Preparation method of antibacterial fiber and fabric

Abstract

The invention discloses a preparation method of antibacterial fibers and a fabric, and relates to the technical field of textile fabrics. When the antibacterial fiber is prepared, 1, 6-hexanediol, 2-(bromomethyl) diethyl succinate and diethyl 2, 2 ': 6', 2 '-terpyridine-4'-yl phosphonate are polymerized to prepare polyester; the preparation method comprises the following steps: reacting polyester with 7-(dimethylamino) coumarin to prepare modified polyester; the preparation method comprises the following steps: polymerizing maleic anhydride and methyl-vinyl polysiloxane and coating the surface of a phase change microcapsule with the maleic anhydride and the methyl-vinyl polysiloxane to prepare a pre-modified phase change microcapsule; the pre-modified phase change microcapsule and 1-hydroxymethyl-5, 5-dimethyl hydantoin are subjected to a reaction, and a modified phase change microcapsule is prepared; preparing a spinning solution from the modified polyester, the modified phase change microcapsules and copper chloride, performing electrostatic spinning, and performing chlorination finishing to obtain the antibacterial fiber. The antibacterial fiber prepared by the invention has excellent antibacterial, anti-aging, flame-retardant and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of textile fabrics, in particular to a preparation method of antibacterial fiber and fabrics. Background Art

[0002] With the improvement of living standards, people's requirements for clothing materials have shifted from simple warmth and body covering to specific health protection effects. In daily life, people will inevitably come into contact with various pathogenic bacteria, fungi and other microorganisms. These microorganisms will multiply rapidly in a suitable external environment, and spread various diseases through contact, endangering human health and even life. During the use of textiles, human sweat, sebum, etc. will remain. These substances are a good source of nutrition for microorganisms. Therefore, textiles have become an important medium for the spread of microorganisms, endangering the health of users. In response to the above problems, the present application proposes a method for preparing antibacterial fibers. The fibers prepared by this method have excellent antibacterial properties and protect people's health. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing antibacterial fiber and fabric to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A method for preparing an antibacterial fiber, the method comprising reacting polyester and 7-(dimethylamino)coumarin to obtain a modified polyester; reacting pre-modified phase change microcapsules and 1-hydroxymethyl-5,5-dimethylhydantoin to obtain a modified phase change microcapsule; preparing a spinning solution with the modified polyester, the modified phase change microcapsule and copper chloride, and performing electrostatic spinning followed by chlorination finishing to obtain the antibacterial fiber;

[0006] The polyester is prepared by polymerizing 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-ylphosphonate;

[0007] The pre-modified phase-change microcapsules are prepared by polymerizing maleic anhydride and methyl-vinyl polysiloxane and coating the surfaces of the phase-change microcapsules.

[0008] As an optimization, the preparation method of the antibacterial fiber includes the following preparation steps:

[0009] (1) 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate were added to a reaction kettle in a molar ratio of 1:(0.5-0.6):(0.3-0.4), and then tetrabutyl titanate (0.01-0.03 times the mass of 1,6-hexanediol) and a heat stabilizer (0.02-0.04 times the mass of 1,6-hexanediol) were added and mixed evenly. The mixture was heated at 180-190°C and 400-600r / min in a nitrogen atmosphere. min stirring reaction for 2-3h, heating to 230-240°C, stirring reaction at 60-70Pa for 40-50min, cooling to room temperature to obtain polyester; mixing polyester, 7-(dimethylamino)coumarin, and N,N-dimethylformamide in a mass ratio of 1:(0.6-0.8):(10-12), stirring reaction at 50-60°C and 300-500r / min for 3-4h, and drying at 50-60°C under vacuum conditions for 8-10h to obtain modified polyester;

[0010] (2) Phase change microcapsules, maleic anhydride, methyl-vinyl polysiloxane, and toluene are mixed uniformly in a mass ratio of 1:(0.6-0.8):(0.5-0.7):(12-14) to prepare a mixed reaction liquid; under a nitrogen atmosphere, at 70-80°C and 300-500 r / min stirring conditions, azobisisobutyronitrile solution is uniformly added to the mixed reaction liquid within 20 minutes, and the stirring reaction is continued for 5-6 hours, cooled to room temperature, filtered and washed with methanol and deionized water for 3-5 times, and vacuum-dried. The pre-modified phase change microcapsules were prepared by drying at 50-60°C for 6-8h; the pre-modified phase change microcapsules, 1-hydroxymethyl-5,5-dimethylhydantoin, 1,4-benzoquinone and toluene were uniformly mixed in a mass ratio of 1:(2-3):(0.02-0.04):(14-16), stirred at 50-60°C and 300-500r / min for 10-12h, filtered and washed with methanol and deionized water for 3-5 times respectively, and dried at 50-60°C for 8-10h under vacuum conditions to obtain modified phase change microcapsules;

