CN113417026B - Graphene high-thermal-insulation fiber and preparation method thereof - Google Patents

Abstract

The invention discloses a graphene high-thermal-insulation fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials; step 2, preparing a graphene-silicon dioxide dispersion liquid; step 3, spraying the dispersion liquid on a receiver through an ultrasonic spraying device to form microbeads, then freezing and drying the microbeads, and finally heating the microbeads in inert gas to obtain graphene-silicon dioxide aerogel microspheres; step 4, uniformly mixing the aerogel microspheres and the chinlon slices, and extruding and granulating; step 5, drying the master batch, heating and melting, filtering by a spinning box, and spinning into bundles; step 6, immersing the fiber into an acid solution to finish etching treatment on the surface of the fiber; and 7, preparing coating slurry, keeping the temperature of the slurry, placing the fiber into a slurry tank for sizing, and finally drying and winding. The invention also provides the graphene high-thermal-insulation fiber prepared by the method. The fiber prepared by the method disclosed by the invention has the advantages that the high heat insulation performance is greatly improved, the graphene antibacterial function can be exerted, and the human health is protected.

Description

Graphene high-thermal-insulation fiber and preparation method thereof

Technical Field

The invention relates to a graphene composite high-thermal-insulation fiber and a preparation method thereof, belonging to the technical field of novel functional polymer materials, in particular to a graphene high-thermal-insulation fiber and a preparation method thereof.

Background

Graphene is a single-layer carbon atom material stripped from graphite, and a single-layer two-dimensional honeycomb lattice structure is formed by tightly packing carbon atoms, and is known to be the material with the thinnest thickness, the hardest texture and the best conductivity. Graphene has excellent mechanical, optical and electrical properties and a very stable structure, researchers have not found that graphene has a missing carbon atom, the linkage between carbon atoms is very flexible, and is harder than diamond, the strength is 100 times higher than that of the world's best steel, if graphene is used for making a packaging bag, the graphene can bear about two tons of articles, the graphene is almost completely transparent, but is very compact, waterproof and airtight, helium gas with the minimum atomic size cannot pass through the graphene, the graphene has good conductivity, the movement speed of electrons in graphene reaches 1/300 of the light speed, the conductivity exceeds that of any traditional conductive material, the chemical properties are similar to the surface of graphite, various atoms and molecules can be adsorbed and desorbed, and the graphene also has the capability of resisting strong acid and strong alkali.

The heat preservation is a scientific and efficient energy-saving technical measure, and can slow down the heat dissipation and conduction speed. Good heat preservation technology and materials are adopted in industry and buildings, and the effect of achieving twice the result with half the effort can be achieved. The traditional heat-insulating material is mainly used for improving gas phase void ratio and reducing heat conductivity coefficient and conduction coefficient. The fiber heat-insulating material needs a thicker coating layer to increase the convective heat transfer and the radiant heat transfer in the use environment; the section inorganic heat-insulating material needs to be assembled and constructed, and has the defects of more seams, attractive appearance, poor waterproofness, short service life and the like.

Meanwhile, the heat preservation in the living field is also of great significance. Since temperature has a great role in maintaining the health of the human body, preventing and treating diseases, heat preservation has been one of the most important and basic functions of clothes. How to effectively strengthen the heat preservation function of the fabric without influencing the comfort level is always a major subject in the fields of textile, clothing and the like.

Disclosure of Invention

The invention aims to provide a graphene nylon high-heat-insulation fiber and a preparation method thereof.

In order to achieve the above object, the present invention provides a method for preparing graphene high thermal insulation fibers, wherein the method comprises: step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, modifiers, silicon dioxide and aqueous slurry; step 2, adding silicon dioxide, a part of graphene materials and a modifier into distilled water, heating and performing ultrasonic dispersion to prepare a graphene-silicon dioxide dispersion liquid; step 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder in an inert gas atmosphere to prepare graphene-silicon dioxide aerogel microspheres; step 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon slices, adding the mixture into a double-screw extruder, and extruding and granulating to obtain graphene aerogel nylon composite master batches; step 5, drying the master batch obtained in the step 4, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and then spinning the master batch into bundles to obtain the graphene aerogel polyamide composite fiber; step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution to finish etching treatment on the surfaces of the fibers; and 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, preparing coating slurry, keeping the temperature of the slurry, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment, and finally drying and winding to obtain the graphene high-heat-insulation composite fiber.

