CN112030269B - Special lasting electric heating self-heating composite functional fiber material for military police and preparation method and application thereof - Google Patents
Special lasting electric heating self-heating composite functional fiber material for military police and preparation method and application thereof Download PDFInfo
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- CN112030269B CN112030269B CN202010921487.2A CN202010921487A CN112030269B CN 112030269 B CN112030269 B CN 112030269B CN 202010921487 A CN202010921487 A CN 202010921487A CN 112030269 B CN112030269 B CN 112030269B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/002—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment
- A41D13/005—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment with controlled temperature
- A41D13/0051—Heated garments
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/06—Thermally protective, e.g. insulating
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2400/00—Functions or special features of garments
- A41D2400/10—Heat retention or warming
- A41D2400/12—Heat retention or warming using temperature-controlled means
Abstract
The invention provides a lasting electric heating self-heating composite functional fiber material special for military police, and a preparation method and application thereof.A stable graphene electric heating functional system is prepared by adopting a two-dimensional nano new material graphene as a main conductive functional material and fusing materials such as graphene nanosheets, graphene quantum dots and carbon nano tubes through high-pressure homogenization and ultrasonic treatment; the substrate is a ternary complex of cellulose acetate, polyurethane and polyacrylic acid, the flexibility is excellent, a pore structure can be formed on the skin layer after coaxial spinning and freeze drying, the moisture and heat penetrating performance is achieved, and the requirement for wearing comfort can be met.
Description
Technical Field
The invention belongs to the field of new material preparation, and particularly relates to a lasting electric heating self-heating composite functional fiber material special for military police, and a preparation method and application thereof.
Background
Warmth retention is one of the most basic requirements of human life, and the development of textile terminal products with electric heating functions is an important way for implementing a 'personal heat management' scheme. Especially, military police personnel in service at northwest edge defense and high mountains need extremely cold environment for a long time, are greatly tested for body health, and urgently need durable high-efficiency warm-keeping functional textiles, so that the development of the fiber material with the durable electrothermal self-heating composite function is of great significance.
At present, electric heating materials on the market are mainly metal resistance wires, but the metal resistance wires have the defects of low heat conversion efficiency, serious electromagnetic radiation, rigidity, inflexibility and the like, and are difficult to be used in the field of textiles.
Disclosure of Invention
The invention aims to provide a lasting electric heating and self-heating composite functional fiber material special for military police, which has a graphene fiber with a hollow structure and has the performances of electric heating, self-heating, high efficiency and lasting heat preservation.
The invention also aims to provide a preparation method of the lasting electric heating self-heating composite functional fiber material special for military police.
The last purpose of the invention is to provide application of the lasting electric heating self-heating composite functional fiber material special for military police, which is used for manufacturing flexible wearable graphene electric heating fabric and is used as far infrared electric heating intelligent clothes, medical health protection clothes, tapestry, steering wheel covers and other intelligent temperature control new products for the automobile industry and special clothes for military police.
The specific technical scheme of the invention is as follows:
a preparation method of a lasting electric heating self-heating composite functional fiber material special for military police comprises the following steps:
1) Under the condition of high-pressure homogenization, carrying out homogeneous dispersion on a graphene material, isomeric tridecanol polyoxyethylene ether phytate, ammonia water, sodium dodecyl benzene sulfonate and ultrapure water to prepare a graphene dispersion system;
2) Adding a polymer spinning solution into the graphene dispersion system, and dispersing and dissolving to obtain a graphene spinning solution;
3) Carrying out coaxial spinning, wherein the skin layer is graphene spinning solution, and the core layer is air or water component, so as to obtain nascent fiber;
4) And (3) soaking the nascent fiber to remove the solvent, freezing, and freeze-drying to obtain the graphene hollow fiber.
The high-pressure homogenization condition in the step 1) refers to 26000-35000psi high-pressure homogenization condition, and the homogenization and dispersion are carried out for 15-40min at normal temperature.
The graphene material in the step 1) is composed of one or more of graphene nanosheets, graphene quantum dots and carbon nanotubes. When only the graphene nanosheets are adopted, 5-7 layers of graphene nanosheets are adopted, and the thickness of the nanosheets is not higher than 60 nanometers, so that cost is saved.
