CN113150530B - Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof - Google Patents
Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof Download PDFInfo
- Publication number
- CN113150530B CN113150530B CN202110427873.0A CN202110427873A CN113150530B CN 113150530 B CN113150530 B CN 113150530B CN 202110427873 A CN202110427873 A CN 202110427873A CN 113150530 B CN113150530 B CN 113150530B
- Authority
- CN
- China
- Prior art keywords
- polypyrrole
- zirconium carbide
- polyurethane
- composite film
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/50—Synthetic resins or rubbers
- A41D2500/52—Synthetic resins or rubbers in sheet form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a polypyrrole-zirconium carbide-polyurethane composite film and a preparation method and application thereof, wherein the composite film comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane; the preparation method comprises the following steps: dissolving pyrrole and lithium bis (trifluoromethylsulfonyl) imide in deionized water, stirring, adding an oxidant, and dispersing polypyrrole in dimethylformamide to obtain a polypyrrole dispersion liquid; dispersing zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion liquid; dissolving polyurethane and a pore-foaming agent in dimethylformamide to obtain a polyurethane solution; adding the polypyrrole dispersion liquid and the zirconium carbide dispersion liquid into a polyurethane solution and stirring to obtain a mixed stock solution; the mixed stock solution is processed by a wet film forming process; by adopting a wet film forming technology, the light and thin uniform film can be manufactured, can be directly used as a material for garment design to improve the heat insulation performance of garments, and provides more choices for material selection of autumn and winter thermal fabrics.
Description
Technical Field
The invention belongs to the technical field of composite films, and particularly relates to a polypyrrole-zirconium carbide-polyurethane composite film as well as a preparation method and application thereof.
Background
In winter, down jackets can only maintain the basic heat for people to live. Insulation based on air conditioning and heating is another strategy for people to cope with cold climate by maintaining constant body temperature and normal activities. However, the use of air conditioners and heating presents serious environmental hazards, such as ozone holes, greenhouse effect, and the like. Therefore, in order to reduce the use of air conditioners and heating, the textile with the more excellent heat preservation function has certain development prospect.
Polypyrrole is a semiconductor material which has both a photothermal conversion function and an electrothermal conversion function. Although polypyrrole absorbs heat, polypyrrole absorbs light energy mainly in the near infrared band. Zirconium carbide is a transition metal carbide having an excellent photothermal conversion function, and can absorb not only light energy in the visible light band but also light energy in the near-infrared band. At present, there is little research report on combining two materials to develop a film material having both an electrothermal function and a photothermal conversion function.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to provide a polypyrrole-zirconium carbide-polyurethane composite film.
The second purpose of the invention is to provide a preparation method of the polypyrrole-zirconium carbide-polyurethane composite film.
The third purpose of the invention is to provide the application of the polypyrrole-zirconium carbide-polyurethane composite film.
In order to achieve the above primary object, the solution of the present invention is:
a polypyrrole-zirconium carbide-polyurethane composite film comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane, wherein the content of the polyurethane is 80-99.9wt%, and the content of the polypyrrole and zirconium carbide particles is 0.1-20wt%.
After the polyurethane film is formed, the polypyrrole and zirconium carbide particles are uniformly distributed in the polyurethane film, and when visible light and near infrared light irradiate the composite film, the polypyrrole and zirconium carbide particles absorb light energy to increase the internal energy of the composite film, and then the energy is released. Therefore, the composite film has a photothermal conversion function. In addition, the polypyrrole doped with bis (trifluoromethylsulfonyl) imide ions has excellent conductivity, when the composite film contains a proper amount of polypyrrole particles, the composite film has obvious Joule heating effect under low voltage, and heat generated under the low voltage can be used for heating human bodies.
