A kind of antibacterial polyester yarn based on graphene and its preparation process

Abstract

The present invention relates to the technical field of polyester fibers, and in particular to an antibacterial polyester yarn based on graphene and a preparation process thereof; in order to improve the strength and performance of PET fibers, the present invention uses graphene as a reinforcing material and performs modification treatment on the graphene, and improves the compatibility of graphene and polyester by introducing a PET-like structure on the graphene surface, and on this basis, the present invention further introduces a halogenamine group on the graphene surface, greatly enhancing the antibacterial performance of the graphene, and the introduction of the halogenamine can also effectively improve the hydrophilicity of the PET fibers, and can effectively improve the comfort of the polyester fibers.

Description

Technical Field

[0001] The invention relates to the technical field of polyester fibers, and in particular to an antibacterial polyester yarn based on graphene and a preparation process thereof. Background Art

[0002] Polyester fiber occupies an important position in the textile industry due to its excellent properties. It has high strength, excellent elasticity, heat resistance, light resistance, acid and alkali resistance, and is easy to process and weave. It is widely used in clothing, household goods and decorations, and has a huge market share. However, polyester fiber has poor antibacterial properties and weak water absorption. It is not skin-friendly when worn, so it is necessary to overcome this defect to meet market demand. Summary of the invention

[0003] The object of the present invention is to provide an antibacterial polyester yarn based on graphene and a preparation process thereof, so as to solve the problems raised in the above-mentioned background technology.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: a graphene-based antibacterial polyester yarn having the following technical features: measured by weight, the graphene-based antibacterial polyester yarn consists of: 100 parts of polyester masterbatch, 3-12 parts of modified graphene material, 1-3 parts of antioxidant, 0.5-1.5 parts of lubricant, and 0.5-1.5 parts of thermal stabilizer.

[0005] Further, the antioxidant is any one or more of antioxidant 1076 and antioxidant 168;

[0006] The heat stabilizer is 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate; and the lubricant is stearic acid.

[0007] Furthermore, the preparation method of the modified graphene material is:

[0008] a. Disperse the carboxylated graphene in xylene, ultrasonically disperse for 30-45 minutes, add 4,4'-diaminobiphenyl thereto, heat to 75-90°C, stir to react for 1-12 hours, centrifuge to separate the precipitate, collect the precipitate and disperse it again in dimethyl sulfoxide, ultrasonically disperse for 30-45 minutes, add terephthalic acid thereto, heat to 105-120°C, stir to react for 4-8 hours, centrifuge to separate the precipitate, wash the precipitate 2-3 times with pure dimethyl sulfoxide, disperse the precipitate again in ethylene glycol, add dibutyltin diacetate, heat to 185-197°C, react for 4-8 hours, centrifuge to separate the precipitate, heat the obtained product to 260-285°C, keep the temperature for 2-5 minutes, cool to room temperature, grind the product through a 200-400 mesh sieve to obtain PET modified graphene;

[0009] b. Disperse 2-hydroxybenzophenone in ethanol, stir and mix for 5-10 minutes, add sodium hydroxide, heat to 55-60°C, stir and react for 30-45 minutes, add 1,3-dibromopropane, keep the temperature for 12-24 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at a temperature of 4-8°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate;

[0010] c. Disperse 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 3-5 minutes, add sodium hydroxide, heat to 65-75°C, stir and react for 30-45 minutes, cool to 45-50°C, add brominated benzophenone intermediate, stir and react for 24-48 hours, remove excess solvent by rotary evaporation, wash the reaction product 1-3 times with deionized water at a temperature of 2-4°C, disperse the reaction product again in acetone, add trichloroisocyanuric acid, heat to 35-45°C, react for 12-24 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at a temperature of 75-80°C, and evaporate in vacuo to constant weight to obtain halogenated benzophenone;

[0011] d. Disperse the PET modified graphene in dichlorotoluene, ultrasonically disperse for 10-15 minutes, add halogenated benzophenone, continue mixing for 30-45 minutes, irradiate with ultraviolet light for 8-15 minutes, centrifuge to separate the precipitate, vacuum dry to constant weight, and grind through a 200-400 mesh sieve to obtain a modified graphene material.

