CN116676068A - Low-modulus high-strength polyurethane structural adhesive for power battery assembly and preparation method thereof - Google Patents
Low-modulus high-strength polyurethane structural adhesive for power battery assembly and preparation method thereof Download PDFInfo
- Publication number
- CN116676068A CN116676068A CN202310705202.5A CN202310705202A CN116676068A CN 116676068 A CN116676068 A CN 116676068A CN 202310705202 A CN202310705202 A CN 202310705202A CN 116676068 A CN116676068 A CN 116676068A
- Authority
- CN
- China
- Prior art keywords
- isocyanate
- component
- parts
- structural adhesive
- polyether polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 73
- 150000003077 polyols Chemical class 0.000 claims abstract description 72
- 239000004721 Polyphenylene oxide Chemical class 0.000 claims abstract description 56
- 229920000570 polyether Chemical class 0.000 claims abstract description 56
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 37
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003063 flame retardant Substances 0.000 claims abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229920001451 polypropylene glycol Polymers 0.000 claims description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 235000019438 castor oil Nutrition 0.000 claims description 11
- 239000004359 castor oil Substances 0.000 claims description 11
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 10
- 229910021485 fumed silica Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 7
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical group CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- -1 polyhexamethylene Polymers 0.000 claims description 5
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000004448 titration Methods 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 2
- DWTNKIPXNGXQBV-UHFFFAOYSA-N CCC[SiH](OC)OC.N=C=O Chemical compound CCC[SiH](OC)OC.N=C=O DWTNKIPXNGXQBV-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 claims description 2
- VKSCZTWQDPUHIK-UHFFFAOYSA-N isocyanic acid;trimethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OC)(OC)OC VKSCZTWQDPUHIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 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 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- XKCQNWLQCXDVOP-UHFFFAOYSA-N tris(2-chloropropan-2-yl) phosphate Chemical compound CC(C)(Cl)OP(=O)(OC(C)(C)Cl)OC(C)(C)Cl XKCQNWLQCXDVOP-UHFFFAOYSA-N 0.000 claims description 2
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 claims description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 239000002540 palm oil Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 79
- 238000005516 engineering process Methods 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000012974 tin catalyst Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VXCNUUJPBZCEJW-UHFFFAOYSA-N 3-isocyanatopropyl(dimethoxy)silane Chemical compound N(=C=O)CCC[SiH](OC)OC VXCNUUJPBZCEJW-UHFFFAOYSA-N 0.000 description 1
- 229910018173 Al—Al Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0404—Machines for assembling batteries
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3284—Hydroxyamines containing at least three hydroxy groups containing four hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group 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
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
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- 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
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention discloses a low-modulus high-strength polyurethane structural adhesive for power battery assembly and a preparation method thereof, wherein the structural adhesive comprises the following components: the volume ratio of the component A to the component B is 1:1; the component A comprises the following components: bio-based polyol, aromatic ring modified polyol, polyether polyol, crosslinking agent, catalyst, flame retardant, water and thixotropic agent; the component B comprises the following components: isocyanate, isocyanate-terminated polyurethane prepolymer, isocyanate-terminated silane coupling agent modified polyether polyol, flame retardant, coupling agent, water absorbent, thixotropic agent and catalyst. The structural adhesive has excellent adhesive strength to base materials such as aluminum, steel, PC, PET and the like, has low modulus, high strength, excellent flame retardance, excellent wet heat aging and other performances, effectively ensures the stable performance of the power battery in the complex environments such as high-frequency vibration, wet heat, severe cold, heat accumulation and the like for long-term use, and improves the reliability and the safety.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a low-modulus high-strength polyurethane structural adhesive for power battery assembly and a preparation method thereof.
Background
The power battery is used as one of core components of the new energy automobile, and the production and assembly quality of the power battery directly influences key performances such as the endurance mileage, the service life, the use safety and reliability, the charging time and the temperature of the new energy automobile.
Along with the innovation of the power battery structure, the power battery assembly technology (namely the PACK technology) is developed from the traditional CTM technology to the CTP technology and to the CTC and CTB technology, the higher the grouping rate of modules and systems is, the number of the modules is reduced, more and more metal structural members in the PACK assembly process are replaced by using adhesives, and the adhesive consumption are continuously increased. The adhesive directly influences the heat-conducting property, the ageing-resistant property, the service life, the use safety and the like of the power battery, directly determines the product quality of a battery PACK, and is one of core factors for realizing stable, efficient, durable and safe operation of an electric drive system no matter how the power battery PACK technology is developed, the importance of the adhesive is incapacitated, the effect is irreplaceable, the whole power battery industry is optimized and promoted, and the adhesive contributes to the realization of double-carbon targets.
The polyurethane adhesive has the advantages of higher tensile strength, moderate rigidity, better high and low temperature resistance and the like, has obvious advantages when being used as an adhesive for structural bonding between electric cores, but needs to be applied to severe environments such as high-frequency vibration, high and low temperature, high humidity and the like, and has good bonding performance on materials such as Al, steel, PET, PC and the like, so polyol containing aromatic ring functional groups is generally required to be added, compatibility with a base material is improved, interaction force is improved, and macroscopic appearance is improved in bonding performance. The addition of the aromatic ring polyol can reduce the molecular chain flexibility of the polyurethane structural adhesive, enhance the rigidity and increase the modulus, and is insufficient for buffering high-frequency vibration in the running process of the new energy automobile. At present, the polyurethane structural adhesive for the power battery PACK still has the defects of relatively high modulus (more than 500 MPa), poor adhesive property (Al-Al shearing strength is less than 8 MPa) and the like, and has the risks of reduced reliability and safety when the polyurethane structural adhesive is used for a long time in a complex environment, thereby threatening the safety of life and property.
In view of the above, it is an urgent need to provide a polyurethane structural adhesive for power battery assembly with a low modulus of less than 400MPa and a high strength of more than 8 MPa.
In view of this, the present invention has been made.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the low-modulus high-strength polyurethane structural adhesive for power battery assembly and the preparation method thereof, wherein the structural adhesive is solvent-free, safe and environment-friendly, has excellent adhesive strength to aluminum, steel, PC, PET and other base materials, has the performances of high strength, low modulus, excellent flame retardance, excellent wet heat aging and the like, can meet the performance requirements of the PACK structural adhesive of the power battery, and effectively ensures the stable performance of the power battery in the complex environments of high-frequency vibration, wet heat, severe cold, summer heat accumulation and the like for long-term use, thereby improving the reliability and the safety.
The invention is realized by the following technical scheme:
a low modulus, high strength polyurethane structural adhesive for power cell assembly comprising:
the component A and the component B are used in a volume ratio of 1:1, and the mole ratio of the functional groups is as follows: NCO oh=1.05: 1 to 2.0:1, a step of;
the component A consists of the following raw materials in parts by mass: 5-30 parts of bio-based polyol, 10-30 parts of aromatic ring modified polyol, 0.001-15 parts of polyether polyol, 0.001-3 parts of cross-linking agent, 0.001-0.1 part of catalyst, 15-45 parts of flame retardant, 0.001-0.3 part of water and 0.001-5 parts of thixotropic agent;
the component B consists of the following raw materials in parts by mass: 0.001-15 parts of isocyanate, 35-75 parts of isocyanate-terminated polyurethane prepolymer, 5-25 parts of isocyanate-terminated silane coupling agent modified polyether polyol and 10-25 parts of flame retardant; 0.001-5 parts of coupling agent, 0.001-0.3 part of water absorbent, 0.001-5 parts of thixotropic agent and 0.001-0.1 part of catalyst.
The invention discloses a preparation method of a low-modulus high-strength polyurethane structural adhesive for power battery assembly, which comprises the following steps:
preparing isocyanate-terminated prepolymer and isocyanate-terminated silane coupling agent modified polyether polyol respectively;
according to the formula of the A component and the B component, the raw materials of the A component and the B component are respectively taken, the raw materials of the A component and the B component are respectively and uniformly mixed to prepare the A component and the B component, and the prepared A component and the B component are combined according to the volume ratio of 1:1 to obtain the low-modulus high-strength polyurethane structural adhesive for power battery assembly.
Compared with the prior art, the low-modulus high-strength polyurethane structural adhesive for power battery assembly has the beneficial effects that:
the modulus of the polyurethane adhesive is effectively reduced by adding a proper amount of isocyanate-based silane coupling agent modified polyether polyol into the component B, the silane coupling agent can be subjected to condensation reaction with hydroxyl on the surface of a substrate to form covalent bond effect, and the sufficient tensile strength and shearing strength can still be maintained; the cured isocyanate silane coupling agent modified polyether polyol and polyurethane can form an interpenetrating crosslinked network structure, so that water vapor can be prevented from entering, and the humidity and heat aging resistance is improved; the bio-based polyol containing long carbon chains and the poly dimer acid hexanediol polyester diol are added, so that the hydrophobicity of a molecular chain can be improved, the resistance to wet heat aging can be improved, meanwhile, the flexibility of the molecular chain can be improved, and the modulus is lower to a certain extent; the addition of the polyatomic alcohol containing aromatic rings improves the rigidity of molecular chains, the glass transition temperature and the heat resistance, and in addition, the bonding strength of PET, PC and metal substrates is effectively improved; compared with the prior art, the invention has at least the following beneficial effects: (1) The modulus is lower, the storage modulus is less than or equal to 400MPa at 25 ℃, and the buffer damping effect is excellent when the buffer damping agent is applied to the PACK adhesive of the power battery. (2) The strength is higher, the tensile strength of the body is more than or equal to 8MPa, the shearing strength of the base materials such as PET, PC, aluminum alloy, steel and the like is more than or equal to 8MPa, and the safety and the reliability in the driving process are ensured. (3) The wet heat aging resistance is excellent, and the tensile strength and the shear strength decay is less than 20 percent after double-85 aging for 1000 hours.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below in combination with the specific content of the invention; it will be apparent that the described embodiments are only some embodiments of the invention, but not all embodiments, which do not constitute limitations of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The terms that may be used herein will first be described as follows:
the term "and/or" is intended to mean that either or both may be implemented, e.g., X and/or Y are intended to include both the cases of "X" or "Y" and the cases of "X and Y".
The terms "comprises," "comprising," "includes," "including," "has," "having" or other similar referents are to be construed to cover a non-exclusive inclusion. For example: including a particular feature (e.g., a starting material, component, ingredient, carrier, formulation, material, dimension, part, means, mechanism, apparatus, step, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article of manufacture, etc.), should be construed as including not only a particular feature but also other features known in the art that are not explicitly recited.
The term "consisting of … …" is meant to exclude any technical feature element not explicitly listed. If such term is used in a claim, the term will cause the claim to be closed, such that it does not include technical features other than those specifically listed, except for conventional impurities associated therewith. If the term is intended to appear in only a clause of a claim, it is intended to limit only the elements explicitly recited in that clause, and the elements recited in other clauses are not excluded from the overall claim.
The term "parts by mass" means a mass ratio relationship between a plurality of components, for example: if the X component is described as X parts by mass and the Y component is described as Y parts by mass, the mass ratio of the X component to the Y component is expressed as x:y;1 part by mass may represent any mass, for example: 1 part by mass may be expressed as 1kg or 3.1415926 kg. The sum of the mass parts of all the components is not necessarily 100 parts, and may be more than 100 parts, less than 100 parts, or 100 parts or equal. The parts, proportions and percentages described herein are by mass unless otherwise indicated.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as a range of values, the range is to be understood as specifically disclosing all ranges formed from any pair of upper and lower values within the range of values, regardless of whether ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, that numerical range should be interpreted to include the ranges of "2 to 7", "2 to 6", "5 to 7", "3 to 4 and 6 to 7", "3 to 5 and 7", "2 and 5 to 7", and the like. Unless otherwise indicated, numerical ranges recited herein include both their endpoints and all integers and fractions within the numerical range.
The high-barrier heat-resistant solvent-free polyurethane composite material and the preparation method thereof provided by the invention are described in detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. The specific conditions are not noted in the examples of the present invention and are carried out according to the conditions conventional in the art or suggested by the manufacturer. The reagents or apparatus used in the examples of the present invention were conventional products commercially available without the manufacturer's knowledge.
The embodiment of the invention provides a low-modulus high-strength polyurethane structural adhesive for power battery assembly, which comprises the following components:
the component A and the component B are used in a volume ratio of 1:1, and the mole ratio of the functional groups is as follows: NCO oh=1.05: 1 to 2.0:1, a step of;
the component A consists of the following raw materials in parts by mass: 5-30 parts of bio-based polyol, 10-30 parts of aromatic ring modified polyol, 0.001-15 parts of polyether polyol, 0.001-3 parts of cross-linking agent, 0.001-0.1 part of catalyst, 15-45 parts of flame retardant, 0.001-0.3 part of water and 0.001-5 parts of thixotropic agent;
the component B consists of the following raw materials in parts by mass: 0.001-15 parts of isocyanate, 35-75 parts of isocyanate-terminated polyurethane prepolymer, 5-25 parts of isocyanate-terminated silane coupling agent modified polyether polyol and 10-25 parts of flame retardant; 0.001-5 parts of coupling agent, 0.001-0.3 part of water absorbent, 0.001-5 parts of thixotropic agent and 0.001-0.1 part of catalyst.
Preferably, in the component A of the structural adhesive, the bio-based polyol is one or more of soybean oil, castor oil, palm wood oil, hydrogenated castor oil and aromatic ring modified castor oil;
the aromatic ring modified polyol is bisphenol A or bisphenol F modified polyether glycol with the molecular weight of 400-3000 or one or more of phthalic anhydride polyester glycol;
the polyether polyol is polypropylene glycol with molecular weight of 400-2000.
Preferably, in the component A of the structural adhesive, the cross-linking agent is one or more of polyether polyol or amine with the functionality of 4-6.
Preferably, in the component A and the component B of the structural adhesive, the catalyst is one or more of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate, zinc isooctanoate, zinc neodecanoate, dibutyl tin, stannous octoate and chelated tin;
the flame retardant is one or more of solid flame retardants such as aluminum hydroxide, magnesium hydroxide, aluminum hypophosphite, diethyl aluminum phosphinate and the like or liquid flame retardants such as tricresyl phosphate, triethyl phosphate, tri (chloroisopropyl) phosphate and the like;
in the component A and the component B, the thixotropic agent is one or more of fumed silica and bentonite.
Preferably, in the component B of the structural adhesive, the isocyanate is one or more of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, liquefied MDI, polymeric MDI, HDI trimer and TDI trimer;
the isocyanate-terminated polyurethane prepolymer is formed by reacting dihydric alcohol with the molecular weight of 1000-3000 with isocyanate, and the mass fraction of NCO is controlled to be 6-22%;
the isocyanate silane coupling agent modified polyether polyol is formed by reacting an isocyanate silane coupling agent with polyether polyol, and the molar ratio is controlled as follows: NCO oh=1.005: 1 to 1.3:1.
preferably, in the isocyanate-terminated polyurethane prepolymer, the dihydric alcohol is one or more of polypropylene glycol, polyethylene glycol adipate dihydric alcohol, neopentyl glycol adipate dihydric alcohol and poly hexamethylene glycol adipate dihydric alcohol; the isocyanate in the isocyanate-terminated polyurethane prepolymer is one or more of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, liquefied MDI, polymeric MDI, HDI trimer and TDI trimer.
Preferably, in the isocyanate silane coupling agent modified polyether polyol, the isocyanate silane coupling agent is one or more of isocyanate propyl triethoxysilane, isocyanate propyl trimethoxysilane and isocyanate propyl dimethoxy silane; the polyether polyol is polypropylene glycol with a molecular weight of 3000-16000.
Preferably, in the above component B, the water absorbing agent is p-toluenesulfonyl isocyanate.
The embodiment of the invention also provides a preparation method of the low-modulus high-strength polyurethane structural adhesive for power battery assembly, which comprises the following steps:
preparing isocyanate-terminated prepolymer and isocyanate-terminated silane coupling agent modified polyether polyol respectively;
and respectively taking the raw materials of the A component and the B component according to the formula of the A component and the B component, respectively and uniformly mixing the raw materials of the A component and the B component to prepare the A component and the B component, and combining the prepared A component and B component according to the volume ratio of 1:1 to obtain the low-modulus high-strength polyurethane structural adhesive for power battery assembly.
Preferably, in the above method, the isocyanate-terminated prepolymer is prepared in the following manner, comprising:
heating dihydric alcohol to 110-120 ℃, stirring while vacuumizing, dehydrating for 1-3 hours, cooling to below 50 ℃, charging nitrogen, adding isocyanate according to a proportion that the theoretical NCO content is 6-20%, heating to 65-85 ℃, continuously stirring for reacting for 1-3 hours until the titration NCO content is no longer changed, ending the reaction, and cooling to room temperature to obtain isocyanate-terminated prepolymer;
an isocyanatosilane coupling agent modified polyether polyol is prepared in the following manner, comprising:
heating polyether polyol to 110-120 ℃, stirring while vacuumizing, dehydrating for 1-3h, cooling to below 50 ℃, and charging nitrogen according to NCO: oh=1.005: 1 to 1.3:1, adding an isocyanate silane coupling agent, heating to 70-90 ℃, continuously stirring and reacting for 1-3h until the titration NCO content is no longer changed, ending the reaction, and cooling to room temperature to obtain the isocyanate silane coupling agent modified polyether polyol.
In order to clearly show the technical scheme and the technical effects, the low-modulus high-strength polyurethane structural adhesive for power battery assembly and the preparation method thereof are described in detail in the following.
Example 1
The embodiment provides a low-modulus high-strength polyurethane structural adhesive for power battery assembly, and a preparation method thereof comprises the following steps:
preparing isocyanate silane coupling agent modified polyether polyol and isocyanate-terminated prepolymer in advance, wherein the isocyanate silane coupling agent modified polyether polyol and the isocyanate-terminated prepolymer are prepared from the following raw materials in parts by mass;
(1) Preparing an isocyanato silane coupling agent modified polyether polyol comprising: taking 100 parts of polypropylene glycol with the molecular weight of 12000, stirring and heating to 120 ℃, maintaining the vacuum pumping and water removal for 2 hours, cooling to 45 ℃, charging nitrogen, adding 3.59 parts of isocyanatopropyl trimethoxy silane, slowly heating to 85 ℃, stirring and reacting for 3 hours, and cooling to room temperature to obtain the isocyanatosilane coupling agent modified polyether polyol.
(2) Preparing a terminal isocyanate-based prepolymer comprising: taking 50 parts of polypropylene glycol with molecular weight of 2000, stirring and heating to 120 ℃, maintaining vacuumizing and removing water for 2 hours, cooling to 40 ℃, charging nitrogen, adding 50 parts of liquefied MDI, slowly heating to 80 ℃, stirring and reacting for 2 hours, and cooling to room temperature to obtain the isocyanate-terminated prepolymer.
Respectively preparing a component A and a component B, wherein the raw materials in the component A and the component B are calculated according to parts by mass;
(3) Preparing a component A: taking 20 parts of hydrogenated castor oil polyol, 15 parts of bisphenol A polyether polyol, 20 parts of polypropylene glycol with the molecular weight of 1000, 0.04 part of 4-functionality polyether polyol, 0.05 part of bismuth isooctanoate, 35 parts of aluminum hydroxide, 8 parts of aluminum hypophosphite, 1 part of fumed silica and 0.1 part of water, dispersing and stirring uniformly, and stirring for 2 hours to obtain a component A;
(4) And (3) preparing a component B: 60 parts of isocyanate-terminated prepolymer, 15 parts of isocyanate-terminated silane coupling agent modified polyether polyol, 23 parts of aluminum hydroxide, 2 parts of gamma-methacryloxypropyl trimethoxy silane, 0.2 part of p-toluenesulfonyl isocyanate, 1 part of fumed silica and 0.04 part of chelating tin catalyst are taken, and the mixture is stirred for 2 hours to obtain a component B;
example 2
The embodiment provides a low-modulus high-strength polyurethane structural adhesive for power battery assembly, and a preparation method thereof comprises the following steps:
preparing isocyanate silane coupling agent modified polyether polyol and isocyanate-terminated prepolymer in advance, wherein the isocyanate silane coupling agent modified polyether polyol and the isocyanate-terminated prepolymer are prepared from the following raw materials in parts by mass;
(1) Preparing an isocyanato silane coupling agent modified polyether polyol comprising: 10 parts of polypropylene glycol with 4000 molecular weight and 90 parts of polypropylene glycol with 12000 molecular weight are taken, stirred and heated to 120 ℃, vacuumized and dehydrated for 2 hours, cooled to 45 ℃, filled with nitrogen, added with 4.305 parts of isocyanatopropyl trimethoxy silane, slowly heated to 85 ℃, stirred and reacted for 2 hours, and cooled to room temperature to obtain the isocyanate silane coupling agent modified polyether polyol.
(2) Preparing a terminal isocyanate-based prepolymer comprising: taking 40 parts of polypropylene glycol with the molecular weight of 2000, stirring and heating to 110 ℃, maintaining vacuumizing and removing water for 3 hours, cooling to 40 ℃, charging nitrogen, adding 60 parts of liquefied MDI, slowly heating to 75 ℃, stirring and reacting for 2.5 hours, and cooling to room temperature to obtain the isocyanate-terminated prepolymer.
Respectively preparing a component A and a component B, wherein the raw materials in the component A and the component B are calculated according to parts by mass;
(3) Preparing a component A: 10 parts of castor oil, 30 parts of hydrogenated castor oil polyol, 20 parts of bisphenol A polyether polyol, 0.7 part of 4-functionality polyether polyol as a cross-linking agent, 0.08 part of bismuth isooctanoate, 23 parts of aluminum hydroxide, 8 parts of aluminum hypophosphite, 2 parts of fumed silica and 0.2 part of water are taken, dispersed and stirred uniformly, and the component A is obtained after stirring for 3 hours;
(4) And (3) preparing a component B: 60 parts of isocyanate-terminated prepolymer, 10 parts of isocyanate-terminated silane coupling agent modified polyether polyol, 28 parts of aluminum hydroxide, 2 parts of gamma-methacryloxypropyl trimethoxy silane, 0.2 part of p-toluenesulfonyl isocyanate, 2 parts of fumed silica and 0.04 part of chelating tin catalyst are taken, and the mixture is stirred for 3 hours to obtain a component B;
example 3
The embodiment provides a low-modulus high-strength polyurethane structural adhesive for power battery assembly, and a preparation method thereof comprises the following steps:
preparing isocyanate silane coupling agent modified polyether polyol and isocyanate-terminated prepolymer in advance, wherein the isocyanate silane coupling agent modified polyether polyol and the isocyanate-terminated prepolymer are prepared from the following raw materials in parts by mass;
(1) Preparing an isocyanato silane coupling agent modified polyether polyol comprising: 100 parts of polypropylene glycol with molecular weight of 8000 are taken, stirred and heated to 120 ℃ at the same time, vacuumized and dehydrated for 2 hours, cooled to 45 ℃, filled with nitrogen, added with 5.23 parts of isocyanatopropyl dimethoxy silane, slowly heated to 80 ℃, stirred and reacted for 3 hours, cooled to room temperature, and the isocyanatosilane coupling agent modified polyether polyol is obtained.
(2) Preparing a terminal isocyanate-based prepolymer comprising: taking 20 parts of polypropylene glycol with the molecular weight of 2000 and 20 parts of poly (hexamethylene glycol) dimer with the molecular weight of 2000, stirring and heating to 120 ℃, maintaining the vacuum pumping and dewatering for 2 hours, cooling to 40 ℃, charging nitrogen, adding 60 parts of liquefied MDI, slowly heating to 80 ℃, stirring and reacting for 2 hours, and cooling to room temperature to obtain the isocyanate-terminated prepolymer.
Respectively preparing a component A and a component B, wherein the raw materials in the component A and the component B are calculated according to parts by mass;
(3) Preparing a component A: taking 40 parts of hydrogenated castor oil polyol, 20 parts of bisphenol A polyether polyol, 10 parts of polypropylene glycol with the molecular weight of 1000, 0.8 part of N, N, N ', N' -tetra- (2-hydroxypropyl) ethylenediamine, 0.05 part of bismuth isooctanoate, 30 parts of aluminum hydroxide, 8 parts of aluminum hypophosphite, 2 parts of fumed silica and 0.1 part of water, dispersing and stirring uniformly, and stirring for 2 hours to obtain a component A;
(4) And (3) preparing a component B: taking 65 parts of isocyanate-terminated prepolymer, 10 parts of isocyanate-terminated silane coupling agent modified polyether polyol, 23 parts of aluminum hydroxide, 2 parts of gamma-methacryloxypropyl trimethoxy silane, 0.2 part of p-toluenesulfonyl isocyanate, 2 parts of fumed silica and 0.04 part of chelating tin catalyst, and stirring for 2 hours to obtain a component B;
example 4
The embodiment provides a low-modulus high-strength polyurethane structural adhesive for power battery assembly, and a preparation method thereof comprises the following steps:
preparing isocyanate silane coupling agent modified polyether polyol and isocyanate-terminated prepolymer in advance, wherein the isocyanate silane coupling agent modified polyether polyol and the isocyanate-terminated prepolymer are prepared from the following raw materials in parts by mass;
(1) Preparation of isocyanate-terminated prepolymer: 40 parts of poly dimer acid hexanediol ester dihydric alcohol with the molecular weight of 2000 is taken, stirred and heated to 120 ℃ simultaneously, vacuumized and dehydrated for 2 hours, cooled to 40 ℃, filled with nitrogen, added with 60 parts of liquefied MDI, slowly heated to 80 ℃, stirred and reacted for 2 hours, cooled to room temperature, and isocyanate-terminated prepolymer is obtained.
(2) Preparing a component A: taking 30 parts of hydrogenated castor oil polyol, 20 parts of bisphenol A polyether polyol, 10 parts of polypropylene glycol with the molecular weight of 1000, 0.4 part of N, N, N ', N' -tetra- (2-hydroxypropyl) ethylenediamine, 0.05 part of bismuth isooctanoate, 30 parts of aluminum hydroxide, 8 parts of aluminum hypophosphite, 2 parts of fumed silica and 0.1 part of water, dispersing and stirring uniformly, and stirring for 2 hours to obtain a component A;
respectively preparing a component A and a component B, wherein the raw materials in the component A and the component B are calculated according to parts by mass;
(3) And (3) preparing a component B: taking 60 parts of isocyanate-terminated prepolymer, 15 parts of MS resin S203H,23 parts of aluminum hydroxide, 2 parts of gamma-methacryloxypropyl trimethoxy silane, 0.2 part of p-toluenesulfonyl isocyanate, 2 parts of fumed silica and 0.04 part of chelating tin catalyst, and stirring for 2 hours to obtain a component B;
the low-modulus high-strength polyurethane structural adhesive for power battery assembly prepared in each embodiment is used in combination with the component A and the component B according to the volume ratio of 1:1, and the tensile strength, the shear strength, the modulus and the flame retardant property at 25 ℃ are tested, wherein the tensile strength and the shear strength after double-85 aging for 1000 hours are tested, and untreated aluminum alloy and PET are selected as the base materials.
The test data of the table show that the low-modulus high-strength polyurethane structural adhesive for power battery assembly has lower modulus, less than 400MPa, excellent tensile strength, excellent shearing strength for untreated Al and PET, flame retardant performance reaching a flame retardant level, and after double-85 aging for 1000 hours, the attenuation is less than 20%, so that the stability of the performance of the power battery in the complex environments of high-frequency vibration, damp heat, severe cold, heat accumulation and the like can be effectively ensured, and the reliability and safety are improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background section herein is only for enhancement of understanding of the general background of the invention and is not to be taken as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Claims (10)
1. A low modulus, high strength polyurethane structural adhesive for power cell assembly comprising:
the component A and the component B are used in a volume ratio of 1:1, and the mole ratio of the functional groups is as follows: NCO oh=1.05: 1 to 2.0:1, a step of;
the component A consists of the following raw materials in parts by mass: 5-30 parts of bio-based polyol, 10-30 parts of aromatic ring modified polyol, 0.001-15 parts of polyether polyol, 0.001-3 parts of cross-linking agent, 0.001-0.1 part of catalyst, 15-45 parts of flame retardant, 0.001-0.3 part of water and 0.001-5 parts of thixotropic agent;
the component B consists of the following raw materials in parts by mass: 0.001-15 parts of isocyanate, 35-75 parts of isocyanate-terminated polyurethane prepolymer, 5-25 parts of isocyanate-terminated silane coupling agent modified polyether polyol and 10-25 parts of flame retardant; 0.001-5 parts of coupling agent, 0.001-0.3 part of water absorbent, 0.001-5 parts of thixotropic agent and 0.001-0.1 part of catalyst.
2. The low modulus, high strength polyurethane structural adhesive for power cell assembly of claim 1, wherein in the a-component, the bio-based polyol is one or more of soybean oil, castor oil, palm oil, hydrogenated castor oil, aromatic ring modified castor oil;
the aromatic ring modified polyol is bisphenol A or bisphenol F modified polyether glycol with the molecular weight of 400-3000 or one or more of phthalic anhydride polyester glycol;
the polyether polyol is polypropylene glycol with molecular weight of 400-2000.
3. The low modulus, high strength polyurethane structural adhesive for power cell assembly of claim 1 or 2, wherein in the a-component, the cross-linking agent is one or more of a polyether polyol or an amine having a functionality of 4-6.
4. The low-modulus high-strength polyurethane structural adhesive for power battery assembly according to claim 1 or 2, wherein the catalyst is one or more of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, bismuth naphthenate, zinc isooctanoate, zinc neodecanoate, dibutyltin, stannous octoate, and chelated tin in the component a and the component B;
the flame retardant is one or more of solid flame retardants such as aluminum hydroxide, magnesium hydroxide, aluminum hypophosphite, diethyl aluminum phosphinate and the like or liquid flame retardants such as tricresyl phosphate, triethyl phosphate, tri (chloroisopropyl) phosphate and the like;
in the component A and the component B, the thixotropic agent is one or more of fumed silica and bentonite.
5. The low modulus, high strength polyurethane structural adhesive for power cell assembly of claim 1 or 2, wherein in the B component, the isocyanate is one or more of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, liquefied MDI, polymeric MDI, HDI trimer, TDI trimer;
the isocyanate-terminated polyurethane prepolymer is formed by reacting dihydric alcohol with the molecular weight of 1000-3000 with isocyanate, and the mass fraction of NCO is controlled to be 6-22%;
the isocyanate silane coupling agent modified polyether polyol is formed by reacting an isocyanate silane coupling agent with polyether polyol, and the molar ratio is controlled as follows: NCO oh=1.005: 1 to 1.3:1.
6. the low-modulus, high-strength polyurethane structural adhesive for power battery assembly according to claim 5, wherein the diol in the isocyanate-terminated polyurethane prepolymer is one or more of polypropylene glycol, polyethylene glycol adipate, neopentyl glycol adipate, and polyhexamethylene glycol dimer acid;
the isocyanate in the isocyanate-terminated polyurethane prepolymer is one or more of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, liquefied MDI, polymeric MDI, HDI trimer and TDI trimer.
7. The low-modulus high-strength polyurethane structural adhesive for power battery assembly according to claim 5, wherein in the isocyanate-based silane coupling agent modified polyether polyol, the isocyanate-based silane coupling agent is one or more of isocyanate propyl triethoxysilane, isocyanate propyl trimethoxysilane, isocyanate propyl dimethoxysilane; the polyether polyol is polypropylene glycol with a molecular weight of 3000-16000.
8. The low-modulus, high-strength polyurethane structural adhesive for power cell assembly according to claim 1 or 2, wherein in the B component, the water absorbing agent is p-toluenesulfonyl isocyanate.
9. A method for preparing the low-modulus high-strength polyurethane structural adhesive for power battery assembly according to any one of claims 1 to 9, comprising the following steps:
preparing isocyanate-terminated prepolymer and isocyanate-terminated silane coupling agent modified polyether polyol respectively;
the low-modulus high-strength polyurethane structural adhesive for power battery assembly is prepared by taking the raw materials of the component A and the component B according to the formula of any one of claims 1-8, respectively, uniformly mixing the raw materials of the component A and the component B to prepare the component A and the component B, and combining the prepared component A and component B according to the volume ratio of 1:1.
10. The method for preparing a low modulus, high strength polyurethane structural adhesive for power cell assembly of claim 9, wherein the isocyanate-terminated prepolymer is prepared in the following manner, comprising:
heating dihydric alcohol to 110-120 ℃, stirring while vacuumizing, dehydrating for 1-3 hours, cooling to below 50 ℃, charging nitrogen, adding isocyanate according to a proportion that the theoretical NCO content is 6-20%, heating to 65-85 ℃, continuously stirring for reacting for 1-3 hours until the titration NCO content is no longer changed, ending the reaction, and cooling to room temperature to obtain isocyanate-terminated prepolymer;
an isocyanatosilane coupling agent modified polyether polyol is prepared in the following manner, comprising:
heating polyether polyol to 110-120 ℃, stirring while vacuumizing, dehydrating for 1-3h, cooling to below 50 ℃, and charging nitrogen according to NCO: oh=1.005: 1 to 1.3:1, adding an isocyanate silane coupling agent, heating to 70-90 ℃, continuously stirring and reacting for 1-3h until the titration NCO content is no longer changed, ending the reaction, and cooling to room temperature to obtain the isocyanate silane coupling agent modified polyether polyol.
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