In order to achieve the second objective, the solution of the invention is:
the preparation method of the polypyrrole-zirconium carbide-polyurethane composite film comprises the following steps:
(1) Dissolving pyrrole and lithium bis (trifluoromethylsulfonyl) imide in deionized water and stirring, then adding an oxidant into the solution to synthesize polypyrrole doped with bis (trifluoromethylsulfonyl) imide ions, and dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion liquid;
(2) Dispersing zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion liquid;
(3) Dissolving polyurethane and a pore-foaming agent in dimethylformamide to obtain a polyurethane solution;
(4) Adding the polypyrrole dispersion liquid and the zirconium carbide dispersion liquid into the polyurethane solution and stirring to obtain a mixed stock solution;
(5) And carrying out wet film forming on the mixed stock solution to obtain the polypyrrole-zirconium carbide-polyurethane composite film.
Further, in the step (1), the oxidizing agent is one or more selected from the group consisting of ferric chloride and ceric ammonium nitrate. Under the action of an oxidant, one electron of an electroneutral pyrrole monomer molecule is oxidized into a cation free radical after losing one electron, then two cation free radicals are combined to generate dication of a PPy dimer, the electroneutral PPy dimer is generated through disproportionation, then the PPy dimer is oxidized to be combined with the cation free radical, the mixture is disproportionated to generate a trimer, and the reaction is carried out until a chain-shaped Ppy with the polymerization degree of n is generated.
Further, in the step (1), the content of the lithium bis (trifluoromethylsulfonyl) imide is 0.1-10wt%, and the polypyrrole doped with the lithium bis (trifluoromethylsulfonyl) imide can enhance the electron transfer of the polypyrrole, so that the conductivity of the polypyrrole can be enhanced. The content of pyrrole is 0.1-20wt%, the molar ratio of oxidant and pyrrole is 1:1-3:1, the temperature of solution is 0-10 deg.C; the content of polypyrrole in the polypyrrole dispersion liquid is 10-25wt%.
Further, in the step (2), the content of zirconium carbide in the zirconium carbide dispersion liquid is 10 to 25wt%.
Further, in step (3), dimethylformamide was selected as the solvent because: when the polyurethane is added into the dimethylformamide, the small molecules of the dimethylformamide solvent can permeate into the gaps of the polyurethane macromolecules, and finally the two are mixed to form a uniform phase in one state.
Further, in the step (3), the pore-forming agent is selected from one or more of sodium chloride and polyethylene glycol. The action of the porogen may cause the thin film to have a rough surface, increasing the specific surface area of the film surface, which helps to increase absorption of light energy.
Further, in the step (3), the content of polyurethane in the polyurethane solution is 10-25wt%, and the content of the pore-forming agent is 0.01-8wt%.
Further, in the step (4), the content of polyurethane in the mixed stock solution is 80-99.9wt%, and the content of polypyrrole and zirconium carbide particles is 0.1-20wt%.
Further, in the step (5), the wet film forming process includes:
(5-1) uniformly spreading the mixed stock solution on a glass substrate by adopting a rotary coating, blade coating or spraying mode;
and (5-2) placing the glass substrate and the mixed stock solution into a solidification water tank for standing, taking out the composite film after the polypyrrole-zirconium carbide-polyurethane composite film is solidified and molded, and drying.
Further, in the step (5-1), the mixed stock solution can be uniformly spread by means of rotary coating, blade coating or spraying; in addition, the glass substrate is selected to facilitate easy film separation after film formation.
Further, in the step (5-2), the dimethylformamide phase and the water phase are subjected to double diffusion in the polyurethane phase, and the polyurethane is solidified from the liquid state into a film-like solid state.
In order to achieve the third object, the solution of the invention is:
the application of the polypyrrole-zirconium carbide-polyurethane composite film in autumn and winter heat-insulating fabrics.
Due to the adoption of the scheme, the invention has the beneficial effects that:
firstly, combining polypyrrole with photothermal conversion and electrothermal conversion functions, a zirconium carbide material with photothermal conversion efficiency and a polyurethane material with excellent mechanical property to obtain a polypyrrole-zirconium carbide-polyurethane composite film with photothermal conversion and electrothermal conversion functions and good mechanical property; meanwhile, a thin and uniform film can be manufactured by adopting a wet film forming technology, can be directly used as a material for clothing design to improve the heat insulation performance of clothing, can be bonded with other fabrics by glue to manufacture clothing fabric, and further can be used as a raw material for clothing design to improve the heat insulation performance of clothing, so that more choices are provided for the selection of the material of autumn and winter heat-insulation clothing fabric, the thermal comfort of people wearing the clothing is improved, the use of air conditioners is reduced, certain fossil energy is saved, and the pressure of the environment is reduced.
