阅读说明：本技术 一种长效抗静电锁温面料及其制备方法 (Long-acting antistatic temperature-locking fabric and preparation method thereof ) 是由 肖猷海 于 2021-08-24 设计创作，主要内容包括：本发明提出了一种长效抗静电锁温面料及其制备方法,属于面料技术领域,由有机/无机复合导电纤维、涤纶纤维、亲水柔软剂、起毛剂、涤纶抗静电助剂制备而成,其中,有机/无机复合导电纤维为聚苯胺包覆的C@Ag导电多孔纳米中空球经过静电纺丝制得的纤维。本发明制得的长效抗静电锁温面料具有极好的长效抗静电性能,力学性能佳,锁温性能好,同时,还具有很好的柔软性、爽滑感和亲肤感,抗菌抗螨、抗紫外线性能佳,还具有很好的耐水洗性能和色牢度,具有广阔的应用前景。(The invention provides a long-acting antistatic temperature-locking fabric and a preparation method thereof, belonging to the technical field of fabrics. The long-acting antistatic temperature-locking fabric prepared by the invention has excellent long-acting antistatic performance, good mechanical property, good temperature-locking performance, good softness, smoothness, skin-friendly feeling, good antibacterial, anti-mite and anti-ultraviolet performances, good washing resistance and color fastness, and wide application prospect.)

1. The long-acting antistatic temperature-locking fabric is characterized by being prepared from organic/inorganic composite conductive fibers, polyester fibers, a phase change energy storage material, a hydrophilic softening agent, a fluffing agent and a polyester antistatic auxiliary agent, wherein the organic/inorganic composite conductive fibers are fibers prepared by performing electrostatic spinning on polyaniline-coated C @ Ag conductive porous nano hollow spheres.

2. The long-acting antistatic temperature-locking fabric according to claim 1, wherein the organic/inorganic composite conductive fibers are prepared by the following method:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dispersing acrylonitrile, divinyl benzene and a pore-foaming agent in water under the action of an emulsifier to obtain emulsion; adding a water-soluble initiator, heating, carrying out polymerization reaction on acrylonitrile and divinyl benzene, and obtaining a cross-linked polyacrylonitrile porous hollow sphere under the action of a pore-foaming agent;

s2, preparing a polyacrylonitrile porous hollow sphere with carboxyl on the surface: carrying out hydrolysis reaction on the cross-linked polyacrylonitrile porous hollow sphere obtained in the step S1 in NaOH solution, centrifuging, adding the solid into hydrochloric acid solution, and reacting for 2-5h to obtain a polyacrylonitrile porous hollow sphere with carboxyl on the surface;

s3, surface deposition of metal silver: dispersing the polyacrylonitrile hollow spheres with the carboxyl on the surface obtained in the step S2 in water, ultrasonically dispersing the polyacrylonitrile hollow spheres uniformly, adding a silver nitrate solution, stirring the mixture for 10 to 20min, dropwise adding an ammonia water solution until the solution becomes clear again, centrifuging the solution, dispersing the solid in the water again, ultrasonically dispersing the mixture uniformly, dropwise adding a glucose solution, and reacting the mixture for 1 to 2 hours to obtain the polyacrylonitrile porous hollow spheres with Ag deposition;

s4.C @ Ag conductive porous nano hollow sphere preparation: calcining the Ag deposited polyacrylonitrile porous hollow spheres obtained in the step S3 to obtain C @ Ag conductive porous nano hollow spheres;

s5, preparing organic/inorganic composite conductive fibers: adding aniline into an HCl solution, then adding the C @ Ag conductive porous nano hollow spheres prepared in the step S4, performing ultrasonic dispersion uniformly to obtain a suspension liquid, then adding an initiator, stirring and reacting for 3-6h, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, drying, and performing electrostatic spinning to obtain the organic/inorganic composite conductive fiber.

3. The long-acting antistatic temperature-locking fabric according to claim 2, wherein the pore-forming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether and polyoxyethylene sorbitan fatty acid ester; the emulsifier is at least one selected from tween-80, span-80, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate and sodium stearate; the water-soluble initiator is selected from at least one of potassium persulfate, ammonium persulfate, sodium persulfate, azodiisobutyl amidine hydrochloride and azodiisobutyl imidazoline hydrochloride.

4. The long-acting antistatic temperature-locking fabric according to claim 2, wherein the mass ratio of the acrylonitrile to the divinylbenzene to the pore-forming agent to the emulsifying agent is (3-10): 1: (0.01-0.1): (0.1-0.3).

5. The long-acting antistatic temperature-locking fabric according to claim 2, wherein the concentration of the NaOH solution is 10-20 wt%; the hydrolysis reaction temperature is 85-100 ℃, and the reaction time is 3-5 h; the mass concentration of the hydrochloric acid solution is 2-5 mol/L.

6. The long-acting antistatic temperature-locking fabric according to claim 2, wherein the mass ratio of the aniline to the C @ Ag conductive porous nano hollow spheres to the initiator is 100: (25-40): (1-2).

7. The long-acting antistatic temperature-locking fabric according to claim 1, which is prepared from the following raw materials in parts by weight: 10-20 parts of organic/inorganic composite conductive fiber, 300 parts of 200-doped polyester fiber, 3-7 parts of phase change energy storage material, 2-5 parts of hydrophilic softening agent, 1-2 parts of raising agent and 2-3 parts of polyester antistatic auxiliary agent.

8. The long-acting antistatic temperature-locking fabric according to claim 1 or 7, wherein the hydrophilic softening agent is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is (2-5): 1, preferably, is (3-4): 1.

9. the long-acting antistatic temperature-locking fabric according to claim 1 or 7, wherein the polyester antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is (5-10): 2, preferably, is (6-7): 2.

