CN113150530B - Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof - Google Patents

Abstract

The invention provides a polypyrrole-zirconium carbide-polyurethane composite film and a preparation method and application thereof, the composite film comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane; the preparation method comprises: mixing pyrrole and bis( Lithium trifluoromethylsulfonyl)imide was dissolved in deionized water and stirred, an oxidant was added, and polypyrrole was dispersed in dimethylformamide to obtain a polypyrrole dispersion; zirconium carbide was dispersed in dimethylformamide obtaining a zirconium carbide dispersion; dissolving the polyurethane and the porogen in dimethylformamide to obtain a polyurethane solution; adding the polypyrrole dispersion and the zirconium carbide dispersion into the polyurethane solution and stirring to obtain a mixed stock solution; passing the mixed stock solution through wet The film forming process can be used; by using the wet film forming technology, a thin and uniform film can be made, which can be directly used as a material for clothing design to improve the thermal insulation performance of clothing and provide more choices for the selection of thermal fabrics in autumn and winter.

Description

Polypyrrole-zirconium carbide-polyurethane composite film and its preparation method and application

technical field

The invention belongs to the technical field of composite films, and in particular relates to a polypyrrole-zirconium carbide-polyurethane composite film and a preparation method and application thereof.

Background technique

In winter, down jackets can only maintain the basic heat for people to survive. Insulation based on equipment such as air conditioning and heating is another strategy for people to cope with cold climates to maintain a constant body temperature and normal activities. However, the use of air conditioning and heating will bring serious environmental hazards, such as the ozone layer hole, greenhouse effect and so on. Therefore, in order to reduce the use of air conditioning and heating, textiles with better thermal insulation function have certain development prospects.

Polypyrrole is a semiconductor material with both photothermal and electrothermal conversion functions. Although polypyrrole can absorb light and generate heat, polypyrrole mainly absorbs light energy in the near-infrared band. Zirconium carbide is a transition metal carbide with excellent photothermal conversion function, which can not only absorb light energy in the visible light band, but also absorb light energy in the near-infrared band. At present, there are few reports on combining the two materials to develop membrane materials with both electrothermal and photothermal conversion functions.

SUMMARY OF THE INVENTION

In view of the deficiencies in the prior art, the primary purpose of the present invention is to provide a polypyrrole-zirconium carbide-polyurethane composite film.

The second object of the present invention is to provide a method for preparing the above-mentioned polypyrrole-zirconium carbide-polyurethane composite film.

The third object of the present invention is to provide the application of the above-mentioned polypyrrole-zirconium carbide-polyurethane composite film.

In order to achieve the above-mentioned primary purpose, the solution of the present invention is:

A polypyrrole-zirconium carbide-polyurethane composite film, which comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane, the content of the polyurethane is 80-99.9wt%, and the content of the polypyrrole and the zirconium carbide particles is 0.1- 20wt%.

Among them, after the polyurethane film is formed, the polypyrrole and zirconium carbide particles will be evenly distributed in the polyurethane film. When visible light and near-infrared light are irradiated to the composite film, the polypyrrole and zirconium carbide particles absorb light energy to increase their internal energy, and then Energy is released. Therefore, the composite film has the function of photothermal conversion. In addition, polypyrrole doped with bis(trifluoromethylsulfonyl)imide ions has excellent electrical conductivity. When the composite film contains an appropriate amount of this polypyrrole particle, the film can have obvious Joule heating effect at low voltage. The heat generated at low voltage can be used to heat the human body.

In order to achieve the above-mentioned second purpose, the solution of the present invention is:

A preparation method of the above-mentioned polypyrrole-zirconium carbide-polyurethane composite film, comprising the following steps:

(1) Dissolve pyrrole and lithium bis(trifluoromethylsulfonyl)imide in deionized water and stir, then add an oxidant to the solution to synthesize bis(trifluoromethylsulfonyl)imide ions doped with bis(trifluoromethylsulfonyl)imide ions The polypyrrole obtained is obtained by dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion;

(2), disperse zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion;

(3), dissolving polyurethane and porogen in dimethylformamide to obtain polyurethane solution;

(4), adding polypyrrole dispersion liquid and zirconium carbide dispersion liquid to polyurethane solution and stirring to obtain mixed stock solution;

(5) The polypyrrole-zirconium carbide-polyurethane composite film is obtained by using the mixed stock solution through a wet film-forming process.