[0011] (3) The modified polyester, modified phase change microcapsules, copper chloride and dichloromethane are mixed uniformly in a mass ratio of 1: (0.06-0.08): (0.03-0.04): (8-10), and stirred at 20-30°C and 300-500 r / min for 1-2 h to prepare a spinning solution; the spinning solution is loaded into a micro pump, and electrospinning is performed in an electrospinning device to obtain primary fibers; the primary fibers are immersed in a chlorinated finishing solution, immersed at room temperature for 1-2 h, taken out, washed with deionized water for 3-5 times, and dried at 50-60°C under vacuum conditions for 8-10 h to obtain antibacterial fibers.

[0012] As an optimization, the thermal stabilizer in step (1) is triphenyl phosphate.

[0013] As an optimization, the model of the phase change microcapsule in step (2) is PCM32.

[0014] As an optimization, the molecular weight of the methyl-vinyl polysiloxane in step (2) is 2000.

[0015] As an optimization, the preparation method of the azobisisobutyronitrile solution in step (2) is: 0.01 to 0.03 times the mass of maleic anhydride azobisisobutyronitrile and toluene are mixed uniformly in a mass ratio of 1:(20 to 30) to prepare an azobisisobutyronitrile solution.

[0016] As an optimization, the preparation method of the chlorination finishing liquid in step (3) is: sodium hypochlorite and deionized water are mixed uniformly in a mass ratio of 1:(9-11), and the pH is adjusted to neutral with a sulfuric acid aqueous solution with a mass fraction of 10% to 12% to prepare a chlorination finishing liquid.

[0017] As an optimization, the process parameters of the electrospinning in step (3) are as follows: the spinning solution is loaded into a micro pump, an ice plate covered with aluminum foil is used as a receiving device, the receiving distance is adjusted to 16 to 18 cm, the voltage during the spinning process is 23 to 25 kV, the propulsion rate is 0.6 to 0.7 mL / h, the ambient temperature is 20 to 30°C, and the spinning humidity is 50% to 60%.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] When preparing the antibacterial fiber, the present invention comprises the following steps: 1,6-hexanediol, 2-(bromomethyl) diethyl succinate and diethyl 2,2':6',2"-terpyridine-4'-phosphonate are polymerized to obtain polyester; polyester and 7-(dimethylamino) coumarin are reacted to obtain modified polyester; maleic anhydride and methyl-vinyl polysiloxane are polymerized and coated on the surface of phase change microcapsules to obtain pre-modified phase change microcapsules; pre-modified phase change microcapsules and 1-hydroxymethyl-5,5-dimethylhydantoin are reacted to obtain modified phase change microcapsules; the modified polyester, the modified phase change microcapsules and cupric chloride are prepared into a spinning solution, and the antibacterial fiber is prepared by chlorination finishing after electrostatic spinning.

[0020] Firstly, 1,6-hexanediol, diethyl 2-(bromomethyl)succinate and diethyl 2,2':6',2"-terpyridine-4'-phosphonate were polymerized to prepare polyester. Phosphorus was introduced into the main chain of polyester molecule by transesterification reaction, and bromine atom and terpyridine structure were introduced into the side chain. The introduction of phosphorus can improve the flame retardant properties of antibacterial fiber. Terpyridine structure can form coordination complex with copper ions to form cross-linked structure, inhibit the relative slip between molecular chains, improve the mechanical properties of antibacterial fiber, and copper ions can be fixed in antibacterial fiber. A long-lasting antibacterial effect is achieved; the bromine atoms introduced on the polyester react with the dimethylamino group on 7-(dimethylamino)coumarin to obtain a modified polyester, a benzopyrone structure is introduced on the side chain of the modified polyester, and a quaternary ammonium salt cation structure is generated; the benzopyrone structure can absorb ultraviolet light, giving the antibacterial fiber excellent anti-aging properties, and the quaternary ammonium salt cation can not only play a certain antibacterial role, but also can combine with the carboxyl group on the modified phase change microcapsule through positive and negative charges to form a cross-linked network, inhibit the relative slip between molecular chains, and further improve the mechanical properties of the antibacterial fiber.