In the step 1, the raw materials include, by mass, 70% -99% of nylon chips, 0.1% -15% of graphene materials, 0.1% -1% of modifiers, 0.1% -1% of silicon dioxide, and 0.1% -15% of aqueous slurry.

In the preparation method of the graphene high-thermal-insulation fiber, the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and a redox method; the modifier is one or more of polyvinyl alcohol, hydroxymethyl cellulose, polyvinylpyrrolidone and silane coupling agent; the water-based sizing agent is any one or more of water-based PU resin, water-based acrylic resin, water-based polyester resin, water-based epoxy resin and water-based alkyd resin.

In the step 2, silicon dioxide, a part of graphene material and a modifier are added into distilled water, heated to 30-60 ℃, and ultrasonically dispersed for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of the graphene in the dispersion liquid is 1-5% by mass percent.

In the step 3, the graphene-silica powder is heated to 500-1000 ℃ in an inert gas atmosphere, and the graphene-silica aerogel microspheres are prepared by high-temperature treatment.

In the step 4, the temperatures from the first zone to the fifth zone of the twin-screw extruder are respectively 210-.

In the step 5, the master batch is dried at the drying temperature of 50-100 ℃, the water content of the dried master batch is lower than 100ppm, then the dried master batch is added into a screw extruder for heating and melting, and is filtered by a spinning manifold and spun into bundles at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500 m/min.

In the step 6, the graphene aerogel nylon composite fiber is immersed in an acid solution and treated at 40-60 ℃ for 20-30 min; the acid solution is obtained by dissolving 0.1 to 1 percent of acid reagent in deionized water according to the mass percentage and uniformly mixing; the acidic reagent comprises any one or more of hydrochloric acid, sulfuric acid, nitric acid, and strong protonic acid.

In the step 7, the remaining graphene material, the modifier and the aerogel microspheres are added into the aqueous slurry, fully stirred for 30-60min to prepare the coating slurry, the temperature of the slurry is kept at 30-60 ℃, then the modified graphene nylon fiber is placed into a continuous slurry tank, sizing treatment is carried out for 5-10s, and finally drying and winding are carried out.

The invention also provides the graphene high-thermal-insulation fiber prepared by the method.

The graphene high-thermal-insulation fiber and the preparation method thereof provided by the invention have the following advantages:

the graphene aerogel high-heat-preservation composite polyamide fiber prepared by the invention has more pores, so that the thermal conductivity of the fiber is greatly reduced, the pores in the fiber can effectively improve the content of static air, reduce the air flow around the fiber and further reduce the heat loss, and meanwhile, the bright infrared function of the graphene enables the fiber to absorb and release far infrared rays, so that the high heat-preservation property of the fiber is improved. And the aerogel water-based slurry is coated on the surface of the graphene nylon fiber, so that the heat conductivity coefficient of the surface of the fiber is effectively reduced, the heat loss is reduced, and the heat dissipation speed is reduced, therefore, the high heat insulation performance of the graphene aerogel high-heat-insulation composite fiber is greatly improved, the graphene antibacterial function can be exerted, and the human health is protected.

The graphene high-heat-insulation composite fiber prepared by the melting method has excellent high heat-insulation performance, and also has the functions of antibiosis, far infrared and the like, so that the wearing comfort of the composite fiber on outdoor sports clothes, winter underwear and other clothes is improved. The antibacterial property of the fiber is also very excellent, wherein the antibacterial rate of escherichia coli, staphylococcus aureus and candida albicans reaches 99.9%, the mite inhibition rate is more than 90%, the far infrared temperature rise reaches 0.88, and the functionality is good.

The fusion method graphene high-thermal-insulation composite fiber prepared by the method has the advantages of simple process, easy operation, low cost and high economic benefit, and is suitable for large-scale industrial production.

Detailed Description

The following further describes embodiments of the present invention.