Secondly, the preparation method of the invention has simple steps, unique process and easy popularization.
Drawings
Fig. 1 is a flow chart of a preparation process of the polypyrrole-zirconium carbide-polyurethane composite film of the invention.
Fig. 2 is an SEM image of the polypyrrole-zirconium carbide-polyurethane composite thin film of example 1 of the present invention.
Fig. 3 is an SEM image of the zirconium carbide-polyurethane composite thin film of comparative example 1 of the present invention.
Fig. 4 is an SEM image of the polypyrrole-polyurethane composite thin film of comparative example 2 of the present invention.
Fig. 5 is a graph showing absorbance curves of the composite films of example 1, comparative example 1 and comparative example 2 of the present invention.
Fig. 6 is a graph showing the photothermal conversion of the composite films of example 1, comparative example 1 and comparative example 2 of the present invention.
Fig. 7 is a graph showing electrothermal conversion curves of the composite films of example 1, comparative example 1 and comparative example 2 of the present invention.
Fig. 8 is a mechanical graph of the composite films of example 1, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
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 comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane, wherein the content of the polyurethane is 80-99.9wt%, and the content of the polypyrrole and zirconium carbide particles is 0.1-20wt%.
< preparation method of polypyrrole-zirconium carbide-polyurethane composite film >
As shown in fig. 1, the preparation method of the polypyrrole-zirconium carbide-polyurethane composite film of the present invention comprises the following steps:
(1) Dissolving pyrrole and lithium bis (trifluoromethylsulfonyl) imide in deionized water and stirring, then adding an oxidant into the solution to synthesize polypyrrole doped with lithium bis (trifluoromethylsulfonyl) imide, and dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion liquid;
(2) Dispersing zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion liquid;
(3) Dissolving polyurethane and a pore-foaming agent in dimethylformamide to obtain a polyurethane solution;
(4) Adding the polypyrrole dispersion liquid and the zirconium carbide dispersion liquid into the polyurethane solution and stirring to obtain a mixed stock solution;
(5) And carrying out a wet film forming process on the mixed stock solution to obtain the polypyrrole-zirconium carbide-polyurethane composite film.
Wherein, in the step (1), the oxidant is selected from more than one of ferric chloride and ceric ammonium nitrate.
In the step (1), the content of lithium bis (trifluoromethylsulfonyl) imide is 0.1-10wt%, the content of pyrrole is 0.1-20wt%, the molar ratio of oxidant and pyrrole is 1:1-3:1, and the temperature of the solution is in the range of 0-10 ℃; the content of polypyrrole in the polypyrrole dispersion liquid is 10-25wt%.
In the step (2), the content of zirconium carbide in the zirconium carbide dispersion liquid is 10 to 25wt%.
In the step (3), the pore-forming agent is selected from one or more of sodium chloride and polyethylene glycol.
In the step (3), the content of polyurethane in the polyurethane solution is 10-25wt%, and the content of the pore-forming agent is 0.01-8wt%.
In the step (4), the content of polyurethane in the mixed stock solution is 80-99.9wt%, and the content of polypyrrole and zirconium carbide particles is 0.1-20wt%.
In the step (5), the wet film forming process includes:
(5-1) uniformly spreading the mixed stock solution on a glass substrate by adopting a rotary coating, blade coating or spraying mode;
and (5-2) placing the glass substrate and the mixed stock solution into a water tank for standing, taking out the composite film after the polypyrrole-zirconium carbide-polyurethane composite film is solidified and molded, and drying.
