CN116497474B - Antistatic fabric and preparation method thereof - Google Patents

Antistatic fabric and preparation method thereof Download PDF

Info

Publication number
CN116497474B
CN116497474B CN202310546358.3A CN202310546358A CN116497474B CN 116497474 B CN116497474 B CN 116497474B CN 202310546358 A CN202310546358 A CN 202310546358A CN 116497474 B CN116497474 B CN 116497474B
Authority
CN
China
Prior art keywords
aqueous solution
temperature
uniformly mixing
pyrrole
absorbing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310546358.3A
Other languages
Chinese (zh)
Other versions
CN116497474A (en
Inventor
袁正强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Yuancheng Clothing Co ltd
Original Assignee
Ningbo Yuancheng Clothing Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Yuancheng Clothing Co ltd filed Critical Ningbo Yuancheng Clothing Co ltd
Priority to CN202310546358.3A priority Critical patent/CN116497474B/en
Publication of CN116497474A publication Critical patent/CN116497474A/en
Application granted granted Critical
Publication of CN116497474B publication Critical patent/CN116497474B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/13—Unsaturated aldehydes, e.g. acrolein; Unsaturated ketones; Ketenes ; Diketenes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses an antistatic fabric and a preparation method thereof, and relates to the technical field of textile materials. When the antistatic fabric is prepared, pyrrole and 1-H-pyrrole-3-vinyl allyl formate are polymerized and deposited on the surface of a phase-change microcapsule to prepare the modified phase-change microcapsule; the modified light-absorbing and heating powder is prepared by reacting light-absorbing and heating powder, 3-aminopropyl triethoxysilane and allyl triethoxysilane; silk fibroin liquid, modified light-absorbing heating powder and polyethylene glycol are used as shell fluid, modified phase-change microcapsule, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate are used as core fluid, spinning is carried out, and the spinning fiber is prepared after the spinning fiber is treated by a calcium chloride aqueous solution and an ammonium persulfate aqueous solution in sequence, and then the spinning fiber is woven into the antistatic fabric after the spinning fiber reacts with 4-vinylbenzaldehyde and single-end hydrogen polysiloxane in sequence. The antistatic fabric prepared by the invention has excellent warm-keeping effect and antistatic performance.