[0021] Secondly, maleic anhydride and methyl-vinyl polysiloxane are polymerized and coated on the surface of phase change microcapsules to obtain pre-modified phase change microcapsules; Si-O bonds and dianhydride structures are introduced on the surface of phase change microcapsules. The introduction of Si-O bonds can further improve the flame retardant properties of the antibacterial fiber. The dianhydride structure on the pre-modified phase change microcapsules is reacted with the hydroxymethyl group on 1-hydroxymethyl-5,5-dimethylhydantoin to obtain modified phase change microcapsules. Chloramine precursors and carboxyl groups are introduced into the modified phase change microcapsules. The carboxyl groups introduced into the modified phase change microcapsules can combine with the quaternary ammonium salt cations generated on the modified polyester through positive and negative charges to form a cross-linked network, inhibit the relative slip between molecular chains, and further improve the mechanical properties of the antibacterial fiber; phase change microcapsules are a type of intelligent material that can automatically sense changes in external temperature and human body temperature, and respond to temperature changes by absorbing or releasing heat, giving the antibacterial fiber excellent thermal insulation properties.

[0022] Finally, the modified polyester, modified phase change microcapsules and cupric chloride are prepared into a spinning solution, and the antibacterial fiber is obtained by chlorination after electrospinning. The chloramine precursor on the modified phase change microcapsules is chlorinated to generate N-Cl bonds. In the presence of water molecules, the N-Cl bonds in the chloramines slowly decompose to release hypohalous acids or hypohalous acid radicals with strong oxidizing properties, which directly attack some groups in bacteria to denature proteins and inhibit enzyme metabolism, thereby giving the antibacterial fiber excellent antibacterial properties. Cupric chloride is added to introduce copper ions into the spinning solution. The copper ions form a coordination complex with the terpyridine structure introduced on the side chain of the modified polyester to form a cross-linked structure, which inhibits the relative slip between molecular chains and improves the mechanical properties of the antibacterial fiber. At the same time, the copper ions can be fixed in the antibacterial fiber to achieve a lasting antibacterial effect. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] Example 1

[0025] A method for preparing an antibacterial fiber, the method comprising the following steps:

[0026] (1) 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate were added to a reactor in a molar ratio of 1:0.5:0.3, and then tetrabutyl titanate (0.01 times the mass of 1,6-hexanediol) and triphenyl phosphate (0.02 times the mass of 1,6-hexanediol) were added and mixed evenly. The mixture was stirred at 180°C and 400 r / min for 3 h in a nitrogen atmosphere, and then heated to 230°C and continued to stir at 60 Pa for 50 min, and then cooled to room temperature to obtain polyester. Polyester, 7-(dimethylamino)coumarin, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.6:10, and stirred at 50°C and 300 r / min for 4 h, and then dried at 50°C for 10 h under vacuum conditions to obtain modified polyester.

[0027] (2) Phase change microcapsules, maleic anhydride, methyl-vinyl polysiloxane, and toluene were mixed in a mass ratio of 1:0.6:0.5:12 to prepare a mixed reaction liquid; 0.01 times the mass of maleic anhydride and toluene were mixed in a mass ratio of 1:20 to prepare an azobisisobutyronitrile solution; under a nitrogen atmosphere, at 70° C., 300 r / min stirring conditions, the azobisisobutyronitrile solution was uniformly added dropwise to the mixed reaction liquid within 20 minutes, and the stirring reaction was continued for 6 hours. h, cooled to room temperature, filtered and washed with methanol and deionized water for 3 times, dried at 50°C for 8h under vacuum conditions to obtain pre-modified phase change microcapsules; the pre-modified phase change microcapsules, 1-hydroxymethyl-5,5-dimethylhydantoin, 1,4-benzoquinone and toluene were mixed uniformly in a mass ratio of 1:2:0.02:14, stirred at 50°C and 300r / min for 12h, filtered and washed with methanol and deionized water for 3 times, dried at 50°C for 10h under vacuum conditions to obtain modified phase change microcapsules;

[0028] (3) Sodium hypochlorite and deionized water were mixed in a mass ratio of 1:9, and the pH was adjusted to neutral with a 10% sulfuric acid aqueous solution to prepare a chlorination finishing solution; modified polyester, modified phase change microcapsules, copper chloride, and dichloromethane were mixed in a mass ratio of 1:0.06:0.03:8, and stirred at 20°C and 300r / min for 2h to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an aluminum foil covered on an ice plate was used as a receiving device. The receiving distance was adjusted to 16cm. During the spinning process, the voltage was 23kV, the propulsion rate was 0.6mL / h, the ambient temperature was 20°C, the spinning humidity was 50%, and electrospinning was performed in an electrospinning device to obtain primary fibers; the primary fibers were immersed in the chlorination finishing solution, immersed at room temperature for 2h, taken out, washed 3 times with deionized water, and dried at 50°C for 10h under vacuum conditions to obtain antibacterial fibers.

