CN118407263B - Graphene heat storage fabric and preparation method and application thereof - Google Patents
Graphene heat storage fabric and preparation method and application thereof Download PDFInfo
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- CN118407263B CN118407263B CN202410874235.7A CN202410874235A CN118407263B CN 118407263 B CN118407263 B CN 118407263B CN 202410874235 A CN202410874235 A CN 202410874235A CN 118407263 B CN118407263 B CN 118407263B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 128
- 239000004744 fabric Substances 0.000 title claims abstract description 105
- 238000005338 heat storage Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 39
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001694 spray drying Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000004753 textile Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000009413 insulation Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 47
- 150000001241 acetals Chemical class 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 15
- 239000004814 polyurethane Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 17
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 19
- 229920000742 Cotton Polymers 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
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- 238000007792 addition Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OQNGNXKLDCKIIH-UHFFFAOYSA-N tetradecyl benzenesulfonate Chemical compound CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 OQNGNXKLDCKIIH-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the technical field of textile products, and relates to a graphene heat storage fabric and a preparation method and application thereof. The graphene heat storage fabric comprises a fabric layer and a heat storage and insulation layer positioned above the fabric layer, wherein the heat storage and insulation layer is prepared by coating a composite finishing agent of graphene coated with polyvinyl acetal on the upper surface of the fabric layer; the graphene coated with the polyvinyl acetal is obtained by mixing graphene aqueous dispersion and polyvinyl acetal ethanol solution and then spray drying. The graphene heat storage fabric provided by the invention keeps the comfort of the fabric under the condition of good air permeability, and greatly improves the heat storage performance of the fabric.
Description
Technical Field
The invention belongs to the technical field of textile products, and relates to a graphene heat storage fabric and a preparation method and application thereof.
Background
Graphene is a two-dimensional cellular planar film formed by carbon atoms through sp 2 hybridization, and the perfect graphene has an ideal two-dimensional crystal structure and is composed of a hexagonal lattice, wherein each carbon atom is tightly connected with the other three carbon atoms through strong sigma bonds, and the connection mode endows the graphene with remarkable structural strength. The graphene has a unique two-dimensional structure, and has potential application value in the fields of electrochemistry, optics, biomedicine, energy sources, spinning and the like. Research shows that graphene has excellent functions of antibiosis, ultraviolet resistance, static resistance, water resistance, heat conduction and the like in the textile field, greatly enriches the functionality of textiles and obviously improves the experience of users.
In the textile field, especially in the clothing field, heat storage and insulation are very important functional requirements; the traditional textile fabric often cannot meet the requirement of long-time heat preservation in a cold environment, so that development of a novel textile fabric with excellent heat storage and heat preservation performance is of great concern. The graphene has excellent photo-thermal conversion capability, can effectively absorb far infrared light, and can rapidly convert absorbed light energy into heat energy, the characteristic opens up a new way for developing high-performance heat storage and insulation textiles, and more durable and comfortable heat insulation experience is expected to be provided in a cold environment.
Currently, there are 2 approaches to preparing heat accumulating textiles from graphene: spinning and finishing processes. The spinning method is to spin graphene or mix graphene fiber and fabric fiber to blend the graphene fiber and the fabric fiber, and the spinning method can improve the binding force of the graphene and the fiber, so that the heat storage and insulation performance is more durable and stable, but the spinning method has the defects of high operation difficulty, high technical threshold and high cost. As disclosed in chinese laid-open patent CN115805737a, a thermal storage insulating layer containing graphene is prepared by a spinning method, and is woven by using blended yarns, wherein the blended yarns are formed by twisting composite fibers containing graphene and chitosan fibers. The after-finishing method is to directly coat or impregnate the finished textile, and has the advantages of simple process, low equipment requirement, convenient operation and the like compared with the spinning method, but the binding force between the graphene layer and the textile substrate may not be as good as that of the direct spinning method, and the original air permeability of the textile may be changed by the coating, so that the wearing comfort is affected. As disclosed in chinese laid-open patent CN110066635A, a conductive heat storage fabric containing graphene is prepared by adopting an after-finishing method, a graphene coating glue is formed by mixing a graphene emulsion, a polyurethane emulsion, a cross-linking agent, an acrylate polymer and water, and then the graphene coating is prepared by coating the graphene glue on the fabric and performing after-treatment.
The improvement of heat storage and insulation performance often affects the air permeability and the comfort of the fabric, so that development of the textile fabric with excellent heat storage and insulation performance and good air permeability has important significance for meeting the requirements of consumers on multifunctional comfortable clothing.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a graphene heat storage fabric, a preparation method and application thereof, and the graphene heat storage fabric has excellent heat storage and insulation properties.
One object of the invention is achieved by the following technical scheme:
The graphene heat storage fabric comprises a fabric layer and a heat storage and insulation layer positioned above the fabric layer, wherein the heat storage and insulation layer is prepared by coating a composite finishing agent of graphene coated with polyvinyl acetal on the upper surface of the fabric layer;
the graphene coated with the polyvinyl acetal is obtained by mixing graphene aqueous dispersion and polyvinyl acetal ethanol solution and then spray drying.
Preferably, the thickness of graphene in the graphene aqueous dispersion is 0.1-100 nm, and more preferably 0.5-20 nm; the particle diameter of graphene is 0.1 to 100 μm, and more preferably 1 to 30 μm.
Preferably, the concentration of graphene in the graphene aqueous dispersion is 0.01 to 100mg/mL, and more preferably 0.1 to 50mg/mL.
Preferably, the polyvinyl acetal ethanol solution is formed by dissolving polyvinyl acetal in ethanol, wherein the concentration of the polyvinyl acetal is 1-500 mg/ml, and more preferably 2-200 mg/ml.
Preferably, the polyvinyl acetal is one or more of polyvinyl formal, polyvinyl acetal, polyvinyl formal, and polyvinyl butyral, and more preferably, the polyvinyl acetal is polyvinyl butyral.
Preferably, the mass ratio of the graphene to the polyvinyl acetal is 1:0.2-1:5; more preferably 1:0.5 to 1:2.
Preferably, the conditions of spray drying include: the feeding amount is 800-2000 ml/h, the caliber of the nozzle is 1-100 mu m, the air inlet temperature is 120-200 ℃, and the air outlet temperature is 70-100 ℃. Further preferably, the nozzle diameter is 5 to 50 μm, and the nozzle diameter is larger than the particle diameter of graphene.
Preferably, the composite finishing agent comprises the following components in parts by weight:
40-60 parts of aqueous polyurethane emulsion and a dispersing agent: 0.1-1 part of graphene wrapping polyvinyl acetal: 6-20 parts of water and 5-20 parts of water.
Preferably, the solid content of the aqueous polyurethane emulsion is 30-70wt%.
Preferably, the dispersant is one or more of alkylbenzene sulfonate (such as dodecylbenzene sulfonate, tetradecyl benzene sulfonate, etc.), alkylnaphthalene sulfonate, polyoxyethylene alkyl ether, lignin sulfonate.
Preferably, the preparation method of the composite finishing agent comprises the following steps: and adding the graphene coated with the polyvinyl acetal into the aqueous polyurethane emulsion under the stirring state, then adding the dispersing agent and water, and uniformly stirring to obtain the composite finishing agent.
The heat storage and insulation layer is positioned above the fabric layer, namely is positioned on the upper surface of the fabric layer, and covers the upper surface of the fabric layer entirely.
The fabric layer is a textile, and the material is not particularly limited, and may be cotton fabric, polyester fabric, nylon fabric, blended fabric, or the like, and the textile manner is not particularly limited, and may be woven, knitted, nonwoven, or the like.
Preferably, the preparation method of the heat storage and insulation layer comprises the following steps: and (3) coating the composite finishing agent containing the graphene coated with the polyvinyl acetal on the upper surface of the fabric layer, drying, and baking at 150-180 ℃ to obtain the heat storage and insulation layer.
Preferably, the thickness of the coating is 0.1-3 mm.
Preferably, the drying temperature is 60-90 ℃ and the drying time is 5-20 min. Preferably, the baking time is1 to 5 minutes.
Another object of the invention is achieved by the following technical solutions:
the preparation method of the graphene heat storage fabric comprises the following steps of:
Adding the graphene coated with the polyvinyl acetal into the aqueous polyurethane emulsion in a stirring state, then adding a dispersing agent and water, and uniformly stirring to obtain a composite finishing agent;
and fixing the fabric layer on a coating machine, uniformly coating the composite finishing agent on the upper surface of the fabric layer, drying, and baking at 150-180 ℃ to obtain the graphene heat storage fabric.
The third object of the present invention is achieved by the following technical scheme:
the graphene heat storage fabric is applied to clothing industry, home textile products, military field, aerospace field and medical care products.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the invention, the graphene aqueous dispersion liquid and the polyvinyl acetal ethanol solution are mixed and then subjected to spray drying, ethanol can be used as a pore-forming agent in the spray drying process to obtain porous polyvinyl acetal, so that the surface of graphene is wrapped by the porous polyvinyl acetal to obtain novel graphene which is actually wrapped by the porous polyvinyl acetal;
2. compared with the composite finishing agent only added with graphene, the novel graphene coated with polyvinyl acetal is added into the composite finishing agent, and the fabric has excellent air permeability when being coated on the fabric, and the coating layer and the fabric substrate have excellent combination property;
3. The graphene heat storage fabric provided by the invention keeps the comfort of the fabric under the condition of good air permeability, greatly improves the heat storage performance of the fabric, and meets the requirements of consumers on multifunctional heat storage and ventilation clothes.
Detailed Description
The technical scheme of the present invention will be further described by the following specific examples, and it should be understood that the specific examples described herein are only for aiding in understanding the present invention, and are not intended to be limiting. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
In the following examples and comparative examples, the sources of the raw materials were:
the graphene aqueous dispersion is purchased from Litt nanometer, the thickness of graphene is 2-10 nm, the particle size is 1-10 mu m, and the concentration is 40mg/mL.
The aqueous polyurethane emulsion is kesi chuang DispercollU, 54, and the solid content is 50%.
The polyvinyl butyral is cola MowitalB H.
The fabric layer is cotton fabric, plain weave fabric, warp and weft yarn fineness is 28tex, warp yarn density is 420 pieces/10 cm, and weft yarn density is 360 pieces/10 cm.
Example 1
The graphene coated with polyvinyl butyral of the present embodiment is prepared by the following preparation method:
Dissolving polyvinyl butyral in ethanol to form a polyvinyl butyral ethanol solution with the concentration of 50mg/ml, mixing 100ml of graphene aqueous dispersion with 80ml of polyvinyl butyral ethanol solution, performing ultrasonic dispersion for 10min at 200w, and performing spray drying, wherein the feeding amount of the spray drying is 1500ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of the spray drying is 160 ℃, and the air outlet temperature is 90 ℃, so as to obtain the graphene coated with the polyvinyl butyral.
The graphene heat-storage fabric of the embodiment is prepared by the following method:
S1, the components of the composite finishing agent are as follows: 50 parts of aqueous polyurethane emulsion, 0.3 part of dispersing agent sodium dodecyl benzene sulfonate, 15 parts of graphene coated with polyvinyl butyral and 10 parts of water; and adding the graphene coated with the polyvinyl butyral into the aqueous polyurethane emulsion under the stirring state of 600rpm, then adding sodium dodecyl benzene sulfonate and water, and continuing stirring for 20min to obtain the composite finishing agent.
S2, pretreatment of cotton fabric: the cotton fabric is cut into a plurality of 15cm multiplied by 15cm, placed in a detergent (10 g of washing powder and 500g of water) for 3min, washed off surface stains, rinsed with water until no foam exists, and dried for later use.
S3, fixing the pretreated cotton fabric on a coating machine, controlling the thickness of the coating to be 0.5mm, uniformly scraping and coating the composite finishing agent on the upper surface of the cotton fabric, drying at 80 ℃ for 10min, and finally baking at 160 ℃ for 2min to obtain the graphene heat-accumulating fabric.
Example 2
The graphene coated with polyvinyl butyral of the present embodiment is prepared by the following preparation method:
Dissolving polyvinyl butyral in ethanol to form a polyvinyl butyral ethanol solution with the concentration of 30mg/ml, mixing 100ml of graphene aqueous dispersion with 100ml of polyvinyl butyral ethanol solution, performing ultrasonic dispersion for 8min at 300w, and then performing spray drying, wherein the feeding amount of the spray drying is 1200ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of the spray drying is 150 ℃, and the air outlet temperature is 80 ℃, so as to obtain the graphene coated with the polyvinyl butyral.
The graphene heat-storage fabric of the embodiment is prepared by the following method:
s1, the components of the composite finishing agent are as follows: 40 parts of aqueous polyurethane emulsion, 0.2 part of dispersing agent sodium tetradecyl benzenesulfonate, 8 parts of graphene coated with polyvinyl butyral and 8 parts of water; and adding the graphene coated with the polyvinyl butyral into the aqueous polyurethane emulsion under the stirring state of 700rpm, then adding sodium tetradecyl benzenesulfonate and water, and continuing stirring for 15min to obtain the composite finishing agent.
S2, pretreatment of cotton fabric: the cotton fabric is cut into a plurality of 15cm multiplied by 15cm, placed in a detergent (10 g of washing powder and 500g of water) for 3min, washed off surface stains, rinsed with water until no foam exists, and dried for later use.
S3, fixing the pretreated cotton fabric on a coating machine, controlling the thickness of the coating to be 0.7mm, uniformly scraping and coating the composite finishing agent on the upper surface of the cotton fabric, drying at 75 ℃ for 12min, and finally baking at 150 ℃ for 2.5min to obtain the graphene heat-accumulating fabric.
Example 3
The graphene coated with polyvinyl butyral of the present embodiment is prepared by the following preparation method:
Dissolving polyvinyl butyral in ethanol to form a polyvinyl butyral ethanol solution with the concentration of 60mg/ml, mixing 100ml of graphene aqueous dispersion with 80ml of polyvinyl butyral ethanol solution, performing ultrasonic dispersion for 15min at 100w, and performing spray drying, wherein the feeding amount of spray drying is 1400ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of spray drying is 170 ℃, and the air outlet temperature is 95 ℃, so as to obtain the graphene coated with the polyvinyl butyral.
The graphene heat-storage fabric of the embodiment is prepared by the following method:
S1, the components of the composite finishing agent are as follows: 60 parts of aqueous polyurethane emulsion, 0.5 part of dispersing agent sodium dodecyl benzene sulfonate, 20 parts of graphene coated with polyvinyl butyral and 20 parts of water; and adding the graphene coated with the polyvinyl butyral into the aqueous polyurethane emulsion under the stirring state of 600rpm, then adding sodium dodecyl benzene sulfonate and water, and continuing stirring for 25min to obtain the composite finishing agent.
S2, pretreatment of cotton fabric: the cotton fabric is cut into a plurality of 15cm multiplied by 15cm, placed in a detergent (10 g of washing powder and 500g of water) for 3min, washed off surface stains, rinsed with water until no foam exists, and dried for later use.
S3, fixing the pretreated cotton fabric on a coating machine, controlling the thickness of the coating to be 1.0mm, uniformly scraping and coating the composite finishing agent on the upper surface of the cotton fabric, drying at 85 ℃ for 8min, and finally baking at 170 ℃ for 2min to obtain the graphene heat-accumulating fabric.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 does not comprise polyaddition of vinyl butyral, in particular:
And (3) carrying out spray drying on 100ml of graphene aqueous dispersion, wherein the feeding amount of spray drying is 1500ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of spray drying is 160 ℃, and the air outlet temperature is 90 ℃, so as to obtain the spray-dried graphene.
The graphene coated with polyvinyl butyral of example 1 was replaced with spray-dried graphene, and the other materials were prepared in the same manner as the graphene heat-storage fabric of example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that comparative example 1 does not incorporate graphene, specifically:
Dissolving polyvinyl butyral in ethanol to form polyvinyl butyral ethanol solution with the concentration of 50mg/ml, carrying out spray drying on 80ml of polyvinyl butyral ethanol solution, wherein the feeding amount of spray drying is 1500ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of spray drying is 160 ℃, and the air outlet temperature is 90 ℃, thus obtaining spray-dried polyvinyl butyral.
The graphene coated with polyvinyl butyral of example 1 was replaced with spray-dried polyvinyl butyral, and the preparation method of the graphene heat-storage fabric of example 1 was otherwise the same.
Comparative example 3
Comparative example 3 the polyvinyl butyral was directly used instead of the graphene coated with polyvinyl butyral of example 1, except for the preparation method of the graphene thermal storage fabric of example 1.
Comparative example 4
And (3) carrying out spray drying on 100ml of graphene aqueous dispersion, wherein the feeding amount of spray drying is 1500ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of spray drying is 160 ℃, and the air outlet temperature is 90 ℃, so as to obtain the spray-dried graphene.
Dissolving polyvinyl butyral in ethanol to form polyvinyl butyral ethanol solution with the concentration of 50mg/ml, carrying out spray drying on 80ml of polyvinyl butyral ethanol solution, wherein the feeding amount of spray drying is 1500ml/h, the caliber of a nozzle is 20 mu m, the air inlet temperature of spray drying is 160 ℃, and the air outlet temperature is 90 ℃, thus obtaining spray-dried polyvinyl butyral.
And physically mixing the spray-dried graphene and the spray-dried polyvinyl butyral to obtain a spray-dried graphene and spray-dried polyvinyl butyral mixture.
The spray-dried graphene and spray-dried polyvinyl butyral mixture were used instead of the polyvinyl butyral-coated graphene of example 1, except that the preparation method of the graphene thermal storage fabric of example 1 was the same.
The reference substance is cotton fabric material layer.
The fabric samples of examples 1 to 3 and comparative examples 1 to 4 were subjected to heat storage and temperature rise performance test, air permeability test and abrasion resistance test.
And (3) heat storage and temperature rising performance test: the heat accumulating fabric sample is tested in an environment with the temperature of 20 ℃ and the relative humidity of 65%, a xenon arc lamp is adopted as an irradiation light source, the sample is irradiated by 500W light for 20min at a position 50cm above the center point of the sample, the temperature of the sample is tested by a temperature sensor, and the temperature change of the sample at each time point within 20min of irradiation is recorded. The heat accumulation and temperature rise test results are shown in table 1.
Air permeability: according to GB/T5453-1997 "textile air permeability test method", an air permeability tester is used for testing the air permeability of a heat accumulating fabric sample at 20 ℃ under the environment of 65% relative humidity, the area of the sample is 20cm 2, and the test pressure difference is 100Pa. The test surface is a fabric surface. The test results are shown in Table 2.
By measuring the wear resistance of the heat storage fabric as a binding force evaluation standard, the wear resistance is tested: the YG401D full-automatic fabric flat grinder is adopted, the size of a test sample is 15cm multiplied by 15cm, and after grinding is performed for 1000 times, an electronic balance is used for testing the mass loss before and after the test sample is worn. The results are shown in Table 2.
Table 1 temperature change meter of heat accumulating fabric
Table 2 breathability and abrasion resistance of heat storage fabric
| Air permeability mm/s | Loss of mass g | |
| Example 1 | 1165 | 0.004 |
| Example 2 | 1110 | 0.005 |
| Example 3 | 1185 | 0.003 |
| Comparative example 1 | 895 | 0.012 |
| Comparative example 2 | 1092 | 0.007 |
| Comparative example 3 | 905 | 0.01 |
| Comparative example 4 | 1010 | 0.009 |
| Reference substance | 1250 | / |
As can be seen from tables 1 and 2, examples 1-3 have excellent heat storage performance relative to the fabric control, and the air permeability is only slightly lower than that of the fabric control, without affecting the comfort of the user. As is clear from comparative example 1 and comparative example 1, when the heat storage capacity of the fabric can be improved by coating the fabric with only the finishing agent containing graphene, the overall air permeability of the fabric is greatly reduced, and the bonding performance between the coating and the fabric is low, and the abrasion resistance is reduced. Comparative example 2 the fabric was coated with a finish containing sprayed polyvinyl butyral alone, and the heat storage performance was greatly reduced compared to example 1 due to the lack of graphene, the air permeability was slightly lower than example 1, and the abrasion resistance was lower than example 1. As is apparent from comparison of comparative example 2 and comparative example 3, porous polyvinyl butyral ethanol obtained by spray drying of polyvinyl butyral ethanol solution is advantageous in permeation of air, and thus, comparative example 2 is more breathable than comparative example 3. Comparative example 4 spray-dried graphene obtained by respective spray-drying and spray-dried polyvinyl butyral were physically mixed, and the mixture obtained by physical mixing was applied to a finishing agent, and the fabric obtained after coating was reduced in heat storage property, air permeability and bonding property as compared with the case where example 1 was applied to a finishing agent in the form of polyvinyl butyral-coated graphene.
In general, the graphene heat storage fabric prepared by the method has better air permeability, and the heat storage performance of the fabric is greatly improved.
The various aspects, embodiments, features of the invention are to be considered as illustrative in all respects and not restrictive, the scope of the invention being indicated only by the appended claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In the preparation method of the invention, the sequence of each step is not limited to the listed sequence, and the sequential change of each step is also within the protection scope of the invention without the inventive labor for the person skilled in the art. Furthermore, two or more steps or actions may be performed simultaneously.
Finally, it should be noted that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention's embodiments. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions in a similar manner, and need not and cannot fully practice all of the embodiments. While these obvious variations and modifications, which come within the spirit of the invention, are within the scope of the invention, they are to be construed as being without departing from the spirit of the invention.
Claims (11)
1. The graphene heat storage fabric is characterized by comprising a fabric layer and a heat storage and insulation layer positioned above the fabric layer, wherein the heat storage and insulation layer is prepared by coating the upper surface of the fabric layer with a composite finishing agent containing graphene wrapped with polyvinyl acetal;
The graphene coated with the polyvinyl acetal is obtained by mixing graphene aqueous dispersion and polyvinyl acetal ethanol solution and then spray drying;
In the graphene aqueous dispersion, the concentration of graphene is 0.01-100 mg/mL;
in the polyvinyl acetal ethanol solution, the concentration of the polyvinyl acetal is 1-500 mg/ml;
The mass ratio of the graphene to the polyvinyl acetal is 1:0.2-1:5;
the conditions of spray drying include: the feeding amount is 800-2000 ml/h, the caliber of the nozzle is 1-100 mu m, the air inlet temperature is 120-200 ℃, and the air outlet temperature is 70-100 ℃.
2. The graphene heat storage fabric according to claim 1, wherein in the graphene aqueous dispersion liquid, the thickness of graphene is 0.1-100 nm, and the particle size of graphene is 0.1-100 μm.
3. The graphene thermal storage fabric according to claim 1 or 2, wherein in the graphene aqueous dispersion, the thickness of graphene is 0.5-20 nm, and the particle size of graphene is 1-30 μm.
4. The graphene heat storage fabric according to claim 1, wherein the concentration of graphene in the graphene aqueous dispersion is 0.1-50 mg/mL;
In the polyvinyl acetal ethanol solution, the concentration of the polyvinyl acetal is 2-200 mg/ml;
the mass ratio of the graphene to the polyvinyl acetal is 1:0.5-1:2.
5. The graphene thermal storage fabric according to claim 3, wherein the caliber of the nozzle is 5-50 μm, and the caliber of the nozzle is larger than the particle size of graphene.
6. The graphene thermal storage fabric according to claim 1, wherein the polyvinyl acetal is one or more of polyvinyl formal, polyvinyl acetal, polyvinyl formal and polyvinyl butyral.
7. The graphene heat storage fabric according to claim 1, wherein the composite finishing agent comprises the following components in parts by weight:
40-60 parts of aqueous polyurethane emulsion and a dispersing agent: 0.1-1 part of graphene wrapping polyvinyl acetal: 6-20 parts of water and 5-20 parts of water.
8. The graphene heat storage fabric according to claim 7, wherein the solid content of the aqueous polyurethane emulsion is 30-70wt%;
The dispersing agent is one or more of alkylbenzene sulfonate, alkyl naphthalene sulfonate, polyoxyethylene alkyl ether and lignin sulfonate.
9. The method for preparing the graphene heat storage fabric as claimed in claim 1, which is characterized by comprising the following steps:
Adding the graphene coated with the polyvinyl acetal into the aqueous polyurethane emulsion in a stirring state, then adding a dispersing agent and water, and uniformly stirring to obtain a composite finishing agent;
and fixing the fabric layer on a coating machine, uniformly coating the composite finishing agent on the upper surface of the fabric layer, drying, and baking at 150-180 ℃ to obtain the graphene heat storage fabric.
10. The preparation method according to claim 9, wherein the thickness of the coating is 0.1-3 mm;
the drying temperature is 60-90 ℃ and the drying time is 5-20 min;
the baking time is 1-5 min.
11. The application of the graphene heat-storage fabric in the clothing industry, home textile products, military field, aerospace field and medical care products.
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| CN114479328A (en) * | 2022-02-24 | 2022-05-13 | 杭州高烯科技有限公司 | Preparation method of acetal polymer-graphene composite material |
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