Modified graphene antistatic fiber and preparation method thereof

Abstract

The invention discloses a modified graphene antistatic fiber and a preparation method thereof, and relates to the technical field of chemical fibers. When the modified graphene antistatic fiber is prepared, polyethylene glycol terephthalate, an ultraviolet absorption monomer and dimethyl (vinyl) silane react to prepare modified polyester; the preparation method comprises the following steps: polymerizing thiophene, hydantoin thiophene and 3-vinyl thiophene, and coating the phase change microcapsule with the polymerized thiophene, hydantoin thiophene and 3-vinyl thiophene to prepare a pre-modified phase change microcapsule; reacting the pre-modified phase change microcapsule with sodium hypochlorite to obtain a modified phase change microcapsule; the pre-modified graphene and 5-chloro-1-pentene are subjected to a reaction, and modified graphene is prepared; preparing a spinning solution from the modified polyester, the modified phase change microcapsules, the modified graphene, chloroplatinic acid and N, N-dimethylformamide, and performing wet spinning to obtain the modified graphene antistatic fiber. The modified graphene antistatic fiber prepared by the invention has excellent anti-aging, antibacterial, flame-retardant, antistatic, warm-keeping and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of chemical fibers, in particular to a modified graphene antistatic fiber and a preparation method thereof. Background Art

[0002] Static electricity is everywhere in people's daily life. We carry thousands or even tens of thousands of volts of static electricity on and around us. When people walk on chemical fiber carpets, there is about 35,000 volts of static electricity, and when reading plastic instructions, there is about 7,000 volts of static electricity. These static electricity voltages may not be felt at ordinary times, but for some sensitive instruments, this voltage may cause great harm. In daily life and production, many materials are prone to static electricity accumulation during use, causing dust, electric shock, and even sparks, leading to explosions and other malignant accidents. In the production and processing of synthetic fibers in the fiber and textile industry, there will be hidden dangers to quality and safety. In the use of textiles, static electricity will cause them to absorb dust and stain, and will also make clothing stick to the human body and cause discomfort. In addition, static electricity will stimulate the human body and have an adverse effect on health.

[0003] Since its advent, synthetic fibers have been favored by people and developed rapidly because of their excellent properties that most natural fibers cannot match, such as high elasticity, low price, and resistance to insect infestation. Synthetic fibers are important textile materials, and their status has long surpassed that of natural fibers. They are widely used in various industries and occupy a large proportion in the textile processing chain. However, the generally low antistatic properties of synthetic fibers limit their further development. Therefore, it is necessary to invent a fiber material with excellent antistatic properties. Summary of the invention

[0004] The purpose of the present invention is to provide a modified graphene antistatic fiber and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A modified graphene antistatic fiber, wherein the modified graphene antistatic fiber is prepared by reacting polyethylene terephthalate, an ultraviolet absorption monomer, and dimethyl (vinyl) silane to obtain a modified polyester; reacting a pre-modified phase change microcapsule and sodium hypochlorite to obtain a modified phase change microcapsule; reacting a pre-modified graphene and 5-chloro-1-pentene to obtain a modified graphene; and preparing a spinning solution of the modified polyester, the modified phase change microcapsule, the modified graphene, chloroplatinic acid, and N,N-dimethylformamide, and performing wet spinning.

[0007] The ultraviolet absorption monomer is prepared by reacting (2-iodophenyl)-phenyldiazene with trimethyl borate and sulfuric acid in sequence;

[0008] The pre-modified phase-change microcapsules are prepared by polymerizing thiophene, heinylthiophene, and 3-vinylthiophene and coating them on phase-change microcapsules;

[0009] The hydantoinylthiophene is prepared by reacting 5,5-dimethylhydantoin and 3-chloromethylthiophene;

[0010] The pre-modified graphene is prepared by polymerizing and growing 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol on the pre-treated graphene;

[0011] The pretreated graphene is prepared by reacting graphene oxide and 3-mercaptopropyltriethoxysilane.

[0012] A method for preparing a modified graphene antistatic fiber, the method for preparing the modified graphene antistatic fiber comprising the following preparation steps:

[0013] (1) mixing ultraviolet absorbing monomer, dimethyl (vinyl) silane and N,N-dimethylformamide in a mass ratio of 1:(0.6-0.8):(18-20) to prepare a mixed monomer solution; mixing polyethylene terephthalate and the mixed monomer solution in a mass ratio of 1:(6-8) to prepare a mixed monomer solution; adding benzoyl peroxide in an amount of 0.06-0.08 times the mass of polyethylene terephthalate; stirring at 75-85° C. and 100-200 r / min for reaction for 2-3 hours; and drying at 58-60° C. under vacuum conditions for 9-10 hours to prepare a modified polyester;

[0014] (2) The phase change microcapsules, anhydrous ferric chloride and tetrahydrofuran were mixed uniformly in a mass ratio of 1: (0.03-0.05): (20-22), and ultrasonically dispersed for 10-20 minutes. Under nitrogen protection, at 0-2°C and 200-300 r / min stirring conditions, thiophene reaction solution 6-8 times the mass of the phase change microcapsules was added dropwise at a uniform speed within 10 minutes. After the addition was completed, the reaction was continued to stir for 12-14 hours, filtered, and washed with anhydrous ethanol and deionized water for 3-5 times each. , under vacuum conditions, dried at 50-60°C for 9-10 hours to obtain pre-modified phase change microcapsules; immersed the pre-modified phase change microcapsules in a sodium hypochlorite aqueous solution with a mass fraction of 10%-12%, adjusted the pH to 6.5-6.7 with a sulfuric acid aqueous solution with a mass fraction of 26%-28%, ultrasonically dispersed for 40-50 minutes, filtered, washed with anhydrous ethanol and deionized water for 3-5 times each, and dried at 50-60°C for 7-8 hours under vacuum conditions to obtain modified phase change microcapsules;

[0015] (3) Pre-modified graphene, 5-chloro-1-pentene, and tetrahydrofuran are mixed uniformly in a mass ratio of 1:(5-6):(20-22), stirred at 20-30° C. and 200-300 r / min for 2-3 h, filtered, washed with deionized water for 3-5 times, and dried at 60-70° C. under vacuum conditions for 8-10 h to obtain modified graphene;

[0016] (4) Immersing the spinneret in deionized water, pouring the spinning solution into a wet spinning container for wet spinning to obtain spun fibers, setting the spinning speed to 40-50 m / min, and the aperture of the spinneret holes to 0.1-0.12 mm; leaving the spun fibers at 70-80° C. for 3-4 h, and drying them at 60-70° C. under vacuum conditions for 8-10 h to obtain modified graphene antistatic fibers.

[0017] As an optimization, the preparation method of the ultraviolet absorbing monomer in step (1) is as follows: (2-iodophenyl)-phenyldiazene, n-butyl lithium, and diethyl ether are mixed uniformly in a mass ratio of 1: (0.06-0.08): (8-10), stirred at -114--110°C and 200-300r / min for 20-30min, trimethyl borate in an amount equivalent to (2-iodophenyl)-phenyldiazene is added, stirring is continued for 2-2.2h, and a sulfuric acid aqueous solution having a mass fraction of 30%-40% and a mass fraction of 6-8 times the mass of (2-iodophenyl)-phenyldiazene is added. Liquid, stirred at 0-2°C, 200-300r / min for 30-40min, dried at 40-50°C for 8-10h under vacuum conditions to obtain boric acid azobenzene; boric acid azobenzene and 4-(2-allyl)-catechol are added to toluene with a mass of 8-10 times that of 4-(2-allyl)-catechol in a molar ratio of 1:1, stirred at 100-102°C, 200-300r / min for 2-3h, dried at 40-50°C for 8-10h under vacuum conditions to obtain an ultraviolet absorbing monomer; the reaction process is as follows:

[0018]

[0019] As an optimization, the CAS number of the (2-iodophenyl)-phenyldiazene is 51343-11-4, and the structural formula is:

[0020]

[0021] As an optimization, the molecular weight of the polyethylene terephthalate in step (1) is 20,000.