Description

Antistatic fabric and preparation method thereof
Technical Field
The invention relates to the technical field of textile materials, in particular to an antistatic fabric and a preparation method thereof.
Background
The natural protein fiber has unique luster, good drapability, soft and smooth hand feeling and other excellent characteristics, and is often used as a high-end material. With the development of society and economic culture and the increasing of living standard, people are continuously improving environmental protection, health and safety consciousness, and how to effectively modify natural protein fibers, so that the natural protein fibers can be improved, the additional value of natural protein fiber products is improved, the industrial field of the natural protein fibers is expanded, and the natural protein fibers become the key point of recent and future researches of domestic and foreign students.
Along with the improvement of the living standard of people, the requirements of people on sleep quality are higher and higher. The quality of sleep is closely related to the quality of bed products, and researches show that: one third of the life of the person is in a sleep state, and the person can fully rest in sleep, so that the health degree of the person is determined to a great extent. The natural protein fiber has special skin-friendly property and comfort and is favored by consumers, but the antistatic and thermal insulation properties are not good enough, and the fiber needs to be drawn by full hands and has low efficiency. Based on the factors of the aspects, the natural protein fiber needs to be treated and the process is improved, so that the natural protein-based fabric with good antistatic and thermal properties is developed.
Disclosure of Invention
The invention aims to provide an antistatic fabric and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the antistatic fabric is prepared by taking silk fibroin liquid, modified light-absorbing heating powder and polyethylene glycol as shell fluid, taking modified phase-change microcapsules, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate as core fluid, extruding and spinning through a coaxial nozzle, sequentially treating with a calcium chloride aqueous solution and an ammonium persulfate aqueous solution to prepare spinning fibers, and sequentially reacting the spinning fibers with 4-vinylbenzaldehyde and single-end hydrogen polysiloxane to obtain the antistatic fabric.
As optimization, the modified light-absorbing and heating powder is prepared by reacting ferric nitrate, cupric nitrate and citric acid, calcining and grinding to prepare light-absorbing and heating powder, and reacting the light-absorbing and heating powder, 3-aminopropyl triethoxysilane and allyl triethoxysilane.
As optimization, the modified phase-change microcapsule is prepared by polymerizing and depositing pyrrole and 1-H-pyrrole-3-vinyl allyl formate on the surface of the phase-change microcapsule.
Preferably, the allyl 1-H-pyrrole-3-vinylformate is prepared by reacting methyl 1-H-pyrrole-3-vinylformate with allyl alcohol.
The preparation method of the antistatic fabric comprises the following preparation steps:
(1) Uniformly mixing 3-aminopropyl triethoxysilane, allyl triethoxysilane and absolute ethyl alcohol according to a mass ratio of 1:1:12-16 to prepare silane mixed solution; uniformly mixing the light-absorbing and heating powder and pure water according to the mass ratio of 1:10-12, performing ultrasonic dispersion for 15-20 min at the temperature of 20-30 ℃ and at the frequency of 25-35 kHz, keeping the ultrasonic condition unchanged, dropwise adding a silane mixed solution with the mass of 6-8 times that of the light-absorbing and heating powder at a constant speed within 20-30 min, continuing ultrasonic reaction for 3-5 h after the dropwise adding is finished, performing centrifugal separation, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at the temperature of 30-40 ℃ and at the pressure of 10-20 Pa to obtain modified light-absorbing and heating powder;
(2) Uniformly mixing pyrrole, 1-H-pyrrole-3-vinyl allyl formate and absolute ethyl alcohol according to the mass ratio of 1:0.3-0.4:12-14 to prepare pyrrole mixed solution; uniformly mixing the phase-change microcapsule and pure water according to the mass ratio of 1:14-16, adding pyrrole mixed solution with the mass of 0.3-0.4 times of the phase-change microcapsule at a constant speed within 10-15 min under the stirring state of 300-500 r/min at the temperature of 0-4 ℃, continuing stirring for 30-40 min after the addition, adding ferric trichloride aqueous solution with the mass fraction of 1-1.2% which is 14-16 times of the mass of the phase-change microcapsule at the rate of 1-1.2 mL/min, continuing stirring for reacting for 10-12 h after the addition is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at the temperature of 30-40 ℃ and 1-2 kPa to obtain the modified phase-change microcapsule;
(3) Uniformly mixing silk fibroin liquid and modified light-absorbing heating powder according to a mass ratio of 18-20:1, concentrating under the conditions of 20-30 ℃ and 10-20 Pa until the solute mass fraction is 50-55%, adding polyethylene glycol with the mass of 0.01-0.02 times that of the silk fibroin liquid, and performing ultrasonic dispersion for 15-20 min at the temperature of 30-40 ℃ and the frequency of 25-35 kHz to obtain shell fluid; uniformly mixing the modified phase-change microcapsule, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate according to the mass ratio of 1:0.1-0.2:0.1-0.2:1.4-1.6:0.02-0.03, and performing ultrasonic dispersion for 15-20 min at the temperature of 30-40 ℃ and the frequency of 25-35 kHz to prepare a nucleating fluid; extruding and spinning the shell fluid and the core fluid through a coaxial nozzle, wherein the inner diameter of the outer ring of the nozzle is 0.7mm, the inner diameter of the inner ring of the nozzle is 0.3mm, the extruding speed is 2.8-3.2 mu L/min, the receiving distance is 10-12 cm, the spinning temperature is 23-27 ℃, the relative humidity is 40-50%, immersing in 0.6-0.8 mol/L calcium chloride aqueous solution at 20-30 ℃ for 15-20 s, taking out and immersing in 5-7% sodium persulfate aqueous solution at 20-30 ℃ for 15-20 s, taking out and standing for 30-40 min at 85-95 ℃, repeatedly taking out and standing for 3-5 times after immersing in the sodium persulfate aqueous solution, washing for 3-5 times respectively with pure water and absolute ethyl alcohol, and drying for 6-8 h at 70-80 ℃ to obtain the spinning fiber;
(4) Uniformly mixing single-end hydrogen polysiloxane, normal hexane and chloroplatinic acid according to the mass ratio of 1:10-12:0.03-0.05 to prepare surface treatment liquid; uniformly mixing spinning fiber, 4-vinylbenzaldehyde, acetic acid and N, N-dimethylformamide according to the mass ratio of 1:1:0.1-0.2:20-25, carrying out ultrasonic reaction for 3-5 h at the temperature of 75-85 ℃ and the pressure of 25-35 kHz, naturally cooling to room temperature, centrifugally separating, washing 3-5 times by using absolute ethyl alcohol, drying for 6-8 h at the temperature of 30-40 ℃ and the pressure of 50-100 Pa, immersing in surface treatment liquid with the mass of 12-14 times of the spinning fiber, carrying out ultrasonic reaction for 4-6 h at the temperature of 70-80 ℃ and the pressure of 25-35 kHz, centrifugally separating, washing 3-5 times by using diethyl ether, and drying for 3-4 h at the temperature of 20-30 ℃ and the pressure of 10-100 Pa to obtain the spinning fiber after surface treatment; twisting the surface treated spinning fiber to 100-120D with a fiber braiding machine, and braiding to 250-300 g/m 2 And (5) obtaining the antistatic fabric by using the gram weight fabric.
As optimization, the preparation method of the light-absorbing and heat-generating powder in the step (1) comprises the following steps: uniformly mixing 0.2mol/L aqueous solution of ferric nitrate and 0.1mol/L aqueous solution of copper nitrate according to a volume ratio of 1:1, adding 0.1mol/L aqueous solution of citric acid with a volume of 2.7-3.1 times of that of the aqueous solution of the ferric nitrate at a constant speed within 20-25 min under the stirring condition of 20-30 ℃ and 300-500 r/min, continuously stirring for 6-8 min after the addition is finished, regulating the pH value to 7.4-7.6 by using ammonia water with a mass fraction of 20-25%, standing for 20-24 h, filtering and washing 3-5 times by pure water, drying for 6-8 h at a temperature of 10-20 Pa, preparing a precursor, calcining the precursor at a temperature of 600-700 ℃ for 6-8 h, grinding and sieving with a sieve of 1000-1200 meshes to prepare the precursor.