Further, in step (1), the oxidant is selected from one or more of ferric chloride and ceric ammonium nitrate. Under the action of the oxidant, an electrically neutral pyrrole monomer molecule loses one electron and is oxidized into a cationic radical, and then the two cationic radicals combine to form a double cation of the PPy dimer, and then undergo disproportionation to generate electric neutrality The PPy dimer is then oxidized and combined with cationic radicals, and then disproportionated to form a trimer, and the reaction continues until a chain-like Ppy with a degree of polymerization of n is formed.

Further, in step (1), the content of lithium bis(trifluoromethylsulfonyl)imide is 0.1-10 wt %, and the polypyrrole doped with lithium bis(trifluoromethylsulfonyl)imide can enhance the The transfer of electrons by pyrrole enhances the conductivity of polypyrrole. The content of pyrrole is 0.1-20wt%, the molar ratio of oxidant and pyrrole is 1:1-3:1, the solution temperature is in the range of 0-10°C; the content of polypyrrole in the polypyrrole dispersion liquid is 10-25wt%.

Further, in step (2), the content of zirconium carbide in the zirconium carbide dispersion liquid is 10-25wt%.

Further, in step (3), the reason for selecting dimethylformamide as the solvent is: when the polyurethane is added to the dimethylformamide, the small molecule of the dimethylformamide solvent will penetrate into the gap of the polyurethane polymer, and finally The two are mixed to form a homogeneous phase in one state.

Further, in step (3), the porogen is selected from one or more of sodium chloride and polyethylene glycol. The role of the porogen can make the film have a rough surface and increase the specific surface area of the film surface, which helps to increase the absorption of light energy.

Further, in step (3), the content of the polyurethane in the polyurethane solution is 10-25 wt %, and the content of the porogen is 0.01-8 wt %.

Further, in step (4), the content of polyurethane in the mixed raw solution is 80-99.9 wt %, and the content of polypyrrole and zirconium carbide particles are both 0.1-20 wt %.

Further, in step (5), the wet film forming process includes:

(5-1), spread the mixed stock solution evenly on the glass substrate by means of spin coating, scraping or spraying;

(5-2) Put the glass substrate and the mixed stock solution into the solidification water tank and let it stand. After the polypyrrole-zirconium carbide-polyurethane composite film is solidified and formed, the composite film is taken out and dried.

Further, in step (5-1), spin coating, scraping or spraying can spread the mixed stock solution evenly; in addition, selecting a glass substrate is conducive to the easy separation of the film after the film is formed.

Further, in step (5-2), the dimethylformamide phase and the water phase will undergo double diffusion in the polyurethane phase, and then the polyurethane is cured from a liquid state to a film-like solid state.

In order to achieve the above-mentioned third purpose, the solution of the present invention is:

An application of the above polypyrrole-zirconium carbide-polyurethane composite film in autumn and winter thermal insulation fabrics.

Owing to adopting the above-mentioned scheme, the beneficial effects of the present invention are:

First, the present invention combines polypyrrole with photothermal conversion and electrothermal conversion functions, zirconium carbide material with photothermal conversion efficiency and polyurethane material with excellent mechanical properties, and then obtains photothermal conversion and electrothermal conversion functions and good mechanical properties. The polypyrrole-zirconium carbide-polyurethane composite film; at the same time, by using the wet film forming technology, a thin and uniform film can be made, which can be directly used as a material for clothing design to improve the thermal insulation performance of clothing, and can also be used with other fabrics. It can be used as a raw material for clothing design to improve the thermal insulation performance of clothing, provide more choices for the selection of thermal clothing fabrics in autumn and winter, improve the thermal comfort of people wearing clothing, and reduce the use of air conditioners , save a certain amount of fossil energy and reduce the pressure on the environment.

Second, the preparation method of the present invention has simple steps, unique technology, and is easy to popularize.

Description of drawings

FIG. 1 is a flow chart of the preparation process of the polypyrrole-zirconium carbide-polyurethane composite film of the present invention.

2 is a SEM image of the polypyrrole-zirconium carbide-polyurethane composite film of Example 1 of the present invention.

3 is a SEM image of the zirconium carbide-polyurethane composite film of Comparative Example 1 of the present invention.

4 is a SEM image of the polypyrrole-polyurethane composite film of Comparative Example 2 of the present invention.

5 is a graph showing the absorbance of the composite films of Example 1, Comparative Example 1 and Comparative Example 2 of the present invention.

FIG. 6 is a photothermal conversion curve diagram of the composite films of Example 1, Comparative Example 1 and Comparative Example 2 of the present invention.

