Antibacterial modified full-dull polyester fiber and preparation method thereof

Abstract

The invention discloses an antibacterial modified full-dull polyester fiber and a preparation method thereof, belongs to the technical field of polyester fiber processing, and is used for solving the technical problem that the mechanical property and the antibacterial property of the full-dull polyester fiber in the prior art need to be further improved. The composite material specifically comprises the following components in parts by weight: 50-60 parts of polyethylene glycol terephthalate, 40-50 parts of activated modified polyester, 25-35 parts of epoxy modified polyolefin, 5-7 parts of PEG modified titanium and 2-3 parts of an auxiliary additive. According to the full-dull polyester fiber disclosed by the invention, zinc modified nano titanium is modified by polyethylene glycol, and then polyethylene glycol terephthalate is enhanced by the modified zinc modified nano titanium, cross-linked and bonded activated modified polyester with reaction activity and epoxy modified polyolefin, so that the mechanical strength and the ultraviolet aging resistance of the full-dull polyester fiber are effectively improved; the antibacterial property and the washing resistance of the full-dull polyester fiber are also improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyester fiber processing, and particularly relates to an antibacterial modified full-dull polyester fiber and a preparation method thereof. BACKGROUND

[0002] Polyester fiber is a kind of fiber material taking polyethylene terephthalate as a main component, has become the largest synthetic fiber in the world in terms of output, and is widely used in the fields of clothing, home textiles, medical materials and industrial fabrics, etc. due to its high strength, wear resistance, easy washing and quick drying properties. In order to meet the demand of high-end textiles for matte texture, a duller is usually added to polyester fiber material to achieve full-dull effect.

[0003] In the prior art, inorganic materials such as titanium dioxide are mainly used as dullers. However, in the traditional process, titanium dioxide particles are prone to agglomeration, resulting in uneven dulling and a decrease in fiber mechanical properties. In addition, the hydrophobicity of polyester fiber makes it easy to adsorb organic matter such as sweat and sebum, providing a breeding ground for bacteria such as Staphylococcus aureus and Escherichia coli. In medical textiles, sports clothing and public place fabrics, the breeding of microorganisms may cause cross infection and threaten human health. Although the addition of inorganic or organic antibacterial agents to polyester material can effectively improve the antibacterial performance of polyester fiber, the antibacterial components of traditional antibacterial polyester fiber quickly migrate and lose after multiple washing, resulting in a decrease in the antibacterial performance of polyester fiber material.

[0004] Therefore, a solution is provided. SUMMARY

[0005] The present application aims to provide an antibacterial modified full-dull polyester fiber and a preparation method thereof, which can further improve the mechanical properties and antibacterial properties of full-dull polyester fiber in the prior art.

[0006] The purpose of the present application can be achieved by the following technical solution: an antibacterial modified full-dull polyester fiber, comprising the following components by weight: 50-60 parts of polyethylene terephthalate, 40-50 parts of activated modified polyester, 25-35 parts of epoxy modified polyolefin, 5-7 parts of PEG modified titanium and 2-3 parts of auxiliary additives. The preparation method of the activated modified polyester is: under the atmosphere of inert gas, terephthalic acid, adipic acid, 1,4-butanediol and catalyst are mixed and stirred, the temperature of the reaction system is increased to 200-220 DEG C, and the reaction is kept for 2-3 h, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol is added to the reaction system, and the reaction is kept for 50-60 min, 2,2,6,6-tetramethyl-4-piperidinol is added to the reaction system, and the reaction is kept for 30-50 min, the temperature of the reaction system is increased to 240 DEG C, the system is vacuumized to the pressure of 100-180 pa, the heating is stopped after the reaction until the system appears the effect of climbing the pole, and the product is taken out while hot to obtain the activated modified polyester.

[0007] The synthesis reaction mechanism of the activated modified polyester is: In the formula: In the reaction process, the esterification reaction occurs between the carboxyl on the terephthalic acid and adipic acid molecules and the hydroxyl on the 1,4-butanediol molecules to prepare the polyester prepolymer terminated by carboxyl, the esterification reaction occurs between the trihydroxyl on the 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol molecules and the polyester prepolymer terminated by carboxyl to improve the crosslinking degree between molecules, and 2,2,6,6-tetramethyl-4-piperidinol is used as a terminal group to form the 2,2,6,6-tetramethyl-4-piperidine terminal modification, so that the activated modified polyester is prepared.

[0008] Further, the molar ratio of the terephthalic acid, adipic acid, 1,4-butanediol, catalyst, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol and 2,2,6,6-tetramethyl-4-piperidinol is 0.4:0.2:0.4:0.2:0.15:0.1, and the catalyst is tetrabutyl titanate.

[0009] Further, the preparation method of the epoxy modified polyolefin is: methyl methacrylate, 2-methyl-2-acrylic acid-2,3-dihydroxypropyl ester, glycidyl methacrylate, methyl methacryloyloxyethyl trimethyl ammonium chloride and toluene are mixed and stirred, the temperature of the reaction system is increased to 75-85 DEG C, the initiator solution is added to the reaction system, the dropping is completed, the reaction is kept for 5-7 h, and the post-treatment is performed to obtain the epoxy modified polyolefin.