10. a method for preparing the long-acting antistatic temperature-locking fabric as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:

(1) preparing modified polyester fibers: adding the polyester fiber and the phase change energy storage material into a screw injection molding machine, heating, melting and spraying, and stretching under the action of hot air to obtain modified polyester fiber;

(2) white embryo combing: weaving the modified polyester fiber and the organic/inorganic composite conductive fiber into uniform and soft gray cloth for carding;

(3) ironing: the fabric surface finished by a double-roller natural luster finishing machine is fluffy, thick, full, smooth and bright at the natural luster finishing temperature of 200-240 ℃ and the natural luster finishing speed of about 40-60 m/min;

(4) presetting: setting the fabric at 190-;

(5) dyeing with disperse dyes;

(6) preparing an auxiliary agent: adding the hydrophilic softening agent, the fluffing agent and the terylene antistatic auxiliary agent into water according to a certain proportion, and uniformly mixing to obtain the auxiliary agent;

(7) adding an auxiliary agent into a continuous padder, and performing repeated padding type full treatment;

(8) dehydrating and finishing the cloth;

(9) drying at the temperature of 150 ℃ and 250 ℃ for 80-100 s;

(10) shaping;

(11) napping;

(12) finishing: straightening down the fluff and shearing off the floating fluff;

(13) ironing: finishing natural luster with a double-roller natural luster finishing machine;

(14) shaking: continuously shaking the grains by a direct-pumping dry method for 20-40 min;

(15) the color fastness is not less than 3 grade.

Technical Field

The invention relates to the technical field of fabrics, in particular to a long-acting antistatic temperature-locking fabric and a preparation method thereof.

Background

Static electricity is a discharge phenomenon generated by unbalance of the quantity of positive and negative charges on the surface of an object due to external force factors such as friction, contact and collision of the surface of a solid. In life, a large amount of static electricity is accumulated on the surface of clothes, so that the clothes adsorb dust, the clothes adhere to the body, and people feel strong discomfort in daily activities and work. But also can cause instant shock to human body, which can cause damage to human heart, nerve and other parts, and cause the shock, reaction, discomfort, mental stress and the like. On the other hand, static electricity also affects normal industrial production. For example, in the electronic industry, static electricity is one of the important causes of computer and other electronic components failure, and can break down components seriously, so that the components are directly scrapped; in the textile industry, due to the influence of static electricity, phenomena such as breakage, horn mouth blockage, machine part winding and the like of a loose fiber web can occur; in the medical and health industry, the medicine can adsorb dust due to static electricity, so that the quality of the medicine cannot be guaranteed; especially in a high-grade pathogenic microorganism laboratory, the adsorption effect of static electricity can cause pathogens to be adsorbed on the protective clothing and then taken out of the laboratory, and in severe cases, pathogenic transmission of the pathogens can also be caused, so that unpredictable loss is caused.

Flannel refers to a woolen (cotton) wool fabric with a pattern-sandwiched style woven by mixed-color carded (cotton) wool yarns, and has comfortable wearing feeling and good warm-keeping effect. Although flannel is soft and warm, after being worn on the body in winter, the flannel easily generates static electricity after being rubbed with the skin for many times, so that the skin generates a stabbing pain feeling of being electrified.

The invention discloses a preparation method of a polyester luggage fabric with antistatic and antifouling functions, which is a Chinese patent with an authorization publication number of CN102877303B, and the preparation method comprises the following steps: preparing a finishing working solution, padding the case fabric with the working solution, soaking twice and rolling twice, pre-drying at 80-100 ℃ for 2-3 min, and baking at 150-180 ℃ for 1-2 min to obtain the antistatic and antifouling polyester case fabric. The product has good antistatic and antifouling properties, and is easy to operate, but has hard texture, and is not suitable for making clothes.

The publication No. CN203188011U discloses an antistatic functional fabric, wherein an upper antistatic coating and a lower antistatic coating are respectively coated on the upper and lower surfaces of a fabric base layer, so that the fabric has an antistatic effect. Because the antistatic coating is formed by coating the antistatic finishing agent, the antistatic effect is not permanent, the wear resistance of the fabric is poor, when the antistatic coating is used for sofa fabric, the antistatic coating is worn quickly, the antistatic effect is weakened gradually and easily until the fabric is completely ineffective, and the fabric has a single function and cannot meet the multifunctional use requirement of modern life on home textile fabric.

Disclosure of Invention

The invention aims to provide a long-acting antistatic temperature-locking fabric and a preparation method thereof, and the fabric has a good anti-aging effect.

The technical scheme of the invention is realized as follows:

the invention provides a long-acting antistatic temperature-locking fabric which is prepared from organic/inorganic composite conductive fibers, polyester fibers, a phase change energy storage material, a hydrophilic softening agent, a fluffing agent and a polyester antistatic auxiliary agent, wherein the organic/inorganic composite conductive fibers are fibers prepared by performing electrostatic spinning on polyaniline-coated C @ Ag conductive porous nano hollow spheres.

As a further improvement of the invention, the organic/inorganic composite conductive fiber is prepared by the following method:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dispersing acrylonitrile, divinyl benzene and a pore-foaming agent in water under the action of an emulsifier to obtain emulsion; adding a water-soluble initiator, heating, carrying out polymerization reaction on acrylonitrile and divinyl benzene, and obtaining a cross-linked polyacrylonitrile porous hollow sphere under the action of a pore-foaming agent;

s2, preparing a polyacrylonitrile porous hollow sphere with carboxyl on the surface: carrying out hydrolysis reaction on the cross-linked polyacrylonitrile porous hollow sphere obtained in the step S1 in NaOH solution, centrifuging, adding the solid into hydrochloric acid solution, and reacting for 2-5h to obtain a polyacrylonitrile porous hollow sphere with carboxyl on the surface;

s3, surface deposition of metal silver: dispersing the polyacrylonitrile hollow spheres with the carboxyl on the surface obtained in the step S2 in water, ultrasonically dispersing the polyacrylonitrile hollow spheres uniformly, adding a silver nitrate solution, stirring the mixture for 10 to 20min, dropwise adding an ammonia water solution until the solution becomes clear again, centrifuging the solution, dispersing the solid in the water again, ultrasonically dispersing the mixture uniformly, dropwise adding a glucose solution, and reacting the mixture for 1 to 2 hours to obtain the polyacrylonitrile porous hollow spheres with Ag deposition;

preferably, the concentration of the silver nitrate solution is 15-30 wt%, the concentration of the ammonia water solution is 20-30 wt%, and the concentration of the glucose solution is 5-12 wt%.

