CN117736703A - Composite phase-change material with low thermal resistance, high heat conduction and non-electric conduction and preparation method thereof - Google Patents
Composite phase-change material with low thermal resistance, high heat conduction and non-electric conduction and preparation method thereof Download PDFInfo
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- CN117736703A CN117736703A CN202311759757.4A CN202311759757A CN117736703A CN 117736703 A CN117736703 A CN 117736703A CN 202311759757 A CN202311759757 A CN 202311759757A CN 117736703 A CN117736703 A CN 117736703A
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- Prior art keywords
- change material
- phase change
- stirring
- parts
- thermal resistance
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- 239000012782 phase change material Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 103
- 238000003756 stirring Methods 0.000 claims abstract description 97
- 239000002904 solvent Substances 0.000 claims abstract description 24
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- 238000012986 modification Methods 0.000 claims abstract description 5
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
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- 239000005062 Polybutadiene Substances 0.000 claims description 18
- 229920002857 polybutadiene Polymers 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 239000004014 plasticizer Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
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- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention discloses a composite phase-change material with low thermal resistance, high heat conduction and no electric conduction and a preparation method thereof, wherein the composite phase-change material comprises the following raw materials in parts by weight: the thermal conductive coating comprises a polymer mixed material, solvent oil, a first thermal conductive filler, a second thermal conductive filler, an additive and a coupling agent. According to the invention, the compatibility and dispersibility of the heat-conducting powder and the phase-change matrix material are optimized through powder modification treatment, and the reaction of the coupling agent reaction group and the powder surface but the reaction of the hydroxyl group are carried out, so that the agglomeration problem of the heat-conducting powder is avoided, and the influence of interface thermal resistance of different materials is effectively improved; and compared with the one-time adding and stirring production process, the subsequent sectional production process can avoid the mutual influence of reactive groups among some components, so that the final phase-change heat-conducting material has better comprehensive performance, and the test proves that the final phase-change heat-conducting material can obtain a good application effect.
Description
Technical Field
The invention relates to the technical field of heat conduction fillers, in particular to a composite phase change material with low thermal resistance, high heat conduction and non-electric conduction and a preparation method thereof.
Background
With the development of 5G, the communication application scene of the whole scene is rapidly developed, the requirements on chip performance and the like are higher and higher along with the rapid iteration of the artificial intelligence AI technology, meanwhile, the problem of heat dissipation is brought, how to improve heat dissipation is an important research subject, it is found that in a plurality of application scenes, applications under low pressure (less than 10 psi) occupy most part, some users have certain misareas, more attention is paid to heat conduction coefficients, the heat resistance is a key factor for judging the actual application effect, the heat conduction coefficients can be seen from the actual measurement data of the latest phase change heat conduction product of Honevirol, but the heat conduction coefficients are not high, but the heat resistance is very small under low pressure, the heat conduction coefficients are obviously higher than those of PTM7950 when the test in the reverse market can be seen, but the heat conduction coefficients under low pressure are relatively poor, and the heat resistance performance in the actual machine test process is not as good as that of PTM 7950. The pursuit of thermal resistance under high pressure and high thermal conductivity is obviously a little contrary to the demands of practical application.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the composite phase-change material with low thermal resistance, high heat conduction and no electric conduction and the preparation method thereof, the compatibility and the dispersibility of the heat conduction powder and the phase-change matrix material are optimized through powder modification treatment, the reaction of the reactive groups of the coupling agent and the surface of the powder but the hydroxyl groups is carried out, the problem of agglomeration of the heat conduction powder is avoided, the influence of the interface thermal resistance of different materials is effectively improved, and the follow-up sectional production process is adopted.
The invention provides a composite phase-change material with low thermal resistance, high heat conduction and no electric conduction, which comprises the following raw materials in parts by weight: 2-4 parts of polymer mixed material, 1-3 parts of solvent oil, 70-80 parts of first heat conducting filler, 20-25 parts of second heat conducting filler, 0.3-2 parts of additive and 0.5-1 part of coupling agent.