[0010] The synthesis reaction mechanism of the epoxy modified polyolefin is: In the reaction process, the olefin double bond on the molecule of ethyl methacrylate, 2-methyl-2-propenoic acid-2,3-dihydroxypropyl ester, glycidyl methacrylate, and methacryloxyethyl trimethyl ammonium chloride undergoes free radical polymerization under the action of the initiator to form the epoxy modified polyolefin with hydroxyl and quaternary ammonium salt modification.

[0011] Further, the usage ratio of the ethyl methacrylate, 2-methyl-2-propenoic acid-2,3-dihydroxypropyl ester, glycidyl methacrylate, methacryloxyethyl trimethyl ammonium chloride, toluene and initiator solution is 7-8g:2-3g:3-4g:2-3g:80mL:7mL, the initiator solution is composed of azobis isobutyronitrile and toluene at 1g:20mL, and the post-treatment includes: after the reaction is completed, the reaction system temperature is kept at 75-85℃, negative pressure is extracted to 0.1MPa, and low boiling point substances are removed by vacuum distillation to obtain the epoxy modified polyolefin.

[0012] Further, the PEG modified titanium is obtained by the following steps: A1, under the inert gas atmosphere, polyethylene glycol and tetrahydrofuran are mixed and stirred, the reaction system temperature is raised to 50-60℃, propyl triethoxysilane isocyanate is added to the reaction system, and the reaction is kept for 60-80min to obtain the PEG modified liquid; A2, the zinc modified nano titanium and the PEG modified liquid are mixed and ultrasonically dispersed for 40-60min, the reaction system temperature is raised to 50-60℃, sodium hydroxide solution is added to the reaction system, and the reaction is kept for 80-100min, and then the post-treatment is performed to obtain the PEG modified titanium.

[0013] The synthesis reaction mechanism of the PEG modified titanium is as follows: In the reaction process, the alcohol hydroxyl group on the polyethylene glycol and the isocyanate group on the propyl triethoxysilane isocyanate molecule undergo condensation to form triethoxysilane end-capped modification, under the alkaline condition, the triethoxysilane hydrolysis forms silanol which condenses with the active functional groups on the surface of the zinc modified nano titanium particles to modify the PEG on the surface of the zinc modified nano titanium to obtain the PEG modified titanium.

[0014] Further, in step A1, the usage ratio of the polyethylene glycol and tetrahydrofuran is 1g:20mL, the polyethylene glycol is PEG-1000, and the molar ratio of the propyl triethoxysilane isocyanate and the polyethylene glycol is 2:1.

[0015] Further, in step A2, the amount ratio of the zinc modified nano-titanium, the PEG modified liquid and the sodium hydroxide solution is 5g:30mL:7mL, the concentration of the sodium hydroxide solution is 2-3mol / L, and the post-treatment comprises: after the reaction is completed, the temperature of the reaction system is reduced to room temperature, and then the filter cake is washed with purified water until neutral, and then is dried, the filter cake is transferred to a drying oven with a temperature of 70-80℃, and is dried until the weight is constant, to obtain the PEG modified titanium.

[0016] Further, the preparation method of the zinc modified nano-titanium comprises the following steps: mixing nano-titanium dioxide and a zinc chloride solution, ultrasonic dispersion for 30-50min, adding a sodium hydroxide solution into the reaction system, adjusting the pH value of the system to 8, stirring and dispersing for 20-30min, and post-treatment, to obtain the zinc modified nano-titanium.

[0017] The synthesis reaction mechanism of the zinc modified nano-titanium is as follows: In the reaction process, the surface of the nano-titanium dioxide is rich in hydroxyl groups, and is negatively charged under weak alkaline conditions, when the nano-titanium dioxide is mixed with the zinc chloride solution, the zinc ions are adsorbed on the surface of the nano-titanium dioxide by electrostatic adsorption, at the same time, the zinc ions generate zinc hydroxide under alkaline conditions, and the zinc hydroxide is in the form of solid substance and is coated on the surface of the nano-titanium dioxide, in the subsequent high-temperature treatment process, the zinc hydroxide is decomposed to generate zinc oxide, to obtain the zinc modified nano-titanium.

[0018] Further, the amount ratio of the nano-titanium dioxide and the zinc chloride solution is 5-7g:50mL, the zinc chloride solution is composed of zinc chloride, purified water and sodium dodecyl sulfate according to 1g:30mL:0.2g, and the post-treatment comprises: after the reaction is completed, the temperature of the reaction system is reduced to room temperature, and then the filter cake is washed with purified water for 3 times and is dried, the filter cake is transferred to a tube furnace, the temperature of the tube furnace is increased to 80-90℃ under air atmosphere, and then is dried until the weight is constant, the temperature of the tube furnace is increased to 500℃, and then is kept for 120-150min, the temperature is reduced to take out the material, to obtain the zinc modified nano-titanium.

