Antibacterial and wear-resistant DTY elastic wire and preparation method thereof

Abstract

The invention discloses an antibacterial and wear-resistant DTY elastic wire and a preparation method thereof, which relates to the field of DTY elastic wire and comprises the following raw materials: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, a catalyst and a stabilizer. The antibacterial and wear-resistant DTY elastic wire is obtained by esterification reaction and polycondensation reaction of the raw materials to obtain modified polyester, and the modified polyester is then prepared by POY process and DTY process. The modified polyester has good wear resistance, and the wear resistance of the DTY elastic wire prepared therefrom meets the use requirements. The synthesized functional diol A contains a diimidazole quaternary ammonium salt and a polyether structure in its molecule, which improves the antibacterial and antistatic properties of the DTY elastic wire. The synthesized functional diol B contains a hindered phenol and a DOPO structure in its molecule, which improves the oxidation resistance and flame retardancy of the DTY elastic wire.

Description

Technical Field

[0001] The invention relates to the field of DTY elastic wires, and in particular to an antibacterial and wear-resistant DTY elastic wire and a preparation method thereof. Background Art

[0002] DTY stretch yarn is called false twist textured yarn, also known as stretch yarn; POY is called pre-oriented yarn, which refers to chemical fiber filaments that are not fully stretched and have an orientation degree between unoriented yarn and stretched yarn obtained by high-speed spinning; DTY stretch yarn is made by using POY as raw yarn, stretching and false twisting deformation processing, and has certain elasticity and shrinkage. DTY stretch yarn is divided into high-elastic yarn and low-elastic yarn. High-elastic yarn is mainly nylon, which is used for stretch shirts, pants, socks, etc.; low-elastic yarn includes polyester, polypropylene, nylon, etc. Polyester low-elastic yarn is mostly used for outerwear and interior decoration fabrics; nylon and polypropylene low-elastic yarns are mostly used for furniture fabrics and carpets. Among them, polyester (polyester fiber) has been widely used in the field of textile raw materials such as stretch yarn since its industrial production due to its high strength, good elasticity and wear resistance, excellent heat and corrosion resistance and excellent dimensional stability.

[0003] However, polyester is a hydrophobic fiber with poor hygroscopicity and a high specific resistivity on the surface. When rubbed with other objects, a large amount of charge accumulates on the surface and is not easy to dissipate, which easily generates static electricity. Static electricity not only makes textile processing difficult, but also makes people feel uncomfortable such as adhesion. Polyester stretch yarn is also facing the threat of oxidative damage during long-term use; the polyester molecular chain does not have flame retardant characteristics, and there are fire safety hazards during storage and use; in the use of some special DTY stretch yarns, polyester is also required to have good antibacterial properties.

[0004] Therefore, it is necessary to develop appropriate modification methods to improve the antistatic, antioxidant, flame retardant and antibacterial properties of polyester DTY stretch yarn in order to expand its scope of application. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides an antibacterial and wear-resistant DTY elastic wire and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] An antibacterial and wear-resistant DTY elastic wire comprises the following raw materials: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, a catalyst and a stabilizer; the molar ratio of terephthalic acid to ethylene glycol is 1:1.5-2.5; the sum of the molar amounts of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 6-8% of the molar amount of terephthalic acid; the molar ratio of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 6-8:1-2:1-2:1-2; the catalyst is antimony trioxide, and its usage is 0.04-0.06% of the mass of terephthalic acid; the stabilizer is triphenyl phosphate, and its usage is 0.02-0.04% of the mass of terephthalic acid;

[0008] The preparation of the antibacterial and wear-resistant DTY elastic wire comprises the following steps:

[0009] Step S1: In a nitrogen atmosphere, terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, and functional diol B are added to a reaction kettle, and stirring is started. After 30-40 minutes, a catalyst and a stabilizer are added, and stirring is performed for 10-20 minutes. Then, the reaction is stirred at a pressure of 0.1-0.3 MPa and a temperature of 240-250° C. for 3-4 hours;

