CN115572363A - High-thermal-conductivity polyurethane, preparation method and application thereof - Google Patents

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

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Publication number
CN115572363A
CN115572363A CN202211099461.XA CN202211099461A CN115572363A CN 115572363 A CN115572363 A CN 115572363A CN 202211099461 A CN202211099461 A CN 202211099461A CN 115572363 A CN115572363 A CN 115572363A
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modified
parts
heat
coupling agent
polyurethane
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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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Abstract

The invention belongs to the field of polyurethane, and relates to high-thermal-conductivity polyurethane, a preparation method and application thereof, wherein the high-thermal-conductivity polyurethane comprises the following raw materials in parts by mass: the component A comprises: 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; the component B comprises: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water removing agent, 0.1-1 part of coupling agent and 88-92 parts of second heat-conducting filler. The thermal conductivity coefficient of the high-thermal-conductivity polyurethane is greater 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; the high-thermal-conductivity polyurethane disclosed by the invention has good bonding performance and high thermal conductivity at the same time, and is particularly suitable for bonding of a power battery module.

Description

High-thermal-conductivity polyurethane, preparation method and application thereof
Technical Field
The invention relates to the technical field of polyurethane, and particularly discloses high-thermal-conductivity polyurethane and a preparation method thereof.
Background
In recent years, new energy automobiles develop rapidly, and the rapid development of industries promotes the development and the perfection of related industries. In the aspect of gluing in battery PACK structure bonding, because of power battery PACK module surface material includes various functional materials such as aluminum alloy, require that the structural adhesive has better adhesive strength to various materials under the condition of not going through 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 operation process of the power battery can be quickly conducted to the outside. The two-component polyurethane adhesive is preferred due to the advantages of long storage period, adjustable modulus, safety, environmental protection and the like.
At present, the heat-conducting performance of the heat-conducting structural adhesive is mainly increased by adding heat-conducting filler, but the viscosity is increased and the flowability is poor due to the large-amount addition of the heat-conducting filler, the mechanical performance of the cured structural adhesive is reduced, the bonding performance is poor, and the packaging requirement of a new energy power battery module cannot be met.
At present, no bi-component polyurethane structural adhesive has good bonding performance and high thermal conductivity.
Disclosure of Invention
In view of the above-mentioned defects or shortcomings in the prior art, an object of the present invention is to provide a polyurethane with high thermal conductivity, which comprises the following raw materials in parts by mass:
the component A comprises: 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.
The component B comprises: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water removal agent, 0.1-1 part of coupling agent and 88-92 parts of second heat-conducting filler.
Preferably, the first heat-conducting filler and the second heat-conducting filler are both surface-modified heat-conducting fillers.
Preferably, the modified polyol includes 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 castor oil polyol modified by a benzene ring or a diol.
Preferably, the modified polyether polyol is benzene ring modified polyether polyol, and preferably benzene ring modified polyether polyol with the functionality of 2-3 and the 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.
The first heat-conducting filler and the second heat-conducting filler are respectively and independently selected from one or more of surface-modified aluminum oxide, aluminum hydroxide, magnesium oxide or zinc oxide.
Preferably, the surface modifier of the first heat-conducting filler and the surface modifier of the second heat-conducting filler are respectively and independently selected from one or more of silazane, chlorosilane, a silane coupling agent or a polyether modified silane coupling agent.
Preferably, the first heat-conducting filler and the second heat-conducting filler are the same and are both a mixture of surface-modified spherical alumina and aluminum hydroxide, preferably a mixture of surface-modified spherical alumina having average particle diameters of 1 μm,10 μm, and 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm, and further preferably a mixture of surface-modified spherical alumina and aluminum hydroxide having a mass ratio of 1:2:2:2 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-modified first filler and the second filler are surface-modified with a polyether-modified silane coupling agent, preferably with 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 phenyl 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 organic tin, organic bismuth, organic zinc, organic nickel or amine catalyst, and is preferably organic bismuth catalyst.