[0022] As an optimization, the preparation method of the thiophene reaction solution in step (2) is: thiophene, hyaluronic acid, 3-vinylthiophene, and tetrahydrofuran are uniformly mixed in a mass ratio of 1: (0.4-0.6): (0.2-0.3): (7-8) to prepare a thiophene reaction solution.

[0023] As an optimization, the preparation method of the hydantoin-based thiophene is as follows: 5,5-dimethylhydantoin and potassium hydroxide are added in a molar ratio of 1:1 to deionized water 6 to 8 times the mass of 5,5-dimethylhydantoin, stirred at 10 to 30° C. and 200 to 300 r / min for 55 to 65 min, methanol 0.5 to 0.6 times the volume of deionized water is added and mixed evenly, 3-chloromethylthiophene in an amount equal to 5,5-dimethylhydantoin is added, stirred at 58 to 62° C. and 200 to 300 r / min for 2 to 2.2 h, and dried at 50 to 60° C. under vacuum conditions for 8 to 10 h to obtain hydantoin-based thiophene; the reaction process is as follows:

[0024]

[0025] As an optimization, the model of the phase change microcapsule in step (2) is PCM32.

[0026] As an optimization, the preparation method of the pre-modified graphene in step (3) is as follows: 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol are added in a molar ratio of 1:1 to N,N-dimethylformamide with a mass ratio of 8 to 10 times that of 1,3-propanedithiol, mixed evenly, and prepared into a mixed reaction liquid; pre-treated graphene, potassium carbonate, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(0.4 to 0.6):(28 to 32), and the mixed reaction liquid with a mass ratio of 13 to 15 times that of the pre-treated graphene is added dropwise at a uniform speed within 20 minutes at 0 to 2°C and 200 to 300 r / min stirring conditions. After the addition is completed, the stirring reaction is continued for 1 to 1.2 hours, filtered, and dried at 60 to 70°C under vacuum conditions for 8 to 10 hours to obtain pre-modified graphene.

[0027] As an optimization, the CAS number of the 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide is 42983-36-8, and the structural formula is:

[0028] As an optimization, the preparation method of the pretreated graphene is as follows: 3-mercaptopropyltriethoxysilane and anhydrous ethanol are mixed evenly in a mass ratio of 1: (8-10), stirred at 10-30° C. and 200-300 r / min for 15-25 min to prepare a silane coupling agent solution; graphene oxide and deionized water are mixed evenly in a mass ratio of 1: (50-60), ultrasonically dispersed for 1-2 h, 20-22 times the mass of graphene oxide silane coupling agent solution is added, the pH is adjusted to 4.8-5.2 with a 1 mol / L hydrochloric acid aqueous solution, the reaction is stirred at 50-60° C. and 200-300 r / min for 2-2.2 h, filtered, and dried at 60-70° C. under vacuum conditions for 8-10 h to obtain the pretreated graphene.

[0029] As an optimization, the graphene oxide has a particle size of 1 to 4 μm and is purchased from Jiangxi Shuobang New Materials Technology Co., Ltd.

[0030] As an optimization, the preparation method of the spinning solution in step (4) is as follows: weigh 98 to 102 parts of modified polyester, 9 to 11 parts of modified phase change microcapsules, 2 to 3 parts of modified graphene, 1 to 2 parts of chloroplatinic acid, and 600 to 700 parts of N,N-dimethylformamide, by mass; mix the modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid, and N,N-dimethylformamide evenly, and stir at 20 to 30° C. and 200 to 300 r / min for 2 to 3 hours to prepare the spinning solution.

[0031] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0032] When preparing the modified graphene antistatic fiber, the present invention sequentially reacts (2-iodophenyl)-phenyldiazene with trimethyl borate, sulfuric acid and 4-(2-allyl)-catechol to obtain an ultraviolet absorption monomer; reacts polyethylene terephthalate, an ultraviolet absorption monomer and dimethyl (vinyl) silane to obtain a modified polyester; reacts 5,5-dimethylhydantoin and 3-chloromethylthiophene to obtain hydantoinylthiophene; polymerizes thiophene, hydantoinylthiophene and 3-vinylthiophene on a phase change microcapsule to obtain a pre-modified phase change microcapsule; reacts the pre-modified phase change microcapsule with sodium hypochlorite to obtain a phase change microcapsule. Modified phase change microcapsules are prepared; graphene oxide and 3-mercaptopropyltriethoxysilane are reacted to prepare pretreated graphene; 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol are polymerized and grown on pretreated graphene to prepare premodified graphene; premodified graphene and 5-chloro-1-pentene are reacted to prepare modified graphene; modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid and N,N-dimethylformamide are prepared into spinning solution, and modified graphene antistatic fibers are prepared by wet spinning.

[0033] First, (2-iodophenyl)-phenyldiazene is reacted with trimethyl borate, sulfuric acid, and 4-(2-allyl)-catechol in sequence to obtain an ultraviolet absorbing monomer, and a carbon-carbon double bond is introduced into the ultraviolet absorbing monomer; the ultraviolet absorbing monomer and dimethyl (vinyl) silane are grafted onto the molecular side chain of polyethylene terephthalate to obtain a modified polyester, and Si-H bonds, silicon elements, and B←N azobenzene structures are introduced into the molecular side chains of the modified polyester; the B←N azobenzene structure can undergo cis-trans isomerization changes under the action of ultraviolet light, and the B←N bond undergoes reversible rupture and recombination, thereby absorbing ultraviolet light, giving the modified graphene antistatic fiber excellent anti-aging properties. The mechanism of action is shown in the figure below:

[0034]

[0035] The Si-H bond introduced on the side chain of the modified polyester can undergo addition reaction with the carbon-carbon double bonds introduced on the modified phase change microcapsules and modified graphene to form a cross-linked network structure, inhibiting the relative slip between molecular chains, thereby improving the mechanical properties of the graphene antistatic fiber; the silicon element introduced on the side chain of the modified polyester can also improve the flame retardant properties of the modified graphene antistatic fiber.

[0036] Secondly, 5,5-dimethylhydantoin and 3-chloromethylthiophene are reacted to obtain hydantoinylthiophene; thiophene, hydantoinylthiophene and 3-vinylthiophene are polymerized and coated on phase change microcapsules to obtain pre-modified phase change microcapsules, polythiophene is generated on the surface of the pre-modified phase change microcapsules, and a halamine precursor structure and a carbon-carbon double bond are introduced. Polythiophene is a conductive polymer material that can form a conductive network in the modified graphene antistatic fiber to improve the antistatic performance of the modified graphene antistatic fiber; the pre-modified phase change microcapsules and sodium hypochlorite are reacted to obtain modified phase change microcapsules; the NH bond in the halamine precursor structure can be formed in the sodium hypochlorite. N-Cl is generated under chlorination, and a chloramine structure is formed on the surface of the modified phase change microcapsule, further improving the antibacterial properties of the modified graphene antistatic fiber. The carbon-carbon double bonds introduced on the surface of the modified phase change microcapsule can react with the Si-H bonds introduced on the side chain of the modified polyester to form a cross-linked network, inhibiting the relative slip between molecular chains and improving the mechanical properties of the modified graphene antistatic fiber. Phase change microcapsules are a type of intelligent material that can automatically sense changes in ambient temperature and human body temperature, and regulate the temperature by absorbing or releasing heat, thereby giving the modified graphene antistatic fiber good thermal insulation properties.

