A bio-based antibacterial type spun yarn

Abstract

The application discloses a kind of bio-based antibacterial type spinning yarn, it is related to spinning yarn technical field.The polyester is polymerized by terephthalic acid, vanillin base silicon-containing flame-retardant monomer, 1,3-propanediol when preparing bio-based antibacterial type spinning yarn;Butenyl sulfonium salt is prepared by the reaction of ethyl but-3-enyl sulfide and iodomethane;Modified lignin is prepared by the reaction of lignin, butenyl sulfonium salt and 3-butyl phosphonic acid diethyl ester;Organic zinc complex is prepared by the reaction of zinc acetate, sulfadiazine and kaempferol;Polyester fiber is prepared by mixing polyester, modified lignin and organic zinc complex, melt spinning;Bio-based antibacterial type spinning yarn is prepared by spinning in spinning equipment.The bio-based antibacterial type spinning yarn prepared by the application has excellent antibacterial and flame-retardant properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of spinning yarn, in particular to a bio-based antibacterial spinning yarn. BACKGROUND

[0002] Spinning yarn is a continuous slender body made of textile fibers through twisting, stretching and other processes, is a key intermediate material connecting fibers and fabrics, and is widely used in the fields of textile clothing, industrial cloth and the like. Among synthetic fibers, polyester fiber has high strength and certain elasticity, and becomes the first large variety of synthetic fiber industry with its excellent performance and low price. PET fiber and PBT fiber have been mass produced and widely used, PTT fiber has the advantages of both, and can be spun alone or blended with cotton, wool or other short fibers. PTT spinning yarn has excellent resilience, dyeing and durability, and can be used to produce underwear, shirts, sportswear and carpets. Like most textile products, the textile products prepared from PTT spinning yarn also have the problem of bacterial breeding, therefore, it is necessary to invent a PTT spinning yarn with excellent antibacterial performance. SUMMARY

[0003] The present application relates to the technical field of spinning yarn, in particular to a bio-based antibacterial spinning yarn.

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

[0005] A bio-based antibacterial spinning yarn, the bio-based antibacterial spinning yarn is prepared by polymerizing terephthalic acid, vanillin-based silicon-containing flame-retardant monomer and 1,3-propanediol to obtain polyester; modified lignin is prepared by reacting lignin, butenyl sulfonium salt and 3-butene phosphoric acid diethyl ester; polyester fiber is prepared by mixing polyester, modified lignin and organic zinc complex and melt spinning; and the bio-based antibacterial spinning yarn is prepared by spinning the polyester fiber in a spinning equipment.

[0006] The vanillin-based silicon-containing flame-retardant monomer is prepared by reacting siloxane intermediate and 3-amino-1-propanol;

[0007] The siloxane intermediate is prepared by reacting 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane and vanillin;

[0008] The butenyl sulfonium salt is prepared by reacting ethyl but-3-enyl sulfide and iodomethane;

[0009] The organic zinc complex is prepared by reacting zinc acetate, sulfadiazine and thymol.

[0010] As an optimization, the preparation method of the bio-based antibacterial spinning yarn comprises the following preparation steps:

[0011] (1) mixing terephthalic acid, vanillin-based silicon-containing flame retardant monomer and 1,3-propanediol uniformly, placing in a reaction kettle, adding 0.1-0.12 times of terephthalic acid mass of tetrabutyl titanate, under nitrogen protection, heating to 220-240℃ at a heating rate of 10℃ / min, keeping the temperature constant until the water output reaches 90% of the theoretical value, heating to 260-270℃, vacuumizing to maintain the pressure in the reaction kettle below 70 Pa, continuing to stir for 2-3 h, discharging under nitrogen atmosphere, to obtain polyester;

[0012] (2) mixing lignin, butenyl sulfonium salt, 3-butenyl diethyl phosphate and N,N-dimethylformamide uniformly, stirring at 50-60℃ and 200-300 r / min for 20-30 min, adding 0.6-0.8 times of lignin mass of sodium chloride and 0.5-0.6 times of lignin mass of hydrogen peroxide, continuing to stir at 50-60℃ for 20-24 h, precipitating with 10% hydrochloric acid aqueous solution, suction filtering, washing with deionized water for 5 times, drying at 60-70℃ under vacuum for 10-12 h, to obtain modified lignin;

[0013] (3) mixing zinc acetate and methanol uniformly at a mass ratio of 1:(14-16) to prepare a zinc solution; adding sulfadiazine, thymol and potassium hydroxide into 50-60 times of sulfadiazine mass of methanol, stirring at 70-80℃ and 300-400 r / min for 20-30 min, adding the zinc solution at a uniform speed within 20 min, continuing to stir at 70-80℃ for 3-4 h after the addition is completed, naturally cooling to room temperature, standing for 10-12 h, suction filtering, washing with methanol for 3 times, drying at 50-60℃ under vacuum for 9-10 h, to obtain an organic zinc complex;

[0014] (4) mixing polyester, modified lignin and organic zinc complex at a mass ratio of 1:(0.08-0.10):(0.04-0.06), placing in a melt spinning device for melt spinning, to obtain polyester fiber; spinning the polyester fiber in a spinning device to obtain a bio-based antibacterial type spun yarn.