[0019] The application further provides a preparation method of the antibacterial modified full-dull polyester fiber. S1, polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, PEG modified titanium are added into an oven with a temperature of 150-160℃, and are dried for 20-25h, to obtain dried materials. S2, the dried furnace is mixed with auxiliary additives, and then is added into a double screw extruder, and is melt mixed for 3-5min, and then is extruded into a spinning machine, and then is melt spun, and then is hot stretched, to obtain the full-dull polyester fiber.

[0020] Further, the auxiliary additive is composed of a plasticizer, a dispersant, an antioxidant and an antistatic agent in a weight ratio of 5:4:2:2, the plasticizer is phthalate, the dispersant is stearate, the antioxidant is any one of antioxidants 1010, 1076 and 1035, and the antistatic agent is antistatic agent SN, the temperature of the six temperature zones of the double-screw extruder from the feeding end to the discharging end is sequentially set to 260 DEG C, 270 DEG C, 270 DEG C, 275 DEG C, 275 DEG C and 280 DEG C, the main shaft rotation speed of the double-screw extruder is 15 r / min, the spinning temperature of the melt spinning machine is 290 DEG C, the number of holes of the spinneret of the melt spinning machine is 36 holes, the hole diameter is 0.2 mm, the spinning pressure is 6-8 MPa, air cooling is adopted, the air cooling air supply temperature is 15 DEG C, the air blowing speed is 0.6 m / s, the heat stretching temperature is 85 DEG C, and the stretching ratio is 4-5 times.

[0021] The present application has the following advantages: 1. The present application is by adopting terephthalic acid and adipic acid mixed binary acid system, with 1, 4-butanediol to synthesize the base polyester chain, the introduced adipic acid provides flexible aliphatic chain segment, 2-(aminomethyl)-2-(hydroxymethyl)-1, 3-propanediol can promote the crosslinking between molecular chains, 2, 2, 6, 6-tetramethyl-4-piperidinol as end-capping agent can effectively terminate chain crosslinking, and the steric hindrance effect of hindered amine group inhibits molecular chain entanglement, which is beneficial to the orientation crystallization in the spinning process, so that the polyester can improve the toughness while keeping the strength, in the preparation process of epoxy modified polyolefin, glycidyl methacrylate provides epoxy group, during melt blending, the epoxy group and the active reaction site on the polyester chain in situ occur compatibilization reaction, and the PEG modified titanium coated polyethylene glycol can effectively enhance the compatibility and interfacial bonding force of the polyester matrix, improve the dispersity of inorganic particles in the polyester matrix, reduce stress concentration phenomenon, improve the mechanical strength and extinction performance of the material, meet the demand of high-end textiles for matte texture.

[0022] 2. The present application is by zinc modified nano titanium, modifying zinc oxide on the surface of nano titanium dioxide, using the synergistic effect between zinc oxide and titanium oxide, improving the antibacterial effect, in the synthesis process of epoxy modified polyolefin, by methacryloyloxyethyl trimethyl ammonium chloride, modifying quaternary ammonium salt on its molecular chain, the cationic group of quaternary ammonium salt destroys the bacterial cell membrane potential balance through electrostatic adsorption, further improving the antibacterial effect of the fiber material, PEG modified titanium is linked to isocyanate propyl triethoxysilane by polyethylene glycol, forming an organic coating layer to zinc ions, during melt spinning, PEG modified titanium is wrapped in the crosslinked polyester matrix, only the surface particles participate in the initial antibacterial, the internal particles are slowly released during use, quaternary ammonium salt is modified on the polyester through chemical bonding, thereby improving the water washing resistance of the fiber material.

[0023] 3、 The application is by modifying zinc oxide on the surface of nano titanium oxide, zinc ion has ultraviolet catalytic inertia, and can quench excited state singlet oxygen, reduce photosensitive oxidation, compared with silver ion antibacterial agent under ultraviolet, it is easy to reduce and blacken, zinc system is more suitable for outdoor light environment, zinc oxide and titanium oxide realize full wave band protection in cooperation, PEG modification gives nano titanium excellent dispersibility, so that it forms a continuous protective layer on the surface of the fiber, 2,2,6,6-tetramethyl-4-piperidinol introduced in the activated modified polyester quenches free radicals through a recycling regeneration mechanism, improves the ultraviolet aging resistance of the polyester fiber material, and the activated modified polyester and the epoxy modified polyolefin form a chemical crosslinking network in the polyester fiber material, and crosslinking points are formed in the polyester fiber, so that the main chain photolysis chain scission is inhibited, and the material integrity is maintained after part of the molecular chains are broken by ultraviolet attack, and the mechanical properties are avoided. DETAILED DESCRIPTION

[0024] The technical solutions of the application will be described below in connection with the embodiments, obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the application.