[0010] Step S2: within 40-50 minutes, the pressure in the reaction kettle is evacuated to an absolute pressure of 490-499 Pa, and the reaction is stirred at 240-250° C. for 30-40 minutes; then, the vacuum is continued to be evacuated to reduce the pressure in the reaction kettle to 90-99 Pa, the temperature is raised to 260-270° C., and the reaction is continued to be stirred for 1-1.5 hours to obtain a modified polyester;

[0011] Step S3: After the modified polyester is melted, it is extruded through a triangular spinneret, cooled, oiled and wound to obtain a modified polyester POY yarn. The parameters of the POY process are: spinning temperature 280° C., cooling temperature 20° C., and winding speed 4100 m / min;

[0012] Step S4: The modified polyester POY yarn is guided, heated and stretched, false twisted, heat-set and wound to obtain the antibacterial and wear-resistant DTY elastic yarn. The parameters of the DTY process are: processing speed 600m / min, setting overfeed rate 4.0%, winding overfeed rate 3.5%, first hot box temperature 180°C, second hot box temperature 170°C, and stretch ratio 1.4.

[0013] The functional diol A is prepared by the following steps:

[0014] Step A1: Add double-carboxyl-terminated polyethylene glycol to DMF, add dichlorothionyl under stirring, and reflux and stir at 50° C. for 4-5 hours to obtain an acyl chloride product;

[0015] Further, the usage ratio of double-terminated carboxyl polyethylene glycol, DMF, and dithionyl chloride is 13.8-14.2 g: 70-80 mL: 0.22-0.25 mol;

[0016] During the reaction of step A1, the carboxyl group of the double-terminated carboxyl polyethylene glycol reacts with thionyl chloride to generate an acyl chloride product;

[0017] Step A2: 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2. The mixed solution 2 is slowly added dropwise to the mixed solution 1 in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at a constant temperature for 10 hours to obtain a biimidazole product;

[0018] Further, the usage ratio of 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 20-30 mL; the usage ratio of acyl chloride product and dimethyl sulfoxide is 0.1 mol: 35-45 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 25-35 mL: 40-50 mL;

[0019] During the reaction of step A2, the amino group of 1-methyl-4-aminoimidazole reacts with the acyl chloride product to generate a bisimidazole product;

[0020] Step A3: Place the bisimidazole product and ethanol in a flask, start stirring, then add 3-chloro-1-propanol, raise the temperature to 50-60°C, stir and react at constant temperature for 10-12h, rotary evaporate and recrystallize with acetone, filter and obtain functional diol A;

[0021] Further, the dosage ratio of the bisimidazole product, ethanol, and 3-chloro-1-propanol is 0.1 mol: 85-95 mL: 0.2 mol, and the volume fraction of ethanol is 95%;

[0022] During the reaction of step A3, the imidazole ring of the biimidazole product reacts with the chlorine atom of 3-chloro-1-propanol to generate a functional diol A containing a biimidazole quaternary ammonium salt;

[0023] The functional diol B is prepared by the following steps:

[0024] Step B1: Add 3,5-di-tert-butyl-4-hydroxycinnamic acid and DOPO to a flask, start stirring, raise the temperature to 125-135° C., and react with constant temperature stirring for 3-4 hours to obtain a carboxyl product;

[0025] Further, the usage ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid and DOPO is 0.1 mol:0.1 mol;

[0026] During the reaction of step B1, DOPO adds to the carbon-carbon double bond of 3,5-di-tert-butyl-4-hydroxycinnamic acid to obtain a carboxyl product;

[0027] Step B2: Add 2,5-dimethyl-1,5-hexadiene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, and stir at room temperature for 4-5 hours to obtain a diepoxy product;

[0028] Further, the usage ratio of 2,5-dimethyl-1,5-hexadiene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol:70-80 mL:0.1 mol;

[0029] During the reaction of step B2, the carbon-carbon double bond in 2,5-dimethyl-1,5-hexadiene is oxidized to an epoxy group to obtain a diepoxy product;