[0015] As an optimization, the preparation method of the vanillin-based silicon-containing flame retardant monomer in step (1) is: adding a siloxane intermediate and 3-amino-1-propanol at a molar ratio of 1:2 into 16-18 times of siloxane intermediate mass of anhydrous ethanol, stirring at 60-70℃ and 300-500 r / min for 5-6 h under nitrogen protection, drying at 50-60℃ under vacuum for 9-10 h, to obtain the vanillin-based silicon-containing flame retardant monomer.

[0016] As optimization, the molar ratio of terephthalic acid, vanillin-based silicon-containing flame retardant monomer, 1,3-propanediol in step (1) is 1:(0.4-0.5):(0.6-0.7).

[0017] As optimization, the preparation method of the siloxane intermediate is as follows: 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane and tetrahydrofuran are uniformly mixed in a mass ratio of 1:(7-8) to prepare a siloxane solution; vanillin, triethylamine, and tetrahydrofuran are uniformly mixed in a mass ratio of 1:(0.1-0.2):(10-12) in an amount of 2 times the molar amount of 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane, and the siloxane solution is added at a constant speed under the conditions of nitrogen protection, 0-5°C, and 300-500 r / min stirring for 30 min; after the addition is completed, the temperature is raised to room temperature, and the stirring is continued for 10-12 h; tetrahydrofuran is removed by rotary evaporation, washed with deionized water 4 times, and dried at 50-60°C under vacuum for 9-10 h to obtain the siloxane intermediate.

[0018] As optimization, the CAS number of 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane is 17962-87-7.

[0019] As optimization, the reaction mechanism of the vanillin-based silicon-containing flame retardant monomer in step (1) is as follows:

[0020] .

[0021] As optimization, the preparation method of the butenyl sulfonium salt in step (2) is as follows: ethyl but-3-enyl sulfide and iodomethane are added to acetonitrile in a molar ratio of 1:(1.1-1.3), and iodomethane is added in an amount of 1.1-1.3 times the molar amount of silver tetrafluoroborate; the mixture is stirred at room temperature under argon protection at 300-500 r / min for 10-12 h; the mixture is filtered, and the filtrate is exchanged with basic anion exchange resin in a shaker for 2-3 h; and the mixture is dried at 60-70°C under vacuum for 9-10 h to obtain the butenyl sulfonium salt; the reaction mechanism is as follows:

[0022] .

[0023] As optimization, the brand of the basic anion exchange resin is XN-5X7, and the manufacturer is Maiklin.

[0024] As optimization, the CAS number of ethyl but-3-enyl sulfide is 99116-24-2.

[0025] As optimization, the mass ratio of the lignin, butenyl sulfonium salt and 3-butene phosphoric acid diethyl ester in step (2) is 1: (2~2.2): (3~4).

[0026] As optimization, the molar ratio of the zinc acetate, sulfadiazine, hematoxylin and potassium hydroxide in step (3) is 1:1:1: (0.2~0.3).

[0027] As optimization, the reaction mechanism of the organic zinc complex in step (3) is as follows:

[0028] .

[0029] As optimization, the process parameters of the melt spinning in step (4) are as follows: screw temperature: 240 DEG C in the first zone, 240 DEG C in the second zone, 245 DEG C in the third zone, 250 DEG C in the fourth zone, spinneret aperture is 0.28mm, the number of holes is 48, the metering pump temperature is 260 DEG C, the cooling mode is side blowing, and the spinning rate is 2800r / min.

[0030] Compared with the prior art, the present application has the following beneficial effects:

[0031] In the preparation of the bio-based antibacterial type spinning yarn, first, 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane and vanillin are reacted to prepare a siloxane intermediate; the siloxane intermediate and 3-amino-1-propanol are reacted to prepare a vanillin-based silicon-containing flame retardant monomer; vanillin is a widely used and affordable industrial lignin raw material; a bio-based flame retardant is synthesized by taking vanillin as a carbon source and combining siloxane; the bio-based flame retardant participates in the polymerization reaction of polyester; the bio-based flame retardant is introduced into the molecular main chain of polyester, and the bio-based antibacterial type spinning yarn is endowed with excellent flame retardant performance.

