CN112940340B - Preparation method of polyurethane composite sponge with photo-thermal and electrothermal conversion performance - Google Patents

Preparation method of polyurethane composite sponge with photo-thermal and electrothermal conversion performance Download PDF

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CN112940340B
CN112940340B CN202110357050.5A CN202110357050A CN112940340B CN 112940340 B CN112940340 B CN 112940340B CN 202110357050 A CN202110357050 A CN 202110357050A CN 112940340 B CN112940340 B CN 112940340B
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sponge
thermal
soaking
polyurethane composite
photo
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CN112940340A (en
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杜寒威
李亮
刘玉兰
刘仿军
张桥
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Wuhan Institute of Technology
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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/405—Impregnation with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • 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

Abstract

The invention provides a preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performances, which comprises the steps of soaking the polyurethane sponge in MXene aqueous solution, soaking in ethanol solution containing lauric acid and ferric trichloride, and finally carrying out vapor polymerization on 3, 4-ethylenedioxythiophene or pyrrole monomer in the sponge to obtain the polyurethane composite sponge with the photo-thermal and electro-thermal conversion performances. The polyurethane composite sponge prepared by the invention has excellent photo-thermal and electro-thermal conversion performance, can store and release converted heat energy, and conductive polymer obtained by steam polymerization coats lauric acid to avoid leakage in the phase change process. And the preparation process of the polyurethane composite sponge is simple, complex instruments and equipment are not needed, and the polyurethane composite sponge is suitable for large-scale industrial production.