Further, in the step (5-1), a rotary coating machine is selected to uniformly spread the mixed stock solution on the glass substrate. And (3) putting the mixed stock solution into the charging barrel, injecting the mixed stock solution onto a glass slide under the action of a slurry pushing pump, driving the glass slide to rotate by the rotary coating instrument, and further uniformly spreading the mixed stock solution on the glass slide.
Further, in the step (5-2), the solution in the water tank is water, and the temperature in the water tank is room temperature; the rotating speed of the rotating film coating instrument is 1000rpm, and the rotating time is 8min; the drying temperature is 60 deg.C, and the drying time is 30min.
And observing the surface appearance of the film by an electronic scanning electron microscope, and measuring the absorbance of the film by using an ultraviolet-visible-near infrared spectrophotometer.
The film is irradiated with infrared light, and then the surface temperature of the film is measured with a thermocouple thermometer, and the surface temperature of the film increases as the time of irradiation of infrared light increases. When the infrared lamp was removed, the temperature of the film surface dropped rapidly.
A voltage of 20V is applied to two ends of a film (with the length of 2cm and the width of 1 cm), then the surface temperature of the film is measured by a thermocouple thermometer, and the surface temperature of the film is increased and then becomes flat along with the time.
A mechanical property tester is used for obtaining a mechanical curve graph of the polypyrrole-zirconium carbide-polyurethane composite film, and the film is firstly elongated and then suddenly broken.
< application of polypyrrole-zirconium carbide-polyurethane composite film >
The polypyrrole-zirconium carbide-polyurethane composite film can be applied to thermal insulation clothing fabrics in autumn and winter.
The present invention will be further described with reference to the following examples.
Example 1:
(1) Weighing pyrrole, adding into a beaker, keeping the content of pyrrole at 5wt%, and then adding lithium bis (trifluoromethylsulfonyl) imide into the beaker, keeping the content of lithium bis (trifluoromethylsulfonyl) imide at 2wt%. Stirring for half an hour to disperse the pyrrole uniformly, dissolving lithium bis (trifluoromethylsulfonyl) imide, and keeping the solution temperature at 0 ℃. Then, a fixed amount of ferric chloride (as an oxidizing agent) was added, the molar ratio of ferric chloride to pyrrole being 2.5:1. and filtering, drying and grinding the synthesized polypyrrole, and then dispersing the polypyrrole in dimethylformamide to obtain polypyrrole dispersion liquid, wherein the content of the polypyrrole is 20wt%.
(2) And dispersing zirconium carbide in dimethylformamide to obtain a zirconium carbide dispersion liquid.
(3) 5.5g of dimethylformamide is weighed and added into a beaker, and then 1.5g of polyurethane and 0.5g of polyethylene glycol (used as a pore-foaming agent) are added into the beaker to obtain a polyurethane solution with the polyurethane content of 20wt% and the polyethylene glycol content of 6.7 wt%.
(4) Adding the zirconium carbide dispersion liquid and the polypyrrole dispersion liquid into a polyurethane solution, wherein the ratio of the two solutions is 1: and 9, obtaining a polypyrrole-zirconium carbide-polyurethane mixed stock solution.
(5) And preparing the polypyrrole-zirconium carbide-polyurethane composite film by adopting a rotary coating technology. Firstly, placing mixed stock solution into a charging barrel, injecting the mixed stock solution onto a glass slide under the action of a slurry pushing pump, driving the glass slide to rotate by a rotary coating instrument, further uniformly spreading the mixed stock solution on the glass slide, taking the glass slide down, placing the glass slide into a water tank, standing for a period of time, taking out the glass slide from the water tank after a polypyrrole-zirconium carbide-polyurethane composite film is formed, and drying to obtain the polypyrrole-zirconium carbide-polyurethane composite film with photothermal and electrothermal conversion functions, 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 rotating speed of the rotating film coating instrument is 1000rpm, and the rotating time is 8min; the drying temperature is 60 deg.C, and the drying time is 30min.