[0032] Secondly, ethyl but-3-enyl sulfide and iodomethane are reacted to prepare butenyl sulfonium salt; lignin, butenyl sulfonium salt and 3-butene phosphoric acid diethyl ester are reacted to prepare modified lignin; NaCl-H2O2 is used as an initiation system, and butenyl sulfonium salt and 3-butene phosphoric acid diethyl ester are grafted onto lignin through free radical copolymerization to prepare modified lignin; sulfonium salt structure and phosphorus element are introduced into lignin; the introduction of sulfonium salt structure can improve the antibacterial performance of the bio-based antibacterial type spinning yarn; the introduction of phosphorus element can improve the flame retardant performance of the bio-based antibacterial type spinning yarn; lignin is the second most abundant biomass resource in the world after cellulose; there are a large number of aromatic ring structures in lignin, which has a high initial thermal degradation temperature and excellent thermal stability; however, lignin is not fully utilized as a byproduct of the papermaking industry; the modification and application of lignin are of great significance to resource conservation and environmental protection.

[0033] Finally, zinc acetate, sulfadiazine, and thymol were reacted to obtain an organic zinc complex; sulfadiazine and thymol were used as ligands to coordinate with zinc ions to obtain a ternary metal complex. Thymol is a natural flavonoid compound and exists in large quantities in fruits, vegetables, and herbs. A large number of clinical studies have shown that thymol and some of its glycosides have a wide range of biological activities, including antioxidant, anti-inflammatory, and antibacterial activities. However, the antibacterial activity of thymol is not high. After thymol is combined with metal ions to form a complex, the biological activity of thymol can be enhanced, and the antibacterial ability can be improved, thereby further improving the antibacterial performance of the bio-based antibacterial type spun yarn. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0035] The basic anion exchange resin used in the following examples and comparative examples is XN-5X7 from Macklin, and the lignin used is industrial grade from Shandong Longli Science and Technology Co., Ltd. The hydrogen peroxide used has a concentration of 30 wt.% and is purchased from Shanghai Aladdin.

[0036] Example 1

[0037] A bio-based antibacterial type spun yarn, and a preparation method of the bio-based antibacterial type spun yarn includes the following preparation steps:

[0038] (1) 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane, tetrahydrofuran are mixed uniformly according to a mass ratio of 1:7 to prepare a siloxane solution; vanillin, triethylamine, tetrahydrofuran are mixed uniformly according to a molar ratio of 1:0.1:10, 2 times of 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane in molar amount, under nitrogen protection, 0℃, 300r / min stirring, the siloxane solution is added uniformly at a constant speed within 30min, after the addition is completed, the temperature is raised to room temperature, and the stirring is continued to react for 10h, tetrahydrofuran is removed by rotary evaporation, washed with deionized water for 4 times, dried at 50℃ under vacuum for 10h to prepare a siloxane intermediate; the siloxane intermediate, 3-amino-1-propanol are added into anhydrous ethanol according to a molar ratio of 1:2, the siloxane intermediate is 16 times of anhydrous ethanol in mass, under nitrogen protection, 60℃, 300r / min stirring, reaction for 6h, dried at 50℃ under vacuum for 10h to prepare a vanillin-based siliceous flame-retardant monomer; terephthalic acid, the vanillin-based siliceous flame-retardant monomer, 1,3-propanediol are mixed uniformly according to a molar ratio of 1:0.4:0.6, placed in a reaction kettle, titanium tetrabutoxide is added according to 0.1 times of terephthalic acid in mass, under nitrogen protection, the temperature is raised to 220℃ at a temperature rising speed of 10℃ / min, the temperature is kept constant until the water output reaches 90% of the theoretical value, the temperature is raised to 260℃, the pressure in the reaction kettle is maintained below 70Pa by vacuumizing, the stirring is continued to react for 3h, the material is discharged under nitrogen atmosphere to prepare a polyester;