[0030] Step B3: In a nitrogen atmosphere, add the carboxyl product and toluene into a flask, heat to 45°C, add pyridine, start stirring, add the diepoxy product into the flask, stir and react for 8-10 hours to obtain functional diol B;

[0031] Further, the ratio of the carboxyl product, toluene, pyridine and diepoxy product is 0.2 mol: 230-240 mL: 0.004-0.006 mol: 0.1 mol;

[0032] During the reaction of step B3, the carboxyl group of the carboxyl product and the epoxy group of the diepoxy product undergo ring-opening to generate a dihydroxy product, namely, functional diol B.

[0033] Beneficial effects of the invention: The invention discloses an antibacterial and wear-resistant DTY elastic yarn, comprising the following raw materials: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, a catalyst and a stabilizer; in the preparation process of the antibacterial and wear-resistant DTY elastic yarn, the above raw materials are first subjected to an esterification reaction to obtain an esterification product, and then subjected to a polycondensation reaction to obtain a modified polyester, the modified polyester is melted and subjected to a POY process to obtain a POY yarn, and then the POY yarn is subjected to a DTY process to obtain an antibacterial and wear-resistant DTY elastic yarn. The modified polyester has the excellent wear resistance of polyester and meets the use requirements of the antibacterial and wear-resistant DTY elastic yarn.

[0034] Functional diol A molecules contain a diimidazole quaternary ammonium salt structure and a polyether structure. When bacteria come into contact with DTY elastic wire containing imidazolium quaternary ammonium salt, the negatively charged bacteria will be attracted by the cations on its surface, resulting in the restriction of the freedom of movement of the bacteria, inhibiting the respiratory function of the bacteria, and interfering with the synthesis process of the bacterial cell wall and the activity of metabolic enzymes, thereby playing an antibacterial role. Imidazole quaternary ammonium salt antibacterial agents have good durability and no problems of drug resistance and antibacterial failure. Diimidazole quaternary ammonium salts can quickly and efficiently exert their antibacterial function. Compared with single-chain Quaternary ammonium salts have higher stability and significantly enhance the antibacterial properties of modified polyesters. The introduction of diimidazole quaternary ammonium salts also increases the hydrophilicity of DTY elastic yarns made from modified polyesters. Compared with DTY elastic yarns made from ordinary polyester, the hygroscopicity is enhanced, so it is not easy to generate static electricity. The molecular chain of the polyether structure contains a large number of ether bonds, which can associate with water molecules through hydrogen bonds, so that the surface resistance of DTY elastic yarns decreases, and polyether has good heat resistance. The diimidazole quaternary ammonium salt and polyether in the functional diol A molecule can synergistically and stably play an antistatic role. Therefore, the use of functional diol A enhances the antibacterial and antistatic properties of DTY elastic yarns.

[0035] Functional diol B contains hindered phenol structure and DOPO structure in the molecule; hindered phenol structure has good antioxidant properties, and the hindered phenol structure is grafted into the polymer matrix through reaction to improve the disadvantage of easy migration and failure of small molecule hindered phenol antioxidants, improve the antioxidant stability of modified polyester, and avoid the shortening of the service life of DTY elastic yarn due to oxidation and aging; DOPO structure can dehydrate and degrade the combustion surface of the polymer to form a carbon layer when the matrix burns, and the phosphorus-containing derivatives produced at the same time cover the polymer surface, isolate the combustible gas, block heat transfer, and form a physical shield. DOPO is grafted into the polymer matrix through reaction to avoid the migration and failure of small molecule DOPO, and enhance the flame retardant properties of modified polyester. Therefore, the use of synthetic functional diol B can improve the antioxidant and flame retardant properties of DTY elastic yarn. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Example 1: A functional diol A, the preparation of which comprises the following steps:

[0038] Step A1: Add double-carboxyl-terminated polyethylene glycol to DMF, add dithionyl chloride under stirring, and reflux and stir at 50° C. for 4 h to obtain an acyl chloride product; the dosage ratio of double-carboxyl-terminated polyethylene glycol, DMF, and dithionyl chloride is 13.8 g:70 mL:0.22 mol;

[0039] Step A2: 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2. In a 0°C ice-water bath, the mixed solution 2 is slowly added dropwise to the mixed solution 1. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at a constant temperature for 10 hours to obtain a biimidazole product; the amount ratio of 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 20 mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide is 0.1 mol: 35 mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 25 mL: 40 mL;

[0040] Step A3: Place the biimidazole product and ethanol in a flask, start stirring, then add 3-chloro-1-propanol, raise the temperature to 50°C, react with constant temperature stirring for 10 hours, recrystallize with acetone after rotary evaporation, and filter to obtain functional diol A; the dosage ratio of the biimidazole product, ethanol, and 3-chloro-1-propanol is 0.1 mol: 85 mL: 0.2 mol, and the volume fraction of ethanol is 95%.

[0041] Example 2: A functional diol A, the preparation of which comprises the following steps:

[0042] Step A1: Add double-carboxyl-terminated polyethylene glycol to DMF, add dithionyl chloride under stirring, and reflux and stir at 50° C. for 4.5 h to obtain an acyl chloride product; the dosage ratio of double-carboxyl-terminated polyethylene glycol, DMF, and dithionyl chloride is 14.0 g: 75 mL: 0.23 mol;

[0043] Step A2: 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide are added into a flask to obtain a mixed solution 1, and then the acyl chloride product is added into dimethyl sulfoxide to obtain a mixed solution 2. In a 0°C ice-water bath, the mixed solution 2 is slowly added dropwise into the mixed solution 1. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at a constant temperature for 10 hours to obtain a biimidazole product; the amount ratio of 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 25 mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide is 0.1 mol: 40 mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 30 mL: 45 mL;

[0044] Step A3: Place the biimidazole product and ethanol in a flask, start stirring, then add 3-chloro-1-propanol, raise the temperature to 55°C, stir and react at a constant temperature for 11 hours, rotary evaporation and recrystallization with acetone, filter and obtain functional diol A; the dosage ratio of the biimidazole product, ethanol and 3-chloro-1-propanol is 0.1 mol: 90 mL: 0.2 mol, and the volume fraction of ethanol is 95%.

[0045] Example 3: A functional diol A, the preparation of which comprises the following steps:

[0046] Step A1: Add double-carboxyl-terminated polyethylene glycol to DMF, add dithionyl chloride under stirring, and reflux and stir at 50° C. for 5 h to obtain an acyl chloride product; the dosage ratio of double-carboxyl-terminated polyethylene glycol, DMF, and dithionyl chloride is 14.2 g: 80 mL: 0.25 mol;

[0047] Step A2: 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide are added into a flask to obtain a mixed solution 1, and then the acyl chloride product is added into dimethyl sulfoxide to obtain a mixed solution 2. In a 0°C ice-water bath, the mixed solution 2 is slowly added dropwise into the mixed solution 1. After the addition is completed, the temperature is raised to 40°C and the mixture is stirred at a constant temperature for 10 hours to obtain a biimidazole product. The amount ratio of 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 30 mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide is 0.1 mol: 45 mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 35 mL: 50 mL;

[0048] Step A3: Place the biimidazole product and ethanol in a flask, start stirring, then add 3-chloro-1-propanol, raise the temperature to 60°C, stir and react at a constant temperature for 12 hours, rotary evaporation and recrystallization with acetone, filter and obtain functional diol A; the dosage ratio of the biimidazole product, ethanol and 3-chloro-1-propanol is 0.1 mol: 95 mL: 0.2 mol, and the volume fraction of ethanol is 95%.