Preferably, the graphene material is composed of graphene nanosheets, graphene quantum dots and carbon nanotubes in a mass ratio of 95-105. The thickness of the nanosheet is not higher than 60 nanometers, and the size of the graphene quantum dot is 15-25 nanometers; the carbon nano tube is a single-wall tube, and the size of the carbon nano tube is 5-15 nanometers.
The mass ratio of the graphene material, the isomeric tridecanol polyoxyethylene ether phytate, the ammonia water, the sodium dodecyl benzene sulfonate and the ultrapure water in the step 1) is as follows: 2-5; preferably 3.
The isomeric tridecanol polyoxyethylene ether phytate is prepared by an isomeric tridecanol polyoxyethylene ether direct phosphating method, and the specific preparation method comprises the following steps: sequentially adding phosphorus pentoxide and phytic acid into isomeric tridecanol polyoxyethylene ether, wherein the esterification temperature is 90 ℃, and the esterification time is 4 hours; adding distilled water with the same volume as the reaction system after esterification for hydrolysis at the hydrolysis temperature of 90 ℃ for 3 hours to obtain the product. Wherein, isomeric tridecanol polyoxyethylene ether: phosphorus pentoxide: the mol fraction ratio of the phytic acid is 2-4: 0.8-1.1; preferably 3: 1: 2.
In the esterification and hydrolysis processes, active multidentate phosphate groups of the phytic acid can be subjected to condensation reaction with hydroxyl groups to generate a 'tree-like' three-dimensional macromolecular compound. The invention selects the isotridecanol polyoxyethylene ether phytate to obtain the macromolecular penetrating agent, and increases the compatibility and the penetrating dispersibility with a spinning polymer system added subsequently. Meanwhile, the isomeric tridecanol polyoxyethylene ether phytate can be naturally degraded and is a chemical agent harmless to the environment.
The ammonia water with the volume concentration of 50% in the step 1) is used as a buffer system to adjust the pH value of the system; the system stability is increased;
in the step 1), sodium dodecyl benzene sulfonate is used as a surfactant, so that the sodium dodecyl benzene sulfonate has excellent acid and alkali resistance and stability, and the system stability can be improved. The effect of the sodium dodecyl benzene sulfonate adopted in the invention is better than that of other anionic surfactants.
Step 1) in order to solve the problems that a graphene system is difficult to disperse and easy to agglomerate and the like, the method disclosed by the invention integrates physical, chemical and physicochemical means to prepare the graphene homodisperse system. The physical effect is high-pressure homogenization; the chemistry is that the components such as a novel macromolecular osmotic dispersant with a tree structure are optimized and selected, so that the stability is ensured; the physical chemistry refers to the selection of a surfactant, so that the chemical energy of agglomeration is reduced, and the stability is improved.
In the step 2), the mass ratio of the graphene dispersion system to the polymer spinning solution is 1; the mass ratio is adjusted according to the functional attributes and indexes of the prepared fibers, the component proportion of the graphene is increased, and the electric heating effect is improved.
The polymer spinning solution in the step 2) is prepared by dissolving cellulose acetate, polyurethane and polyacrylic acid in N, N-dimethylacetamide. The mass ratio of the cellulose acetate to the polyurethane to the polyacrylic acid is 80-105: 13-16; preferably 100; the polymer dope has a solid content of 7 to 12%. The N, N-dimethylacetamide is the optimal solvent, has excellent dissolving performance on three components of cellulose acetate, polyurethane and polyacrylic acid, and has low toxicity; in addition, the solvent is easy to dissolve in water in the subsequent spinning process, so that the solvent is convenient to remove.
The dispersing and dissolving conditions in the step 2) are as follows: ultrasonic dispersion is carried out for 60-90min under the ultrasonic condition with the power of 30000-32000 Hz.
The step 3) is specifically as follows: and (3) respectively filling the graphene spinning solution serving as a skin layer solution and air serving as a core layer solution into different injectors, injecting at the same injection rate by using a micro injection pump, continuously wet-spinning the graphene spinning solution into a coagulating bath through an outer needle head and an inner needle head, and continuously collecting fibers to obtain nascent fibers.
Or, the step 3) is specifically: and respectively filling the graphene spinning solution serving as a skin layer solution and water serving as a core layer solution into different injectors, injecting at the same injection rate by using a micro injection pump, continuously wet-spinning the graphene spinning solution into a coagulating bath through an outer needle head and an inner needle head, and continuously collecting fibers to obtain nascent fibers. The core aqueous phase will escape from the micro-voids of the skin layer during subsequent freeze-drying.