[0037] Finally, graphene oxide and 3-mercaptopropyltriethoxysilane are reacted to obtain pretreated graphene, and thiol groups are introduced into the pretreated graphene; the bromine atoms on 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide are reacted with the thiol groups on 1,3-propanedithiol, and polymerized and grown on the pretreated graphene to obtain premodified graphene, thioether is generated on the premodified graphene, and phosphorus is introduced. The introduction of phosphorus can improve the flame retardant properties of the modified graphene antistatic fiber; the thioether generated on the premodified graphene is reacted with the chlorine atoms on 5-chloro-1-pentene to obtain modified graphene, and the modified graphene is prepared on the modified graphene. Sulfonium salt is generated on the graphene and a carbon-carbon double bond is introduced. The sulfonium salt is a cationic antibacterial agent, which can improve the antibacterial properties of the modified graphene antistatic fiber. The carbon-carbon double bond introduced on the modified graphene can react with the Si-H bond introduced on the side chain of the modified polyester molecule to form a cross-linked network, which inhibits the relative slip between the molecular chains and improves the mechanical properties of the modified graphene antistatic fiber. Graphene oxide has good conductivity. Surface modification of graphene oxide can improve the dispersibility of graphene oxide in polymer materials, avoid agglomeration, give full play to the conductive properties of graphene, and further improve the antistatic properties of the modified graphene antistatic fiber. DETAILED DESCRIPTION

[0038] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0039] Embodiment 1:

[0040] A method for preparing a modified graphene antistatic fiber, the method for preparing the modified graphene antistatic fiber comprising the following preparation steps:

[0041] (1) (2-iodophenyl)-phenyldiazene, n-butyl lithium and diethyl ether were mixed uniformly at a mass ratio of 1:0.06:8, stirred at -114°C and 200 r / min for 30 min, trimethyl borate in an amount equivalent to (2-iodophenyl)-phenyldiazene was added, and stirring was continued for 2.2 h, and a 30% sulfuric acid aqueous solution with a mass fraction of 6 times the mass of (2-iodophenyl)-phenyldiazene was added, stirred at 0°C and 200 r / min for 40 min, and dried at 40°C under vacuum conditions for 10 h to obtain boronate azobenzene; boronate azobenzene and 4-(2-allyl)-catechol were added to 4-(2 -allyl)-catechol in toluene with a mass of 8 times, stirring at 100°C, 200r / min for 3h, and drying at 40°C for 10h under vacuum conditions to obtain an ultraviolet absorbing monomer; the ultraviolet absorbing monomer, dimethyl (vinyl) silane, and N,N-dimethylformamide are mixed evenly at a mass ratio of 1:0.6:18 to prepare a mixed monomer solution; polyethylene terephthalate and the mixed monomer solution are mixed evenly at a mass ratio of 1:6, benzoyl peroxide with a mass of 0.06 times the mass of polyethylene terephthalate is added, stirring at 75°C, 100r / min for 3h, and drying at 58°C for 10h under vacuum conditions to obtain a modified polyester;

[0042] (2) 5,5-dimethylhydantoin and potassium hydroxide were added in a molar ratio of 1:1 to deionized water (6 times the mass of 5,5-dimethylhydantoin), stirred at 10°C and 200 r / min for 65 min, methanol (0.5 times the volume of deionized water) was added and mixed evenly, 3-chloromethylthiophene (equimolar amount) of 5,5-dimethylhydantoin was added, stirred at 58°C and 200 r / min for 2.2 h, and dried at 50°C under vacuum conditions for 10 h to obtain hydantoin-based thiophene; thiophene, hydantoin-based thiophene, 3-vinylthiophene, and tetrahydrofuran were mixed evenly in a mass ratio of 1:0.4:0.2:7 to prepare a thiophene reaction solution; phase change microcapsules, anhydrous ferric chloride, and tetrahydrofuran were mixed in a mass ratio of 1:0.03 :20, mix evenly, ultrasonically disperse for 10 minutes, under nitrogen protection, at 0°C, 200r / min stirring conditions, uniformly add thiophene reaction solution 6 times the mass of phase change microcapsules within 10 minutes, continue stirring and reacting for 14 hours after the addition is completed, filter, wash with anhydrous ethanol and deionized water 3 times each, dry at 50°C for 10 hours under vacuum conditions to obtain pre-modified phase change microcapsules; immerse the pre-modified phase change microcapsules in a 10% sodium hypochlorite aqueous solution, adjust the pH to 6.5 with a 26% sulfuric acid aqueous solution, ultrasonically disperse for 40 minutes, filter, wash with anhydrous ethanol and deionized water 3 times each, dry at 50°C for 8 hours under vacuum conditions to obtain modified phase change microcapsules;

[0043] (3) 3-Mercaptopropyltriethoxysilane and anhydrous ethanol were mixed at a mass ratio of 1:8, stirred at 10°C and 200 r / min for 25 min to prepare a silane coupling agent solution; graphene oxide and deionized water were mixed at a mass ratio of 1:50, ultrasonically dispersed for 1 h, 20 times the mass of graphene oxide silane coupling agent solution was added, the pH was adjusted to 4.8 with a 1 mol / L hydrochloric acid aqueous solution, stirred at 50°C and 200 r / min for 2.2 h, filtered, and dried at 60°C under vacuum conditions for 10 h to obtain pretreated graphene; 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol were added to 1,3-propanedithiol at a molar ratio of 1:1. The pre-treated graphene, potassium carbonate and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:0.4:28, and the mixed reaction solution of 13 times the mass of the pre-treated graphene is added dropwise at a uniform speed within 20 minutes at 0°C and 200r / min stirring conditions. After the addition is completed, the stirring reaction is continued for 1.2 hours, filtered, and dried at 60°C for 10 hours under vacuum conditions to obtain pre-modified graphene; the pre-modified graphene, 5-chloro-1-pentene and tetrahydrofuran are mixed evenly in a mass ratio of 1:5:20, stirred and reacted at 20°C and 200r / min for 3 hours, filtered, washed with deionized water 3 times, and dried at 60°C for 10 hours under vacuum conditions to obtain modified graphene;

[0044] (4) According to the mass fraction, 98 parts of modified polyester, 9 parts of modified phase change microcapsules, 2 parts of modified graphene, 1 part of chloroplatinic acid, and 600 parts of N,N-dimethylformamide were weighed; the modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid, and N,N-dimethylformamide were mixed evenly, stirred at 20°C and 200 r / min for 3 h to prepare a spinning solution, the spinneret was immersed in deionized water, and the spinning solution was poured into a wet spinning container for wet spinning to obtain nascent fibers, the spinning speed was set to 40 m / min, and the aperture of the spinneret on the spinneret was 0.1 mm; the nascent fibers were allowed to stand at 70°C for 4 h, and dried at 60°C for 10 h under vacuum conditions to obtain modified graphene antistatic fibers.