Comparative example 1:
(1) 5.5g of dimethylformamide is weighed and added into a beaker, and then 1.5g of polyurethane and 0.5g of sodium chloride are added into the beaker to obtain a polyurethane solution with the polyurethane content of 20wt% and the sodium chloride content of 6.7 wt%.
(2) Weighing 8g of dimethylformamide, adding the dimethylformamide into a beaker, adding 2g of zirconium carbide into the beaker, and carrying out ultrasonic treatment for 50min to obtain a zirconium carbide dispersion liquid with the content of 20wt%, wherein the ultrasonic frequency is 25KHz, and the power is 2.5KW.
(3) Adding the zirconium carbide dispersion liquid into a polyurethane solution, wherein the ratio of the two solutions is 1: and 9, obtaining zirconium carbide-polyurethane mixed stock solution.
(4) And preparing the zirconium carbide-polyurethane composite film by adopting a rotary coating technology. Firstly, placing mixed stock solution into a charging barrel, injecting the mixed stock solution onto a glass slide under the action of a slurry pushing pump, driving the glass slide to rotate by a rotary coating instrument, further uniformly spreading the mixed stock solution on the glass slide, taking the glass slide down, placing the glass slide into a water tank, standing for a period of time, taking out the glass slide from the water tank after a zirconium carbide-polyurethane composite film is formed, and drying to obtain the zirconium carbide-polyurethane composite film with the photo-thermal conversion function, 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 rotating speed of the rotating film coating instrument is 1000rpm, and the rotating time is 8min; the drying temperature is 60 deg.C, and the drying time is 30min.
Comparative example 2:
(1) Weighing pyrrole, adding into a beaker, keeping the content of pyrrole at 5wt%, and then adding lithium bis (trifluoromethylsulfonyl) imide into the beaker, keeping the content of lithium bis (trifluoromethylsulfonyl) imide at 2wt%. Stirring for half an hour to disperse the pyrrole uniformly, dissolving lithium bis (trifluoromethylsulfonyl) imide, and keeping the solution temperature at 0 ℃. Then a fixed amount of ferric chloride (as oxidant) was added, the molar ratio of ferric chloride to pyrrole being 2.5. And filtering, drying and grinding the synthesized polypyrrole, and then dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion liquid, wherein the content of the polypyrrole is 20wt%.
(2) 5.5g of dimethylformamide is weighed and added into a beaker, and then 1.5g of polyurethane and 0.5g of sodium chloride (serving as a pore-foaming agent) are added into the beaker to obtain a polyurethane solution with the polyurethane content of 20wt% and the sodium chloride content of 6.7 wt%.
(3) And adding the polypyrrole dispersion liquid into the polyurethane solution, wherein the proportion of the two solutions is 3:36, obtaining the polypyrrole-polyurethane mixed stock solution.
(4) And preparing the polypyrrole-polyurethane composite film by adopting a rotary coating technology. Firstly, placing mixed stock solution into a charging barrel, injecting the mixed stock solution onto a glass slide under the action of a slurry pushing pump, driving the glass slide to rotate by a rotary coating instrument, further uniformly spreading the mixed stock solution on the glass slide, taking the glass slide down, placing the glass slide into a water tank, standing for a period of time, taking out the glass slide from the water tank after a polypyrrole-polyurethane composite film is formed, and drying to obtain the polypyrrole-polyurethane composite film with the photothermal and electrothermal conversion functions, wherein the content of polypyrrole in the film is 7.5wt%, and the content of zirconium carbide in the film is 2.5wt%.
In this embodiment, the solution in the water tank is water, and the temperature in the water tank is room temperature; the rotating speed of the rotating film coating instrument is 1000rpm, and the rotating time is 8min; the drying temperature is 60 deg.C, and the drying time is 30min.
