CN117165230A - Aluminum-plastic composite film hot melt adhesive and preparation method thereof, and aluminum-plastic composite film and preparation method thereof - Google Patents
Aluminum-plastic composite film hot melt adhesive and preparation method thereof, and aluminum-plastic composite film and preparation method thereof Download PDFInfo
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- CN117165230A CN117165230A CN202311144011.2A CN202311144011A CN117165230A CN 117165230 A CN117165230 A CN 117165230A CN 202311144011 A CN202311144011 A CN 202311144011A CN 117165230 A CN117165230 A CN 117165230A
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- Prior art keywords
- aluminum
- composite film
- plastic composite
- hot melt
- melt adhesive
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- 239000002131 composite material Substances 0.000 title claims abstract description 114
- 239000004033 plastic Substances 0.000 title claims abstract description 110
- 229920003023 plastic Polymers 0.000 title claims abstract description 110
- 239000004831 Hot glue Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 94
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000011888 foil Substances 0.000 claims abstract description 89
- 229920001971 elastomer Polymers 0.000 claims abstract description 31
- 239000000806 elastomer Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 26
- -1 polypropylene Polymers 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000004743 Polypropylene Substances 0.000 claims abstract description 20
- 229920001155 polypropylene Polymers 0.000 claims abstract description 20
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 48
- 239000011651 chromium Substances 0.000 claims description 46
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 44
- 229910052804 chromium Inorganic materials 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 32
- 230000001070 adhesive effect Effects 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 28
- 238000005238 degreasing Methods 0.000 claims description 28
- 230000004913 activation Effects 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000002161 passivation Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- 239000004677 Nylon Substances 0.000 claims description 14
- 229920001778 nylon Polymers 0.000 claims description 14
- 238000007731 hot pressing Methods 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 30
- 239000003792 electrolyte Substances 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 238000004026 adhesive bonding Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000003628 erosive effect Effects 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 37
- 238000001035 drying Methods 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000003213 activating effect Effects 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000005025 cast polypropylene Substances 0.000 description 8
- 238000007739 conversion coating Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 244000078856 Prunus padus Species 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 3
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- MNUHUVIZSPCLFF-UHFFFAOYSA-N 1-methylhept-6-ene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)CC(C(O)=O)C(C=C)C(O)=O MNUHUVIZSPCLFF-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 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
- 150000008064 anhydrides Chemical group 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an aluminum-plastic composite film hot melt adhesive and a preparation method thereof, and an aluminum-plastic composite film and a preparation method thereof, belonging to the technical field of composite materials. The invention takes the propenyl elastomer as the main component of the hot melt adhesive, has higher chemical stability and can resist the erosion of hydrofluoric acid in electrolyte; in addition, the propenyl elastomer has lower storage modulus and is easier to spread on the surface of the matrix, so that the prepared hot melt adhesive can build a larger adhesive bonding area with the aluminum foil and is more beneficial to bonding with the aluminum foil; the grafting monomer adopted by the invention has better electron donating ability, can form more coordination chemical bonds with metal oxides on the surface of the aluminum foil, and further can improve the bonding strength of the hot melt adhesive. When the hot melt adhesive provided by the invention is used for preparing the aluminum-plastic composite film, the bonding strength of the aluminum foil and the polypropylene layer can be obviously improved, and the electrolyte corrosion resistance of the aluminum-plastic composite film can be improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to an aluminum-plastic composite film hot melt adhesive and a preparation method thereof, and an aluminum-plastic composite film and a preparation method thereof.
Background
The aluminum-plastic composite film is widely applied to lithium ion battery packaging due to light weight, high plasticity and excellent air and moisture resistance. The aluminum-plastic composite film used in the flexible package lithium ion battery sequentially comprises nylon, an adhesive, aluminum foil, an adhesive and a cast polypropylene (CPP) layer from inside to outside. In the use process of the lithium battery, lithium hexafluorophosphate in the electrolyte can react with water to form hydrofluoric acid, which is highly corrosive acid, can corrode aluminum foil and an adhesive layer, and causes delamination and debonding failure of an aluminum-plastic composite film, so that the electrolyte leaks, and the safety of the lithium ion battery is endangered. Therefore, for the aluminum plastic composite film, the adhesive strength of the adhesive between the CPP and the aluminum foil should be as high as possible.