[0025] In the application, the particle size of nano titanium dioxide is 30-50 nm, and the purity is 99.9%; In the application, the effective component content of the polyethylene glycol is 99%. In the application, the effective component content of the polyethylene terephthalate is 99%, the density is 1.68 g / mL, and the melting point is 250-255 DEG C.

[0026] Embodiment 1 The embodiment provides a preparation method of antibacterial modified full-dull polyester fiber, comprising the following steps. S1, preparing activated modified polyester Take: terephthalic acid 332.3g, adipic acid 146.1g, 1,4-butanediol 180.2g and tetrabutyl titanate 340.3g are added into an argon-protected reaction bottle and stirred, the temperature of the reaction bottle is increased to 200 DEG C, and the reaction is kept for 2h, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol 101.4g is added into the reaction bottle, and the reaction is kept for 50min, 2,2,6,6-tetramethyl-4-piperidinol 78.6g is added into the reaction bottle, and the reaction is kept for 30min, the temperature of the reaction bottle is increased to 240 DEG C, the vacuum is extracted to reduce the pressure of the system to 180pa, the heating is stopped after the system appears the climbing rod effect, and the material is taken out while hot, to obtain the activated modified polyester.

[0027] S2, preparing epoxy modified polyolefin Mix azobisisobutyronitrile and toluene uniformly according to 1g:20mL to obtain initiator solution; Take: methyl methacrylate 350g, 2-methyl-2-acrylic acid-2, 3-dihydroxy propyl 100g, glycidyl methacrylate 150g, methyl methacryloyloxyethyl trimethyl ammonium chloride 100g, toluene 4000mL into the reaction bottle and stir, the temperature of the reaction bottle is raised to 75℃, 350mL of initiator solution is added to the reaction bottle, and the reaction is kept for 5h after the dropwise addition is completed. The temperature of the reaction bottle is kept at 75℃, and the low boiling point is removed by negative pressure to 0.1MPa. Epoxy modified polyolefin is obtained by vacuum distillation.

[0028] S3, preparing zinc modified nano titanium Take: zinc chloride, purified water, and sodium dodecyl sulfate according to 1g:30mL:0.2g, mix uniformly to obtain zinc chloride solution; Take: nano titanium dioxide 50g, zinc chloride solution 500mL into the reaction bottle and mix, ultrasonic dispersion for 30min, fix the reaction bottle on the iron stand with mechanical stirring, add 2mol / L sodium hydroxide solution to the reaction bottle, adjust the pH of the system to 8, stir and disperse for 20min, reduce the temperature of the reaction bottle to room temperature, filter, wash the filter cake with purified water for 3 times, then dry, and transfer the filter cake to the tube furnace. In air atmosphere, the temperature of the tube furnace is raised to 80℃, dried to constant weight, then the temperature of the tube furnace is raised to 500℃, and the temperature is kept for 120min. After cooling, the product is obtained.

[0029] S4, preparing PEG modified titanium Take: polyethylene glycol 100g, tetrahydrofuran 2000mL into the reaction bottle under argon protection and stir, raise the temperature of the reaction bottle to 50℃, add n 聚乙二醇-OH :n 异氰酸丙基三乙氧基硅烷 =1:2, add calculated amount of isocyanate propyl triethoxysilane to the reaction system, keep the temperature for 60min to obtain PEG modified liquid; Take: zinc modified nano titanium 50g, PEG modified liquid 300mL into the reaction bottle and mix, ultrasonic dispersion for 40min, fix the reaction bottle on the iron stand with mechanical stirring, raise the temperature of the reaction bottle to 50℃, add 2mol / L sodium hydroxide solution 70mL to the reaction bottle, keep the temperature for 80min, reduce the temperature of the reaction bottle to room temperature, filter, wash the filter cake with purified water to neutral, then dry, and transfer the filter cake to the drying oven with temperature of 70℃. Dry to constant weight to obtain PEG modified titanium.

[0030] S5, preparing full-dull polyester fiber Dimethyl phthalate, sodium stearate, antioxidant 1010 and antistatic agent SN were mixed uniformly in a weight ratio of 5:4:2:2 to obtain auxiliary additives; The following were weighed by parts by weight: 50 parts of polyethylene terephthalate, 40 parts of activated modified polyester, 25 parts of epoxy modified polyolefin, 5 parts of PEG modified titanium and 2 parts of auxiliary additives, for standby; The polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin and PEG modified titanium were added to an oven with a temperature of 150℃ and dried for 20h to obtain dried materials; The dried furnace was mixed with auxiliary additives and added to a twin-screw extruder. The temperatures of the six temperature zones of the twin-screw extruder from the feeding end to the discharging end were set to 260℃, 270℃, 270℃, 275℃, 275℃ and 280℃, respectively. The main shaft rotation speed of the twin-screw extruder was 15r / min. The melt mixing time was 3min. The melt was extruded into a spinning machine. The spinning temperature was set to 290℃. The number of holes of the spinneret of the melt spinning machine was 36 holes, and the hole diameter was 0.2mm. The spinning pressure was 6MPa. Air cooling was used for solidification, with an air cooling temperature of 15℃ and a blowing rate of 0.6m / s. The heat stretching temperature was 85℃, and the stretching ratio was 4 times. A full-dull polyester fiber was obtained.