The prepared film was tested to find that the zirconium carbide particles of comparative example 1 were small and uniformly dispersed in the film (see fig. 3), and the polypyrrole particles of comparative example 1 were large and easily agglomerated (see fig. 4). Agglomeration of the polypyrrole of example 1 was reduced when both zirconium carbide and polypyrrole were mixed in the film (see fig. 2). The absorbance of the zirconium carbide-polyurethane composite film having a content of 10wt% was higher than that of the polypyrrole-zirconium carbide-polyurethane composite film having a content of 10wt% (7.5 wt% of polypyrrole and 2.5wt% of zirconium carbide) and that of the polypyrrole-polyurethane composite film having a content of 10wt% (see fig. 5). When three samples were irradiated with a lamp source simulating sunlight, the temperature of the zirconium carbide-polyurethane composite film having a solid content of 10wt% was higher than that of the 10wt% polypyrrole-zirconium carbide-polyurethane composite film (7.5 wt% polypyrrole and 2.5wt% zirconium carbide) and that of the 10wt% polypyrrole-polyurethane composite film (see fig. 6). This is mainly because zirconium carbide has a wider absorption band than polypyrrole, zirconium carbide can absorb visible light and near infrared light efficiently, and polypyrrole has a stronger absorption mainly for near infrared light. In addition, because the polypyrrole contains part of the dopant and the oxidant in the synthesis process, the absorbance of polypyrrole with the same quality is lower than that of zirconium carbide. Therefore, the polypyrrole-zirconium carbide-polyurethane composite film has a stronger light absorption effect and a higher photothermal conversion performance than the polypyrrole-polyurethane composite film. When a voltage was applied across the film, the temperature of the zirconium carbide-polyurethane composite film having a content of 10wt% hardly changed. However, the polypyrrole-polyurethane composite film with a content of 10wt% and the polypyrrole-zirconium carbide-polyurethane composite film with a content of 10wt% (7.5 wt% for polypyrrole and 2.5wt% for zirconium carbide) tend to be balanced after increasing with time (see fig. 7), because polypyrrole containing a conductive dopant has excellent conductivity, while zirconium carbide has weak conductivity, and thus the electric heating performance of the polypyrrole-zirconium carbide-polyurethane composite film is superior to that of the zirconium carbide-polyurethane composite film. The fracture strength of the zirconium carbide-polyurethane composite film having a content of 10wt% was higher than that of the polypyrrole-zirconium carbide-polyurethane composite film having a content of 10wt% (7.5 wt% for polypyrrole and 2.5wt% for zirconium carbide) and that of the polypyrrole-polyurethane composite film having a content of 10wt% (see fig. 8), but the initial modulus and the elongation at fracture were lower than those of the latter two. This is probably because ZrC particles are not easily agglomerated and uniformly dispersed in the film, and a good frictional force is generated between zirconium carbide ZrC and polyurethane PU or PPy, so that the fracture strength of the zirconium carbide-polyurethane composite film is optimal, and the fracture strength of the polypyrrole-zirconium carbide-polyurethane composite film is inferior. But polypyrrole granules are easy to agglomerate, and larger granules can cause weak joints, so that the composite film is firstly broken from the weak joints when being stretched, and therefore the fracture strength of the polypyrrole-polyurethane composite film is weakest. In addition, the increase of the content of the PPy is beneficial to improving the fracture strength and the elongation of the PPy/ZrC/PU film. There may be some binding sites between PPy and PU. Even if they move relative to each other, the force between them resists the external pulling force.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (10)
1. A polypyrrole-zirconium carbide-polyurethane composite film is characterized in that: the coating comprises polyurethane and polypyrrole and zirconium carbide particles uniformly dispersed in the polyurethane, wherein the content of the polyurethane is 80-99.9wt%, and 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) Dissolving pyrrole and lithium bis (trifluoromethylsulfonyl) imide in deionized water and stirring, then adding an oxidant into the solution to synthesize polypyrrole doped with bis (trifluoromethylsulfonyl) imide ions, and dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion liquid;
(2) Dispersing zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion liquid;
(3) Dissolving polyurethane and a pore-foaming agent in dimethylformamide to obtain a polyurethane solution;
(4) Adding the polypyrrole dispersion liquid and the zirconium carbide dispersion liquid into a polyurethane solution and stirring to obtain a mixed stock solution;
(5) And carrying out a wet film forming process on the mixed stock solution to obtain the polypyrrole-zirconium carbide-polyurethane composite film.