Description

Preparation method of polyurethane composite sponge with photo-thermal and electric-thermal conversion performance
Technical Field
The invention relates to the technical field of functional composite materials, in particular to a preparation method of a polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
Background
Thermal energy conversion and storage has important implications in the field of energy conversion. Various phase transition materials are widely applied to the fields of waste heat recovery, solar energy conversion, electric energy conversion and the like due to good heat absorption and heat release performance. However, in the currently common phase-change materials, there is a possibility that liquid materials may leak during the solid-liquid phase change. Therefore, people utilize the techniques of pore adsorption, microcapsule coating, coaxial electrostatic spinning and the like to fix the phase change material, but the fixed phase change material is too rigid and fragile, and the contact performance with other materials is poor. On the other hand, the phase transition material has low thermal conductivity, low electrical conductivity and poor light absorption capability, and limits the transmission rate of heat and the conversion between electric heat and light heat.
At present, materials for photothermal conversion and electrothermal conversion include noble metals such as gold, silver, palladium, etc., but their practical application is limited by the expensive price. Graphene, which has been widely studied in recent years, has poor dispersibility in water due to its hydrophobicity, and is easily agglomerated due to its high specific surface area, so that it is difficult to separate between sheets and to effectively complex with other materials. Therefore, it is necessary to develop and prepare a flexible composite material with good photothermal and electrothermal conversion performance, which is low in cost and free of environmental pollution.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing a polyurethane composite sponge with photo-thermal and electro-thermal conversion properties, so as to solve the problems of the existing phase transition material, such as rigidity, fragility, poor contact performance with other materials, low thermal conductivity, low electrical conductivity, and poor light absorption capability.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance comprises the following steps:
1) the volume is 12-25cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 10-30 mg/mL-1Soaking MXene in the aqueous solution of MXene for several times, taking out and drying;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride for several times, taking out and drying;
3) placing the sponge obtained in the step 2) into a container containing 3, 4-ethylenedioxythiophene or pyrrole monomers, vacuumizing, and carrying out steam polymerization reaction on the 3, 4-ethylenedioxythiophene or pyrrole monomers in the sponge;
4) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
Optionally, the MXene in the step 1) is Ti3C2TxWherein, Txis-O, -F and-OH.
Optionally, the soaking times of the repeated soaking in the step 1) are 1 to 3 times, and the soaking time of each soaking is 30 minutes.
Optionally, the concentration of the lauric acid in the step 2) is 100-200 mg-mL-1The concentration of the ferric trichloride is 20-100 mg.mL-1。
Optionally, the soaking times of the repeated soaking in the step 2) are 1 to 5 times, and the soaking time of each soaking is 30 minutes.
Optionally, the reaction temperature of the steam polymerization reaction in the step 3) is 20-70 ℃, and the reaction time is 6-12 hours.
Compared with the prior art, the preparation method of the polyurethane composite sponge with photo-thermal and electro-thermal conversion performance has the following advantages:
1. the invention takes the commercialized polyurethane sponge as the matrix of the composite material, provides good mechanical property, MXene and conductive polymer have good electricity and light absorption performance, so that the composite sponge has photo-thermal conversion and electro-thermal conversion capabilities, and lauric acid as the phase conversion material can store and release heat.
2. According to the invention, lauric acid is coated by the conductive polymer obtained by steam polymerization of 3, 4-ethylenedioxythiophene or pyrrole, so that the possibility of leakage of the lauric acid in the phase transition process is greatly reduced.
3. The polyurethane composite sponge with the photothermal and electrothermal conversion performance is obtained by soaking the polyurethane sponge in MXene aqueous solution, then soaking in ethanol solution containing lauric acid and ferric trichloride, and finally carrying out vapor polymerization on 3, 4-ethylenedioxythiophene or pyrrole monomer in the sponge.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance comprises the following steps:
1) the volume is 12cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 15 mg/mL-1Soaking in MXene aqueous solution for 30 min for 3 times, and drying3C2Tx，Txis-O, -F and-OH, namely MXene contains three functional groups of-O, -F and-OH;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride, wherein the concentration of the lauric acid is 120mg mL-1The concentration of ferric trichloride is 30mg mL-1Soaking for 3 times, each time for 30 minutes, taking out and drying;
3) placing the sponge obtained in the step 2) in a container containing 3, 4-ethylenedioxythiophene monomer, vacuumizing, volatilizing the 3, 4-ethylenedioxythiophene monomer, contacting with the sponge, and carrying out steam polymerization reaction at the reaction temperature of 60 ℃ for 10 hours;
4) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
Example 2
A preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance comprises the following steps:
1) the volume is 20cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 20 mg/mL-1Soaking in MXene aqueous solution for 30 min for 1 time, and drying after taking out, wherein MXene is Ti3C2Tx，Txis-O, -F and-OH, namely MXene contains three functional groups of-O, -F and-OH;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride, wherein the concentration of the lauric acid is 200 mg/mL-1The concentration of ferric trichloride is 50 mg/mL-1Soaking for 5 times, each time for 30 minutes, taking out and drying;