The invention provides a preparation method of graphene high-thermal-insulation fibers, which comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, modifiers, silicon dioxide and aqueous slurry; step 2, preparing a dispersion liquid: adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating and performing ultrasonic dispersion to prepare a graphene-silicon dioxide dispersion liquid; step 3, preparation of aerogel microspheres: spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifying agent on the receiver to form graphene-silicon dioxide micro-beads, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder in an inert gas atmosphere to prepare graphene-silicon dioxide aerogel microspheres; step 4, preparing the composite master batch: uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step (3) with nylon slices, adding the mixture into a double-screw extruder, and extruding and granulating to obtain graphene aerogel nylon composite master batches; step 5, spinning: drying the master batch obtained in the step 4, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and then spinning the master batch into bundles to obtain the graphene aerogel polyamide composite fiber; step 6, modifying the surface of the graphene polyamide fiber: soaking the graphene aerogel polyamide composite fiber obtained in the step 5 into an acid solution to finish etching treatment on the surface of the fiber, increasing the surface roughness of the fiber and improving the interface strength between the slurry and the surface of the fiber; step 7, coating the surface of the fiber: and (3) adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, preparing coating slurry, keeping the temperature of the slurry, placing the modified graphene polyamide fiber obtained in the step (6) into a slurry tank, performing sizing treatment, and finally drying and winding to obtain the graphene high-heat-insulation composite fiber.

Preferably, the raw materials in the step 1 comprise, by mass, 70-99% of nylon chips, 0.1-15% of graphene materials, 0.1-1% of modifiers, 0.1-1% of silicon dioxide and 0.1-15% of aqueous slurry.

The silicon dioxide is nano-grade superfine silicon dioxide powder, and the average particle size ranges from 1 nm to 100 nm.

The graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and a redox method.

The modifier is one or more of polyvinyl alcohol, hydroxymethyl cellulose, polyvinylpyrrolidone (PVP), silane coupling agent, etc.

The water-based slurry is one or more of water-based PU resin (polyurethane), water-based acrylic resin, water-based polyester resin, water-based epoxy resin, water-based alkyd resin and the like.

In the step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion solution; the content of the graphene in the dispersion liquid is 1-5% by mass percent.

In the step 3, the graphene-silicon dioxide powder is heated to 500-1000 ℃ in an inert gas atmosphere, and the graphene-silicon dioxide aerogel microspheres are prepared by high-temperature treatment.

In step 4, the temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And step 5, drying the master batch at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, then adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box body, and spinning into bundles at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500 m/min.

Step 6, immersing the graphene aerogel chinlon composite fiber into an acid solution, and treating for 20-30min at 40-60 ℃; the acid solution is obtained by dissolving 0.1 to 1 percent of acid reagent in deionized water according to the mass percentage and uniformly mixing; the acidic reagent comprises any one or more of hydrochloric acid, sulfuric acid, nitric acid, and strong protonic acid.

And step 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene nylon fiber into a continuous slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding.

The equipment used in the present invention is known to those skilled in the art.

The invention also provides the graphene high-thermal-insulation fiber prepared by the method.

The graphene high thermal insulation fiber and the preparation method thereof provided by the invention are further described below with reference to the embodiments.

Example 1

A preparation method of graphene high thermal insulation fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, a modifier, silicon dioxide and water-based slurry.

Preferably, the raw materials comprise, by mass, 99% of nylon chips, 0.1% of graphene materials, 0.1% of modifiers, 0.1% of silicon dioxide and 0.7% of aqueous slurry.

The graphene material is prepared by a mechanical stripping method.

The modifier is polyvinyl alcohol.

The aqueous sizing agent is aqueous PU resin.

Step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of graphene in the dispersion liquid is 1% by mass.

And 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder to 500-1000 ℃ in an inert gas atmosphere to obtain the graphene-silicon dioxide aerogel microspheres through high-temperature treatment.

And 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon chips, adding the mixture into a double-screw extruder, and extruding and granulating to obtain the graphene aerogel nylon composite master batch. The temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And 5, drying the master batch obtained in the step 4 at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and spinning the master batch into a bundle at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500m/min to obtain the graphene aerogel nylon composite fiber.

Step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution, and treating for 20-30min at the temperature of 40-60 ℃; and finishing etching treatment on the surface of the fiber.

The acid solution is obtained by dissolving 0.1 percent of acid reagent in deionized water according to mass percentage and mixing evenly.

The acidic reagent comprises hydrochloric acid.

And 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding to obtain the graphene high-heat-preservation composite fiber.

The embodiment also provides the graphene high-thermal-insulation fiber prepared by the method.

Example 2

A preparation method of graphene high thermal insulation fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, a modifier, silicon dioxide and water-based slurry.

Preferably, the raw materials comprise, by mass, 90.7% of nylon chips, 3% of graphene materials, 0.3% of modifiers, 1% of silicon dioxide and 5% of aqueous slurry.

The graphene material is graphene oxide prepared by a mechanical stripping method.