[0031] Example 2 The present embodiment provides a preparation method of an antibacterial modified full-dull polyester fiber, comprising the following steps: S1, preparation of activated modified polyester 332.3g of terephthalic acid, 146.1g of adipic acid, 180.2g of 1,4-butanediol and 340.3g of tetrabutyl titanate were weighed and added to an argon-protected reaction bottle for stirring. The temperature of the reaction bottle was raised to 210℃, and the reaction was kept for 2.5h. 101.4g of 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol was added to the reaction bottle, and the reaction was kept for 55min. 78.6g of 2,2,6,6-tetramethyl-4-piperidinol was added to the reaction bottle, and the reaction was kept for 40min. The temperature of the reaction bottle was raised to 240℃, and the system was vacuumed to a pressure of 140pa. The heating was stopped after the system showed a climbing rod effect, and the material was taken out while hot to obtain the activated modified polyester.

[0032] S2, preparation of epoxy modified polyolefin Azoisobutyronitrile and toluene were mixed uniformly in a weight ratio of 1g:20mL to obtain an initiator solution; Take: methyl methacrylate 375g, 2-methyl-2-acrylic acid-2, 3-dihydroxy propyl 125g, glycidyl methacrylate 175g, methyl methacryloyloxyethyl trimethyl ammonium chloride 125g, toluene 4000ml is added into the reaction bottle stirring, the reaction bottle temperature rises to 80℃, 350ml initiator solution is added into the reaction bottle, dropwise addition is completed, the reaction is kept for 6h, the reaction bottle temperature is kept at 80℃, the negative pressure is extracted to 0.1MPa, the low boiling point is removed by vacuum distillation, and the epoxy modified polyolefin is obtained.

[0033] S3, preparation of zinc modified nano titanium Take: zinc chloride, purified water, sodium dodecyl sulfate, mix uniformly according to 1g:30ml:0.2g, get zinc chloride solution; Take: nano titanium dioxide 60g, zinc chloride solution 500ml is added into the reaction bottle and mixed, ultrasonic dispersion for 40min, the reaction bottle is fixed on the iron stand with mechanical stirring, 2.5mol / l sodium hydroxide solution is added into the reaction bottle, the system pH is adjusted to 8, stirring and dispersing for 25min, the reaction bottle temperature is reduced to room temperature, filtration, the filter cake is washed with purified water for 3 times and then dried, the filter cake is transferred to the tube furnace, the tube furnace temperature is raised to 85℃ under air atmosphere, dried to constant weight, the tube furnace temperature is raised to 500℃, and the temperature is kept for 135min, the temperature is reduced to get the zinc modified nano titanium.

[0034] S4, preparation of PEG modified titanium Take: polyethylene glycol 100g, tetrahydrofuran 2000ml is added into the reaction bottle under argon protection stirring, the reaction bottle temperature is raised to 55℃, n 聚乙二醇-OH :n 异氰酸丙基三乙氧基硅烷 =1:2, the calculated amount of isocyanate propyl triethoxysilane is added into the reaction system, and the reaction is kept for 70min to get the PEG modified liquid; Take: zinc modified nano titanium 50g, PEG modified liquid 300ml is added into the reaction bottle and mixed, ultrasonic dispersion for 50min, the reaction bottle is fixed on the iron stand with mechanical stirring, the reaction bottle temperature is raised to 55℃, 2.5mol / l sodium hydroxide solution 70ml is added into the reaction bottle, the reaction is kept for 90min, the reaction bottle temperature is reduced to room temperature, filtration, the filter cake is washed with purified water to neutral and then dried, the filter cake is transferred to the drying oven with temperature of 75℃, dried to constant weight to get the PEG modified titanium.

[0035] S5, preparation of full-dull polyester fiber The diisobutyl phthalate, calcium stearate, antioxidant 1076 and antistatic agent SN are mixed uniformly according to the weight ratio of 5:4:2:2 to get the auxiliary additive; Take by weight parts: polyethylene terephthalate 55 parts, activated modified polyester 45 parts, epoxy modified polyolefin 30 parts, PEG modified titanium 6 parts and auxiliary additive 2.5 parts, standby; The polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, PEG modified titanium are added to the oven with a temperature of 155℃, dried for 23h, and dried material is obtained; After mixing the dried furnace with the auxiliary additive, it is added to the twin-screw extruder. The temperature of the six temperature zones of the twin-screw extruder from the feeding end to the discharging end is set to 260℃, 270℃, 270℃, 275℃, 275℃, and 280℃, respectively. The main shaft rotation speed of the twin-screw extruder is 15r / min. The melt mixing is carried out for 4min. The melt is extruded into a spinning machine. The spinning temperature is set to 290℃. The number of holes of the spinneret of the melt spinning machine is 36 holes, and the hole diameter is 0.2mm. The spinning pressure is 7MPa. Air cooling is used for solidification. The air cooling air supply temperature is 15℃. The blowing rate is 0.6m / s. The hot stretching temperature is 85℃. The stretching ratio is 4.5 times. The full-dull polyester fiber is obtained.