3) placing the sponge obtained in the step 2) in a container containing pyrrole monomers, vacuumizing, volatilizing the pyrrole monomers, contacting with the sponge, and carrying out steam polymerization reaction at 40 ℃ for 8 hours;
4) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
Example 3
A preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance comprises the following steps:
1) the volume is 12cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 25 mg/mL-1Soaking in MXene aqueous solution for 30 min for 2 times, and drying after taking out, wherein MXene is Ti3C2Tx，Txis-O, -F and-OH, namely MXene contains three functional groups of-O, -F and-OH;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride, wherein the concentration of the lauric acid is 150 mg/mL-1The concentration of ferric trichloride is 60 mg/mL-1Soaking for 3 times, each time for 30 minutes, taking out and drying;
3) placing the sponge obtained in the step 2) in a container containing 3, 4-ethylenedioxythiophene monomer, vacuumizing, volatilizing the 3, 4-ethylenedioxythiophene monomer, contacting with the sponge, and carrying out steam polymerization reaction at the reaction temperature of 70 ℃ for 7 hours;
4) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
Example 4
A preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance comprises the following steps:
1) the volume is 25cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 30 mg/mL-1Soaking the MXene in the aqueous solution for 30 minutes for 1 time, and taking out and drying the MXeneIs Ti3C2Tx，Txis-O, -F and-OH, namely MXene contains three functional groups of-O, -F and-OH;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride, wherein the concentration of the lauric acid is 150 mg/mL-1The concentration of ferric chloride is 50 mg/mL-1(ii) a Soaking for 4 times, each time for 30 minutes, taking out and drying;
3) placing the sponge obtained in the step 2) in a container containing pyrrole monomers, vacuumizing, volatilizing the pyrrole monomers, contacting with the sponge, and carrying out steam polymerization reaction at the reaction temperature of 50 ℃ for 6 hours;
4) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
Example 5
A preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance comprises the following steps:
1) the volume is 16cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 20 mg/mL-1Soaking in MXene aqueous solution for 30 min for 2 times, and drying3C2Tx，Txis-O, -F and-OH, namely MXene contains three functional groups of-O, -F and-OH;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride, wherein the concentration of the lauric acid is 100 mg/mL-1The concentration of ferric chloride is 30 mg/mL-1(ii) a Soaking for 5 times, each time for 30 minutes, taking out and drying;
3) placing the sponge obtained in the step 2) in a container containing pyrrole monomers, vacuumizing, volatilizing the pyrrole monomers, contacting with the sponge, and carrying out steam polymerization reaction at the reaction temperature of 30 ℃ for 8 hours;
4) and (3) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performances.
The polyurethane composite sponge with photo-thermal and electro-thermal conversion performance prepared in example 1 is subjected to a performance test by an external electric field or external solar illumination.
Under the voltage of 15V, the temperature of the sponge can reach 56 ℃, and a temperature plateau area appears near 42 ℃; under the irradiation of a xenon lamp simulating the sun, the temperature of the sponge can reach 61 ℃, and a platform area with the temperature near 42 ℃ appears; after 100 times of cold-hot phase change circulation, the composite material is basically not lost, which shows that the polyurethane composite sponge has good photo-thermal and electro-thermal conversion performance.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of a polyurethane composite sponge with photo-thermal and electro-thermal conversion performance is characterized by comprising the following steps:
1) the volume is 12-25cm3The polyurethane sponge is repeatedly soaked in the solution with the concentration of 10-30 mg/mL-1Soaking MXene in the aqueous solution of MXene for several times, taking out and drying;
2) repeatedly soaking the sponge obtained in the step 1) in an ethanol solution containing lauric acid and ferric trichloride for several times, taking out and drying;
3) placing the sponge obtained in the step 2) into a container containing 3, 4-ethylenedioxythiophene or pyrrole monomers, vacuumizing, and carrying out steam polymerization reaction on the 3, 4-ethylenedioxythiophene or pyrrole monomers in the sponge;
4) cleaning the sponge obtained in the step 3) with deionized water, and drying in vacuum to obtain the polyurethane composite sponge with photo-thermal and electric-thermal conversion performance.
2. The method for preparing polyurethane composite sponge with photo-thermal and electro-thermal conversion performance as claimed in claim 1, wherein MXene is Ti in step 1)3C2TxWherein, Txis-O, -F and-OH.
3. The method for preparing the polyurethane composite sponge having the photothermal and electrothermal conversion properties according to claim 1, wherein the soaking times of the repeated soaking in step 1) is 1-3 times, and the soaking time for each soaking is 30 minutes.
4. The method for preparing the polyurethane composite sponge with photothermal and electrothermal conversion performance as recited in claim 1, wherein the concentration of lauric acid in step 2) is 100-200 mg-mL-1The concentration of the ferric trichloride is 20-100 mg.mL-1。
5. The method for preparing the polyurethane composite sponge having the photothermal and electrothermal conversion properties according to claim 1, wherein the soaking times of the repeated soaking in step 2) are 1-5 times, and the soaking time of each soaking is 30 minutes.
6. The method for preparing polyurethane composite sponge with photo-thermal and electro-thermal conversion properties as claimed in claim 1, wherein the reaction temperature of the vapor polymerization reaction in the step 3) is 20-70 ℃ and the reaction time is 6-12 hours.
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CN114163683A (en) * 2021-12-09 2022-03-11 哈尔滨工程大学 Preparation method and application of polypyrrole/polyurethane photothermal composite sponge
CN115354412A (en) * 2022-08-31 2022-11-18 嘉兴自然三禾新材料科技有限公司 Temperature-adjusting cotton and preparation method thereof

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