[0049] Example 4: A functional diol B, the preparation of which comprises the following steps:

[0050] Step B1: Add 3,5-di-tert-butyl-4-hydroxycinnamic acid and DOPO to a flask, start stirring, heat to 125°C, and react at constant temperature and stirring for 3 hours to obtain a carboxyl product; the amount ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid to DOPO is 0.1 mol:0.1 mol;

[0051] Step B2: Add 2,5-dimethyl-1,5-hexadiene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, and stir at room temperature for 4 hours to obtain a diepoxy product; the amount ratio of 2,5-dimethyl-1,5-hexadiene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol:70 mL:0.1 mol;

[0052] Step B3: In a nitrogen atmosphere, add the carboxyl product and toluene into a flask, heat to 45°C, add pyridine, start stirring, add the diepoxy product into the flask, stir and react for 8 hours to obtain functional diol B; the amount ratio of the carboxyl product, toluene, pyridine and diepoxy product is 0.2 mol: 230 mL: 0.004 mol: 0.1 mol.

[0053] Example 5: A functional diol B, the preparation of which comprises the following steps:

[0054] Step B1: Add 3,5-di-tert-butyl-4-hydroxycinnamic acid and DOPO to a flask, start stirring, heat to 130°C, and react at constant temperature and stirring for 3.5 hours to obtain a carboxyl product; the amount ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid to DOPO is 0.1 mol:0.1 mol;

[0055] Step B2: Add 2,5-dimethyl-1,5-hexadiene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, and stir at room temperature for 4.5 hours to obtain a diepoxy product; the amount ratio of 2,5-dimethyl-1,5-hexadiene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol:75 mL:0.1 mol;

[0056] Step B3: In a nitrogen atmosphere, add the carboxyl product and toluene into a flask, heat to 45°C, add pyridine, start stirring, add the diepoxy product into the flask, stir and react for 9 hours to obtain functional diol B; the amount ratio of the carboxyl product, toluene, pyridine and diepoxy product is 0.2 mol: 235 mL: 0.005 mol: 0.1 mol.

[0057] Example 6: A functional diol B, the preparation of which comprises the following steps:

[0058] Step B1: Add 3,5-di-tert-butyl-4-hydroxycinnamic acid and DOPO to a flask, start stirring, heat to 135°C, and react at constant temperature and stirring for 4 hours to obtain a carboxyl product; the amount ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid to DOPO is 0.1 mol:0.1 mol;

[0059] Step B2: Add 2,5-dimethyl-1,5-hexadiene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, and stir at room temperature for 5 hours to obtain a diepoxy product; the amount ratio of 2,5-dimethyl-1,5-hexadiene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol: 80 mL: 0.1 mol;

[0060] Step B3: In a nitrogen atmosphere, add the carboxyl product and toluene into a flask, heat to 45°C, add pyridine, start stirring, add the diepoxy product into the flask, stir and react for 10 hours to obtain functional diol B; the amount ratio of the carboxyl product, toluene, pyridine and diepoxy product is 0.2 mol: 240 mL: 0.006 mol: 0.1 mol.

[0061] Embodiment 7: An antibacterial and wear-resistant DTY elastic wire comprises the following raw materials: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, a catalyst and a stabilizer; the molar ratio of terephthalic acid to ethylene glycol is 1:1.5; the sum of the molar amounts of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 6% of the molar amount of terephthalic acid, and the molar ratio of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 6:1:1:1; the catalyst is antimony trioxide, and its amount is 0.04% of the mass of terephthalic acid; the stabilizer is triphenyl phosphate, and its amount is 0.02% of the mass of terephthalic acid;

[0062] The preparation of the antibacterial and wear-resistant DTY elastic wire comprises the following steps:

[0063] Step S1: In a nitrogen atmosphere, terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, the functional diol A obtained in Example 1, and the functional diol B obtained in Example 4 were added to a reaction kettle, and stirring was started. After 30 minutes, a catalyst and a stabilizer were added, and after stirring for 10 minutes, the reaction was stirred at a pressure of 0.1 MPa and a temperature of 240° C. for 3 hours;