7 is an electrothermal conversion curve diagram of the composite films of Example 1, Comparative Example 1 and Comparative Example 2 of the present invention.

8 is a mechanical curve diagram of the composite films of Example 1, Comparative Example 1 and Comparative Example 2 of the present invention.

Detailed ways

The invention provides a polypyrrole-zirconium carbide-polyurethane composite film and a preparation method and application thereof.

<Polypyrrole-Zirconium Carbide-Polyurethane Composite Film>

The polypyrrole-zirconium carbide-polyurethane composite film of the invention comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane, the content of the polyurethane is 80-99.9wt%, and the content of the polypyrrole and the zirconium carbide particles is 0.1-20wt% %.

<Preparation method of polypyrrole-zirconium carbide-polyurethane composite film>

As shown in Figure 1, the preparation method of the polypyrrole-zirconium carbide-polyurethane composite film of the present invention comprises the following steps:

(1) Dissolve pyrrole and lithium bis(trifluoromethylsulfonyl)imide in deionized water and stir, then add an oxidant to the solution to synthesize lithium doped with bis(trifluoromethylsulfonyl)imide The polypyrrole obtained is obtained by dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion;

(2), disperse zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion;

(3), dissolving polyurethane and porogen in dimethylformamide to obtain polyurethane solution;

(4), adding polypyrrole dispersion liquid and zirconium carbide dispersion liquid to polyurethane solution and stirring to obtain mixed stock solution;

(5) The polypyrrole-zirconium carbide-polyurethane composite film is obtained by using the mixed stock solution through a wet film-forming process.

Wherein, in step (1), the oxidant is selected from one or more of ferric chloride and ceric ammonium nitrate.

In step (1), the content of lithium bis(trifluoromethylsulfonyl)imide is 0.1-10 wt %, the content of pyrrole is 0.1-20 wt %, and the molar ratio of oxidant and pyrrole is 1:1-3:1 , the solution temperature is in the range of 0-10° C.; the content of polypyrrole in the polypyrrole dispersion liquid is 10-25 wt %.

In step (2), the content of zirconium carbide in the zirconium carbide dispersion liquid is 10-25wt%.

In step (3), the porogen is one or more selected from sodium chloride and polyethylene glycol.

In step (3), the content of polyurethane in the polyurethane solution is 10-25 wt %, and the content of porogen is 0.01-8 wt %.

In step (4), the content of polyurethane in the mixed raw solution is 80-99.9 wt %, and the content of polypyrrole and zirconium carbide particles are both 0.1-20 wt %.

In step (5), the wet film forming process includes:

(5-1), spread the mixed stock solution evenly on the glass substrate by means of spin coating, scraping or spraying;

(5-2) Put the glass substrate and the mixed stock solution in a water tank and let it stand. After the polypyrrole-zirconium carbide-polyurethane composite film is solidified and formed, the composite film is taken out and dried.

Further, in step (5-1), a spin coater is selected to evenly spread the mixed stock solution on the glass substrate. Put the mixed stock solution into the barrel, under the action of the slurry pump, the mixed stock solution is injected into the glass slide, and the glass slide is driven to rotate by the spin coater, and then the mixed stock solution is evenly spread on the glass slide.

Further, in step (5-2), the solution in the water tank is water, and the temperature in the water tank is room temperature; the rotation speed of the spin coater is 1000rpm, and the rotation time is 8min; the drying temperature is 60 ° C, and the drying time is 30min .

The surface morphology of the film was observed by electron scanning electron microscope, and the absorbance of the film was measured by ultraviolet-visible-near-infrared spectrophotometer.

The film was irradiated with infrared light, and then the temperature of the film surface was measured with a thermocouple thermometer. The temperature of the film surface increased with the time of irradiation with infrared light. When the infrared lamp was removed, the temperature of the film surface dropped rapidly.

A voltage of 20V was applied to both ends of the film (length 2cm, width 1cm), and then the surface temperature of the film was measured with a thermocouple thermometer.

The mechanical curve of the polypyrrole-zirconium carbide-polyurethane composite film was obtained by a mechanical property tester. The film was elongated first and then suddenly fractured.

<Application of polypyrrole-zirconium carbide-polyurethane composite film>

The polypyrrole-zirconium carbide-polyurethane composite film of the present invention can be used in autumn and winter thermal insulation clothing fabrics.

The present invention will be further described below in conjunction with the examples.