Preferably, the first and second thermally conductive fillers are each selected from one or more of metals, alloys, non-metals, metal oxides, metal nitrides, and ceramics;
the metal is selected from one or more of aluminum, copper, silver, zinc, nickel, tin, indium, lead, silver plated metal (such as silver plated copper or silver plated aluminum), metal plated carbon fiber, and nickel plated fiber;
the nonmetal is selected from one of carbon, carbon black, graphite, carbon nano tube, carbon fiber, graphene, diamond, glass, silicon dioxide, silicon nitride and boron-plated particles;
the metal oxide, metal nitride, and ceramic each include one or more of aluminum oxide, aluminum nitride, boron nitride, zinc oxide, and tin oxide.
Preferably, the first heat-conducting filler is selected from modified aluminum powder, and the second heat-conducting filler is selected from zinc oxide, wherein the modified aluminum powder is specifically prepared by the following steps:
step X1, uniformly mixing the modifier, the dispersion medium and the solvent according to a preset proportion, condensing and refluxing, and continuously stirring for 10-60min at the temperature of 30-60 ℃;
and step X2, regulating the pH value of the mixed solution obtained in the step S1, then adding aluminum powder, condensing and refluxing, continuously stirring at the temperature of 30-100 ℃ for 2-12h, and vacuum drying to obtain the modified aluminum powder.
Preferably, during the preparation of the modified aluminum powder, the surface of an aluminum powder interface layer can be regulated and controlled by adjusting the type and the addition amount of the modifier, the type of the solvent, controlling the reaction pH and the temperature, the prepolymerization degree of the modifier, the continuous reaction time and the times and the like, and the thickness of the aluminum powder interface layer is 0.5-150nm; the retention rate of the particle size D50 (median particle diameter) of the aluminum powder is 100.2-110%.
Preferably, the modifier is selected from one or more of silane coupling agent, titanate coupling agent, silane coupling agent oligomer, alkoxy polymer, modified silane coupling agent oligomer and modified alkoxy polymer, more specifically, the modifier can be one or more of silane coupling agent containing vinyl, epoxy, alkyl, amino, mercapto, phenyl and the like, and oligomer thereof or alkoxy polymer; further, the modifier may be one or more of vinyltrimethoxysilane, propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane.
Preferably, the dispersion medium is selected from one or more of deionized water, ethanol, methanol, isopropanol, toluene, xylene, ethyl acetate; the dispersion medium is preferably toluene;
the solvent is selected from one or more of water, ethanol, methanol, isopropanol, toluene, xylene and ethyl acetate;
the mass portion ratio of the modifier, the deionized water and the solvent is 0.5:4:6.
preferably, the mass fraction ratio of the modifier to the aluminum powder is 0.1-3%, the particle size of the aluminum powder is 1-10 μm, the first particle size of the aluminum powder is about 1-10 μm, the second particle size is about 1-5 μm, and the second heat conducting filler particle size is about 0.1-1 μm.
Preferably, the pH is adjusted in real time by an alkaline substance selected from one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, and sodium bicarbonate, or an acidic substance selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and benzoic acid.
Preferably, the polymeric blend material is one or more of ethylene-propylene rubber (EPR, EPDM), polyethylene/butylene, polyethylene-butylene-styrene, polyethylene-propylene-styrene, hydrogenated polyalkyldiene "mono-ol", hydrogenated polybutadiene mono-ol, hydrogenated polypropylene diene mono-ol, hydrogenated polypentadiene mono-ol, hydrogenated polyalkyldiene "diol", hydrogenated polybutadiene diol, hydrogenated polypropylene diene diol, hydrogenated polypentadiene diol, and hydrogenated polyisoprene, polyolefin elastomer, the polymer consisting essentially of polyethylene-propylene-styrene and hydrogenated polybutadiene diol, plus a first plasticizer, a first tackifying resin, a first paraffinic oil, a first antioxidant.
