CN114940885A - Heat-conducting bi-component polyurethane adhesive and preparation method and application thereof - Google Patents
Heat-conducting bi-component polyurethane adhesive and preparation method and application thereof Download PDFInfo
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- CN114940885A CN114940885A CN202210698789.7A CN202210698789A CN114940885A CN 114940885 A CN114940885 A CN 114940885A CN 202210698789 A CN202210698789 A CN 202210698789A CN 114940885 A CN114940885 A CN 114940885A
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- polyurethane adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 79
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 79
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 37
- 150000003077 polyols Chemical class 0.000 claims abstract description 37
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 26
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 26
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 63
- 238000002156 mixing Methods 0.000 claims description 55
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 27
- 239000007822 coupling agent Substances 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- -1 polymethylene Polymers 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 5
- 239000013638 trimer Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 150000003384 small molecules Chemical group 0.000 claims description 3
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HEBTZZBBPUFAFE-UHFFFAOYSA-N 2-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=CC=C1S(=O)(=O)N=C=O HEBTZZBBPUFAFE-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- 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
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- 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
Abstract
The application relates to the technical field of adhesives, in particular to a heat-conducting bi-component polyurethane adhesive and a preparation method and application thereof. The heat-conducting bi-component polyurethane adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 5-10 parts of aromatic polyether polyol, 4-8 parts of polyolefin polyol, 0-1 part of micromolecular chain extender, 0.02-0.04 part of catalyst, 75-90 parts of heat-conducting filler and 0-2 parts of molecular sieve; the component B comprises the following raw materials in parts by weight: 5-10 parts of isocyanate-terminated polyurethane prepolymer, 5-10 parts of polyisocyanate, 0.4-0.7 part of silane coupling agent, 0.1-0.2 part of water removing agent, 75-90 parts of heat conducting filler and 0-3 parts of plasticizer. The heat-conducting double-component polyurethane adhesive provided by the application can solve the problem that the humidity resistance and the heat resistance of the polyurethane adhesive are reduced in the related technology, has the heat conductivity coefficient of more than 2 (W/m.k), and has good bonding mechanical property and humidity resistance, heat resistance and aging resistance.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a heat-conducting bi-component polyurethane adhesive and a preparation method and application thereof.
Background
In the power battery cell bonding application technology, compared with single-component silica gel and double-component silica gel, the double-component polyurethane has the characteristics of longer storage period, consistent and adjustable inner and outer curing speeds of a glue layer, good flexibility of the cured glue layer, low shrinkage rate, water resistance, good impact resistance, high bonding strength, low cost and the like, so that the double-component polyurethane is more and more widely applied. With the rapid development of new energy automobiles, the power battery technology develops towards the direction of higher energy density and better heat dissipation performance, and the use demand of the adhesive is larger and larger. In practical use, the battery components face environments of vibration, high and low temperature, and high humidity and heat, and the requirements on the shear strength, the pull strength and the elongation at break of the adhesive are higher and higher. Thus, there is a need for an adhesive having both good mechanical properties and high thermal conductivity.
In the prior art, the aging resistance and the attenuation of medium and low heat conduction products can meet the requirements, but with the increasing energy density of power batteries, the heat release amount of charge and discharge in unit time of the batteries is higher, the heat conduction performance of the adhesive is higher, the heat conduction requirement of the polyurethane is more and more higher, the heat conduction performance of the adhesive is more and more higher, and as is known, with the increasing of heat conduction fillers and the reduction of resin, the humidity and heat resistance of the adhesive is gradually reduced. Therefore, how to effectively solve the problem of moisture and heat resistance of the polyurethane adhesive on the premise of ensuring high heat conductivity is a current problem.
Disclosure of Invention
The embodiment of the application provides a heat-conducting double-component polyurethane adhesive to solve the problem that the humidity and heat resistance of polyurethane adhesives is reduced in the related art.