[0029] Example 2

[0030] A method for preparing an antibacterial fiber, the method comprising the following steps:

[0031] (1) 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate were added to a reactor in a molar ratio of 1:0.55:0.35, and then tetrabutyl titanate (0.02 times the mass of 1,6-hexanediol) and triphenyl phosphate (0.03 times the mass of 1,6-hexanediol) were added and mixed evenly. The mixture was stirred at 185°C and 500 r / min for 2.5 h in a nitrogen atmosphere, and the mixture was heated to 235°C and continued to stir for 45 min at 65 Pa, and cooled to room temperature to obtain polyester. The polyester, 7-(dimethylamino)coumarin, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.7:11, and the mixture was stirred at 55°C and 400 r / min for 3.5 h. The mixture was dried at 55°C for 9 h under vacuum conditions to obtain a modified polyester.

[0032] (2) Phase change microcapsules, maleic anhydride, methyl-vinyl polysiloxane, and toluene were mixed in a mass ratio of 1:0.7:0.6:13 to prepare a mixed reaction liquid; azobisisobutyronitrile (0.02 times the mass of maleic anhydride) and toluene were mixed in a mass ratio of 1:25 to prepare an azobisisobutyronitrile solution; under a nitrogen atmosphere, at 75° C. and 400 r / min stirring conditions, the azobisisobutyronitrile solution was uniformly added dropwise to the mixed reaction liquid within 20 minutes, and the stirring reaction was continued for 5.5 h, cooled to room temperature, filtered and washed with methanol and deionized water 4 times each, dried at 55°C for 7h under vacuum conditions to obtain pre-modified phase change microcapsules; the pre-modified phase change microcapsules, 1-hydroxymethyl-5,5-dimethylhydantoin, 1,4-benzoquinone and toluene were mixed uniformly in a mass ratio of 1:2.5:0.03:15, stirred at 55°C and 400r / min for 11h, filtered and washed with methanol and deionized water 4 times each, dried at 55°C for 9h under vacuum conditions to obtain modified phase change microcapsules;

[0033] (3) Sodium hypochlorite and deionized water were mixed in a mass ratio of 1:10, and the pH was adjusted to neutral with a sulfuric acid aqueous solution with a mass fraction of 11% to prepare a chlorination finishing solution; the modified polyester, modified phase change microcapsules, copper chloride, and dichloromethane were mixed in a mass ratio of 1:0.07:0.035:9, and stirred at 25°C and 400r / min for 1.5h to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an aluminum foil covered on an ice plate was used as a receiving device. The receiving distance was adjusted to 17cm. During the spinning process, the voltage was 24kV, the propulsion rate was 0.65mL / h, the ambient temperature was 25°C, and the spinning humidity was 55%. Electrospinning was performed in an electrospinning device to obtain primary fibers; the primary fibers were immersed in the chlorination finishing solution, immersed at room temperature for 1.5h, taken out, washed 4 times with deionized water, and dried at 55°C under vacuum conditions for 9h to obtain antibacterial fibers.

[0034] Example 3

[0035] A method for preparing an antibacterial fiber, the method comprising the following steps:

[0036] (1) 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate were added to a reactor in a molar ratio of 1:0.6:0.4, and then tetrabutyl titanate (0.03 times the mass of 1,6-hexanediol) and triphenyl phosphate (0.04 times the mass of 1,6-hexanediol) were added and mixed evenly. The mixture was stirred at 190°C and 600 r / min for 2 h in a nitrogen atmosphere, and the mixture was heated to 240°C and continued to stir at 70 Pa for 40 min, and cooled to room temperature to obtain polyester. Polyester, 7-(dimethylamino)coumarin, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.8:12, and the mixture was stirred at 60°C and 500 r / min for 3 h, and dried at 60°C for 8 h under vacuum conditions to obtain modified polyester.