Example 1:

(1), weigh pyrrole, add in the beaker, keep the content of pyrrole at 5wt%, then add bis(trifluoromethylsulfonyl)imide lithium to the beaker, keep bis(trifluoromethylsulfonyl)imide The content of lithium was 2 wt %. Stir for half an hour so that the pyrrole is uniformly dispersed, the lithium bis(trifluoromethylsulfonyl)imide is dissolved, and the solution temperature is 0°C. Then a quantitative amount of ferric chloride (as an oxidant) was added in a molar ratio of ferric chloride to pyrrole of 2.5:1. The synthesized polypyrrole was filtered, dried, ground, and then dispersed in dimethylformamide, and the content of the polypyrrole was 20 wt % to obtain a polypyrrole dispersion.

(2), dispersing zirconium carbide in dimethylformamide to obtain a zirconium carbide dispersion.

(3), weigh 5.5g of dimethylformamide, add it in the beaker, then add 1.5g of polyurethane and 0.5g of polyethylene glycol (as a porogen) to the beaker, obtain a polyurethane content of 20wt%, polyethylene glycol Polyurethane solution with a glycol content of 6.7 wt%.

(4), adding the zirconium carbide dispersion and the polypyrrole dispersion into the polyurethane solution, and the ratio of the two solutions is 1:9, to obtain a polypyrrole-zirconium carbide-polyurethane mixed stock solution.

(5) The polypyrrole-zirconium carbide-polyurethane composite film was prepared by spin coating technology. First, put the mixed stock solution into the barrel, under the action of the slurry pump, the mixed stock solution is injected into the glass slide, and the glass slide is driven to rotate by the spin coater, and then the mixed stock solution is evenly spread on the glass slide, and then Remove the glass slide, put the glass slide into the water tank and let it stand for a period of time. After the polypyrrole-zirconium carbide-polyurethane composite film is formed, it is taken out from the water tank and dried to obtain a photothermal and electrothermal conversion function. The polypyrrole-zirconium carbide-polyurethane composite film, wherein the content of polypyrrole in the film is 10wt%.

In this embodiment, the solution in the water tank is water, and the temperature in the water tank is room temperature; the rotation speed of the spin coater is 1000 rpm, and the rotation time is 8 minutes; the drying temperature is 60° C., and the drying time is 30 minutes.

Comparative Example 1:

(1), take by weighing 5.5g dimethylformamide, add in the beaker, then add 1.5g polyurethane and 0.5g sodium chloride in the beaker, obtain the polyurethane content that is 20wt%, and the sodium chloride content is 6.7wt% Polyurethane solution.

(2), weigh 8g of dimethylformamide, add it into the beaker, then add 2g of zirconium carbide to the beaker, and obtain a zirconium carbide dispersion with a content of 20wt% after ultrasonic treatment for 50min, the ultrasonic frequency is 25KHz, and the power is 2.5KW.

(3), adding the zirconium carbide dispersion into the polyurethane solution, and the ratio of the two solutions is 1:9, to obtain a zirconium carbide-polyurethane mixed stock solution.

(4) The zirconium carbide-polyurethane composite film was prepared by spin coating technology. First, put the mixed stock solution into the barrel, under the action of the slurry pump, the mixed stock solution is injected into the glass slide, and the glass slide is driven to rotate by the spin coater, and then the mixed stock solution is evenly spread on the glass slide, and then Remove the glass slide, put the glass slide into the water tank and let it stand for a period of time. After the zirconium carbide-polyurethane composite film is formed, it is taken out from the water tank and dried to obtain a zirconium carbide-polyurethane with photothermal conversion function. The composite film, wherein the content of zirconium carbide in the film is 10wt%.

In this comparative example, the solution in the water tank was water, and the temperature in the water tank was room temperature; the rotation speed of the spin coater was 1000 rpm, and the rotation time was 8 minutes; the drying temperature was 60°C, and the drying time was 30 minutes.

Comparative Example 2:

(1), weigh pyrrole, add in the beaker, keep the content of pyrrole at 5wt%, then add bis(trifluoromethylsulfonyl)imide lithium to the beaker, keep bis(trifluoromethylsulfonyl)imide The content of lithium was 2 wt %. Stir for half an hour so that the pyrrole is uniformly dispersed, the lithium bis(trifluoromethylsulfonyl)imide is dissolved, and the solution temperature is 0°C. Then a quantitative amount of ferric chloride (as oxidant) was added in a molar ratio of ferric chloride to pyrrole of 2.5. The synthesized polypyrrole was filtered, dried, ground, and then dispersed in dimethylformamide, and the content of the polypyrrole was 20 wt % to obtain a polypyrrole dispersion.