In a first aspect, the application provides a heat-conducting bi-component polyurethane adhesive, which comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 5-10 parts of aromatic polyether polyol, 4-8 parts of polyolefin polyol, 0-1 part of micromolecular chain extender, 0.02-0.04 part of catalyst, 75-90 parts of heat-conducting filler and 0-2 parts of molecular sieve; the component B comprises the following raw materials in parts by weight: 5-10 parts of isocyanate-terminated polyurethane prepolymer, 5-10 parts of polyisocyanate, 0.4-0.7 part of silane coupling agent, 0.1-0.2 part of water removing agent, 75-90 parts of heat conducting filler and 0-3 parts of plasticizer.
In some embodiments, the isocyanate-terminated polyurethane prepolymer in the component B is prepared from polyol and polyisocyanate according to a mass ratio of 30-50: 50-70; wherein the polyisocyanate is at least one selected from 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, liquefied MDI, polymethylene polyphenyl polyisocyanate and hexamethylene diisocyanate trimer.
In some embodiments, the isocyanate-terminated polyurethane prepolymer is prepared by: mixing polyester polyol and a plasticizer, heating to 115-120 ℃, vacuumizing, stirring and dehydrating for 2h, cooling to 60 ℃, removing vacuum by using nitrogen, adding polyisocyanate, heating to 70 ℃, reacting for 1.5-2h in a heat preservation manner, cooling to 60 ℃ while stirring to obtain the isocyanate-terminated polyurethane prepolymer, and sealing and storing for later use.
In some embodiments, the aromatic polyether polyol in the component A is polyether polyol containing a bisphenol A structure, the relative molecular weight is 300-800, and the hydroxyl value is 159-325 mgKOH/g. In some preferred embodiments, the aromatic polyether polyol in the A component is a BPIP polyol available from Saybolt.
In some examples, the polyolefin polyol in component A has a relative molecular weight of 2000-3500 and a hydroxyl value of 35 to 56 mgKOH/g.
In some embodiments, the polyolefin polyol in the A component is selected from Cray Valley Poly bd R-45M.
In some embodiments, the small molecule chain extender in the a component is at least one of dipropylene glycol, diethylene glycol, 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 3-butanediol, trimethylolpropane.
In some embodiments, the catalyst in component a is at least one of dibutyltin dilaurate, stannous octoate, and bismuth neodecanoate.
In some embodiments, the thermally conductive filler in both the a and B components is selected from modified alumina obtained by modifying alumina with an alkoxysilane coupling agent or a titanate coupling agent.
In some embodiments, the water scavenger in the B component is selected from at least one of tosylisocyanate, triethyl orthoformate.
In some embodiments, the polyisocyanate in the B component is selected from at least one of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, liquefied MDI, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate trimer; the silane coupling agent in the component B is selected from at least one of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-mercaptopropyltrimethoxysilane. In some preferred embodiments, the polyisocyanate in the B component is selected from at least one of the group consisting of Nicotiana H12MDI, IPDI, MDI-100L, PM200 and Bayer desmodur N3300.
In some embodiments, the plasticizer in the B component is diisononyl phthalate.
In a second aspect, the application also provides a preparation method of the heat-conducting two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: mixing aromatic polyether polyol, polyolefin polyol, a small molecular chain extender, a catalyst, a heat-conducting filler and a molecular sieve, vacuumizing, and uniformly stirring to obtain a component A;
preparing a component B: mixing the isocyanate-terminated polyurethane prepolymer, polyisocyanate, a silane coupling agent, a water removing agent, a heat conducting filler and a plasticizer, vacuumizing and uniformly stirring to obtain a component B;
mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the heat-conducting bi-component polyurethane adhesive.
In some embodiments, the isocyanate-terminated polyurethane prepolymer in the component B is prepared from polyol and polyisocyanate according to a mass ratio of 30-50: 50-70.
In some embodiments, the isocyanate-terminated polyurethane prepolymer is prepared by: mixing polyester polyol and a plasticizer, heating to 115-120 ℃, vacuumizing, stirring and dehydrating for 2h, cooling to 60 ℃, removing vacuum by using nitrogen, adding polyisocyanate, heating to 70 ℃, reacting for 1.5-2h while stirring, cooling to 60 ℃ to obtain an isocyanate-terminated polyurethane prepolymer, and sealing and storing for later use.