[0036] Example 3 The present embodiment provides a preparation method of antibacterial modified full-dull polyester fiber, comprising the following steps: S1, preparation of activated modified polyester Take: terephthalic acid 332.3g, adipic acid 146.1g, 1,4-butanediol 180.2g and tetrabutyl titanate 340.3g are added to an argon-protected reaction bottle and stirred. The temperature of the reaction bottle is raised to 220℃. The reaction is kept for 3h. 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol 101.4g is added to the reaction bottle. The reaction is kept for 60min. 2,2,6,6-tetramethyl-4-piperidinol 78.6g is added to the reaction bottle. The reaction is kept for 50min. The temperature of the reaction bottle is raised to 240℃. The system is vacuumed to a pressure of 100pa. The heating is stopped after the system shows a climbing rod effect. The material is taken out while hot. The activated modified polyester is obtained.

[0037] S2, preparation of epoxy modified polyolefin The azobisisobutyronitrile and toluene are mixed uniformly at 1g:20mL to obtain an initiator solution; Take: methyl methacrylate 400g, 2-methyl-2-acrylic acid-2,3-dihydroxypropyl 150g, glycidyl methacrylate 200g, methyl methacryloyloxyethyl trimethyl ammonium chloride 150g, toluene 4000mL are added to a reaction bottle and stirred. The temperature of the reaction bottle is raised to 85℃. The initiator solution 350mL is added to the reaction bottle. After the dropwise addition is completed, the reaction is kept for 7h. The temperature of the reaction bottle is kept at 85℃. The negative pressure is extracted to 0.1MPa. The low boiling point substances are removed by vacuum distillation. The epoxy modified polyolefin is obtained.

[0038] S3, preparation of zinc modified nano titanium Take: zinc chloride, purified water, sodium dodecyl sulfate 1 g: 30 mL: 0.2 g mixed uniformly, get zinc chloride solution; Take: nano titanium dioxide 70 g, zinc chloride solution 500 mL into the reaction bottle mixed, ultrasonic dispersion for 50 min, the reaction bottle is fixed on the iron stand with mechanical stirring, stirring, add 3 mol / L sodium hydroxide solution to the reaction bottle, adjust the system pH=8, stirring dispersion for 30 min, the reaction bottle temperature is reduced to room temperature, suction filtration, the filter cake is washed with purified water for 3 times and then suction dried, the filter cake is transferred to the tube furnace, the temperature of the tube furnace is increased to 90℃ under air atmosphere, dried to constant weight, the temperature of the tube furnace is increased to 500℃, keep dry for 150 min, cooling, get zinc modified nano titanium.

[0039] S4, preparation of PEG modified titanium Take: polyethylene glycol 100 g, tetrahydrofuran 2000 mL into the reaction bottle under argon protection stirring, the reaction bottle temperature is increased to 60℃, add n 聚乙二醇-OH :n 异氰酸丙基三乙氧基硅烷 =1:2, add calculated amount of isocyanate propyl triethoxysilane to the reaction system, keep warm for 80 min, get PEG modified liquid; Take: zinc modified nano titanium 50 g, PEG modified liquid 300 mL into the reaction bottle mixed, ultrasonic dispersion for 60 min, the reaction bottle is fixed on the iron stand with mechanical stirring, stirring, the reaction bottle temperature is increased to 60℃, add 3 mol / L sodium hydroxide solution 70 mL to the reaction bottle, keep warm for 100 min, the reaction bottle temperature is reduced to room temperature, suction filtration, the filter cake is washed with purified water to neutral and then suction dried, the filter cake is transferred to the drying oven with temperature of 80℃, dried to constant weight, get PEG modified titanium.

[0040] S5, preparation of full-dull polyester fiber Mix dioctyl phthalate, zinc stearate, antioxidant 1035 and antistatic agent SN uniformly according to weight ratio of 5:4:2:2, get auxiliary additive; Take: polyethylene terephthalate 60 parts, activated modified polyester 50 parts, epoxy modified polyolefin 35 parts, PEG modified titanium 7 parts and auxiliary additive 3 parts by weight, standby; Put polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin, PEG modified titanium into the oven with temperature of 160℃, dry for 25 h, get dry material; The dry furnace is mixed with auxiliary additives and then added to a twin-screw extruder. The temperature of the six temperature zones of the twin-screw extruder from the feeding end to the discharging end is set to 260℃, 270℃, 270℃, 275℃, 275℃, and 280℃, respectively. The main shaft rotation speed of the twin-screw extruder is 15 r / min. The melt mixing is performed for 5 min. The melt is extruded into a spinning machine. The spinning temperature is set to 290℃. The number of holes of the spinneret of the melt spinning machine is 36 holes. The hole diameter is 0.2 mm. The spinning pressure is 8 MPa. Air cooling is adopted. The air cooling air supply temperature is 15℃. The air blowing rate is 0.6 m / s. The heat stretching temperature is 85℃. The stretching ratio is 5 times. A full-dull polyester fiber is obtained.