[0045] Embodiment 2:

[0046] A method for preparing a modified graphene antistatic fiber, the method for preparing the modified graphene antistatic fiber comprising the following preparation steps:

[0047] (1) (2-iodophenyl)-phenyldiazene, n-butyl lithium and diethyl ether were mixed uniformly at a mass ratio of 1:0.07:9, stirred at -112°C and 250 r / min for 25 min, trimethyl borate in an amount equivalent to (2-iodophenyl)-phenyldiazene was added, stirring was continued for 2.1 h, a 35% sulfuric acid aqueous solution with a mass fraction of 7 times the mass of (2-iodophenyl)-phenyldiazene was added, stirred at 1°C and 250 r / min for 35 min, and dried at 45°C under vacuum conditions for 9 h to obtain boronic acid azobenzene; boronic acid azobenzene and 4-(2-allyl)-catechol were added to 4-(2-allyl)-pyrocatechol in a molar ratio of 1:1. The ultraviolet absorbing monomer was prepared by mixing the ultraviolet absorbing monomer, dimethyl (vinyl) silane and N,N-dimethylformamide in a mass ratio of 1:0.7:19 to prepare a mixed monomer solution; polyethylene terephthalate and the mixed monomer solution were mixed in a mass ratio of 1:7, benzoyl peroxide in an amount of 0.07 times the mass of polyethylene terephthalate was added, the mixture was stirred at 80°C and 150r / min for 2.5h, and dried at 59°C for 9.5h under vacuum conditions to obtain a modified polyester;

[0048] (2) 5,5-dimethylhydantoin and potassium hydroxide were added in a molar ratio of 1:1 to deionized water (7 times the mass of 5,5-dimethylhydantoin), stirred at 20°C and 250 r / min for 60 min, methanol (0.55 times the volume of deionized water) was added and mixed evenly, 3-chloromethylthiophene (equimolar amount of 5,5-dimethylhydantoin) was added, stirred at 60°C and 250 r / min for 2.1 h, and dried at 55°C under vacuum conditions for 9 h to obtain hydantoin-based thiophene; thiophene, hydantoin-based thiophene, 3-vinylthiophene, and tetrahydrofuran were mixed evenly in a mass ratio of 1:0.5:0.25:7.5 to prepare a thiophene reaction solution; phase change microcapsules, anhydrous ferric chloride, and tetrahydrofuran were mixed in a mass ratio of 1:0.04 :21 mixed evenly, ultrasonically dispersed for 15 minutes, under nitrogen protection, at 1 ° C, 250r / min stirring conditions, uniformly add thiophene reaction solution 7 times the mass of phase change microcapsules within 10 minutes, continue stirring and reacting for 13 hours after the addition is completed, filter, wash with anhydrous ethanol and deionized water 4 times each, dry at 55 ° C for 9.5 hours under vacuum conditions to obtain pre-modified phase change microcapsules; immerse the pre-modified phase change microcapsules in a sodium hypochlorite aqueous solution with a mass fraction of 11%, adjust the pH to 6.6 with a sulfuric acid aqueous solution with a mass fraction of 27%, ultrasonically disperse for 45 minutes, filter, wash with anhydrous ethanol and deionized water 4 times each, and dry at 55 ° C for 7.5 hours under vacuum conditions to obtain modified phase change microcapsules;

[0049] (3) 3-Mercaptopropyltriethoxysilane and anhydrous ethanol were mixed at a mass ratio of 1:9, stirred at 20°C and 250 r / min for 20 min to prepare a silane coupling agent solution; graphene oxide and deionized water were mixed at a mass ratio of 1:55, ultrasonically dispersed for 1.5 h, 21 times the mass of graphene oxide silane coupling agent solution was added, the pH was adjusted to 5 with a 1 mol / L hydrochloric acid aqueous solution, stirred at 55°C and 250 r / min for 2.1 h, filtered, and dried at 65°C under vacuum conditions for 9 h to obtain pretreated graphene; 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol were added to 1,3-propanedithiol in a molar ratio of 1:1. 9 times the mass of N, N-dimethylformamide, mixed evenly to prepare a mixed reaction liquid; pretreated graphene, potassium carbonate, and N, N-dimethylformamide were mixed evenly at a mass ratio of 1:0.5:30, and the mixed reaction liquid of 14 times the mass of the pretreated graphene was uniformly added dropwise at 1°C and 250r / min under stirring conditions within 20min. After the addition was completed, the stirring reaction was continued for 1.1h, filtered, and dried at 65°C for 9h under vacuum conditions to obtain pre-modified graphene; pre-modified graphene, 5-chloro-1-pentene, and tetrahydrofuran were mixed evenly at a mass ratio of 1:5.5:21, stirred and reacted at 25°C and 250r / min for 2.5h, filtered, washed with deionized water 4 times, and dried at 65°C for 9h under vacuum conditions to obtain modified graphene;

[0050] (4) According to the mass fraction, 100 parts of modified polyester, 10 parts of modified phase change microcapsules, 2.5 parts of modified graphene, 1.5 parts of chloroplatinic acid, and 650 parts of N,N-dimethylformamide were weighed; the modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid, and N,N-dimethylformamide were mixed evenly, stirred at 25°C and 250 r / min for 2.5 h to prepare a spinning solution, the spinneret was immersed in deionized water, and the spinning solution was poured into a wet spinning container for wet spinning to obtain nascent fibers, the spinning speed was set to 45 m / min, and the aperture of the spinneret on the spinneret was 0.11 mm; the nascent fibers were allowed to stand at 75°C for 3.5 h, and dried at 65°C under vacuum for 9 h to obtain modified graphene antistatic fibers.

[0051] Embodiment 3:

[0052] A method for preparing a modified graphene antistatic fiber, the method for preparing the modified graphene antistatic fiber comprising the following preparation steps:

[0053] (1) (2-iodophenyl)-phenyldiazene, n-butyl lithium and diethyl ether were mixed uniformly at a mass ratio of 1:0.08:10, stirred at -110°C and 300 r / min for 20 min, trimethyl borate in an amount equivalent to (2-iodophenyl)-phenyldiazene was added, and stirring was continued for 2 h, a 40% sulfuric acid aqueous solution with a mass fraction of 8 times the mass of (2-iodophenyl)-phenyldiazene was added, and the mixture was stirred at 2°C and 300 r / min for 30 min, and dried at 50°C for 10 h under vacuum conditions to obtain boronic acid azobenzene; boronic acid azobenzene and 4-(2-allyl)-catechol were added to 4-(2 -allyl)-catechol in toluene with a mass 10 times that of catechol, stirred at 102°C and 300r / min for 2h, dried at 50°C for 8h under vacuum conditions to obtain an ultraviolet absorbing monomer; the ultraviolet absorbing monomer, dimethyl (vinyl) silane, and N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:0.8:20 to prepare a mixed monomer solution; polyethylene terephthalate and the mixed monomer solution were mixed uniformly at a mass ratio of 1:8, benzoyl peroxide with a mass 0.08 times that of polyethylene terephthalate was added, stirred at 85°C and 200r / min for 2h, and dried at 60°C for 9h under vacuum conditions to obtain a modified polyester;