As optimization, the preparation method of the allyl 1-H-pyrrole-3-vinyl formate in the step (2) comprises the following steps: uniformly mixing 1-H-pyrrole-3-methyl vinylformate, allyl alcohol and p-toluenesulfonic acid according to the mass ratio of 1:1:0.01-0.02, stirring at 90-95 ℃ for reaction for 4-6H at 300-500 r/min, heating to 150-160 ℃ for continuous stirring for 1-2H, keeping the temperature unchanged and standing for 3-4H.
As optimization, the manufacturer of the phase-change microcapsule in the step (2) is Hangzhou Yingxing New material Co., ltd, the shell is melamine resin, the core is paraffin, and the particle size is less than or equal to 10 mu m.
As optimization, the preparation method of the silk fibroin liquid in the step (3) comprises the following steps: stripping cocoons into a single layer, placing the single layer in sodium carbonate aqueous solution with the mass fraction of 0.5-0.7%, boiling for 25-30 min, cooling to room temperature, washing with pure water for 3-5 times, and naturally air-drying to obtain degummed silk; uniformly mixing degummed silk and 9-10 mol/L lithium bromide aqueous solution according to the mass ratio of 1:8-10, stirring for 25-30 min at 35-45 ℃ at 600-800 r/min, centrifugally separating to obtain supernatant, diluting with 1.5-1.7 times of pure water of the supernatant, placing into a cellulose dialysis bag with the molecular weight cut-off of 6000-8000, continuously dialyzing with pure water for 70-80 h, and concentrating under the conditions of 20-30 ℃ and 10-20 Pa until the solute mass fraction is 18-22%; the silkworm cocoons are double-uterine cocoons, and the production place is Jiangsu Suzhou.
As an optimization, the preparation method of the single-end hydrogen polysiloxane in the step (4) comprises the following steps: uniformly mixing pentamethyldisiloxane and decamethyl cyclopentasiloxane according to the mass ratio of 1:4-6, dropwise adding a trifluoromethanesulfonic acid aqueous solution with the mass fraction of 8-10% which is 3-4 times that of the pentamethyldisiloxane at a constant speed within 15-20 min under the stirring condition of 300-500 r/min at the temperature of 70-80 ℃, continuing stirring for reacting for 60-80 min after the dropwise adding, adding pure water for washing, standing for layering, separating liquid, taking an oil phase, repeatedly washing and separating liquid for 3-5 times, and drying for 6-8 h at the temperature of 100-120 ℃ and the pressure of 10-50 Pa.
Compared with the prior art, the invention has the following beneficial effects:
when the antistatic fabric is prepared, silk fibroin liquid, modified light-absorbing and heating powder and polyethylene glycol are taken as shell fluid, modified phase-change microcapsules, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate are taken as core fluid, extrusion spinning is carried out through a coaxial spray head, then calcium chloride aqueous solution and ammonium persulfate aqueous solution are sequentially carried out, spinning fiber is prepared after the aqueous solution treatment of the calcium chloride aqueous solution, and the spinning fiber is sequentially reacted with 4-vinylbenzaldehyde and single-end hydrogen polysiloxane to prepare the antistatic fabric.
Firstly, methyl 1-H-pyrrole-3-vinyl formate and allyl alcohol react to prepare allyl 1-H-pyrrole-3-vinyl formate, pyrrole and allyl 1-H-pyrrole-3-vinyl formate are polymerized and deposited on the surface of a phase-change microcapsule to prepare a modified phase-change microcapsule, the phase-change microcapsule is modified, pyrrole is polymerized and deposited on the surface of the phase-change microcapsule to form a polypyrrole surface layer, the conjugated structure of the polypyrrole surface layer has good photo-thermal conversion effect and good heat conduction effect, so that the modified phase-change microcapsule has good photo-thermal energy storage efficiency, the conjugated structure of the polypyrrole surface layer has good conductive effect, a conductive path is formed inside an antistatic fabric, thus the antistatic performance is improved, and the modified phase-change microcapsule has carbon-carbon double bonds and can participate in polymerization of free radical unsaturated bonds initiated by a thermal initiator to form a crosslinked network, thus the fracture resistance is improved.
And secondly, reacting ferric nitrate, copper nitrate and citric acid, calcining and grinding to prepare light-absorbing heating powder, reacting the light-absorbing heating powder, 3-aminopropyl triethoxysilane and allyl triethoxysilane to prepare modified light-absorbing heating powder, modifying the light-absorbing heating powder to ensure that the modified light-absorbing heating powder is not easy to agglomerate, improving the dispersibility of the modified light-absorbing heating powder, simultaneously enabling amino generated on the surface of the modified light-absorbing heating powder to be combined with carboxyl on fibroin electrostatically, enabling carbon-carbon double bonds generated on the surface to participate in polymerization of free radical unsaturated bonds initiated by a thermal initiator, and crosslinking carbon-carbon double bonds on the modified phase-change microcapsule to form a crosslinking network, thereby improving the fracture resistance.
Finally, the spinning fiber sequentially reacts with 4-vinyl benzaldehyde and single-end hydrogen polysiloxane to form a polysiloxane long chain on the surface, the polysiloxane long chain has good flexibility, the surface friction force is reduced, the surface is not easy to rub and electrify, and the antistatic performance is improved; the modified light-absorbing heating powder in the shell layer of the thermal-insulation antistatic silk fiber prepared by the method can absorb and convert infrared radiation of a human body into heat energy, and is conducted to the inside modified phase-change microcapsule for storage, so that the thermal-insulation antistatic silk fiber has a good thermal-insulation effect.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Uniformly mixing 3-aminopropyl triethoxysilane, allyl triethoxysilane and absolute ethyl alcohol according to a mass ratio of 1:1:12 to prepare silane mixed solution; uniformly mixing 0.2mol/L aqueous solution of ferric nitrate and 0.1mol/L aqueous solution of cupric nitrate according to a volume ratio of 1:1, adding 0.1mol/L aqueous solution of citric acid with a volume of 2.7 times of that of the aqueous solution of ferric nitrate at a uniform speed in 20min under the stirring condition of 300r/min at 20 ℃, continuously stirring for 6min after the addition is finished, regulating the pH value to 7.4 by using 20% ammonia water by mass fraction, standing for 24h, filtering and washing for 3 times by using pure water, drying for 8h at 30 ℃ under 10Pa to obtain a precursor, calcining the precursor at 600 ℃ for 8h, and sieving with a 1000-mesh sieve after grinding to obtain light-absorbing and heating powder; uniformly mixing the light-absorbing and heating powder and pure water according to the mass ratio of 1:10, performing ultrasonic dispersion for 20min at 20 ℃ and 25kHz, keeping the ultrasonic condition unchanged, uniformly dripping a silane mixed solution with the mass 6 times of the light-absorbing and heating powder in 20min, continuing ultrasonic reaction for 5h after dripping, performing centrifugal separation, washing 3 times by using pure water and absolute ethyl alcohol respectively, and drying for 8h at 30 ℃ and 10Pa to obtain modified light-absorbing and heating powder;
(2) Uniformly mixing 1-H-pyrrole-3-vinylmethyl formate, allyl alcohol and p-toluenesulfonic acid according to the mass ratio of 1:1:0.01, stirring at 90 ℃ for reaction for 6 hours at 300r/min, heating to 150 ℃ and continuously stirring for 2 hours, keeping the temperature unchanged and standing for 3 hours to prepare 1-H-pyrrole-3-vinylmethyl formate; uniformly mixing pyrrole, 1-H-pyrrole-3-vinyl allyl formate and absolute ethyl alcohol according to a mass ratio of 1:0.3:12 to prepare pyrrole mixed solution; uniformly mixing the phase-change microcapsule and pure water according to the mass ratio of 1:14, adding pyrrole mixed liquid with the mass of 0.3 times of the phase-change microcapsule at a constant speed within 15min under the stirring state of 300r/min at the temperature of 0 ℃, continuously stirring for 30min after the addition is finished, adding ferric trichloride aqueous solution with the mass fraction of 1% with the mass of 14 times of the phase-change microcapsule at the rate of 1mL/min, continuously stirring for reacting for 12h after the addition is finished, centrifugally separating, washing 3 times by pure water and absolute ethyl alcohol respectively, and drying for 8h at the temperature of 30 ℃ under the pressure of 1kPa to obtain the modified phase-change microcapsule;