Whereas the adhesive between the CPP and the aluminum foil developed at present has a problem of low adhesive strength. For example, chinese patent CN 201811617308.5 discloses a novel aluminum-plastic composite film hot melt adhesive and a preparation method thereof, and the adhesive has the advantages of simplicity, low cost, convenient operation, mass production and the like, but has lower adhesive strength. When the adhesive between the CPP and the aluminum foil is low in adhesive strength, electrolyte can be more easily permeated into the aluminum-plastic composite film when the adhesive is used for preparing the aluminum-plastic composite film, so that layering and debonding failure of the aluminum-plastic composite film are caused, and the electrolyte is leaked.
Therefore, it is necessary to develop an aluminum-plastic composite film hot melt adhesive with high adhesive force and electrolyte corrosion resistance.
Disclosure of Invention
The invention aims to provide an aluminum-plastic composite film hot melt adhesive with high adhesive force and electrolyte corrosion resistance, and an aluminum-plastic composite film with electrolyte corrosion resistance is prepared by using the aluminum-plastic composite film hot melt adhesive.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an aluminum-plastic composite film hot melt adhesive which is prepared from the following raw materials in parts by weight:
the grafting monomer comprises one or more of maleic anhydride, maleic acid, itaconic acid, acrylic acid, norbornene anhydride, glycidyl methacrylate and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride.
Preferably, the propylene-based elastomer comprises elsen mobil Vistamaxx6102, elsen mobil Vistamaxx 8380, or elsen mobil Vistamaxx 7020.
Preferably, the initiator comprises one or more of dicumyl peroxide, dibenzoyl peroxide, t-butyl peroxylaurate, t-butyl peroxybenzoate and t-butyl peroxyacetate.
Preferably, the comonomer comprises one or more of styrene, diallyl phthalate and triallyl isocyanurate.
Preferably, the temperature of the melt blending is 100-250 ℃, and the time of the melt blending is 4-12 min.
The invention also provides a preparation method of the aluminum-plastic composite film hot melt adhesive, which comprises the following steps: and (3) carrying out melt blending on the propenyl elastomer, the initiator, the grafting monomer and the comonomer to obtain the aluminum-plastic composite film hot melt adhesive.
The invention provides a preparation method of an aluminum-plastic composite film, which comprises the following steps:
(1) Sequentially carrying out degreasing, acid activation and trivalent chromium chemical conversion on the aluminum foil to obtain a pretreated aluminum foil; the passivation solution for the chemical conversion of trivalent chromium comprises the following components in parts by weight:
(2) Sequentially stacking nylon, an adhesive, the pretreated aluminum foil obtained in the step (1), an aluminum-plastic composite film hot melt adhesive and a polypropylene layer, and then carrying out hot pressing to obtain an aluminum-plastic composite film; the aluminum-plastic composite film hot melt adhesive is prepared by the technical scheme or the preparation method.
Preferably, the agent used for degreasing in the step (1) is an alkaline degreasing solution.
Preferably, the hot pressing temperature in the step (2) is 100-300 ℃, and the hot pressing time is 1-3 min.
The invention also provides the aluminum-plastic composite film prepared by the preparation method of the technical scheme, which comprises a nylon layer, an adhesive layer, an aluminum foil layer, a trivalent chromium conversion film layer, an aluminum-plastic composite film hot melt adhesive layer and a polypropylene layer which are sequentially arranged from bottom to top.
