CN116606625A - Moisture-heat-resistant polyurethane heat-conducting structural adhesive and preparation method thereof - Google Patents
Moisture-heat-resistant polyurethane heat-conducting structural adhesive and preparation method thereof Download PDFInfo
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- CN116606625A CN116606625A CN202310563912.9A CN202310563912A CN116606625A CN 116606625 A CN116606625 A CN 116606625A CN 202310563912 A CN202310563912 A CN 202310563912A CN 116606625 A CN116606625 A CN 116606625A
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- Prior art keywords
- amino
- heat
- modified
- structural adhesive
- component
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- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 239000004814 polyurethane Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000945 filler Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- KVKWRSNRAXOBFC-UHFFFAOYSA-N methyl 4-(4-hydroxybutyl)benzoate Chemical compound COC(=O)C1=CC=C(CCCCO)C=C1 KVKWRSNRAXOBFC-UHFFFAOYSA-N 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 150000002009 diols Chemical class 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
- 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 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- VBWFYEFYHJRJER-UHFFFAOYSA-N methyl 4-(hydroxymethyl)benzoate Chemical compound COC(=O)C1=CC=C(CO)C=C1 VBWFYEFYHJRJER-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000003384 small molecules Chemical group 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- DJOFSJDUMIIGMC-UHFFFAOYSA-N 3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]benzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1NC(=O)OC(C)(C)C DJOFSJDUMIIGMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- KIDZPYBADRFBHD-UHFFFAOYSA-N methyl 4-(2-hydroxyethyl)benzoate Chemical compound COC(=O)C1=CC=C(CCO)C=C1 KIDZPYBADRFBHD-UHFFFAOYSA-N 0.000 claims description 2
- BANBEJVSLPOVCM-UHFFFAOYSA-N methyl 4-(3-hydroxy-2-methylpropyl)benzoate Chemical compound COC(=O)C1=CC=C(CC(C)CO)C=C1 BANBEJVSLPOVCM-UHFFFAOYSA-N 0.000 claims description 2
- ARNGRGQYXABYAT-UHFFFAOYSA-N methyl 4-(3-hydroxypropyl)benzoate Chemical compound COC(=O)C1=CC=C(CCCO)C=C1 ARNGRGQYXABYAT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000413 hydrolysate Substances 0.000 description 4
- 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 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- -1 methylene, ethylene, propylene, butylene Chemical group 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LPWZCJFZJCOBHO-UHFFFAOYSA-N 11-triethoxysilylundecan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCCCCN LPWZCJFZJCOBHO-UHFFFAOYSA-N 0.000 description 1
- XSPASXKSXBJFKB-UHFFFAOYSA-N 11-trimethoxysilylundecan-1-amine Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCN XSPASXKSXBJFKB-UHFFFAOYSA-N 0.000 description 1
- KIJDMKUPUUYDLN-UHFFFAOYSA-N 2,2-dimethyl-4-trimethoxysilylbutan-1-amine Chemical compound CO[Si](OC)(OC)CCC(C)(C)CN KIJDMKUPUUYDLN-UHFFFAOYSA-N 0.000 description 1
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 1
- 241001428166 Eucheuma Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PFXFKBDDQUKKTF-UHFFFAOYSA-N amino(phenyl)silicon Chemical compound N[Si]C1=CC=CC=C1 PFXFKBDDQUKKTF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Chemical class 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Chemical class 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 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MNEXIOKPOFUXLA-UHFFFAOYSA-N n'-(11-trimethoxysilylundecyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCNCCN MNEXIOKPOFUXLA-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- XCOASYLMDUQBHW-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](OC)(OC)OC XCOASYLMDUQBHW-UHFFFAOYSA-N 0.000 description 1
- DVYVMJLSUSGYMH-UHFFFAOYSA-N n-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCCC[Si](OC)(OC)OC DVYVMJLSUSGYMH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002540 palm oil Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000003549 soybean oil Chemical class 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08G18/4829—Polyethers containing 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5039—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides polyurethane heat-conducting structural adhesive and a preparation method thereof, wherein the polyurethane heat-conducting structural adhesive comprises a A, B component, and the A component comprises the following raw materials: the modified polyol is formed by compounding modified dihydric alcohol and polyether polyol, the structural formula of the modified dihydric alcohol is shown as formula I, and the component B comprises the following raw materials: isocyanate and modified heat conducting filler. The invention provides a modified dihydric alcohol with benzene rings and amide bonds at two ends, and the polyurethane structural adhesive prepared from the polyhydric alcohol raw material compounded by the modified dihydric alcohol and polyether polyol has good resistance to wet heat aging, does not reduce other mechanical properties of the structural adhesive, and provides safety guarantee for reliable operation of new energy automobiles. The polyurethane heat-conducting structural adhesive has good heat-conducting property and shear strength, and can be used for structural bonding of new energy batteries.
Description
Technical Field
The invention belongs to the technical field of polyurethane structural adhesives, and particularly relates to a wet heat resistant polyurethane heat conducting structural adhesive and a preparation method thereof.
Background
With the improvement of environmental awareness and the rising of oil price and government support, new energy automobiles gradually become market hot spots. The battery of the new energy automobile is equivalent to the engine of the traditional fuel oil automobile, and is the heart of the new energy automobile. The new energy automobile battery is more than 80% of the volume of which is composed of organic chemical materials, and comprises a structural bonding material, a heat conducting material, an insulating material, a heat insulating material, a sealing material and the like, wherein the structural bonding material plays a key role in the process of integrating the battery core and the module due to the fact that the structural bonding material is responsible for bonding the battery core and the battery core, the battery core and the foam, the battery core and the module shell and the like.
In general, in order to make the battery operate normally and stably, the structural adhesive needs to have both good heat conduction function and bonding function, for example, patent CN111995979B discloses a polyurethane heat conduction structural adhesive fast cured at room temperature, wherein component a is formed by combining the following components in percentage by mass: 2 to 10 percent of polyether glycol, 2 to 10 percent of chain extender, 2 to 10 percent of polyether triol, 30 to 80 percent of heat conducting filler, 5 to 20 percent of flame retardant, 0.1 to 1.0 percent of water scavenger and 0.1 to 1.0 percent of catalyst; the component B is formed by combining the following components in percentage by mass: 15-40% of polyether glycol, 5-12% of 4,4' -diphenylmethane diisocyanate, 30-80% of heat conducting filler and 5-20% of flame retardant. Patent CN111303820B discloses a double-component polyurethane structural adhesive for bonding a power battery and a preparation method thereof, wherein the polyurethane structural adhesive comprises a component a and a component B; the component A comprises 40-65 parts of polymethylene polyphenyl isocyanate, 30-50 parts of aluminum hydroxide, 2-5 parts of hydrophobic fumed silica and 0-5 parts of plasticizer; the component B comprises 40 to 65 parts of biological polyol, 1 to 4 parts of gas-phase white carbon black, 25 to 50 parts of flame retardant, 1 to 5 parts of adhesion promoter and 0.01 to 0.5 part of catalyst; the bio-based polyol is selected from one or more of rapeseed oil modified polyol, castor oil modified polyol, soybean oil modified polyol and palm oil modified polyol; the adhesion promoter is prepared by reacting aminophenylsilane with a silane modifier.
The polyurethane structural adhesive not only has excellent shearing resistance, but also has good heat conductivity, and can be applied to the effective heat transfer of a new energy power battery module and the structural adhesion of a battery PACK bag. However, the polyurethane structural adhesive is very sensitive to ageing effect brought by a damp-heat environment, and the battery is sometimes in a damp-heat working condition for a long time, so that the bonding strength and the mechanical strength are reduced due to ageing, and unsafe and unstable accidents such as disconnection, leakage and the like are easy to occur. Therefore, the polyurethane structural adhesive is only required to have good bonding strength and heat conductivity, can not meet the use requirements of the polyurethane structural adhesive in new energy batteries, and also has to have good moisture and heat resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides the wet heat resistant polyurethane heat conducting structural adhesive and the preparation method thereof, and provides the modified dihydric alcohol with benzene rings and amide bonds at two ends, wherein the polyurethane structural adhesive prepared from the modified dihydric alcohol and the polyhydric alcohol raw material compounded from polyether polyol has good wet heat aging resistant performance, and provides safety guarantee for the reliable operation of new energy automobiles.
In order to achieve the above purpose, the invention adopts the following specific technical scheme:
a polyurethane heat-conducting structural adhesive comprises A, B components,
the component A comprises the following raw materials: the mixed alcohol is formed by compounding modified dihydric alcohol and polyether polyol, the structural formula of the modified dihydric alcohol is shown as the following formula I,
formula I:
wherein n is an integer of 4-12 (e.g., 5, 6, 8, 10, 11), R 1 、R 2 Alkylene groups independently selected from C1-C4 (e.g., methylene, ethylene, propylene, butylene);
the component B comprises the following raw materials: isocyanate and modified heat conducting filler.
A polyurethane heat-conducting structural adhesive comprises A, B components, wherein the weight ratio of A component to B component is 1:1-1.2,
the component A comprises the following raw materials in parts by weight: 30-40 parts of polyol, 0.5-2 parts of small molecule chain extender, 40-80 parts of modified heat conducting filler and 0.1-0.5 part of catalyst; the compound mass ratio of the modified dihydric alcohol to the polyether polyol is 5.5-7.5:1;
the component B comprises the following raw materials in parts by weight: 20-32 parts of isocyanate and 40-80 parts of modified heat conducting filler.
The modified dihydric alcohol is formed by amino-polyethylene glycol-amino (H) 2 N-PEG-NH 2 ) Is prepared by amidation reaction with hydroxybenzoate derivatives, and the molar ratio of the hydroxybenzoate derivatives to the hydroxybenzoate derivatives is 1:2.07-2.15.
The polymer of the polyethylene glycol in the amino-polyethylene glycol-amino group is 4-12, and is specifically selected from one or more of amino-tetra-polyethylene glycol-amino group, amino-pentapolyethylene glycol-amino group, amino-hexapolyethylene glycol-amino group, amino-heptapolyethylene glycol-amino group, amino-octapolyethylene glycol-amino group, amino-nonapolyethylene glycol-amino group, amino-decapolyethylene glycol-amino group, amino-undecanepolyethylene glycol-amino group and amino-dodecapolyethylene glycol-amino group.
The hydroxybenzoate derivative is selected from one or more of methyl 4- (hydroxymethyl) benzoate, methyl 4- (1-hydroxyethyl) benzoate, methyl 4- (2-hydroxyethyl) benzoate, methyl 4- (3-hydroxy-2-methylpropyl) -benzoate, methyl 4- (3-hydroxypropyl) benzoate, methyl 4- (3-hydroxybutyl) benzoate, methyl 4- (4-hydroxybutyl) benzoate and methyl 4- (4-hydroxybutyl) benzoate.
The modified dihydric alcohol is prepared by a method comprising the following steps:
adding amino-polyethylene glycol-amino, hydroxybenzoate derivatives and solvent into a reaction kettle, heating to reflux state, maintaining reflux state for reaction, and distilling under reduced pressure to obtain modified dihydric alcohol.
The solvent is selected from one or more of methanol, ethanol, water, isopropanol, chloroform and acetone; the reaction time is 5-8h under the reflux state.
The modifier of the modified heat-conducting filler is one or a combination of two or more of an aminosilane coupling agent, a hydroxyl silane coupling agent, an epoxy silane coupling agent and an isocyanate silane coupling agent, and is preferably an aminosilane coupling agent; the heat conducting filler is selected from one or a combination of two or more of aluminum oxide, aluminum hydroxide, aluminum nitride, boron nitride and magnesium oxide.
The preparation method of the modified heat-conducting filler is not particularly limited, and the preparation method is a method commonly used in the field, wherein the method can be used for dripping acid liquor into a mixture of a coupling agent, water and ethanol to adjust the pH, standing at room temperature for hydrolysis, adding the hydrolysate into the ethanol, adding the heat-conducting filler, heating and reacting at constant temperature, and finally filtering, washing, drying and grinding to obtain the modified heat-conducting filler; further, the volume ratio of the coupling agent to the water to the ethanol in the hydrolysate is 1-2:1-2:8, and the pH value is adjusted to 3-4; the volume ratio of the hydrolysate to the ethanol is 1-2:20, the mass ratio of the hydrolysate to the heat conducting filler is 1-2:20, the room temperature standing time is 1-3h, the temperature is raised to 60-80 ℃, and the constant temperature reaction time is 3-5h.
The aminosilane coupling agent is selected from one or more of 4-aminobutyltriethoxysilane, 4-amino-3, 3-dimethylbutyl trimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl ] N-butylamine, N-methyl-3-aminopropyl trimethoxysilane, 11-aminoundecyltrimethoxysilane, (3-aminopropyl) trimethoxysilane, 11-aminoundecyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- [ 3-trimethoxysilyl ] propyl ] -1, 6-hexamethylenediamine, and N-ethyl-3-trimethoxysilane-2-methylpropylamine.
The heat conducting filler is selected from one or a combination of two or more of aluminum oxide, aluminum hydroxide, aluminum nitride, boron nitride and magnesium oxide.
The small molecule chain extender is selected from one or a combination of two or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
The catalyst is an organotin catalyst and is selected from one or a combination of two or more of dibutyl tin dilaurate, stannous octoate and dibutyl tin mercaptide.
The functionality of the polyether polyol is 2-4, and the number average molecular weight is 800-1600g/mol. The polyether polyol is not particularly limited, and may be one or a combination of two or more selected from polypropylene glycol, polypropylene oxide triol, polypropylene oxide tetrol, and the like, which are commonly used in the art.
The functionality of the isocyanate is 2-3, and the isocyanate is one or the combination of two or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, diphenylmethane diisocyanate and triphenylmethane triisocyanate.
The invention also provides a preparation method of the polyurethane heat conduction structural adhesive, which comprises the following steps:
(S1) weighing the mixed alcohol of the raw materials of the component A, the micromolecular chain extender and the modified heat-conducting filler, adding the mixed alcohol, the micromolecular chain extender and the modified heat-conducting filler into a mixing kettle, mixing the materials in vacuum until the materials are uniform, adding the catalyst, mixing the materials in vacuum until the materials are uniform, and discharging the materials to obtain the component A;
and (S2) weighing the raw materials of isocyanate and modified heat-conducting filler of the component B, adding the raw materials into a mixing kettle, mixing the materials in vacuum until the materials are uniform, and discharging the materials to obtain the component B.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a modified dihydric alcohol with benzene rings and amide bonds at two ends, and the polyurethane structural adhesive prepared from the modified dihydric alcohol and a mixed alcohol raw material compounded from polyether polyol has good resistance to wet heat aging, does not reduce other mechanical properties of the structural adhesive, and provides safety guarantee for reliable operation of new energy automobiles. The polyurethane heat-conducting structural adhesive has good heat-conducting property, shear strength and damp-heat aging resistance, and can be used for structural bonding of new energy batteries.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. Unless otherwise specified, "parts" are parts by weight in the examples of the present invention. All reagents used are those commercially available in the art.
Amino-tetra-polyethylene glycol-amino, amino-decapolyethylene glycol-amino, amino-dodecapolyethylene glycol-amino were purchased from the company of the biological sciences, cissima.
Al 2 O 3 Spherical alumina having an average particle diameter of 8 to 10 μm, manufactured by Kaiki Kaisha.
Polypropylene oxide triol was purchased from Eucheuma chemical Co., ltd.Guangzhou and has a number average molecular weight of 1100g/mol.
Preparing a modified heat conduction filler:
preparation example a1
To N- [ 3-trimethoxysilyl group with the volume ratio of 1:1:8]Propyl group]Dripping 10wt% diluted hydrochloric acid solution into a mixture of 1, 6-hexamethylenediamine, water and ethanol to adjust the pH to 3, standing at room temperature for 1h for hydrolysis, adding 10mL of hydrolyzed solution into 100mL of ethanol, and adding 100g of Al 2 O 3 Heating to 80 ℃ and reacting for 3 hours at constant temperature, and finally filtering, washing with ethanol for 3 times, drying and grinding to obtain the modified heat-conducting filler.
Preparation example a2
The remainder was the same as in preparation a1 except that N- [ 3-trimethoxysilyl ] propyl ] -1, 6-hexamethylenediamine was replaced with an equal volume of 3- (2, 3-glycidoxypropoxy) propyloxy silane.
Preparation of modified diols
Preparation example b1
1mol of amino-tetra polyethylene glycol-amino and 2.15mol of 4- (hydroxymethyl) methyl benzoate are added into 700mL of ethanol solvent, the mixture is heated to a reflux state and kept in the reflux state for reaction for 8 hours, and finally the modified dihydric alcohol is obtained by reduced pressure distillation.
Preparation example b2
The remainder was the same as in preparation example b1, except that amino-tetra-polyethylene glycol-amino group was replaced with an equimolar amount of amino-dodecapolyethylene glycol-amino group.
Preparation example b3
The remainder was the same as in preparation example b1, except that methyl 4- (4-hydroxybutyl) benzoate was replaced with an equimolar amount of methyl 4- (hydroxymethyl) benzoate.
Preparation example b4
The remainder was the same as in preparation example b1, except that amino-tetra-polyethylene glycol-amino group was replaced with an equimolar amount of amino-decapolyethylene glycol-amino group.
Preparation of polyurethane heat-conducting structural adhesive
Example 1
Mixing alcohol: the modified dihydric alcohol and the polypropylene oxide triol prepared in the preparation example b1 are mixed according to the mass ratio of 7.5:1;
s1, weighing 40 parts of mixed alcohol, 1 part of ethylene glycol and 80 parts of modified heat-conducting filler prepared in preparation example a1, adding into a mixing kettle, mixing in vacuum until the mixture is uniform, adding 0.5 part of dibutyltin dilaurate, mixing in vacuum until the mixture is uniform, and discharging to obtain a component A;
s2, weighing 32 parts of 2, 4-toluene diisocyanate serving as a raw material of the component B and 80 parts of the modified heat-conducting filler prepared in the preparation example a1, adding the materials into a mixing kettle, heating to 70 ℃, mixing in vacuum until the materials are uniform, and discharging to obtain the component B.
The weight ratio of the component A to the component B is 1:1.
Examples 2 to 4
The remainder was the same as in example 1, except that the modified diols used corresponded to preparation examples b2 to b4, respectively.
Example 5
The remainder is the same as example 1, except that the mixed alcohol is a compound of the modified diol and the polypropylene oxide triol prepared in preparation example b1 in a mass ratio of 5.5:1.
Example 6
The mixed alcohol is the compound of the modified dihydric alcohol and the polypropylene oxide triol prepared in the preparation example b1 according to the mass ratio of 7.5:1;
s1, weighing 30 parts of mixed alcohol, 1 part of ethylene glycol and 40 parts of the modified heat-conducting filler prepared in the preparation example a1, adding into a mixing kettle, mixing in vacuum until the mixture is uniform, adding 0.5 part of dibutyltin dilaurate, mixing in vacuum until the mixture is uniform, and discharging to obtain a component A;
s2, weighing 20 parts of 2, 4-toluene diisocyanate serving as a raw material of the component B and 40 parts of the modified heat-conducting filler prepared in the preparation example a1, adding the materials into a mixing kettle, heating to 70 ℃, mixing in vacuum until the materials are uniform, and discharging to obtain the component B. The weight ratio of the component A to the component B is 1:1.
Comparative example 1
The remainder was the same as in example 1 except that the mixed alcohol was replaced with polypropylene oxide triol.
The polyurethane heat-conducting structural adhesives prepared in examples 1-6 and comparative example 1 above were subjected to the following performance tests:
thermal conductivity coefficient: the thermal conductivity is determined with reference to standard ASTM D5470.
Humid heat aging: and (3) aging for 1000 hours in a damp-heat aging box at the temperature of 85 ℃ and the humidity of 85%.
Shear strength: with reference to the measurement of tensile shear strength of the standard GB/T7124-2008 adhesive (rigid material to rigid material), the single lap tensile shear strength of PET films and PET films, 30003 aluminum alloy and 30003 aluminum alloy is tested, the tensile speed is 2mm/min, the number of samples is 5, the maximum load of shear failure is recorded as the failure load, the test result is expressed as the arithmetic average value of the tensile shear strength, and the tensile shear strength is calculated by dividing the failure load by the shear area; the shear strength loss rate,%, before and after humid heat aging was measured.
TABLE 1
From table 1, it can be seen that the polyurethane structural adhesive raw material prepared by the invention has good heat conduction performance, shear strength and wet heat aging resistance, can be used for structural bonding of new energy batteries, and can provide safety guarantee for reliable operation of new energy automobiles.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (10)
1. A polyurethane heat conduction structural adhesive is characterized by comprising A, B components,
the component A comprises the following raw materials: the mixed alcohol is the compound of modified dihydric alcohol and polyether polyol, the structural formula of the modified dihydric alcohol is shown as the following formula I,
formula I:
wherein n is an integer of 4-12 (e.g., 5, 6, 8, 10, 11), R 1 、R 2 An alkylene group independently selected from C1-C4;
the component B comprises the following raw materials: isocyanate and modified heat conducting filler.
2. The polyurethane heat-conducting structural adhesive of claim 1, wherein the weight ratio of the component A to the component B is 1:1-1.2;
the component A comprises the following raw materials in parts by weight: 30-40 parts of polyol, 0.5-2 parts of small molecule chain extender, 40-80 parts of modified heat conducting filler and 0.1-0.5 part of catalyst; the compound mass ratio of the modified dihydric alcohol to the polyether polyol is 5.5-7.5:1;
the component B comprises the following raw materials in parts by weight: 20-32 parts of isocyanate and 40-80 parts of modified heat conducting filler.
3. The polyurethane heat-conducting structural adhesive of claim 1, wherein the modified dihydric alcohol consists of amino-polyethylene glycol-amino (H) 2 N-PEG-NH 2 ) Is prepared by amidation reaction with hydroxybenzoate derivatives, and the molar ratio of the hydroxybenzoate derivatives to the hydroxybenzoate derivatives is 1:2.07-2.15.
4. The polyurethane heat-conducting structural adhesive according to claim 3, wherein the polymerization degree of polyethylene glycol in the amino-polyethylene glycol-amino group is 4-12, and specifically is one or a combination of two or more selected from the group consisting of amino-tetra-polyethylene glycol-amino group, amino-pentapolyethylene glycol-amino group, amino-hexapolyethylene glycol-amino group, amino-heptapolyethylene glycol-amino group, amino-octapolyethylene glycol-amino group, amino-nonapolyethylene glycol-amino group, amino-decapolyethylene glycol-amino group, amino-undecanepolyethylene glycol-amino group, and amino-dodecapolyethylene glycol-amino group; the hydroxybenzoate derivative is selected from one or more of methyl 4- (hydroxymethyl) benzoate, methyl 4- (1-hydroxyethyl) benzoate, methyl 4- (2-hydroxyethyl) benzoate, methyl 4- (3-hydroxy-2-methylpropyl) -benzoate, methyl 4- (3-hydroxypropyl) benzoate, methyl 4- (3-hydroxybutyl) benzoate, methyl 4- (4-hydroxybutyl) benzoate and methyl 4- (4-hydroxybutyl) benzoate.
5. The polyurethane heat-conducting structural adhesive of claim 1, wherein the modifying agent of the modified heat-conducting filler is one or a combination of two or more of an aminosilane coupling agent, a hydroxysilane coupling agent, an epoxy silane coupling agent and an isocyanate silane coupling agent, and is preferably an aminosilane coupling agent; the heat conducting filler is selected from one or a combination of two or more of aluminum oxide, aluminum hydroxide, aluminum nitride, boron nitride and magnesium oxide.
6. The polyurethane heat transfer structural adhesive of claim 1, wherein the modified diol is prepared by a process comprising the steps of:
adding amino-polyethylene glycol-amino, hydroxybenzoate derivatives and solvent into a reaction kettle, heating to reflux state, maintaining reflux state for reaction, and distilling under reduced pressure to obtain modified dihydric alcohol.
7. The polyurethane heat-conducting structural adhesive of claim 6, wherein the solvent is selected from one or a combination of two or more of methanol, ethanol, water, isopropanol, chloroform, and acetone; the reaction time is 5-8h under the reflux state.
8. The polyurethane heat transfer structural adhesive of claim 1, wherein the polyether polyol has a functionality of 2 to 4 and a number average molecular weight of 800 to 1600g/mol.
9. The polyurethane heat-conducting structural adhesive according to claim 1, wherein the isocyanate has a functionality of 2-3, and is specifically selected from one or a combination of two or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, diphenylmethane diisocyanate and triphenylmethane triisocyanate.
10. The method for preparing the polyurethane heat conduction structural adhesive according to any one of claims 1 to 9, comprising the following steps:
(S1) weighing the mixed alcohol of the raw materials of the component A, the micromolecular chain extender and the modified heat-conducting filler, adding the mixed alcohol, the micromolecular chain extender and the modified heat-conducting filler into a mixing kettle, mixing the materials in vacuum until the materials are uniform, adding the catalyst, mixing the materials in vacuum until the materials are uniform, and discharging the materials to obtain the component A;
and (S2) weighing the raw materials of isocyanate and modified heat-conducting filler of the component B, adding the raw materials into a mixing kettle, mixing the materials in vacuum until the materials are uniform, and discharging the materials to obtain the component B.
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| CN117447958A (en) * | 2023-12-21 | 2024-01-26 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant aging-resistant heat-conducting polyurethane structural adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117447958A (en) * | 2023-12-21 | 2024-01-26 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant aging-resistant heat-conducting polyurethane structural adhesive and preparation method thereof |
| CN117447958B (en) * | 2023-12-21 | 2024-04-19 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant aging-resistant heat-conducting polyurethane structural adhesive and preparation method thereof |
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