(3) Stripping cocoons into a single layer, placing the single layer in a sodium carbonate aqueous solution with the mass fraction of 0.5%, boiling for 25min, cooling to room temperature, washing with pure water for 3 times, and naturally air-drying to obtain degummed silk; uniformly mixing degummed silk and 9mol/L lithium bromide aqueous solution according to a mass ratio of 1:8, stirring for 30min at 35 ℃ and 600r/min, centrifugally separating to obtain supernatant, diluting with pure water 1.5 times of the supernatant, placing into a cellulose dialysis bag with a molecular weight cut-off of 6000, continuously dialyzing with pure water for 80h, and concentrating under the condition of 20 ℃ and 10Pa until the solute mass fraction is 18%, thus obtaining silk fibroin solution; uniformly mixing silk fibroin liquid and modified light-absorbing and heating powder according to a mass ratio of 18:1, concentrating at 20 ℃ and 10Pa until the solute mass fraction is 55%, adding polyethylene glycol with the mass of 0.01 times that of the silk fibroin liquid, and performing ultrasonic dispersion at 30 ℃ and 25kHz for 20min to obtain shell fluid; uniformly mixing the modified phase-change microcapsule, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate according to the mass ratio of 1:0.1:0.1:1.4:0.02, and performing ultrasonic dispersion for 20min at 30 ℃ and 35kHz to prepare a nucleation fluid; extruding and spinning the shell fluid and the core fluid through a coaxial nozzle, wherein the inner diameter of the outer ring of the nozzle is 0.7mm, the inner diameter of the inner ring of the nozzle is 0.3mm, the extruding speed is 2.8 mu L/min, the receiving distance is 10cm, the spinning temperature is 23 ℃, the relative humidity is 40%, the shell fluid and the core fluid are immersed in a calcium chloride aqueous solution of 20 ℃ and 0.6mol/L for 20s, taken out and immersed in a sodium persulfate aqueous solution of 20 ℃ and 5% in mass fraction for 20s, taken out and kept stand for 40min at 85 ℃, the soaking in the sodium persulfate aqueous solution is repeated, the standing process is taken out for 3 times, the water and the absolute ethyl alcohol are respectively used for washing 3 times, and the water and the absolute ethyl alcohol are dried for 8h at 70 ℃ to obtain the spinning fiber;
(4) Uniformly mixing pentamethyldisiloxane and decamethyl cyclopentasiloxane according to a mass ratio of 1:4, dropwise adding an aqueous solution of trifluoromethanesulfonic acid with a mass fraction of 8% which is 3 times that of the pentamethyldisiloxane at a constant speed within 15min under a stirring condition of 70 ℃ and 300r/min, continuously stirring for reaction for 80min after the dropwise adding is finished, adding pure water for washing, standing for layering, separating liquid, taking an oil phase, repeatedly washing and separating liquid for 3 times, and standing at 100 DEG CDrying for 8 hours under 10Pa to obtain single-end hydrogen polysiloxane; uniformly mixing single-end hydrogen polysiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:10:0.03 to prepare a surface treatment liquid; uniformly mixing spinning fiber, 4-vinylbenzaldehyde, acetic acid and N, N-dimethylformamide according to the mass ratio of 1:1:0.1:20, performing ultrasonic reaction at 75 ℃ for 5 hours at 25kHz, naturally cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol for 3 times, drying at 30 ℃ for 8 hours at 50Pa, immersing in a surface treatment liquid with the mass ratio of 12 times of the spinning fiber, performing ultrasonic reaction at 70 ℃ for 6 hours at 25kHz, performing centrifugal separation, washing with diethyl ether for 3 times, and drying at 20 ℃ for 4 hours at 10Pa to obtain the spinning fiber after surface treatment; twisting the surface treated spinning fiber to 110D with a fiber braiding machine, and braiding to 270g/m 2 And (5) obtaining the antistatic fabric by using the gram weight fabric.
Example 2
(1) Uniformly mixing 3-aminopropyl triethoxysilane, allyl triethoxysilane and absolute ethyl alcohol according to a mass ratio of 1:1:14 to prepare silane mixed solution; uniformly mixing 0.2mol/L aqueous solution of ferric nitrate and 0.1mol/L aqueous solution of cupric nitrate according to a volume ratio of 1:1, adding 0.1mol/L aqueous solution of citric acid with a volume of 2.9 times of that of the aqueous solution of ferric nitrate at a uniform speed in 22min under the stirring condition of 400r/min at 25 ℃, continuously stirring for 7min after the addition is finished, regulating the pH value to 7.5 by using 22% ammonia water by mass fraction, standing for 22h, filtering and washing for 4 times by using pure water, drying for 7h at 35 ℃ under 15Pa to obtain a precursor, calcining the precursor at 650 ℃ for 7h, and sieving the precursor with a 1100-mesh sieve after grinding to obtain light-absorbing and heating powder; uniformly mixing the light-absorbing and heating powder and pure water according to the mass ratio of 1:11, performing ultrasonic dispersion for 18min at 25 ℃ and 30kHz, keeping the ultrasonic condition unchanged, uniformly dripping a silane mixed solution with the mass 7 times of the light-absorbing and heating powder in 25min, continuing ultrasonic reaction for 4h after dripping, performing centrifugal separation, washing for 4 times by using pure water and absolute ethyl alcohol respectively, and drying for 7h at 35 ℃ and 15Pa to obtain modified light-absorbing and heating powder;
(2) Uniformly mixing 1-H-pyrrole-3-vinylmethyl formate, allyl alcohol and p-toluenesulfonic acid according to the mass ratio of 1:1:0.015, stirring at 92 ℃ and 400r/min for reaction for 5H, heating to 155 ℃ and continuously stirring for 1.5H, keeping the temperature unchanged and standing for 3.5H to obtain 1-H-pyrrole-3-vinylallyl formate; uniformly mixing pyrrole, 1-H-pyrrole-3-vinyl allyl formate and absolute ethyl alcohol according to a mass ratio of 1:0.35:13 to prepare pyrrole mixed solution; uniformly mixing the phase-change microcapsule and pure water according to the mass ratio of 1:15, adding pyrrole mixed solution with the mass of 0.35 times of the phase-change microcapsule at a constant speed within 12min under the stirring state of 400r/min at the temperature of 2 ℃, continuously stirring for 35min after the addition is finished, adding ferric trichloride aqueous solution with the mass fraction of 1.1% and the mass of 15 times of the phase-change microcapsule at the speed of 1.1mL/min, continuously stirring for reacting for 11h after the addition is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying for 7h at the temperature of 35 ℃ and 1.5kPa to obtain the modified phase-change microcapsule;
(3) Stripping cocoons into a single layer, placing the single layer in a sodium carbonate aqueous solution with the mass fraction of 0.6%, boiling for 27min, cooling to room temperature, washing with pure water for 4 times, and naturally air-drying to obtain degummed silk; uniformly mixing degummed silk and 9.5mol/L lithium bromide aqueous solution according to a mass ratio of 1:9, stirring for 28min at 40 ℃ at 700r/min, centrifugally separating to obtain supernatant, diluting with 1.6 times of pure water of the supernatant, placing into a cellulose dialysis bag with a molecular weight cutoff of 7000, continuously dialyzing with pure water for 75h, and concentrating under 15Pa at 25 ℃ until the solute mass fraction is 20%, thus obtaining silk fibroin solution; uniformly mixing silk fibroin liquid and modified light-absorbing and heating powder according to a mass ratio of 19:1, concentrating at 25 ℃ and 15Pa until the solute mass fraction is 52%, adding polyethylene glycol with the mass of 0.015 times of that of the silk fibroin liquid, and performing ultrasonic dispersion at 35 ℃ and 30kHz for 18min to obtain shell fluid; uniformly mixing the modified phase-change microcapsule, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate according to the mass ratio of 1:0.15:0.15:1.5:0.025, and performing ultrasonic dispersion for 18min at 35 ℃ and 30kHz to prepare a nucleating fluid; extruding and spinning the shell fluid and the core fluid through a coaxial nozzle, wherein the inner diameter of the outer ring of the nozzle is 0.7mm, the inner diameter of the inner ring of the nozzle is 0.3mm, the extruding speed is 3 mu L/min, the receiving distance is 11cm, the spinning temperature is 25 ℃, the relative humidity is 45%, the shell fluid and the core fluid are immersed in a calcium chloride aqueous solution of 25 ℃ for 18 seconds, taken out and immersed in a sodium persulfate aqueous solution of 6% in mass fraction for 17 seconds, taken out and kept stand at 90 ℃ for 35 minutes, the soaking in the sodium persulfate aqueous solution is repeated, the taking out and standing process is repeated for 4 times, pure water and absolute ethyl alcohol are used for washing for 4 times respectively, and the drying is carried out at 75 ℃ for 7 hours, so that the spinning fiber is prepared;