The invention provides an aluminum-plastic composite film hot melt adhesive which is prepared from the following raw materials in parts by weight: 100 parts of propenyl elastomer, 0.1 to 0.4 part of initiator, 5.0 to 8.0 parts of grafting monomer and 5.12 to 7.44 parts of comonomer; the grafting monomer comprises one or more of maleic anhydride, maleic acid, itaconic acid, acrylic acid, norbornene anhydride, glycidyl methacrylate and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride. The invention takes the propenyl elastomer as the main component of the hot melt adhesive, has higher chemical stability and can resist the erosion of hydrofluoric acid in electrolyte; in addition, the propenyl elastomer has lower storage modulus and is easier to spread on the surface of the matrix, so that the prepared hot melt adhesive can build a larger adhesive bonding area with the aluminum foil and is more beneficial to bonding with the aluminum foil; the grafting monomer adopted by the invention has better electronic capability, can form more coordination chemical bonds with metal oxides on the surface of the aluminum foil, and further can improve the bonding strength of the hot melt adhesive. The example results show that the initial tensile force of the aluminum-plastic composite film prepared by the aluminum-plastic composite film hot melt adhesive provided by the invention can reach 24N/15mm, the stripping force can still reach 21N/15mm after the electrolyte is soaked for 5 days, and the aluminum-plastic composite film hot melt adhesive has excellent cohesive force and electrolyte corrosion resistance.
Drawings
FIG. 1 is a schematic structural diagram of an aluminum-plastic composite film provided by the invention; wherein, 1 is nylon layer, 2 is adhesive layer, 3 is aluminium foil layer, 4 is trivalent chromium conversion coating layer, 5 is plastic-aluminum composite film hot melt adhesive layer, 6 is polypropylene layer.
Detailed Description
The invention provides an aluminum-plastic composite film hot melt adhesive which is prepared from the following raw materials in parts by weight:
the grafting monomer comprises one or more of maleic anhydride, maleic acid, itaconic acid, acrylic acid, norbornene anhydride, glycidyl methacrylate and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride.
In the present invention, the reagents used in the present invention are commercially available products well known to those skilled in the art unless specified otherwise.
The raw materials for preparing the aluminum-plastic composite film hot melt adhesive comprise 100 parts of propenyl elastomer according to the parts by weight. In the present invention, the propylene-based elastomer preferably includes exxon mobil Vistamaxx6102, exxon mobil Vistamaxx 8380, or exxon mobil Vistamaxx 7020, more preferably Vistamaxx 6102. In the invention, the propenyl elastomer has lower storage modulus and is easier to spread on the surface of the matrix, so that the prepared hot melt adhesive can build a larger adhesive bonding area with the aluminum foil and is more beneficial to bonding with the aluminum foil; the propenyl elastomer has excellent chemical stability and can resist the erosion of hydrofluoric acid in electrolyte; when the propylene-based elastomer is of the type, the ethylene-propylene random copolymer is small in ethylene side group and high in molecular chain flexibility, the chemical structure of the propylene-based elastomer is similar to that of the CPP, and in the hot pressing process, the molecular chain can be mutually diffused with the molecular chain of the CPP, so that the adhesion force between the propylene-based elastomer and the CPP is increased.
The raw materials for preparing the aluminum-plastic composite film hot melt adhesive comprise 0.1-0.4 part of initiator, preferably 0.2-0.3 part of initiator, based on 100 parts by weight of propenyl elastomer. In the present invention, the initiator preferably includes one or more of dicumyl peroxide, dibenzoyl peroxide, t-butyl peroxylaurate, t-butyl peroxybenzoate and t-butyl peroxyacetate, and more preferably dicumyl peroxide. In the present invention, the initiator is capable of initiating a polymerization reaction.
The raw materials for preparing the aluminum-plastic composite film hot melt adhesive comprise 5.0-8.0 parts of grafting monomer, preferably 6-7 parts, based on 100 parts by mass of the propenyl elastomer. In the present invention, the grafting monomer includes one or more of maleic anhydride, maleic acid, itaconic acid, acrylic acid, norbornene anhydride, glycidyl methacrylate and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, preferably bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride. In the invention, when the grafting monomer is of the type, the grafting monomer has better electronic capability, and can form more coordination chemical bonds with metal oxides on the surface of the aluminum foil, so that the bonding strength of the hot melt adhesive can be further improved.
The raw materials for preparing the aluminum-plastic composite film hot melt adhesive comprise 5.12-7.44 parts of comonomer, preferably 6-7 parts, based on 100 parts by weight of the propenyl elastomer. In the present invention, the comonomer preferably includes one or more of styrene, diallyl phthalate and triallyl isocyanurate, and more preferably styrene. In the present invention, the co-monomer functions to increase the grafting ratio of the graft monomer to the propylene-based elastomer molecular chain, and when the co-monomer is of the above-described type, it is more advantageous to increase the grafting ratio of the graft monomer to the propylene-based elastomer molecular chain.
The invention takes the propenyl elastomer as the main component of the hot melt adhesive, has higher chemical stability and can resist the erosion of hydrofluoric acid in electrolyte; in addition, the propenyl elastomer has lower storage modulus and is easier to spread on the surface of the matrix, so that the prepared hot melt adhesive can build a larger adhesive bonding area with the aluminum foil and is more beneficial to bonding with the aluminum foil; the grafting monomer adopted by the invention has better electronic capability, can form more coordination chemical bonds with metal oxides on the surface of the aluminum foil, and further can improve the bonding strength of the hot melt adhesive.
The invention also provides a preparation method of the aluminum-plastic composite film hot melt adhesive, which comprises the following steps: and (3) carrying out melt blending on the propenyl elastomer, the initiator, the grafting monomer and the comonomer to obtain the aluminum-plastic composite film hot melt adhesive.
In the present invention, the temperature of the melt blending is preferably 100 to 250 ℃, more preferably 180 ℃; the time for melt blending is preferably 4 to 12 minutes, more preferably 8 minutes. In the present invention, when the temperature and time of the melt blending are within the above ranges, the propylene-based elastomer, the initiator, the graft monomer and the comonomer can be sufficiently melted and polymerization can be caused. The apparatus for melt blending is not particularly limited, and may be any apparatus known to those skilled in the art. In the present invention, the melt blending device is preferably a haak torque rheometer. The rotating speed of the Hark torque rheometer is not particularly limited, and the Hark torque rheometer can be adjusted according to the melting effect. In the present invention, the rotational speed of the haak torque rheometer is preferably 60r/min.
After the melt blending is finished, the product obtained after the melt blending is preferably cooled to room temperature and then purified to obtain the aluminum-plastic composite film hot melt adhesive.
The method of operation of the purification is not particularly limited, and purification methods well known to those skilled in the art may be employed. In the invention, the purification is preferably to dissolve the product cooled to room temperature in dimethylbenzene, then add acetone, place the precipitate in the acetone for soxhlet extraction, and then dry to obtain the aluminum-plastic composite film hot melt adhesive. The dosage of the dimethylbenzene and the acetone is not particularly limited, and the dosage is adjusted according to the needs; the method for operating the cable-type extraction and drying is not particularly limited, and the method for operating the cable-type extraction and drying, which is well known to those skilled in the art, can be adopted.
The invention also provides a preparation method of the aluminum-plastic composite film, which comprises the following steps:
(1) Sequentially carrying out degreasing, acid activation and trivalent chromium chemical conversion on the aluminum foil to obtain a pretreated aluminum foil; the passivation solution for the chemical conversion of trivalent chromium comprises the following components in parts by weight:
(2) And (3) sequentially stacking nylon, an adhesive, the pretreated aluminum foil obtained in the step (1), the aluminum-plastic composite film hot melt adhesive and the polypropylene layer, and then carrying out hot pressing to obtain the aluminum-plastic composite film.
The method sequentially carries out degreasing, acid activation and trivalent chromium chemical conversion on the aluminum foil to obtain the pretreated aluminum foil.