[0054] (2) 5,5-dimethylhydantoin and potassium hydroxide were added in a molar ratio of 1:1 to deionized water (8 times the mass of 5,5-dimethylhydantoin), stirred at 30°C and 300 r / min for 55 min, methanol (0.6 times the volume of deionized water) was added and mixed evenly, 3-chloromethylthiophene (equimolar amount) of 5,5-dimethylhydantoin was added, stirred at 62°C and 300 r / min for 2 h, and dried at 60°C under vacuum conditions for 8 h to obtain hydantoin-based thiophene; thiophene, hydantoin-based thiophene, 3-vinylthiophene, and tetrahydrofuran were mixed evenly in a mass ratio of 1:0.6:0.3:8 to prepare a thiophene reaction solution; phase change microcapsules, anhydrous ferric chloride, and tetrahydrofuran were mixed in a mass ratio of 1:0.05: 22. Mix evenly, disperse ultrasonically for 20 minutes, under nitrogen protection, at 2°C, 300r / min stirring conditions, uniformly add thiophene reaction solution 8 times the mass of phase change microcapsules within 10 minutes, continue stirring and reacting for 12 hours after the addition is completed, filter, wash with anhydrous ethanol and deionized water 5 times each, dry at 60°C for 9 hours under vacuum conditions to obtain pre-modified phase change microcapsules; immerse the pre-modified phase change microcapsules in a 12% sodium hypochlorite aqueous solution, adjust the pH to 6.7 with a 28% sulfuric acid aqueous solution, ultrasonically disperse for 50 minutes, filter, wash with anhydrous ethanol and deionized water 5 times each, dry at 60°C for 7 hours under vacuum conditions to obtain modified phase change microcapsules;

[0055] (3) 3-Mercaptopropyltriethoxysilane and anhydrous ethanol were mixed at a mass ratio of 1:10, stirred at 30°C and 300 r / min for 15 min to prepare a silane coupling agent solution; graphene oxide and deionized water were mixed at a mass ratio of 1:60, ultrasonically dispersed for 2 h, 22 times the mass of graphene oxide silane coupling agent solution was added, the pH was adjusted to 5.2 with a 1 mol / L hydrochloric acid aqueous solution, stirred at 60°C and 300 r / min for 2 h, filtered, and dried at 70°C under vacuum conditions for 8 h to obtain pretreated graphene; 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphorinane-2-oxide and 1,3-propanedithiol were added to 1,3-propanedithiol at a molar ratio of 1:1. The pre-treated graphene, potassium carbonate and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.6:32, and the mixed reaction solution of 15 times the mass of the pre-treated graphene was added dropwise at a uniform speed within 20 minutes under the stirring conditions of 2°C and 300r / min. After the addition was completed, the mixture was stirred for 1 hour, filtered, and dried at 70°C for 8 hours under vacuum conditions to obtain pre-modified graphene; the pre-modified graphene, 5-chloro-1-pentene and tetrahydrofuran were mixed evenly in a mass ratio of 1:6:22, stirred at 30°C and 300r / min for 2 hours, filtered, washed with deionized water 5 times, and dried at 70°C for 8 hours under vacuum conditions to obtain modified graphene;

[0056] (4) According to the mass fraction, 102 parts of modified polyester, 11 parts of modified phase change microcapsules, 3 parts of modified graphene, 2 parts of chloroplatinic acid, and 700 parts of N,N-dimethylformamide were weighed; the modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid, and N,N-dimethylformamide were mixed evenly, stirred at 30°C and 300 r / min for 2 h to prepare a spinning solution, the spinneret was immersed in deionized water, and the spinning solution was poured into a wet spinning container for wet spinning to obtain nascent fibers, the spinning speed was set to 50 m / min, and the aperture of the spinneret on the spinneret was 0.12 mm; the nascent fibers were allowed to stand at 80°C for 3 h, and dried at 70°C under vacuum conditions for 8 h to obtain modified graphene antistatic fibers.

[0057] Comparative Example 1:

[0058] The difference between the preparation method of the modified graphene antistatic fiber of Comparative Example 1 and Example 2 is that step (1) is not performed, and step (4) is modified as follows: by mass, 100 parts of polyethylene terephthalate, 10 parts of modified phase change microcapsules, 2.5 parts of modified graphene, 1.5 parts of chloroplatinic acid, and 650 parts of N,N-dimethylformamide are weighed; polyethylene terephthalate, modified phase change microcapsules, modified graphene, chloroplatinic acid, N,N-dimethylformamide are added; The methacrylate was mixed evenly, stirred at 25°C and 250r / min for 2.5h to prepare a spinning solution, the spinneret was immersed in deionized water, the spinning solution was poured into a wet spinning container for wet spinning to obtain nascent fibers, the spinning speed was set to 45m / min, and the aperture of the spinneret on the spinneret was 0.11mm; the nascent fibers were allowed to stand at 75°C for 3.5h, and dried at 65°C under vacuum for 9h to obtain modified graphene antistatic fibers. The remaining steps were the same as in Example 2.

[0059] Comparative Example 2:

[0060] The difference between the preparation method of the modified graphene antistatic fiber of Comparative Example 2 and Example 2 lies in the difference in step (2), and step (2) is modified as follows: thiophene, 3-vinylthiophene, and tetrahydrofuran are mixed evenly in a mass ratio of 1.5:0.25:7.5 to prepare a thiophene reaction solution; phase change microcapsules, anhydrous ferric chloride, and tetrahydrofuran are mixed evenly in a mass ratio of 1:0.04:21, ultrasonically dispersed for 15 minutes, under nitrogen protection, at 1°C, 250r / min stirring conditions, thiophene reaction solution 7 times the mass of phase change microcapsules is added dropwise at a uniform speed within 10 minutes, and after the addition is completed, the reaction is continued to stir for 13 hours, filtered, washed 4 times with anhydrous ethanol and deionized water respectively, and dried at 55°C for 9.5 hours under vacuum conditions to obtain modified phase change microcapsules. The remaining steps are the same as in Example 2.

[0061] Comparative Example 3:

[0062] The preparation method of the modified graphene antistatic fiber of Comparative Example 3 is different from that of Example 2 only in step (2). Step (2) is modified as follows: 5,5-dimethylhydantoin and potassium hydroxide are added in a molar ratio of 1:1 to deionized water 7 times the mass of 5,5-dimethylhydantoin, stirred at 20°C and 250r / min for 60min, methanol 0.55 times the volume of deionized water is added and mixed evenly, 3-chloromethylthiophene in an amount equivalent to 5,5-dimethylhydantoin is added, stirred at 60°C and 250r / min for 2.1h, and dried at 55°C under vacuum for 9h to obtain hydantoin; thiophene, hydantoin and tetrahydrofuran are mixed evenly in a mass ratio of 1.25:0.5:7.5 to prepare a thiophene reaction solution; phase change microcapsules, anhydrous trichloroethane, Ferric chloride and tetrahydrofuran were mixed evenly in a mass ratio of 1:0.04:21, ultrasonically dispersed for 15 minutes, and under nitrogen protection, at 1°C, 250r / min stirring conditions, 7 times the mass of the phase change microcapsule was uniformly added with thiophene reaction solution within 10 minutes. After the addition was completed, the reaction was continued to stir for 13 hours, filtered, washed with anhydrous ethanol and deionized water 4 times each, and dried at 55°C for 9.5 hours under vacuum conditions to obtain pre-modified phase change microcapsules; the pre-modified phase change microcapsules were immersed in a sodium hypochlorite aqueous solution with a mass fraction of 11%, and the pH was adjusted to 6.6 with a sulfuric acid aqueous solution with a mass fraction of 27%, ultrasonically dispersed for 45 minutes, filtered, washed with anhydrous ethanol and deionized water 4 times each, and dried at 55°C for 7.5 hours under vacuum conditions to obtain modified phase change microcapsules. The remaining steps are the same as in Example 2.