Preferably, the water scavenger is one or more of p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane or oxazolidine latent curing agent, and is 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 the silane coupling agent KH560.
The second purpose of the invention is to provide a preparation method of high thermal conductivity polyurethane, which comprises the following steps:
and mixing the components of the component A to obtain the component A.
Reacting polyester polyol with isocyanate in a protective atmosphere to obtain an 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, preparation of component a: after all raw materials are dehydrated, adding polyalcohol, a diluent, a chain extender and a catalyst, and mixing under a vacuum condition; then adding molecular sieve and heat-conducting filler, and mixing under vacuum condition.
Preferably, the preparation of the component B: adding polyester polyol, and heating for dehydration; cooling, adding isocyanate, reacting in nitrogen atmosphere to obtain isocyanate-terminated polyurethane prepolymer, adding a water removing agent, a coupling agent and a heat conducting filler, and mixing under vacuum condition.
The invention also aims to provide the application of the high-thermal-conductivity polyurethane, namely the component A and the component B are mixed and then cured to be used as the structural adhesive.
The fourth object of the present invention is to provide a battery module, which comprises the structural adhesive prepared from the high thermal conductivity polyurethane of the present invention.
The beneficial effects of the invention include:
(1) According to the invention, the surface-modified first heat-conducting filler and the surface-modified second heat-conducting filler are added, so that the high filling quantity and low viscosity are realized, the operability is good, and the heat conductivity coefficient after curing is more than 3.5 w/(m.k);
(2) Meanwhile, the modified castor oil polyol and the modified polyether polyol are used, and the influence of various polyols on the interface bonding force and the body strength of the polyurethane is comprehensively considered, so that the polyurethane can achieve stronger bonding performance;
(3) The molecular sieve can be used for adsorbing the carbon dioxide generated during the mixing and curing of the A, B component, so that the generation of bubbles is avoided, and the interface bonding force and the body 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 remover, coupling agent and second heat-conducting filler with specific content, and the component A and the component B can achieve better adhesive property and heat-conducting property after mixed and cured;
(5) The preparation method provided by the invention has the advantages of easily available raw materials, simple operation and mild use conditions, the component A and the component B can be mixed and cured at room temperature, the surface of the bonding material can be directly used without treatment, the bonding strength is high, and the method has an excellent industrial application prospect.
In summary, compared with the prior art, the high thermal conductivity polyurethane provided by the invention adopts components with specific contents, realizes better overall interaction, has good bonding performance and high thermal conductivity, and is particularly suitable for bonding of power battery modules.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
In the present invention, the "highly thermally conductive polyurethane" means a polyurethane having a thermal conductivity after curing of 3.5 w/(m.k) or more, as measured by an interfacial material thermal resistance and thermal conductivity meter LW-9389 in accordance with ASTM D5470.
The specific scheme is as follows:
according to a first aspect of the invention, a high thermal conductivity polyurethane is provided, which comprises the following raw materials in parts by mass:
the component A comprises: 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.
The component B comprises: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water removing agent, 0.1-1 part of coupling agent and 88-92 parts of second heat-conducting filler.
The first heat-conducting filler and the second heat-conducting filler are both surface-modified heat-conducting fillers.
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 part, 0.55 part, 1 part and 1.5 parts;
the diluent is present in the present invention in an amount of 1 to 3 parts, for example 1.5 parts, 2 parts and 2.5 parts;
the catalyst is present in the present invention in an amount of 0.01 to 0.05 parts, for example 0.02 parts, 0.03 parts and 0.04 parts;
the molecular sieve is present 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 polyester polyol is contained in an amount of 2 to 5 parts, for example, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts and 4 parts;
the amount 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, such as 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,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,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,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 benzene ring modified polyether polyol, preferably benzene ring modified polyether polyol with the functionality of 2-3 and the 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.