The modifier is any one of polyvinyl alcohol, hydroxymethyl cellulose, polyvinylpyrrolidone and silane coupling agent.

The water-based slurry is any one of water-based PU resin, water-based acrylic resin, water-based polyester resin, water-based epoxy resin and water-based alkyd resin.

Step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of graphene in the dispersion liquid was 1.5% by mass.

And 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder to 500-1000 ℃ in an inert gas atmosphere to obtain the graphene-silicon dioxide aerogel microspheres through high-temperature treatment.

And 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon chips, adding the mixture into a double-screw extruder, and extruding and granulating to obtain the graphene aerogel nylon composite master batch. The temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And 5, drying the master batch obtained in the step 4 at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and spinning the master batch into a bundle at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500m/min to obtain the graphene aerogel nylon composite fiber.

Step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution, and treating for 20-30min at the temperature of 40-60 ℃; and finishing etching treatment on the surface of the fiber.

The acid solution is obtained by dissolving 0.2 percent of acid reagent in deionized water according to mass percentage and mixing evenly.

The acidic reagent comprises hydrochloric acid.

And 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding to obtain the graphene high-heat-preservation composite fiber.

The embodiment also provides the graphene high-thermal-insulation fiber prepared by the method.

Example 3

A preparation method of graphene high thermal insulation fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, a modifier, silicon dioxide and water-based slurry.

Preferably, the raw materials comprise 94.5% of nylon chips, 5% of graphene materials, 0.2% of modifiers, 0.2% of silicon dioxide and 0.1% of aqueous slurry in percentage by mass.

The graphene material is prepared by a chemical vapor deposition method.

The modifier is hydroxymethyl cellulose.

The aqueous sizing agent is aqueous acrylic resin.

Step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of graphene in the dispersion liquid is 2% by mass.

And 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder to 500-1000 ℃ in an inert gas atmosphere to obtain the graphene-silicon dioxide aerogel microspheres through high-temperature treatment.

And 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon chips, adding the mixture into a double-screw extruder, and extruding and granulating to obtain the graphene aerogel nylon composite master batch. The temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And 5, drying the master batch obtained in the step 4 at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and spinning the master batch into a bundle at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500m/min to obtain the graphene aerogel nylon composite fiber.

Step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution, and treating for 20-30min at the temperature of 40-60 ℃; and finishing etching treatment on the surface of the fiber.

The acid solution is obtained by dissolving 0.3 percent of acid reagent in deionized water according to mass percentage and mixing evenly.

The acidic reagent comprises sulfuric acid.

And 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding to obtain the graphene high-heat-preservation composite fiber.

The embodiment also provides the graphene high-thermal-insulation fiber prepared by the method.

Example 4

A preparation method of graphene high thermal insulation fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, a modifier, silicon dioxide and water-based slurry.

Preferably, the raw materials comprise, by mass, 74% of nylon chips, 10% of graphene materials, 0.5% of modifiers, 0.5% of silicon dioxide and 15% of aqueous slurry.

The graphene material is graphene oxide prepared by a chemical vapor deposition method.

The modifier is polyvinylpyrrolidone.

The aqueous sizing agent is aqueous polyester resin.

Step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of graphene in the dispersion liquid was 3% by mass.

And 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder to 500-1000 ℃ in an inert gas atmosphere to obtain the graphene-silicon dioxide aerogel microspheres through high-temperature treatment.

And 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon chips, adding the mixture into a double-screw extruder, and extruding and granulating to obtain the graphene aerogel nylon composite master batch. The temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And 5, drying the master batch obtained in the step 4 at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and spinning the master batch into a bundle at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500m/min to obtain the graphene aerogel nylon composite fiber.

Step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution, and treating for 20-30min at the temperature of 40-60 ℃; and finishing etching treatment on the surface of the fiber.

The acid solution is obtained by dissolving 0.5 percent of acid reagent in deionized water according to mass percentage and mixing evenly.

The acidic reagent comprises nitric acid.

And 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding to obtain the graphene high-heat-preservation composite fiber.

The embodiment also provides the graphene high-thermal-insulation fiber prepared by the method.

Example 5

A preparation method of graphene high thermal insulation fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, a modifier, silicon dioxide and water-based slurry.

Preferably, the raw materials comprise 73.8% of nylon chips, 12% of graphene materials, 0.6% of modifiers, 0.6% of silicon dioxide and 13% of aqueous slurry in percentage by mass.

The graphene material is prepared by a redox method.