2. A method for preparing a polypyrrole-zirconium carbide-polyurethane composite film according to claim 1, wherein: which comprises the following steps:
(1) Dissolving pyrrole and lithium bis (trifluoromethylsulfonyl) imide in deionized water and stirring, then adding an oxidant into the solution to synthesize polypyrrole doped with bis (trifluoromethylsulfonyl) imide ions, and dispersing the polypyrrole in dimethylformamide to obtain a polypyrrole dispersion liquid;
(2) Dispersing zirconium carbide in dimethylformamide to obtain zirconium carbide dispersion liquid;
(3) Dissolving polyurethane and a pore-foaming agent in dimethylformamide to obtain a polyurethane solution;
(4) Adding the polypyrrole dispersion liquid and the zirconium carbide dispersion liquid into a polyurethane solution and stirring to obtain a mixed stock solution;
(5) And carrying out a wet film forming process on the mixed stock solution to obtain the polypyrrole-zirconium carbide-polyurethane composite film.
3. The method of claim 2, wherein: in the step (1), the oxidant is selected from more than one of ferric chloride and ammonium ceric nitrate.
4. The method of claim 2, wherein: in the step (1), the content of the lithium bis (trifluoromethylsulfonyl) imide is 0.1-10wt%, the content of the pyrrole is 0.1-20wt%, the molar ratio of the oxidant to the pyrrole is 1:1-3:1, and the temperature of the solution is 0-10 ℃; the content of polypyrrole in the polypyrrole dispersion liquid is 10-25wt%.
5. The method of claim 2, wherein: in the step (2), the content of zirconium carbide in the zirconium carbide dispersion liquid is 10-25wt%.
6. The method of claim 2, wherein: in the step (3), the pore-forming agent is selected from one or more of sodium chloride and polyethylene glycol.
7. The method of claim 2, wherein: in the step (3), the content of polyurethane in the polyurethane solution is 10-25wt%, and the content of the pore-forming agent is 0.01-8wt%.
8. The production method according to claim 2, characterized in that: in the step (4), the content of polyurethane in the mixed stock solution is 80-99.9wt%, and the content of polypyrrole and zirconium carbide particles is 0.1-20wt%.
9. The method of claim 2, wherein: in the step (5), the wet film forming process includes:
(5-1) uniformly spreading the mixed stock solution on a glass substrate by adopting a rotary coating, blade coating or spraying mode;
and (5-2) placing the glass substrate and the mixed stock solution into a water tank for standing, and taking out and drying the composite film after the polypyrrole-zirconium carbide-polyurethane composite film is solidified and formed.
10. The application of the polypyrrole-zirconium carbide-polyurethane composite film of claim 1 in autumn and winter thermal insulation fabrics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110427873.0A CN113150530B (en) | 2021-04-21 | 2021-04-21 | Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110427873.0A CN113150530B (en) | 2021-04-21 | 2021-04-21 | Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113150530A CN113150530A (en) | 2021-07-23 |
| CN113150530B true CN113150530B (en) | 2022-10-14 |
Family
ID=76869146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110427873.0A Active CN113150530B (en) | 2021-04-21 | 2021-04-21 | Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113150530B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017078990A1 (en) * | 2015-11-03 | 2017-05-11 | Dow Global Technologies Llc | Polyurethane foam for noise and vibration absorption |
| CN108587120A (en) * | 2017-12-21 | 2018-09-28 | 东莞市雄林新材料科技股份有限公司 | A kind of TPU film and preparation method thereof with infrared Absorption function |
| CN109912816A (en) * | 2019-03-05 | 2019-06-21 | 中原工学院 | A kind of preparation method of polypyrrole/polyurethane composite conducting hydrogel |
| CN110330675A (en) * | 2019-06-19 | 2019-10-15 | 天津市职业大学 | A kind of preparation method of pressure-sensitive film, pressure-sensitive film and pressure sensor |