Specifically, the modified castor oil polyol in the invention is selected from one or more of Sovermol 750, sovermol 760, sovermol 810 and Sovermol 815 produced by basf, 941 and 912 produced by Abutant in Germany, H57 and H854 produced by Ito oil production or AP11 and A4100 produced by Shanghai Jing.
In the present invention, the modified castor oil polyol is, for example, basf Sovermol 750, basf Sovermol 760, basf Sovermol 810, basf Sovermol 815, german Abutine 941, german Abutine 912, icell oil H57, icell oil H854, shanghai essence day AP11, shanghai essence day A4100, the combination of German Abutine 941 and Shanghai essence day AP11, the combination of German Abutine 941 and Icell oil H854, the combination of Shanghai essence day AP11 and Shanghai essence day A4100, the combination of basf Sovermol 750 and German Abutine 941A 4100, the combination of Pasteur essence day AP 750, german Abutine 941 and Icell oil H57, the combination of German Abutine essence day AP 912, shanghai essence day AP 941 oil H4100, the combination of Shanghai essence day AP 941 Abutine H41078, the combination of German Abutine Ashbyne essence day AP 941 oil H41011, the combination of Shanghai essence day AP 941 and the German Abutine oil H41078, or the combination of Shanghai essence day AP11, shanghai essence A4100.
In the present invention, the modified polyether polyol is selected from one or two of Su Telin ST-350 or white wave BPP-03, such as 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 is 1.8-1.2, such as 1.
In a preferred embodiment of the present invention, the first and second thermally conductive fillers are each independently selected from one or more of surface-modified aluminum oxide, aluminum hydroxide, magnesium oxide, or zinc oxide.
The first thermally conductive filler is, for example, surface-modified aluminum oxide, aluminum hydroxide, magnesium oxide, zinc oxide, a combination of aluminum oxide and aluminum hydroxide, a combination of aluminum oxide and magnesium oxide, a combination of aluminum oxide and zinc oxide, a combination of aluminum hydroxide and magnesium oxide, a combination of aluminum hydroxide and zinc oxide, a combination of magnesium oxide and zinc oxide, a combination of aluminum oxide, aluminum hydroxide and magnesium oxide, a combination of aluminum oxide, magnesium oxide and zinc oxide, a combination of aluminum hydroxide, magnesium oxide and zinc oxide, a combination of aluminum oxide, aluminum hydroxide, magnesium oxide and zinc oxide.
The second thermally 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 magnesium oxide and zinc oxide, a combination of alumina, aluminum hydroxide and magnesium oxide, a combination of alumina, magnesium oxide and zinc oxide, a combination of aluminum hydroxide, magnesium oxide and zinc oxide, a combination of alumina, aluminum hydroxide, magnesium oxide and zinc oxide, and a combination of alumina, aluminum hydroxide, magnesium oxide and zinc oxide.
Preferably, the surface modifier of the first heat-conducting filler and the surface modifier of the second heat-conducting filler are respectively and independently selected from one or more of silazane, chlorosilane, a silane coupling agent or a polyether modified silane coupling agent.
The surface modifier of the first thermally conductive filler is, for example, a silazane, a chlorosilane, a silane coupling agent, a polyether-modified silane coupling agent, a combination of a silazane and a chlorosilane, a combination of a silazane and a silane coupling agent, a combination of a silazane and a polyether-modified silane, a combination of a chlorosilane and a polyether-modified silane coupling agent, a combination of a silane coupling agent and a polyether-modified silane coupling agent, a combination of a silazane, a chlorosilane and a silane coupling agent, a combination of a silazane silane coupling agent and a polyether-modified silane coupling agent, a combination of a chlorosilane, a silane coupling agent and a polyether-modified silane coupling agent, or a combination of a silazane, a chlorosilane, a silane coupling agent and a polyether-modified silane coupling agent.