[0064] Step S2: the pressure in the reactor is evacuated to an absolute pressure of 490 Pa within 40 minutes, and the reaction is stirred at 240° C. for 30 minutes; then the vacuum is continued to be evacuated to reduce the pressure in the reactor to 90 Pa, the temperature is raised to 260° C., and the reaction is stirred for 1 hour to obtain a modified polyester;

[0065] Step S3: After the modified polyester is melted, it is extruded through a triangular spinneret, cooled, oiled and wound to obtain a modified polyester POY yarn. The parameters of the POY process are: spinning temperature 280° C., cooling temperature 20° C., and winding speed 4100 m / min;

[0066] Step S4: The modified polyester POY yarn is guided, heated and stretched, false twisted, heat-set and wound to obtain the antibacterial and wear-resistant DTY elastic yarn. The parameters of the DTY process are: processing speed 600m / min, setting overfeed rate 4.0%, winding overfeed rate 3.5%, first hot box temperature 180°C, second hot box temperature 170°C, and stretch ratio 1.4.

[0067] Embodiment 8: An antibacterial and wear-resistant DTY elastic wire comprises the following raw materials: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, a catalyst and a stabilizer; the molar ratio of terephthalic acid to ethylene glycol is 1:2.0; the sum of the molar amounts of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 7% of the molar amount of terephthalic acid, and the molar ratio of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 7:1.5:1.5:1.5; the catalyst is antimony trioxide, and its amount is 0.05% of the mass of terephthalic acid; the stabilizer is triphenyl phosphate, and its amount is 0.03% of the mass of terephthalic acid;

[0068] The preparation of the antibacterial and wear-resistant DTY elastic wire comprises the following steps:

[0069] Step S1: In a nitrogen atmosphere, terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A obtained in Example 2, and functional diol B obtained in Example 5 were added to a reaction kettle, and stirring was started. After 35 minutes, a catalyst and a stabilizer were added, and after stirring for 15 minutes, the reaction was stirred at a pressure of 0.2 MPa and a temperature of 245° C. for 3.5 hours;

[0070] Step S2: The pressure in the reactor was evacuated to an absolute pressure of 495 Pa within 45 minutes, and the reaction was stirred at 245° C. for 30-40 minutes; then, the pressure in the reactor was further evacuated to reduce to 95 Pa, the temperature was raised to 265° C., and the reaction was stirred for 1.3 hours to obtain a modified polyester;

[0071] Step S3: After the modified polyester is melted, it is extruded through a triangular spinneret, cooled, oiled and wound to obtain a modified polyester POY yarn. The parameters of the POY process are: spinning temperature 280° C., cooling temperature 20° C., and winding speed 4100 m / min;

[0072] Step S4: The modified polyester POY yarn is guided, heated and stretched, false twisted, heat-set and wound to obtain the antibacterial and wear-resistant DTY elastic yarn. The parameters of the DTY process are: processing speed 600m / min, setting overfeed rate 4.0%, winding overfeed rate 3.5%, first hot box temperature 180°C, second hot box temperature 170°C, and stretch ratio 1.4.

[0073] Embodiment 9: An antibacterial and wear-resistant DTY elastic wire comprises the following raw materials: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, a catalyst and a stabilizer; the molar ratio of terephthalic acid to ethylene glycol is 1:2.5; the sum of the molar amounts of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 8% of the molar amount of terephthalic acid, and the molar ratio of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 8:2:2:2; the catalyst is antimony trioxide, and its amount is 0.06% of the mass of terephthalic acid; the stabilizer is triphenyl phosphate, and its amount is 0.04% of the mass of terephthalic acid;

[0074] The preparation of the antibacterial and wear-resistant DTY elastic wire comprises the following steps:

[0075] Step S1: In a nitrogen atmosphere, terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, the functional diol A obtained in Example 3, and the functional diol B obtained in Example 6 were added to a reaction kettle, and stirring was started. After 40 minutes, a catalyst and a stabilizer were added, and after stirring for 20 minutes, the reaction was stirred at a pressure of 0.3 MPa and a temperature of 250° C. for 4 hours;