Preferably, in step 3), the injection rate is 280-350. Mu.L.min -1 (ii) a Preferably 300. Mu.L/min -1 (ii) a The outer needle head is 17G, and the inner needle head is 23G; the coagulating bath is pure water.
And 4) soaking the obtained nascent fiber in pure water to remove the solvent DMAc, freezing, and freeze-drying to obtain the graphene hollow fiber, namely the lasting electric heating self-heating composite functional fiber material special for military police.
Further, in the step 4), the collected nascent fiber is put into pure water to be soaked for 3-4h, and the solvent DMAc is removed; the freezing is to freeze for 15-20h at the temperature of-25 ℃ to-20 ℃; the freeze drying refers to freeze drying at-60 deg.C to-50 deg.C for 2-3 days.
The invention provides a lasting electric heating self-heating composite functional fiber material special for military police, which is prepared by adopting the method.
The invention provides application of a lasting electric heating self-heating composite functional fiber material special for military police, which is used for manufacturing flexible wearable graphene electric heating clothes. The method is particularly suitable for manufacturing military and police clothes, far infrared electric heating intelligent clothes, medical and health protection clothes, tapestry, steering wheel covers and other intelligent temperature control new products for the automobile industry.
According to the invention, materials such as graphene nanosheets, graphene quantum dots and carbon nanotubes are fused in the developed fiber, so that the electric conduction and electric heating functions of the fiber are improved, the product is endowed with heat preservation durability, and the lasting heat preservation effect within 4 hours can be met after the fiber is electrified for 3 min. In addition, the substrate selected for the graphene fiber is a ternary complex of cellulose acetate, polyurethane and polyacrylic acid, so that the graphene fiber has excellent flexibility, and after coaxial spinning and freeze drying, the skin layer can form a pore structure, so that the graphene fiber has the moisture and heat penetrating performance and can meet the requirement of wearing comfort. According to the graphene fiber with the hollow structure, the hollow structure fiber has the advantages of heat preservation, light weight and the like, the electric heating property of the graphene is fused, the heat preservation performance of the product is obviously improved, and the graphene fiber is particularly suitable for outdoor operation in extremely cold areas.
Graphene as a two-dimensional carbon nanomaterial has excellent properties of electric conduction, heat conduction, electric heating, infrared radiation heating and the like. Meanwhile, the hollow structure fiber can retain a large amount of static air in the fiber structure, the air heat conduction coefficient is low, and the fiber has a high-efficiency warm-keeping effect. For this purpose. The method adopts a two-dimensional new nano material graphene as a main conductive functional material, and prepares a stable graphene electrothermal functional system by high-pressure homogenization and ultrasonic treatment and doping and fusing materials such as carbon nanotubes and the like; on the basis, the hollow fiber rich in the graphene component is prepared by adopting a coaxial wet spinning technology in combination with the heat preservation characteristic of the hollow fiber; the flexible wearable graphene electric heating fabric is formed by weaving, and the defects of high rigidity, low electric heating conversion efficiency, unsafe electricity consumption and the like of the traditional electric heating material are overcome. The far infrared electric heating intelligent clothing, the medical health care protective clothing, the tapestry, the steering wheel cover and other automobile industry intelligent temperature control new products are designed and developed based on the fabric, and the research and development technology and the products have wide application prospect and popularization value.
Drawings
Fig. 1 is a stability test of the graphene spinning solution prepared in example 1;
FIG. 2 is a rheological curve test representation of graphene spinning solutions with different mass ratios of graphene dispersion systems to polymer spinning solutions; 1-example 1, 2-example 2;
FIG. 3 is a schematic view of the spinning process of the present invention;
FIG. 4 is a schematic view of a drying and removing process of the present invention with water as the core layer;
FIG. 5 is an SEM representation of a graphene hollow fiber prepared according to the present invention;
FIG. 6 shows mechanical property test results of graphene hollow fibers of the present invention, wherein 1 represents example 1 and 2 represents example 2;
fig. 7 is a schematic diagram of a functional test of the graphene hollow fiber cyclic garment of the present invention.