Preferably, the coupling agent comprises a titanate coupling agent comprising: titanium IV2,2 (bis-2-acryloylmethyl) butoxy, tris (dioctyl) pyrophosphate-O, zirconium IV2,2 (bis-2-acryloylmethyl) butoxy, tris (diisooctyl) pyrophosphate-O, titanium IV 2-propionate, tris (dioctyl) -pyridinylphosphoric acid-O, diisooctyl phosphite, titanium IV bis (dioctyl) pyrophosphate-O, oxoethylene glycol, bis (dioctyl) (hydrogen) phosphite-O; one or more of titanium IV bis (dioctyl) pyrophosphate-O, ethylene glycol (adduct), bis (dioctyl) hydrogen phosphite, zirconium IV2, 2-bis (2-propenylmethyl) butoxy, cyclo-bis [2,2- (bis-2-propenylmethyl) butoxy ], pyrophosphate-O.
Preferably, the additive comprises an antioxidant and a cross-linking agent, the additive being selected from one or more of a second antioxidant, an ageing agent, a second tackifying resin and a second plasticizer, the cross-linking agent comprising a methylated amino resin.
Preferably, the mineral spirits generally fall into three categories: aliphatic, cyclic, and aromatic. Aliphatic hydrocarbon solvent oils include straight-chain compounds and branched and possibly crosslinked compounds, however, aliphatic hydrocarbon solvent oils are not generally considered cyclic, cyclic hydrocarbon solvent oils are solvent oils comprising at least three carbon atoms oriented in a ring structure having properties similar to aliphatic hydrocarbon solvents, aromatic hydrocarbon solvent oils are solvent oils generally comprising three or more unsaturated bonds, with a single ring or multiple rings attached by a common bond and/or multiple rings fused together. The solvent oil is selected from one or more of toluene, xylene, para-xylene, meta-xylene, mesitylene, solvent naphtha H, solvent naphtha A, second paraffinic oil, isoparaffinic fluids, alkanes (such as pentane, hexane, isohexane, heptane, nonane, octane, dodecane, 2-methylbutane, hexadecane, tridecane, pentadecane, cyclopentane, 2, 4-trimethylpentane), petroleum ether, halogenated hydrocarbons (such as chlorohydrocarbons, nitrohydrocarbons), benzene, 1, 2-dimethylbenzene, 1,2, 4-trimethylbenzene, mineral spirits, kerosene, isobutylbenzene, methylnaphthalene, ethyltoluene, tetrahydrofuran. In more specific embodiments the solvent oil is preferably one or more of pentane, hexane, heptane, cyclohexane, paraffin oil, isoparaffinic fluids, benzene, toluene, xylene.
The invention also provides a preparation method of the composite phase-change material with low thermal resistance, high heat conduction and no electric conduction, which comprises the following steps:
step S1: adding polyethylene-propylene-styrene, hydrogenated polybutadiene glycol, a first plasticizer, a first tackifying resin, a first paraffin oil, a first antioxidant and a coupling agent into a double-planetary mixer, and stirring and dispersing the mixture into a viscous liquid;
step S2: adding modified aluminum powder and zinc oxide into viscous liquid, then adding an oxidant and second paraffin oil, vacuumizing, stirring and dispersing for 5H, scraping materials adhered to the stirring slurry and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stable, placing the material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil material is attached to the surfaces of both sides contacted with the PI.