[0039] (2) ethyl but-3-enyl sulfide, iodomethane are added into acetonitrile according to a molar ratio of 1:1.1, the iodomethane is added into silver tetrafluoroborate according to an equimolar amount, under argon protection, at room temperature, 300r / min stirring, reaction for 10h, filtration, the filtrate is exchanged with basic anion exchange resin in a shaker for 2h, dried at 60℃ under vacuum for 10h to prepare a butenyl sulfonium salt; lignin, butenyl sulfonium salt, 3-butyl phosphonic acid diethyl ester, N,N-dimethylformamide are mixed uniformly according to a mass ratio of 1:2:3:30, 50℃, 200r / min stirring for 30min, sodium chloride is added according to 0.6 times of lignin in mass, and hydrogen peroxide is added according to 0.5 times of lignin in mass, 50℃, the stirring is continued to react for 24h, precipitated with 10% hydrochloric acid aqueous solution, suction filtration, washed with deionized water for 5 times, dried at 60℃ under vacuum for 12h to prepare a modified lignin;

[0040] (3) zinc acetate, sulfadiazine, hematoxylin, potassium hydroxide were weighed according to the molar ratio of 1:1:1:0.2, zinc acetate and methanol were mixed uniformly according to the mass ratio of 1:14 to prepare a zinc solution; sulfadiazine, hematoxylin and potassium hydroxide were added to methanol with a mass of 50 times of sulfadiazine, stirred at 70°C and 300r / min for 30min, the zinc solution was added at a uniform speed within 20min, after the addition was completed, the stirring and reflux were continued at 70°C for 4h, after natural cooling to room temperature, it was placed for 10h, then filtered, washed with methanol for 3 times, dried at 50°C under vacuum for 10h to prepare an organic zinc complex;

[0041] (4) polyester, modified lignin and organic zinc complex were mixed according to the mass ratio of 1:0.08:0.04, and placed in a melt spinning device for melt spinning, the process parameters of melt spinning were set as follows: screw temperature: zone 1 240°C, zone 2 240°C, zone 3 245°C, zone 4 250°C, spinneret hole diameter 0.28mm, hole number 48, metering pump temperature 260°C, cooling method side blowing, spinning rate 2800r / min, to prepare polyester fiber; the polyester fiber was spun in a spinning device to prepare a bio-based antibacterial type spun yarn.

[0042] Example 2:

[0043] A bio-based antibacterial type spun yarn, the preparation method of the bio-based antibacterial type spun yarn comprises the following preparation steps:

[0044] (1) 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane, tetrahydrofuran are mixed uniformly according to a mass ratio of 1:7.5 to prepare a siloxane solution; vanillin, triethylamine, tetrahydrofuran are mixed uniformly according to a molar ratio of 1:0.15:11, 2.5℃, 400r / min stirring under nitrogen protection, the siloxane solution is added at a uniform speed within 30min, after the addition is completed, the temperature is increased to room temperature, and the stirring is continued to react for 11h, tetrahydrofuran is removed by rotary evaporation, washed with deionized water for 4 times, and dried at 55℃ under vacuum for 9.5h to prepare a siloxane intermediate; the siloxane intermediate and 3-amino-1-propanol are added to anhydrous ethanol with a mass of 17 times of the siloxane intermediate according to a molar ratio of 1:2, stirred at 65℃ under nitrogen protection for 5.5h, and dried at 55℃ under vacuum for 9.5h to prepare a vanillin-based siliceous flame-retardant monomer; terephthalic acid, the vanillin-based siliceous flame-retardant monomer, and 1,3-propanediol are mixed uniformly according to a molar ratio of 1:0.45:0.65, placed in a reaction kettle, and titanium tetrabutoxide with a mass of 0.11 times of the terephthalic acid is added, the temperature is increased to 230℃ at a temperature increasing speed of 10℃ / min under nitrogen protection, the temperature is kept constant until the water output reaches 90% of the theoretical value, the temperature is increased to 265℃, the pressure in the reaction kettle is maintained below 70Pa by vacuumizing, and the stirring is continued to react for 2.5h, and the product is discharged in a nitrogen atmosphere to prepare a polyester;

[0045] (2) ethyl but-3-enyl sulfide and iodomethane are added to acetonitrile with a mass of 13 times of the ethyl but-3-enyl sulfide according to a molar ratio of 1:1.2, and silver tetrafluoroborate with a molar amount equal to that of the iodomethane is added, stirred at room temperature under argon protection at 400r / min for 11h, filtered, and the filtrate is exchanged with basic anion exchange resin in a shaker for 2.5h, and dried at 65℃ under vacuum for 9.5h to prepare a butenyl sulfonium salt; lignin, the butenyl sulfonium salt, 3-butyl phosphonic acid diethyl ester, and N,N-dimethylformamide are mixed uniformly according to a mass ratio of 1:2.1:3.5:31, stirred at 55℃ for 25min at 250r / min, sodium chloride with a mass of 0.7 times of the lignin and hydrogen peroxide with a mass of 0.55 times of the lignin are added, and the stirring is continued to react at 55℃ for 22h, precipitated with 10% hydrochloric acid aqueous solution, filtered, washed with deionized water for 5 times, and dried at 65℃ under vacuum for 11h to prepare a modified lignin;