S4.C @ Ag conductive porous nano hollow sphere preparation: calcining the Ag deposited polyacrylonitrile porous hollow spheres obtained in the step S3 to obtain C @ Ag conductive porous nano hollow spheres;

preferably, the calcination conditions are: calcining for 2-4h at the temperature of 600-800 ℃ in the environment of nitrogen or argon protection.

S5, preparing organic/inorganic composite conductive fibers: adding aniline into an HCl solution, then adding the C @ Ag conductive porous nano hollow spheres prepared in the step S4, performing ultrasonic dispersion uniformly to obtain a suspension liquid, then adding an initiator, stirring and reacting for 3-6h, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, drying, and performing electrostatic spinning to obtain the organic/inorganic composite conductive fiber.

Preferably, the initiator is selected from at least one of ammonium persulfate, potassium persulfate and sodium persulfate.

Preferably, the electrospinning process is: refer to patent CN108796632B method.

As a further improvement of the present invention, the pore-forming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene octyl phenyl ether and polyoxyethylene sorbitan fatty acid ester; the emulsifier is at least one selected from tween-80, span-80, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate and sodium stearate; the water-soluble initiator is selected from at least one of potassium persulfate, ammonium persulfate, sodium persulfate, azodiisobutyl amidine hydrochloride and azodiisobutyl imidazoline hydrochloride.

As a further improvement of the invention, the mass ratio of the acrylonitrile to the divinylbenzene to the pore-foaming agent to the emulsifying agent is (3-10): 1: (0.01-0.1): (0.1-0.3).

As a further improvement of the invention, the concentration of the NaOH solution is 10-20 wt%; the hydrolysis reaction temperature is 85-100 ℃, and the reaction time is 3-5 h; the mass concentration of the hydrochloric acid solution is 2-5 mol/L.

As a further improvement of the invention, the mass ratio of the aniline to the C @ Ag conductive porous nano hollow spheres to the initiator is 100: (25-40): (1-2).

As a further improvement of the invention, the long-acting antistatic temperature-locking fabric is prepared from the following raw materials in parts by weight: 10-20 parts of organic/inorganic composite conductive fiber, 300 parts of 200-doped polyester fiber, 3-7 parts of phase change energy storage material, 2-5 parts of hydrophilic softening agent, 1-2 parts of raising agent and 2-3 parts of polyester antistatic auxiliary agent.

Preferably, the phase change energy storage material is selected from at least one of liquid paraffin, polyethylene glycol 1000, polyethylene glycol 2000, polyvinyl alcohol, stearic acid, pentaerythritol, neopentyl glycol and trimethylolethane.

As a further improvement of the invention, the hydrophilic softener is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is (2-5): 1, preferably, is (3-4): 1.

as a further improvement of the invention, the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is (5-10): 2, preferably, is (6-7): 2.

preferably, the raising agent is at least one selected from raising agents RS-WR, RS-CO, ZJ-Z01 and SL-606.

The invention further provides a preparation method of the long-acting antistatic temperature-locking fabric, which comprises the following steps:

(1) preparing modified polyester fibers: adding the polyester fiber and the phase change energy storage material into a screw injection molding machine, heating, melting and spraying, and stretching under the action of hot air to obtain modified polyester fiber;

(2) white embryo combing: weaving the modified polyester fiber and the organic/inorganic composite conductive fiber into uniform and soft gray cloth for carding;

(3) ironing: the fabric surface finished by a double-roller natural luster finishing machine is fluffy, thick, full, smooth and bright at the natural luster finishing temperature of 200-240 ℃ and the natural luster finishing speed of about 40-60 m/min;

(4) presetting: setting the fabric at 190-;

(5) dyeing with disperse dyes;

(6) preparing an auxiliary agent: adding the hydrophilic softening agent, the fluffing agent and the terylene antistatic auxiliary agent into water according to a certain proportion, and uniformly mixing to obtain the auxiliary agent;

(7) adding an auxiliary agent into a continuous padder, and performing repeated padding type full treatment;

(8) dehydrating and finishing the cloth;

(9) drying at the temperature of 150 ℃ and 250 ℃ for 80-100 s;

(10) shaping;

(11) napping;

(12) finishing: straightening down the fluff and shearing off the floating fluff;

(13) ironing: finishing natural luster with a double-roller natural luster finishing machine;

(14) shaking: continuously shaking the grains by a direct-pumping dry method for 20-40 min;

(15) the color fastness is not less than 3 grade.

The invention has the following beneficial effects: the invention provides an organic/inorganic composite conductive fiber, which comprises the steps of firstly carrying out polymerization reaction on acrylonitrile and divinyl benzene, preparing a cross-linked polyacrylonitrile porous hollow sphere under the action of a pore-forming agent, further hydrolyzing amido bonds in the polyacrylonitrile under an alkaline condition, further neutralizing to form carboxylate radicals on the surface of microspheres, carrying out electrostatic adsorption on the carboxylate radicals and silver ammonia ions, inducing the silver ammonia ions to react with reducing glucose on the surface of the porous hollow sphere in situ, depositing Ag particles, further cracking the cross-linked polyacrylonitrile into carbon under a calcining condition, thus obtaining a C @ Ag conductive porous nano hollow sphere, dispersing the porous hollow sphere in a solution with aniline, enabling a large number of aniline molecules to be gathered in the hollow sphere, generating polyaniline molecular chains through the pores of the shell layer of the hollow sphere by the polymerization reaction, and enabling the hollow sphere to be connected in series by polyaniline, therefore, the antistatic effect is not deteriorated due to washing or long service time, a good long-term antistatic effect is achieved, and the mechanical properties can be improved. In addition, after the organic/inorganic composite conductive fiber prepared by the invention is added, the prepared fabric also has good antibacterial and anti-mite performance and ultraviolet resistance;

the hydrophilic softener is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, the amino silicone oil CS-1800 has an incomparable super-soft effect compared with common softeners, so that the fabric has softness, smoothness, hydrophilicity and good water washing resistance and antistatic performance, the organic silicone 8803 has excellent softness and antistatic performance, the compound of the amino silicone oil CS-1800 and the common softener has a good synergistic effect, and the water washing resistance and the antistatic performance are both obviously enhanced;

the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, the tween-80 has a certain antistatic effect, and also has good emulsibility and heat resistance, the friction coefficient can be further reduced, so that the fiber has good holding and bundling properties, the density of positive charges of the poly dimethyl diallyl ammonium chloride is high, the cost is low, the color fastness, the tearing strength and the hand feeling are not influenced, after the two are compounded, the terylene antistatic auxiliary agent can play a good antistatic enhancement effect and has a certain washing resistance, and the compound of the two has a good synergistic effect;

according to the invention, the phase-change energy storage material is added into the polyester fiber for melt blending, the modified polyester fiber is obtained by spinning, and the phase-change energy storage material is encapsulated in the polyester polymer under the wrapping of the polyester polymer to form the phase-change energy storage microcapsule, so that the prepared fabric co-woven by the modified polyester fiber and the organic/inorganic composite conductive fiber also has good temperature locking performance;

the long-acting antistatic temperature-locking fabric prepared by the invention has excellent long-acting antistatic performance, good mechanical property, good temperature-locking performance, good softness, smoothness, skin-friendly feeling, good antibacterial, anti-mite and anti-ultraviolet performances, good washing resistance and color fastness, and wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is an SEM image of C @ Ag conductive porous nano hollow spheres prepared in preparation example 1 of the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Polyethylene glycol octyl phenyl ether CAS number 9036-19-5; sodium dodecyl sulfate CAS number 2386-53-0; acrylonitrile CAS number 107-13-1; divinylbenzene CAS number 1321-74-0; sodium persulfate CAS number 7775-27-1; silver nitrate CAS number 7761-88-8; glucose CAS number 50-99-7; aniline CAS number 62-53-3; polyester fiber CAS number 25135-51-7; poly dimethyl diallyl ammonium chloride CAS number 26062-79-3; tween-80 CAS number 9005-65-6; liquid paraffin CAS number 8020-83-5; polyethylene glycol CAS number 25322-68-3. Amino silicone oil CS-1800 with ammonia value of 0.6-0.65 and viscosity of 15000, purchased from available company of gold macro chemical industry in cigarette end; organosilicone 8803 having an ammonia value of 0.2 to 0.25 and a viscosity of 2000-10000 available from Dow Corning; all reagents were commercially available. 150D/288F full dull DTY fiber and 150D/48F semi dull DTY fiber were purchased from Jiangsu Shenghong Ju group. The raising agent RS-WR is purchased from Chenghui chemical development company Limited in Foshan City.

Preparation example 1 organic/inorganic composite conductive fiber

The preparation method comprises the following steps:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dissolving 0.05g of polyethylene glycol octyl phenyl ether and 0.2g of sodium dodecyl sulfate in 100mL of water, adding 8g of acrylonitrile and 1g of divinylbenzene, and emulsifying for 3min at 10000/min to obtain emulsion; adding 0.5g of sodium persulfate, heating to 85 ℃, stirring at 400r/min for 6h, centrifuging at 3000/min for 15min, and washing the solid with ethanol to obtain the cross-linked polyacrylonitrile porous hollow spheres;

s2, preparing a polyacrylonitrile porous hollow sphere with carboxyl on the surface: adding 5g of the cross-linked polyacrylonitrile porous hollow spheres obtained in the step S1 into 50mL of 15 wt% NaOH solution, heating to 95 ℃, reacting for 4h, centrifuging at 3000r/min for 15min, adding the solid into 50mL of 4mol/L hydrochloric acid solution, and reacting for 4h to obtain polyacrylonitrile porous hollow spheres with carboxyl on the surface;

s3, surface deposition of metal silver: dispersing 4g of polyacrylonitrile hollow spheres with carboxyl on the surface obtained in the step S2 in 20mL of water, ultrasonically dispersing for 20min at 1000W, adding 20mL of 20 wt% silver nitrate solution, stirring for 15min, dropwise adding 25 wt% of ammonia water solution until the solution becomes clear again, centrifuging for 15min at 3000/min, adding the solid into 50mL of water, ultrasonically dispersing for 20min at 1000W, dropwise adding 50mL of 10 wt% glucose solution, reacting for 2h, and centrifuging for 15min at 3000/min to obtain the polyacrylonitrile porous hollow spheres with Ag deposition;

s4.C @ Ag conductive porous nano hollow sphere preparation: calcining 4g of the Ag deposited polyacrylonitrile porous hollow spheres obtained in the step S3 for 3h at the temperature of 700 ℃ in the nitrogen protection environment to obtain C @ Ag conductive porous nano hollow spheres; fig. 1 is an SEM image of the C @ Ag conductive porous nano hollow sphere prepared in the present invention, and it can be seen that the shell layer of the hollow sphere has a porous structure.

S5, preparing organic/inorganic composite conductive fibers: adding 10g of aniline into 2mol/L HCl solution, then adding 3g of C @ Ag conductive porous nano hollow spheres prepared in the step S4, performing ultrasonic dispersion for 20min at 1000W to obtain suspension liquid, then adding 0.5g of sodium persulfate, performing stirring reaction for 5h, performing 3000/min centrifugation for 15min, washing the solid with absolute ethyl alcohol and deionized water in sequence, drying at 90 ℃ for 2h, and performing electrostatic spinning to obtain the organic/inorganic composite conductive fiber.

Comparative preparation example 1

Compared with the preparation example 1, the step S2 is not carried out, the cross-linked polyacrylonitrile porous hollow sphere is not subjected to hydrolysis reaction, and other conditions are not changed.

The preparation method comprises the following steps:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dissolving 0.05g of polyethylene glycol octyl phenyl ether and 0.2g of sodium dodecyl sulfate in 100mL of water, adding 8g of acrylonitrile and 1g of divinylbenzene, and emulsifying for 3min at 10000/min to obtain emulsion; adding 0.5g of sodium persulfate, heating to 85 ℃, stirring at 400r/min for 6h, centrifuging at 3000/min for 15min, and washing the solid with ethanol to obtain the cross-linked polyacrylonitrile porous hollow spheres;

s2, surface deposition of metal silver: dispersing 4g of the cross-linked polyacrylonitrile porous hollow spheres obtained in the step S1 in 20mL of water, performing ultrasonic dispersion at 1000W for 20min, adding 20mL of 20 wt% silver nitrate solution, stirring for 15min, dropwise adding 25 wt% ammonia water solution until the solution becomes clear again, centrifuging at 3000/min for 15min, adding the solid into 50mL of water, performing ultrasonic dispersion at 1000W for 20min, dropwise adding 50mL of 10 wt% glucose solution, reacting for 2h, and centrifuging at 3000/min for 15min to obtain Ag-deposited polyacrylonitrile porous hollow spheres;

s3.C @ Ag conductive porous nano hollow sphere preparation: calcining 4g of the Ag deposited polyacrylonitrile porous hollow spheres obtained in the step S2 for 3h at the temperature of 700 ℃ in the nitrogen protection environment to obtain C @ Ag conductive porous nano hollow spheres;

s4, preparing organic/inorganic composite conductive fibers: adding 10g of aniline into 2mol/L HCl solution, then adding 3g of C @ Ag conductive porous nano hollow spheres prepared in the step S3, performing ultrasonic dispersion for 20min at 1000W to obtain suspension liquid, then adding 0.5g of sodium persulfate, performing stirring reaction for 5h, performing 3000/min centrifugation for 15min, washing the solid with absolute ethyl alcohol and deionized water in sequence, drying at 90 ℃ for 2h, and performing electrostatic spinning to obtain the organic/inorganic composite conductive fiber.

Comparative preparation example 2

Compared with preparation example 1, step S3 was not performed, Ag particles were not deposited on the surface of the polyacrylonitrile porous hollow sphere, and other conditions were not changed.

The preparation method comprises the following steps:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dissolving 0.05g of polyethylene glycol octyl phenyl ether and 0.2g of sodium dodecyl sulfate in 100mL of water, adding 8g of acrylonitrile and 1g of divinylbenzene, and emulsifying for 3min at 10000/min to obtain emulsion; adding 0.5g of sodium persulfate, heating to 85 ℃, stirring at 400r/min for 6h, centrifuging at 3000/min for 15min, and washing the solid with ethanol to obtain the cross-linked polyacrylonitrile porous hollow spheres;

s2, preparing a polyacrylonitrile porous hollow sphere with carboxyl on the surface: adding 5g of the cross-linked polyacrylonitrile porous hollow spheres obtained in the step S1 into 50mL of 15 wt% NaOH solution, heating to 95 ℃, reacting for 4h, centrifuging at 3000r/min for 15min, adding the solid into 50mL of 4mol/L hydrochloric acid solution, and reacting for 4h to obtain polyacrylonitrile porous hollow spheres with carboxyl on the surface;

s3.C @ Ag conductive porous nano hollow sphere preparation: calcining 4g of polyacrylonitrile porous hollow spheres with carboxyl on the surfaces obtained in the step S2 for 3h at the temperature of 700 ℃ in the environment of nitrogen protection to obtain C @ Ag conductive porous nano hollow spheres;

s4, preparing organic/inorganic composite conductive fibers: adding 10g of aniline into 2mol/L HCl solution, then adding 3g of conductive porous nano hollow spheres prepared in the step S3, performing ultrasonic dispersion for 20min at 1000W to obtain suspension liquid, then adding 0.5g of sodium persulfate, performing stirring reaction for 5h, centrifuging for 15min at 3000/min, washing the solid with absolute ethyl alcohol and deionized water in sequence, drying for 2h at 90 ℃, and performing electrostatic spinning to obtain the organic/inorganic composite conductive fiber.

Comparative preparation example 3

Compared with preparation example 1, the polyacrylonitrile porous hollow sphere which is not subjected to step S4 and is Ag-deposited is not calcined, and other conditions are not changed.

The preparation method comprises the following steps:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dissolving 0.05g of polyethylene glycol octyl phenyl ether and 0.2g of sodium dodecyl sulfate in 100mL of water, adding 8g of acrylonitrile and 1g of divinylbenzene, and emulsifying for 3min at 10000/min to obtain emulsion; adding 0.5g of sodium persulfate, heating to 85 ℃, stirring at 400r/min for 6h, centrifuging at 3000/min for 15min, and washing the solid with ethanol to obtain the cross-linked polyacrylonitrile porous hollow spheres;

s2, preparing a polyacrylonitrile porous hollow sphere with carboxyl on the surface: adding 5g of the cross-linked polyacrylonitrile porous hollow spheres obtained in the step S1 into 50mL of 15 wt% NaOH solution, heating to 95 ℃, reacting for 4h, centrifuging at 3000r/min for 15min, adding the solid into 50mL of 4mol/L hydrochloric acid solution, and reacting for 4h to obtain polyacrylonitrile porous hollow spheres with carboxyl on the surface;

s3, surface deposition of metal silver: dispersing 4g of polyacrylonitrile hollow spheres with carboxyl on the surface obtained in the step S2 in 20mL of water, ultrasonically dispersing for 20min at 1000W, adding 20mL of 20 wt% silver nitrate solution, stirring for 15min, dropwise adding 25 wt% of ammonia water solution until the solution becomes clear again, centrifuging for 15min at 3000/min, adding the solid into 50mL of water, ultrasonically dispersing for 20min at 1000W, dropwise adding 50mL of 10 wt% glucose solution, reacting for 2h, and centrifuging for 15min at 3000/min to obtain the polyacrylonitrile porous hollow spheres with Ag deposition;

s4, preparing organic/inorganic composite conductive fibers: adding 10g of aniline into 2mol/L HCl solution, then adding 3g of polyacrylonitrile porous hollow spheres deposited with Ag prepared in the step S3, performing ultrasonic dispersion for 20min at 1000W to obtain suspension liquid, then adding 0.5g of sodium persulfate, performing stirring reaction for 5h, performing 3000/min centrifugation for 15min, washing the solid with absolute ethyl alcohol and deionized water in sequence, drying at 90 ℃ for 2h, and performing electrostatic spinning to obtain the organic/inorganic composite conductive fiber.

Comparative preparation example 4

Compared with preparation example 1, in step S5, the polyaniline is replaced by the polyester, and other conditions are not changed.

The preparation method comprises the following steps:

s1, preparing a cross-linked polyacrylonitrile porous hollow sphere: dissolving 0.05g of polyethylene glycol octyl phenyl ether and 0.2g of sodium dodecyl sulfate in 100mL of water, adding 8g of acrylonitrile and 1g of divinylbenzene, and emulsifying for 3min at 10000/min to obtain emulsion; adding 0.5g of sodium persulfate, heating to 85 ℃, stirring at 400r/min for 6h, centrifuging at 3000/min for 15min, and washing the solid with ethanol to obtain the cross-linked polyacrylonitrile porous hollow spheres;

s2, preparing a polyacrylonitrile porous hollow sphere with carboxyl on the surface: adding 5g of the cross-linked polyacrylonitrile porous hollow spheres obtained in the step S1 into 50mL of 15 wt% NaOH solution, heating to 95 ℃, reacting for 4h, centrifuging at 3000r/min for 15min, adding the solid into 50mL of 4mol/L hydrochloric acid solution, and reacting for 4h to obtain polyacrylonitrile porous hollow spheres with carboxyl on the surface;

s3, surface deposition of metal silver: dispersing 4g of polyacrylonitrile hollow spheres with carboxyl on the surface obtained in the step S2 in 20mL of water, ultrasonically dispersing for 20min at 1000W, adding 20mL of 20 wt% silver nitrate solution, stirring for 15min, dropwise adding 25 wt% of ammonia water solution until the solution becomes clear again, centrifuging for 15min at 3000/min, adding the solid into 50mL of water, ultrasonically dispersing for 20min at 1000W, dropwise adding 50mL of 10 wt% glucose solution, reacting for 2h, and centrifuging for 15min at 3000/min to obtain the polyacrylonitrile porous hollow spheres with Ag deposition;

s4.C @ Ag conductive porous nano hollow sphere preparation: calcining 4g of the Ag deposited polyacrylonitrile porous hollow spheres obtained in the step S3 for 3h at the temperature of 700 ℃ in the nitrogen protection environment to obtain C @ Ag conductive porous nano hollow spheres;

s5, preparing organic/inorganic composite conductive fibers: and (3) adding 10g of terylene and 3g of the C @ Ag conductive porous nano hollow sphere prepared in the step S4 into a screw injection molding machine, heating, melting and spinning, and stretching under the action of hot air to obtain the organic/inorganic composite conductive fiber.

Example 1 Long-acting antistatic temperature-locking fabric

The raw materials comprise the following components in parts by weight: 10 parts of organic/inorganic composite conductive fiber prepared in preparation example 1, 200 parts of polyester fiber, 3 parts of liquid paraffin, 2 parts of hydrophilic softening agent, 1 part of raising agent RS-WR and 2 parts of polyester antistatic auxiliary agent. The hydrophilic softening agent is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is 3: 1. the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is 6: 2. the polyester fiber is a uniform mixture of 150D/288F full-dull DTY fiber and 150D/48F semi-dull DTY fiber, and the mass ratio is 5: 1.

The preparation method comprises the following steps:

(1) preparing modified polyester fibers: adding the polyester fiber and the liquid paraffin into a screw injection molding machine, uniformly mixing, heating, melting and spraying, and stretching under the action of hot air to obtain modified polyester fiber;

(2) white embryo combing: weaving polyester fibers and organic/inorganic composite conductive fibers into uniform and soft gray cloth for carding;

(3) ironing: the surface of the fabric finished by using a double-roller natural luster finishing machine is fluffy, thick, full, smooth and bright, and the natural luster finishing temperature is 220 ℃ and the natural luster finishing speed is about 50 m/min;

(4) presetting: the state of the fabric is finished at the shaping temperature of 195 ℃;

(5) dyeing with disperse dyes;

(6) preparing an auxiliary agent: adding the hydrophilic softening agent, the fluffing agent and the terylene antistatic auxiliary agent into water according to a certain proportion, and uniformly mixing to obtain the auxiliary agent;

(7) adding an auxiliary agent into a continuous padder, and performing repeated padding type full treatment;

(8) dehydrating and finishing the cloth;

(9) drying at 200 ℃ for 90 s;

(10) shaping;

(11) napping;

(12) finishing: straightening down the fluff and shearing off the floating fluff;

(13) ironing: finishing natural luster with a double-roller natural luster finishing machine;

(14) shaking: continuously shaking the grains by a direct-pumping dry method for 30 min;

(15) the color fastness is not less than 3 grade.

Example 2

Compared with the example 1, the raw material proportion is different, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 20 parts of organic/inorganic composite conductive fiber prepared in preparation example 1, 300 parts of polyester fiber, 10007 parts of polyethylene glycol, 5 parts of hydrophilic softening agent, 2 parts of fluffing agent RS-WR and 3 parts of polyester antistatic auxiliary agent. The hydrophilic softening agent is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is 4: 1. the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is 7: 2.

example 3

Compared with the example 1, the raw material proportion and the composition are different, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 15 parts of organic/inorganic composite conductive fiber prepared in preparation example 1, 250 parts of polyester fiber, 20005 parts of polyethylene glycol, 3 parts of hydrophilic softening agent, 1.5 parts of raising agent RS-WR and 2.5 parts of polyester antistatic auxiliary agent. The hydrophilic softening agent is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is 3.5: 1. the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is 6.5: 2.

example 4

Compared with example 3, the organic/inorganic composite conductive fiber was prepared from comparative preparation example 1 without changing other conditions.

Example 5

Compared with example 3, the organic/inorganic composite conductive fiber was prepared from comparative preparation example 2 without changing other conditions.

Example 6

Compared with example 3, the organic/inorganic composite conductive fiber was prepared from comparative preparation example 3 without changing other conditions.

Example 7

Compared with example 3, the organic/inorganic composite conductive fiber was prepared from comparative preparation example 4 without changing other conditions.

Example 8

Compared with the example 3, the hydrophilic softening agent is amino silicone oil CS-1800, and other conditions are not changed.

Example 9

The hydrophilic softener was an organic silicone 8803 as compared to example 3, all other conditions being unchanged.

Example 10

Compared with the embodiment 3, the hydrophilic softening agent is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is 1: 1, the other conditions are not changed.

Example 11

Compared with the embodiment 3, the hydrophilic softening agent is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, and the mass ratio is 7: 1, the other conditions are not changed.

Example 12

Compared with the embodiment 3, the terylene antistatic auxiliary agent is poly dimethyl diallyl ammonium chloride, and other conditions are not changed compared with the embodiment 3.

Example 13

Compared with the example 3, the terylene antistatic auxiliary agent is Tween-80, and other conditions are not changed.

Example 14

Compared with the embodiment 3, the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is 3: 2, other conditions are not changed.

Example 15

Compared with the embodiment 3, the terylene antistatic auxiliary agent is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, and the mass ratio is 13: 2, other conditions are not changed.

Comparative example 1

Compared with example 3, the organic/inorganic composite conductive fiber is replaced by polyaniline fiber, and other conditions are not changed.

Comparative example 2

Compared with example 3, the organic/inorganic composite conductive fiber is replaced by carbon fiber, and other conditions are not changed.

Comparative example 3

Compared with the embodiment 3, the organic/inorganic composite conductive fiber prepared in the preparation example 1 is not added, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 265 parts of polyester fiber, 3 parts of hydrophilic softening agent, 1.5 parts of raising agent RS-WR and 2.5 parts of polyester antistatic auxiliary agent.

Comparative example 4

Compared with example 3, the hydrophilic softener was not added, and other conditions were not changed.

The raw materials comprise the following components in parts by weight: 15 parts of organic/inorganic composite conductive fiber prepared in preparation example 1, 253 parts of polyester fiber, 1.5 parts of raising agent RS-WR and 2.5 parts of polyester antistatic auxiliary agent.

Comparative example 5

Compared with the example 3, the polyester antistatic auxiliary agent is not added, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 15 parts of organic/inorganic composite conductive fiber prepared in preparation example 1, 252.5 parts of polyester fiber, 3 parts of hydrophilic softening agent and 1.5 parts of raising agent RS-WR.

Test example 1 antistatic Property test

The performance test of the long-acting antistatic temperature-locking fabric prepared in the above examples 1 to 15 and comparative examples 1 to 5 is performed, the test result is shown in table 1, and the test method is as follows: GB/T12703.4-2010 evaluation of textile Electrostatic Properties part 4: detecting the resistivity of the fabric by resistivity; GB/T12703.3-2009 evaluation of textile Electrostatic Properties part 3: the charge quantity of the fabric is detected; detecting the friction voltage of the fabric according to GB 12014-2009 antistatic garment; GB/T12703.1-2008 section 1 evaluation of textile Electrostatic Properties: the electrostatic voltage half-life period of the fabric is detected.

TABLE 1

As can be seen from Table 1, the long-acting antistatic temperature-locking fabric prepared by the method has excellent antistatic performance.

Test example 2

The performance test of the long-acting antistatic temperature-locking fabric prepared in the above examples 1 to 15 and comparative examples 1 to 5 is performed, the test result is shown in table 2, and the test method is as follows: GB/T4745-1997 test for measuring the surface moisture resistance of textile fabrics for wetting.

TABLE 2

As can be seen from Table 2, the long-acting antistatic temperature-locking fabric prepared by the method has good water resistance and wear resistance.

Test example 3

The long-acting antistatic temperature-locking shell fabrics prepared in examples 1-15 and comparative examples 1-5 are tested by an oscillation method (GB/T20944.3-2008), and the results are shown in Table 3.