[0037] (2) Phase change microcapsules, maleic anhydride, methyl-vinyl polysiloxane, and toluene were mixed in a mass ratio of 1:0.8:0.7:14 to prepare a mixed reaction liquid; azobisisobutyronitrile (0.03 times the mass of maleic anhydride) and toluene were mixed in a mass ratio of 1:30 to prepare an azobisisobutyronitrile solution; under a nitrogen atmosphere, at 80° C., 500 r / min stirring conditions, the azobisisobutyronitrile solution was uniformly added dropwise to the mixed reaction liquid within 20 minutes, and the stirring reaction was continued for 5 minutes. h, cooled to room temperature, filtered and washed with methanol and deionized water for 5 times, dried at 60°C for 6 hours under vacuum conditions to obtain pre-modified phase change microcapsules; the pre-modified phase change microcapsules, 1-hydroxymethyl-5,5-dimethylhydantoin, 1,4-benzoquinone and toluene were mixed uniformly in a mass ratio of 1:3:0.04:16, stirred at 60°C and 500r / min for 10 hours, filtered and washed with methanol and deionized water for 5 times, dried at 60°C for 8 hours under vacuum conditions to obtain modified phase change microcapsules;

[0038] (3) Sodium hypochlorite and deionized water were mixed in a mass ratio of 1:11, and the pH was adjusted to neutral with a 12% sulfuric acid aqueous solution to prepare a chlorination finishing solution; the modified polyester, modified phase change microcapsules, copper chloride, and dichloromethane were mixed in a mass ratio of 1:0.08:0.04:10, and stirred at 30°C and 500r / min for 1h to prepare a spinning solution; the spinning solution was loaded into a micro pump, and an aluminum foil covered on an ice plate was used as a receiving device. The receiving distance was adjusted to 18cm. During the spinning process, the voltage was 25kV, the propulsion rate was 0.7mL / h, the ambient temperature was 30°C, and the spinning humidity was 60%. Electrospinning was performed in an electrospinning device to obtain primary fibers; the primary fibers were immersed in the chlorination finishing solution, immersed at room temperature for 1h, taken out, washed 5 times with deionized water, and dried at 60°C under vacuum conditions for 8h to obtain antibacterial fibers.

[0039] Comparative Example 1

[0040] The difference between the preparation method of the antibacterial fiber of Comparative Example 1 and Example 2 lies in the difference in step (1). Step (1) is modified as follows: 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate are added to a reactor in a molar ratio of 1:0.55:0.35, and then 0.02 times the mass of 1,6-hexanediol tetrabutyl titanate and 0.03 times the mass of 1,6-hexanediol triphenyl phosphate are added and mixed evenly. In a nitrogen atmosphere, the mixture is stirred at 185°C and 500r / min for 2.5h, the mixture is heated to 235°C and 65Pa, the mixture is stirred for 45min, and the mixture is cooled to room temperature to obtain a modified polyester. The remaining steps are the same as those in Example 2.

[0041] Comparative Example 2

[0042] The difference between the preparation method of the antibacterial fiber of Comparative Example 2 and Example 2 lies in the difference in step (1). Step (1) is modified as follows: 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl adipate are added to a reactor in a molar ratio of 1:0.55:0.35, and then 0.02 times the mass of 1,6-hexanediol tetrabutyl titanate and 0.03 times the mass of 1,6-hexanediol triphenyl phosphate are added and mixed evenly, and the mixture is heated in a nitrogen atmosphere. The reaction was stirred at 185°C and 500r / min for 2.5h, the temperature was raised to 235°C, and the reaction was continued with stirring at 65Pa for 45min, and the polyester was obtained by cooling to room temperature; the polyester, 7-(dimethylamino)coumarin, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:0.7:11, the reaction was stirred at 55°C and 400r / min for 3.5h, and the modified polyester was obtained by drying at 55°C for 9h under vacuum conditions. The remaining steps were the same as those in Example 2.

[0043] Comparative Example 3

[0044] The preparation method of the antibacterial fiber of Comparative Example 3 is different from that of Example 2 only in step (2), and step (2) is modified as follows: phase change microcapsules, maleic anhydride, methyl-vinyl polysiloxane, and toluene are mixed uniformly in a mass ratio of 1:0.7:0.6:13 to prepare a mixed reaction liquid; azobisisobutyronitrile with a mass ratio of 0.02 times that of maleic anhydride and toluene are mixed uniformly in a mass ratio of 1:25 to prepare an azobisisobutyronitrile solution, and under a nitrogen atmosphere, at 75°C, 400r / min stirring conditions, the azobisisobutyronitrile solution is uniformly added dropwise to the mixed reaction liquid within 20min, and the stirring reaction is continued for 5.5h, cooled to room temperature, filtered and washed with methanol and deionized water 4 times each, and dried at 55°C for 7h under vacuum conditions to obtain modified phase change microcapsules. The remaining steps are the same as those of Example 2.