[0046] (3) zinc acetate, sulfadiazine, hematoxylin, potassium hydroxide were weighed according to the molar ratio of 1:1:1:0.25, zinc acetate and methanol were mixed uniformly according to the mass ratio of 1:15 to prepare a zinc solution; sulfadiazine, hematoxylin and potassium hydroxide were added to methanol with a mass of 55 times of sulfadiazine, stirred at 75°C and 350r / min for 25min, the zinc solution was added at a uniform speed within 20min, after the addition was completed, the stirring and reflux were continued at 75°C for 3.5h, after natural cooling to room temperature, it was placed for 11h, filtered, washed with methanol for 3 times, dried at 55°C under vacuum for 9.5h to prepare an organic zinc complex;

[0047] (4) polyester, modified lignin and organic zinc complex were mixed according to the mass ratio of 1:0.09:0.05, placed in a melt spinning device for melt spinning, the process parameters of melt spinning were set as follows: screw temperature: zone 1 240°C, zone 2 240°C, zone 3 245°C, zone 4 250°C, spinneret hole diameter 0.28mm, hole number 48, metering pump temperature 260°C, cooling method side blowing, spinning rate 2800r / min, to prepare polyester fiber; the polyester fiber was spun in a spinning device to prepare a bio-based antibacterial type spun yarn.

[0048] Example 3:

[0049] A bio-based antibacterial type spun yarn, the preparation method of the bio-based antibacterial type spun yarn comprises the following preparation steps:

[0050] (1) 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane, tetrahydrofuran are mixed uniformly according to a mass ratio of 1:8 to prepare a siloxane solution; vanillin, triethylamine, tetrahydrofuran are mixed uniformly according to a molar ratio of 1:0.2:12, 2 times of 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane in molar amount, under nitrogen protection, 5℃, 500r / min stirring, the siloxane solution is added uniformly at a constant speed within 30min, after the addition is completed, the temperature is raised to room temperature, and the stirring reaction is continued for 10h, tetrahydrofuran is removed by rotary evaporation, washed with deionized water for 4 times, dried at 60℃ under vacuum for 9h to prepare a siloxane intermediate; the siloxane intermediate, 3-amino-1-propanol are added into anhydrous ethanol according to a molar ratio of 1:2, the siloxane intermediate is 18 times of anhydrous ethanol in mass, under nitrogen protection, 70℃, 500r / min stirring for 5h, dried at 60℃ under vacuum for 9h to prepare a vanillin-based siliceous flame-retardant monomer; terephthalic acid, vanillin-based siliceous flame-retardant monomer, 1,3-propanediol are mixed uniformly according to a molar ratio of 1:0.5:0.7, placed in a reaction kettle, titanium tetrabutoxide is added according to 0.12 times of terephthalic acid in mass, under nitrogen protection, the temperature is raised to 240℃ at a temperature rising speed of 10℃ / min, the temperature is kept constant until the water output reaches 90% of the theoretical value, the temperature is raised to 270℃, the pressure in the reaction kettle is maintained below 70Pa by vacuumizing, the stirring reaction is continued for 2h, the material is discharged under nitrogen atmosphere to prepare a polyester;

[0051] (2) ethyl but-3-enyl sulfide, iodomethane are added into acetonitrile according to a molar ratio of 1:1.3, the iodomethane is added into silver tetrafluoroborate in an equal molar amount, under argon protection, at room temperature, 500r / min stirring for 12h, filtration, the filtrate is exchanged with basic anion exchange resin in a shaker for 3h, dried at 70℃ under vacuum for 9h to prepare a butenyl sulfonium salt; lignin, butenyl sulfonium salt, 3-butyl phosphonic acid diethyl ester, N,N-dimethylformamide are mixed uniformly according to a mass ratio of 1:2.2:4:32, stirred at 60℃ for 20min, sodium chloride is added according to 0.8 times of lignin in mass, and hydrogen peroxide is added according to 0.6 times of lignin in mass, the stirring reaction is continued at 60℃ for 20h, precipitated with 10% hydrochloric acid aqueous solution, suction filtration, washed with deionized water for 5 times, dried at 70℃ under vacuum for 10h to prepare a modified lignin;

