CN112608708A - Polyurethane heat-conducting insulating adhesive and preparation method thereof - Google Patents
Polyurethane heat-conducting insulating adhesive and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a polyurethane heat-conducting insulating adhesive which comprises the following components in parts by weight: 10-30 parts of liquid polyester polyol; 30-60 parts of solid polyester polyol; 15-30 parts of thermoplastic resin; 35-50 parts of polypropylene carbonate; 1-5 parts of tackifying resin; 5-25 parts of isocyanate; 0.01-3 parts of a catalyst; 100-200 parts of heat-conducting filler. According to the invention, the specific weight part of the polypropylene carbonate is added into the formula of the polyurethane heat-conducting insulating adhesive, and the form and the proportion of the heat-conducting filler in the polyurethane heat-conducting insulating adhesive product are adjusted by adding the specific compound mass fraction ratio and the specific types of the electric-conducting fillers, so that the heat-conducting and insulating properties of the obtained polyurethane heat-conducting insulating adhesive are obviously improved, the electric conductivity of the carbon filler is inhibited, and the problem of viscosity increase caused by the nano-filler can be avoided.
Description
Technical Field
The invention belongs to the technical field of preparation of hot melt adhesives, and particularly relates to a polyurethane heat-conducting insulating adhesive and a preparation method thereof.
Background
Hot melt adhesives, also known as hot melt adhesives, are solid at room temperature and melt to a viscous liquid when heated to a certain temperature. After cooling to room temperature, the mixture becomes solid again and has strong bonding effect. The hot melt adhesive has the advantages of high bonding speed, no toxicity, simple bonding process and the like, and is widely applied to the fields of book binding, package sealing, shoe making, textile and the like. Along with the development of new forms of energy trade, the hot melt adhesive is also in the secret overall arrangement in the lithium electricity trade, the bonding between the present mainly used battery, needs to satisfy certain heat conductivity and higher electrical insulation nature this moment. Meanwhile, along with the limitation of the service life of the lithium battery, a large number of waste batteries cause environmental pollution, so that the degradability of the adhesive is also a performance requirement which needs to be considered urgently at present.
At present, most hot melt adhesives are prepared from ethylene-vinyl acetate (EVA), polyurethane, polyamide and other hot melt resins, and the EVA and the polyester hot melt adhesives have poor elasticity and strength and cannot bear too large external force. The melting point and hardness of polyamide hot melt adhesives are relatively high, and therefore, the application of polyamide hot melt adhesives is limited. Compared with the prior art, the polyurethane hot melt adhesive has the advantage of high degree of freedom of the polymer, and the components can be adjusted according to actual needs to meet the needs. The polyurethane hot melt adhesive is prepared by using thermoplastic polyurethane as a base material and adding thermoplastic resin, tackifying resin, filler, antioxidant, catalyst and other auxiliaries, and has excellent elasticity and strength. It can lose hydrogen bond action after heated, and then becomes molten viscous liquid, and after cooled, it can restore original physical property. Therefore, the polyurethane hot melt adhesive has the characteristics of high adhesive strength, solvent resistance, wear resistance and the like. Since the moisture-curing polyurethane hot melt adhesive enters the market, the moisture-curing polyurethane hot melt adhesive gradually replaces the common hot melt adhesive due to excellent performance, simple use and wide application range. However, due to the existence of terminal active groups, the storage stability of the moisture-curing hot melt adhesive is poor, and the heat resistance is poor. The moisture-curing polyurethane hot melt adhesive reacts with water to generate carbon dioxide gas, so that bubbles are easy to appear in the curing process, and the service performance of the adhesive is influenced. The high cost is also a great factor influencing the large-scale popularization of the moisture-curing polyurethane hot melt adhesive.
The viscosity of the hot melt adhesive is generally greatly influenced, the heat-conducting filler has poor dispersibility in the hot melt adhesive matrix, the heat-conducting filler is easy to agglomerate in the processing process, the bonding property is influenced, and the optimization and optimization of the heat-conducting filler obviously influence the heat-conducting insulating property. In recent years, some hot melt adhesive patent technologies with partial heat conduction and insulation functions are developed around graphene, such as patents cn201310447910.x, CN201711151394.0, CN201711275263.3, and the like, but from the practical effect, the thermal resistance at the interface of graphene/polymer has a great influence on the heat conduction performance, and the expected thermal conductivity value cannot be achieved. Some researchers propose to improve the heat conduction function by using inorganic powder, such as common ceramic powder alumina, zirconia, etc., such as patents, such as CN201010239015.5, CN201310525198.0, CN201811476166.5, etc., the ceramic powder selected in these patents has very limited thermal conductivity and is mostly spherical in shape, and the practicability is very limited from the perspective of heat conduction effect, and meanwhile, the addition of a large amount of fillers and the addition of a part of nano-scale fillers greatly affect the processability of the heat conduction hot melt adhesive. It is clear that a compromise between adhesion, thermal conductivity and processability has become an urgent problem to be solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the polyurethane heat-conducting insulating adhesive which does not contain any organic solvent, has strong cohesiveness and excellent heat-conducting and insulating properties.
The invention also aims to provide a preparation method of the polyurethane heat-conducting insulating adhesive.
The invention is realized by the following technical scheme:
a polyurethane heat-conducting insulating adhesive comprises the following components in parts by weight:
10-30 parts of liquid polyester polyol;
30-60 parts of solid polyester polyol;
15-30 parts of thermoplastic resin;
35-50 parts of polypropylene carbonate;
1-5 parts of tackifying resin;
5-25 parts of isocyanate;
0.01-3 parts of a catalyst;
100-200 parts of heat-conducting filler.
Wherein the number average molecular weight of the liquid polyester polyol is 1000-5000; the liquid polyester polyol is one or more derivatives selected from castor oil, soybean oil, palm oil, cashew nut shell oil, pine nut oil and rosin oil.
Wherein the solid polyester polyol is selected from hydroxyl-terminated polylactic acid with the number average molecular weight of 5000-8000.
The thermoplastic resin is selected from olefin copolymers with the glass transition temperature of 30-70 ℃, the number average molecular weight of 30000-80000 and the crystallinity of not higher than 15%, and is preferably one or more random copolymers of ethylene-octene, ethylene-pentene and ethylene-hexene.
Wherein the softening point of the tackifying resin is 70-150 ℃; preferably one or more of rosin derivatives, C5 petroleum resin and C9 petroleum resin.
Wherein the isocyanate is selected from at least one of HDI, MDI, TDI, HMDI, IPDI and TMXDI; the catalyst is selected from one of dibutyltin dilaurate and stannous octoate.
The heat-conducting filler is prepared by compounding a heat-conducting filler I, a heat-conducting filler II and a heat-conducting filler III, and the mass fraction ratio of the heat-conducting filler I to the heat-conducting filler II to the heat-conducting filler III is (5-6): (3-4): 1; preferably 6: 3: 1.
the heat-conducting filler I is spherical ceramic powder with the average particle size of 0.1-0.5 mm, and is preferably one or more of aluminum oxide, boron nitride, silicon carbide and aluminum nitride; the heat-conducting filler II is a fibrous ceramic whisker with the diameter of 0.01-0.03 mm and the length-diameter ratio of more than 10, and is preferably one or more of silicon nitride, silicon carbide and aluminum oxide; the heat-conducting filler III is an extended carbon nanotube/carbon black chemical bonding conductive filler.
The invention also discloses a preparation method of the polyurethane heat-conducting insulating adhesive, which comprises the following steps:
weighing the components according to the formula content, uniformly mixing the components except isocyanate, heating at 140-160 ℃, mechanically dispersing, vacuumizing to remove water for about 1-3 hours until the water content of the mixture is lower than 200ppm, cooling to 70-100 ℃, adding the isocyanate under the protection of nitrogen, carrying out polymerization for 1-10 hours, sampling to analyze that the NCO% content of a polymerization product reaches 1% -3%, and testing the viscosity at 100 ℃ to reach 6000-30000 mPa.
Wherein the initial peel strength of the polyurethane heat-conducting and insulating hot melt adhesive is more than 0.5N/mm; the final peel strength is more than 4.0N/mm, and the thermal conductivity is more than 2.8W/mK.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, the specific weight part of the polypropylene carbonate is added into the formula of the polyurethane heat-conducting insulating adhesive, and the form and distribution of the heat-conducting filler in the polyurethane heat-conducting insulating adhesive product are adjusted by adding the specific compound mass fraction ratio and the specific types of the electric-conducting fillers, so that the heat-conducting and insulating properties of the obtained polyurethane heat-conducting insulating adhesive are obviously improved, the electric conductivity of the carbon filler is inhibited, and the problem of viscosity increase caused by the nano-filler can be avoided.
2) The heat-conducting and insulating degradable polyurethane hot melt adhesive disclosed by the invention does not contain any organic solvent, has the solid content of 100%, does not release a small-molecule organic solvent in the processing and using processes, can be quickly degraded in a waste port, and has the advantage of environmental protection.
3) The polyurethane insulating glue prepared by the method is cured by moisture, has no drying process, is quick to cure, is simple to operate, is beneficial to improving the working efficiency and automation, and can be widely applied to the fields of automobiles, aviation, new energy sources and the like.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
Test criteria or methods for each property:
test method of initial peel strength: peel force test specification (GB 2792-1998);
test method of final peel strength: peel force test specification (GB 2792-1998);
the thermal conductivity test method comprises the following steps: laser flash method, test standard ASTM E1461.
Liquid polyester polyol used in the present invention:
castor oil derivatives: molecular weight 1000, GR-35, Ascensus Specialties LLC;
cashew nut shell oil derivatives: molecular weight 3000, NX-9005, Cardolite;
soybean oil derivatives: molecular weight 5000, Soyoyl R137, USSC;
solid polyester polyol used in the present invention:
hydroxyl-terminated polylactic acid-1: molecular weight 5000, DG-DOH030, the organism of the gorgeon handle;
hydroxyl-terminated polylactic acid-2: molecular weight 8000, DG-DOH050, the organism of the gorgeon handle;
thermoplastic resin used in the present invention:
ethylene octene copolymer: molecular weight 30000, EXACT 0203, ExxonMobil;
ethylene hexene copolymer: molecular weight 80000, Exceed ™ 2018KB, ExxonMobil;
ethylene pentene copolymer: molecular weight 80000, Evolue SP2530S, japanese priman;
the polypropylene carbonate used in the present invention, PPC2202P, huizhou da zhi;
tackifying resins used in the present invention:
rosin derivative tackifying resins: KOMOTAC JB100W, Kemao chemical engineering;
c5 tackifying resin: t-100, Ikes;
c9 tackifying resin: YL120H, taiwan yuan good;
isocyanate used in the present invention:
HDI: hexamethylene diisocyanate, wanhua chemistry;
MDI: diphenylmethane diisocyanate, wanhua chemistry;
TDI: toluene diisocyanate, wanhua chemistry;
the catalyst used in the present invention:
dibutyltin dilaurate: chemistry of denying Jinan;
the heat conductive filler used in the present invention:
heat-conductive filler I: spherical alumina having an average particle diameter of 0.1mm, AHP100G, light metals Japan;
spherical silicon carbide having an average particle diameter of 0.5mm, AHP500G, light metals of Japan;
and (3) heat-conducting filler II: fibrous silicon nitride whisker-1, the diameter is 0.01mm, the length-diameter ratio is 12, NS1, Shanghai Kai Yifeng industry;
fibrous silicon nitride whisker-2, the diameter is 0.03mm, the length-diameter ratio is 13, NS3, Shanghai Kai Yifeng industry;
heat conductive filler III: and (3) extending the carbon nano tube/carbon black chemical bonding powder.
Examples 1 to 5 and comparative examples 1 to 7: preparation of polyurethane heat-conducting insulating adhesive
Weighing the components according to the formula content in the table 1, uniformly mixing the components except isocyanate, heating at 140-160 ℃, performing mechanical dispersion, vacuumizing to remove water for about 1-3 hours until the water content of the mixture is lower than 200ppm, cooling to 70-100 ℃, adding isocyanate under the protection of nitrogen, performing polymerization for 1-10 hours, sampling to analyze that the NCO% content of a polymerization product reaches 1% -3%, and testing the viscosity at 100 ℃ to reach 6000-30000 mPa.s to obtain the polyurethane heat-conducting insulating hot melt adhesive; the performance indexes of the prepared polyurethane heat-conducting and insulating hot melt adhesive are shown in table 1.
TABLE 1 concrete compounding ratio (parts by weight) of each component in each example and comparative example and each performance test result
TABLE 1
Claims (10)
1. The polyurethane heat-conducting insulating glue is characterized by comprising the following components in parts by weight:
10-30 parts of liquid polyester polyol;
30-60 parts of solid polyester polyol;
15-30 parts of thermoplastic resin;
35-50 parts of polypropylene carbonate;
1-5 parts of tackifying resin;
5-25 parts of isocyanate;
0.01-3 parts of a catalyst;
100-200 parts of heat-conducting filler.
2. The polyurethane heat-conducting insulating glue as claimed in claim 1, wherein the number average molecular weight of the liquid polyester polyol is 1000-5000; the liquid polyester polyol is one or more derivatives selected from castor oil, soybean oil, palm oil, cashew nut shell oil, pine nut oil and rosin oil.
3. The polyurethane heat-conducting insulating adhesive as claimed in claim 1, wherein the solid polyester polyol is selected from hydroxyl-terminated polylactic acid with a number average molecular weight of 5000-8000.
4. The polyurethane heat-conducting insulating adhesive as claimed in claim 1, wherein the thermoplastic resin is selected from olefin copolymers with a glass transition temperature of 30-70 ℃, a number average molecular weight of 30000-80000 and a crystallinity of not higher than 15%, and is preferably one or more random copolymers of ethylene-octene, ethylene-pentene and ethylene-hexene.
5. The polyurethane heat-conducting insulating adhesive as claimed in claim 1, wherein the softening point of the tackifying resin is 70-150 ℃; preferably one or more of rosin derivatives, C5 petroleum resin and C9 petroleum resin.
6. The polyurethane thermal insulation paste according to claim 1 or 5, wherein the isocyanate is selected from at least one of HDI, MDI, TDI, HMDI, IPDI, TMXDI; the catalyst is selected from one of dibutyltin dilaurate and stannous octoate.
7. The polyurethane heat-conducting insulating glue according to claim 1, characterized in that the heat-conducting filler is compounded by a heat-conducting filler I, a heat-conducting filler II and a heat-conducting filler III, and the mass fraction ratio of the three is (5-6): (3-4): 1; preferably 6: 3: 1.
8. the polyurethane heat-conducting insulating adhesive as claimed in claim 7, wherein the heat-conducting filler I is spherical ceramic powder with an average particle size of 0.1-0.5 mm, preferably one or more of alumina, boron nitride, silicon carbide and aluminum nitride; the heat-conducting filler II is a fibrous ceramic whisker with the diameter of 0.01-0.03 mm and the length-diameter ratio of more than 10, and is preferably one or more of silicon nitride, silicon carbide and aluminum oxide; the heat-conducting filler III is an extended carbon nanotube/carbon black chemical bonding conductive filler.
9. A preparation method of the polyurethane heat-conducting insulating glue containing any one of claims 1 to 8 is characterized by comprising the following steps:
weighing the components according to the formula content, uniformly mixing the components except isocyanate, heating at 140-160 ℃, mechanically dispersing, vacuumizing to remove water for about 1-3 hours until the water content of the mixture is lower than 200ppm, cooling to 70-100 ℃, adding the isocyanate under the protection of nitrogen, carrying out polymerization for 1-10 hours, sampling to analyze that the NCO% content of a polymerization product reaches 1% -3%, and testing the viscosity at 100 ℃ to reach 6000-30000 mPa.
10. The preparation method of the polyurethane heat-conducting insulating adhesive according to claim 9, wherein the initial peel strength of the polyurethane heat-conducting insulating hot melt adhesive is greater than 0.5N/mm; the final peel strength is more than 4.0N/mm, and the thermal conductivity is more than 2.8W/mK.
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CN115160537A (en) * | 2022-08-03 | 2022-10-11 | 广东粤港澳大湾区国家纳米科技创新研究院 | High-heat-conduction material with bonding and sealing performances and preparation method thereof |
CN115572569A (en) * | 2022-10-19 | 2023-01-06 | 东莞市佳迪新材料有限公司 | PUR hot melt adhesive for bonding power battery and liquid cooling plate and preparation method thereof |
CN115975607A (en) * | 2022-12-30 | 2023-04-18 | 蜂巢能源科技(无锡)有限公司 | Heat absorption composite material, heat absorption composite structure and preparation method thereof, and lithium ion battery unit |
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WO2024053089A1 (en) * | 2022-09-09 | 2024-03-14 | 三菱電機株式会社 | Thermal-conductive resin composition and cured product of same, and thermal-conductive sheet and method for manufacturing same |
CN115572569A (en) * | 2022-10-19 | 2023-01-06 | 东莞市佳迪新材料有限公司 | PUR hot melt adhesive for bonding power battery and liquid cooling plate and preparation method thereof |
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