CN115181549B - Phase-change energy-storage heat-conducting film material based on crystalline trans-rubber and preparation method thereof - Google Patents
Phase-change energy-storage heat-conducting film material based on crystalline trans-rubber and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 111
- 239000005060 rubber Substances 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000004146 energy storage Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 18
- 230000003712 anti-aging effect Effects 0.000 claims description 17
- 235000021355 Stearic acid Nutrition 0.000 claims description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000008117 stearic acid Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000004134 energy conservation Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 claims description 2
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims 1
- 239000012782 phase change material Substances 0.000 abstract description 10
- 239000011232 storage material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 36
- 230000007704 transition Effects 0.000 description 20
- 229920001195 polyisoprene Polymers 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
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- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 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
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- 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
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- 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
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Abstract
The invention belongs to the technical field of phase change energy storage materials, and particularly relates to an energy storage heat conduction film material taking crystalline trans-rubber as a phase change material and a preparation technology thereof. Compared with the existing polymer-based phase-change material, the phase-change temperature of the slightly crosslinked trans-rubber is adjustable at 130 ℃, the application range is wide, the stability is high, and the heat transfer performance is enhanced.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage film materials, relates to an energy storage heat conduction film material containing a polymer phase change material, and particularly relates to a phase change energy storage heat conduction film material based on crystalline trans-rubber and a preparation method thereof.
Background
The phase change energy storage material is capable of absorbing and releasing a large amount of latent heat at a constant temperature by utilizing the transformation of the phase change material state, can be used as an advanced high-efficiency energy storage and temperature control medium, and is widely applied to the field of electronic device heat management. At present, the phase change energy storage materials are commonly used as solid-liquid phase change materials, and include inorganic phase change materials such as inorganic molten salt, crystalline hydrated salt, metal alloy and the like, and organic phase change materials such as paraffin, fatty acid and the like. However, these materials can leak during the phase change process, requiring the vessel to separate the phase change material from the heat transfer medium, or to be encapsulated with a polymer capsule, thus increasing the complexity and cost of the system construction. Based on the solid-solid phase transition material, particularly the solid-solid phase transition material represented by the polymer material, the solid-solid phase transition material can be directly used as a structural material of a system due to the characteristics of easy preparation of various forms, has obvious application advantages, and becomes a research hot spot in the field of phase change energy storage materials.
However, the common polymer phase-change materials, such as cross-linked polyolefin crystalline materials (Journal of Thermophysics and Heat Transfer,1991,5 (1), 122), have high phase-change temperature and narrow application range, and polyethylene glycol polymer (CN 99116025.8) phase-change materials need to be grafted onto a solid carrier, so that the preparation process is complex and the material cost is high. Trans-rubber is a type of elastomeric material with a high stereoregularity structure, with a melting temperature substantially below 130 ℃, a different composition, and a different phase transition temperature, but lower than the phase transition temperature of the polyolefin crystalline materials currently used. When the trans-rubber is lightly crosslinked, the thermal stability of the material is increased, the crystallization capability is still remained, and the phase transition temperature is slightly reduced along with the increase of the crosslinking degree. In addition, the trans-rubber has high raw rubber strength, excellent fatigue resistance and better heat resistance after vulcanization, and is expected to be applied to phase change materials. Currently, the application of crystalline trans-rubber in energy storage materials has not been widely developed.
Disclosure of Invention
The invention aims to provide a high-efficiency phase change energy storage film material based on crystalline trans-rubber and a preparation method thereof by fully utilizing the performance advantage of the crystalline trans-rubber; the second purpose of the invention is to solve the defect of thermal conductivity of the polymer phase change material, and keep the heat storage capacity of the polymer as much as possible, provide a double-layer phase change energy storage film material with Janus structure, in order to achieve the dual functions of energy storage and heat conduction, in addition, in Janus structure, the double-layer film has strong adhesion between two layers due to homogeneity and interface co-vulcanization, which is beneficial to heat transfer; the third object of the present invention is to widen the application range of the trans rubber.
The preparation method and the technical principle of the invention are as follows: the preparation method comprises (1) dissolving trans-rubber in toluene dispersed with antioxidant, zinc oxide and stearic acid at 60deg.C to obtain trans-rubber solution; dispersing or dissolving a vulcanization accelerator and a vulcanizing agent in toluene at room temperature, mixing with a trans-rubber solution, pouring the mixture on a clean glass substrate while the mixture is hot, placing the glass substrate on a 60 ℃ hot table, drying until the solvent volatilizes, casting a trans-rubber toluene solution containing a heat conducting filler, an anti-aging agent, stearic acid, zinc oxide, the vulcanizing agent and the vulcanization accelerator on the surface of the glass substrate, placing the glass substrate in hot water at 75-80 ℃ after the glass substrate is further dried on the 60 ℃ hot table, and heating, vulcanizing and crosslinking for 1-5 hours to obtain the energy storage heat conducting film material with a double-layer Janus structure; (2) Adding trans-rubber into a torque rheometer at 70 ℃ and 70rpm, adding an anti-aging agent, zinc oxide and stearic acid after 2min, banburying for 12min, and discharging rubber; sequentially adding the mixed rubber, the vulcanizing agent and the accelerator in the upper section in an internal mixer at 60 ℃ and 70rpm, uniformly mixing, discharging rubber after 6min, and discharging to obtain mixed rubber (b); and (3) adding a heat-conducting filler on the basis of the formula of the rubber compound (a), repeating the same processing procedure of the rubber compound (a), adding the heat-conducting filler after adding an anti-aging agent, discharging rubber and discharging sheets to obtain a rubber compound (b) after uniformly mixing, respectively placing the rubber compound a and the rubber compound b in a flat vulcanizing machine, pressing the rubber compound a and the rubber compound b into films with required thickness at 10MPa and 120 ℃, overlapping the two films up and down, placing the films in hot water at 75-80 ℃, and heating, vulcanizing and crosslinking for 1-10 hours to obtain the energy-storage heat-conducting film material with a double-layer Janus structure.
The phase change energy storage heat conduction film material based on crystalline trans-rubber is characterized in that the film material is a double-layer film with a Janus structure, one layer is a slightly crosslinked trans-rubber film, and the other layer is a composite film formed by slightly crosslinked trans-rubber and a heat conduction filler.
The phase change energy storage heat conduction film material based on crystalline trans-rubber is characterized in that in a double-layer film with a Janus structure, a cross-linked trans-rubber film comprises: 3-15 parts by weight of other (anti-aging agent, vulcanizing agent and vulcanizing auxiliary agent); crosslinked trans-rubber and heat-conducting filler composite membrane group: 100 parts of trans-rubber, 5-70 parts of heat conducting filler and 3-15 parts of other (anti-aging agent, vulcanizing agent and vulcanizing aid).
The thickness of the phase change energy storage heat conduction film material based on crystalline trans-rubber is 0.1-3 mm, and the thickness ratio of the trans-rubber film to the trans-rubber and heat conduction filler composite film is 0.2-1.
The crystalline trans-rubber is one or more of trans-1, 4-polyisoprene, trans-1, 4-polybutadiene and trans-butyl-pentyl copolymer rubber.
The weight average molecular weight of the trans-rubber is 20000 ～ 1000000; trans content greater than 90%; in the trans-butyl-pentyl copolymer rubber, the butadiene unit content is 5-60%.
The lightly crosslinked trans-rubber has a degree of crosslinking of 0.2 to 1% (i.e., about 100 to 500 structural units have one structural unit crosslinked).
The heat conducting filler is Al 2 O 3 、ZnO、MgO、NiO、BN、AlN、Si 3 N 4 One or more of SiC porcelain, metal powder (including any one or more of gold, silver, copper, nickel, aluminum and the like), graphite, carbon black, carbon fiber, carbon nano tube, graphene, MXene and the like.
The phase transition temperature of the energy storage heat conduction phase change film material is lower than 130 ℃, and the heat conductivity of the energy storage heat conduction phase change film material is 0.50-5W/mK.
The preparation method of the phase change energy storage heat conduction film material based on crystalline trans-rubber is characterized by comprising the following steps of: the rubber is prepared from (by weight parts) anti-aging agent 1-5, vulcanizing agent 0.5-1.5, and vulcanizing auxiliary (stearic acid, zinc oxide, and accelerator) 1-10.
The phase change energy storage heat conduction film material based on crystalline trans-rubber can be used for various purposes such as building energy conservation, wearable heat management devices, cold chain transportation, medical care, waste heat utilization and the like.
Drawings
FIG. 1 differential scanning calorimetry (Mw= 375000, phase transition temperature below 70 ℃) of trans-1-4-polyisoprene.
FIG. 2 is a differential scanning calorimetry plot of a trans-polybutylece copolymer rubber (Mw= 1580000, butadiene unit content 56.2mol%, phase transition temperature below 130 ℃).
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The parts referred to in the examples below are parts by weight.
Example 1
200mg of trans-polyisoprene (Mw= 375000, trans-1, 4-structure >99mol%, phase transition temperature 52-64 ℃) was dissolved in 80ml of toluene in which 4mg of antioxidant 264, 4mg of zinc oxide, 3mg of stearic acid had been dispersed at 60 ℃ to prepare a trans-polyisoprene solution; dispersing 2mg of accelerator CZ and 1mg of sulfur into 20ml of toluene, rapidly mixing with a trans-polyisoprene toluene solution, casting the mixture on a clean glass substrate while the mixture is hot, drying the mixture on a hot table at the temperature of 60 ℃ until the solvent volatilizes, forming a 0.4mm sheet, casting a Janus-structure double-layer energy-storage heat-conducting film material with the phase change temperature of 50-62 ℃ and the heat conductivity of 0.98W/mK, which is prepared from 250mg of trans-polyisoprene (Mw= 375000, trans-1, 4-structure >99 mol%), 50mg of carbon nano tube, 5mg of antioxidant 264, 5mg of zinc oxide, 4mg of stearic acid, 2.4mg of accelerator CZ, 1.2mg of sulfur and 100ml of toluene on the surface of the sheet, and further drying the sheet on a hot table at the temperature of 60 ℃, and then placing the sheet in hot water at the temperature of 75-80 ℃ for heat vulcanization for 5 hours.
Example 2
100mg of trans-butyl-pentyl copolymer rubber (Mw=550000, trans-1, 4-structure >92mol%, butadiene unit content 16.4mol%, phase transition temperature 30-45 ℃) and 100mg of trans-polyisoprene (Mw= 375000, trans-1, 4-structure >99mol%, phase transition temperature 52-64 ℃) were dissolved in 80ml of toluene, in which 4mg of antioxidant 4010NA, 6mg of zinc oxide, 4mg of stearic acid had been dispersed, at 60℃to prepare a trans-butyl-pentyl copolymer rubber and a trans-polyisoprene solution; dispersing 2mg of accelerator CZ and 1.2mg of sulfur into 20ml of toluene, rapidly mixing with a trans-butyl-pentyl copolymer rubber/trans-polyisoprene toluene solution, pouring the mixture on a clean glass substrate while the mixture is hot, placing the mixture on a 60 ℃ hot stage, drying the mixture until a solvent volatilizes to form a 0.6mm sheet, casting a film with the total thickness of 1.4mm on the surface of the sheet, and then placing the film in hot water with the temperature of 75-80 ℃ for heat vulcanization and cross-linking for 5 hours, wherein the total thickness of the film is 1.4mm, and the film is prepared from 100mg of trans-butyl copolymer rubber (Mw=55000, trans-1, 4-structure is more than 92mol percent, butadiene unit content is 16.4mol percent, and phase transition temperature is 30-45 ℃), 100mg of trans-polyisoprene (Mw= 375000, trans-1, 4-structure is more than 99mol percent, and the phase transition temperature is 52-64 ℃), 70mg of carbon nano tubes, 4mg of antioxidant 4010NA, 6mg of zinc oxide, 4mg of stearic acid, 2mg of accelerator CZ, 1.5mg of sulfur and 100ml toluene combined solution, and further drying the film at 60 ℃ to obtain the heat-conducting material with the phase transition temperature of 1.14 JamW/nus.
Example 3
200mg of trans-polyisoprene (Mw= 773000, trans-1, 4-structure >99mol%, phase transition temperature 52-64 ℃) was dissolved in 80ml of toluene in which 4mg of antioxidant 264, 4mg of zinc oxide, 3mg of stearic acid had been dispersed at 60℃to prepare a trans-polyisoprene solution; 3mg of accelerator CZ and 2mg of sulfur are dispersed into 20ml of toluene, quickly mixed with a trans-polyisoprene toluene solution, cast on a clean glass substrate while the glass substrate is hot, placed on a hot table at 60 ℃, dried until the solvent volatilizes, formed into a 0.5mm sheet, and cast on the surface of the sheet again a Janus structure double-layer energy-storage heat-conducting film material with a phase change temperature of 30-60 ℃ and a thermal conductivity of 1.08W/mK, which is formed by 250mg of trans-butadiene-isoprene copolymer rubber (Mw= 690000, trans-1, 4-structure >92mol%, butadiene unit content of 19.0mol%, and a phase change temperature of <60 ℃), 70mg of boron nitride, 5mg of an anti-aging agent 4010NA, 6mg of zinc oxide, 4mg of stearic acid, 3mg of accelerator CZ, 2mg of sulfur and 100ml of toluene combined solution, and further dried on a hot table at 60 ℃.
Example 4
Adding 100phr of trans-polyisoprene (Mw= 773000, trans-1, 4-structure >99mol percent, phase transition temperature 52-64 ℃) into a torque rheometer at 70 ℃ and 70rpm in sequence, adding 4010 phr of anti-aging agent, 3phr of zinc oxide and 2phr of stearic acid after 2 minutes, banburying for 12 minutes, and discharging rubber; sequentially adding the mixed rubber of the previous section, 0.8phr of sulfur and 2phr of accelerator NS in an internal mixer at 60 ℃ and 70rpm, uniformly mixing, discharging rubber after 6min, and discharging tablets to obtain mixed rubber (a); adding 45phr of boron nitride based on the formula of the rubber compound (a), repeating the same processing procedure of the rubber compound (a), adding the heat-conducting filler after adding the anti-aging agent, discharging rubber and discharging sheets to obtain rubber compound (b), respectively placing the rubber compound a and the rubber compound b into a flat vulcanizing machine, pressing into films with the thickness of 0.4mm and 1mm at the temperature of 10MPa and 120 ℃, finally overlapping the two films up and down, placing into hot water at the temperature of 75-80 ℃, heating, vulcanizing and crosslinking for 7h, and obtaining the Janus structure double-layer energy storage heat-conducting film material with the phase change temperature of 50-62 ℃ and the heat conductivity of 2.55W/mK.
Example 5
100phr of trans-polyisoprene (Mw= 375000, trans-1, 4-structure >99mol percent, phase transition temperature 52-64 ℃) is sequentially added into a torque rheometer at 70 ℃ and 70rpm, 2 minutes later, 4010 phr of anti-aging agent, 3phr of zinc oxide and 2phr of stearic acid are added, and after banburying for 12 minutes, rubber is discharged; sequentially adding the mixed rubber of the previous section, 1phr of sulfur and 2phr of accelerator NS in an internal mixer at 60 ℃ and 70rpm, uniformly mixing, discharging rubber after 6min, and discharging tablets to obtain mixed rubber (a); based on the formula of the rubber compound (a), trans-butyl-pentyl copolymer rubber (Mw=550000, trans-1, 4-structure is more than 92mol%, butadiene unit content is 16.4mol%, phase transition temperature is 30-45 ℃) is substituted for trans-polyisoprene, sulfur consumption is changed into 1.5phr, 60phr of boron nitride is added, the same processing procedure of the rubber compound (a) is repeated, heat conducting filler is added after the anti-aging agent is added, after uniform mixing, rubber compound (b) is obtained by discharging and blanking, the rubber compound (a) and the rubber compound (b) are respectively placed in a flat vulcanizing machine, the rubber compound (a) and the rubber compound (b) are respectively pressed into 1mm and 1mm at 10MPa and 120 ℃, finally, two layers of films are overlapped up and down, and are placed in hot water at 75-80 ℃ for heating vulcanization and crosslinking for 7 hours, and the Janus structure double-layer heat-storage heat conducting film material with the phase transition temperature of 30-60 ℃ and the heat conductivity of 2.72W/mK is obtained.
Claims (6)
1. The phase change energy storage heat conduction film material based on crystalline trans-rubber is characterized in that the film material is a double-layer film with a Janus structure, and consists of a trans-rubber film with the crosslinking degree of 0.2-1% and a composite film composed of trans-rubber with the crosslinking degree of 0.2-1% and a heat conduction filler; the total film thickness is 0.1-3 mm, and the thickness ratio of the trans-rubber film to the trans-rubber and the heat-conducting filler composite film is 0.2-1;
in the Janus structure double-layer film, the cross-linked trans-rubber film consists of: 100 parts of trans-rubber and 3-15 parts of other components; the crosslinked trans-rubber and heat-conducting filler composite film consists of: 100 parts of trans-rubber, 5-70 parts of heat conducting filler and 3-15 parts of other heat conducting filler; the other components consist of an anti-aging agent, a vulcanizing agent and a vulcanizing aid; the vulcanization aid consists of zinc oxide, stearic acid and a vulcanization accelerator;
the trans-rubber is one or more of trans-1, 4-polyisoprene, trans-1, 4-polybutadiene and trans-butyl-pentyl copolymer rubber; the weight average molecular weight of the trans-rubber was 20000 ～ 1000000; trans content greater than 90%; in the trans-butyl-pentyl copolymer rubber, the butadiene unit content is 5 to 60mol percent.
2. The phase-change energy-storage heat-conducting film material according to claim 1, wherein the heat-conducting filler is Al 2 O 3 、ZnO、MgO、NiO、BN、AlN、Si 3 N 4 One or more of SiC porcelain, metal powder, graphite, carbon black, carbon fiber, carbon nanotube, graphene and MXene; the metal powder is one or more of gold, silver, copper, nickel and aluminum.
3. The phase-change energy-storage heat-conducting film material according to claim 1, wherein the phase-change temperature is lower than 130 ℃, and the heat conductivity is 0.5-5W/mK.
4. The method for preparing the crystalline trans-rubber-based phase-change energy storage heat conduction film material according to any one of claims 1 to 3, wherein the preparation steps are as follows: the asymmetric phase-change energy-storage heat-conducting film material with Janus structure is prepared by taking trans-rubber as a phase-change polymer matrix and adopting a mixing or solution pouring mode, and the preparation method comprises the following steps: in the solution casting mode (1), dissolving trans-rubber in toluene dispersed with an anti-aging agent, zinc oxide and stearic acid at 60 ℃ to prepare a trans-rubber solution; dispersing or dissolving a vulcanization accelerator and a vulcanizing agent in toluene at room temperature, mixing with a trans-rubber solution, pouring the mixture on a clean glass substrate while the mixture is hot, placing the glass substrate on a 60 ℃ hot table, drying until the solvent volatilizes, casting a trans-rubber toluene solution containing a heat conducting filler, an anti-aging agent, stearic acid, zinc oxide, the vulcanizing agent and the vulcanization accelerator on the surface of the glass substrate, placing the glass substrate in hot water at 75-80 ℃ after the glass substrate is further dried on the 60 ℃ hot table, and heating, vulcanizing and crosslinking for 1-5 hours to obtain the energy storage heat conducting film material with a double-layer Janus structure; adding trans-rubber into a torque rheometer in the mixing mode (2) at 70 ℃ and 70rpm, adding an anti-aging agent, zinc oxide and stearic acid after 2min, and discharging rubber after banburying for 12 min; sequentially adding the mixed rubber, the vulcanizing agent and the vulcanization accelerator in the previous section in an internal mixer at 60 ℃ and 70rpm, uniformly mixing, discharging rubber after 6min, and discharging to obtain mixed rubber (a); and (3) adding a heat-conducting filler on the basis of the formula of the rubber compound (a), repeating the same processing procedure of the rubber compound (a), adding the heat-conducting filler after adding an anti-aging agent, discharging rubber and discharging sheets to obtain a rubber compound (b) after uniformly mixing, respectively placing the rubber compound a and the rubber compound b in a flat vulcanizing machine, pressing the rubber compound a and the rubber compound b into films with required thickness at 10MPa and 120 ℃, overlapping the two films up and down, placing the films in hot water at 75-80 ℃, and heating, vulcanizing and crosslinking for 1-10 hours to obtain the energy-storage heat-conducting film material with a double-layer Janus structure.
5. The preparation method of the phase change energy storage heat conduction film material based on crystalline trans-rubber, which is characterized by comprising the following steps: the rubber is prepared from (by weight parts) anti-aging agent 1-5, vulcanizing agent 0.5-1.5, and vulcanizing auxiliary 1-10.
6. The crystalline trans-rubber-based phase change energy storage heat conducting film material according to any one of claims 1-3, for multiple uses of building energy conservation, wearable thermal management devices, cold chain transportation, waste heat utilization.
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Citations (4)
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|---|---|---|---|---|
| JPH09268208A (en) * | 1996-01-31 | 1997-10-14 | Ube Ind Ltd | Trans-1,4-polybutadiene and regenerative material |
| JP2004359886A (en) * | 2003-06-06 | 2004-12-24 | Ube Ind Ltd | Rubber composition |
| CN108943921A (en) * | 2018-07-20 | 2018-12-07 | 四川大学 | A kind of multilayer insulation thermal interfacial material and preparation method thereof |
| CN114716982A (en) * | 2022-05-11 | 2022-07-08 | 青岛科技大学 | Trans-rubber-based phase change energy storage microcapsule material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09268208A (en) * | 1996-01-31 | 1997-10-14 | Ube Ind Ltd | Trans-1,4-polybutadiene and regenerative material |
| JP2004359886A (en) * | 2003-06-06 | 2004-12-24 | Ube Ind Ltd | Rubber composition |
| CN108943921A (en) * | 2018-07-20 | 2018-12-07 | 四川大学 | A kind of multilayer insulation thermal interfacial material and preparation method thereof |
| CN114716982A (en) * | 2022-05-11 | 2022-07-08 | 青岛科技大学 | Trans-rubber-based phase change energy storage microcapsule material and preparation method thereof |
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