[0052] (3) The zinc acetate, sulfadiazine, hematoxylin, and potassium hydroxide are weighed according to a molar ratio of 1:1:1:0.3, the zinc acetate and methanol are mixed uniformly according to a mass ratio of 1:16 to prepare a zinc solution; the sulfadiazine, hematoxylin, and potassium hydroxide are added into methanol with a mass of 60 times that of the sulfadiazine, stirred at 80°C and 400 r / min for 20 min, the zinc solution is added at a constant speed within 20 min, after the addition is completed, the stirring and reflux are continued at 80°C for 3 h, the temperature is naturally cooled to room temperature, and then the mixture is left to stand for 12 h, filtered, washed with methanol for 3 times, and dried at 60°C under vacuum for 9 h to prepare the organic zinc complex;

[0053] (4) The polyester, modified lignin, and organic zinc complex are mixed according to a mass ratio of 1:0.10:0.06, and placed in a melt spinning device to perform melt spinning, the process parameters of melt spinning are set as follows: screw temperature: zone 1, 240°C; zone 2, 240°C; zone 3, 245°C; zone 4, 250°C; spinneret hole diameter, 0.28 mm; hole number, 48; metering pump temperature, 260°C; cooling method, side blowing; spinning rate, 2800 r / min, to prepare polyester fibers; and the polyester fibers are spun in a spinning device to prepare the bio-based antibacterial type spun yarn.

[0054] Comparative Example 1

[0055] The preparation method of the bio-based antibacterial type spun yarn of Comparative Example 1 is different from that of Example 2 in step (1), which is modified as follows: the terephthalic acid and 1,3-propanediol are mixed uniformly according to a molar ratio of 1:1.1, placed in a reaction kettle, and 0.11 times the mass of terephthalic acid of tetrabutyl titanate is added, the temperature is raised to 230°C at a temperature rising speed of 10°C / min under nitrogen protection, the temperature is kept constant until the water output reaches 90% of the theoretical value, the temperature is raised to 265°C, the pressure in the reaction kettle is maintained below 70 Pa by vacuumizing, and the stirring is continued for 2.5 h, and the product is discharged under nitrogen atmosphere to prepare polyester. The other steps are the same as those of Example 2.

[0056] Comparative Example 2

[0057] The preparation method of the bio-based antibacterial type spun yarn of Comparative Example 2 is different from that of Example 2 in step (2), which is modified as follows: the lignin, 3-butenyl diethyl phosphate, and N,N-dimethylformamide are mixed uniformly according to a mass ratio of 1:3.5:31, stirred at 55°C and 250 r / min for 25 min, 0.7 times the mass of sodium chloride and 0.55 times the mass of hydrogen peroxide of the lignin are added, the stirring is continued at 55°C for 22 h, the product is precipitated with 10% hydrochloric acid aqueous solution, filtered, washed with deionized water for 5 times, and dried at 65°C under vacuum for 11 h to prepare modified lignin. The other steps are the same as those of Example 2.

[0058] Comparative Example 3

[0059] The preparation method of the biobased antibacterial type spun yarn of Comparative Example 3 is different from that of Example 2 only in step (2), which is modified as follows: ethyl but-3-enyl sulfide, iodomethane are added to acetonitrile with the mass of ethyl but-3-enyl sulfide being 13 times, iodomethane is added in an equimolar amount of silver tetrafluoroborate, stirring is carried out at room temperature under argon protection at 400 r / min for 11 h, filtration is carried out, the filtrate is exchanged with basic anion exchange resin in a shaker for 2.5 h, and drying is carried out under vacuum at 65°C for 9.5 h to obtain butenyl sulfonium salt; lignin, butenyl sulfonium salt, N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:2.1:31, stirring is carried out at 55°C at 250 r / min for 25 min, sodium chloride with the mass of lignin being 0.7 times and hydrogen peroxide with the mass of lignin being 0.55 times are added, stirring is continued at 55°C for 22 h, precipitation is carried out with 10% hydrochloric acid aqueous solution, suction filtration is carried out, washing is carried out with deionized water for 5 times, and drying is carried out under vacuum at 65°C for 11 h to obtain modified lignin. The remaining steps are the same as those of Example 2.

[0060] Comparative Example 4:

[0061] The preparation method of the biobased antibacterial type spun yarn of Comparative Example 4 is different from that of Example 2 in that step (3) is not carried out, and step (4) is modified as follows: polyester and modified lignin are mixed in a mass ratio of 1:0.09, and are placed in a melt spinning device for melt spinning, the process parameters of melt spinning are set as follows: screw temperature: zone 1 240°C, zone 2 240°C, zone 3 245°C, zone 4 250°C, spinneret hole diameter is 0.28 mm, hole number is 48, metering pump temperature is 260°C, cooling method is side blowing, and spinning rate is 2800 r / min to obtain polyester fiber; the polyester fiber is spun in a spinning device to obtain a biobased antibacterial type spun yarn. The remaining steps are the same as those of Example 2.

[0062] Test Example 1

[0063] Test of antibacterial performance

[0064] Test method: the biobased antibacterial type spun yarns prepared in the examples and comparative examples are woven into fabric samples with the same size according to the same textile process, each fabric sample is cut into a size of 20 mm x 20 mm, and quantitative test of antibacterial property is carried out according to national standard GB / T 20944.2-2007 “Evaluation of antibacterial property of textiles Part 2: absorption method”, and the test bacteria is Escherichia coli. The results are shown in Table 1.

[0065] Table 1

[0066] ;

[0067] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 1, it can be found that the bio-based antibacterial type spun yarn prepared by the application has good antibacterial performance.

[0068] By comparison, the bacteriostatic rate of Examples 1-3 is greater than that of Comparative Example 2, which shows that the butenyl sulfonium salt is prepared by reacting ethyl but-3-enyl sulfide and iodomethane; the modified lignin is prepared by reacting lignin, butenyl sulfonium salt and 3-butyl phosphoric acid diethyl ester; the butenyl sulfonium salt and 3-butyl phosphoric acid diethyl ester are grafted onto the lignin by free radical copolymerization with NaCl-H2O2 as the initiation system, and the modified lignin is prepared, which introduces sulfonium salt structure into the lignin, and the introduction of sulfonium salt structure can improve the antibacterial performance of the bio-based antibacterial type spun yarn.

[0069] By comparison, the bacteriostatic rate of Examples 1-3 is greater than that of Comparative Example 4, which shows that the organic zinc complex is prepared by reacting zinc acetate, sulfadiazine and kaempferol; the ternary metal complex is obtained by coordinating sulfadiazine and kaempferol with zinc ions, and kaempferol is one of natural flavonoids, which exists in large quantities in fruits, vegetables and herbs; a large number of clinical studies show that kaempferol and some of its glycosides have a wide range of biological activities, including antioxidant, anti-inflammatory, antibacterial and the like, but its antibacterial activity is not high, and the formation of the complex of kaempferol and metal ions can enhance its biological activity and improve the antibacterial ability, and further improve the antibacterial performance of the bio-based antibacterial type spun yarn.

[0070] Test Example 2

[0071] Test of flame retardant performance

[0072] Test method: the bio-based antibacterial type spun yarn prepared by the examples and comparative examples is woven into fabric samples with the same size according to the same textile process, and the limiting oxygen index of each fabric sample is tested according to GB / T5454-1997 "Textiles-Test for Combustion Performance-Oxygen Index Method". The results are shown in Table 2.

[0073] Table 2

[0074] ;

[0075] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 2, it can be found that the bio-based antibacterial type spun yarn prepared by the application has good flame retardant performance.

[0076] By comparison, the limiting oxygen index of examples 1~3 is greater than that of comparative example 1, which shows that the siloxane intermediate is prepared by reacting 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyl trisiloxane and vanillin; the vanillin-based siliceous flame-retardant monomer is prepared by reacting the siloxane intermediate and 3-amino-1-propanol; vanillin is a widely used and affordable industrial lignin raw material; a bio-based flame retardant is synthesized by taking vanillin as a carbon source and combining siloxane; the bio-based flame retardant participates in the polymerization reaction of polyester; the bio-based flame retardant is introduced into the molecular main chain of polyester; and the bio-based antibacterial type spinning yarn is endowed with excellent flame retardant performance.

[0077] By comparison, the limiting oxygen index of examples 1~3 is greater than that of comparative example 3, which shows that the modified lignin is prepared by grafting butenyl sulfonium salt and 3-butenyl diethyl phosphate to lignin through radical copolymerization with NaCl-H2O2 as an initiation system; the phosphorus element is introduced into the lignin; and the introduction of the phosphorus element can improve the flame retardant performance of the bio-based antibacterial type spinning yarn.

[0078] The above specific embodiments further illustrate the purpose, technical solutions and advantages of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application, and any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A bio-based antibacterial yarn, characterized in that, The bio-based antibacterial yarn is prepared by polymerizing terephthalic acid, vanillin-based silicon-containing flame-retardant monomer, and 1,3-propanediol to obtain polyester; reacting lignin, butenyl sulfonate, and diethyl 3-butenyl phosphate to obtain modified lignin; mixing polyester, modified lignin, and organozinc complex, and melt spinning to obtain polyester fiber; and spinning the polyester fiber in a spinning machine to obtain the bio-based antibacterial yarn. The vanillin-based silicon-containing flame retardant monomer is prepared by reacting a siloxane intermediate with 3-amino-1-propanol. The siloxane intermediate is prepared by reacting 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane with vanillin. The butenyl sulfonate is prepared by reacting ethylbut-3-enyl sulfide with iodomethane. The organozinc complex is prepared by reacting zinc acetate, sulfadiazine, and kaempferol. The molar ratio of terephthalic acid, vanillin-based silicon-containing flame retardant monomer, and 1,3-propanediol is 1:(0.4~0.5):(0.6~0.7). The mass ratio of lignin, butenylsulfonate, and diethyl 3-butenyl phosphate is 1:(2~2.2):(3~4); The mass ratio of the polyester, modified lignin, and organozinc complex is 1:(0.08~0.10):(0.04~0.06).

2. The bio-based antibacterial yarn according to claim 1, characterized in that, The method for preparing the bio-based antibacterial yarn includes the following preparation steps: (1) Terephthalic acid, vanillin-based silicon flame retardant monomer and 1,3-propanediol are mixed evenly and placed in a reaction vessel. Tetrabutyl titanate is added. Under nitrogen protection, the temperature is raised to 220~240℃ and reacted at a constant temperature until the water output reaches 90% of the theoretical value. Then the temperature is raised to 260~270℃ and vacuum is applied to maintain the pressure inside the reaction vessel below 70Pa. The reaction is continued to be stirred for 2~3 hours. The product is discharged under a nitrogen atmosphere to obtain polyester. (2) Mix lignin, butenyl sulfonate, diethyl 3-butenyl phosphate, and N,N-dimethylformamide evenly, stir at 50~60℃ for 20~30 min, add sodium chloride and hydrogen peroxide, continue stirring at 50~60℃ for 20~24 h, precipitate with hydrochloric acid aqueous solution, filter, wash, and dry to obtain modified lignin; (3) Mix zinc acetate and methanol evenly to prepare a zinc solution; add sulfadiazine, kaempferol and potassium hydroxide to methanol, stir and reflux at 70~80℃ for 20~30min, add zinc solution dropwise, continue stirring and reflux at 70~80℃ for 3~4h after the addition is complete, let it stand for 10~12h after naturally cooling to room temperature, filter, wash and dry to obtain organozinc complex; (4) The polyester, modified lignin and organic zinc complex are mixed and melt-spun in a melt spinning device to obtain polyester fiber; the polyester fiber is spun in a spinning device to obtain bio-based antibacterial yarn.

3. The bio-based antibacterial yarn according to claim 2, characterized in that, The preparation method of vanillin-based silicon-containing flame retardant monomer in step (1) is as follows: add siloxane intermediate and 3-amino-1-propanol to anhydrous ethanol at a molar ratio of 1:2, react at 60~70℃ for 5~6h under nitrogen protection, and dry to obtain vanillin-based silicon-containing flame retardant monomer.

4. The bio-based antibacterial yarn according to claim 3, characterized in that, The method for preparing the siloxane intermediate is as follows: 1,5-dichloro-1,1,3,5,5-pentamethyl-3-phenyltrisiloxane and tetrahydrofuran are mixed evenly to prepare a siloxane solution; vanillin, triethylamine and tetrahydrofuran are mixed evenly, and the siloxane solution is added dropwise under nitrogen protection and stirring at 0~5℃. After the addition is complete, the temperature is raised to room temperature, and the reaction is continued to be stirred for 10~12h. The tetrahydrofuran is removed by rotary evaporation, washed, and dried to obtain the siloxane intermediate.

5. The bio-based antibacterial yarn according to claim 2, characterized in that, The preparation method of the butenyl sulfonium salt in step (2) is as follows: Ethylbut-3-enyl sulfide and iodomethane are added to acetonitrile, silver tetrafluoroborate is added, and the mixture is stirred and reacted at room temperature for 10-12 hours under argon protection. After filtration, the filtrate is exchanged with alkaline anion exchange resin in a shaker for 2-3 hours and then dried to obtain the butenyl sulfonium salt.

6. The bio-based antibacterial yarn according to claim 2, characterized in that, The molar ratio of zinc acetate, sulfadiazine, kaempferol, and potassium hydroxide in step (3) is 1:1:1:(0.2~0.3).

7. The bio-based antibacterial yarn according to claim 2, characterized in that, The process parameters for melt spinning in step (4) are as follows: screw temperature: zone 1 240℃, zone 2 240℃, zone 3 245℃, zone 4 250℃, spinneret orifice diameter 0.28mm, number of orifices 48, metering pump temperature 260℃, cooling method is side blowing, and spinning rate is 2800r / min.