Detailed Description
The invention comprises the following raw materials:
graphene nanoplatelets, graphene quantum dots, carbon nanotubes, ammonia water, cellulose acetate, polyurethane, polyacrylic acid, N-dimethylacetamide DMAc were purchased from shanghai mclin biochemical technologies, ltd.
Example 1
A preparation method of a lasting electric heating self-heating composite functional fiber material special for military police comprises the following steps:
1) Under the condition of 35000psi high-pressure homogenization, 3.0g of graphene nanosheet, graphene quantum dot and carbon nanotube composite powder, 1.5g of isotridecanol polyoxyethylene ether phytate, 0.5g of ammonia water, 0.3g of sodium dodecyl benzene sulfonate and 100g of ultrapure water are mixed according to the mass ratio of 100;
the thickness of the nano sheet is not higher than 60 nanometers, and the size of the graphene quantum dot is 15-25 nanometers; the carbon nano tube is a single-wall tube, and the size of the carbon nano tube is 5-15 nanometers.
The preparation method of the isomeric tridecanol polyoxyethylene ether phytate comprises the following steps: sequentially adding phosphorus pentoxide and phytic acid into isomeric tridecanol polyoxyethylene ether, wherein the esterification temperature is 90 ℃, and the esterification time is 4 hours; adding distilled water with the same volume for hydrolysis after esterification, wherein the hydrolysis temperature is 90 ℃, and the hydrolysis time is 3h. Wherein, isomeric tridecanol polyoxyethylene ether: phosphorus pentoxide: the mol fraction ratio of the phytic acid is 3: 1: 2.
2) Cellulose acetate with a mass of 100: polyurethane: placing the polyacrylic acid ternary complex in N, N-dimethylacetamide (DMAc) to prepare a polymer spinning solution with a solid content of 10%; adding a polymer spinning solution into the graphene dispersion system, and dispersing and dissolving for 60min under the 32000Hz ultrasonic wave condition to obtain the graphene spinning solution, wherein the mass ratio of the graphene dispersion system to the polymer spinning solution is 1:20; performing rheological curve test characterization on the obtained graphene spinning solution, wherein the result is shown in figure 2;
3) Preparing a hollow graphene fiber based on coaxial spinning, wherein a skin layer is a graphene spinning solution, and the graphene spinning solution is spun through an outer shaft to construct a fiber skin layer; the core layer is composed of air or distilled water, the outer needle is 17G, the inner needle is 23G, when the core layer is composed of distilled water, the water volatilizes to form a hollow structure in the spinning post-treatment process, the spinning process is shown as figure 3, and the drying and removing process is shown as figure 4 when the core layer is water.
The specific spinning process operation is as follows: the graphene spinning solution as a skin layer solution and pure water as a core layer solution were respectively filled into two 50mL syringes, and a ZS1001 type micro syringe pump was used at the same injection rate of 300. Mu.L.min -1 And continuously wet-spinning the fiber into a pure water coagulation bath through an outer needle 17G and an inner needle 23G at a fiber spinning speed of 2.0 m.min -1 Continuously collecting the mixture at the linear speed of the collecting device;
4) Soaking the collected nascent fiber in pure water for 3h to remove a solvent DMAc, freezing the nascent fiber in an environment of-20 ℃ for 15h, and then carrying out freeze drying by an LGJ-10 vacuum freeze dryer at-50 ℃ for 2d to prepare the graphene hollow fiber, namely the lasting electric heating self-heating composite functional fiber material special for military police.
The stability of the graphene spinning solution prepared in the step 2) is tested, and as shown in fig. 1, the graphene spinning solution has no phenomena of layering, agglomeration and the like within 2 hours, which shows that the graphene spinning solution has a good dispersion and homogenization effect.
SEM characterization of the graphene hollow fibers prepared in example 1 is shown in FIG. 5, with fiber diameters ranging from 500 to 800 microns.
Example 2
A preparation method of a lasting electric heating self-heating composite functional fiber material special for military police changes the mass ratio of a graphene dispersion system to a polymer spinning solution in the step 2) in the embodiment 1 into 1:50, the other examples are the same as example 1.
The obtained graphene spinning solution prepared in example 2 is characterized by a rheological curve test, as shown in fig. 2.
As can be obtained from figure 2, the spinning solution has a shear thinning phenomenon at the beginning of stress, but after the stress is stable, the viscosity is kept stable and is not changed by the change of the shear speed, so the spinning process parameters are easy to control.