In some embodiments, the aromatic polyether polyol in the component A is polyether polyol containing a bisphenol A structure, the relative molecular weight is 300-800, and the hydroxyl value is 159-325 mgKOH/g. In some preferred embodiments, the aromatic polyether polyol in the A component is a BPIP polyol available from Saybolt.
In some embodiments, the polyolefin polyol in the A component is selected from Cray Valey Poly bd R-45M.
In some embodiments, the small molecule chain extender in the a component is at least one of dipropylene glycol, diethylene glycol, 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 3-butanediol, trimethylolpropane.
In some embodiments, the catalyst in component a is at least one of dibutyltin dilaurate, stannous octoate, and bismuth neodecanoate.
In some embodiments, the heat conductive filler in both the a component and the B component is selected from modified alumina obtained by modifying alumina with an alkoxysilane coupling agent or a titanate coupling agent, and the modified alumina is a free combination of three modified aluminas with different particle sizes, specifically a combination of modified alumina with a particle size of 5-10 μm, modified alumina with a particle size of 25-40 μm, and modified alumina with a particle size of 50-80 μm. The matching use of different grain sizes is beneficial to forming a heat conduction channel, the viscosity and the dispersion wettability of the adhesive can be adjusted, if the modified alumina with small grain size is used, the specific surface area of the filler is large, the resin is adsorbed, the viscosity is increased, and the construction is inconvenient; if the modified alumina with large particle size is used, the filler has poor dispersion and wetting effects, and is easy to form sedimentation, thereby influencing a heat conduction path.
In some embodiments, the water scavenger in the B component is selected from at least one of tosylisocyanate, triethyl orthoformate.
In some embodiments, the polyisocyanate in the B component is selected from at least one of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, liquefied MDI, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate trimer; the silane coupling agent in the component B is selected from at least one of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-mercaptopropyltrimethoxysilane. In some preferred embodiments, the polyisocyanate in the B component is selected from at least one of the group consisting of Nicotiana H12MDI, IPDI, MDI-100L, PM200 and Bayer desmodur N3300.
In some embodiments, the plasticizer in the B component is diisononyl phthalate.
In a third aspect, the application also provides an application of the heat-conducting double-component polyurethane adhesive, and the heat-conducting double-component polyurethane adhesive is used for bonding a power battery cell.
The beneficial effect that technical scheme that this application provided brought includes: the application improves the heat conductivity coefficient of the adhesive by adding the modified alumina into the component A and the component B, and the heat conductivity coefficient of the prepared heat-conducting bi-component polyurethane adhesive is more than 2 (W/m.k); according to the application, the aromatic polyether polyol and the polyolefin polyol are added into the raw materials, so that the bonding mechanical property and the humidity and heat aging resistance of the adhesive are improved, the adhesive is used for bonding 3003 aluminum materials without surface treatment and a primer, and a performance test is carried out on the polyurethane adhesive, so that the result shows that the strength of the adhesive is kept above 80% at 95% DEG C, 95% RH and 1000h after aging.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a thermal conductive two-component polyurethane adhesive according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a heat-conducting double-component polyurethane adhesive, which can solve the problem that the humidity and heat resistance of polyurethane adhesives is reduced in the related art.
The application provides a heat-conducting bi-component polyurethane adhesive, which comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 5-10 parts of aromatic polyether polyol, 4-8 parts of polyolefin polyol, 0-1 part of micromolecular chain extender, 0.02-0.04 part of catalyst, 75-90 parts of heat-conducting filler and 0-2 parts of molecular sieve; the component B comprises the following raw materials in parts by weight: 5-10 parts of isocyanate-terminated polyurethane prepolymer, 5-10 parts of polyisocyanate, 0.4-0.7 part of silane coupling agent, 0.1-0.2 part of water removing agent, 75-90 parts of heat conducting filler and 0-3 parts of plasticizer.