(4) Uniformly mixing pentamethyldisiloxane and decamethyl cyclopentasiloxane according to a mass ratio of 1:5, dropwise adding a trifluoromethanesulfonic acid aqueous solution with a mass fraction of 9% which is 3.5 times that of the pentamethyldisiloxane at a uniform speed within 18min under a stirring condition of 400r/min, continuously stirring and reacting for 70min after the dropwise adding, adding pure water for washing, standing and layering, separating liquid to obtain an oil phase, repeatedly washing and separating liquid for 4 times, and drying for 7h at 110 ℃ under 30Pa to obtain single-end hydrogen polysiloxane; uniformly mixing single-end hydrogen polysiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:11:0.04 to prepare a surface treatment liquid; uniformly mixing spinning fiber, 4-vinylbenzaldehyde, acetic acid and N, N-dimethylformamide according to the mass ratio of 1:1:0.15:22, performing ultrasonic reaction for 4 hours at 80 ℃ and 30kHz, naturally cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol for 4 times, drying for 7 hours at 35 ℃ and 70Pa, immersing in surface treatment liquid with the mass ratio of 13 times of the spinning fiber, performing ultrasonic reaction for 5 hours at 75 ℃ and 30kHz, performing centrifugal separation, washing with diethyl ether for 4 times, and drying for 3.5 hours at 25 ℃ and 50Pa to obtain the spinning fiber after surface treatment; twisting the surface treated spinning fiber to 110D with a fiber braiding machine, and braiding to 270g/m 2 And (5) obtaining the antistatic fabric by using the gram weight fabric.
Example 3
(1) Uniformly mixing 3-aminopropyl triethoxysilane, allyl triethoxysilane and absolute ethyl alcohol according to a mass ratio of 1:1:16 to prepare silane mixed solution; uniformly mixing 0.2mol/L aqueous solution of ferric nitrate and 0.1mol/L aqueous solution of cupric nitrate according to a volume ratio of 1:1, adding 3.1 times of aqueous solution of citric acid with a volume of 0.1mol/L at a constant speed in 25min under the stirring condition of 30 ℃ and 500r/min, continuously stirring for 8min after the addition, regulating the pH value to 7.6 by using 25% ammonia water with a mass fraction of 25%, standing for 20h, filtering and washing for 5 times by using pure water, drying for 6h at 40 ℃ and 20Pa to obtain a precursor, calcining the precursor at 700 ℃ for 6h, and grinding and then sieving by a 1200-mesh sieve to obtain light-absorbing and heating powder; uniformly mixing the light-absorbing and heating powder and pure water according to the mass ratio of 1:12, performing ultrasonic dispersion for 15min at 30 ℃ at 35kHz, keeping the ultrasonic condition unchanged, uniformly dripping silane mixed solution with the mass 8 times of the light-absorbing and heating powder in 30min, continuing ultrasonic reaction for 3h after dripping, performing centrifugal separation, washing with pure water and absolute ethyl alcohol for 5 times respectively, and drying for 6h at 40 ℃ at 20Pa to obtain modified light-absorbing and heating powder;
(2) Uniformly mixing 1-H-pyrrole-3-vinylmethyl formate, allyl alcohol and p-toluenesulfonic acid according to the mass ratio of 1:1:0.02, stirring at 95 ℃ and 500r/min for reaction for 4 hours, heating to 160 ℃ and continuously stirring for 1 hour, keeping the temperature unchanged and standing for 4 hours to prepare 1-H-pyrrole-3-vinylmethyl formate; uniformly mixing pyrrole, 1-H-pyrrole-3-vinyl allyl formate and absolute ethyl alcohol according to a mass ratio of 1:0.4:14 to prepare pyrrole mixed solution; uniformly mixing the phase-change microcapsule and pure water according to the mass ratio of 1:16, adding pyrrole mixed solution with the mass of 0.4 times of the phase-change microcapsule at a constant speed within 15min under the stirring state of 500r/min at the temperature of 4 ℃, continuously stirring for 30min after the addition is finished, adding ferric trichloride aqueous solution with the mass fraction of 1.2% with the mass of 16 times of the phase-change microcapsule at the speed of 1.2mL/min, continuously stirring for reacting for 10h after the addition is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 5 times respectively, and drying for 6h at the temperature of 40 ℃ under the pressure of 2kPa to obtain the modified phase-change microcapsule;
(3) Stripping cocoons into a single layer, placing the single layer in a sodium carbonate aqueous solution with the mass fraction of 0.7%, boiling for 25min, cooling to room temperature, washing with pure water for 5 times, and naturally air-drying to obtain degummed silk; uniformly mixing degummed silk and 10mol/L lithium bromide aqueous solution according to a mass ratio of 1:10, stirring for 25min at 45 ℃ and 800r/min, centrifugally separating to obtain supernatant, diluting with 1.7 times of pure water of the supernatant, placing into a cellulose dialysis bag with a molecular weight cutoff of 8000, continuously dialyzing with pure water for 80h, and concentrating under the condition of 30 ℃ and 20Pa until the solute mass fraction is 18%, thus obtaining silk fibroin solution; uniformly mixing silk fibroin liquid and modified light-absorbing and heating powder according to a mass ratio of 20:1, concentrating at 30 ℃ and 20Pa until the solute mass fraction is 55%, adding polyethylene glycol with the mass of 0.02 times that of the silk fibroin liquid, and performing ultrasonic dispersion at 40 ℃ and 35kHz for 15min to obtain shell fluid; uniformly mixing the modified phase-change microcapsule, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate according to the mass ratio of 1:0.2:0.2:1.6:0.03, and performing ultrasonic dispersion for 15min at 40 ℃ and 35kHz to prepare a nucleation fluid; extruding and spinning the shell fluid and the core fluid through a coaxial nozzle, wherein the inner diameter of the outer ring of the nozzle is 0.7mm, the inner diameter of the inner ring of the nozzle is 0.3mm, the extruding speed is 3.2 mu L/min, the receiving distance is 12cm, the spinning temperature is 27 ℃, the relative humidity is 50%, the shell fluid and the core fluid are immersed in 30 ℃ and 0.8mol/L calcium chloride aqueous solution for 15s, taken out and immersed in 30 ℃ and 7% sodium persulfate aqueous solution for 15s, taken out and kept stand at 95 ℃ for 40min, the standing process is taken out for 5 times after repeated immersing in the sodium persulfate aqueous solution, the pure water and absolute ethyl alcohol are used for 5 times respectively, and the spinning fiber is prepared after drying at 80 ℃ for 6 h;
(4) Uniformly mixing pentamethyldisiloxane and decamethyl cyclopentasiloxane according to a mass ratio of 1:6, dropwise adding a 10% aqueous solution of trifluoromethanesulfonic acid with a mass fraction of 4 times that of the pentamethyldisiloxane at a uniform speed within 20min under the stirring condition of 500r/min at 80 ℃, continuing stirring and reacting for 60min after the dropwise adding, adding pure water for washing, standing and layering, separating liquid to obtain an oil phase, repeatedly washing and separating liquid for 5 times, and drying for 6h at 50Pa at 120 ℃ to obtain single-end hydrogen polysiloxane; uniformly mixing single-end hydrogen polysiloxane, n-hexane and chloroplatinic acid according to the mass ratio of 1:12:0.05 to prepare a surface treatment liquid; uniformly mixing spinning fiber, 4-vinylbenzaldehyde, acetic acid and N, N-dimethylformamide according to the mass ratio of 1:1:0.2:25, carrying out ultrasonic reaction for 3 hours at 85 ℃, naturally cooling to room temperature at 35kHz, carrying out centrifugal separation, washing with absolute ethyl alcohol for 5 times, drying for 6 hours at 40 ℃ under 100Pa, immersing in surface treatment liquid with the mass ratio of 14 times of the spinning fiber, carrying out ultrasonic reaction for 4 hours at 80 ℃ under 35kHz, carrying out centrifugal separation, washing with diethyl ether for 5 times, and drying for 3 hours at 30 ℃ under 100Pa to obtain the spinning fiber after surface treatment; twisting the surface treated spinning fiber to 110D with a fiber braiding machine, and braiding to 270g/m 2 And (5) obtaining the antistatic fabric by using the gram weight fabric.