The rheological curve test characterizes the detection conditions as follows: in thatTesting the rheological property by using an RST type rheometer at normal temperature; wherein the selected rotor is RCT-75-1 plate type rotor with diameter of 75mm, the clearance with the test platform is 0.046mm, and the shear rate is set to be 0-800 s -1 The test temperature was 20 ℃.
The mechanical properties of the hollow fibers prepared in examples 1 and 2 were measured using an Instron 5543 universal tester with standard distance and draw rate set at 20mm and 1mm min, respectively -1 . The samples to be tested, which are 5cm in length, are coated with epoxy adhesive at both ends, respectively, to protect them from damage during clamping. The different fiber samples were tested at least 5 times and the tensile strength, young's modulus and elongation at break were recorded and averaged together with the standard deviation. The results are shown in FIG. 6.
As can be obtained from fig. 6, the graphene hollow fibers prepared by the invention all show typical plastic deformation stress-strain curves under tensile load, and have elongation at break of 10.1 ± 1.3% and 9.2 ± 0.8%, respectively, and have good elasticity; meanwhile, the tensile strength of the fiber is 2.6 +/-0.4 MPa and 2.2 +/-0.2 MPa respectively, and the fiber can meet the requirements of textile clothing. In addition, the content of the graphene dispersion system in the embodiment 1 is higher than that in the embodiment 2, the elasticity is higher mainly due to the fact that the content of the graphene dispersion system is high, meanwhile, the content of the isomeric tridecanol polyoxyethylene ether phytate is correspondingly improved, and due to the 'tree-shaped' three-dimensional macromolecular structure of the isomeric tridecanol polyoxyethylene ether phytate, the uniformity and the integrity of the dispersion system are improved, and the fiber elasticity is further improved.
The electric heating performance of the graphene hollow fiber prepared in the example 1 is tested according to EN61255:1994 standard, and the results are as follows:
the hollow graphene fibers have a resistivity of 1.20-1.35m Ω cm;
the hollow graphene fiber can rapidly heat within 3-5 seconds at a low voltage of 5V; electrifying for 3min, increasing the temperature from room temperature to 65 ℃, and after powering off for 4h, keeping the temperature above 36 ℃.
The surface temperature of the fiber bundle is increased by 5.8-6.5 ℃ by radiating for 30s by a 150w ceramic infrared source, and the fiber bundle has the function of infrared radiation temperature rise (self-heating);
the circulating taking function is tested at the same time:
weaving the prepared hollow graphene fiber into a fiber sheet, and testing the heat preservation and heat insulation performance of the fiber sheet, wherein the specific operation is as follows:
firstly, 20 unidirectional fibers with the length of 5cm are closely arranged into a fiber layer to construct a representative test sample, and commercial conventional fabrics made of cotton, wool, terylene and the like are used for comparison (the thickness of the selected comparison fabrics is about 1.0mm, and the thickness of the selected comparison fabrics is the same as or similar to that of a fiber sheet woven by the hollow graphene fiber prepared by the method provided by the invention). The sample was placed on a hot plate and the sample surface temperature was measured as the hot plate rose from 28 ℃ to 100 ℃ using a thermocouple connected to a temperature controller.
When the heater plate temperature was increased from 28 ℃ to 100 ℃, all sample surfaces were heated but with different response rates and temperatures, indicating that they had different thermal insulation properties. Compared with the commercial conventional fabrics made of all cotton, wool, terylene and the like, the heat transfer rate of the hollow graphene fiber is minimum, when the temperature of the heating plate reaches the equilibrium temperature (100 ℃), the surface temperature is minimum, and the temperature of a fiber sheet woven by 1 layer of hollow graphene fiber is only 73 ℃. In addition, the dynamic temperature change of the graphene hollow fiber during the heating-cooling cycle is also tested, although the temperature of the heating plate is cycled between 28 and 100 ℃, the surface temperature of the hollow fiber is only cycled between 26 and 73 ℃, and the temperature range is much narrower, which further proves that the hollow fiber has excellent heat preservation and insulation performance.