(2), take by weighing 5.5g dimethylformamide, add in the beaker, then add 1.5g polyurethane and 0.5g sodium chloride (as porogen) in the beaker, obtain the polyurethane content and be 20wt%, sodium chloride A polyurethane solution with a content of 6.7 wt%.

(3), adding the polypyrrole dispersion liquid to the polyurethane solution, and the ratio of the two solutions is 3:36 to obtain a polypyrrole-polyurethane mixed stock solution.

(4) The polypyrrole-polyurethane composite film was prepared by spin coating technology. First, put the mixed stock solution into the barrel, under the action of the slurry pump, the mixed stock solution is injected into the glass slide, and the glass slide is driven to rotate by the spin coater, and then the mixed stock solution is evenly spread on the glass slide, and then Remove the glass slide, put the glass slide into the water tank and let it stand for a period of time. After the polypyrrole-polyurethane composite film is formed, it is taken out from the water tank and dried to obtain a polypyrrole with photothermal and electrothermal conversion functions. -Polyurethane composite film, wherein the content of polypyrrole in the film is 7.5 wt %, and the content of zirconium carbide in the film is 2.5 wt %.

In this embodiment, the solution in the water tank is water, and the temperature in the water tank is room temperature; the rotation speed of the spin coater is 1000 rpm, and the rotation time is 8 minutes; the drying temperature is 60° C., and the drying time is 30 minutes.

The prepared films were tested and found that the zirconium carbide particles of Comparative Example 1 were small and could be uniformly dispersed in the film (see Figure 3), while the polypyrrole particles of Comparative Example 1 were large and easy to agglomerate (see Figure 4). When both zirconium carbide and polypyrrole were mixed in the film, the agglomeration of the polypyrrole of Example 1 was reduced (see Figure 2). The absorbance of 10wt% zirconium carbide-polyurethane composite film is higher than that of 10wt% polypyrrole-zirconium carbide-polyurethane composite film (polypyrrole accounts for 7.5wt%, zirconium carbide accounts for 2.5wt%) and 10wt% polypyrrole-polyurethane composite film (see Figure 5). When the three samples were irradiated with a light source simulating sunlight, the temperature of the zirconium carbide-polyurethane composite film with a solid content of 10 wt% was higher than that of the 10 wt% polypyrrole-zirconium carbide-polyurethane composite film (polypyrrole accounted for 7.5 wt%, carbonized 2.5 wt% zirconium) and 10 wt% polypyrrole-polyurethane composite film (see Figure 6). This is mainly because zirconium carbide has a wider absorption band than polypyrrole, and zirconium carbide can effectively absorb visible light and near-infrared light, while polypyrrole mainly has strong absorption for near-infrared light. In addition, due to the inclusion of some dopants and oxidants in the synthesis process of polypyrrole, the absorbance of polypyrrole of the same quality will be lower than that of zirconium carbide. Therefore, the polypyrrole-zirconium carbide-polyurethane composite film has stronger light absorption effect and photothermal conversion performance than the polypyrrole-polyurethane composite film. When a voltage is applied across the film, the temperature of the zirconium carbide-polyurethane composite film with a content of 10 wt% hardly changes. However, the content of 10wt% polypyrrole-polyurethane composite film and 10wt% polypyrrole-zirconium carbide-polyurethane composite film (polypyrrole accounted for 7.5wt%, zirconium carbide accounted for 2.5wt%) increased first and then maintained with time. The trend is balanced (see Figure 7), which is because the polypyrrole containing conductive dopants has excellent electrical conductivity, while the zirconium carbide has a weaker conductivity, so the electrothermal performance of the polypyrrole-zirconium carbide-polyurethane composite film is better than that of carbonized Zirconium-polyurethane composite film. The breaking strength of the zirconium carbide-polyurethane composite film with a content of 10wt% is higher than that of the 10wt% polypyrrole-zirconium carbide-polyurethane composite film (polypyrrole accounts for 7.5wt%, zirconium carbide accounts for 2.5wt%) and 10wt% polypyrrole-polyurethane composite film film (see Figure 8), but the initial modulus and elongation at break are lower than the latter two. This may be due to the fact that ZrC particles are not easy to agglomerate and are uniformly dispersed in the film, and good frictional force is generated between zirconium carbide ZrC and polyurethane PU or PPy, which finally makes the fracture strength of the zirconium carbide-polyurethane composite film optimal, polypyrrole-carbonized Zirconium-polyurethane composite film is second. However, the polypyrrole particles are easy to agglomerate, and the larger particles will cause "weak joints", so that the composite film first breaks from the weak joints when being stretched, so the breaking strength of the polypyrrole-polyurethane composite film is the weakest. In addition, the increase of PPy content is beneficial to improve the breaking strength and elongation of PPy/ZrC/PU films. It may be that there are some binding sites between PPy and PU. Even if they move relative to each other, the force between them still hinders the external pulling force.