The modifier is a silane coupling agent.

The water-based slurry is water-based epoxy resin or water-based alkyd resin.

Step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of graphene in the dispersion liquid was 4% by mass.

And 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder to 500-1000 ℃ in an inert gas atmosphere to obtain the graphene-silicon dioxide aerogel microspheres through high-temperature treatment.

And 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon chips, adding the mixture into a double-screw extruder, and extruding and granulating to obtain the graphene aerogel nylon composite master batch. The temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And 5, drying the master batch obtained in the step 4 at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and spinning the master batch into a bundle at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500m/min to obtain the graphene aerogel nylon composite fiber.

Step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution, and treating for 20-30min at the temperature of 40-60 ℃; and finishing etching treatment on the surface of the fiber.

The acid solution is obtained by dissolving 0.8 percent of acid reagent in deionized water according to mass percentage and mixing evenly.

The acidic agent comprises a strong protic acid.

And 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding to obtain the graphene high-heat-preservation composite fiber.

The embodiment also provides the graphene high-thermal-insulation fiber prepared by the method.

Example 6

A preparation method of graphene high thermal insulation fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, a modifier, silicon dioxide and water-based slurry.

Preferably, the raw materials comprise, by mass, 70% of nylon chips, 15% of graphene materials, 1% of modifiers, 0.5% of silicon dioxide and 13.5% of aqueous slurry.

The graphene material is graphene oxide prepared by a redox method.

The modifier is any of polyvinyl alcohol, hydroxymethyl cellulose, polyvinylpyrrolidone and silane coupling agent.

The water-based sizing agent is any of water-based PU resin, water-based acrylic resin, water-based polyester resin, water-based epoxy resin and water-based alkyd resin.

Step 2, adding silicon dioxide, a part of graphene material and a modifier into distilled water, heating to 30-60 ℃, and performing ultrasonic dispersion for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of graphene in the dispersion liquid is 5% by mass.

And 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder to 500-1000 ℃ in an inert gas atmosphere to obtain the graphene-silicon dioxide aerogel microspheres through high-temperature treatment.

And 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon chips, adding the mixture into a double-screw extruder, and extruding and granulating to obtain the graphene aerogel nylon composite master batch. The temperatures from the first zone to the fifth zone of the double-screw extruder are respectively 210-.

And 5, drying the master batch obtained in the step 4 at the drying temperature of 50-100 ℃, wherein the water content of the dried master batch is lower than 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and spinning the master batch into a bundle at the spinning temperature of 250-280 ℃ and the spinning speed of 500-1500m/min to obtain the graphene aerogel nylon composite fiber.

Step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution, and treating for 20-30min at the temperature of 40-60 ℃; and finishing etching treatment on the surface of the fiber.

The acid solution is obtained by dissolving 1 percent of acid reagent in deionized water according to mass percentage and uniformly mixing.

The acidic agent comprises any of hydrochloric acid, sulfuric acid, nitric acid, and strong protonic acid.

And 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, fully stirring for 30-60min to prepare coating slurry, keeping the temperature of the slurry at 30-60 ℃, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment for 5-10s, and finally drying and winding to obtain the graphene high-heat-preservation composite fiber.

The embodiment also provides the graphene high-thermal-insulation fiber prepared by the method.

The finished products from the examples were tested for functionality and the results are shown in table 1 below.

TABLE 1 test results.

According to the graphene high-thermal-insulation fiber and the preparation method thereof, the graphene aerogel microspheres are preferentially prepared, then the graphene aerogel microspheres are added into nylon chips to prepare the graphene nylon composite master batch, and finally the modified graphene high-thermal-insulation composite fiber is prepared through melt spinning. The invention aims to develop a graphene nylon high-thermal-insulation fiber by utilizing a modified graphene dispersion system, an aerogel sphere preparation technology and a slurry coating technology, wherein a graphene aerogel microsphere is compounded in the fiber, so that the fiber is rich in a microporous structure, more still air can be stored in the fiber, the air flow and the thermal conductivity of the fiber are reduced, graphene has antibacterial and far infrared effects, the high-thermal-insulation characteristic is better exerted, the graphene aerogel microsphere in the graphene composite high-thermal-insulation fiber is uniformly dispersed and is not easy to fall off, and the functionality has durability.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.