[0041] Comparative Example 1 The difference between this comparative example and Example 3 is that, in step S1, the addition amount of 1,4-butanediol is calculated according to 1,4-butanediol: 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol = 1.5 mol: 1 mol, and 1,4-butanediol is used to replace 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol in the calculated amount.

[0042] Comparative Example 2 The difference between this comparative example and Example 3 is that, in step S2, no glycidyl methacrylate is added.

[0043] Comparative Example 3 The difference between this comparative example and Example 3 is that step S3 is cancelled, and the zinc-modified nano-titanium in step S4 is replaced by the nano-titanium dioxide in step S3.

[0044] Comparative Example 4 The difference between this comparative example and Example 3 is that step S4 is cancelled, and the zinc-modified nano-titanium prepared in step S3 is used to replace the PEG-modified titanium in step S5.

[0045] Performance test: The breaking strength, elongation at break, and antibacterial rate of the full-dull polyester fiber samples prepared in Examples 1-3 and Comparative Examples 1-4 are determined according to the standard FZ / T 52035-2014 “Antibacterial polyester staple fiber”. The full-dull polyester fiber samples prepared in Examples 1-3 and Comparative Examples 1-4 are placed under irradiation of a fluorescent ultraviolet lamp with a temperature of 65℃ and an irradiation intensity of 1.2 W / m 2 for 100 h. The breaking strength and elongation at break retention rate of the samples after aging are determined. The full-dull polyester fiber samples prepared in Examples 1-3 and Comparative Examples 1-4 are washed with water and then dried. After 200 cycles of water washing, the antibacterial rate of the samples is determined according to the standard. The specific test data are shown in Table 1-2.

[0046] Table 1 - mechanical properties and anti-aging test data table of the sample Table 2 - antibacterial properties and water washing resistance test data table of the sample Data analysis: Comparative analysis of the data in Table 1 above, the breaking strength of the full-dull polyester fiber prepared by the present application reaches 6.55 cN / dtex, the elongation at break reaches 39%, after ultraviolet aging, the breaking strength of the full-dull polyester fiber reaches 5.96 cN / dtex, the elongation at break reaches 36%, the antibacterial rate against Staphylococcus aureus reaches 99.7%, the antibacterial rate against Escherichia coli reaches 99.6%, after 200 times of washing, the antibacterial rate against Staphylococcus aureus reaches 95.4%, the antibacterial rate against Escherichia coli reaches 95.6%, the performance test data are all better than the comparative example, which shows that, after the zinc-modified nano-titanium is modified by polyethylene glycol and bonded with the activated modified polyester containing reactive cross-linking and the epoxy-modified polyolefin to enhance the polyethylene terephthalate, not only the mechanical strength and ultraviolet aging resistance of the full-dull polyester fiber are effectively improved, but also the antibacterial performance and water washing resistance of the full-dull polyester fiber are improved.

[0047] The preferred embodiments of the present application disclosed above are only used to help explain the present application. The preferred embodiments do not describe all the details and limit the present application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited only by the claims and their full scope and equivalents.

Claims

1. An antibacterial modified full-dull polyester fiber, characterized by, Comprise the following components by weight parts: polyethylene terephthalate 50-60 parts, activated modified polyester 40-50 parts, epoxy modified polyolefin 25-35 parts, PEG modified titanium 5-7 parts and auxiliary additives 2-3 parts; The preparation method of the activated modified polyester is: under the atmosphere of inert gas, terephthalic acid, adipic acid, 1,4-butanediol and catalyst are mixed and stirred, the temperature of the reaction system is increased to 200-220 DEG C, and the reaction is kept for 2-3h, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol is added to the reaction system, and the reaction is kept for 50-60min, 2,2,6,6-tetramethyl-4-piperidinol is added to the reaction system, and the reaction is kept for 30-50min, the temperature of the reaction system is increased to 240 DEG C, the system is vacuumized to reduce the pressure to 100-180pa, the heating is stopped after the reaction until the system appears the effect of climbing the pole, and the product is taken out while hot to obtain the activated modified polyester.

2. The anti-bacterial modified full-dull polyester fiber of claim 1, wherein the anti-bacterial agent is selected from the group consisting of silver ions, copper ions, zinc ions, and combinations thereof. The molar ratio of the terephthalic acid, adipic acid, 1,4-butanediol, catalyst, 2-(aminomethyl)-2-(hydroxymethyl)-1,3-propanediol and 2,2,6,6-tetramethyl-4-piperidinol is 0.4:0.2:0.4:0.2:0.15:0.1, and the catalyst is tetrabutyl titanate.