The technical scheme of the invention has the following beneficial effects:
according to the invention, the compatibility and the dispersibility of the heat conducting powder and the phase change matrix material are optimized through powder modification treatment, the reaction of the reactive groups of the coupling agent and the powder surface but the reaction of the hydroxyl groups are carried out, so that the problem of agglomeration of the heat conducting powder is avoided, the influence of interface thermal resistance of different materials is effectively improved, and the subsequent sectional production process is adopted.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a schematic structural diagram of a phase change heat conductive material according to the present invention.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
Example 1:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 50 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 25 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, and adding additives, wherein the additives comprise 0.27 part of an oxidant 1076,0.1 part of an oxidant 168,1.3 parts of polyisobutene and 0.5 part of a silane coupling agent, the stirring speed is set to be 30r/S, the dispersing speed is set to be 40r/S, vacuumizing, stirring and dispersing are carried out for 5H, scraping materials attached to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, attaching a layer of tearable PET release film coil material on the surfaces of both sides contacted with the PI, and cutting the coiled composite material into the size required by customers through a die cutting machine.
Example 2:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: 50 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 25 parts of zinc oxide with the particle size of 1 mu m are added into the viscous polymer mixed material prepared in the step S1, 0.5 part of additive and silane coupling agent are added, the additive is selected from 0.27 part of oxidant 1076,0.1 part of oxidant 168 and 1.1 part of polyisobutene, 0.15 part of hydroxyl-terminated polybutadiene, the stirring speed is set to 30r/S, the dispersing speed is set to 40r/S, the mixture is vacuumized, stirred and dispersed for 5H, the materials adhered to the stirring paddles and the inner wall are scraped once every 1H, and the whole material is discharged after being changed into a uniform gray paste.
Step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, attaching a layer of tearable PET release film coil material on the surfaces of both sides contacted with the PI, and cutting the coiled composite material into the size required by customers through a die cutting machine.
Example 3:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 50 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 25 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 1076,0.1 parts of oxidant 168,1.3 parts of polyisobutene with the particle size of 0.27 part of oxidant and 0.5 part of silane coupling agent, setting the stirring speed to be 30r/S, dispersing at the dispersing speed of 40r/S, vacuumizing, stirring and dispersing for 5H, scraping materials attached to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, attaching a layer of tearable PET release film coil material on the surfaces of both sides contacted with the PI, and cutting the coiled composite material into the size required by customers through a die cutting machine.
Example 4:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of antioxidant, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials adhered to a stirring paddle and an inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 16 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 1076,0.1 parts of oxidant 168,1.3 parts of polyisobutene with the particle size of 0.27 part of oxidant, and 0.5 part of silane coupling agent, wherein the stirring speed is set to be 30r/S, the dispersing speed is set to be 40r/S, vacuumizing, stirring and dispersing for 5H, scraping materials attached to a stirring paddle and an inner wall once every 1H, and discharging until the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stable, placing the material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil material is attached to the surfaces of both sides contacted with the PI.
Example 5:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 51 parts of modified aluminum powder with the particle size of 10 mu m, 22 parts of aluminum powder with the particle size of 1 mu m and 25 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 1076,0.1 parts of oxidant 168,1.3 parts of polyisobutene with the particle size of 0.27 part of oxidant and 0.5 part of silane coupling agent, setting the stirring speed to be 30r/S, dispersing the mixture at the dispersing speed of 40r/S, vacuumizing, stirring and dispersing the mixture for 5H, scraping materials attached to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, attaching a layer of tearable PET release film coil material on the surfaces of both sides contacted with the PI, and cutting the coiled composite material into the size required by customers through a die cutting machine.
Example 6:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 16 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 1076,0.1 parts of oxidant 168 with the particle size of 0.27 part, adding 1.3 parts of polyisobutene with the particle size of 0.5 part of silane coupling agent, setting the stirring speed to be 30r/S, dispersing at 40r/S, vacuumizing, stirring and dispersing for 5H, scraping materials attached to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil is attached to the surfaces of both sides contacted with the PI, wherein the process flow chart and the structure chart are as follows.
Example 7:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 22 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 1076,0.08 parts of oxidant 168 with the particle size of 0.27 part of oxidant, adding 1.2 parts of second paraffin oil and 0.5 part of silane coupling agent, setting the stirring speed to be 30r/S, dispersing at the dispersing speed of 40r/S, vacuumizing, stirring and dispersing for 5H, scraping materials attached to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil is attached to the surfaces of both sides contacted with the PI, wherein the process flow chart and the structure chart are as follows.
Example 8:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 25 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 0.27 part of oxidant 1076,0.08 parts of second paraffin oil with the particle size of 168,1.2 parts of oxidant, 0.5 part of silane coupling agent, setting the stirring speed to be 30r/S, dispersing at the dispersing speed of 40r/S, vacuumizing, stirring and dispersing for 5H, scraping materials adhered to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil is attached to the surfaces of both sides contacted with the PI, wherein the process flow chart and the structure chart are as follows.
Example 9:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 22 parts of zinc oxide with the particle size of 1 mu m are added into the viscous polymer mixed material prepared in the step S1, and then the following steps are added: 0.27 parts of oxidant 1076,0.08 parts of oxidant 168,1.41 parts of second paraffin oil, the stirring rotating speed is set to be 30HZ, the dispersing rotating speed is set to be 40HZ, the materials adhered to the stirring paddles and the inner wall are scraped once every 1H for dispersing for 5H, and the materials are discharged after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil is attached to the surfaces of both sides contacted with the PI, wherein the process flow chart and the structure chart are as follows.
Example 10:
referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 25 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 0.27 part of oxidant 1076,0.08 parts of second paraffin oil with the particle size of 168,1.21 parts of oxidant, 0.5 part of silane coupling agent, setting the stirring speed to be 30r/S, dispersing at the dispersing speed of 40r/S, vacuumizing, stirring and dispersing for 5H, scraping materials adhered to a stirring paddle and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil is attached to the surfaces of both sides contacted with the PI, wherein the process flow chart and the structure chart are as follows.
Example 11
Referring to fig. 1 to 2, step S1: weighing 0.4 part of polyethylene-propylene-styrene, 0.3 part of hydrogenated polybutadiene glycol, 0.1 part of first plasticizer, 0.7 part of first tackifying resin, 1.2 parts of first paraffin oil and 0.3 part of first antioxidant 1010, adding into a 125 ℃ double-planetary stirrer, stirring at a speed of 30r/s and a dispersing speed of 40r/s, stirring and dispersing for 4 hours, scraping materials attached to a stirring paddle and the inner wall once every 1 hour, and when the whole material becomes uniform viscous liquid, reducing the temperature to 100 ℃, setting the stirring speed to 30r/s and the dispersing speed to 40r/s, and vacuumizing and stirring and dispersing for 1 hour;
step S2: adding 57 parts of modified aluminum powder with the particle size of 10 mu m, 20 parts of aluminum powder with the particle size of 1 mu m and 24 parts of zinc oxide with the particle size of 1 mu m into the viscous polymer mixed material prepared in the step S1, adding 1076,0.08 parts of oxidant with the particle size of 0.27 part of oxidant with the particle size of 168,1.5 parts of second paraffin oil, setting the stirring speed to be 30r/S and the dispersing speed to be 40r/S, vacuumizing and stirring for dispersing for 5 hours, scraping materials adhered to a stirring paddle and the inner wall once every 1 hour, and discharging after the whole materials become uniform gray paste;
step S3: heating a roller of a calender and a heating plate of a calendering platform to 100 ℃, after the temperature is stabilized, placing a material on a film material with a PET release film at the lower part and a PI film at the upper part, setting the thickness of the single-sided phase change material to be 0.05 mu m, repeating the operation on the other side after the single-sided phase change material is finished, so that the final product is the PI film and the phase change materials with the thickness of 0.05mm are both sides, and a layer of tearable PET release film coil is attached to the surfaces of both sides contacted with the PI, wherein the process flow chart and the structure chart are as follows.