[0076] Step S2: the pressure in the reactor was evacuated to an absolute pressure of 499 Pa within 50 min, and the reaction was stirred at 250° C. for 40 min; then the pressure in the reactor was further evacuated to reduce to 99 Pa, the temperature was raised to 270° C., and the reaction was stirred for 1.5 h to obtain a modified polyester;

[0077] Step S3: After the modified polyester is melted, it is extruded through a triangular spinneret, cooled, oiled and wound to obtain a modified polyester POY yarn. The parameters of the POY process are: spinning temperature 280° C., cooling temperature 20° C., and winding speed 4100 m / min;

[0078] Step S4: The modified polyester POY yarn is guided, heated and stretched, false twisted, heat-set and wound to obtain the antibacterial and wear-resistant DTY elastic yarn. The parameters of the DTY process are: processing speed 600m / min, setting overfeed rate 4.0%, winding overfeed rate 3.5%, first hot box temperature 180°C, second hot box temperature 170°C, and stretch ratio 1.4.

[0079] Comparative Example 1

[0080] Compared with Example 9, the functional diol A was replaced with ethylene glycol, and the rest was exactly the same as Example 9 to obtain DTY elastic yarn.

[0081] Comparative Example 2

[0082] Compared with Example 9, the functional diol B was replaced with 1,4-butanediol, and the rest was exactly the same as Example 9 to obtain DTY elastic yarn.

[0083] The antibacterial and wear-resistant DTY elastic yarn prepared by the present invention is further tested for its effect, and the test results are as follows.

[0084] In order to test the DTY elastic yarn prepared by the present invention, the breaking strength and breaking elongation are determined according to GB / T14344-2022 "Test method for tensile properties of chemical fiber filaments"; the aging method is: the DTY elastic yarns obtained in Examples 7-9 and Comparative Examples 1-3 are placed in an air oven at 150°C for aging for 7 days, and then the breaking strength retention rate and breaking elongation retention rate are determined according to GB / T14344-2022; the antibacterial rate is determined with reference to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method"; the surface resistivity test is performed according to GB / T12703.4-2010 "Evaluation of electrostatic properties of textiles"; the limiting oxygen index is determined according to GB / T5454-1997 "Textile combustion performance test oxygen index method", and the results are recorded in Table 1;

[0085]

[0086] According to the data in Table 1, the antibacterial and wear-resistant DTY elastic yarn prepared by the present invention has good antioxidant properties, antistatic properties, flame retardancy and antibacterial properties. Comparison between Example 9 and Comparative Example 1 shows that the use of functional diol A introduced with diimidazole quaternary ammonium salt and polyether improves the antibacterial and antistatic properties of the DTY elastic yarn. Comparison between Example 9 and Comparative Example 2 shows that the use of functional diol B introduced with hindered phenol and DOPO structure makes the DTY elastic yarn have good antioxidant properties and flame retardancy.