The aromatic polyether polyol in the component A is polyether polyol containing a bisphenol A structure, the relative molecular weight is 300-800, and the hydroxyl value is 159-325 mgKOH/g; the polyolefin polyol in the A component is selected from Cray Valley Poly bd R-45M; the micromolecular chain extender in the component A is at least one of dipropylene glycol, diethylene glycol, 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 3-butanediol and trimethylolpropane; the catalyst in the component A is at least one of dibutyltin dilaurate, stannous octoate and bismuth neodecanoate.
The isocyanate-terminated polyurethane prepolymer in the component B is prepared from polyol and polyisocyanate according to the mass ratio of 30-50:50-70, and the preparation process comprises the following steps: adding polyester polyol and a plasticizer (DINP) into a flask, mixing, heating to 115-120 ℃, vacuumizing, stirring and dehydrating for 2h, cooling to 60 ℃, removing vacuum by using nitrogen, adding polyisocyanate, heating to 70 ℃, preserving heat and reacting for 1.5-2h, cooling to 60 ℃ while stirring to obtain the isocyanate-terminated polyurethane prepolymer, and sealing and storing for later use.
The water removing agent in the component B is at least one selected from tosyl isocyanate and triethyl orthoformate; the polyisocyanate in the component B is selected from at least one of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, liquefied MDI, polymethylene polyphenyl polyisocyanate and hexamethylene diisocyanate trimer; the silane coupling agent in the component B is selected from at least one of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-mercaptopropyltrimethoxysilane.
The heat-conducting filler in the component A and the heat-conducting filler in the component B are both selected from modified alumina, and the modified alumina is obtained by modifying alumina by using an alkoxy silane coupling agent or a titanate coupling agent; specifically, the process of modifying alumina with an alkoxysilane coupling agent is as follows: preparing an 8-16 carbon chain trimethoxy silane or 8-16 carbon chain triethoxy silane aqueous solution with the mass concentration of 3% -4%, adjusting the pH value to be approximately equal to 3 by using glacial acetic acid, and fully hydrolyzing a silane coupling agent to obtain a silane coupling agent aqueous solution; adding methanol solution into alumina powder with different particle sizes, and performing ultrasonic dispersion to obtain alumina dispersion liquid with the mass concentration of 2% -3%; and (3) adding a silane coupling agent aqueous solution into the alumina dispersion, stirring for 2-3h at 60 ℃, and removing methanol at 150 ℃ to obtain the modified alumina modified by the alkoxy silane coupling agent. The process of modifying alumina by using titanate coupling agent is as follows: uniformly mixing 10-20 wt% of water, alumina powder with different particle sizes and 2-3 wt% of titanate coupling agent at room temperature to form dispersion liquid of alumina powder with titanate coupling agent adsorbed on the surface; dissolving an organic amine curing agent in water to obtain an aqueous solution of the organic amine curing agent with the concentration of 0.2-1 wt%, and dissolving a titanate coupling agent in water to obtain an aqueous solution of the titanate coupling agent with the concentration of 3-5 wt%; heating the dispersion liquid of the alumina powder with the titanate coupling agent adsorbed on the surface to 30-80 ℃ while stirring, respectively and slowly adding an aqueous solution of an organic amine curing agent and an aqueous solution of the titanate coupling agent into the dispersion liquid so as to enable the titanate coupling agent and the organic amine curing agent to be cross-linked and polymerized on the surfaces of the alumina powder particles, continuously stirring for at least 1 hour to fully react, and drying in an oven at 80 ℃ for 24 hours to obtain the modified alumina modified by the titanate coupling agent.
Referring to fig. 1, the present application also provides a method for preparing a thermally conductive two-component polyurethane adhesive, comprising the steps of:
step S101, preparing a component A: mixing 5-10 parts by weight of aromatic polyether polyol, 4-8 parts by weight of polyolefin polyol, 0-1 part by weight of small molecular chain extender, 0.02-0.04 part by weight of catalyst, 75-90 parts by weight of heat-conducting filler and 0-2 parts by weight of molecular sieve, vacuumizing and uniformly stirring to obtain a component A;
step S102, preparing a component B: mixing 5-10 parts of isocyanate-terminated polyurethane prepolymer, 5-10 parts of polyisocyanate, 0.4-0.7 part of silane coupling agent, 0.1-0.2 part of water removing agent, 75-90 parts of heat conducting filler and 0-3 parts of plasticizer in parts by weight, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the heat-conducting bi-component polyurethane adhesive.
The following will explain the thermally conductive two-component polyurethane adhesive and the preparation method thereof provided by the present application in detail with reference to the examples.
Description of raw materials:
molecular sieve: 4A molecular sieve, type: HX-G103, available from Dalian Haixin chemical Co., Ltd;
plasticizer: diisononyl phthalate, available from Zhongshan Co-Industrial Co., Ltd;
modified alumina: the aluminum oxide is modified by alkoxy silane coupling agent.
Example 1:
the embodiment 1 of the application provides a preparation method of a heat-conducting bi-component polyurethane adhesive, which comprises the following steps:
step S101, preparing a component A: mixing 5 parts by weight of BPIP, 6 parts by weight of Poly bd R-45M, 1 part by weight of diethylene glycol, 0.03 part by weight of dibutyltin dilaurate, 88 parts by weight of modified alumina and 1 part by weight of molecular sieve, vacuumizing, and stirring and mixing uniformly to obtain a component A;
step S102, preparing a component B: mixing 6 parts of isocyanate-terminated polyurethane prepolymer, 2005.4 parts of PM, 0.5 part of beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 0.1 part of toluene sulfonyl isocyanate, 88 parts of modified alumina and 1 part of plasticizer in parts by weight, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the heat-conducting bi-component polyurethane adhesive.
In example 1, the particle size distribution of the modified alumina used for the a component and the B component was: 50% of modified alumina with the particle size of 5-10 mu m, 30% of modified alumina with the particle size of 25-40 mu m and 20% of modified alumina with the particle size of 50-80 mu m.
The composition of each raw material in example 1 is shown in table 1.
Table 1: composition Table of two-component polyurethane adhesive of example 1
The thermally conductive two-component polyurethane adhesive obtained in example 1 was subjected to performance tests according to the following criteria, and the results are shown in Table 2.
(1) And (3) testing the density: the test was carried out according to the GB/T13354 standard.
(2) And (3) testing the heat conductivity coefficient: the test was carried out according to ISO22007-2 standard.
(3) And (3) testing the shear strength: testing according to GB/T7124-2008 standard, evenly mixing A, B components according to the volume ratio of 1:1, adhering 3003 aluminum material without base coating and surface treatment and 3003 aluminum material to prepare a shear test piece, curing the shear test piece for 7 days at the temperature of 23 +/-2 ℃ and the relative humidity of 50 +/-5% RH, wherein the thickness of a glue layer is 0.5mm, and testing the shear strength.
(4) And (3) testing the drawing strength: tested according to ASTM D1002-1.
(5) Tensile strength and elongation at break test: a, B components are uniformly mixed according to the volume ratio of 1:1, pressed into a sheet with the thickness of about 2mm, cured for 7 days in the environment of temperature (23 +/-2) DEG C and relative humidity (50 +/-5)% RH, and tested according to the standard and a type 1 cutter is adopted. Testing according to GB/T528.
(6) And (5) testing weather resistance. And (3) placing the completely cured shear test piece in a test box with the temperature of 95 ℃ and the relative humidity of 95% RH for aging for 1000h, then taking out the shear test piece, placing the shear test piece at room temperature for 24h, and testing the shear strength.
Table 2: test data for thermally conductive two-component polyurethane adhesive prepared in example 1
| Serial number | Detecting items | Results |
| 1 | Density after mixing (g/cm3) | 2.3 |
| 2 | Coefficient of thermal conductivity (W/m. k) | 2.5 |
| 3 | Shear strength (MPa) | 8.7 |
| 4 | Tensile Strength (MPa) | 8.1 |
| 5 | Tensile Strength (MPa) | 8.5 |
| 6 | Elongation at Break (%) | 36％ |
| 7 | Shear strength (MPa) after resistance to Damp-Heat aging | 8.3 |
| 8 | Tensile Strength after Damp and Heat aging (MPa) | 8.32 |
Comparative example 1:
the application comparative example 1 provides a preparation method of a heat-conducting bi-component polyurethane adhesive, which comprises the following steps:
step S101, preparing a component A: mixing 5 parts by weight of BPIP, 1 part by weight of diethylene glycol, 0.03 part by weight of dibutyltin dilaurate, 88 parts by weight of modified alumina and 1 part by weight of molecular sieve, vacuumizing, and stirring and mixing uniformly to obtain a component A;
step S102, preparing a component B: mixing 6 parts of isocyanate-terminated polyurethane prepolymer, 2005.4 parts of PM, 0.5 part of beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 0.1 part of toluene sulfonyl isocyanate, 88 parts of modified alumina and 1 part of plasticizer in parts by weight, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the bi-component polyurethane adhesive.
In comparative example 1, the particle size distribution of the modified alumina used for the a component and the B component was: 50% of modified alumina with the particle size of 5-10 mu m, 30% of modified alumina with the particle size of 25-40 mu m and 20% of modified alumina with the particle size of 50-80 mu m.
The composition of each raw material in comparative example 1 is shown in table 3.
Table 3: composition table of each raw material in comparative example 1
The two-component polyurethane adhesive prepared in comparative example 1 was subjected to a performance test, and the results are shown in Table 4.
Table 4: test data for the two-component polyurethane adhesive prepared in comparative example 1
| Serial number | Detecting items | Results |
| 1 | Density after mixing (g/cm3) | 2.3 |
| 2 | Coefficient of thermal conductivity (W/m. k) | 2.5 |
| 3 | Shear strength (MPa) | 7.9 |
| 4 | Tensile Strength (MPa) | 7.8 |
| 5 | Tensile Strength (MPa) | 8.2 |
| 6 | Elongation at Break (%) | 30％ |
| 7 | Shear strength (MPa) after resistance to Damp-Heat aging | 4.7 |
| 8 | Tensile Strength after Damp and Heat aging (MPa) | 3.9 |
As can be seen from Table 4, when no polyolefin polyol was added to the raw materials, the shear strength and the pull strength after wet heat aging resistance of the adhesive obtained were lowered.
Comparative example 2:
the application comparative example 2 provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
step S101, preparing a component A: mixing 5 parts by weight of BPIP, 6 parts by weight of Poly bd R-45M, 1 part by weight of diethylene glycol, 0.03 part by weight of dibutyltin dilaurate, 88 parts by weight of modified alumina and 1 part by weight of molecular sieve, vacuumizing, and stirring and mixing uniformly to obtain a component A;
step S102, preparing a component B: mixing 6 parts of isocyanate-terminated polyurethane prepolymer, 2005.4 parts of PM, 0.5 part of beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 0.1 part of toluene sulfonyl isocyanate, 88 parts of modified alumina and 1 part of plasticizer in parts by weight, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and obtaining the bi-component polyurethane adhesive.
In comparative example 2, the particle size of the modified alumina in the A-component and the B-component was 50 to 80 μm.
In comparative example 2, the composition of each raw material is shown in table 5.
Table 5: composition table of each raw material in comparative example 2
The adhesive prepared in comparative example 2 was subjected to performance test, and the results are shown in Table 6.
Table 6: test data for the two-component polyurethane adhesive prepared in comparative example 2
| Serial number | Detecting items | Results |
| 1 | Density after mixing (g/cm3) | 2.5 |
| 2 | Thermal conductivity coefficient (W/m.k) | 1.7 |
| 3 | Shear strength (MPa) | 8.5 |
| 4 | Tensile Strength (MPa) | 7.8 |
| 5 | Tensile Strength (MPa) | 8.4 |
| 6 | Elongation at Break (%) | 36％ |
| 7 | Shear Strength after Damp and Heat aging (MPa) | 7.2 |
| 8 | Tensile Strength after Damp and Heat aging (MPa) | 6.7 |
As can be seen from table 6, when alumina having a large particle size is used in its entirety, the adhesive has a low thermal conductivity because the filler has a poor dispersion wetting effect and is liable to form sedimentation, which affects the thermal conduction path.
Example 2:
the embodiment 2 of the application provides a preparation method of a heat-conducting bi-component polyurethane adhesive, which comprises the following steps:
step S101, preparing a component A: mixing 5 parts by weight of BPIP, 5.5 parts by weight of Poly bd R-45M, 0.8 part by weight of diethylene glycol, 0.03 part by weight of dibutyltin dilaurate, 80 parts by weight of modified alumina and 1 part by weight of molecular sieve, vacuumizing, and uniformly stirring to obtain a component A;
step S102, preparing a component B: mixing 6.5 parts of isocyanate-terminated polyurethane prepolymer, 2005.4 parts of PM, 0.6 part of beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane, 0.1 part of toluene sulfonyl isocyanate, 88 parts of modified alumina and 1 part of plasticizer in parts by weight, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the heat-conducting bi-component polyurethane adhesive.
In example 2, the particle size distribution of the modified alumina used for the a component and the B component was: 40% of modified alumina with the particle size of 5-10 mu m, 30% of modified alumina with the particle size of 25-40 mu m and 30% of modified alumina with the particle size of 50-80 mu m.
The composition of each raw material in example 2 is shown in Table 7.
Table 7: composition Table of two-component polyurethane adhesive of example 2
The adhesive prepared in example 2 was subjected to performance testing and the results are shown in table 8.
Table 8: performance data for the adhesive prepared in example 2
Example 3:
the embodiment 3 of the application provides a preparation method of a heat-conducting bi-component polyurethane adhesive, which comprises the following steps:
step S101, preparing a component A: mixing 7 parts by weight of BPIP, 6.5 parts by weight of Poly bd R-45M, 1 part by weight of diethylene glycol, 0.03 part by weight of dibutyltin dilaurate, 90 parts by weight of modified alumina and 1 part by weight of molecular sieve, vacuumizing, and uniformly stirring to obtain a component A;
step S102, preparing a component B: mixing 6 parts of isocyanate-terminated polyurethane prepolymer, 2006 parts of PM, 0.5 part of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 0.1 part of tosylisocyanate, 88 parts of modified alumina and 1 part of plasticizer in parts by weight, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the heat-conducting bi-component polyurethane adhesive.
In example 3, the particle size distribution of the alumina used for the a component and the B component was: 25% of modified alumina with the particle size of 5-10 μm, 50% of modified alumina with the particle size of 25-40 μm and 25% of modified alumina with the particle size of 50-80 μm.
The composition of each raw material in example 3 is shown in Table 9.
Table 9: composition Table of two-component polyurethane adhesive of example 3
The adhesive prepared in example 3 was subjected to performance testing and the results are shown in Table 10.
Table 10: performance data for the adhesive prepared in example 3
| Serial number | Detecting items | Results |
| 1 | Density after mixing (g/cm3) | 2.5 |
| 2 | Coefficient of thermal conductivity (W/m. k) | 2.6 |
| 3 | Shear strength (MPa) | 8.7 |
| 4 | Tensile Strength (MPa) | 7.9 |
| 5 | Tensile Strength (MPa) | 8.1 |
| 6 | Elongation at Break (%) | 30％ |
| 7 | Shear strength (MPa) after resistance to Damp-Heat aging | 8.2 |
| 8 | Tensile Strength after Damp and Heat aging (MPa) | 8.0 |
Example 4:
the embodiment 4 of the application provides a preparation method of a heat-conducting bi-component polyurethane adhesive, which comprises the following steps:
step S101, preparing a component A: mixing, by weight, 6 parts of BPIP, 6 parts of Poly bd R-45M, 0.6 part of diethylene glycol, 0.03 part of dibutyltin dilaurate, 78 parts of modified alumina and 1.5 parts of molecular sieve, vacuumizing, and stirring uniformly to obtain a component A;
step S102, preparing a component B: mixing 7 parts by weight of isocyanate-terminated polyurethane prepolymer, 2006 parts by weight of PM, 0.5 part by weight of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 0.1 part by weight of tosylisocyanate, 88 parts by weight of modified alumina and 1 part by weight of plasticizer, vacuumizing and uniformly stirring to obtain a component B;
step S103, mixing: mixing the component A and the component B according to a volume ratio of 1:1, and mixing to obtain the heat-conducting bi-component polyurethane adhesive.
In example 4, the particle size distribution of the modified alumina used for the a and B components was: 40% of modified alumina with the particle size of 5-10 mu m, 30% of modified alumina with the particle size of 25-40 mu m and 30% of modified alumina with the particle size of 50-80 mu m.
The composition of each raw material in example 4 is shown in Table 11.
Table 11: composition Table of two-component polyurethane adhesive of example 4
The adhesive prepared in example 4 was subjected to performance testing and the results are shown in Table 12.
Table 12: performance data for the adhesive prepared in example 4
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
It is noted that, in this application, relational terms such as "first" and "second," and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element. In this application, "plurality" means at least two, e.g., two, three, etc., unless specifically stated otherwise.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The heat-conducting bi-component polyurethane adhesive is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 5-10 parts of aromatic polyether polyol, 4-8 parts of polyolefin polyol, 0-1 part of micromolecular chain extender, 0.02-0.04 part of catalyst, 75-90 parts of heat-conducting filler and 0-2 parts of molecular sieve; the component B comprises the following raw materials in parts by weight: 5-10 parts of isocyanate-terminated polyurethane prepolymer, 5-10 parts of polyisocyanate, 0.4-0.7 part of silane coupling agent, 0.1-0.2 part of water removing agent, 75-90 parts of heat conducting filler and 0-3 parts of plasticizer.
2. The heat-conducting two-component polyurethane adhesive as claimed in claim 1, wherein the isocyanate-terminated polyurethane prepolymer in the component B is prepared from polyol and polyisocyanate according to a mass ratio of 30-50: 50-70.
3. The two-component polyurethane adhesive as claimed in claim 1, wherein the aromatic polyether polyol in the component A is a polyether polyol containing bisphenol A structure, and has a relative molecular weight of 300-800 and a hydroxyl value of 159-325 mgKOH/g.
4. The two-component polyurethane adhesive according to claim 1, wherein the small-molecule chain extender in the component A is at least one of dipropylene glycol, diethylene glycol, 1, 4-butanediol, 1, 2-propanediol, ethylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 3-butanediol, and trimethylolpropane.
5. The two-component polyurethane adhesive of claim 1, wherein the catalyst of component A is at least one of dibutyltin dilaurate, stannous octoate, and bismuth neodecanoate.
6. The heat-conducting two-component polyurethane adhesive as claimed in claim 1, wherein the heat-conducting filler in both the component A and the component B is selected from modified alumina, and the modified alumina is obtained by modifying alumina with an alkoxy silane coupling agent or a titanate coupling agent.
7. The heat-conducting two-component polyurethane adhesive as claimed in claim 1, wherein the water scavenger in the B component is at least one selected from tosylisocyanate and triethyl orthoformate.
8. The two-component polyurethane adhesive according to claim 1, wherein the polyisocyanate in the component B is at least one selected from the group consisting of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, liquefied MDI, polymethylene polyphenyl polyisocyanate, and hexamethylene diisocyanate trimer; the silane coupling agent in the component B is at least one selected from beta- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane, gamma-glycidyl ether oxygen propyl trimethoxy silane and gamma-mercapto propyl trimethoxy silane.
9. A process for preparing a thermally conductive two-component polyurethane adhesive as claimed in any one of claims 1 to 8, comprising the steps of:
preparing a component A: mixing aromatic polyether polyol, polyolefin polyol, a small molecular chain extender, a catalyst, a heat-conducting filler and a molecular sieve, vacuumizing, and uniformly stirring to obtain a component A;
preparing a component B: mixing the isocyanate-terminated polyurethane prepolymer, polyisocyanate, a silane coupling agent, a water removing agent, a heat conducting filler and a plasticizer, vacuumizing and uniformly stirring to obtain a component B;
mixing: and mixing the component A and the component B to obtain the heat-conducting bi-component polyurethane adhesive.
10. Use of a thermally conductive two-component polyurethane adhesive according to any one of claims 1 to 8, characterized in that the thermally conductive two-component polyurethane adhesive is used for bonding power battery cells.
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