterized in that, The ratio of N,N'-bis(2-hydroxyethyl)ethylenediamine, N,N-diisopropylethylamine and N,N'-di-Boc-S-methyl isothiourea in step S1 is 1 mol: (2.5-3.5) mol: (2.05-2.2) mol.

4. The method for preparing polyester fiber fabric according to claim 3, characterized in that, The reaction temperature in step S1 is 20-35 DEG C, and the reaction time is 8-16 h.

5. The method for preparing polyester fiber fabric according to claim 4, characterized in that, The ratio of bisguanidine alcohol tertiary amine intermediate and perfluorodecyl ethyl iodine in step S2 is 1 mol: (2.3-2.8) mol, the reaction temperature is 110-130 DEG C, and the reaction time is 24-48 h.

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