[0012] Furthermore, in step a, the mass ratio of the carboxylated graphene, 4,4'-diaminobiphenyl and terephthalic acid is 10:(0.5-5):(1-5).

[0013] Furthermore, in step a, the mass ratio of the carboxylated graphene, ethylene glycol, and dibutyltin diacetate is 10:(100-500):(0.1-0.2).

[0014] Furthermore, in step b, the mass ratio of 2-hydroxybenzophenone, sodium hydroxide and 1,3-dibromopropane is 1:(0.1-0.25):(0.8-1.1).

[0015] Furthermore, in step c, the mass ratio of the 5-benzylhydantoin, sodium hydroxide, and benzophenone bromide intermediate is 1:(0.2-0.3):(1.3-1.8).

[0016] Furthermore, in step c, the mass ratio of 5-benzylhydantoin to trichloroisocyanuric acid is 1:1.05.

[0017] Furthermore, in step d, the mass ratio of the PET modified graphene to the halogenated benzophenone is 10:(0.5-3).

[0018] A preparation process of graphene-based antibacterial polyester yarn comprises the following steps:

[0019] S1. The modified graphene material is mixed with a polyester masterbatch, an antioxidant, a lubricant, and a heat stabilizer, melted by a twin-screw, blended at a high speed for 20-30 minutes, and extruded and pelletized to obtain a modified graphene polyester masterbatch;

[0020] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] In order to improve the strength and performance of PET fiber, the present invention uses graphene as a reinforcing material. Graphene is a two-dimensional crystal composed of carbon atoms, has high strength, can effectively improve the mechanical properties of PET materials, and graphene materials also have antibacterial properties. When the graphene material contacts the cell membrane, it will generate free radicals through charge transfer, thereby destroying the activity and structure of the cell membrane, thereby achieving the inhibition of bacterial activity.

[0023] On the basis of the above, the present invention further uses the modified graphene. The present invention first uses carboxylated graphene as a raw material, uses 4,4'-diaminobiphenyl to modify the surface of the graphene by amination to graft free amino groups, and then further uses terephthalic acid and ethylene glycol to modify the surface of the graphene. After further high-temperature polycondensation reaction, a PET-like structure is generated on the graphene surface, thereby improving the compatibility and bonding strength between the graphene and PET.

[0024] The present invention further prepares a halogenated benzophenone having a halogenamine and benzophenone structure; the present invention firstly utilizes 2-hydroxybenzophenone to react with 1,3-dibromopropane, thereby introducing a bromine element into the 2-hydroxybenzophenone, and after further mixing it with 5-benzylhydantoin, the bromine element in the brominated benzophenone intermediate reacts and replaces with the amino group in the hydantoin, thereby introducing the amino group structure of the hydantoin into the brominated benzophenone intermediate, and after a halogenation reaction, a halogenated benzophenone having a halogenamine and benzophenone structure is generated;

[0025] Afterwards, under ultraviolet light irradiation, the benzophenone structure will react and graft with the methylene group in the PET-like structure on the graphene surface, thereby introducing halamine groups on the graphene surface, greatly enhancing the antibacterial properties of graphene. The introduction of halamine can also effectively improve the hydrophilic properties of PET fibers and effectively improve the comfort of polyester fibers. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] The carboxylated graphene used in this application is XF004 carboxylated graphene oxide, with a sheet diameter of 0.5-5 microns and a thickness of 0.8-1.2 nanometers; the PET masterbatch used is WK801 PET plastic particles;

[0028] Example 1. A process for preparing antibacterial polyester yarn based on graphene, comprising the following steps:

[0029] S1. By weight, 5 parts of modified graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0030] Wherein, the preparation method of the modified graphene material is:

[0031] a. By weight, 10 parts of carboxylated graphene were dispersed in xylene, ultrasonically dispersed for 35 minutes, 0.5 parts of 4,4'-diaminobiphenyl were added thereto, the temperature was raised to 75°C, stirred for reaction for 8 hours, and the precipitate was separated by centrifugation. The precipitate was collected and dispersed again in dimethyl sulfoxide, ultrasonically dispersed for 45 minutes, 1 part of terephthalic acid was added thereto, the temperature was raised to 115°C, stirred for reaction for 6 hours, and the precipitate was separated by centrifugation. The precipitate was washed 3 times with pure dimethyl sulfoxide, and the precipitate was dispersed again in 100 parts of ethylene glycol, 0.1 parts of dibutyltin diacetate were added, the temperature was raised to 197°C, the reaction was continued for 4 hours, and the precipitate was separated by centrifugation. The obtained product was heated to 275°C, kept for reaction for 2 minutes, cooled to room temperature, and the product was ground through a 400-mesh sieve to obtain PET modified graphene;

[0032] b. Disperse 1 part of 2-hydroxybenzophenone in ethanol by weight, stir and mix for 5 minutes, add 0.1 parts of sodium hydroxide, heat to 55°C, stir and react for 30 minutes, add 0.8 parts of 1,3-dibromopropane, keep the temperature for 12 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at 4°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate;

[0033] c. Disperse 1 part of 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 5 minutes, add 0.2 parts of sodium hydroxide, heat to 65°C, stir and react for 45 minutes, cool to 50°C, add 1.3 parts of benzophenone bromide intermediate, stir and react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product twice with deionized water at 2°C, disperse the reaction product again in acetone, add 1.05 parts of trichloroisocyanuric acid, heat to 35°C, react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product three times with deionized water at 80°C, and evaporate in vacuo to constant weight to obtain halogenated benzophenone;

[0034] d. Disperse 10 parts of PET modified graphene in dichlorotoluene by weight, and after ultrasonic dispersion for 10-15 minutes, add 0.5 parts of halogenated benzophenone, continue mixing for 30 minutes, irradiate with ultraviolet light for 15 minutes, centrifuge to separate the precipitate, vacuum dry to constant weight, and grind through a 400-mesh sieve to obtain a modified graphene material;

[0035] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0036] Example 2. A preparation process of graphene-based antibacterial polyester yarn, comprising the following steps:

[0037] Compared with Example 1, this embodiment increases the amount of modified graphene material added in step S1;

[0038] S1. By weight, 12 parts of modified graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0039] Wherein, the preparation method of the modified graphene material is:

[0040] a. By weight, 10 parts of carboxylated graphene were dispersed in xylene, ultrasonically dispersed for 35 minutes, 0.5 parts of 4,4'-diaminobiphenyl were added thereto, the temperature was raised to 75°C, stirred for reaction for 8 hours, and the precipitate was separated by centrifugation. The precipitate was collected and dispersed again in dimethyl sulfoxide, ultrasonically dispersed for 45 minutes, 1 part of terephthalic acid was added thereto, the temperature was raised to 115°C, stirred for reaction for 6 hours, and the precipitate was separated by centrifugation. The precipitate was washed 3 times with pure dimethyl sulfoxide, and the precipitate was dispersed again in 100 parts of ethylene glycol, 0.1 parts of dibutyltin diacetate were added, the temperature was raised to 197°C, the reaction was continued for 4 hours, and the precipitate was separated by centrifugation. The obtained product was heated to 275°C, kept for reaction for 2 minutes, cooled to room temperature, and the product was ground through a 400-mesh sieve to obtain PET modified graphene;

[0041] b. Disperse 1 part of 2-hydroxybenzophenone in ethanol by weight, stir and mix for 5 minutes, add 0.1 parts of sodium hydroxide, heat to 55°C, stir and react for 30 minutes, add 0.8 parts of 1,3-dibromopropane, keep the temperature for 12 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at 4°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate;