For simulating cold environment, the hollow graphene fiber is woven into a fiber sheet and is placed on a metal plate as a sample to be tested, dry ice with the thickness of about 2.5cm is placed below the metal plate, and a thermocouple is used for monitoring and recording the surface temperature of the sample, and the method specifically comprises the following steps:
dry ice having a thickness of 2.5cm was placed under the metal plate. At the same time, the T of the fiber surface at a metal substrate temperature (Ts) of-20 ℃ to 20 ℃ was measured f And calculates its corresponding absolute temperature difference | Δ T |. Wherein when Ts is-20 ℃, the | Delta T | of the 1-layer graphene hollow fiber sheet is 7.7 ℃, which proves that the graphene hollow fiber sheet has better performance in cold environmentHeat preservation and insulation performance. In addition, the heat insulating properties of the fiber sheets woven with 2-layer, 3-layer, 4-layer and 5-layer hollow graphene fibers were respectively tested, with the result that | Δ T | reached 10.8 ℃ when 5 layers were used as the number of layers increased.
The detection process is schematically shown in fig. 7. The invention calculates the corresponding absolute temperature difference (| delta T |) between the surface of the fiber and a heat source or a cold source to represent the heat preservation and insulation performance of the fiber. During the measurement, the ambient temperature was about 23 ℃, and the temperature value was recorded when the fiber surface temperature was stable.
In conclusion, the graphene hollow fiber mat prepared by the method shows excellent heat preservation and heat insulation performance in hot and cold environments.
The reason that the graphene hollow fiber prepared by the invention has the advantages of electric heating, self-heating and high-efficiency and lasting heat preservation is mainly as follows: the functional component mainly containing graphene has electrothermal property, and can generate heat after being electrified, which is the source of electrothermal electricity; the self-heating function is due to the fact that the nano material represented by graphene can absorb infrared radiation with the wavelength of 7-14 mu m existing in nature, and simultaneously absorb infrared radiation released outwards by a human body, and the energy is reflected to the human body to achieve the purposes of heat storage and warm keeping; the hollow structure reserves a large amount of static air, has low heat conductivity coefficient, can keep the warm-keeping effect for a long time, and has durability.
Claims (8)
1. A preparation method of a lasting electric heating self-heating composite functional fiber material special for military police is characterized by comprising the following steps:
1) Under the condition of high-pressure homogenization, carrying out homogeneous dispersion on a graphene material, isomeric tridecanol polyoxyethylene ether phytate, ammonia water, sodium dodecyl benzene sulfonate and ultrapure water to prepare a graphene dispersion system;
2) Adding a polymer spinning solution into the graphene dispersion system, and dispersing and dissolving to obtain a graphene spinning solution;
3) Carrying out coaxial spinning, wherein the skin layer is graphene spinning solution, and the core layer is air or water component, so as to obtain nascent fiber;
4) Soaking the nascent fiber to remove the solvent, freezing, and freeze-drying to obtain the graphene hollow fiber;
the mass ratio of the graphene material, the isomeric tridecanol polyoxyethylene ether phytate, the ammonia water, the sodium dodecyl benzene sulfonate and the ultrapure water in the step 1) is as follows: 2-5;
the polymer spinning solution in the step 2) is prepared by dissolving cellulose acetate, polyurethane and polyacrylic acid in N, N-dimethylacetamide, wherein the mass ratio of the cellulose acetate, the polyurethane and the polyacrylic acid is 80-105:13-16, and the solid content of the polymer spinning solution is 7-12%.
2. The method according to claim 1, wherein the high-pressure homogenization conditions in step 1) are 26000-35000psi, and the homogenization dispersion is carried out at room temperature for 15-40min.
3. The preparation method of claim 1, wherein the graphene material in step 1) is composed of one or more of graphene nanosheets, graphene quantum dots and carbon nanotubes.
4. The preparation method according to claim 1 or 3, wherein the graphene material is composed of graphene nanoplatelets, graphene quantum dots and carbon nanotubes in a mass ratio of 95-105.
5. The preparation method according to claim 1, wherein the mass ratio of the graphene dispersion system to the polymer spinning solution in the step 2) is 1.
6. The method according to claim 1, wherein the dispersion and dissolution conditions in step 2) are: ultrasonic dispersion is carried out for 60-90min under the ultrasonic condition with the power of 30000-32000 Hz.
7. A durable electrothermal self-heating composite functional fiber material prepared by the preparation method of any one of claims 1 to 6.
8. The application of the durable electrothermal self-heating composite functional fiber material prepared by the preparation method of any one of claims 1 to 6 in manufacturing flexible wearable graphene electrothermal clothes.
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