[0063] Comparative Example 4:

[0064] The difference between the preparation method of the modified graphene antistatic fiber of Comparative Example 4 and Example 2 is that step (2) is not performed, and step (4) is modified as follows: 100 parts of modified polyester, 2.5 parts of modified graphene, 1.5 parts of chloroplatinic acid, and 650 parts of N,N-dimethylformamide are weighed by mass; the modified polyester, modified graphene, chloroplatinic acid, and N,N-dimethylformamide are mixed uniformly, stirred at 25°C and 250r / min for 2.5h, and the spinning solution is prepared, the spinneret is immersed in deionized water, and the spinning solution is poured into a wet spinning container for wet spinning to obtain a nascent fiber, the spinning speed is set to 45m / min, and the aperture of the spinneret on the spinneret is 0.11mm; the nascent fiber is left to stand at 75°C for 3.5h, and dried at 65°C for 9h under vacuum conditions to obtain a modified graphene antistatic fiber. The remaining steps are the same as in Example 2.

[0065] Comparative Example 5:

[0066] The difference between the preparation method of the modified graphene antistatic fiber of Comparative Example 5 and that of Example 2 lies in the difference in step (3). Step (3) is modified as follows: 3-mercaptopropyltriethoxysilane and anhydrous ethanol are mixed in a mass ratio of 1:9, stirred at 20°C and 250r / min for 20min to prepare a silane coupling agent solution; graphene oxide and deionized water are mixed in a mass ratio of 1:55, ultrasonically dispersed for 1.5h, 21 times the mass of graphene oxide silane coupling agent solution is added, the pH is adjusted to 5 with a 1mol / L hydrochloric acid aqueous solution, the reaction is stirred at 55°C and 250r / min for 2.1h, filtered, and dried at 65°C under vacuum for 9h to obtain a prepreg. Treating graphene: adding 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol in a molar ratio of 1:1 to N,N-dimethylformamide with a mass ratio of 9 times that of 1,3-propanedithiol, mixing evenly, and preparing a mixed reaction liquid; mixing pretreated graphene, potassium carbonate, and N,N-dimethylformamide in a mass ratio of 1:0.5:30, adding the mixed reaction liquid with a mass ratio of 14 times that of the pretreated graphene at a uniform speed within 20 minutes at 1°C and 250r / min stirring conditions, continuing to stir and react for 1.1 hours after the addition is complete, filtering, and drying at 65°C for 9 hours under vacuum conditions to obtain modified graphene. The remaining steps are the same as in Example 2.

[0067] Comparative Example 6:

[0068] The difference between the preparation method of the modified graphene antistatic fiber of Comparative Example 6 and Example 2 is that step (3) is not performed, and step (4) is modified as follows: 100 parts of modified polyester, 10 parts of modified phase change microcapsules, 2.5 parts of graphene oxide, 1.5 parts of chloroplatinic acid, and 650 parts of N,N-dimethylformamide are weighed by mass; the modified polyester, modified phase change microcapsules, graphene oxide, chloroplatinic acid, and N,N-dimethylformamide are mixed; The spinning solution was prepared by stirring the spinneret at 25 °C and 250 r / min for 2.5 h. The spinneret was immersed in deionized water and the spinning solution was poured into a liquid container for wet spinning to obtain spun fibers. The spinning speed was set to 45 m / min and the diameter of the spinneret holes on the spinneret was 0.11 mm. The spun fibers were allowed to stand at 75 °C for 3.5 h and dried at 65 °C for 9 h under vacuum to obtain modified graphene antistatic fibers.

[0069] Test Example 1

[0070] Antistatic performance test

[0071] Test method: The volume resistivity of the examples and comparative examples was tested according to GB / T14342-2015. The results are shown in Table 1.

[0072] Table 1

[0073]

[0074] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 1, it can be found that the modified graphene antistatic fiber prepared in the present invention has good antistatic performance.

[0075] By comparison, the volume specific resistance of Examples 1 to 3 is smaller than that of Comparative Example 4, indicating that thiophene, heinylthiophene and 3-vinylthiophene are polymerized and coated on phase change microcapsules to prepare pre-modified phase change microcapsules, and polythiophene is generated on the surface of the pre-modified phase change microcapsules. Polythiophene is a conductive polymer material that can form a conductive network in the modified graphene antistatic fiber, thereby improving the antistatic properties of the modified graphene antistatic fiber.

[0076] By comparison, the volume resistivity of Examples 1 to 3 is smaller than that of Comparative Example 6, indicating that graphene oxide has good conductivity. Surface modification of graphene oxide can improve the dispersibility of graphene oxide in polymer materials, avoid agglomeration, give full play to the conductive properties of graphene, and further improve the antistatic properties of the modified graphene antistatic fiber.

[0077] Test Example 2

[0078] Testing of mechanical properties and anti-aging properties

[0079] Test method: The mechanical properties of the embodiment and the comparative example were tested using the XL-1A filament tensile tester. The sample was passed around the yarn guide hook and the yarn guide wheel, and passed downward through the upper and lower clamps to ensure that the sample was straightened without relaxation. A pre-tension of about 10 cN was applied to the sample. The lower clamp drove the sample downward until the sample broke and then returned to its original position to obtain the breaking strength M of the sample; the embodiment and the comparative example were irradiated with a xenon arc lamp for 14 days, and then the breaking strength N was tested using the same method. The breaking strength change rate of the embodiment and the comparative example before and after ultraviolet aging treatment was calculated, and the breaking strength change rate = (MN) / M×100%. The results are shown in Table 2.

[0080] Table 2

[0081]

[0082] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 2, it can be found that the modified graphene antistatic fiber prepared in the present invention has good mechanical properties and anti-aging properties.

[0083] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Example 1, indicating that the ultraviolet absorbing monomer and dimethyl (vinyl) silane are grafted onto the molecular side chains of polyethylene terephthalate to obtain modified polyester, and Si-H bonds are introduced into the molecular side chains of the modified polyester. The Si-H bonds introduced into the side chains of the modified polyester can react with the carbon-carbon double bonds introduced into the modified phase change microcapsules and modified graphene to form a cross-linked network, thereby inhibiting the relative slip between the molecular chains and improving the mechanical properties of the modified graphene antistatic fiber.

[0084] By comparison, the breaking strength of Examples 1 to 3 is greater than that of Comparative Examples 3 to 4, indicating that secondly, 5,5-dimethylhydantoin and 3-chloromethylthiophene are reacted to obtain hydantoinylthiophene; thiophene, hydantoinylthiophene and 3-vinylthiophene are polymerized and coated on phase change microcapsules to obtain pre-modified phase change microcapsules, and carbon-carbon double bonds are introduced on the surface of the phase change microcapsules. The carbon-carbon double bonds introduced on the surface of the phase change microcapsules can undergo addition reaction with the Si-H bonds introduced on the side chains of the modified polyester to form a cross-linked network, thereby inhibiting the relative slip between molecular chains and improving the mechanical properties of the modified graphene antistatic fiber.

[0085] By comparison, the fracture strength of Examples 1 to 3 is greater than that of Comparative Examples 5 to 6, indicating that graphene oxide and 3-mercaptopropyltriethoxysilane are reacted to obtain pretreated graphene, and thiol groups are introduced into the pretreated graphene; the bromine atoms on 5,5-di(bromomethyl)-2-methoxy-1,3,2-dioxaphosphorinane-2-oxide react with the thiol groups on 1,3-propanedithiol, and polymerize and grow on the pretreated graphene to obtain pre-modified graphene, and thioether is generated on the pre-modified graphene; the thioether generated on the pre-modified graphene is reacted with the chlorine atoms on 5-chloro-1-pentene to obtain modified graphene, and carbon-carbon double bonds are introduced into the modified graphene. The carbon-carbon double bonds introduced into the modified graphene can undergo addition reaction with the Si-H bonds introduced into the side chains of the modified polyester molecules to form a cross-linked network, thereby inhibiting the relative slip between the molecular chains, thereby improving the mechanical properties of the modified graphene antistatic fiber.