[0042] c. Disperse 1 part of 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 5 minutes, add 0.2 parts of sodium hydroxide, heat to 65°C, stir and react for 45 minutes, cool to 50°C, add 1.3 parts of benzophenone bromide intermediate, stir and react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product twice with deionized water at 2°C, disperse the reaction product again in acetone, add 1.05 parts of trichloroisocyanuric acid, heat to 35°C, react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product three times with deionized water at 80°C, and evaporate in vacuo to constant weight to obtain halogenated benzophenone;

[0043] d. Disperse 10 parts of PET modified graphene in dichlorotoluene by weight, and after ultrasonic dispersion for 10-15 minutes, add 0.5 parts of halogenated benzophenone, continue mixing for 30 minutes, irradiate with ultraviolet light for 15 minutes, centrifuge to separate the precipitate, vacuum dry to constant weight, and grind through a 400-mesh sieve to obtain a modified graphene material;

[0044] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0045] Example 3. A preparation process of graphene-based antibacterial polyester yarn, comprising the following steps:

[0046] Compared with Example 2, this example increases the amount of 1,3-dibromopropane added in step b;

[0047] S1. By weight, 12 parts of modified graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0048] Wherein, the preparation method of the modified graphene material is:

[0049] a. By weight, 10 parts of carboxylated graphene were dispersed in xylene, ultrasonically dispersed for 35 minutes, 0.5 parts of 4,4'-diaminobiphenyl were added thereto, the temperature was raised to 75°C, stirred for reaction for 8 hours, and the precipitate was separated by centrifugation. The precipitate was collected and dispersed again in dimethyl sulfoxide, ultrasonically dispersed for 45 minutes, 1 part of terephthalic acid was added thereto, the temperature was raised to 115°C, stirred for reaction for 6 hours, and the precipitate was separated by centrifugation. The precipitate was washed 3 times with pure dimethyl sulfoxide, and the precipitate was dispersed again in 100 parts of ethylene glycol, 0.1 parts of dibutyltin diacetate were added, the temperature was raised to 197°C, the reaction was continued for 4 hours, and the precipitate was separated by centrifugation. The obtained product was heated to 275°C, kept for reaction for 2 minutes, cooled to room temperature, and the product was ground through a 400-mesh sieve to obtain PET modified graphene;

[0050] b. Disperse 1 part of 2-hydroxybenzophenone in ethanol by weight, stir and mix for 5 minutes, add 0.1 parts of sodium hydroxide, heat to 55°C, stir and react for 30 minutes, add 1.1 parts of 1,3-dibromopropane, keep the temperature for 12 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at 4°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate;

[0051] c. Disperse 1 part of 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 5 minutes, add 0.2 parts of sodium hydroxide, heat to 65°C, stir and react for 45 minutes, cool to 50°C, add 1.3 parts of benzophenone bromide intermediate, stir and react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product twice with deionized water at 2°C, disperse the reaction product again in acetone, add 1.05 parts of trichloroisocyanuric acid, heat to 35°C, react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product three times with deionized water at 80°C, and evaporate in vacuo to constant weight to obtain halogenated benzophenone;

[0052] d. Disperse 10 parts of PET modified graphene in dichlorotoluene by weight, and after ultrasonic dispersion for 10-15 minutes, add 0.5 parts of halogenated benzophenone, continue mixing for 30 minutes, irradiate with ultraviolet light for 15 minutes, centrifuge to separate the precipitate, vacuum dry to constant weight, and grind through a 400-mesh sieve to obtain a modified graphene material;

[0053] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0054] Example 4. A process for preparing antibacterial polyester yarn based on graphene, comprising the following steps:

[0055] Compared with Example 2, this example increases the amount of brominated benzophenone intermediate added in step c;

[0056] S1. By weight, 12 parts of modified graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0057] Wherein, the preparation method of the modified graphene material is:

[0058] a. By weight, 10 parts of carboxylated graphene were dispersed in xylene, ultrasonically dispersed for 35 minutes, 0.5 parts of 4,4'-diaminobiphenyl were added thereto, the temperature was raised to 75°C, stirred for reaction for 8 hours, and the precipitate was separated by centrifugation. The precipitate was collected and dispersed again in dimethyl sulfoxide, ultrasonically dispersed for 45 minutes, 1 part of terephthalic acid was added thereto, the temperature was raised to 115°C, stirred for reaction for 6 hours, and the precipitate was separated by centrifugation. The precipitate was washed 3 times with pure dimethyl sulfoxide, and the precipitate was dispersed again in 100 parts of ethylene glycol, 0.1 parts of dibutyltin diacetate were added, the temperature was raised to 197°C, the reaction was continued for 4 hours, and the precipitate was separated by centrifugation. The obtained product was heated to 275°C, kept for reaction for 2 minutes, cooled to room temperature, and the product was ground through a 400-mesh sieve to obtain PET modified graphene;

[0059] b. Disperse 1 part of 2-hydroxybenzophenone in ethanol by weight, stir and mix for 5 minutes, add 0.1 parts of sodium hydroxide, heat to 55°C, stir and react for 30 minutes, add 0.8 parts of 1,3-dibromopropane, keep the temperature for 12 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at 4°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate;

[0060] c. Disperse 1 part of 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 5 minutes, add 0.2 parts of sodium hydroxide, heat to 65°C, stir and react for 45 minutes, cool to 50°C, add 1.8 parts of benzophenone bromide intermediate, stir and react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product twice with deionized water at 2°C, disperse the reaction product again in acetone, add 1.05 parts of trichloroisocyanuric acid, heat to 35°C, react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product three times with deionized water at 80°C, and evaporate to constant weight in vacuo to obtain halogenated benzophenone;

[0061] d. Disperse 10 parts of PET modified graphene in dichlorotoluene by weight, and after ultrasonic dispersion for 10-15 minutes, add 0.5 parts of halogenated benzophenone, continue mixing for 30 minutes, irradiate with ultraviolet light for 15 minutes, centrifuge to separate the precipitate, vacuum dry to constant weight, and grind through a 400-mesh sieve to obtain a modified graphene material;

[0062] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0063] Example 5. A process for preparing antibacterial polyester yarn based on graphene, comprising the following steps:

[0064] Compared with Example 2, this example increases the amount of halogenated benzophenone added in step d;

[0065] S1. By weight, 12 parts of modified graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0066] Wherein, the preparation method of the modified graphene material is:

[0067] a. By weight, 10 parts of carboxylated graphene were dispersed in xylene, ultrasonically dispersed for 35 minutes, 0.5 parts of 4,4'-diaminobiphenyl were added thereto, the temperature was raised to 75°C, stirred for reaction for 8 hours, and the precipitate was separated by centrifugation. The precipitate was collected and dispersed again in dimethyl sulfoxide, ultrasonically dispersed for 45 minutes, 1 part of terephthalic acid was added thereto, the temperature was raised to 115°C, stirred for reaction for 6 hours, and the precipitate was separated by centrifugation. The precipitate was washed 3 times with pure dimethyl sulfoxide, and the precipitate was dispersed again in 100 parts of ethylene glycol, 0.1 parts of dibutyltin diacetate were added, the temperature was raised to 197°C, the reaction was continued for 4 hours, and the precipitate was separated by centrifugation. The obtained product was heated to 275°C, kept for reaction for 2 minutes, cooled to room temperature, and the product was ground through a 400-mesh sieve to obtain PET modified graphene;

[0068] b. Disperse 1 part of 2-hydroxybenzophenone in ethanol by weight, stir and mix for 5 minutes, add 0.1 parts of sodium hydroxide, heat to 55°C, stir and react for 30 minutes, add 0.8 parts of 1,3-dibromopropane, keep the temperature for 12 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at 4°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate;