[0045] Comparative Example 4

[0046] The difference between the preparation method of the antibacterial fiber of Comparative Example 4 and Example 2 is that step (2) is not performed, and step (3) is modified as follows: sodium hypochlorite and deionized water are mixed uniformly in a mass ratio of 1:10, and the pH is adjusted to neutral with a sulfuric acid aqueous solution with a mass fraction of 11% to prepare a chlorination finishing liquid; modified polyester, phase change microcapsules, copper chloride, and dichloromethane are mixed uniformly in a mass ratio of 1:0.07:0.035:9, stirred at 25°C and 400r / min for 1.5h, and prepared into a spinning solution ; The spinning solution is loaded into a micro pump, and an aluminum foil is covered on an ice plate as a receiving device, and the receiving distance is adjusted to 17 cm. During the spinning process, the voltage is 24 kV, the propulsion rate is 0.65 mL / h, the ambient temperature is 25°C, and the spinning humidity is 55%. Electrospinning is performed in an electrospinning device to obtain primary fibers; the primary fibers are immersed in a chlorinated finishing solution, immersed at room temperature for 1.5 hours, taken out, washed with deionized water 4 times, and dried at 55°C for 9 hours under vacuum conditions to obtain antibacterial fibers. The remaining steps are the same as in Example 2.

[0047] Test Example 1

[0048] Antimicrobial performance testing

[0049] Test method: The antibacterial performance of the embodiment and the comparative example was analyzed by comparing the number of E. coli colonies cultured in agar medium for 16 hours using the oscillation method GB / T20944.3. The results are shown in Table 1.

[0050] Table 1

[0051] Antibacterial rate (%) Antibacterial rate (%) Example 1 99.72 Comparative Example 1 92.27 Example 2 99.81 Comparative Example 2 95.16 Example 3 99.79 Comparative Example 3 89.48 Comparative Example 4 88.39

[0052] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the antibacterial fiber prepared in the present invention has good antibacterial properties.

[0053] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate are polymerized to prepare polyester, bromine atoms are introduced into the side chains of the polyester molecules through an ester exchange reaction, and the bromine atoms introduced into the polyester react with the dimethylamino group on 7-(dimethylamino)coumarin to prepare the modified polyester, and generate a quaternary ammonium salt cation structure; the quaternary ammonium salt cation can play a certain antibacterial role.

[0054] By comparison, the antibacterial rates of Examples 1 to 3 are greater than those of Comparative Examples 3 to 4, indicating that maleic anhydride and methyl-vinyl polysiloxane are polymerized and coated on the surface of phase change microcapsules to obtain pre-modified phase change microcapsules; a dianhydride structure is introduced on the surface of the phase change microcapsules, and the dianhydride structure on the pre-modified phase change microcapsules reacts with the hydroxymethyl group on 1-hydroxymethyl-5,5-dimethylhydantoin to obtain modified phase change microcapsules; a chloramine precursor is introduced into the modified phase change microcapsules, and the modified polyester, the modified phase change microcapsules, and copper chloride are prepared into a spinning solution, and the antibacterial fiber is obtained by chlorination after electrospinning; the chloramine precursor on the modified phase change microcapsules is chlorinated to generate N-Cl bonds, and the N-Cl bonds in the chloramines are slowly decomposed in the presence of water molecules to release hypohalous acids or hypohalite radicals with strong oxidizing properties, which directly attack some groups in bacteria to denature proteins and inhibit enzyme metabolism, thereby giving the antibacterial fiber excellent antibacterial properties.

[0055] Test Example 2

[0056] Flame retardant performance test

[0057] Test method: According to GB / T5454 "Textile Combustion Performance Test Oxygen Index Method" an oxygen index instrument was used to test the limiting oxygen index of the examples and comparative examples. The results are shown in Table 2

[0058] Table 2

[0059] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 30.59 Comparative Example 1 30.21 Example 2 31.07 Comparative Example 2 25.61 Example 3 30.88 Comparative Example 3 30.01 Comparative Example 4 26.33

[0060] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 2, it can be found that the antibacterial fiber prepared in the present invention has good flame retardant properties.

[0061] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that the polyester is prepared by polymerizing 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate, and phosphorus is introduced into the main chain of the polyester molecule through an ester exchange reaction. The introduction of phosphorus can improve the flame retardant properties of the antibacterial fiber.