The surface modifier of the second thermally 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 a silane coupling agent, a combination of silazane and a polyether-modified silane, a combination of chlorosilane and a silane coupling agent, a combination of chlorosilane and a polyether-modified silane coupling agent, a combination of silazane, chlorosilane and a silane coupling agent, a combination of silazane silane coupling agent and a polyether-modified silane coupling agent, a combination of chlorosilane, a silane coupling agent and a polyether-modified silane coupling agent, a combination of silazane, chlorosilane, a silane coupling agent and a polyether-modified silane coupling agent.
Preferably, the first heat-conducting filler and the second heat-conducting filler are the same and are both a mixture of surface-modified spherical alumina and aluminum hydroxide, preferably a mixture of surface-modified spherical alumina having average particle diameters of 1 μm,10 μm, and 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm, and further preferably a mixture of surface-modified spherical alumina and aluminum hydroxide having a mass ratio of 1:2:2:2 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 fillers with different particle sizes are matched, so that a heat-conducting passage is formed in the high-heat-conducting polyurethane composition, and the heat-conducting property of the composition is improved; also helps to reduce the viscosity of the high thermal conductivity polyurethane composition; and contributes to the improvement of mechanical properties of the highly thermally conductive polyurethane composition after curing.
Preferably, the surface-modified first filler and the second filler are surface-modified with a polyether-modified silane coupling agent, preferably with 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, so that the viscosity of the high-heat-conductivity polyurethane composition is reduced, the gluing is facilitated, and the operability in use is improved.
The weight of the polyether modified silane coupling agent is preferably 1 to 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, and 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 and a dimer acid-modified polyester polyol, a combination of 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 in the invention is selected from one or two of herboria 3026 and cereal 3190, such as a combination of herboria 3026, cereal 3190, herboria 3026 and cereal 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, glycerol, trimethylolpropane, ethylene glycol or diethylene glycol, and more preferably dipropylene glycol.
The chain extender in the present invention is for example 1,2 propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, ethylene glycol or diethylene glycol, 1,2 propylene glycol and dipropylene glycol combination, dipropylene glycol and glycerol combination, dipropylene glycol and trimethylolpropane combination, ethylene glycol and diethylene glycol combination, 1,2 propylene glycol, dipropylene glycol and glycerol combination, 1,2 propylene glycol, dipropylene glycol and trimethylolpropane combination, dipropylene glycol, ethylene glycol and diethylene glycol combination, 1,2 propylene glycol, dipropylene glycol, glycerol and trimethylolpropane combination, dipropylene glycol, glycerol, trimethylolpropane and ethylene glycol combination, 1,2 propylene glycol, dipropylene glycol, glycerol, and ethylene glycol combination, 1,2 propylene glycol, dipropylene glycol and ethylene glycol combination.
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 alkyl phenyl sulfonate, preferably diisononyl phthalate DINP.
The diluent in the present invention is, for example, dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP, propylene carbonate, chlorinated paraffin, phenyl alkylsulfonate, a combination of diisononyl phthalate DINP and dioctyl adipate DOA, a combination of dioctyl sebacate DOS and dibutyl phthalate DBP, a combination of propylene carbonate and chlorinated paraffin, a combination of dioctyl phthalate DOP and phenyl alkylsulfonate, dioctyl phthalate DOP, a combination of diisononyl phthalate DINP and dioctyl adipate DOA, a combination of dioctyl sebacate DOS, dibutyl phthalate DBP and propylene carbonate, a combination of diisononyl phthalate DINP, chlorinated paraffin and phenyl alkylsulfonate, a combination of dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA and dioctyl sebacate DOS, a combination of dioctyl phthalate DOP, dibutyl carbonate, chlorinated paraffin and alkyl sulfonic acid.
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 sieve in the present invention is, 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 and a 5A molecular sieve, or a combination of a 4A molecular sieve, a 5A molecular sieve and a 13X molecular sieve, a combination of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve and a 13X molecular sieve.
Preferably, the catalyst is one or more of organic tin, organic bismuth, organic zinc, organic nickel or amine catalyst, preferably organic bismuth catalyst;
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, 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 organobismuth, organozinc, organonickel and amine catalyst.
The selection of the catalyst influences the curing time of the mixed A component and B component, and does not influence the heat-conducting property and the bonding property of the high-heat-conducting polyurethane.
Preferably, the water scavenger is one or more of p-toluenesulfonyl isocyanate Ti, methyltrimethoxysilane or oxazolidine latent curing agent, and is preferably p-toluenesulfonyl isocyanate Ti;
the water scavenger in the present invention is, for example, p-toluenesulfonylisocyanate Ti, methyltrimethoxysilane, oxazolidine latent curing agent, a combination of toluenesulfonylisocyanate Ti and methyltrimethoxysilane, methyltrimethoxysilane and oxazolidine latent curing agent, or a combination of p-toluenesulfonylisocyanate Ti, methyltrimethoxysilane and 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 the 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, or a combination of KH550, KH560 and KH 570.
According to a second aspect of the present invention, there is provided a preparation method of a high thermal conductive polyurethane, the preparation method comprising:
mixing the components of the component A to obtain a component A;
reacting polyester polyol with isocyanate in a protective atmosphere to obtain an 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, preparation of component a: after all raw materials are dehydrated, adding polyalcohol, a diluent, a chain extender and a catalyst, and mixing under a vacuum condition; then adding a molecular sieve and a heat-conducting filler, and mixing under a vacuum condition;
preferably, the preparation of the component B: adding polyester polyol, and heating for dehydration; cooling, adding isocyanate, reacting in nitrogen atmosphere to obtain isocyanate-terminated polyurethane prepolymer, adding a water removing agent, a coupling agent and a heat conducting filler, and mixing under vacuum condition.
Specifically, the preparation method of the high thermal conductivity polyurethane comprises the following steps:
preparation of the component A: heating the modified polyol, the chain extender and the diluent to 120 ℃, and dehydrating for 1h under the vacuum degree of-0.9 MPa; vacuum baking the heat-conducting filler at 120 ℃ for dehydration, and controlling the water content to be below 300 ppm; cooling all the raw materials to below 40 ℃, putting the polyol, the diluent, the chain extender and the catalyst into a planetary stirring kettle, stirring for 30min under a vacuum state, 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.
Preparation of the component B: adding polyester polyol into a three-neck flask, heating to 120 ℃, and dehydrating for 1h under the 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. After the reaction is finished, transferring the mixture into a planetary stirring kettle, 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 a component B.
According to a third aspect of the invention, a high thermal conductivity polyurethane is provided, wherein the component A and the component B are mixed and then cured to be used as a structural adhesive.
The specific method for using the high-thermal-conductivity polyurethane as the structural adhesive comprises the following steps of respectively placing the component A and the component B in a volume ratio of 1:1, using an AB pneumatic glue gun, using a certain air pressure, and mixing and gluing by using a mixing tube.
According to a fourth aspect of the present invention, a battery module is provided, which comprises 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 relevant invention and not restrictive of the invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Materials used in the examples
1) Modified castor oil polyol: ambudin 941 in Germany, shanghai Jingri A4100, shanghai Jingri AP11, and Ito oil H854;
2) Modified polyether polyol: su Telin ST-350, BAOWAN BPP-03;
3) Chain extender: dipropylene glycol DPG;
4) Diluent agent: 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 size of 1 μm,10 μm and 70 μm and aluminum hydroxide having an average particle size of 1.5 μm were mixed in a ratio of 1:2:2:2, performing 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 the weight of the heat-conducting filler powder;
8) Unmodified thermally conductive filler: spherical alumina having an average particle size of 1 μm,10 μm and 70 μm and aluminum hydroxide having an average particle size of 1.5 μm were mixed in a ratio of 1:2:2:2, mixing in a mass ratio;
9) Polyester polyol: dimer acid polyester modified polyol Baiyuan 3026, dimer acid polyester modified polyol Jida 3190;
10 Isocyanate): polymethylene polyphenyl isocyanate PAPI, warfarin MDI-50;
11 Water scavenger: toluene sulfonyl isocyanate Ti;
12 Coupling agent): KH560 silane coupling agent.
Performance testing
1) Shear strength: a lap joint sample piece with the length of 25mm, the width of 12.5mm and the thickness of 0.2mm is prepared by using an unground 3003 aluminum sheet, after glue application, curing is carried out for 7 days under the conditions of the temperature of 23 ℃ and the relative humidity of 50 percent, and then a shearing performance test is carried out on an electronic universal testing machine.
2) Coefficient of thermal conductivity: the interface material thermal resistance and thermal conductivity coefficient measuring instrument LW-9389 is used for testing according to ASTM D5470 standard.
Example 1
The preparation method comprises the following steps:
(1) Heating modified castor oil polyol German albuterol 941, modified polyether polyol Shanghai essence Nippon 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 organic bismuth catalyst, 4A molecular sieve and first heat-conducting filler at 120 ℃, vacuumizing to below-0.9 MPa, and dehydrating for 1h; dehydrating all the raw materials and cooling to below 40 ℃; firstly putting the polyol, the diluent, the chain extender and the catalyst into a planetary stirring kettle, stirring for 30min under a vacuum state, then adding the molecular sieve and the heat-conducting filler, stirring for 1h under the condition that the vacuum degree is-0.9 MPa, and discharging to obtain the component A.
(2) Adding a dimer acid polyester polyol Baiyuan 3026 into a three-neck flask according to the formula amount, heating to 120 ℃, and dehydrating for 1h under the vacuum degree of-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; after the reaction is finished, transferring the mixture into a planetary stirring kettle, 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) Preparing a plurality of lap joint sample wafers with the length of 25mm, the width of 12.5mm and the thickness of 0.2mm by using unground 3003 aluminum sheets, and respectively placing the component A and the component B in a volume ratio of 1:1, using an AB pneumatic glue gun, using a certain air pressure, mixing and gluing by using a mixing tube, and curing at 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 results of the tests on the composition ratios and properties of examples 1 to 7.
Figure BDA0003839529420000141
Table 2 shows the composition ratios and performance test results of examples 8 to 10 and comparative examples 1 to 3
Figure BDA0003839529420000151
In the above comparative example, the other raw materials in comparative example 1 are not changed, the unmodified heat-conducting filler is used as the component A and the component B, and it can be known from the performance index experimental data of comparative example 1 that when the unmodified heat-conducting filler is used, the viscosity is too thick to glue when the filling amount of the heat-conducting filler is large. And the heat-conducting fillers with modified surfaces are used in the embodiments 1 to 10, so that when the filling amount of the heat-conducting fillers is large, gluing can be performed smoothly, and the operability is good.
Comparative example 2 the other raw materials were unchanged, the isocyanate in component A was Wanhua MDI-50, MDI-50 was a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, although the thermal conductivity coefficient reached 3.53 w/(m.k), the shear strength was lower after the A, B component mixed bonded aluminum + aluminum surface was cured, only 2.2MPa, which did not meet the use requirements.
Comparative example 3 the other raw materials are unchanged, the unmodified castor oil polyol is used as the component B, and although the thermal conductivity coefficient reaches 3.51 w/(m.k), the shearing strength of the A, B component after the surface of the mixed bonding aluminum and aluminum is cured is lower, and is only 2.55MPa, so that the use requirement cannot be met.
The foregoing description is only exemplary of the preferred embodiments of the invention and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the invention is not limited to the specific combination of the above-mentioned features, but also encompasses other embodiments in which any combination of the above-mentioned features or their equivalents is made without departing from the inventive concept. For example, the above features and the technical features (but not limited to) having similar functions disclosed in the present invention are mutually replaced to form the technical solution.

Claims (10)

1. The high-thermal-conductivity polyurethane comprises the following raw materials in parts by mass:
the component A comprises: 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;
the component B comprises: 4-8 parts of isocyanate, 2-5 parts of polyester polyol, 0.1-1 part of water removing agent, 0.1-1 part of coupling agent and 88-92 parts of second heat conducting filler;
the first heat-conducting filler and the second heat-conducting filler are both surface-modified heat-conducting fillers;
the modified polyol comprises a modified castor oil polyol and a modified polyether polyol;
the isocyanate is one or more of 1,6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, polymethylene polyphenyl isocyanate PAPI or toluene diisocyanate TDI.
2. The polyurethane with high thermal conductivity according to claim 1, wherein:
the modified castor oil polyhydric alcohol is castor oil polyhydric alcohol modified by a benzene ring or dihydric alcohol;
preferably, the modified polyether polyol is benzene ring modified polyether polyol, preferably benzene ring modified polyether polyol with the functionality of 2-3 and the 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.
3. The polyurethane with high thermal conductivity according to claim 1, wherein:
the first heat-conducting filler and the second heat-conducting filler are respectively and independently selected from one or more of surface-modified aluminum oxide, aluminum hydroxide, magnesium oxide or zinc oxide;
preferably, the surface modifier of the first heat-conducting filler and the surface modifier of the second heat-conducting filler are respectively and independently selected from one or more of silazane, chlorosilane, a silane coupling agent or a polyether modified silane coupling agent;
preferably, the first heat-conducting filler and the second heat-conducting filler are the same and are both a mixture of surface-modified spherical alumina and aluminum hydroxide, preferably a mixture of surface-modified spherical alumina having average particle diameters of 1 μm,10 μm, and 70 μm and aluminum hydroxide having an average particle diameter of 1.5 μm, and further preferably a mixture of surface-modified spherical alumina and aluminum hydroxide having a mass ratio of 1:2:2:2 a mixture 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 first filler and the second filler are surface-modified by a polyether-modified silane coupling agent, preferably a polyether-modified silane coupling agent with 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.
4. The polyurethane with high thermal conductivity 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, and preferably dimer acid modified polyester polyol.
5. The polyurethane with high thermal conductivity according to claim 1, wherein 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 more preferably dipropylene glycol.
6. The polyurethane with high thermal conductivity according to claim 1, wherein the diluent is one or more selected from dioctyl phthalate DOP, diisononyl phthalate DINP, dioctyl adipate DOA, dioctyl sebacate DOS, dibutyl phthalate DBP, propylene carbonate, chlorinated paraffin or alkyl phenyl sulfonate, and is preferably diisononyl phthalate DINP.
7. The polyurethane with high thermal conductivity according to 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, and is preferably a 4A molecular sieve;
preferably, the catalyst is one or more of organic tin, organic bismuth, organic zinc, organic nickel or amine catalyst, preferably organic bismuth catalyst;
preferably, the water removal agent 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 the silane coupling agent KH560.
8. The method for preparing polyurethane with high thermal conductivity according to any one of claims 1 to 7, wherein:
mixing the components of the component A to obtain a component A;
reacting polyester polyol with isocyanate in a protective atmosphere to obtain an 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, preparation of component a: after all raw materials are dehydrated, adding polyalcohol, a diluent, a chain extender and a catalyst, and mixing under a vacuum condition; then adding a molecular sieve and a heat-conducting filler, and mixing under a vacuum condition;
preferably, the preparation of the component B: adding polyester polyol, and heating for dehydration; cooling, adding isocyanate, reacting in nitrogen atmosphere to obtain isocyanate-terminated polyurethane prepolymer, adding a water removing agent, a coupling agent and a heat conducting filler, and mixing under vacuum condition.
9. The use of the polyurethane with high thermal conductivity as structural adhesive according to claim 8, wherein the component A and the component B are mixed and then cured.
10. A battery module comprising a structural adhesive prepared from the highly thermally conductive polyurethane of claim 9.
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