[0069] c. Disperse 1 part of 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 5 minutes, add 0.2 parts of sodium hydroxide, heat to 65°C, stir and react for 45 minutes, cool to 50°C, add 1.3 parts of benzophenone bromide intermediate, stir and react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product twice with deionized water at 2°C, disperse the reaction product again in acetone, add 1.05 parts of trichloroisocyanuric acid, heat to 35°C, react for 24 hours, remove excess solvent by rotary evaporation, wash the reaction product three times with deionized water at 80°C, and evaporate in vacuo to constant weight to obtain halogenated benzophenone;

[0070] d. Disperse 10 parts of PET modified graphene in dichlorotoluene by weight, and add 3 parts of halogenated benzophenone after ultrasonic dispersion for 10-15 minutes, and continue mixing for 30 minutes. After ultraviolet irradiation for 15 minutes, centrifuge and separate the precipitate, vacuum dry to constant weight, and grind through a 400-mesh sieve to obtain a modified graphene material;

[0071] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0072] Comparative Example 1. A process for preparing antibacterial polyester yarn based on graphene, comprising the following steps:

[0073] Compared with Example 2, only carboxylated graphene was added in this example;

[0074] S1. By weight, 12 parts of carboxylated graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0075] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0076] Comparative Example 2. A process for preparing antibacterial polyester yarn based on graphene, comprising the following steps:

[0077] Compared with Example 2, this comparative example only prepared graphene modified with PET;

[0078] S1. By weight, 12 parts of PET modified graphene material and 100 parts of polyester masterbatch, 1 part of antioxidant, 1 part of lubricant, 0.8 parts of heat stabilizer were mixed, melted by twin screw, blended at high speed for 20min, extruded and pelletized to obtain modified graphene polyester masterbatch;

[0079] Wherein, the preparation method of the PET modified graphene material is:

[0080] a. By weight, 10 parts of carboxylated graphene were dispersed in xylene, ultrasonically dispersed for 35 minutes, 0.5 parts of 4,4'-diaminobiphenyl were added thereto, the temperature was raised to 75°C, stirred for reaction for 8 hours, and the precipitate was separated by centrifugation. The precipitate was collected and dispersed again in dimethyl sulfoxide, ultrasonically dispersed for 45 minutes, 1 part of terephthalic acid was added thereto, the temperature was raised to 115°C, stirred for reaction for 6 hours, and the precipitate was separated by centrifugation. The precipitate was washed 3 times with pure dimethyl sulfoxide, and the precipitate was dispersed again in 100 parts of ethylene glycol, 0.1 parts of dibutyltin diacetate were added, the temperature was raised to 197°C, the reaction was continued for 4 hours, and the precipitate was separated by centrifugation. The obtained product was heated to 275°C, kept for reaction for 2 minutes, cooled to room temperature, and the product was ground through a 400-mesh sieve to obtain PET modified graphene;

[0081] S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

[0082] Testing: The antibacterial polyester yarns prepared in Examples 1-5 and Comparative Examples 1-2 were used to prepare fibers with a fineness of 2.3±1 dtex, and the tensile strength was tested according to GB / T 14337-2008; the elongation at break was tested according to GB / T 9997-88; and the antibacterial activity against Escherichia coli and Staphylococcus aureus was tested according to GB / T 20944.3-2008;

[0083] The antibacterial polyester yarns prepared in Examples 1-5 and Comparative Examples 1-2 were woven into 32S polyester plain weave fabrics with a gram weight of 130 g / m 2 , the water drop diffusion time of the above fabrics was tested according to GB / T 21665.1-2008;

[0084] The test results are shown in the table below;

[0085]