[0062] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 4. Secondly, it indicates that maleic anhydride and methyl-vinyl polysiloxane are polymerized and coated on the surface of phase change microcapsules to obtain pre-modified phase change microcapsules; Si-O bonds are introduced on the surface of phase change microcapsules, and the introduction of Si-O bonds can further improve the flame retardant properties of the antibacterial fiber.

[0063] Test Example 3

[0064] Mechanical properties and anti-aging properties.

[0065] Test method: The mechanical properties of the embodiment and the comparative example were tested using an XL-1A filament tensile tester. The sample was passed around the yarn guide hook and the yarn guide wheel, and passed downward through the upper and lower clamps to ensure that the sample was straightened without relaxation. A pre-tension of about 10 cN was applied to the sample. The lower clamp drove the sample downward until the sample broke and then returned to its original position to obtain the breaking strength of the sample. After that, the original sample that was not subjected to the breaking test was irradiated with a xenon arc lamp for 72 hours, and then its breaking strength was tested using the same method, and the breaking strength change rate of the embodiment and the comparative example before and after the ultraviolet aging treatment was calculated. The results are shown in Table 3.

[0066] Table 3

[0067]

[0068] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the antibacterial fiber prepared by the present invention has good mechanical properties and anti-aging properties.

[0069] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 1, indicating that 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate are polymerized to prepare polyester, bromine atoms are introduced into the side chains of the polyester molecules through an ester exchange reaction, and the bromine atoms introduced into the polyester react with the dimethylamino groups on 7-(dimethylamino)coumarin to prepare the modified polyester, and generate a quaternary ammonium salt cation structure; the quaternary ammonium salt cation can combine with the carboxyl groups on the modified phase change microcapsules through positive and negative charges to form a cross-linked network, thereby inhibiting the relative slip between molecular chains and improving the mechanical properties of the antibacterial fiber.

[0070] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that the polyester is prepared by polymerizing 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate, and the terpyridine structure is introduced into the side chain of the polyester molecule through an ester exchange reaction. The terpyridine structure can form a coordination complex with copper ions to form a cross-linked structure, thereby inhibiting the relative slip between molecular chains and improving the mechanical properties of the antibacterial fiber.

[0071] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Examples 3 to 4, indicating that maleic anhydride and methyl-vinyl polysiloxane are polymerized and coated on the surface of phase change microcapsules to obtain pre-modified phase change microcapsules; a dianhydride structure is introduced on the surface of the phase change microcapsules, and the dianhydride structure on the pre-modified phase change microcapsules is reacted with the hydroxymethyl group on 1-hydroxymethyl-5,5-dimethylhydantoin to obtain modified phase change microcapsules, and carboxyl groups are introduced into the modified phase change microcapsules. The carboxyl groups introduced into the modified phase change microcapsules can combine with the quaternary ammonium salt cations generated on the modified polyester through positive and negative charges to form a cross-linked network, thereby inhibiting the relative slip between molecular chains and further improving the mechanical properties of the antibacterial fiber.

[0072] By comparison, the breaking strength change rate of Examples 1 to 3 is less than that of Comparative Example 1, indicating that 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate are polymerized to prepare polyester, bromine atoms are introduced into the side chains of the polyester molecules through an ester exchange reaction, the bromine atoms introduced into the polyester are reacted with the dimethylamino group on 7-(dimethylamino)coumarin to prepare a modified polyester, a benzopyrone structure is introduced into the side chains of the modified polyester, and the benzopyrone structure can absorb ultraviolet light, thereby giving the antibacterial fiber excellent anti-aging properties.

[0073] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an antibacterial fiber, characterized in that: The preparation method of the antibacterial fiber comprises the following steps: reacting polyester and 7-(dimethylamino)coumarin to obtain modified polyester; reacting pre-modified phase change microcapsules and 1-hydroxymethyl-5,5-dimethylhydantoin to obtain modified phase change microcapsules; preparing a spinning solution by mixing the modified polyester, the modified phase change microcapsules and copper chloride, and performing electrostatic spinning followed by chlorination finishing to obtain the antibacterial fiber; The polyester is prepared by polymerizing 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-ylphosphonate; The pre-modified phase-change microcapsules are prepared by polymerizing maleic anhydride and methyl-vinyl polysiloxane and coating the surfaces of the phase-change microcapsules.