The thermal resistance and thermal conductivity of each of the solutions are shown in the following chart 1, comparative example 1 is Honival but PTM7950, comparative example 2 is the T-PCM 5000 series of Lylde, by comparison, we can see that example eleven shows thermal resistance at low pressure (10 psi) and high pressure (50 psi) under the same conditions to be better than the best batch of products of the current mainstream manufacturer, and the three aging tests of-45-125 ℃,85% RH and 85 ℃,125 ℃ are passed, and the thermal resistance change rate is less than 15%. The inventive formulation is shown to have reliable stability.
TABLE 1
Compared with the traditional single-sided PI phase change material, the composite material with PI obtained through the double-sided calendaring process of the PI film has the advantages that the back glue does not need to be attached to the periphery of the double-sided PI composite phase change material, a die does not need to be designed, and a die cutting machine can be directly used for cutting the composite material into the required size. And the volume resistivity of the composite material is higher than that of a single-sided PI phase change composite material, so that the requirement of non-conductivity of the material in multiple scenes is met.
According to the invention, the compatibility and dispersibility of the heat conducting powder and the phase change matrix material are optimized through powder modification treatment, the reaction of the reactive groups of the coupling agent and the hydroxyl groups on the surface of the powder is carried out, so that the problem of agglomeration of the heat conducting powder is avoided, the influence of interface thermal resistance of different materials is effectively improved, and the subsequent sectional production process is adopted.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the description of the present invention and the accompanying drawings or direct/indirect application in other related technical fields are included in the scope of the invention.
Claims (10)
1. The composite phase-change material with low thermal resistance, high heat conduction and no electric conduction is characterized by comprising the following raw materials in parts by weight: 2-4 parts of polymer mixed material, 1-3 parts of solvent oil, 70-80 parts of first heat conducting filler, 20-25 parts of second heat conducting filler, 0.3-2 parts of additive and 0.5-1 part of coupling agent.
2. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material of claim 1, wherein said first and second thermally conductive fillers are each selected from one or more of metals, alloys, non-metals, metal oxides, metal nitrides, and ceramics;
the metal is selected from one or more of aluminum, copper, silver, zinc, nickel, tin, indium, lead, silver-plated metal, metal-plated carbon fiber and nickel-plated fiber;
the nonmetal is selected from one of carbon, carbon black, graphite, carbon nano tube, carbon fiber, graphene, diamond, glass, silicon dioxide, silicon nitride and boron-plated particles;
the metal oxide, metal nitride, and ceramic each include one or more of aluminum oxide, aluminum nitride, boron nitride, zinc oxide, and tin oxide.
3. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material of claim 1, wherein the first thermal conductive filler is selected from the group consisting of modified aluminum powder and the second thermal conductive filler is selected from the group consisting of zinc oxide, wherein the aluminum powder modification is specifically prepared as follows:
step X1, uniformly mixing the modifier, the dispersion medium and the solvent according to a preset proportion, condensing and refluxing, and continuously stirring for 10-60min at the temperature of 30-60 ℃;
and step X2, regulating the pH value of the mixed solution obtained in the step S1, then adding aluminum powder, condensing and refluxing, continuously stirring at the temperature of 30-100 ℃ for 2-12h, and vacuum drying to obtain the modified aluminum powder.
4. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material according to claim 3, wherein said modifier is selected from one or more of silane coupling agents, titanate coupling agents, silane coupling agent oligomers, alkoxy polymers, modified silane coupling agents, modified silane coupling agent oligomers, modified alkoxy polymers.
5. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material according to claim 4, wherein said dispersion medium is selected from one or more of deionized water, ethanol, methanol, isopropanol, toluene, xylene, ethyl acetate; the solvent is selected from one or more of water, ethanol, methanol, isopropanol, toluene, xylene and ethyl acetate; the mass portion ratio of the modifier, the deionized water and the solvent is 0.5:4:6.
