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CN115572363B - High-heat-conductivity polyurethane, preparation method and application thereof - Google Patents

High-heat-conductivity polyurethane, preparation method and application thereof Download PDF

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Publication number
CN115572363B
CN115572363B CN202211099461.XA CN202211099461A CN115572363B CN 115572363 B CN115572363 B CN 115572363B CN 202211099461 A CN202211099461 A CN 202211099461A CN 115572363 B CN115572363 B CN 115572363B
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polyurethane
parts
coupling agent
modified
polyol
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CN115572363A (en
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黄世明
阿地拉
徐凯
吴俊�
高鹏
曹晓明
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Tianjin Aopulint Technology Co ltd
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Tianjin Aopulint Technology Co ltd
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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
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • 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
    • C08G18/48—Polyethers
    • 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
    • C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the field of polyurethane, and relates to high-heat-conductivity polyurethane, a preparation method and application thereof, wherein the high-heat-conductivity polyurethane comprises the following raw materials in parts by mass: a component: 6-12 parts of modified polyol, 0-2 parts of chain extender, 1-3 parts of diluent, 0.01-0.05 part of catalyst, 1-3 parts of molecular sieve and 87-90 parts of first heat conducting filler; and the component B comprises the following components: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water scavenger, 0.1-1 part of coupling agent and 88-92 parts of second heat conducting filler. The high-heat-conductivity polyurethane has a heat conductivity coefficient of more than 3.5 w/(m.k), and the polyurethane can achieve stronger bonding performance by using the modified castor oil polyol and the modified polyether polyol simultaneously; the polyurethane with high heat conductivity can have good bonding performance and high heat conductivity at the same time, and is particularly suitable for bonding power battery modules.

Description

High-heat-conductivity polyurethane, preparation method and application thereof
Technical Field
The invention relates to the technical field of polyurethane, and particularly discloses high-heat-conductivity polyurethane and a preparation method thereof.
Background
In recent years, new energy automobiles are rapidly developed, and the rapid development of industries promotes the development and perfection of related industries. In the aspect of the adhesive for bonding the battery PACK structure, as the surface material of the power battery PACK module comprises various functional materials such as aluminum alloy, the structural adhesive is required to have better bonding strength on various materials under the condition of not carrying out surface treatment. Meanwhile, along with the continuous upgrading and iteration of the power battery technology, the heat dissipation problem of the battery cell is increasingly remarkable, so that the structural adhesive is required to have excellent heat conduction performance, and a large amount of heat generated in the running process of the power battery can be quickly conducted to the outside. The double-component polyurethane adhesive is the first choice with the advantages of long storage period, adjustable modulus, safety, environmental protection and the like.
At present, the heat conduction structural adhesive increases the heat conduction performance mainly by adding the heat conduction filler, but a large amount of heat conduction filler is added to cause the viscosity to become large, the fluidity to become poor, the mechanical property of the cured structural adhesive is reduced, the bonding performance is poor, and the packaging requirement of the new energy power battery module cannot be met.
At present, no double-component polyurethane structural adhesive has good bonding performance and high thermal conductivity.
Disclosure of Invention
In view of the above-mentioned drawbacks or shortcomings in the prior art, one of the purposes of the present invention is to provide a polyurethane with high thermal conductivity, which comprises the following raw materials in parts by mass:
A component: 6-12 parts of modified polyol, 0-2 parts of chain extender, 1-3 parts of diluent, 0.01-0.05 part of catalyst, 1-3 parts of molecular sieve and 87-90 parts of first heat conducting filler.
And the component B comprises the following components: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water scavenger, 0.1-1 part of coupling agent and 88-92 parts of second heat conducting filler.
Preferably, the first heat conductive filler and the second heat conductive filler are both heat conductive fillers subjected to surface modification.
Preferably, the modified polyol comprises a modified castor oil polyol and a modified polyether polyol.
Preferably, the isocyanate is one or more of 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, polymethylene polyphenyl isocyanate PAPI or toluene diisocyanate TDI.
The modified castor oil polyol is preferably a benzene ring modified castor oil polyol or a glycol modified castor oil polyol.
Preferably, the modified polyether polyol is a benzene ring modified polyether polyol, preferably a benzene ring modified polyether polyol having a functionality of 2 to 3 and a number average molecular weight of 300 to 500.
Preferably, the isocyanate is polymethylene polyphenyl isocyanate PAPI.
Preferably, the volume ratio of the component A to the component B is 1:0.8-1.2.
The first heat conducting filler and the second heat conducting filler are respectively and independently selected from one or more of aluminum oxide, aluminum hydroxide, magnesium oxide or zinc oxide which are subjected to surface modification.
Preferably, the surface modifier of the first heat conductive filler and the second heat conductive filler are each independently selected from one or more of silazane, chlorosilane, silane coupling agent or polyether modified silane coupling agent.
Preferably, the first heat conductive filler and the second heat conductive filler are the same, and are a mixture of spherical aluminum oxide and aluminum hydroxide which are subjected to surface modification, preferably a mixture of spherical aluminum oxide with surface modification having average particle diameters of 1 μm, 10 μm and 70 μm and aluminum hydroxide with average particle diameter of 1.5 μm, and further preferably a mixture of spherical aluminum oxide with surface modification having a mass ratio of 1:2:2:2 of spherical alumina having an average particle diameter of 1 μm, 10 μm and 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm.
Preferably, the surface modification of the first filler and the second filler is performed using a polyether modified silane coupling agent, preferably a polyether modified silane coupling agent having a number average molecular weight of 500 to 3000.
Preferably, the weight of the polyether modified silane coupling agent is 1-2% of the weight of the heat conducting filler powder.
The polyester polyol is one or more of adipic acid type polyester polyol, sebacic acid type polyester polyol, phthalic anhydride type polyester polyol or dimer acid modified polyester polyol, and preferably dimer acid modified polyester polyol.
The chain extender is one or more of dihydric alcohol or polyhydric alcohol, preferably one or more of 1,2 propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, ethylene glycol or diethylene glycol, and further preferably dipropylene glycol.
The diluent is one or more of dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP, propylene carbonate, chlorinated paraffin or alkyl benzene sulfonate, and is preferably diisononyl phthalate DINP.
The molecular sieve is one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve or a 13X molecular sieve, and is preferably a 4A molecular sieve.
Preferably, the catalyst is one or more of organotin, organobismuth, organozinc, organonickel or amine catalysts, preferably organobismuth catalysts.
Preferably, the water scavenger is one or more of p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane or oxazolidine latent curing agent, preferably p-toluenesulfonyl isocyanate Ti.
Preferably, the coupling agent is one or more of a silane coupling agent KH550, a silane coupling agent KH560 or a silane coupling agent KH570, and is preferably a silane coupling agent KH560.
The second purpose of the invention is to provide a preparation method of the polyurethane with high heat conductivity, which comprises the following steps:
and mixing the components of the component A to obtain the component A.
Reacting polyester polyol with isocyanate under protective atmosphere to obtain isocyanate-terminated polyurethane prepolymer, and then adding a water removing agent, a coupling agent and a second heat conducting filler to obtain a component B.
Preferably, the preparation of component A: after all the raw materials are dehydrated, adding polyalcohol, diluent, chain extender and catalyst, and mixing under vacuum condition; then adding molecular sieve and heat-conducting filler, mixing under vacuum condition.
Preferably, the preparation of the component B: adding polyester polyol, and heating and dehydrating; cooling, adding isocyanate, reacting in nitrogen atmosphere to obtain isocyanate-terminated polyurethane prepolymer, adding water scavenger, coupling agent and heat conducting filler, and mixing under vacuum condition.
The invention further aims to provide the high-heat-conductivity polyurethane which is used for curing the mixed component A and the mixed component B as the structural adhesive.
The fourth object of the invention is to provide a battery module, which comprises the structural adhesive prepared from the polyurethane with high heat conductivity.
The beneficial effects of the invention include:
(1) The invention realizes high filling quantity and low viscosity by adding the first heat conduction filler and the second heat conduction filler with surface modification, has good operability, and has the heat conduction coefficient of more than 3.5 w/(m.k) after solidification;
(2) Meanwhile, the modified castor oil polyol and the modified polyether polyol are used, the influence of a plurality of polyols on the interface adhesive force and the bulk strength of the polyurethane is comprehensively considered, and the polyurethane can achieve stronger adhesive property;
(3) The molecular sieve can be used for adsorbing A, B components to generate carbon dioxide during mixing and curing, so that bubbles are avoided, and the interface adhesion and the bulk strength of the cured polyurethane are further improved;
(4) The component A adopts modified polyol, chain extender, diluent, catalyst, molecular sieve and first heat-conducting filler with specific content, the component B adopts isocyanate, polyester polyol, water scavenger, coupling agent and second heat-conducting filler with specific content, and the component A and the component B can achieve better bonding property and heat-conducting property after mixed solidification;
(5) The preparation method provided by the invention has the advantages of easily available raw materials, simplicity in operation, mild use conditions, capability of mixing and curing the component A and the component B at room temperature, capability of directly using the surface of the bonding material without treatment, high bonding strength and excellent industrial application prospect.
In summary, compared with the prior art, the high-heat-conductivity polyurethane provided by the invention adopts specific content of each component, realizes better overall interaction, has good bonding performance and high heat conductivity, and is particularly suitable for bonding of power battery modules.
Detailed Description
The technical features in the technical scheme provided by the invention are further and clearly described below in combination with the specific embodiments, and the protection scope is not limited.
In the present invention, the "high thermal conductivity polyurethane" means that the thermal conductivity of the polyurethane after curing, as measured by ASTM D5470, is greater than or equal to 3.5 w/(m.k) using an interface material thermal resistance and thermal conductivity meter LW-9389.
The specific scheme is as follows:
According to a first aspect of the invention, there is provided a high thermal conductivity polyurethane comprising the following raw materials in parts by mass:
A component: 6-12 parts of modified polyol, 0-2 parts of chain extender, 1-3 parts of diluent, 0.01-0.05 part of catalyst, 1-3 parts of molecular sieve and 87-90 parts of first heat conducting filler.
And the component B comprises the following components: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water scavenger, 0.1-1 part of coupling agent and 88-92 parts of second heat conducting filler.
Wherein, the first heat conduction filler and the second heat conduction filler are heat conduction fillers subjected to surface modification.
The modified polyols include modified castor oil polyols and modified polyether polyols.
The isocyanate is one or more of 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, polymethylene polyphenyl isocyanate PAPI or toluene diisocyanate TDI.
The content of the modified polyol in the present invention is 6 to 12 parts, for example, 7 parts, 8 parts, 9 parts, 10 parts and 11 parts;
The content of the chain extender in the present invention is 0 to 2 parts, for example, 0.5 parts, 0.55 parts, 1 part and 1.5 parts;
the content of the diluent in the present invention is 1 to 3 parts, for example, 1.5 parts, 2 parts and 2.5 parts;
the catalyst content in the present invention is 0.01 to 0.05 parts, for example, 0.02 parts, 0.03 parts and 0.04 parts;
The molecular sieve is contained in the present invention in an amount of 1 to 3 parts, for example, 1.5 parts, 2 parts and 2.5 parts;
The content of the first heat conductive filler in the present invention is 87 to 90 parts, for example, 87.5 parts, 88 parts, 88.5 parts, 89 parts, and 89.5 parts.
The isocyanate content in the present invention is 4 to 8 parts, for example, 5 parts, 6 parts, 6.5 parts, 6.6 parts, 6.8 parts and 7 parts;
the content of the polyester polyol in the present invention is 2 to 5 parts, for example, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts and 4 parts;
the content of the water scavenger in the present invention is 0.1 to 1 part, for example, 0.2 part, 0.5 part and 0.7 part;
The content of the coupling agent in the present invention is 0.1 to 1 part, for example, 0.2 part, 0.5 part and 0.7 part;
The content of the second heat conductive filler in the present invention is 88 to 92 parts, for example 88.5 parts, 89 parts, 89.5 parts, 90 parts, 90.5 parts, 91 parts and 91.5 parts;
In the present invention, the isocyanate is, for example, 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, polymethylene polyphenyl isocyanate PAPI, toluene diisocyanate TDI, a combination of 1, 6-hexamethylene diisocyanate HDI and isophorone diisocyanate IPDI, a combination of polymethylene polyphenyl isocyanate PAPI and toluene diisocyanate TDI, a combination of isophorone diisocyanate IPDI and polymethylene polyphenyl isocyanate PAPI, a combination of isophorone diisocyanate IPDI and toluene diisocyanate TDI, a combination of 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI and polymethylene polyphenyl isocyanate PAPI, a combination of isophorone diisocyanate IPDI, polymethylene polyphenyl isocyanate PAPI and toluene diisocyanate TDI, a combination of 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, polymethylene polyphenyl isocyanate PAPI and toluene diisocyanate TDI.
In a preferred embodiment of the present invention, the modified castor oil polyol is preferably a benzene ring modified or glycol modified castor oil polyol;
Preferably, the modified polyether polyol is a benzene ring modified polyether polyol, preferably a benzene ring modified polyether polyol having a functionality of 2-3 and a number average molecular weight of 300-500;
Preferably, the isocyanate is polymethylene polyphenyl isocyanate PAPI;
preferably, the volume ratio of the component A to the component B is 1:0.8-1.2.
Specifically, the modified castor oil polyol is one or more selected from Sovermol 750, sovermol 760, sovermol 810, sovermol 815 produced by Basfu, 941 and 912 produced by Abdine, germany, H57 and H854 produced by Eartan oil, and AP11 and A4100 produced by Shanghai smart day.
In the present invention, the modified castor oil polyol is, for example, bafstev Sovermol 750, bafstev Sovermol 760, bafstev Sovermol 810, bafstev Sovermol 815, german abadine 941, german abadine 912, ibary oil H57, ibary oil H854, abary oil AP11, abary oil a4100, a combination of german abary 941 and abary oil AP11, a combination of german abary oil 941 and abary oil H854, a combination of abary oil AP11 and abary oil a4100, a combination of bastarry Sovermol 750 and german abary 941, a combination of germany abary oil 912 and abary oil a4100, a combination of bastarry oil b 4100, a combination of abary oil a4100, a combination of abary oil a 9425, germany abary oil a, and abary oil a 9457, or a combination of germany abary oil a 9420, abary oil a 9420 and abary oil a.
In the present invention, the modified polyether polyol is selected from one or two of Su Telin ST-350 or white wave BPP-03, for example, su Telin ST-350, white wave BPP-03, su Telin ST-350 and white wave BPP-03 in combination.
The volume ratio of the component A to the component B in the invention is 1:0.8-1.2, for example, 1:0.9, 1:1 and 1:1.1.
In a preferred embodiment of the present invention, the first and second heat conductive fillers are each independently selected from one or more of surface-modified aluminum oxide, aluminum hydroxide, magnesium oxide, or zinc oxide.
The first heat conductive filler is, for example, surface-modified alumina, aluminum hydroxide, magnesium oxide, zinc oxide, a combination of alumina and aluminum hydroxide, a combination of alumina and magnesium oxide, a combination of alumina and zinc oxide, a combination of aluminum hydroxide and magnesium oxide, a combination of aluminum hydroxide and zinc oxide, a combination of alumina, aluminum hydroxide and magnesium oxide, a combination of alumina, magnesium oxide and zinc oxide, a combination of alumina, aluminum hydroxide, magnesium oxide and zinc oxide.
The second heat conductive filler is, for example, surface-modified alumina, aluminum hydroxide, magnesium oxide, zinc oxide, a combination of alumina and aluminum hydroxide, a combination of alumina and magnesium oxide, a combination of alumina and zinc oxide, a combination of aluminum hydroxide and magnesium oxide, a combination of aluminum hydroxide and zinc oxide, a combination of alumina, aluminum hydroxide and magnesium oxide, a combination of alumina, magnesium oxide and zinc oxide, a combination of alumina, aluminum hydroxide, magnesium oxide and zinc oxide.
Preferably, the surface modifier of the first heat conductive filler and the second heat conductive filler are each independently selected from one or more of silazane, chlorosilane, silane coupling agent or polyether modified silane coupling agent.
The surface modifier of the first heat conductive filler is, for example, silazane, chlorosilane, a silane coupling agent, a polyether-modified silane coupling agent, a combination of silazane and chlorosilane, a combination of silazane and polyether-modified silane, a combination of chlorosilane and silane coupling agent, a combination of chlorosilane and polyether-modified silane coupling agent, a combination of silane coupling agent and polyether-modified silane coupling agent, a combination of silazane, chlorosilane and silane coupling agent, a combination of silazane silane coupling agent and polyether-modified silane coupling agent, a combination of chlorosilane, silane coupling agent and polyether-modified silane coupling agent, a combination of silazane, chlorosilane, silane coupling agent and polyether-modified silane coupling agent.
The surface modifier of the second heat conductive filler is, for example, silazane, chlorosilane, a silane coupling agent, a polyether-modified silane coupling agent, a combination of silazane and chlorosilane, a combination of silazane and polyether-modified silane, a combination of chlorosilane and silane coupling agent, a combination of chlorosilane and polyether-modified silane coupling agent, a combination of silane coupling agent and polyether-modified silane coupling agent, a combination of silazane, chlorosilane and silane coupling agent, a combination of silazane silane coupling agent and polyether-modified silane coupling agent, a combination of chlorosilane, silane coupling agent and polyether-modified silane coupling agent, a combination of silazane, chlorosilane, silane coupling agent and polyether-modified silane coupling agent.
Preferably, the first heat conductive filler and the second heat conductive filler are the same, and are a mixture of spherical aluminum oxide and aluminum hydroxide which are subjected to surface modification, preferably a mixture of spherical aluminum oxide with surface modification having average particle diameters of 1 μm, 10 μm and 70 μm and aluminum hydroxide with average particle diameter of 1.5 μm, and further preferably a mixture of spherical aluminum oxide with surface modification having a mass ratio of 1:2:2:2 of spherical alumina having an average particle diameter of 1 μm, 10 μm and 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm.
In the invention, the heat-conducting filler with different particle diameters is used for matching, which is not only beneficial to forming a heat-conducting passage in the high heat-conducting polyurethane composition, but also improves the heat-conducting property of the composition; but also helps to reduce the viscosity of the highly thermally conductive polyurethane composition; and helps to improve the mechanical properties of the high thermal conductivity polyurethane composition after curing.
Preferably, the surface modification of the first filler and the second filler is performed using a polyether modified silane coupling agent, preferably a polyether modified silane coupling agent having a number average molecular weight of 500 to 3000. The polyether modified silane coupling agent is used for carrying out surface modification on the heat conducting filler, which is beneficial to reducing the viscosity of the high heat conducting polyurethane composition, facilitating the sizing and improving the operability in use.
Preferably, the weight of the polyether modified silane coupling agent is 1-2% of the weight of the heat conductive filler powder, for example, 1.2%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%.
In a preferred embodiment of the present invention, the polyester polyol is one or more of adipic acid type polyester polyol, sebacic acid type polyester polyol, phthalic anhydride type polyester polyol or dimer acid modified polyester polyol, preferably dimer acid modified polyester polyol.
The polyester polyol in the present invention is, for example, an adipic acid type polyester polyol, a sebacic acid type polyester polyol, a phthalic anhydride type polyester polyol, a dimer acid modified polyester polyol, a combination of a polyester polyol and a dimer acid modified polyester polyol, a combination of a sebacic acid type polyester polyol and a phthalic anhydride type polyester polyol, a combination of a phthalic anhydride type polyester polyol and a dimer acid modified polyester polyol, a combination of an adipic acid type polyester polyol and a sebacic acid type polyester polyol, a combination of a diacid type polyester polyol and a phthalic anhydride type polyester polyol, a combination of an adipic acid type polyester polyol, a sebacic acid type polyester polyol, a phthalic anhydride type polyester polyol or a dimer acid modified polyester polyol, a combination of an adipic acid type polyester polyol, a sebacic acid type polyester polyol, a phthalic anhydride type polyester polyol and a dimer acid modified polyester polyol.
Specifically, the dimer acid modified polyester polyol is selected from one or two of Bai source 3026 and He Da 3190, for example, a combination of Bai source 3026, he Da 3190, bai source 3026 and He Da 3190.
In a preferred embodiment of the present invention, the chain extender is one or more of dihydric alcohol or polyhydric alcohol, preferably one or more of 1,2 propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, ethylene glycol or diethylene glycol, and further preferably dipropylene glycol.
The chain extender in the present invention is, for example, 1, 2-propanediol, dipropylene glycol, glycerin, trimethylolpropane, ethylene glycol or diethylene glycol, a combination of 1, 2-propanediol and dipropylene glycol, a combination of dipropylene glycol and glycerin, a combination of dipropylene glycol and trimethylolpropane, a combination of ethylene glycol and diethylene glycol, 1, 2-propanediol, a combination of dipropylene glycol and glycerin, a combination of 1, 2-propanediol, dipropylene glycol and trimethylolpropane, a combination of dipropylene glycol, ethylene glycol and diethylene glycol, a combination of 1, 2-propanediol, dipropylene glycol, glycerin and trimethylolpropane, a combination of dipropylene glycol, glycerin, trimethylolpropane and ethylene glycol, a combination of 1, 2-propanediol, dipropylene glycol, glycerin, trimethylolpropane and ethylene glycol, a combination of dipropylene glycol, glycerin, trimethylolpropane, ethylene glycol or diethylene glycol, a combination of 1, 2-propanediol, dipropylene glycol, trimethylolpropane, glycerin, ethylene glycol, trimethylolpropane and diethylene glycol.
In a preferred embodiment of the present invention, the diluent is one or more of dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP, propylene carbonate, chlorinated paraffin or phenyl alkyl sulfonate, preferably diisononyl phthalate DINP.
In the present invention, the diluent is exemplified by dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP, propylene carbonate, chlorinated paraffin, phenyl alkylsulfonate, diisononyl phthalate DINP and dioctyl adipate DOA, dioctyl sebacate DOS and dibutyl phthalate DBP, propylene carbonate and chlorinated paraffin, dioctyl phthalate DOP and phenyl alkylsulfonate, dioctyl phthalate DOP, diisononyl phthalate DINP and dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP and propylene carbonate, diisononyl phthalate DINP, chlorinated paraffin and phenyl alkylsulfonate, dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA and dioctyl sebacate DOS, dibutyl phthalate, propylene carbonate, chlorinated paraffin and phenyl alkylsulfonate.
In a preferred embodiment of the present invention, the molecular sieve is one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve or a 13X molecular sieve, preferably a 4A molecular sieve.
The molecular sieves described in the present invention are, for example, a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, a 13X molecular sieve, a combination of a 3A molecular sieve and a 4A molecular sieve, a combination of a 4A molecular sieve and a 5A molecular sieve, a combination of a 3A molecular sieve and a 5A molecular sieve, a combination of a 4A molecular sieve and a 13X molecular sieve, a combination of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve and a 5A molecular sieve, or a combination of a 4A molecular sieve, a 5A molecular sieve and a 13X molecular sieve.
Preferably, the catalyst is one or more of organotin, organobismuth, organozinc, organonickel or amine catalysts, preferably organobismuth catalysts;
the catalyst in the present invention is, for example, organotin, organobismuth, organozinc, organonickel, amine catalyst, a combination of organotin and organobismuth catalyst, a combination of organozinc and organonickel catalyst, a combination of organobismuth and amine catalyst, an organotin, organobismuth and organozinc catalyst, a combination of organobismuth, organozinc and organonickel catalyst, a combination of organobismuth, organonickel and amine catalyst, a combination of organotin, organobismuth, organozinc and organonickel catalyst, a combination of organozinc, organonickel and amine catalyst.
The selection of the catalyst affects the curing time of the mixed components A and B, but does not affect the heat conduction performance and the bonding performance of the high heat conduction polyurethane.
Preferably, the water scavenger is one or more of p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane or oxazolidine latent curing agent, preferably p-toluenesulfonyl isocyanate Ti;
The water scavenger in the invention is, for example, p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane, an oxazolidine latent curing agent, a combination of toluenesulfonyl isocyanate Ti and methyltrimethoxysilane, a combination of methyltrimethoxysilane and an oxazolidine latent curing agent, and a combination of p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane and an oxazolidine latent curing agent.
Preferably, the coupling agent is one or more of a silane coupling agent KH550, a silane coupling agent KH560 or a silane coupling agent KH570, and is preferably a silane coupling agent KH560.
The coupling agent in the present invention is, for example, KH550, KH560, KH570, a combination of KH550 and KH560, a combination of KH560 and KH570, a combination of KH550, KH560 and KH 570.
According to a second aspect of the present invention, there is provided a method for preparing a polyurethane with high thermal conductivity, the method comprising:
mixing the components of the component A to obtain the component A;
Reacting polyester polyol with isocyanate under protective atmosphere to obtain isocyanate-terminated polyurethane prepolymer, and then adding a water removing agent, a coupling agent and a second heat conducting filler to obtain a component B.
Preferably, the preparation of component A: after all the raw materials are dehydrated, adding polyalcohol, diluent, chain extender and catalyst, and mixing under vacuum condition; then adding a molecular sieve and a heat-conducting filler, and mixing under vacuum condition;
Preferably, the preparation of the component B: adding polyester polyol, and heating and dehydrating; cooling, adding isocyanate, reacting in nitrogen atmosphere to obtain isocyanate-terminated polyurethane prepolymer, adding water scavenger, coupling agent and heat conducting filler, and mixing under vacuum condition.
Specifically, the preparation method of the high-heat-conductivity polyurethane comprises the following steps:
And (3) preparation of a component A: heating the modified polyol, the chain extender and the diluent to 120 ℃, and dehydrating for 1h in a state of vacuum degree of-0.9 MPa; vacuum baking the heat conducting filler to 120 ℃ for dehydration, and controlling the water content below 300 ppm; cooling all the raw materials to below 40 ℃, firstly putting the polyol, the diluent, the chain extender and the catalyst into a planetary stirring kettle, stirring for 30min under vacuum, then adding the molecular sieve and the heat conducting filler, and stirring for 1h under the condition that the vacuum degree is-0.9 MPa to obtain the component A.
And (3) preparing a component B: adding polyester polyol into a three-neck flask, heating to 120 ℃, and dehydrating for 1h in a state of vacuum degree of-0.9 MPa; then cooling to below 60 ℃, adding isocyanate, introducing nitrogen and stirring for 10min; gradually heating to 80 ℃, introducing nitrogen and reacting for 2 hours at constant temperature. Transferring the mixture to a planetary stirring kettle after the reaction is finished, adding a water removing agent, a coupling agent and a heat conducting filler, stirring for 1h under the condition of the vacuum degree of-0.9 MPa, and discharging to obtain the component B.
According to a third aspect of the invention, there is provided a use of a polyurethane of high thermal conductivity, wherein the component A and the component B are mixed and cured, and the mixture is used as a structural adhesive.
The specific method for using the high-heat-conductivity polyurethane as the structural adhesive in the invention is that for example, the component A and the component B are respectively arranged in the volume ratio of 1:1, using an AB pneumatic glue gun, using a certain air pressure, and mixing and sizing by using a mixing tube.
According to a fourth aspect of the present invention, there is provided a battery module including a structural adhesive prepared from the high thermal conductive polyurethane of the present invention.
Examples
The present invention will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Examples materials used
1) Modified castor oil polyol: the method comprises the following steps of (1) preparing oil H854 by using German Abdine 941, shanghai smart day A4100, shanghai smart day AP11 and Embecto;
2) Modified polyether polyol: su Telin ST-350, white wave BPP-03;
3) Chain extender: dipropylene glycol DPG;
4) A diluent: diisononyl phthalate DINP;
5) Catalyst: an organobismuth catalyst;
6) Molecular sieve: 4A molecular sieve;
7) First and second thermally conductive fillers: spherical alumina having an average particle diameter of 1 μm, spherical alumina having an average particle diameter of 10 μm and spherical alumina having an average particle diameter of 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm were prepared in a ratio of 1:2:2:2, carrying out surface modification by using a polyether modified silane coupling agent with the number average molecular weight of 500-3000, wherein the weight of the polyether modified silane coupling agent is 1.5% of that of the heat conducting filler powder;
8) Unmodified thermally conductive filler: spherical alumina having an average particle diameter of 1 μm, spherical alumina having an average particle diameter of 10 μm and spherical alumina having an average particle diameter of 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm were prepared in a ratio of 1:2:2:2 mass ratio mixing;
9) Polyester polyol: dimer acid polyester modified polyol source 3026, dimer acid polyester modified polyol Heda 3190;
10 Isocyanate): polymethylene polyphenyl isocyanate PAPI, van der Waals MDI-50;
11 Water scavenger: toluene sulfonic acid isocyanate Ti;
12 Coupling agent): KH560 silane coupling agent.
Performance testing
1) Shear strength: an overlap sample piece with a length of 25mm, a width of 12.5mm and a thickness of 0.2mm was prepared from a 3003 aluminum sheet which was not polished, and after sizing, it was cured at a temperature of 23℃and a relative humidity of 50% for 7 days, and then subjected to a shear performance test on an electronic universal tester.
2) Thermal conductivity coefficient: the interface material was used for thermal resistance and thermal conductivity measurements LW-9389 according to ASTM D5470 standard.
Example 1
The components are prepared according to the following proportion shown in Table 1:
(1) Heating modified castor oil polyol Germany Albumin 941, modified polyether polyol Shanghai refined day AP11, modified polyether polyol Su Telin ST-350, chain extender dipropylene glycol DPG and diluent diisononyl phthalate DINP to 120 ℃ under stirring, vacuumizing to below-0.9 MPa, and dehydrating for 1h; heating the organic bismuth catalyst, the 4A molecular sieve and the first heat-conducting filler to 120 ℃, vacuumizing to below-0.9 MPa, and dehydrating for 1h; dehydrating all the raw materials, and cooling to below 40 ℃; firstly, putting polyalcohol, diluent, chain extender and catalyst into a planetary stirring kettle, stirring for 30min under vacuum state, then adding molecular sieve and heat conducting filler, stirring for 1h under the condition of vacuum degree of-0.9 MPa, and discharging to obtain component A.
(2) Adding dimer acid polyester polyol source 3026 into the three-neck flask according to the formula amount, heating to 120 ℃, and dehydrating for 1h under the vacuum degree-0.9 MPa; then cooling to below 60 ℃, adding polymethylene polyphenyl isocyanate PAPI, introducing nitrogen and stirring for 10min; gradually heating to 80 ℃, introducing nitrogen and reacting for 2 hours at constant temperature; transferring the mixture to a planetary stirring kettle after the reaction is finished, adding a water removing agent, a coupling agent and a heat conducting filler, stirring for 1h under the condition that the vacuum degree is-0.9 MPa, and discharging to obtain the component B.
(3) A plurality of lap joint sample pieces with the length of 25mm, the width of 12.5mm and the thickness of 0.2mm are prepared by using unground 3003 aluminum sheets, and the A component and the B component are respectively placed in a volume ratio of 1:1, using an AB pneumatic glue gun, using a certain air pressure, mixing and sizing by using a mixing tube, and curing under the conditions of the temperature of 23 ℃ and the relative humidity of 50%.
The high thermal conductive polyurethanes of examples 2 to 10 and comparative examples 1 to 3 were prepared according to the preparation method of example 1.
Table 1 shows the proportions of the components and the results of the performance tests in examples 1 to 7.
Table 2 shows the proportions of the components and the results of the performance tests of examples 8 to 10 and comparative examples 1 to 3
In the comparative example, other raw materials in the comparative example 1 are unchanged, unmodified heat-conducting fillers are used as the component A and the component B, and the performance index experimental data in the comparative example 1 show that when the heat-conducting fillers are used, the heat-conducting fillers have large filling quantity, and the viscosity is too thick to glue. In the embodiments 1 to 10, the surface modified heat conducting filler is used, and when the filling amount of the heat conducting filler is large, the glue can be smoothly applied, and the operability is good.
The other raw materials in comparative example 2 are unchanged, the isocyanate in the component A is the mixture of the Wanhua MDI-50, the MDI-50 is the 2,4 '-diphenylmethane diisocyanate and the 4,4' -diphenylmethane diisocyanate, and the heat conductivity coefficient reaches 3.53 w/(m.k), but the shear strength of the component A, B after the mixture of the components is mixed and adhered with the aluminum and the aluminum surface is solidified is lower, and the use requirement is not met, namely, the shearing strength is only 2.2 MPa.
The other raw materials in comparative example 3 are unchanged, the unmodified castor oil polyol is used as the component B, and the heat conductivity coefficient reaches 3.51 w/(m.k), but the shear strength of the A, B component mixed and adhered with the aluminum and the aluminum surface is lower after solidification, and the use requirement is not met only by 2.55 MPa.
The above description is only illustrative of the preferred embodiments of the present invention and of the principles of the technology employed. It will be appreciated by persons skilled in the art that the scope of the invention referred to in the present invention is not limited to the specific combinations of the technical features described above, but also covers other technical features formed by any combination of the technical features described above or their equivalents without departing from the inventive concept. Such as the above-mentioned features and the technical features disclosed in the present invention (but not limited to) having similar functions are replaced with each other.

Claims (23)

1. The high-heat-conductivity polyurethane comprises the following raw materials in parts by mass:
A component: 6-12 parts of modified polyol, 0-2 parts of chain extender, 1-3 parts of diluent, 0.01-0.05 part of catalyst, 1-3 parts of molecular sieve and 87-90 parts of first heat conducting filler;
And the component B comprises the following components: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of a water scavenger, 0.1-1 part of a coupling agent and 88-92 parts of a second heat conducting filler;
Wherein, the first heat conduction filler and the second heat conduction filler are both subjected to surface modification, and the mass ratio is 1:2:2:2, carrying out surface modification on the first heat conduction filler and the second heat conduction filler by adopting a polyether modified silane coupling agent, wherein the average particle size of the mixture is 1 mu m, the average particle size of spherical alumina is 10 mu m, the average particle size of spherical alumina is 70 mu m, and the average particle size of aluminum hydroxide is 1.5 mu m;
the modified polyol comprises a modified castor oil polyol and a modified polyether polyol;
The modified castor oil polyol is one or more selected from Sovermol 750, sovermol 760, sovermol 810, sovermol 815, 941 and 912 produced by Abdine, germany, H57 and H854 produced by Eartan oil or AP11 and A4100 produced by Shanghai smart day;
The modified polyether polyol is one or two selected from Su Telin ST-350 or white wave BPP-03;
the isocyanate is polymethylene polyphenyl isocyanate PAPI;
the volume ratio of the component A to the component B is 1:0.8-1.2.
2. The high thermal conductivity polyurethane of claim 1, wherein:
the polyether modified silane coupling agent has a number average molecular weight of 500-3000.
3. The high thermal conductivity polyurethane of claim 2, wherein:
the weight of the polyether modified silane coupling agent is 1-2% of the weight of the heat conducting filler powder.
4. The high thermal conductivity polyurethane according to claim 1, wherein the polyester polyol is one or more of adipic acid type polyester polyol, sebacic acid type polyester polyol, phthalic anhydride type polyester polyol or dimer acid modified polyester polyol.
5. The high thermal conductivity polyurethane according to claim 4, wherein said polyester polyol is a dimer acid modified polyester polyol.
6. The polyurethane of claim 1, wherein the chain extender is one or more of a glycol or a polyol.
7. The polyurethane of claim 6, wherein the chain extender is one or more of 1,2 propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, ethylene glycol, or diethylene glycol.
8. The polyurethane of claim 7, wherein the chain extender is dipropylene glycol.
9. The polyurethane of claim 1, wherein the diluent is one or more of dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP, propylene carbonate, chlorinated paraffin or alkyl phenyl sulfonate.
10. The polyurethane of claim 9, wherein the diluent is diisononyl phthalate DINP.
11. The high thermal conductivity polyurethane of claim 1, wherein:
The molecular sieve is one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve or a 13X molecular sieve.
12. The polyurethane of claim 11, wherein the molecular sieve is a 4A molecular sieve.
13. The polyurethane of claim 11, wherein the catalyst is one or more of an organotin, organobismuth, organozinc, organonickel, or amine catalyst.
14. The high thermal conductivity polyurethane of claim 13, wherein the catalyst is an organobismuth catalyst.
15. The high thermal conductivity polyurethane according to claim 11, wherein the water scavenger is one or more of p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane or oxazolidine latent curing agent.
16. The high thermal conductivity polyurethane of claim 15, wherein the water scavenger is p-toluenesulfonyl isocyanate Ti.
17. The high thermal conductivity polyurethane according to claim 11, wherein the coupling agent is one or more of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH 570.
18. The polyurethane of claim 17, wherein the coupling agent is a silane coupling agent KH560.
19. The method for producing a polyurethane having high thermal conductivity according to any one of claims 1 to 18, wherein:
mixing the components of the component A to obtain the component A;
Reacting polyester polyol with isocyanate under protective atmosphere to obtain isocyanate-terminated polyurethane prepolymer, and then adding a water removing agent, a coupling agent and a second heat conducting filler to obtain a component B.
20. The method for preparing high thermal conductivity polyurethane according to claim 19, wherein:
and (3) preparation of a component A: after all the raw materials are dehydrated, adding polyalcohol, diluent, chain extender and catalyst, and mixing under vacuum condition; then adding molecular sieve and heat-conducting filler, mixing under vacuum condition.
21. The method for preparing high thermal conductivity polyurethane according to claim 19, wherein:
and (3) preparing a component B: adding polyester polyol, and heating and dehydrating; cooling, adding isocyanate, reacting in nitrogen atmosphere to obtain isocyanate-terminated polyurethane prepolymer, adding water scavenger, coupling agent and heat conducting filler, and mixing under vacuum condition.
22. The use of highly thermally conductive polyurethane as a structural adhesive of claim 19 wherein the a and B components are mixed and cured.
23. A battery module comprising a structural adhesive made from the high thermal conductivity polyurethane of claim 22.
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118359784A (en) * 2023-01-17 2024-07-19 巴斯夫欧洲公司 Isocyanate prepolymer and polyurethane adhesive prepared from same
CN116532109B (en) * 2023-05-04 2024-05-28 济南大学 A method for preparing a supported catalyst and the resulting product and application
CN116606625B (en) * 2023-05-18 2024-11-15 广东德聚技术股份有限公司 Moisture-heat-resistant polyurethane heat-conducting structural adhesive and preparation method thereof
CN116731659A (en) * 2023-06-27 2023-09-12 深圳市安伯斯科技有限公司 Double-component polyurethane structural adhesive and preparation method thereof
CN117143554B (en) * 2023-11-01 2024-08-09 江苏三纳科技材料有限公司 Polyurethane heat-conducting structural adhesive and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369885A (en) * 2018-09-21 2019-02-22 山东扬名新材料技术有限公司 A kind of plastic cement race track one-component is from knot line spray plane
CN112708389A (en) * 2020-12-23 2021-04-27 无锡市万力粘合材料股份有限公司 Double-component heat-conducting polyurethane adhesive and preparation method thereof
CN113667443A (en) * 2021-09-15 2021-11-19 杭州之江新材料有限公司 Double-component polyurethane heat-conducting structural adhesive and preparation method thereof

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4197141B2 (en) * 2003-08-22 2008-12-17 電気化学工業株式会社 Spherical alumina powder and use thereof
CN106753119A (en) * 2016-12-01 2017-05-31 刘德玉 Acoustic mastic and preparation method thereof is built in a kind of one-component epoxy resin capital construction of high intensity
CN110776869B (en) * 2019-06-21 2024-05-17 南京威邦新材料有限公司 High-temperature-resistant high-strength polyurethane structural adhesive and preparation method thereof
JP7339505B2 (en) * 2019-07-01 2023-09-06 横浜ゴム株式会社 Polyurethane adhesive composition
EP3835332A1 (en) * 2019-12-13 2021-06-16 Henkel AG & Co. KGaA Thermally conductive polyurethane adhesive composition
CN111019587B (en) * 2019-12-17 2022-04-12 格丽泰新材料科技（苏州）有限公司 Two-component polyurethane adhesive for bonding power battery and preparation method thereof
CN111303820B (en) * 2020-03-09 2021-03-26 杭州之江新材料有限公司 Double-component polyurethane structural adhesive for bonding power battery and preparation method thereof
CN111320959B (en) * 2020-03-24 2021-08-06 上海汉司实业有限公司 Polyurethane structural adhesive and preparation method and application thereof
CN111534268B (en) * 2020-04-22 2022-10-11 湖北回天新材料股份有限公司 Low-viscosity high-thermal-conductivity bi-component polyurethane adhesive and preparation method and application thereof
CN111777983A (en) * 2020-06-23 2020-10-16 山东一诺威聚氨酯股份有限公司 High-hardness heat-conducting polyurethane structural adhesive and preparation method thereof
CN112175566B (en) * 2020-09-28 2022-11-25 杭州应星新材料有限公司 Room-temperature curing bi-component polyurethane heat-conducting composition and preparation method thereof
CN112552863A (en) * 2020-12-03 2021-03-26 上海回天新材料有限公司 Solvent-free bi-component polyurethane adhesive for structural bonding and application
CN113736419B (en) * 2021-10-19 2022-04-12 杭州之江新材料有限公司 Double-component polyurethane heat-conducting structural adhesive and preparation method thereof
CN114015408B (en) * 2021-11-26 2023-08-22 浙江福斯特新材料研究院有限公司 Structural adhesive
CN114133910A (en) * 2021-12-21 2022-03-04 华东理工大学 Two-component polyurethane structural adhesive with high thermal conductivity and its preparation method and application
CN114196365B (en) * 2021-12-24 2023-09-05 山东一诺威聚氨酯股份有限公司 High-hardness high-cohesiveness heat-conducting polyurethane structural adhesive and preparation method thereof
CN114181658B (en) * 2021-12-28 2023-03-14 广东金戈新材料股份有限公司 Anti-settling thixotropic two-component polyurethane adhesive and preparation method thereof
CN114940885B (en) * 2022-06-20 2024-04-05 东风汽车集团股份有限公司 Heat-conducting bi-component polyurethane adhesive and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369885A (en) * 2018-09-21 2019-02-22 山东扬名新材料技术有限公司 A kind of plastic cement race track one-component is from knot line spray plane
CN112708389A (en) * 2020-12-23 2021-04-27 无锡市万力粘合材料股份有限公司 Double-component heat-conducting polyurethane adhesive and preparation method thereof
CN113667443A (en) * 2021-09-15 2021-11-19 杭州之江新材料有限公司 Double-component polyurethane heat-conducting structural adhesive and preparation method thereof

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