CN116676068B - 动力电池组装用低模量高强度聚氨酯结构胶及其制备方法 - Google Patents
动力电池组装用低模量高强度聚氨酯结构胶及其制备方法 Download PDFInfo
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- CN116676068B CN116676068B CN202310705202.5A CN202310705202A CN116676068B CN 116676068 B CN116676068 B CN 116676068B CN 202310705202 A CN202310705202 A CN 202310705202A CN 116676068 B CN116676068 B CN 116676068B
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- Prior art keywords
- isocyanate
- component
- parts
- structural adhesive
- polyether polyol
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- 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 38
- 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 15
- 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 7
- 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 21
- 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
- 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
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-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
- 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 3
- 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
- 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
- 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 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
- 239000012975 dibutyltin dilaurate Substances 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
- 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
- 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
- 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
- 239000007788 liquid Substances 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
- 239000007787 solid 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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Abstract
本发明公开了一种用于动力电池组装用低模量高强度聚氨酯结构胶及其制备方法,结构胶包括:A组分与B组分使用体积比为1:1;A组分组成:生物基多元醇、芳环改性多元醇、聚醚多元醇、交联剂、催化剂、阻燃剂份、水和触变剂;B组分组成:异氰酸酯、端异氰酸酯基聚氨酯预聚物、异氰酸酯基硅烷偶联剂改性聚醚多元醇、阻燃剂、偶联剂、吸水剂、触变剂和催化剂。该结构胶对铝、钢材、PC、PET等基材均具有优异粘接强度,并具有低模量、高强度、优异阻燃、优异湿热老化等性能,有效保证动力电池在高频震动、湿热、严寒、酷暑、热量堆积等复杂环境下长期使用的性能稳定,提高可靠性和安全性。
Description
技术领域
本发明涉及高分子材料制备领域,尤其涉及一种动力电池组装用低模量高强度聚氨酯结构胶及其制备方法。
背景技术
动力电池作为新能源汽车的核心部件之一,其生产装配质量直接影响新能源汽车的续航里程、使用寿命、使用安全可靠性、充电时间和温度等关键性能。
随动力电池结构的革新,动力电池组装技术(即PACK技术)从传统CTM技术,发展至CTP技术,又发展到CTC和CTB技术,模组、系统的成组率越高,模组数量减少,PACK组装过程中越来越多的金属结构件使用胶粘剂进行替代,用胶点和用胶量持续增加。胶粘剂直接影响动力电池的导热性能、耐老化性能、使用寿命和使用安全性等,直接决定电池包的产品质量,无论动力电池PACK技术如何发展,动力电池PACK胶粘剂是实现电力驱动系统稳定、高效、持久、安全工作的一个核心因素之一,其重要性是无法撼动的,作用不可替代,有助于优化和提升整个动力电池产业,为双碳目标的实现贡献力量。
聚氨酯胶具有拉伸强度较高、刚度适中、耐高低温性能较好等性能优势,作为胶粘剂用于电芯与电芯之间的结构粘接时优势明显,但须应用于高频震动、高低温高湿等恶劣环境,还需对Al、钢材、PET、PC等材质均具有足够好的粘接性能,因此通常需要加入含芳环功能官能团的多元醇,改善与基材间的相容性,提高相互作用力,宏观表现为粘接性能的提高。芳环多元醇的添加会使聚氨酯结构胶的分子链柔顺性下降,刚性增强,模量增大,不足以缓冲新能源汽车行驶中的高频震动。目前,动力电池PACK用聚氨酯结构胶仍然存在模量相对较高(>500MPa)、粘接性能较差(Al-Al剪切强度<8MPa)等不足,在复杂环境长期使用时,存在可靠性和安全性降低的风险,威胁生命财产安全。
综上所述,如何提供一种小于400MPa的低模量、大于8MPa的高强度的动力电池组装用的聚氨酯结构胶是急需解决的问题。
有鉴于此,特提出本发明。
发明内容
为解决现有技术中存在的上述问题,本发明提供了一种动力电池组装用低模量高强度聚氨酯结构胶及其制备方法,该结构胶不含溶剂、安全环保,对于铝、钢材、PC、PET等基材均具有优异的粘接强度,具有高强度、低模量、优异阻燃、优异湿热老化等性能,能满足动力电池PACK结构胶的性能要求,有效保证动力电池在高频震动、湿热、严寒、酷暑、热量堆积等复杂环境下长期使用时的性能稳定,进而提高可靠性和安全性。
本发明是通过以下技术方案实现的:
一种动力电池组装用低模量高强度聚氨酯结构胶,包括:
A组分和B组分,所述A组分与B组分使用体积比为1:1,官能团摩尔比为:NCO:OH=1.05:1~2.0:1;
所述A组分由按质量份计的以下原料组成:生物基多元醇5-30份、芳环改性多元醇10-30份、聚醚多元醇0.001-15份、交联剂0.001-3份、催化剂0.001-0.1份、阻燃剂15-45份、水0.001-0.3份和触变剂0.001-5份;
所述B组分由按质量份计的以下原料组成:异氰酸酯0.001-15份、端异氰酸酯基聚氨酯预聚物35-75份、异氰酸酯基硅烷偶联剂改性聚醚多元醇5-25份、阻燃剂10-25份;偶联剂0.001-5份、吸水剂0.001-0.3份、触变剂0.001-5份和催化剂0.001-0.1份。
一种本发明所述的动力电池组装用低模量高强度聚氨酯结构胶的制备方法,包括以下步骤:
分别制备端异氰酸酯基预聚物与异氰酸酯基硅烷偶联剂改性聚醚多元醇;
按本发明所述A组分与B组分的配方分别取A组分与B组分的各组成原料,将A组分与B组分的各原料分别混合均匀制得A组分与B组分,将制得的所述A组分与B组分按体积比为1:1组合使用,即得到动力电池组装用低模量高强度聚氨酯结构胶。
与现有技术相比,本发明所提供的动力电池组装用低模量高强度聚氨酯结构胶,其有益效果包括:
通过在B组分中加入适量的异氰酸酯基硅烷偶联剂改性聚醚多元醇,有效降低聚氨酯胶的模量,硅烷偶联剂可与基材表面羟基发生缩合反应,形成共价键作用,仍然能保持足够高的拉伸强度和剪切强度;固化后的异氰酸酯基硅烷偶联剂改性聚醚多元醇和聚氨酯可形成互穿交联网络结构,可阻隔水汽进入,提高耐湿热老化性能;加入含长碳链的生物基多元醇和聚二聚酸己二醇聚酯二元醇,可提高分子链的疏水性,提高耐湿热老化性能,同时可增加分子链柔顺性,一定程度上模量更低;含芳环多元醇的加入,提高了分子链刚性,提高了玻璃化转变温度,改善了耐热性能,另外还有效提高了对于PET、PC及金属基材的粘接强度;与现有技术相比,本发明至少具有以下有益效果:(1)模量较低,25℃下储能模量≤400MPa,应用于动力电池PACK胶具有优异的缓冲减震作用。(2)强度较高,本体拉伸强度≥8MPa,对于PET、PC、铝合金、钢材等基材的剪切强度≥8MPa,保证了行驶过程中的安全性和可靠性。(3)耐湿热老化性能优异,双85老化1000h后,拉伸强度和剪切强度衰减<20%。
具体实施方式
下面结合本发明的具体内容,对本发明实施例中的技术方案进行清楚、完整地描述;显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例,这并不构成对本发明的限制。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。
首先对本文中可能使用的术语进行如下说明:
术语“和/或”是表示两者任一或两者同时均可实现,例如,X和/或Y表示既包括“X”或“Y”的情况也包括“X和Y”的三种情况。
术语“包括”、“包含”、“含有”、“具有”或其它类似语义的描述,应被解释为非排它性的包括。例如:包括某技术特征要素(如原料、组分、成分、载体、剂型、材料、尺寸、零件、部件、机构、装置、步骤、工序、方法、反应条件、加工条件、参数、算法、信号、数据、产品或制品等),应被解释为不仅包括明确列出的某技术特征要素,还可以包括未明确列出的本领域公知的其它技术特征要素。
术语“由……组成”表示排除任何未明确列出的技术特征要素。若将该术语用于权利要求中,则该术语将使权利要求成为封闭式,使其不包含除明确列出的技术特征要素以外的技术特征要素,但与其相关的常规杂质除外。如果该术语只是出现在权利要求的某子句中,那么其仅限定在该子句中明确列出的要素,其他子句中所记载的要素并不被排除在整体权利要求之外。
术语“质量份”是表示多个组分之间的质量比例关系,例如:如果描述了X组分为x质量份、Y组分为y质量份,那么表示X组分与Y组分的质量比为x:y;1质量份可表示任意的质量,例如:1质量份可以表示为1kg也可表示3.1415926kg等。所有组分的质量份之和并不一定是100份,可以大于100份、小于100份或等于100份。除另有说明外,本文中所述的份、比例和百分比均按质量计。
当浓度、温度、压力、尺寸或者其它参数以数值范围形式表示时,该数值范围应被理解为具体公开了该数值范围内任何上限值、下限值、优选值的配对所形成的所有范围,而不论该范围是否被明确记载;例如,如果记载了数值范围“2~8”时,那么该数值范围应被解释为包括“2~7”、“2~6”、“5~7”、“3~4和6~7”、“3~5和7”、“2和5~7”等范围。除另有说明外,本文中记载的数值范围既包括其端值也包括在该数值范围内的所有整数和分数。
下面对本发明所提供的高阻隔耐热无溶剂聚氨酯复合材料及其制备方法进行详细描述。本发明实施例中未作详细描述的内容属于本领域专业技术人员公知的现有技术。本发明实施例中未注明具体条件者,按照本领域常规条件或制造商建议的条件进行。本发明实施例中所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
本发明实施例提供一种动力电池组装用低模量高强度聚氨酯结构胶,包括:
A组分和B组分,所述A组分与B组分使用体积比为1:1,官能团摩尔比为:NCO:OH=1.05:1~2.0:1;
所述A组分由按质量份计的以下原料组成:生物基多元醇5-30份、芳环改性多元醇10-30份、聚醚多元醇0.001-15份、交联剂0.001-3份、催化剂0.001-0.1份、阻燃剂15-45份、水0.001-0.3份和触变剂0.001-5份;
所述B组分由按质量份计的以下原料组成:异氰酸酯0.001-15份、端异氰酸酯基聚氨酯预聚物35-75份、异氰酸酯基硅烷偶联剂改性聚醚多元醇5-25份、阻燃剂10-25份;偶联剂0.001-5份、吸水剂0.001-0.3份、触变剂0.001-5份和催化剂0.001-0.1份。
优选的,上述结构胶的A组分中,所述生物基多元醇为大豆油、蓖麻油、棕桐油、氢化蓖麻油、芳环改性蓖麻油中的一种或多种;
所述芳环改性多元醇为分子量400-3000的双酚A或双酚F改性聚醚二元醇,或苯酐聚酯二元醇中的一种或多种;
所述聚醚多元醇为分子量400-2000的聚丙二醇。
优选的,上述结构胶的A组分中,所述交联剂为官能度4-6的聚醚多元醇或胺中的一种或多种。
优选的,上述结构胶的A组分与B组分中,所述催化剂为异辛酸铋、月桂酸铋、新癸酸铋、环烷酸铋、异辛酸锌、新癸酸锌、二月桂酸二丁基锡、辛酸亚锡、螯合锡中的一种或多种;
所述阻燃剂为氢氧化铝、氢氧化镁、次磷酸铝、二乙基次膦酸铝等固体阻燃剂或磷酸三甲苯酯、磷酸三乙酯、三(氯异丙基)磷酸酯等液体阻燃剂中的一种或多种;
所述A组分与B组分中,所述触变剂为气相二氧化硅、膨润土中的一种或多种。
优选的,上述结构胶的B组分中,所述异氰酸酯为二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基异氰酸酯、液化MDI、聚合MDI、HDI三聚体、TDI三聚体的一种或多种;
所述端异氰酸酯基聚氨酯预聚物为分子量1000-3000的二元醇与异氰酸酯反应生成,控制NCO的质量分数为6~22%;
所述异氰酸酯基硅烷偶联剂改性聚醚多元醇为异氰酸酯基硅烷偶联剂与聚醚多元醇反应生成,控制摩尔比为:NCO:OH=1.005:1~1.3:1。
优选的,上述端异氰酸酯基聚氨酯预聚物中的端异氰酸酯基聚氨酯预聚物中,所述二元醇为聚丙二醇、聚乙二醇、聚己二酸乙二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚二聚酸己二醇酯二元醇的一种或多种;该端异氰酸酯基聚氨酯预聚物中的异氰酸酯为二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基异氰酸酯、液化MDI、聚合MDI、HDI三聚体、TDI三聚体的一种或多种。
优选的,上述异氰酸酯基硅烷偶联剂改性聚醚多元醇中,所述异氰酸酯基硅烷偶联剂为异氰酸酯丙基三乙氧基硅烷、异氰酸酯丙基三甲氧基硅烷、异氰酸酯丙基二甲氧基硅烷的一种或多种;所述聚醚多元醇为分子量3000-16000的聚丙二醇。
优选的,上述B组分中,所述吸水剂为对甲苯磺酰异氰酸酯。
本发明实施例还提供一种上述的动力电池组装用低模量高强度聚氨酯结构胶的制备方法,包括以下步骤:
分别制备端异氰酸酯基预聚物与异氰酸酯基硅烷偶联剂改性聚醚多元醇;
按上述A组分与B组分的配方分别取A组分与B组分的各组成原料,将A组分与B组分的各原料分别混合均匀制得A组分与B组分,将制得的所述A组分与B组分按体积比为1:1组合使用,即得到动力电池组装用低模量高强度聚氨酯结构胶。
优选的,上述方法中,按以下方式制备端异氰酸酯基预聚物,包括:
将二元醇加热至110-120℃,搅拌同时抽真空,脱水1-3h后,降温至50℃以下,充入氮气,按理论NCO含量为6-20%的配比加入异氰酸酯,升温至65-85℃,持续搅拌反应1-3h,直至滴定NCO含量不再变化结束反应,冷却至室温,得到端异氰酸酯基预聚物;
按以下方式制备异氰酸酯基硅烷偶联剂改性聚醚多元醇,包括:
将聚醚多元醇加热至110-120℃,搅拌同时抽真空,脱水1-3h后,降温至50℃以下,充入氮气,按照NCO:OH=1.005:1~1.3:1的配比,加入异氰酸酯基硅烷偶联剂,升温至70-90℃,持续搅拌反应1-3h,直至滴定NCO含量不再变化结束反应,冷却至室温,即得到异氰酸酯基硅烷偶联剂改性聚醚多元醇。
为了更加清晰地展现出本发明所提供的技术方案及所产生的技术效果,下面以具体实施例对本发明实施例所提供的一种动力电池组装用低模量高强度聚氨酯结构胶及其制备方法进行详细描述。
实施例1
本实施例提供一种动力电池组装用低模量高强度聚氨酯结构胶,其制备方法包括:
预先分别制备异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物,其中,异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物各原料均按质量份计;
(1)制备异氰酸酯基硅烷偶联剂改性聚醚多元醇,包括:取100份分子量为12000的聚丙二醇,搅拌同时升温至120℃,保持抽真空除水2h,降温至45℃,充入氮气,加入3.59份异氰酸酯基丙基三甲氧基硅烷,缓慢升温至85℃,搅拌反应3h,冷却至室温,得到异氰酸酯基硅烷偶联剂改性聚醚多元醇。
(2)制备端异氰酸酯基预聚物,包括:取50份分子量2000的聚丙二醇,搅拌同时升温至120℃,保持抽真空除水2h,降温至40℃,充入氮气,加入50份液化MDI,缓慢升温至80℃,搅拌反应2h,冷却至室温,得到端异氰酸酯基预聚物。
再分别制备A组分与B组分,其中,A组分与B组分中各原料均按质量份计;
(3)制备A组分:取20份氢化蓖麻油多元醇,15份双酚A聚醚多元醇,20份分子量为1000的聚丙二醇,0.04份的4官能度聚醚多元醇,0.05份异辛酸铋,35份氢氧化铝,8份次磷酸铝,1份气相二氧化硅,0.1份水,分散搅拌均匀,搅拌2h后即得A组份;
(4)制备B组分:取60份端异氰酸酯基预聚物,15份异氰酸酯基硅烷偶联剂改性聚醚多元醇,23份氢氧化铝,2份γ-甲基丙烯酰氧基丙基三甲氧基硅烷,0.2份对甲苯磺酰异氰酸酯,1份气相二氧化硅,0.04份螯合锡催化剂,搅拌2h后得到B组分;
实施例2
本实施例提供一种动力电池组装用低模量高强度聚氨酯结构胶,其制备方法包括:
预先分别制备异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物,其中,异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物各原料均按质量份计;
(1)制备异氰酸酯基硅烷偶联剂改性聚醚多元醇,包括:取10份分子量为4000的聚丙二醇和90份分子量为12000的聚丙二醇,搅拌同时升温至120℃,保持抽真空除水2h,降温至45℃,充入氮气,加入4.305份异氰酸酯基丙基三甲氧基硅烷,缓慢升温至85℃,搅拌反应2h,冷却至室温,得到异氰酸酯基硅烷偶联剂改性聚醚多元醇。
(2)制备端异氰酸酯基预聚物,包括:取40份分子量2000的聚丙二醇,搅拌同时升温至110℃,保持抽真空除水3h,降温至40℃,充入氮气,加入60份液化MDI,缓慢升温至75℃,搅拌反应2.5h,冷却至室温,得到端异氰酸酯基预聚物。
再分别制备A组分与B组分,其中,A组分与B组分中各原料均按质量份计;
(3)制备A组分:取10份蓖麻油、30份氢化蓖麻油多元醇,20份双酚A聚醚多元醇,0.7份的4官能度聚醚多元醇作为交联剂,0.08份异辛酸铋,23份氢氧化铝,8份次磷酸铝,2份气相二氧化硅,0.2份水,分散搅拌均匀,搅拌3h后即得A组份;
(4)制备B组分:取60份端异氰酸酯基预聚物,10份异氰酸酯基硅烷偶联剂改性聚醚多元醇,28份氢氧化铝,2份γ-甲基丙烯酰氧基丙基三甲氧基硅烷,0.2份对甲苯磺酰异氰酸酯,2份气相二氧化硅,0.04份螯合锡催化剂,搅拌3h后得到B组分;
实施例3
本实施例提供一种动力电池组装用低模量高强度聚氨酯结构胶,其制备方法包括:
预先分别制备异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物,其中,异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物各原料均按质量份计;
(1)制备异氰酸酯基硅烷偶联剂改性聚醚多元醇,包括:取100份分子量为8000的聚丙二醇,搅拌同时升温至120℃,保持抽真空除水2h,降温至45℃,充入氮气,加入5.23份异氰酸酯丙基二甲氧基硅烷,缓慢升温至80℃,搅拌反应3h,冷却至室温,得到异氰酸酯基硅烷偶联剂改性聚醚多元醇。
(2)制备端异氰酸酯基预聚物,包括:取20份分子量2000的聚丙二醇,20份分子量为2000的聚二聚酸己二醇酯二元醇,搅拌同时升温至120℃,保持抽真空除水2h,降温至40℃,充入氮气,加入60份液化MDI,缓慢升温至80℃,搅拌反应2h,冷却至室温,得到端异氰酸酯基预聚物。
再分别制备A组分与B组分,其中,A组分与B组分中各原料均按质量份计;
(3)制备A组分:取40份氢化蓖麻油多元醇,20份双酚A聚醚多元醇,10份分子量为1000的聚丙二醇,0.8份N,N,N',N'-四-(2羟基丙基)乙二胺,0.05份异辛酸铋,30份氢氧化铝,8份次磷酸铝,2份气相二氧化硅,0.1份水,分散搅拌均匀,搅拌2h后即得A组份;
(4)制备B组分:取65份端异氰酸酯基预聚物,10份异氰酸酯基硅烷偶联剂改性聚醚多元醇,23份氢氧化铝,2份γ-甲基丙烯酰氧基丙基三甲氧基硅烷,0.2份对甲苯磺酰异氰酸酯,2份气相二氧化硅,0.04份螯合锡催化剂,搅拌2h后得到B组分;
实施例4
本实施例提供一种动力电池组装用低模量高强度聚氨酯结构胶,其制备方法包括:
预先分别制备异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物,其中,异氰酸酯基硅烷偶联剂改性聚醚多元醇与端异氰酸酯基预聚物各原料均按质量份计;
(1)端异氰酸酯基预聚物制备:取40份分子量为2000的聚二聚酸己二醇酯二元醇,搅拌同时升温至120℃,保持抽真空除水2h,降温至40℃,充入氮气,加入60份液化MDI,缓慢升温至80℃,搅拌反应2h,冷却至室温,得到端异氰酸酯基预聚物。
(2)制备A组分:取30份氢化蓖麻油多元醇,20份双酚A聚醚多元醇,10份分子量为1000的聚丙二醇,0.4份N,N,N',N'-四-(2羟基丙基)乙二胺,0.05份异辛酸铋,30份氢氧化铝,8份次磷酸铝,2份气相二氧化硅,0.1份水,分散搅拌均匀,搅拌2h后即得A组份;
再分别制备A组分与B组分,其中,A组分与B组分中各原料均按质量份计;
(3)制备B组分:取60份端异氰酸酯基预聚物,15份MS树脂S203H,23份氢氧化铝,2份γ-甲基丙烯酰氧基丙基三甲氧基硅烷,0.2份对甲苯磺酰异氰酸酯,2份气相二氧化硅,0.04份螯合锡催化剂,搅拌2h后得到B组分;
将以上各实施例制成的动力电池组装用低模量高强度聚氨酯结构胶,A组分与B组分按照体积比为1:1组合使用,测试25℃的拉伸强度、剪切强度、模量、阻燃性能,双85老化1000h后的拉伸强度、剪切强度,基材选用未处理的铝合金和PET。
通过上表的测试数据可以看出,本发明的动力电池组装用低模量高强度聚氨酯结构胶具有较低的模量,小于400MPa,具有优异的拉伸强度,对于未处理的Al和PET具有优异的剪切强度,阻燃性能可以达到难燃级别,双85老化1000h后,衰减小于20%,可有效保证动力电池在高频震动、湿热、严寒、酷暑、热量堆积等复杂环境下长期使用时的性能稳定,提高可靠性和安全性。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。本文背景技术部分公开的信息仅仅旨在加深对本发明的总体背景技术的理解,而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。
Claims (10)
1.一种动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,包括:
A组分和B组分,所述A组分与B组分使用体积比为1:1,官能团摩尔比为:NCO:OH=1.05:1~2.0:1;
所述A组分由按质量份计的以下原料组成:生物基多元醇5-30份、芳环改性多元醇10-30份、聚醚多元醇0.001-15份、交联剂0.001-3份、催化剂0.001-0.1份、阻燃剂15-45份、水0.001-0.3份和触变剂0.001-5份;
所述B组分由按质量份计的以下原料组成:异氰酸酯0.001-15份、端异氰酸酯基聚氨酯预聚物35-75份、异氰酸酯基硅烷偶联剂改性聚醚多元醇5-25份、阻燃剂10-25份;偶联剂0.001-5份、吸水剂0.001-0.3份、触变剂0.001-5份和催化剂0.001-0.1份。
2.根据权利要求1所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述A组分中,所述生物基多元醇为大豆油、蓖麻油、棕桐油、氢化蓖麻油、芳环改性蓖麻油中的一种或多种;
所述芳环改性多元醇为分子量400-3000的双酚A或双酚F改性聚醚二元醇,或苯酐聚酯二元醇中的一种或多种;
所述聚醚多元醇为分子量400-2000的聚丙二醇。
3.根据权利要求1或2所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述A组分中,所述交联剂为官能度4-6的聚醚多元醇或胺中的一种或多种。
4.根据权利要求1或2所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述A组分与B组分中,所述催化剂为异辛酸铋、月桂酸铋、新癸酸铋、环烷酸铋、异辛酸锌、新癸酸锌、二月桂酸二丁基锡、辛酸亚锡、螯合锡中的一种或多种;
所述阻燃剂为氢氧化铝、氢氧化镁、次磷酸铝、二乙基次膦酸铝、磷酸三甲苯酯、磷酸三乙酯、三(氯异丙基)磷酸酯中的一种或多种;
所述A组分与B组分中,所述触变剂为气相二氧化硅、膨润土中的一种或多种。
5.根据权利要求1或2所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述B组分中,所述异氰酸酯为二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基异氰酸酯、液化MDI、聚合MDI、HDI三聚体、TDI三聚体的一种或多种;
所述端异氰酸酯基聚氨酯预聚物为分子量1000-3000的二元醇与异氰酸酯反应生成,控制NCO的质量分数为6~22%;
所述异氰酸酯基硅烷偶联剂改性聚醚多元醇为异氰酸酯基硅烷偶联剂与聚醚多元醇反应生成,控制摩尔比为:NCO:OH=1.005:1~1.3:1。
6.根据权利要求5所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述端异氰酸酯基聚氨酯预聚物中的二元醇为聚丙二醇、聚乙二醇、聚己二酸乙二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚二聚酸己二醇酯二元醇的一种或多种;
该端异氰酸酯基聚氨酯预聚物中的异氰酸酯为二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基异氰酸酯、液化MDI、聚合MDI、HDI三聚体、TDI三聚体的一种或多种。
7.根据权利要求5所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述异氰酸酯基硅烷偶联剂改性聚醚多元醇中,所述异氰酸酯基硅烷偶联剂为异氰酸酯丙基三乙氧基硅烷、异氰酸酯丙基三甲氧基硅烷、异氰酸酯丙基二甲氧基硅烷的一种或多种;所述聚醚多元醇为分子量3000-16000的聚丙二醇。
8.根据权利要求1或2所述的动力电池组装用低模量高强度聚氨酯结构胶,其特征在于,所述B组分中,所述吸水剂为对甲苯磺酰异氰酸酯。
9.一种权利要求1-8任一项所述的动力电池组装用低模量高强度聚氨酯结构胶的制备方法,其特征在于,包括以下步骤:
分别制备端异氰酸酯基预聚物与异氰酸酯基硅烷偶联剂改性聚醚多元醇;
按权利要求1-8任一项所述A组分与B组分的配方分别取A组分与B组分的各组成原料,将A组分与B组分的各原料分别混合均匀制得A组分与B组分,将制得的所述A组分与B组分按体积比为1:1组合使用,即得到动力电池组装用低模量高强度聚氨酯结构胶。
10.根据权利要求9所述的动力电池组装用低模量高强度聚氨酯结构胶的制备方法,其特征在于,按以下方式制备端异氰酸酯基预聚物,包括:
将二元醇加热至110-120℃,搅拌同时抽真空,脱水1-3h后,降温至50℃以下,充入氮气,按理论NCO含量为6-20%的配比加入异氰酸酯,升温至65-85℃,持续搅拌反应1-3h,直至滴定NCO含量不再变化结束反应,冷却至室温,得到端异氰酸酯基预聚物;
按以下方式制备异氰酸酯基硅烷偶联剂改性聚醚多元醇,包括:
将聚醚多元醇加热至110-120℃,搅拌同时抽真空,脱水1-3h后,降温至50℃以下,充入氮气,按照NCO:OH=1.005:1~1.3:1的配比,加入异氰酸酯基硅烷偶联剂,升温至70-90℃,持续搅拌反应1-3h,直至滴定NCO含量不再变化结束反应,冷却至室温,即得到异氰酸酯基硅烷偶联剂改性聚醚多元醇。
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