6. the low thermal resistance, high thermal conductivity, non-conductive composite phase change material according to claim 5, wherein the mass fraction ratio of modifier to aluminum powder is 0.1-3%, the particle size of the aluminum powder is 1-10 μm, the first particle size of the aluminum powder is about 1-10 μm, the second particle size is about 1-5 μm, and the second thermally conductive filler particle size is about 0.1-1 μm;
the pH value is regulated in real time by an alkaline substance or an acidic substance, wherein the alkaline substance is selected from one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate, and the acidic substance is selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and benzoic acid.
7. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material according to claim 1, wherein said polymer blend material is a blend of one or more of ethylene-propylene rubber, polyethylene/butylene, polyethylene-butylene-styrene, polyethylene-propylene-styrene, hydrogenated polyalkyldiene "monol", hydrogenated polybutadiene monol, hydrogenated polypropylene diene monol, hydrogenated polypentadiene monol, hydrogenated polyalkyldiene "diol", hydrogenated polybutadiene diol, hydrogenated polypropylene diene diol, hydrogenated polypentadiene diol, and hydrogenated polyisoprene, polyolefin elastomer, with the addition of a first plasticizer, a first tackifying resin, a first paraffinic oil, a first antioxidant.
8. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material according to claim 1, wherein said coupling agent comprises a titanate coupling agent comprising: titanium IV2,2 (bis-2-acryloylmethyl) butoxy, tris (dioctyl) pyrophosphate-O, zirconium IV2,2 (bis-2-acryloylmethyl) butoxy, tris (diisooctyl) pyrophosphate-O, titanium IV 2-propionate, tris (dioctyl) -pyridinylphosphoric acid-O, diisooctyl phosphite, titanium IV bis (dioctyl) pyrophosphate-O, oxoethylene glycol, bis (dioctyl) (hydrogen) phosphite-O; one or more of titanium IV bis (dioctyl) pyrophosphate-O, ethylene glycol, bis (dioctyl) hydrogen phosphite, zirconium IV2, 2-bis (2-propenylmethyl) butoxy, cyclo-bis [2,2- (bis-2-propenylmethyl) butoxy ], pyrophosphate-O.
9. The low thermal resistance, high thermal conductivity, non-conductive composite phase change material according to claim 1, wherein said additives comprise an antioxidant and a cross-linking agent, said additives being selected from one or more of a second antioxidant, an aging agent, a second tackifying resin and a second plasticizer, said cross-linking agent comprising a methylated amino resin;
the solvent oil is selected from one or more of toluene, xylene, paraxylene, m-xylene, mesitylene, solvent naphtha H, solvent naphtha A, second paraffin oil, isoparaffin fluid, alkane, petroleum ether, halogenated hydrocarbon, benzene, 1, 2-dimethylbenzene, 1,2, 4-trimethylbenzene, mineral spirits, kerosene, isobutylbenzene, methylnaphthalene, ethyltoluene and tetrahydrofuran.
10. The method for preparing a composite phase change material with low thermal resistance, high thermal conductivity and non-electrical conductivity according to any one of claims 1 to 9, comprising the following steps:
step S1: adding polyethylene-propylene-styrene, hydrogenated polybutadiene glycol, a first plasticizer, a first tackifying resin, a first paraffin oil, a first antioxidant and a coupling agent into a double-planetary mixer, and stirring and dispersing the mixture into a viscous liquid;
step S2: adding modified aluminum powder and zinc oxide into the S1 to prepare a viscous polymer mixed material, then adding an oxidant and second paraffin oil, vacuumizing, stirring and dispersing for 5H, scraping materials adhered to the stirring slurry and the inner wall once every 1H, and discharging after the whole materials become uniform gray paste;
step S3: heating the calender, placing the material on a film material with a PET release film at the lower part and a PI film at the upper part after the temperature is stable, setting the thickness of the single-sided phase change material, repeating the operation on the other side after the single side is finished, and cutting to the required size by a die cutting machine after the single side is finished.
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