Claims (10)

1. A preparation method of graphene high thermal insulation fibers is characterized by comprising the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise nylon chips, graphene materials, modifiers, silicon dioxide and aqueous slurry;

step 2, adding silicon dioxide, a part of graphene materials and a modifier into distilled water, heating and performing ultrasonic dispersion to prepare a graphene-silicon dioxide dispersion liquid;

step 3, spraying the graphene-silicon dioxide dispersion liquid obtained in the step 2 on a receiver through an ultrasonic spraying device, coating a modifier on the receiver to form graphene-silicon dioxide microspheres, then preparing graphene-silicon dioxide powder through freeze drying, and finally heating the powder in an inert gas atmosphere to prepare graphene-silicon dioxide aerogel microspheres;

step 4, uniformly mixing part of the graphene-silicon dioxide aerogel microspheres obtained in the step 3 with nylon slices, adding the mixture into a double-screw extruder, and extruding and granulating to obtain graphene aerogel nylon composite master batches;

step 5, drying the master batch obtained in the step 4, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and then spinning the master batch into bundles to obtain the graphene aerogel polyamide composite fiber;

step 6, immersing the graphene aerogel polyamide composite fibers obtained in the step 5 into an acid solution to finish etching treatment on the surfaces of the fibers;

and 7, adding the rest graphene material, the modifier and the aerogel microspheres into the aqueous slurry, preparing coating slurry, keeping the temperature of the slurry, then placing the modified graphene polyamide fiber obtained in the step 6 into a slurry tank, carrying out sizing treatment, and finally drying and winding to obtain the graphene high-heat-insulation composite fiber.

2. The preparation method of the graphene high thermal insulation fiber according to claim 1, wherein in the step 1, the raw materials comprise, by mass, 70% -99% of nylon chips, 0.1% -15% of graphene materials, 0.1% -1% of modifiers, 0.1% -1% of silicon dioxide, and 0.1% -15% of aqueous slurry.

3. The method for preparing the graphene high thermal insulation fiber according to claim 2, wherein the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and a redox method; the modifier is one or more of polyvinyl alcohol, hydroxymethyl cellulose, polyvinylpyrrolidone and silane coupling agent; the water-based sizing agent is any one or more of water-based PU resin, water-based acrylic resin, water-based polyester resin, water-based epoxy resin and water-based alkyd resin.

4. The preparation method of the graphene high thermal insulation fiber according to claim 1, wherein in the step 2, silicon dioxide, a part of graphene materials and a modifier are added into distilled water, heated to 30-60 ℃ and ultrasonically dispersed for 30-60min to prepare a graphene-silicon dioxide dispersion liquid; the content of the graphene in the dispersion liquid is 1-5% by mass percent.

5. The method for preparing graphene high thermal insulation fiber according to claim 1, wherein in the step 3, the graphene-silica powder is heated to 500-1000 ℃ in an inert gas atmosphere, and the graphene-silica aerogel microsphere is prepared by high temperature treatment.

6. The method for preparing the graphene high thermal insulation fiber as claimed in claim 1, wherein in the step 4, the temperatures from the first zone to the fifth zone of the twin-screw extruder are respectively 210-.

7. The method for preparing graphene high thermal insulation fiber according to claim 1, wherein in the step 5, the master batch is dried at a drying temperature of 50-100 ℃, the water content of the dried master batch is lower than 100ppm, and then the master batch is added into a screw extruder to be heated and melted, and is filtered by a spinning manifold to be spun into bundles, wherein the spinning temperature is 250-280 ℃, and the spinning speed is 500-1500 m/min.

8. The preparation method of the graphene high thermal insulation fiber according to claim 1, wherein in the step 6, the graphene aerogel nylon composite fiber is immersed in an acid solution and treated at 40-60 ℃ for 20-30 min; the acid solution is obtained by dissolving 0.1 to 1 percent of acid reagent in deionized water according to the mass percentage and uniformly mixing; the acidic reagent comprises any one or more of hydrochloric acid, sulfuric acid, nitric acid, and strong protonic acid.

9. The method for preparing the graphene high thermal insulation fiber according to claim 1, wherein in the step 7, the rest of the graphene material, the modifier and the aerogel microspheres are added into the aqueous slurry, fully stirred for 30-60min to prepare a coating slurry, the temperature of the slurry is kept at 30-60 ℃, then the modified graphene nylon fiber is placed into a continuous slurry tank, sizing treatment is carried out for 5-10s, and finally drying and winding are carried out.

10. A graphene high thermal insulation fiber prepared by the method of any one of claims 1 to 9.