[0086] By comparison, the breaking strength change rate of Examples 1 to 3 is less than that of Comparative Example 1, indicating that (2-iodophenyl)-phenyldiazene is reacted with trimethyl borate, sulfuric acid, and 4-(2-allyl)-catechol in sequence to obtain an ultraviolet absorbing monomer, and a carbon-carbon double bond is introduced into the ultraviolet absorbing monomer; the ultraviolet absorbing monomer and dimethyl (vinyl) silane are grafted onto the molecular side chain of polyethylene terephthalate to obtain a modified polyester, and a B←N azobenzene structure is introduced into the molecular side chain of the modified polyester; the B←N azobenzene structure can undergo cis-trans isomerization under the action of ultraviolet light, and the B←N bond undergoes reversible rupture and recombination, thereby absorbing ultraviolet light, and giving the modified graphene antistatic fiber excellent anti-aging properties.

[0087] Test Example 3

[0088] Antimicrobial performance testing

[0089] Test method: The antibacterial performance of the embodiment and the comparative example was analyzed by comparing the number of E. coli colonies cultured in agar medium for 16 hours using the oscillation method GB / T 20944.3. The results are shown in Table 3.

[0090] Table 3

[0091] Antibacterial rate (%) Antibacterial rate (%) Example 1 99.93 Comparative Example 1 99.91 Example 2 99.96 Comparative Example 2 91.62 Example 3 99.94 Comparative Example 3 99.89 Comparative Example 4 90.74 Comparative Example 5 94.17 Comparative Example 6 93.85

[0092] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 3, it can be found that the modified graphene antistatic fiber prepared in the present invention has good antibacterial properties.

[0093] By comparison, the antibacterial rates of Examples 1 to 3 are greater than those of Comparative Examples 2 and 4, indicating that 5,5-dimethylhydantoin and 3-chloromethylthiophene are reacted to obtain hydantoin-based thiophene; thiophene, hydantoin-based thiophene and 3-vinylthiophene are polymerized and coated on phase change microcapsules to obtain pre-modified phase change microcapsules, and a halamine precursor structure is introduced on the surface of the pre-modified phase change microcapsules. The NH bond in the halamine precursor structure can generate N-Cl under the chlorination of sodium hypochlorite, and a chloramine structure is formed on the surface of the modified phase change microcapsules, thereby further improving the antibacterial properties of the modified graphene antistatic fiber.

[0094] By comparison, the antibacterial rates of Examples 1 to 3 are greater than those of Comparative Examples 5 to 6, indicating that graphene oxide and 3-mercaptopropyltriethoxysilane are reacted to obtain pretreated graphene, and thiol groups are introduced into the pretreated graphene; the bromine atoms on 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphorinane-2-oxide react with the thiol groups on 1,3-propanedithiol, and polymerize and grow on the pretreated graphene to obtain pre-modified graphene, sulfide is generated on the pre-modified graphene, the sulfide generated on the pre-modified graphene is reacted with the chlorine atoms on 5-chloro-1-pentene to obtain modified graphene, and sulfonium salts are generated on the modified graphene. Sulfonium salts are cationic antibacterial agents and can improve the antibacterial properties of modified graphene antistatic fibers.

[0095] Test Example 4

[0096] Flame retardant performance test

[0097] Test method: According to GB / T2406-93, the limiting oxygen index of the embodiment and the comparative example was tested using an oxygen index instrument. The results are shown in Table 4.

[0098] Table 4

[0099] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 30.89 Comparative Example 1 26.25 Example 2 31.07 Comparative Example 2 30.37 Example 3 30.64 Comparative Example 3 30.41 Comparative Example 4 30.52 Comparative Example 5 30.60 Comparative Example 6 25.77

[0100] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 4, it can be found that the modified graphene antistatic fiber prepared in the present invention has good flame retardant properties.

[0101] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 1, indicating that the ultraviolet absorbing monomer and dimethyl (vinyl) silane are grafted onto the molecular side chain of polyethylene terephthalate to obtain modified polyester, and silicon element is introduced into the molecular side chain of the modified polyester. The introduction of silicon element can improve the flame retardant properties of the modified graphene antistatic fiber.

[0102] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 6, indicating that graphene oxide and 3-mercaptopropyltriethoxysilane are reacted to obtain pretreated graphene, and thiol groups are introduced into the pretreated graphene; the bromine atoms on 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphorinane-2-oxide are reacted with the thiol groups on 1,3-propanedithiol, and polymerized and grown on the pretreated graphene to obtain pre-modified graphene, and phosphorus element is introduced into the pre-modified graphene. The introduction of phosphorus element can improve the flame retardant properties of the modified graphene antistatic fiber.

[0103] Test Example 5

[0104] Thermal insulation performance test

[0105] Test method: The embodiment and the comparative example were woven into fabrics using a textile machine, and the thermal insulation rate of the fabrics woven into the embodiment and the comparative example was tested according to GB / T11048 "Test method for thermal insulation performance of textiles". The results are shown in Table 5.

[0106] Table 5

[0107] Insulation rate (%) Insulation rate (%) Example 1 31.46 Comparative Example 1 31.33 Example 2 32.67 Comparative Example 2 31.28 Example 3 31.89 Comparative Example 3 30.97 Comparative Example 4 23.18 Comparative Example 5 31.44 Comparative Example 6 30.95

[0108] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 5, it can be found that the modified graphene antistatic fiber prepared in the present invention has good thermal insulation performance.

[0109] By comparison, the warmth retention rates of Examples 1 to 3 are greater than that of Comparative Example 4, indicating that the phase change microcapsules are a type of intelligent material that can automatically sense changes in ambient temperature and human body temperature, and regulate temperature by absorbing or releasing heat; phase change microcapsules are added to the spinning solution for wet spinning, and the resulting fibers contain phase change microcapsules. After the fibers are woven into fabrics, the fabrics have good warmth retention properties.

[0110] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A modified graphene antistatic fiber, characterized in that: The modified graphene antistatic fiber is prepared by reacting polyethylene terephthalate, ultraviolet absorption monomer and dimethyl (vinyl) silane to obtain modified polyester; reacting pre-modified phase change microcapsules and sodium hypochlorite to obtain modified phase change microcapsules; reacting pre-modified graphene and 5-chloro-1-pentene to obtain modified graphene; and preparing a spinning solution of modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid and N,N-dimethylformamide, and wet spinning to obtain the fiber. The ultraviolet absorption monomer is prepared by reacting (2-iodophenyl)-phenyldiazene with trimethyl borate, sulfuric acid, and 4-(2-allyl)-catechol in sequence; The pre-modified phase-change microcapsules are prepared by polymerizing thiophene, heinylthiophene, and 3-vinylthiophene and coating them on phase-change microcapsules; The hydantoinylthiophene is prepared by reacting 5,5-dimethylhydantoin and 3-chloromethylthiophene; The pre-modified graphene is prepared by polymerizing and growing 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol on the pre-treated graphene; The pretreated graphene is prepared by reacting graphene oxide and 3-mercaptopropyltriethoxysilane.