2. The method for preparing an antibacterial fiber according to claim 1, characterized in that: The preparation method of the antibacterial fiber comprises the following preparation steps: (1) 1,6-hexanediol, diethyl 2-(bromomethyl)succinate, and diethyl 2,2':6',2"-terpyridine-4'-phosphonate were added to a reaction kettle in a molar ratio of 1:(0.5-0.6):(0.3-0.4), and then tetrabutyl titanate (0.01-0.03 times the mass of 1,6-hexanediol) and a heat stabilizer (0.02-0.04 times the mass of 1,6-hexanediol) were added and mixed evenly. The mixture was heated at 180-190°C and 400-600r / min in a nitrogen atmosphere. min stirring reaction for 2-3h, heating to 230-240°C, stirring reaction at 60-70Pa for 40-50min, cooling to room temperature to obtain polyester; mixing polyester, 7-(dimethylamino)coumarin, and N,N-dimethylformamide in a mass ratio of 1:(0.6-0.8):(10-12), stirring reaction at 50-60°C and 300-500r / min for 3-4h, and drying at 50-60°C under vacuum conditions for 8-10h to obtain modified polyester; (2) Phase change microcapsules, maleic anhydride, methyl-vinyl polysiloxane, and toluene are mixed uniformly in a mass ratio of 1:(0.6-0.8):(0.5-0.7):(12-14) to prepare a mixed reaction liquid; under a nitrogen atmosphere, at 70-80°C and 300-500 r / min stirring conditions, azobisisobutyronitrile solution is uniformly added to the mixed reaction liquid within 20 minutes, and the stirring reaction is continued for 5-6 hours, cooled to room temperature, filtered and washed with methanol and deionized water for 3-5 times, and vacuum-dried. The pre-modified phase change microcapsules were prepared by drying at 50-60°C for 6-8h; the pre-modified phase change microcapsules, 1-hydroxymethyl-5,5-dimethylhydantoin, 1,4-benzoquinone and toluene were uniformly mixed in a mass ratio of 1:(2-3):(0.02-0.04):(14-16), stirred at 50-60°C and 300-500r / min for 10-12h, filtered and washed with methanol and deionized water for 3-5 times respectively, and dried at 50-60°C for 8-10h under vacuum conditions to obtain modified phase change microcapsules; (3) The modified polyester, modified phase change microcapsules, copper chloride and dichloromethane are mixed uniformly in a mass ratio of 1: (0.06-0.08): (0.03-0.04): (8-10), and stirred at 20-30°C and 300-500 r / min for 1-2 h to prepare a spinning solution; the spinning solution is loaded into a micro pump, and electrospinning is performed in an electrospinning device to obtain primary fibers; the primary fibers are immersed in a chlorinated finishing solution, immersed at room temperature for 1-2 h, taken out, washed with deionized water for 3-5 times, and dried at 50-60°C under vacuum conditions for 8-10 h to obtain antibacterial fibers.

3. The method for preparing an antibacterial fiber according to claim 2, characterized in that: The thermal stabilizer in step (1) is triphenyl phosphate.

4. The method for preparing an antibacterial fiber according to claim 2, characterized in that: The model of the phase change microcapsule in step (2) is PCM32.

5. The method for preparing an antibacterial fiber according to claim 2, characterized in that: The molecular weight of the methyl-vinyl polysiloxane in step (2) is 2000.

6. The method for preparing an antibacterial fiber according to claim 2, characterized in that: The preparation method of the azobisisobutyronitrile solution in step (2) is as follows: 0.01 to 0.03 times the mass of maleic anhydride azobisisobutyronitrile and toluene are uniformly mixed in a mass ratio of 1:(20 to 30) to prepare an azobisisobutyronitrile solution.

7. The method for preparing an antibacterial fiber according to claim 2, characterized in that: The preparation method of the chlorination finishing liquid in step (3) is as follows: sodium hypochlorite and deionized water are uniformly mixed in a mass ratio of 1:(9-11), and the pH is adjusted to neutral with a sulfuric acid aqueous solution with a mass fraction of 10%-12%, so as to prepare the chlorination finishing liquid.

8. The method for preparing an antibacterial fiber according to claim 2, characterized in that: The process parameters of the electrospinning in step (3) are as follows: the spinning solution is loaded into a micro pump, an aluminum foil is covered on an ice plate as a receiving device, the receiving distance is adjusted to 16 to 18 cm, the voltage during the spinning process is 23 to 25 kV, the propulsion rate is 0.6 to 0.7 mL / h, the ambient temperature is 20 to 30° C., and the spinning humidity is 50% to 60%.

9. A fabric woven from antibacterial fibers prepared by the method for preparing antibacterial fibers according to any one of claims 1 to 8.

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