TABLE 3

Group of	Antibacterial ratio of Escherichia coli (%)	Staphylococcus aureus antibacterial ratio (%)
			Example 1	96	98
Example 2	97	99
			Example 3	>99	>99
Example 4	88	89
			Example 5	72	70
Example 6	92	94
			Example 7	90	87
Example 8	94	96
			Example 9	95	94
Example 10	95	96
			Example 11	96	96
Example 12	92	92
			Example 13	91	90
Example 14	94	93
			Example 15	93	94
Comparative example 1	80	82
			Comparative example 2	74	78
Comparative example 3	60	61
			Comparative example 4	89	86
Comparative example 5	87	85

As can be seen from Table 3, the long-acting antistatic temperature-locking fabric prepared by the method has good antibacterial performance.

The long-acting antistatic temperature-locking fabric prepared in examples 1-15 and comparative examples 1-5 is subjected to an anti-mite test, the test indexes are according to the national standard GBT24253-2009, and the results are shown in Table 4.

TABLE 4

As can be seen from Table 4, the long-acting antistatic temperature-locking fabric prepared by the method has good anti-mite performance.

Test example 4 mechanical Property test

The long-acting antistatic temperature-locking fabrics prepared in examples 1-15 and comparative examples 1-5 are subjected to performance tests according to the technical requirements of GB/T21295-.

TABLE 5

As can be seen from Table 5, the long-acting antistatic temperature-locking fabric prepared by the method has good mechanical properties.

Compared with the embodiment 3, in the preparation process of the organic/inorganic composite conductive fiber, the cross-linked polyacrylonitrile porous hollow spheres are not subjected to hydrolysis reaction, so that no carboxyl group exists on the surfaces of the hollow spheres, silver ammonia ions cannot be electrostatically adsorbed, Ag particles cannot be generated in situ on the surfaces of the spheres, the number of the Ag particles on the surfaces of the spheres is greatly reduced, and the antistatic performance, the antibacterial performance and the anti-mite performance of the fabric are greatly reduced.

Compared with the example 3, Ag particles are not deposited on the surfaces of the polyacrylonitrile porous hollow spheres in the preparation process of the organic/inorganic composite conductive fibers, so that the antistatic performance, the antibacterial performance and the anti-mite performance of the fabric are obviously reduced. Ag particles are attached to the surface of the hollow sphere, so that the antistatic property, the antibacterial property and the anti-mite property of the material are greatly improved.

Compared with the example 3, in the preparation process of the organic/inorganic composite conductive fiber, the polyacrylonitrile porous hollow sphere deposited by Ag is not calcined, so that the polyacrylonitrile in the hollow sphere is not carbonized and is changed into conductive carbon element, the antistatic property of the long-acting antistatic temperature-locking fabric is obviously reduced, and the mechanical property is also reduced to a certain degree.

Compared with the embodiment 3, in the preparation process of the organic/inorganic composite conductive fiber, the polyaniline replaces terylene, so that the antistatic performance and the mechanical performance of the fabric are obviously reduced, and the antibacterial and anti-mite performance of the fabric are reduced.

Examples 8, 9, 10 and 11, and comparative example 4 compared with example 3, the hydrophilic softening agent is single amino silicone oil CS-1800 (example 8) or organic silicone 8803 (example 9), or the ratio of the two is too low (example 10) or too high (example 11), or the hydrophilic softening agent is not added (comparative example 4), which causes the antistatic performance of the fabric to be reduced, but the wetting grade, the water resistance and the wear resistance of the fabric are all reduced, the hydrophilic softening agent of the invention is a compound mixture of amino silicone oil CS-1800 and organic silicone 8803, the amino silicone oil CS-1800 has the effect of 'super-softness' which cannot be compared with the common softening agent, so that the fabric has soft, smooth, hydrophilic, good water washing resistance and antistatic performance, the organic silicone 8803 has excellent softness and antistatic performance, and the compound combination of the two has good synergistic effect, the washing resistance and the antistatic property are both obviously enhanced.

Examples 12, 13, 14, and 15 compared with example 3, the antistatic assistant of dacron is poly dimethyl diallyl ammonium chloride (example 12) or tween-80 (example 13), or the ratio of the two is too low (example 14) or too high (example 15), or no hydrophilic softener is added (comparative example 5), which results in the obvious decrease of antistatic property, mechanical property, wear resistance, and water resistance of the fabric, the antistatic assistant of dacron of the invention is a compound mixture of poly dimethyl diallyl ammonium chloride and tween-80, tween-80 has a certain antistatic effect, and also has good emulsibility and heat resistance, and can further reduce friction coefficient, so that the fiber has good holding and bundling properties, the positive charge density of poly dimethyl diallyl ammonium chloride is high, the cost is low, and the color fastness is not affected, The tear strength and the hand feeling can play a good antistatic enhancement effect after the two are compounded, and the water-washing resistance is certain, and the compounding of the two has a good synergistic effect.

Compared with the embodiment 3, the organic/inorganic composite conductive fiber is replaced by the polyaniline fiber, the antistatic performance is obviously reduced, and the effect is not good although the polyaniline fiber has a certain antistatic effect.

Compared with the embodiment 3, the organic/inorganic composite conductive fiber is replaced by the carbon fiber, the antistatic performance is obviously reduced, and although the carbon fiber also has a certain antistatic effect, the effect is not good.

Compared with the example 3, the organic/inorganic composite conductive fiber prepared in the preparation example 1 is not added, so that the prepared fabric has almost no antistatic performance, and the organic/inorganic composite conductive fiber plays a key role in improving the faced antistatic performance. The mechanical property is also influenced to a certain extent, the antibacterial and anti-mite properties are obviously reduced, and the organic/inorganic composite conductive fiber prepared by the invention has good antistatic effect and can improve the mechanical property. In addition, after the organic/inorganic composite conductive fiber prepared by the invention is added, the prepared fabric also has good antibacterial and anti-mite performance and ultraviolet resistance.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.