[0087] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. An antibacterial and wear-resistant DTY elastic wire, characterized by: The raw materials include: terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, functional diol B, catalyst and stabilizer; The functional diol A is prepared by the following steps: Step A1: Add double-carboxyl-terminated polyethylene glycol to DMF, add dichlorothionyl under stirring, and reflux and stir at 50° C. for 4-5 hours to obtain an acyl chloride product; Step A2: 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide are added to a flask to obtain a mixed solution 1, and then the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2. The mixed solution 2 is slowly added dropwise to the mixed solution 1 in an ice-water bath at 0°C. After the addition is completed, the temperature is raised to 40°C, and the reaction is stirred at a constant temperature for 10 hours to obtain a biimidazole product; Step A3: Place the bisimidazole product and ethanol in a flask, start stirring, then add 3-chloro-1-propanol, raise the temperature to 50-60°C, stir and react at constant temperature for 10-12h, rotary evaporate and recrystallize with acetone, filter and obtain functional diol A; In step A1, the ratio of double-terminated carboxyl polyethylene glycol, DMF, and dichlorothionyl is 13.8-14.2 g: 70-80 mL: 0.22-0.25 mol; In step A2, the usage ratio of 1-methyl-4-aminoimidazole, potassium carbonate and dimethyl sulfoxide is 0.1 mol: 0.015 mol: 20-30 mL; the usage ratio of acyl chloride product and dimethyl sulfoxide is 0.1 mol: 35-45 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 25-35 mL: 40-50 mL; In step A3, the ratio of the bisimidazole product, ethanol, and 3-chloro-1-propanol is 0.1 mol: 85-95 mL: 0.2 mol, and the volume fraction of ethanol is 95%; The functional diol B is prepared by the following steps: Step B1: Add 3,5-di-tert-butyl-4-hydroxycinnamic acid and DOPO to a flask, start stirring, raise the temperature to 125-135° C., and react with constant temperature stirring for 3-4 hours to obtain a carboxyl product; Step B2: Add 2,5-dimethyl-1,5-hexadiene to dichloromethane, start stirring, then add 3-chloroperoxybenzoic acid, and stir at room temperature for 4-5 hours to obtain a diepoxy product; Step B3: In a nitrogen atmosphere, add the carboxyl product and toluene into a flask, heat to 45°C, add pyridine, start stirring, add the diepoxy product into the flask, stir and react for 8-10 hours to obtain functional diol B; In step B1, the ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid to DOPO is 0.1 mol:0.1 mol; In step B2, the ratio of 2,5-dimethyl-1,5-hexadiene, dichloromethane and 3-chloroperoxybenzoic acid is 0.1 mol:70-80 mL:0.1 mol; In step B3, the ratio of carboxyl product, toluene, pyridine and diepoxy product is 0.2 mol: 230-240 mL: 0.004-0.006 mol: 0.1 mol; The molar ratio of terephthalic acid to ethylene glycol is 1:1.5-2.5; the sum of the molar amounts of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 6-8% of the molar amount of terephthalic acid; the molar ratio of tetrafluorosuccinic acid, diphenylsilanediol, functional diol A and functional diol B is 6-8:1-2:1-2:1-2; the catalyst is antimony trioxide, and its usage is 0.04-0.06% of the mass of the terephthalic acid; the stabilizer is triphenyl phosphate, and its usage is 0.02-0.04% of the mass of the terephthalic acid.

2. The method for preparing an antibacterial and wear-resistant DTY elastic wire according to claim 1, characterized in that: The steps include: Step S1: In a nitrogen atmosphere, terephthalic acid, tetrafluorosuccinic acid, ethylene glycol, diphenylsilanediol, functional diol A, and functional diol B are added to a reaction kettle, and stirring is started. After 30-40 minutes, a catalyst and a stabilizer are added, and stirring is performed for 10-20 minutes. Then, the reaction is stirred at a pressure of 0.1-0.3 MPa and a temperature of 240-250° C. for 3-4 hours; Step S2: within 40-50 minutes, the pressure in the reaction kettle is evacuated to an absolute pressure of 490-499 Pa, and the reaction is stirred at 240-250° C. for 30-40 minutes; then, the vacuum is continued to be evacuated to reduce the pressure in the reaction kettle to 90-99 Pa, the temperature is raised to 260-270° C., and the reaction is continued to be stirred for 1-1.5 hours to obtain a modified polyester; Step S3: After the modified polyester is melted, it is extruded through a triangular spinneret, cooled, oiled and wound to obtain a modified polyester POY yarn. The parameters of the POY process are: spinning temperature 280° C., cooling temperature 20° C., and winding speed 4100 m / min; Step S4: The modified polyester POY yarn is guided, heated and stretched, false twisted, heat-set and wound to obtain the antibacterial and wear-resistant DTY elastic yarn. The parameters of the DTY process are: processing speed 600m / min, setting overfeed rate 4.0%, winding overfeed rate 3.5%, first hot box temperature 180°C, second hot box temperature 170°C, and stretch ratio 1.4.

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