Comparative example 1
The method for preparing the antistatic fabric of comparative example 1 is different from example 2 only in the step (1), and the step (1) is modified as follows: uniformly mixing 0.2mol/L aqueous solution of ferric nitrate and 0.1mol/L aqueous solution of copper nitrate according to a volume ratio of 1:1, adding 0.1mol/L aqueous solution of citric acid with a volume of 2.9 times of that of the aqueous solution of the ferric nitrate at a constant speed in 22min under the stirring condition of 400r/min at 25 ℃, continuously stirring for 7min after the addition is finished, regulating the pH value to 7.5 by using 22% ammonia water by mass fraction, standing for 22h, filtering and washing for 4 times by pure water, drying for 7h at 35 ℃ under 15Pa to obtain a precursor, calcining the precursor at 650 ℃ for 7h, and sieving by a 1100-mesh sieve after grinding to obtain the light-absorbing and heat-generating powder. And the modified light-absorbing and heating powder in the step (3) is changed to be light-absorbing and heating powder, and the rest steps are the same as in the example 2.
Comparative example 2
The method for preparing the antistatic fabric of comparative example 2 is different from example 2 only in that step (2) is not performed, and the modified phase-change microcapsule in step (3) is changed to be used as the phase-change microcapsule, and the rest steps are the same as example 2.
Comparative example 3
The method for preparing the antistatic fabric of comparative example 3 is different from example 2 only in the step (2), and the step (2) is modified as follows: uniformly mixing pyrrole and absolute ethyl alcohol according to a mass ratio of 1:13 to prepare pyrrole solution; uniformly mixing the phase-change microcapsule and pure water according to the mass ratio of 1:15, adding pyrrole solution with the mass of 0.35 times of the phase-change microcapsule at a constant speed within 12min under the stirring state of 400r/min at the temperature of 2 ℃, continuously stirring for 35min after the addition is finished, adding ferric trichloride aqueous solution with the mass fraction of 1.1% and the mass of 15 times of the phase-change microcapsule at the speed of 1.1mL/min, continuously stirring for reacting for 11h after the addition is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying for 7h at the temperature of 35 ℃ and 1.5kPa to obtain the modified phase-change microcapsule. The rest of the procedure is the same as in example 2.
Comparative example 4
The method for preparing the antistatic fabric of comparative example 4 is different from example 2 only in the step (4), and the step (1) is modified as follows: twisting the spinning fiber to 110D through a fiber braiding machine, and braiding the spinning fiber into a 270g/m < 2 > gram-weight fabric, thus obtaining the antistatic fabric. The rest of the procedure is the same as in example 2.
Experimental example 1
And (3) testing the photo-thermal energy storage efficiency:
the modified phase-change microcapsules obtained in each example and comparative example 3, and the unmodified phase-change microcapsules were weighed 0.50g each in a plastic surface dish with a diameter of 3.5cm, and were prepared by laying flat and then placing in a heat-insulating foam boxTesting at 27℃using 1kW/m 2 The sample was irradiated for the same time and the change in temperature with time was monitored using a thermal infrared imager.
The calculation formula of the photo-thermal energy storage efficiency (eta) of the sample is as follows:
η＝m*ΔH/[P*A*(t s -t 0 )]
wherein m is the mass of the sample; Δh is the phase change value of the sample when melted; p is the intensity of illumination (kW/m) of the lamp 2 ) The method comprises the steps of carrying out a first treatment on the surface of the A is the effective area of the light irradiation sample; t is t 0 The phase change time of the sample under the illumination condition is the phase change time; t is t s The time at which the sample ends the phase change under light conditions. The results are shown in Table 1.
TABLE 1
Photo-thermal energy storage efficiency Photo-thermal energy storage efficiency
Example 1 86.2％ Comparative example 3 88.1％
Example 2 86.9％ Blank control 23.5％
Implementation of the embodimentsExample 3 86.0％
As can be seen from the data in table 1, the phase-change microcapsule is modified, pyrrole is deposited and polymerized on the surface of the phase-change microcapsule to form a polypyrrole surface layer, and the conjugated structure of the polypyrrole surface layer has good photo-thermal conversion effect and good heat conduction effect, so that the modified phase-change microcapsule has good photo-thermal energy storage efficiency.
Experimental example 2
Test of fracture resistance:
the antistatic fabric obtained in each example and comparative example was drawn to 1m length of sample wire, its mass was weighed on an electronic balance, the line density was calculated, and 50mm of sample wire was taken and clamped in upper and lower clamps of a brute force meter. And (5) stretching according to the set linear density and the set stretching speed until the sample wire breaks. The breaking strength is automatically printed out by the electronic single yarn strength tester. The results are shown in Table 2.
TABLE 2
Breaking strength Breaking strength
Example 1 4.18CN/dtex Comparative example 1 2.98CN/dtex
Example 2 4.23CN/dtex Comparative example 2 3.32CN/dtex
Example 3 4.21CN/dtex Comparative example 3 3.27CN/dtex
Comparative example 4 4.19CN/dtex
As can be seen from the comparison of the experimental data of examples 1 to 3 and comparative examples 1 to 4 in Table 2, the antistatic fabric prepared by the invention has good fracture resistance.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 1, the examples 1, 2 and 3 have high breaking strength compared with comparative example 1, which shows that after the light-absorbing and heating powder is modified, the light-absorbing and heating powder is not easy to agglomerate, the dispersibility of the light-absorbing and heating powder is improved, meanwhile, amino groups generated on the surface of the modified light-absorbing and heating powder can be combined with carboxyl groups on fibroin electrostatically, carbon-carbon double bonds generated on the surface can participate in polymerization of free radical unsaturated bonds initiated by a thermal initiator, and carbon-carbon double bonds on the modified phase-change microcapsule are crosslinked with each other to form a crosslinked network, so that the breaking resistance is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative examples 2 and 3, it can be found that the breaking strength of examples 1, 2 and 3 is high compared with comparative examples 2 and 3, which shows that when the phase-change microcapsule is modified, the modified phase-change microcapsule has double bonds on the surface and participates in polymerization of free radical unsaturated bonds initiated by a thermal initiator to form a crosslinked network, so that the breaking resistance is improved.
Experimental example 3
Test of antistatic Properties:
the antistatic fabrics obtained in each example and the comparative example were subjected to real-time monitoring by using a fabric induction type static tester produced by Shandong textile science institute according to GB/T12703 standard, and half-life was recorded by a half-life method. The results are shown in Table 3.
TABLE 3 Table 3
Half-life period Half-life period
Example 1 1.64s Comparative example 1 1.71s
Example 2 1.67s Comparative example 2 6.15s
Example 3 1.70s Comparative example 3 1.64s
Comparative example 4 1.68s
As can be seen from the comparison of the experimental data of examples 1 to 3 and comparative examples 1 to 4 in Table 3, the antistatic fabric prepared by the invention has good antistatic performance.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 2, examples 1, 2 and 3 have short half lives compared with comparative example 2, which indicates that the phase-change microcapsule is modified, pyrrole is deposited and polymerized on the surface of the phase-change microcapsule to form a polypyrrole surface layer, the conjugated structure of the polypyrrole surface layer has good conductive effect, and a conductive path is formed inside the antistatic fabric, so that the antistatic performance is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (6)

1. The preparation method of the antistatic fabric is characterized in that the antistatic fabric is prepared by taking silk fibroin liquid, modified light-absorbing heating powder and polyethylene glycol as shell fluid, taking modified phase-change microcapsules, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate as core fluid, extruding and spinning through a coaxial nozzle, sequentially treating with calcium chloride aqueous solution and ammonium persulfate aqueous solution to prepare spinning fiber, and sequentially reacting the spinning fiber with 4-vinylbenzaldehyde and single-end hydrogen polysiloxane to obtain the antistatic fabric;
the modified light-absorbing and heating powder is prepared by reacting ferric nitrate, cupric nitrate and citric acid, calcining and grinding to prepare light-absorbing and heating powder, and reacting the light-absorbing and heating powder, 3-aminopropyl triethoxysilane and allyl triethoxysilane;
the modified phase-change microcapsule is prepared by polymerizing and depositing pyrrole and 1-H-pyrrole-3-vinyl allyl formate on the surface of the phase-change microcapsule;
the 1-H-pyrrole-3-vinyl carboxylic acid allyl ester is prepared by reacting 1-H-pyrrole-3-vinyl carboxylic acid methyl ester with allyl alcohol;
the preparation method comprises the following preparation steps:
(1) Uniformly mixing 3-aminopropyl triethoxysilane, allyl triethoxysilane and absolute ethyl alcohol according to a mass ratio of 1:1:12-16 to prepare silane mixed solution; uniformly mixing the light-absorbing and heating powder and pure water according to the mass ratio of 1:10-12, performing ultrasonic dispersion for 15-20 min at the temperature of 20-30 ℃ and at the frequency of 25-35 kHz, keeping the ultrasonic condition unchanged, dropwise adding a silane mixed solution with the mass of 6-8 times that of the light-absorbing and heating powder at a constant speed within 20-30 min, continuing ultrasonic reaction for 3-5 h after the dropwise adding is finished, performing centrifugal separation, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at the temperature of 30-40 ℃ and at the pressure of 10-20 Pa to obtain modified light-absorbing and heating powder;
(2) Uniformly mixing pyrrole, 1-H-pyrrole-3-vinyl allyl formate and absolute ethyl alcohol according to the mass ratio of 1:0.3-0.4:12-14 to prepare pyrrole mixed solution; uniformly mixing the phase-change microcapsule and pure water according to the mass ratio of 1:14-16, adding pyrrole mixed solution with the mass of 0.3-0.4 times of the phase-change microcapsule at a constant speed within 10-15 min under the stirring state of 300-500 r/min at the temperature of 0-4 ℃, continuing stirring for 30-40 min after the addition, adding ferric trichloride aqueous solution with the mass fraction of 1-1.2% which is 14-16 times of the mass of the phase-change microcapsule at the rate of 1-1.2 mL/min, continuing stirring for reacting for 10-12 h after the addition is finished, centrifugally separating, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at the temperature of 30-40 ℃ and 1-2 kPa to obtain the modified phase-change microcapsule;
(3) Uniformly mixing silk fibroin liquid and modified light-absorbing heating powder according to a mass ratio of 18-20:1, concentrating under the conditions of 20-30 ℃ and 10-20 Pa until the solute mass fraction is 50-55%, adding polyethylene glycol with the mass of 0.01-0.02 times that of the silk fibroin liquid, and performing ultrasonic dispersion for 15-20 min at the temperature of 30-40 ℃ and the frequency of 25-35 kHz to obtain shell fluid; uniformly mixing the modified phase-change microcapsule, 1, 3-butadiene, polyethylene glycol, absolute ethyl alcohol and ammonium persulfate according to the mass ratio of 1:0.1-0.2:0.1-0.2:1.4-1.6:0.02-0.03, and performing ultrasonic dispersion for 15-20 min at the temperature of 30-40 ℃ and the frequency of 25-35 kHz to prepare a nucleating fluid; extruding and spinning the shell fluid and the core fluid through a coaxial nozzle, wherein the inner diameter of the outer ring of the nozzle is 0.7mm, the inner diameter of the inner ring of the nozzle is 0.3mm, the extruding speed is 2.8-3.2 mu L/min, the receiving distance is 10-12 cm, the spinning temperature is 23-27 ℃, the relative humidity is 40-50%, immersing in a calcium chloride aqueous solution of 0.6-0.8 mol/L at 20-30 ℃ for 15-20 s, taking out and immersing in an ammonium persulfate aqueous solution of 5-7% in mass fraction at 20-30 ℃ for 15-20 s, taking out and standing for 30-40 min at 85-95 ℃, repeatedly immersing in the aqueous solution, taking out and standing for 3-5 times, washing 3-5 times respectively with pure water and absolute ethyl alcohol, and drying at 70-80 ℃ for 6-8 h to obtain spinning fibers;
(4) Uniformly mixing single-end hydrogen polysiloxane, normal hexane and chloroplatinic acid according to the mass ratio of 1:10-12:0.03-0.05 to prepare surface treatment liquid; uniformly mixing spinning fiber, 4-vinylbenzaldehyde, acetic acid and N, N-dimethylformamide according to the mass ratio of 1:1:0.1-0.2:20-25, carrying out ultrasonic reaction for 3-5 h at the temperature of 75-85 ℃ and the pressure of 25-35 kHz, naturally cooling to room temperature, centrifugally separating, washing 3-5 times by using absolute ethyl alcohol, drying for 6-8 h at the temperature of 30-40 ℃ and the pressure of 50-100 Pa, immersing in surface treatment liquid with the mass of 12-14 times of the spinning fiber, carrying out ultrasonic reaction for 4-6 h at the temperature of 70-80 ℃ and the pressure of 25-35 kHz, centrifugally separating, washing 3-5 times by using diethyl ether, and drying for 3-4 h at the temperature of 20-30 ℃ and the pressure of 10-100 Pa to obtain the spinning fiber after surface treatment; twisting the surface treated spinning fiber to 100-120D by a fiber braiding machineThen knitting into 250-300 g/m 2 And (5) obtaining the antistatic fabric by using the gram weight fabric.
2. The method for preparing the antistatic fabric according to claim 1, wherein the method for preparing the light-absorbing and heat-generating powder in the step (1) comprises the following steps: uniformly mixing 0.2mol/L aqueous solution of ferric nitrate and 0.1mol/L aqueous solution of copper nitrate according to a volume ratio of 1:1, adding 0.1mol/L aqueous solution of citric acid with a volume of 2.7-3.1 times of that of the aqueous solution of the ferric nitrate at a constant speed within 20-25 min under the stirring condition of 20-30 ℃ and 300-500 r/min, continuously stirring for 6-8 min after the addition is finished, regulating the pH value to 7.4-7.6 by using ammonia water with a mass fraction of 20-25%, standing for 20-24 h, filtering and washing 3-5 times by pure water, drying for 6-8 h at a temperature of 10-20 Pa, preparing a precursor, calcining the precursor at a temperature of 600-700 ℃ for 6-8 h, grinding and sieving with a sieve of 1000-1200 meshes to prepare the precursor.
3. The method for preparing the antistatic fabric according to claim 1, wherein the preparation method of the allyl 1-H-pyrrole-3-vinyl formate in the step (2) is as follows: uniformly mixing 1-H-pyrrole-3-methyl vinylformate, allyl alcohol and p-toluenesulfonic acid according to the mass ratio of 1:1:0.01-0.02, stirring at 90-95 ℃ for reaction for 4-6H at 300-500 r/min, heating to 150-160 ℃ for continuous stirring for 1-2H, keeping the temperature unchanged and standing for 3-4H.
4. The method for preparing the antistatic fabric according to claim 1, wherein the manufacturer of the phase-change microcapsule in the step (2) is Hangzhou New material Co., ltd., the shell is melamine resin, the core is paraffin, and the particle size is less than or equal to 10 μm.
5. The method for preparing the antistatic fabric according to claim 1, wherein the method for preparing the silk fibroin solution in the step (3) comprises the following steps: stripping cocoons into a single layer, placing the single layer in sodium carbonate aqueous solution with the mass fraction of 0.5-0.7%, boiling for 25-30 min, cooling to room temperature, washing with pure water for 3-5 times, and naturally air-drying to obtain degummed silk; uniformly mixing degummed silk and 9-10 mol/L lithium bromide aqueous solution according to the mass ratio of 1:8-10, stirring for 25-30 min at 35-45 ℃ at 600-800 r/min, centrifugally separating to obtain supernatant, diluting with 1.5-1.7 times of pure water of the supernatant, placing into a cellulose dialysis bag with the molecular weight cut-off of 6000-8000, continuously dialyzing with pure water for 70-80 h, and concentrating under the conditions of 20-30 ℃ and 10-20 Pa until the solute mass fraction is 18-22%; the silkworm cocoons are double-uterine cocoons, and the production place is Jiangsu Suzhou.
6. The method for preparing an antistatic fabric according to claim 1, wherein the preparation method of the single-end hydrogen polysiloxane in the step (4) is as follows: uniformly mixing pentamethyldisiloxane and decamethyl cyclopentasiloxane according to the mass ratio of 1:4-6, dropwise adding a trifluoromethanesulfonic acid aqueous solution with the mass fraction of 8-10% which is 3-4 times that of the pentamethyldisiloxane at a constant speed within 15-20 min under the stirring condition of 300-500 r/min at the temperature of 70-80 ℃, continuing stirring for reacting for 60-80 min after the dropwise adding, adding pure water for washing, standing for layering, separating liquid, taking an oil phase, repeatedly washing and separating liquid for 3-5 times, and drying for 6-8 h at the temperature of 100-120 ℃ and the pressure of 10-50 Pa.
CN202310546358.3A 2023-05-16 2023-05-16 Antistatic fabric and preparation method thereof Active CN116497474B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310546358.3A CN116497474B (en) 2023-05-16 2023-05-16 Antistatic fabric and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310546358.3A CN116497474B (en) 2023-05-16 2023-05-16 Antistatic fabric and preparation method thereof

Publications (2)

Publication Number Publication Date
CN116497474A CN116497474A (en) 2023-07-28
CN116497474B true CN116497474B (en) 2023-12-22

Family

ID=87326614

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310546358.3A Active CN116497474B (en) 2023-05-16 2023-05-16 Antistatic fabric and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116497474B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117624534B (en) * 2024-01-23 2024-04-19 苏州禾润昌新材料有限公司 Sound-insulation noise-reduction modified plastic and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150100309A (en) * 2014-02-25 2015-09-02 연세대학교 산학협력단 Microcapsules comprising phase change material enclosed by conductive polymers and method for preparing the same
CN105297289A (en) * 2015-12-07 2016-02-03 清华大学深圳研究生院 Preparation method of silk fibroin energy storage and temperature regulation fiber membrane
CN109609100A (en) * 2018-12-26 2019-04-12 上海驰纺材料科技有限公司 A kind of photothermal composite material and preparation method thereof being provided simultaneously with extinction fever heat storage function
WO2021142933A1 (en) * 2020-01-13 2021-07-22 南通纺织丝绸产业技术研究院 Electrically conductive fibroin material, preparation method therefor, and application thereof
CN114420458A (en) * 2021-12-21 2022-04-29 深圳大学 Flexible electrode, preparation method thereof and flexible supercapacitor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150100309A (en) * 2014-02-25 2015-09-02 연세대학교 산학협력단 Microcapsules comprising phase change material enclosed by conductive polymers and method for preparing the same
CN105297289A (en) * 2015-12-07 2016-02-03 清华大学深圳研究生院 Preparation method of silk fibroin energy storage and temperature regulation fiber membrane
CN109609100A (en) * 2018-12-26 2019-04-12 上海驰纺材料科技有限公司 A kind of photothermal composite material and preparation method thereof being provided simultaneously with extinction fever heat storage function
WO2021142933A1 (en) * 2020-01-13 2021-07-22 南通纺织丝绸产业技术研究院 Electrically conductive fibroin material, preparation method therefor, and application thereof
CN114420458A (en) * 2021-12-21 2022-04-29 深圳大学 Flexible electrode, preparation method thereof and flexible supercapacitor

Also Published As

Publication number Publication date
CN116497474A (en) 2023-07-28

Similar Documents

Publication Publication Date Title
CN116497474B (en) Antistatic fabric and preparation method thereof
CN110774680B (en) High-skin-affinity antibacterial fabric and preparation method thereof
CN100393935C (en) High water-absorption fiber and its preparing method
CN103409837A (en) Method for preparing water soluble polyvinyl alcohol fiber through melt spinning
CN110863263A (en) Composite garment fabric with efficient and lasting antibacterial performance
CN114571807B (en) Multilayer composite medical fabric and preparation method thereof
CN114276636A (en) Biomass hydrogel and preparation method thereof
CN108277548A (en) A kind of graphene terylene fire resistance fibre and preparation method thereof
CN102605622A (en) After-finishing technology for reducing shrinkage rate of bamboo fiber fabric and bedding
CN111826809A (en) Preparation method of non-woven fabric material for paper diapers
CN109467683B (en) Preparation method of modified polyester chip, polyester chip and polyester fiber
CN116837482A (en) Meta-aramid filament and preparation method and application thereof
CN115896967B (en) Degradable environment-friendly flame retardant and preparation method thereof
CN115369657B (en) Special anti-allergic underwear fabric and preparation method thereof
CN115029849B (en) Multifunctional warm-keeping knitted fabric and preparation method thereof
CN114381932A (en) Light anti-static fabric and preparation method thereof
CN114635198A (en) Viscose elastic fiber and preparation method thereof
CN111617706B (en) Al (aluminum)2O3-B2O3-SiO2Composite sol, core-shell structure active carbon fiber and preparation method thereof
CN110747640A (en) Preparation method of high-temperature-resistant corrosion-resistant industrial filter cloth
CN104532390B (en) A kind of conductive fabric and preparation method thereof
CN112064135A (en) Manufacturing method of wig fiber with good antibacterial and flame retardant properties
CN116288771B (en) High-toughness silk fiber and preparation method thereof
CN117818156A (en) Radiation-proof breathable fabric and preparation method thereof
CN113430721A (en) Production process of polytetrafluoroethylene glass fiber mesh cloth
CN114351458A (en) Health-care silk fabric and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20231123

Address after: 315000 Haidun 171, Shagang Village, Dongchen Township, Xiangshan County, Ningbo City, Zhejiang Province (self declared)

Applicant after: Ningbo Yuancheng Clothing Co.,Ltd.

Address before: 215231 No.2, east side of Zhentao Road, Zhenze Town, Wujiang District, Suzhou City, Jiangsu Province

Applicant before: SUZHOU LYUZHONGYUAN TEXTILE TECHNOLOGY Co.,Ltd.

GR01 Patent grant
GR01 Patent grant