The foregoing description of the embodiments is provided to facilitate understanding and use of the present invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art according to the principles of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims (10)

1. a polypyrrole-zirconium carbide-polyurethane composite film, is characterized in that: it comprises polyurethane and the polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane, the content of the polyurethane is 80-99.9wt%, and the The content of the polypyrrole and zirconium carbide particles is 0.1-20wt%; The preparation method of the polypyrrole-zirconium carbide-polyurethane composite film comprises the following steps: (1) Dissolve pyrrole and lithium bis(trifluoromethylsulfonyl)imide in deionized water and stir, then add an oxidant to the solution to synthesize bis(trifluoromethylsulfonyl)imide ions doped with bis(trifluoromethylsulfonyl)imide ions The polypyrrole is obtained by dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion; (2) Disperse zirconium carbide in dimethylformamide to obtain a zirconium carbide dispersion; (3) Dissolving polyurethane and porogen in dimethylformamide to obtain a polyurethane solution; (4), adding the polypyrrole dispersion and zirconium carbide dispersion into the polyurethane solution and stirring to obtain a mixed stock solution; (5) The polypyrrole-zirconium carbide-polyurethane composite film is obtained by applying the mixed stock solution through a wet film-forming process. 2. a preparation method of polypyrrole-zirconium carbide-polyurethane composite film according to claim 1, is characterized in that: it comprises the steps: (1) Dissolve pyrrole and lithium bis(trifluoromethylsulfonyl)imide in deionized water and stir, then add an oxidant to the solution to synthesize bis(trifluoromethylsulfonyl)imide ions doped with bis(trifluoromethylsulfonyl)imide ions The polypyrrole obtained is obtained by dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion; (2) Disperse zirconium carbide in dimethylformamide to obtain a zirconium carbide dispersion; (3) Dissolving polyurethane and porogen in dimethylformamide to obtain a polyurethane solution; (4), adding the polypyrrole dispersion and zirconium carbide dispersion into the polyurethane solution and stirring to obtain a mixed stock solution; (5) The polypyrrole-zirconium carbide-polyurethane composite film is obtained by applying the mixed stock solution through a wet film-forming process. 3 . The preparation method according to claim 2 , wherein in step (1), the oxidant is selected from one or more of ferric chloride and ceric ammonium nitrate. 4 . 4 . The preparation method according to claim 2 , wherein in step (1), the content of the lithium bis(trifluoromethylsulfonyl)imide is 0.1-10 wt %, and the content of the pyrrole is 4 . 0.1-20wt%, the molar ratio of the oxidant and pyrrole is 1:1-3:1, the temperature of the solution is 0-10°C; the content of polypyrrole in the polypyrrole dispersion liquid is 10-25wt%. 5 . The preparation method according to claim 2 , wherein in step (2), the content of zirconium carbide in the zirconium carbide dispersion liquid is 10-25 wt %. 6 . 6 . The preparation method according to claim 2 , wherein in step (3), the porogen is selected from one or more of sodium chloride and polyethylene glycol. 7 . 7 . The preparation method according to claim 2 , wherein in step (3), the content of polyurethane in the polyurethane solution is 10-25 wt %, and the content of the porogen is 0.01-8 wt %. 8 . 8 . The preparation method according to claim 2 , wherein in step (4), the content of polyurethane in the mixed stock solution is 80-99.9 wt %, and the content of polypyrrole and zirconium carbide particles is both 0.1-20 wt % %. 9 . The preparation method according to claim 2 , wherein in step (5), the wet film forming process comprises: 10 . (5-1) Spread the mixed solution evenly on the glass substrate by means of spin coating, scraping or spraying; (5-2) Put the glass substrate and the mixed stock solution in a water tank and let it stand. After the polypyrrole-zirconium carbide-polyurethane composite film is solidified and formed, the composite film is taken out and dried. 10. An application of the polypyrrole-zirconium carbide-polyurethane composite film as claimed in claim 1 in a thermal insulation fabric for autumn and winter.

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