[0086] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A graphene-based antibacterial polyester yarn, characterized in that: The graphene-based antibacterial polyester yarn is composed of: 100 parts of polyester masterbatch, 3-12 parts of modified graphene material, 1-3 parts of antioxidant, 0.5-1.5 parts of lubricant, and 0.5-1.5 parts of heat stabilizer by weight; Wherein, the preparation method of the modified graphene material is: a. Disperse the carboxylated graphene in xylene, ultrasonically disperse for 30-45 minutes, add 4,4'-diaminobiphenyl thereto, heat to 75-90°C, stir to react for 1-12 hours, centrifuge to separate the precipitate, collect the precipitate and disperse it again in dimethyl sulfoxide, ultrasonically disperse for 30-45 minutes, add terephthalic acid thereto, heat to 105-120°C, stir to react for 4-8 hours, centrifuge to separate the precipitate, wash the precipitate 2-3 times with pure dimethyl sulfoxide, disperse the precipitate again in ethylene glycol, add dibutyltin diacetate, heat to 185-197°C, react for 4-8 hours, centrifuge to separate the precipitate, heat the obtained product to 260-285°C, keep the temperature for 2-5 minutes, cool to room temperature, grind the product through a 200-400 mesh sieve to obtain PET modified graphene; b. Disperse 2-hydroxybenzophenone in ethanol, stir and mix for 5-10 minutes, add sodium hydroxide, heat to 55-60°C, stir and react for 30-45 minutes, add 1,3-dibromopropane, keep the temperature for 12-24 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at a temperature of 4-8°C, and vacuum dry to constant weight to obtain brominated benzophenone intermediate; c. Disperse 5-benzylhydantoin in anhydrous ethanol, stir and disperse for 3-5 minutes, add sodium hydroxide, heat to 65-75°C, stir and react for 30-45 minutes, cool to 45-50°C, add benzophenone bromide intermediate, stir and react for 24-48 hours, remove excess solvent by rotary evaporation, wash the reaction product 1-3 times with deionized water at a temperature of 2-4°C, disperse the reaction product again in acetone, add trichloroisocyanuric acid, heat to 35-45°C, react for 12-24 hours, remove excess solvent by rotary evaporation, wash the reaction product 2-3 times with deionized water at a temperature of 75-80°C, and evaporate in vacuo to constant weight to obtain halogenated benzophenone; d. Disperse the PET modified graphene in dichlorotoluene, ultrasonically disperse for 10-15 minutes, add halogenated benzophenone, continue mixing for 30-45 minutes, irradiate with ultraviolet light for 8-15 minutes, centrifuge to separate the precipitate, vacuum dry to constant weight, and grind through a 200-400 mesh sieve to obtain a modified graphene material.

2. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: The antioxidant is any one or more of antioxidant 1076 and antioxidant 168; The heat stabilizer is 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate; and the lubricant is stearic acid.

3. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: In step a, the mass ratio of the carboxylated graphene, 4,4'-diaminobiphenyl and terephthalic acid is 10:(0.5-5):(1-5).

4. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: In step a, the mass ratio of the carboxylated graphene, ethylene glycol, and dibutyltin diacetate is 10:(100-500):(0.1-0.2).

5. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: In step b, the mass ratio of 2-hydroxybenzophenone, sodium hydroxide and 1,3-dibromopropane is 1:(0.1-0.25):(0.8-1.1).

6. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: In step c, the mass ratio of the 5-benzylhydantoin, sodium hydroxide and benzophenone bromide intermediate is 1:(0.2-0.3):(1.3-1.8).

7. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: In step c, the mass ratio of 5-benzylhydantoin to trichloroisocyanuric acid is 1:1.

05.

8. The graphene-based antibacterial polyester yarn according to claim 1, characterized in that: In step d, the mass ratio of the PET modified graphene to the halogenated benzophenone is 10:(0.5-3).

9. A process for preparing graphene-based antibacterial polyester yarn according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. The modified graphene material is mixed with a polyester masterbatch, an antioxidant, a lubricant, and a heat stabilizer, melted by a twin-screw, blended at a high speed for 20-30 minutes, and extruded and pelletized to obtain a modified graphene polyester masterbatch; S2. The modified graphene polyester masterbatch is melt-spun, cooled by annular blowing, the single filament is oiled, and then drawn and wound to obtain graphene-based antibacterial polyester filament.

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