2. A method for preparing modified graphene antistatic fiber, characterized in that: The preparation method of the modified graphene antistatic fiber comprises the following preparation steps: (1) mixing ultraviolet absorbing monomer, dimethyl (vinyl) silane and N,N-dimethylformamide in a mass ratio of 1:(0.6-0.8):(18-20) to prepare a mixed monomer solution; mixing polyethylene terephthalate and the mixed monomer solution in a mass ratio of 1:(6-8) to prepare a mixed monomer solution; adding benzoyl peroxide in an amount of 0.06-0.08 times the mass of polyethylene terephthalate; stirring at 75-85° C. and 100-200 r / min for reaction for 2-3 hours; and drying at 58-60° C. under vacuum conditions for 9-10 hours to prepare a modified polyester; (2) The phase change microcapsules, anhydrous ferric chloride and tetrahydrofuran were mixed uniformly in a mass ratio of 1: (0.03-0.05): (20-22), and ultrasonically dispersed for 10-20 minutes. Under nitrogen protection, at 0-2°C and 200-300 r / min stirring conditions, thiophene reaction solution 6-8 times the mass of the phase change microcapsules was added dropwise at a uniform speed within 10 minutes. After the addition was completed, the reaction was continued to stir for 12-14 hours, filtered, and washed with anhydrous ethanol and deionized water for 3-5 times each. , under vacuum conditions, dried at 50-60°C for 9-10 hours to obtain pre-modified phase change microcapsules; immersed the pre-modified phase change microcapsules in a sodium hypochlorite aqueous solution with a mass fraction of 10%-12%, adjusted the pH to 6.5-6.7 with a sulfuric acid aqueous solution with a mass fraction of 26%-28%, ultrasonically dispersed for 40-50 minutes, filtered, washed with anhydrous ethanol and deionized water for 3-5 times each, and dried at 50-60°C for 7-8 hours under vacuum conditions to obtain modified phase change microcapsules; (3) Pre-modified graphene, 5-chloro-1-pentene, and tetrahydrofuran are mixed uniformly in a mass ratio of 1:(5-6):(20-22), stirred at 20-30° C. and 200-300 r / min for 2-3 h, filtered, washed with deionized water for 3-5 times, and dried at 60-70° C. under vacuum conditions for 8-10 h to obtain modified graphene; (4) Immersing the spinneret in deionized water, pouring the spinning solution into a wet spinning container for wet spinning to obtain spun fibers, setting the spinning speed to 40-50 m / min, and the aperture of the spinneret holes to 0.1-0.12 mm; leaving the spun fibers at 70-80° C. for 3-4 h, and drying them at 60-70° C. under vacuum conditions for 8-10 h to obtain modified graphene antistatic fibers.

3. The method for preparing a modified graphene antistatic fiber according to claim 2, characterized in that: The preparation method of the ultraviolet absorbing monomer in step (1) is as follows: (2-iodophenyl)-phenyldiazene, n-butyl lithium, and diethyl ether are mixed uniformly in a mass ratio of 1: (0.06-0.08): (8-10), stirred at -114--110°C, 200-300r / min for 20-30min, trimethyl borate in an amount equivalent to (2-iodophenyl)-phenyldiazene is added, stirring is continued for 2-2.2h, and sulfuric acid water with a mass fraction of 30%-40% and a mass fraction of 6-8 times the mass of (2-iodophenyl)-phenyldiazene is added. The solution is stirred at 0-2°C and 200-300r / min for reaction for 30-40min, and dried at 40-50°C for 8-10h under vacuum conditions to obtain boronic acid azobenzene; boronic acid azobenzene and 4-(2-allyl)-catechol are added to toluene with a mass of 8-10 times that of 4-(2-allyl)-catechol in a molar ratio of 1:1, and the mixture is stirred at 100-102°C and 200-300r / min for reaction for 2-3h, and dried at 40-50°C for 8-10h under vacuum conditions to obtain an ultraviolet absorbing monomer.

4. The method for preparing a modified graphene antistatic fiber according to claim 2, characterized in that: The molecular weight of the polyethylene terephthalate in step (1) is 20,000.

5. The method for preparing a modified graphene antistatic fiber according to claim 2, characterized in that: The preparation method of the thiophene reaction solution in step (2) is: thiophene, hyaluronic acid, 3-vinylthiophene, and tetrahydrofuran are uniformly mixed in a mass ratio of 1: (0.4-0.6): (0.2-0.3): (7-8) to prepare a thiophene reaction solution.

6. The method for preparing a modified graphene antistatic fiber according to claim 5, characterized in that: The preparation method of hydantoin is as follows: 5,5-dimethylhydantoin and potassium hydroxide are added in a molar ratio of 1:1 into deionized water which is 6 to 8 times the mass of 5,5-dimethylhydantoin, and heated at 10 to 30° C. The mixture was stirred at 200-300 r / min for 55-65 min, methanol in an amount 0.5-0.6 times the volume of deionized water was added and mixed evenly, 3-chloromethylthiophene in an amount equal to 5,5-dimethylhydantoin was added, and the mixture was stirred at 58-62° C. and 200-300 r / min for 2-2.2 h. Under vacuum conditions, the mixture was dried at 50-60° C. for 8-10 h to obtain hydantoin.

7. The method for preparing a modified graphene antistatic fiber according to claim 2, characterized in that: The model of the phase change microcapsule in step (2) is PCM32.

8. The method for preparing a modified graphene antistatic fiber according to claim 2, characterized in that: The preparation method of the pre-modified graphene in step (3) is as follows: 5,5-bis(bromomethyl)-2-methoxy-1,3,2-dioxaphosphinane-2-oxide and 1,3-propanedithiol are added in a molar ratio of 1:1 to N,N-dimethylformamide with a mass ratio of 8 to 10 times that of 1,3-propanedithiol, and mixed evenly to prepare a mixed reaction liquid; pre-treated graphene, potassium carbonate, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(0.4 to 0.6):(28 to 32), and the mixed reaction liquid with a mass of 13 to 15 times that of the pre-treated graphene is added dropwise at a uniform speed within 20 minutes at 0 to 2°C and 200 to 300 r / min stirring conditions, and the stirring reaction is continued for 1 to 1.2 hours after the addition is completed, and the mixture is filtered and dried at 60 to 70°C under vacuum conditions for 8 to 10 hours to obtain the pre-modified graphene.

9. The method for preparing a modified graphene antistatic fiber according to claim 8, characterized in that: The preparation method of the pretreated graphene is as follows: 3-mercaptopropyltriethoxysilane and anhydrous ethanol are mixed evenly at a mass ratio of 1:(8-10), stirred at 10-30°C and 200-300r / min for 15-25min to prepare a silane coupling agent solution; graphene oxide and deionized water are mixed evenly at a mass ratio of 1:(50-60), ultrasonically dispersed for 1-2h, 20-22 times the mass of the graphene oxide silane coupling agent solution is added, the pH value is adjusted to 4.8-5.2 with a hydrochloric acid aqueous solution with a concentration of 1 mol / L, reacted at 50-60°C and 200-300r / min for 2-2.2h, filtered, and dried at 60-70°C for 8-10h under vacuum conditions to obtain the pretreated graphene.

10. The method for preparing a modified graphene antistatic fiber according to claim 2, characterized in that: The preparation method of the spinning solution in step (4) is as follows: weigh 98 to 102 parts of modified polyester, 9 to 11 parts of modified phase change microcapsules, 2 to 3 parts of modified graphene, 1 to 2 parts of chloroplatinic acid, and 600 to 700 parts of N,N-dimethylformamide, by mass; uniformly mix the modified polyester, modified phase change microcapsules, modified graphene, chloroplatinic acid, and N,N-dimethylformamide, and stir at 20 to 30° C. and 200 to 300 r / min for 2 to 3 hours to prepare a spinning solution.

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