3. The anti-bacterial modified full-dull polyester fiber of claim 1, wherein the anti-bacterial agent is selected from the group consisting of silver ions, copper ions, zinc ions, and combinations thereof. The preparation method of the epoxy modified polyolefin is: ethyl methacrylate, 2-methyl-2-acrylic acid-2,3-dihydroxypropyl ester, glycidyl methacrylate, methacryloyloxyethyl trimethyl ammonium chloride and toluene are mixed and stirred, the temperature of the reaction system is increased to 75-85 DEG C, initiator solution is added to the reaction system, the dropping is completed, the reaction is kept for 5-7h, and the epoxy modified polyolefin is obtained after the post-treatment.

4. The anti-bacterial modified full-dull polyester fiber of claim 3, wherein the anti-bacterial agent is selected from the group consisting of silver ions, copper ions, zinc ions, and combinations thereof. The dosage ratio of the ethyl methacrylate, 2-methyl-2-acrylic acid-2,3-dihydroxypropyl ester, glycidyl methacrylate, methacryloyloxyethyl trimethyl ammonium chloride, toluene and initiator solution is 7-8g:2-3g:3-4g:2-3g:80mL:7mL, and the initiator solution is composed of azobisisobutyronitrile and toluene at 1g:20mL.

5. The anti-bacterial modified full-dull polyester fiber of claim 1, wherein the anti-bacterial agent is selected from the group consisting of silver, copper, zinc, and combinations thereof. The PEG modified titanium is obtained by the following steps: A1, under the atmosphere of inert gas, polyethylene glycol and tetrahydrofuran are mixed and stirred, the temperature of the reaction system is increased to 50-60 DEG C, propyl triethoxysilane isocyanate is added to the reaction system, and the reaction is kept for 60-80min to obtain PEG modified liquid; A2, zinc modified nano titanium and PEG modified liquid are mixed, ultrasonic dispersion is carried out for 40-60min, the temperature of the reaction system is increased to 50-60 DEG C, sodium hydroxide solution is added to the reaction system, and the reaction is kept for 80-100min, and the PEG modified titanium is obtained after the post-treatment.

6. The anti-bacterial modified full-dull polyester fiber of claim 5, wherein the anti-bacterial agent is selected from the group consisting of silver, copper, zinc, and combinations thereof. In step A1, the amount ratio of polyethylene glycol and tetrahydrofuran is 1g:20mL, the polyethylene glycol is PEG-1000, and the molar ratio of propyl triethoxy silane isocyanate and polyethylene glycol is 2:1; in step A2, the amount ratio of zinc modified nano-titanium, PEG modified solution and sodium hydroxide solution is 5g:30mL:7mL, and the concentration of the sodium hydroxide solution is 2-3mol / L.

7. The anti-bacterial modified full-dull polyester fiber of claim 5, wherein the anti-bacterial agent is selected from the group consisting of silver, copper, zinc, and combinations thereof. The preparation method of the zinc modified nano-titanium is as follows: mixing nano-titanium dioxide and zinc chloride solution, ultrasonic dispersion for 30-50min, adding sodium hydroxide solution into the reaction system, adjusting the pH value of the system to 8, stirring and dispersing for 20-30min, and post-treatment to obtain the zinc modified nano-titanium.

8. The anti-bacterial modified full-dull polyester fiber of claim 7, wherein the anti-bacterial agent is selected from the group consisting of silver, copper, zinc, and combinations thereof. The amount ratio of the nano-titanium dioxide and the zinc chloride solution is 5-7g:50mL, and the zinc chloride solution is composed of zinc chloride, purified water and sodium dodecyl sulfate according to 1g:30mL:0.2g.

9. A process for the preparation of the antibacterial modified full-dull polyester fiber according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: S1, polyethylene terephthalate, activated modified polyester, epoxy modified polyolefin and PEG modified titanium are added into an oven with a temperature of 150-160℃, and dried for 20-25h to obtain dried materials; S2, the dried furnace is mixed with auxiliary additives, and then added into a double screw extruder, melt mixed for 3-5min, extruded into a spinning machine, melt spun, and then hot stretched to obtain full-dull polyester fibers.

10. The method for preparing an antibacterial modified fully dull polyester fiber according to claim 9, characterized in that, The auxiliary additives are composed of plasticizers, dispersants, antioxidants and antistatic agents according to a weight ratio of 5:4:2:2, the plasticizers are phthalate esters, the dispersants are stearate salts, the antioxidants are any one of antioxidants 1010, 1076 and 1035, and the antistatic agents are antistatic agent SN; the temperature of the six temperature zones of the double screw extruder from the feeding end to the discharging end is set as 260℃, 270℃, 270℃, 275℃, 275℃ and 280℃ in sequence, the main shaft rotation speed of the double screw extruder is 15r / min, the spinning temperature of the melt spinning machine is 290℃, the number of holes of the spinneret of the melt spinning machine is 36, the hole diameter is 0.2mm, the spinning pressure is 6-8MPa, air cooling is adopted, the air cooling air supply temperature is 15℃, the air blowing rate is 0.6m / s, and the hot stretching temperature is 85℃ with a stretching ratio of 4-5 times.

Images