| CN110820071A (en) * | 2019-09-29 | 2020-02-21 | 中润科技股份有限公司 | Preparation method of high-performance nano polyester filament yarn |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10629899B1 (en) * | 2018-10-15 | 2020-04-21 | Global Graphene Group, Inc. | Production method for electrochemically stable anode particulates for lithium secondary batteries |
-
2021
- 2021-04-21 CN CN202110427873.0A patent/CN113150530B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017078990A1 (en) * | 2015-11-03 | 2017-05-11 | Dow Global Technologies Llc | Polyurethane foam for noise and vibration absorption |
| CN108587120A (en) * | 2017-12-21 | 2018-09-28 | 东莞市雄林新材料科技股份有限公司 | A kind of TPU film and preparation method thereof with infrared Absorption function |
| CN109912816A (en) * | 2019-03-05 | 2019-06-21 | 中原工学院 | A kind of preparation method of polypyrrole/polyurethane composite conducting hydrogel |
| CN110330675A (en) * | 2019-06-19 | 2019-10-15 | 天津市职业大学 | A kind of preparation method of pressure-sensitive film, pressure-sensitive film and pressure sensor |
| CN110820071A (en) * | 2019-09-29 | 2020-02-21 | 中润科技股份有限公司 | Preparation method of high-performance nano polyester filament yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113150530A (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106700356B (en) | A kind of preparation method of graphene-polymer composite material | |
| CN108495385A (en) | A kind of flexible membrane of graphene-containing and preparation method thereof | |
| CN106750397B (en) | A kind of nano-cellulose-polyaniline-polyvinyl alcohol composite conducting hydrogel and its preparation method and application | |
| CN103073941B (en) | Vanadium dioxide powder slurry and preparation method thereof | |
| CN103525320A (en) | Thermochromic PVB (polyvinyl butyral) intermediate film and preparation method thereof | |
| CN106400506A (en) | Waterborne polyurethane textile size based on graphene modification and preparation method thereof | |
| CN103059636A (en) | Preparation method of graphene nanometer material automobile finish | |
| CN113150530B (en) | Polypyrrole-zirconium carbide-polyurethane composite film and preparation method and application thereof | |
| Liu et al. | A multi-responsive cross-linked supramolecular polymer network constructed by mussel yield coordination interaction and pillar [5] arene-based host–guest complexation | |
| Ding et al. | A waterborne bio-based polymer pigment: colored regenerated cellulose suspension from waste cotton fabrics | |
| CN106893120B (en) | A kind of preparation method of strain-responsive conductive hydrogel | |
| Sedó et al. | Intramolecular electron transfer phenomena in purely organic mixed‐valence high‐spin ions: a triplet anion case | |
| Jiang et al. | Preparation and characterization of viscose composites fiber and its enhancing effect in photothermal conversion property | |
| CN109467683B (en) | Preparation method of modified polyester chip, polyester chip and polyester fiber | |
| CN106044748A (en) | Method for preparing boron-doped graphene | |
| KR101693667B1 (en) | Fabric treatment composition having heat generation function | |
| Wang et al. | Graphene oxide/polyurethane‐based composite solid–solid phase change materials with enhanced energy storage capacity and photothermal performance | |
| CN115233475A (en) | Preparation method of heat-storage printing paste | |
| Pei et al. | Salt-free and alkali-free fixing method of wool fabric dyeing in non-aqueous media dyeing system | |
| CN115028994A (en) | Far infrared radiation material with adjustable resistivity and preparation method thereof | |
| CN113151929B (en) | Zirconium carbide/polyurethane-polypyrrole sheath-core fiber and preparation method and application thereof | |
| Yin et al. | MWCNTs/hydroxypropyl cellulose/polyethylene glycol-based shape-stabilized phase change materials | |
| CN114105906A (en) | Organic charge transfer eutectic crystal and preparation method and application thereof | |
| CN106700446A (en) | Polyester grille and preparation method thereof | |
| CN112818555A (en) | Application of lignin as infrared photothermal conversion material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |