CN113930194A - Environment-friendly adhesive for vehicle film and preparation method thereof - Google Patents
Environment-friendly adhesive for vehicle film and preparation method thereof Download PDFInfo
- Publication number
- CN113930194A CN113930194A CN202111196212.8A CN202111196212A CN113930194A CN 113930194 A CN113930194 A CN 113930194A CN 202111196212 A CN202111196212 A CN 202111196212A CN 113930194 A CN113930194 A CN 113930194A
- Authority
- CN
- China
- Prior art keywords
- parts
- environment
- coupling agent
- photoinitiator
- friendly adhesive
- 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
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 title claims description 70
- 239000000853 adhesive Substances 0.000 title claims description 69
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000003292 glue Substances 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims description 59
- 229920005989 resin Polymers 0.000 claims description 59
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 229910021389 graphene Inorganic materials 0.000 claims description 42
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 38
- 239000007822 coupling agent Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000003085 diluting agent Substances 0.000 claims description 24
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 19
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 18
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 18
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 16
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 150000003505 terpenes Chemical class 0.000 claims description 13
- 235000007586 terpenes Nutrition 0.000 claims description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 150000001721 carbon Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 6
- -1 phenolic aldehyde Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- PWAXQGINNIJNRP-UHFFFAOYSA-N C(C=C)(=O)O.C(CCCCCCCCCCC)(=O)OC Chemical compound C(C=C)(=O)O.C(CCCCCCCCCCC)(=O)OC PWAXQGINNIJNRP-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 14
- 239000012855 volatile organic compound Substances 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MJPRYKBMEQUDDW-VEYOIHGOSA-N (1r,2r,4s)-2-[(1r)-1,2-dihydroxyethyl]-3,6-bis(4-methylphenyl)bicyclo[2.2.0]hexane-1,2,4,5-tetrol Chemical compound C1=CC(C)=CC=C1C1[C@]2(O)[C@](O)([C@H](O)CO)C(C=3C=CC(C)=CC=3)[C@]2(O)C1O MJPRYKBMEQUDDW-VEYOIHGOSA-N 0.000 description 1
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- UHSXWBOPNFPORF-UHFFFAOYSA-N 1-n,3-n,5-n-tritert-butylbenzene-1,3,5-triamine Chemical compound CC(C)(C)NC1=CC(NC(C)(C)C)=CC(NC(C)(C)C)=C1 UHSXWBOPNFPORF-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 239000001736 Calcium glycerylphosphate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- 208000001362 Fetal Growth Retardation Diseases 0.000 description 1
- 206010070531 Foetal growth restriction Diseases 0.000 description 1
- 206010060919 Foetal malformation Diseases 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 206010000210 abortion Diseases 0.000 description 1
- 231100000176 abortion Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 description 1
- 229940095618 calcium glycerophosphate Drugs 0.000 description 1
- 235000019299 calcium glycerylphosphate Nutrition 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 208000030941 fetal growth restriction Diseases 0.000 description 1
- 231100000001 growth retardation Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/02—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The environment-friendly glue film for the vehicle film has excellent bonding performance, environment-friendly raw materials, simple preparation method and larger application prospect.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to an environment-friendly adhesive for a vehicle film and a preparation method thereof.
Background
The mounting of the vehicle to the body structure, the bonding of interior trim, the bonding of seats, etc., may all be by adhesive technology. The adhesive can effectively avoid waste caused by technical materials, and reduce economic loss. The application of the adhesive technology in automobile assembly reduces the waste materials of automobile materials due to riveting, spot welding, punching and the like, and the economic effect is very considerable. In order to adapt to the development trend of energy conservation, environmental protection, low cost and long service life in modern society, higher and higher requirements on the service performance and the process performance of the adhesive are already provided, and the development and the application of the adhesive are certainly adapted to the development requirements of automobiles.
Automotive VOCs are currently one of the most interesting topics. VOC is the acronym for Volatile Organic Compounds (Volatile Organic Compounds), which refers to various Organic Compounds that have a boiling point of 50-260 ℃ at atmospheric pressure. Among over 900 currently identified indoor chemical and biological substances, Volatile Organic Compounds (VOCs) are at least 350 or more (> 1 ppb), of which more than 20 are carcinogens or mutagenic substances, and some can cause cancer (lung cancer, leukemia) or abortion, fetal malformation, growth retardation and the like after long-term exposure. The traditional adhesive is mostly solvent type, is easy to volatilize solvent and other micromolecule substances, and the VOC (volatile organic compound) applied in the middle of the bonding surface is slowly volatilized, so that the air pollution in a vehicle for a long time is further caused. At present, the traditional solvent-based adhesive for the automobile film is gradually replaced by environment-friendly materials such as hot melt adhesive, water-based adhesive and the like, and the influence of the adhesive on the VOC emission in the automobile is greatly reduced.
Graphene is a new material formed by tightly stacking sp hybridized and connected carbon atoms into a single-layer two-dimensional honeycomb lattice structure, has excellent optical, electrical and mechanical properties, and has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like. Zirconia is a nano-powder having excellent characteristics such as high melting point, high hardness, low thermal conductivity, good chemical stability and toughness. Although zirconia and graphene can be used as fillers of polymers, no report has been found that they can be used as fillers of adhesives to improve the performance of adhesives. Therefore, the development of an environment-friendly adhesive for vehicle films, which has strong adhesion and is environment-friendly in raw materials, is a problem to be solved at present.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the environment-friendly adhesive for the vehicle film and the preparation method thereof.
In the present invention, the content percentages are weight percentages unless otherwise specified.
In order to achieve the above object, the present invention is achieved by the following aspects:
in a first aspect, the invention provides an environment-friendly adhesive for a vehicle film, which comprises the following raw materials in parts by weight: 30-60 parts of butyl acrylate (EA), isooctyl acrylate (2-EHA) and Acrylic Acid (AA) in total; 30-60 parts of reactive diluent; 1-10 parts of tackifying resin; 0.1-3 parts of graphene oxide modified nano-zirconia; 1-10 parts of a photoinitiator;
the mass ratio of the butyl acrylate (EA), the isooctyl acrylate (2-EHA) and the Acrylic Acid (AA) is 1: 1-1.2: 0.1-0.5, e.g. 1: 1: 0.2.
in some preferred specific embodiments, the reactive diluent is one or a mixture of hydroxypropyl methacrylate (HPMA), 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), isobornyl methacrylate (IBOA), tetrahydrofuran acrylate (THFA), methyl laurate acrylate (LMA), ethoxyethoxyethyl acrylate (EOEOEA).
In some preferred specific embodiments, the reactive diluent is a mixture of two or more of 1: 1-1.2: 0.5-0.7 of isobornyl methacrylate (IBOA), 1, 6-hexanediol diacrylate (HDDA) and ethoxyethoxyethyl acrylate (EOEOEA). As a preferable embodiment, the reactive diluents with different functional groups in the system provided by the invention cooperate with each other to provide a large number of crosslinking sites for a photocuring system, and the photo-initiated polymerization reaction improves the crosslinking degree of the environment-friendly adhesive for the vehicle film and enhances the mechanical property and the peel strength of the environment-friendly adhesive for the vehicle film.
In some specific embodiments, the tackifying resin is selected from at least one of rosin resins, petroleum resins, coumarone resins, terpene resins, oil-soluble phenolics.
In some embodiments, the tackifying resin is selected from at least two of rosin resins (ring and ball softening point preferably 60-120 ℃), petroleum resins (ring and ball softening point preferably 88-120 ℃), coumarone resins (ring and ball softening point preferably 80-120 ℃), terpene resins (ring and ball softening point preferably 100-125 ℃), and oil-soluble phenolics (ring and ball softening point preferably 62-120 ℃).
In some preferred embodiments, the tackifying resin is a blend of hydrogenated hydrocarbon pentapetroleum resin (ring and ball softening point of 95-105 ℃) and terpene resin (ring and ball softening point of 100-115 ℃) in a mass ratio of 1: 0.5-0.6. The tackifying resin can improve the wettability of the host material, thereby improving the bonding strength of the host material to the substrate.
In some specific embodiments, the graphene oxide-modified nano-zirconia is a graphene oxide-modified nano-zirconia modified with a silane coupling agent.
In some specific embodiments, the graphene oxide modified nano-zirconia is prepared by the following steps:
(1) uniformly mixing 1-5g of graphene with 100-200mL of 95% concentrated sulfuric acid, stirring for 1-2h under an ice bath condition, then adding 5-20g of potassium permanganate solution, continuing stirring for 2-3h, adding 30-50mL of 35% sulfuric acid, standing for 1-2h, washing the mixed solution until the pH value of the solution is neutral, adding the mixture obtained through centrifugation and drying into 100-200mL of ethanol aqueous solution containing 2-4g of silane coupling agent, and stirring, centrifugally separating, washing and drying to obtain silane coupling agent modified graphene oxide;
(2) and (2) uniformly mixing 2-5g of the silane coupling agent modified graphene oxide prepared in the step (1), 10-20mg of nano-zirconia and 100mL of isopropanol 500mL, adding 10-20mL of reducing agent ammonia water and ethylenediamine (the volume ratio of the ammonia water to the ethylenediamine is 1: 2), heating to 80-90 ℃, refluxing for 4-6h, washing the product until the pH value is neutral, and drying to obtain the graphene oxide modified nano-zirconia.
Preferably, the silane coupling agent is any one or a mixture of more than two of a coupling agent KH550, a coupling agent KH560 and a coupling agent KH 570.
In some specific embodiments, the nano zirconia has a particle size of 30 to 40 nanometers.
The inventor finds that the mechanical property and the mechanical property of the system are further improved by adding a certain proportion of graphene oxide modified nano-zirconia into the raw materials of the environment-friendly adhesive for the vehicle membrane. After the graphene is oxidized, oxygen-containing functional groups on the graphene are increased, so that the graphene is more active than the graphene, and the graphene is more easily combined with zirconium oxide powder after being modified by a silane coupling agent and plays a synergistic effect in an acrylate matrix resin system.
Preferably, the mass ratio of the silane coupling agent modified graphene oxide to the nano-zirconia is 200-250: 1. The preferred embodiment can achieve better system performance, probably because the mass ratio is less agglomerated and easy to disperse, and can fully exert the crosslinking effect of the rigid particles.
The photoinitiator is a compound which can absorb energy with certain wavelength in an ultraviolet region (250-420 nm) or a visible light region (400-800 nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers. In some specific embodiments, the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylmethanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, or mixtures thereof, One or more of methyl benzoylformate.
The photoinitiator is preferably 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (otherwise known as photoinitiator TPO) and/or 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (otherwise known as photoinitiator 369).
In some specific embodiments, the raw material for preparing the environment-friendly adhesive for the vehicle film further comprises one or more of a stabilizer, a coupling agent, an antioxidant, a light transmittance modifier, a compatilizer or an antifogging agent.
As examples of stabilizers, including, but not limited to, zinc stearate, calcium glycerophosphate, zinc carbonate; in one embodiment, the weight of the stabilizer is 0-1 wt% of the total weight of the raw materials for preparing the environment-friendly adhesive for the vehicle film.
Examples of the antioxidant include, but are not limited to, one or more of hindered phenol-based antioxidants and phosphite-based antioxidants, and specifically, may be selected from compounds such as Irganox 1141, 1010, 1076, 168, BNX1000, diphenylamine, p-phenylenediamine and dihydroquinoline, and derivatives or polymers thereof, 2, 6-t-butyl-4-methylphenol, bis (3, 5-t-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ β - (3, 5-t-butyl-4-hydroxyphenyl) propionate ], bisdodecanol ester, bistetradecanol ester and bisoctadecanol ester, trioctyl ester, tridecyl ester, tridodecanol ester and trihexadecanol ester; in one embodiment, the weight of the antioxidant is 0-3% of the total weight of the raw materials for preparing the environment-friendly adhesive for the vehicle film.
Examples of light transmission modifiers include, but are not limited to, 1,3, 5-tri-tert-butylaminobenzene, dibenzylidene sorbitol (DBS), 1,3:2, 4-di-p-methylbenzylidene sorbitol, p-chloro-p-methyldibenzylidene sorbitol, polyvinylcyclobutane, polyvinylcyclohexane, polyvinylcyclopentane, polyvinyl-2-methylcyclohexane, and poly-3-methyl-1-butene; in one embodiment, the weight of the light transmittance modifier is 0-1 wt% of the total weight of the raw materials for preparing the environment-friendly adhesive for the vehicle film.
Examples of the anti-fogging agent include, but are not limited to, a polyamide methanol solution, an ionic surfactant methanol solution, a polyethylene glycol perfluoroalkyl ether isopropyl alcohol solution; in one embodiment, the weight of the antifogging agent is 0-1 wt% of the total weight of the raw materials for preparing the environment-friendly adhesive for the vehicle film.
In a second aspect, the invention provides a preparation method of an environment-friendly adhesive for a vehicle film, which comprises the following steps:
(1) mixing butyl acrylate (EA), isooctyl acrylate (2-EHA), Acrylic Acid (AA) and an active diluent with a first photoinitiator for 1-2h, and controlling the temperature to be 40-50 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400-600 mPa.s to obtain a prepolymer for later use;
(2) mixing the prepolymer obtained in the step (1) with tackifying resin, graphene oxide modified nano zirconia and a second photoinitiator for 0.5-2h, and controlling the temperature to be 45-55 ℃ to obtain the environment-friendly adhesive for the vehicle membrane;
wherein the mass ratio of the first photoinitiator to the second photoinitiator is 1: 3-4.
As a preferred embodiment, the first photoinitiator is TPO and the second photoinitiator is 369.
As a preferred embodiment, the step (2) is also added with a coupling agent KH550, a coupling agent KH560 and/or a coupling agent KH 570; and/or, an antioxidant 168 and/or an antioxidant 1010 are/is also added in the step (2).
In some specific embodiments, the preparation method of the environment-friendly adhesive for the vehicle film comprises the following steps:
(1) mixing 25-30 parts of butyl acrylate (EA), 25-30 parts of isooctyl acrylate (2-EHA), 5-7 parts of Acrylic Acid (AA), 45-50 parts of reactive diluent and 0.8-1 part of first photoinitiator TPO for 1-2 hours, and controlling the temperature to be 40-50 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400-600 mPa.s to obtain a prepolymer for later use;
(2) and (2) mixing the prepolymer obtained in the step (1) with 4-6 parts of tackifying resin, 0.5-1.2 parts of graphene oxide modified nano-zirconia, 3-4 parts of second photoinitiator 369, 1-1.5 parts of coupling agent and 0.5-0.7 part of antioxidant for 1-2 hours, and controlling the temperature to be 45-55 ℃ to obtain the environment-friendly adhesive for the vehicle membrane.
The preparation method adopts the two-step method of the invention to be more beneficial to the mixing of raw materials and the stability of a system. The inventor finds that the environment-friendly adhesive for the vehicle film is obtained by adopting specific types of acrylate, tackifying resin and active diluent and adding the graphene oxide modified nano-zirconia through the interaction between the raw materials, so that the environment-friendly adhesive has excellent adhesive property.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention. The reagents and starting materials used in the present invention are not specifically described and are commercially available.
The positive progress effects of the invention are as follows: the environment-friendly adhesive for the vehicle membrane with excellent performance is obtained by controlling the selection and the proportion of each raw material component, and the preparation process of the environment-friendly adhesive for the vehicle membrane is simple and has low cost.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. It should be understood that although a few embodiments of practicing the present invention have been illustrated herein, those skilled in the art will appreciate, in light of the present disclosure, that numerous modifications may be made without departing from the spirit and intended scope of the invention. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting, since the scope of the present invention will be defined only by the appended claims and equivalents thereof.
The starting materials in the following examples and comparative examples are commercially available unless otherwise specified.
Wherein the content of the first and second substances,
the graphene oxide modified nano-zirconia (self-made A) is prepared by the following steps:
(1) uniformly mixing 2g of graphene with 100mL of 95% concentrated sulfuric acid, stirring for 1h under an ice bath condition, then adding 10g of potassium permanganate solution, continuously stirring for 2h, adding 50mL of 35% sulfuric acid, standing for 2h, washing the mixed solution until the pH value of the solution is neutral, adding a mixture obtained through centrifugation and drying into 150mL of ethanol aqueous solution containing 2.5g of silane coupling agent KH560, and stirring, centrifugally separating, washing and drying to obtain silane coupling agent modified graphene oxide;
(2) and (2) uniformly mixing 4g of the silane coupling agent modified graphene oxide prepared in the step (1), 10mg of nano-zirconia and 500mL of isopropanol, adding 15mL of reducing agent ammonia water and ethylenediamine (the volume ratio of the ammonia water to the ethylenediamine is 1: 2), heating to 80 ℃, refluxing for 4h, washing the product until the pH value is neutral, and drying to obtain the graphene oxide modified nano-zirconia.
The preparation method of the graphene oxide modified nano zirconia (self-made B) is the same as that of the graphene oxide modified nano zirconia (self-made A), and the differences are as follows: and (2) uniformly mixing 4g of the silane coupling agent modified graphene oxide prepared in the step (1), 20mg of nano-zirconia and 500mL of isopropanol, adding 15mL of reducing agent ammonia water and ethylenediamine (the volume ratio of the ammonia water to the ethylenediamine is 1: 2), heating to 80 ℃, refluxing for 4h, washing the product until the pH value is neutral, and drying to obtain the graphene oxide modified nano-zirconia.
The preparation method of the graphene oxide modified nano zirconia (self-made C) is the same as that of the graphene oxide modified nano zirconia (self-made A), and the differences are as follows: and (2) uniformly mixing 4g of the silane coupling agent modified graphene oxide prepared in the step (1), 30mg of nano-zirconia and 500mL of isopropanol, adding 15mL of reducing agent ammonia water and ethylenediamine (the volume ratio of the ammonia water to the ethylenediamine is 1: 2), heating to 80 ℃, refluxing for 4h, washing the product until the pH value is neutral, and drying to obtain the graphene oxide modified nano-zirconia.
Example 1
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of tackifying resin hydrogenated carbon five petroleum resin (softening point of 100 ℃ by a ring and ball method); 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 1 part of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly glue for the vehicle film comprises the following steps:
(1) mixing butyl acrylate (EA), isooctyl acrylate (2-EHA), Acrylic Acid (AA) and reactive diluent with a first photoinitiator for 1.5 h, and controlling the temperature to be 50 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 500mPa.s to obtain a prepolymer for later use;
(2) and (2) mixing the prepolymer obtained in the step (1) with tackifying resin, graphene oxide modified nano zirconia, a second photoinitiator, a coupling agent and an antioxidant for 2 hours, and controlling the temperature to be 50 ℃ to obtain the environment-friendly adhesive for the vehicle membrane.
Example 2
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 1 part of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 3
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon pentapetroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin being 1: 1; 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 1 part of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 4
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 1 part of graphene oxide modified nano-zirconia (self-made A); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 5
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 1 part of graphene oxide modified nano-zirconia (self-made C); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 6
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of reactive diluent (IBOA); 1 part of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 7
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of reactive diluent (a mixture of IBOA and EOEOEA in a mass ratio of 1: 1); 1 part of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 8
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 0.5 part of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Example 9
The preparation raw materials of the environment-friendly adhesive for the vehicle film comprise the following components in parts by weight: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of a compound of hydrogenated carbon penta petroleum resin (the softening point of a ring and ball method is 95 ℃) and terpene resin (the softening point of the ring and ball method is 100 ℃) with the mass ratio of tackifying resin of 1: 0.5; 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 2.5 parts of graphene oxide modified nano-zirconia (self-made B); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method of the environment-friendly adhesive for the vehicle film is the same as that of the embodiment 1.
Comparative example 1
The glue for the vehicle membrane is prepared from the following raw materials in parts by weight (without graphene oxide modified nano-zirconia), and comprises the following components: 25 parts butyl acrylate (EA), 25 parts isooctyl acrylate (2-EHA) and 5 parts Acrylic Acid (AA); 6 parts of tackifying resin hydrogenated carbon five petroleum resin (softening point of 100 ℃ by a ring and ball method); 50 parts of an active diluent (a mixture of IBOA, HDDA and EOEOEA in a mass ratio of 1: 1: 0.5); 1 part of a first photoinitiator TPO, 4 parts of a second photoinitiator 369; 1.5 parts of a coupling agent KH 560; 0.6 part of antioxidant 1010.
The preparation method comprises the following steps:
(1) mixing butyl acrylate (EA), isooctyl acrylate (2-EHA), Acrylic Acid (AA) and reactive diluent with a first photoinitiator for 1.5 h, and controlling the temperature to be 50 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 500mPa.s to obtain a prepolymer for later use;
(2) and (2) mixing the prepolymer obtained in the step (1) with tackifying resin, a second photoinitiator, a coupling agent and an antioxidant for 2 hours, and controlling the temperature to be 50 ℃ to obtain the glue for the automobile film.
Comparative example 3
The vehicle membrane adhesive is prepared from the same raw materials as in example 2, except that the preparation method is different: all the raw materials are directly mixed for 3.5h, and the temperature is controlled at 50 ℃ to obtain the vehicle membrane adhesive.
And (3) performance testing:
the samples obtained in the above examples and comparative examples were subjected to the following performance tests, the test standards and methods, and the test results are shown in table 1:
(1) initial viscosity: according to GB4852-84 test, an environment-friendly adhesive sample for a vehicle film is tested by using an inclined plane rolling ball method, the environment-friendly adhesive for the vehicle film is coated on a PET film with the length of 100mm and the width of 50mm and is subjected to ultraviolet light curing, the sample is placed on an inclined plane table with the inclination of 30 degrees in the test process, the initial adhesion is represented by the largest ball which can be stuck by the environment-friendly adhesive for the vehicle film through the test, and the error is eliminated by testing each sample for three times.
(2) Permanent adhesion: with reference to the test of GB4851-2014, the time (hours) for the tape to detach from the test plate was determined by the hanging method, and the test was repeated three times and the average value was taken.
(3) 180 ° peel strength: referring to GB/T2792-81 test, 180-degree peeling force test is carried out on the environment-friendly adhesive for the vehicle film by an intelligent electronic tensile machine (XLW, Jinan Languang Motor technology Co., Ltd.). Coating the environment-friendly glue for the vehicle film on a PET film with the length of 100mm and the width of 25mm, carrying out ultraviolet light curing, then adhering the cured glue film on a special steel plate for carrying out a peeling test, wherein the peeling speed is 300mm/min, and the test temperature is 25 ℃.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 | |
| Initial tack | 12 | 14 | 10 | 10 | 8 | 13 | 15 | 11 | 9 | 8 | 7 |
| Permanent adhesive force (hours) | 27 | 30 | 23 | 29 | 28 | 25 | 26 | 27 | 23 | 24 | 10 |
| 180 degree peel strength (N/25 mm) | 17 | 21 | 20 | 19 | 16 | 18 | 22 | 17 | 15 | 17 | 8 |
As can be seen from Table 1, the environment-friendly adhesive for the automobile film is obtained by adopting specific types of acrylate, tackifying resin and reactive diluent and adding the graphene oxide modified nano-zirconia through interaction among raw materials, so that the environment-friendly adhesive has excellent bonding performance.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. The environment-friendly adhesive for the vehicle film is characterized by comprising the following raw materials in parts by weight: 30-60 parts of butyl acrylate (EA), isooctyl acrylate (2-EHA) and Acrylic Acid (AA) in total; 30-60 parts of reactive diluent; 1-10 parts of tackifying resin; 0.1-3 parts of graphene oxide modified nano-zirconia; 1-10 parts of a photoinitiator;
the mass ratio of the butyl acrylate (EA), the isooctyl acrylate (2-EHA) and the Acrylic Acid (AA) is 1: 1-1.2: 0.1-0.5, e.g. 1: 1: 0.2.
2. the environmentally friendly adhesive for vehicle membranes according to claim 1, wherein the reactive diluent is one or more of hydroxypropyl methacrylate (HPMA), 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), isobornyl methacrylate (IBOA), tetrahydrofuran acrylate (THFA), methyl laurate acrylate (LMA), and ethoxyethyl acrylate (EOEOEA).
3. The environment-friendly adhesive for the vehicle film according to claim 1, wherein the reactive diluent is prepared from the following components in a mass ratio of 1: 1-1.2: 0.5-0.7 of isobornyl methacrylate (IBOA), 1, 6-hexanediol diacrylate (HDDA) and ethoxyethoxyethyl acrylate (EOEOEA).
4. The environment-friendly adhesive for vehicle films according to claim 1, wherein the tackifying resin is at least one selected from rosin resin, petroleum resin, coumarone resin, terpene resin and oil-soluble phenolic aldehyde;
preferably a compound of hydrogenated carbon pentapetroleum resin (ring and ball softening point of 95-105 ℃) and terpene resin (ring and ball softening point of 100-115 ℃) in a mass ratio of 1: 0.5-0.6.
5. The environment-friendly adhesive for the vehicle film according to claim 1, wherein the graphene oxide modified nano-zirconia is graphene oxide modified nano-zirconia modified by a silane coupling agent;
the silane coupling agent is any one or more than two of a coupling agent KH550, a coupling agent KH560 or a coupling agent KH 570;
preferably, the mass ratio of the silane coupling agent modified graphene oxide to the nano-zirconia is 200-250: 1.
6. The eco-friendly adhesive for automotive films according to claim 1, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylmethanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1- [4- (4-hydroxyethoxy) phenyl ] -1-propanone, or a mixture thereof, One or more of methyl benzoylformate.
7. The environment-friendly adhesive for the automotive film as claimed in claim 1, wherein the raw materials for preparing the environment-friendly adhesive for the automotive film further comprise one or more of a stabilizer, a coupling agent, an antioxidant, a light transmission modifier, a compatilizer or an antifogging agent.
8. A preparation method of the environment-friendly glue for the vehicle film as claimed in any one of claims 1 to 7 comprises the following steps:
(1) mixing butyl acrylate (EA), isooctyl acrylate (2-EHA), Acrylic Acid (AA) and an active diluent with a first photoinitiator for 1-2h, and controlling the temperature to be 40-50 ℃; carrying out photopolymerization under the irradiation of UV light, and stopping the reaction when the viscosity of the system reaches 400-600 mPa.s to obtain a prepolymer for later use;
(2) mixing the prepolymer obtained in the step (1) with tackifying resin, graphene oxide modified nano zirconia and a second photoinitiator for 0.5-2h, and controlling the temperature to be 45-55 ℃ to obtain the environment-friendly adhesive for the vehicle membrane;
wherein the mass ratio of the first photoinitiator to the second photoinitiator is 1: 3-4.
9. The method of claim 8, wherein the first photoinitiator is TPO and the second photoinitiator is 369.
10. The process according to claim 8, wherein step (2) further comprises adding a coupling agent KH550, a coupling agent KH560 and/or a coupling agent KH 570; and/or, an antioxidant 168 and/or an antioxidant 1010 are/is also added in the step (2).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554151A (en) * | 2018-10-23 | 2019-04-02 | 厦门韦尔通科技有限公司 | A kind of adhesive and preparation method thereof suitable for electronic device |
| CN110776855A (en) * | 2019-10-31 | 2020-02-11 | 华南理工大学 | UV (ultraviolet) photocuring high-transmittance optical adhesive and preparation method thereof |
| CN111073546A (en) * | 2019-12-05 | 2020-04-28 | 江苏晶华新材料科技有限公司 | Optical-grade AB adhesive tape |
| WO2021098299A1 (en) * | 2019-11-19 | 2021-05-27 | 杭州福斯特应用材料股份有限公司 | Adhesive film, anti-pid encapsulation adhesive film, composition forming adhesive film, and photovoltaic module and laminated glass |
-
2021
- 2021-10-14 CN CN202111196212.8A patent/CN113930194A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554151A (en) * | 2018-10-23 | 2019-04-02 | 厦门韦尔通科技有限公司 | A kind of adhesive and preparation method thereof suitable for electronic device |
| CN110776855A (en) * | 2019-10-31 | 2020-02-11 | 华南理工大学 | UV (ultraviolet) photocuring high-transmittance optical adhesive and preparation method thereof |
| WO2021098299A1 (en) * | 2019-11-19 | 2021-05-27 | 杭州福斯特应用材料股份有限公司 | Adhesive film, anti-pid encapsulation adhesive film, composition forming adhesive film, and photovoltaic module and laminated glass |
| CN111073546A (en) * | 2019-12-05 | 2020-04-28 | 江苏晶华新材料科技有限公司 | Optical-grade AB adhesive tape |
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