The source and thickness of the aluminum foil are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the agent used for degreasing is preferably an alkaline degreasing liquid. In the invention, the alkaline washing degreasing fluid is preferably prepared from water and one or more of sodium hydroxide, sodium carbonate, sodium silicate, sodium fluoride and sodium hypophosphite. The concentration of the alkaline degreasing liquid is not particularly limited, and the concentration of the alkaline degreasing liquid can be adjusted according to the needs, so that grease on the surface of the aluminum foil can be fully dissolved. In the present invention, the alkaline degreasing solution can remove grease from the surface of the aluminum foil, and when the alkaline degreasing solution has the above composition, grease from the surface of the aluminum foil can be sufficiently removed.
In the present invention, the degreasing method is preferably to dip the aluminum foil in an alkaline degreasing solution. In the present invention, the temperature for degreasing is preferably room temperature, and the time for degreasing is preferably 0.5 to 3min, more preferably 1min. In the present invention, the oil removal temperature and time are within the above ranges, so that the grease on the surface of the aluminum foil can be sufficiently dissolved.
The aluminum foil subjected to oil removal is preferably washed and dried sequentially. In the present invention, the washing and drying can remove the alkaline washing degreasing liquid. The number of times of cleaning and the drying temperature are not particularly limited, and conventional adjustment is adopted, so that alkaline cleaning degreasing liquid can be sufficiently removed, and the surface of the aluminum foil can be dried. In the present invention, the reagent used for the washing is preferably water, and the drying temperature is preferably 50 ℃.
In the present invention, the acid activation method is preferably: and immersing the dried aluminum foil obtained after degreasing in an acidic activating solution. In the present invention, the acidic activating solution used for the acid activation is preferably an aqueous solution of one or more of hydrofluoric acid, phosphoric acid and hydrochloric acid, more preferably an aqueous hydrofluoric acid solution. In the present invention, the acidic activating solution is capable of dissolving aluminum oxide or aluminum hydroxide on the surface of the aluminum foil, thereby exposing aluminum intermetallic compounds on the surface of the aluminum foil, and the aluminum foil subjected to the acid activation treatment is easier to deposit a trivalent chromium conversion coating than the aluminum foil not subjected to the acid activation treatment.
In the present invention, the concentration of the acidic activating solution is preferably 10 to 50mg/mL, more preferably 12.27 to 30mg/mL. In the present invention, when the concentration of the acidic activating solution is in the above range, alumina or aluminum hydroxide on the surface of the aluminum foil can be sufficiently dissolved.
In the present invention, the temperature of the acid activation is preferably room temperature, and the time of the acid activation is preferably 1 to 3 minutes. In the present invention, when the temperature and time of the acid activation are within the above ranges, aluminum oxide or aluminum hydroxide on the surface of the aluminum foil can be sufficiently dissolved.
The present invention preferably sequentially cleans and dries the acid-activated aluminum foil. In the present invention, the washing and drying can remove the acid-activated liquid. The number of times of the cleaning and the drying temperature are not particularly limited, and the conventional adjustment is adopted, so that the acid activating solution can be sufficiently removed and the surface of the aluminum foil can be dried. In the present invention, the reagent used for the washing is preferably water, and the drying temperature is preferably 50 ℃.
In the present invention, the method of chemical conversion of trivalent chromium is preferably to impregnate a dried aluminum foil obtained after acid activation in a passivation solution. In the present invention, the temperature of the chemical conversion of trivalent chromium is preferably 20 to 30 ℃, and the time of the chemical conversion of trivalent chromium is preferably 0.5 to 4 minutes, more preferably 2 minutes. In the present invention, the trivalent chromium conversion can form a trivalent chromium conversion film on the surface of the aluminum foil.
In the invention, the passivation solution comprises 250 parts of water in parts by weight. In the present invention, the water serves as a solvent for the passivation solution.
In the present invention, the passivation solution includes 2.0 to 7.0 parts, preferably 3.0 to 5.0 parts of a trivalent chromium compound, based on 250 parts by weight of water. In the present invention, the trivalent chromium compound preferably includes one or more of chromium chloride hexahydrate, chromium sulfate, and chromium nitrate, more preferably chromium chloride hexahydrate. In the invention, the trivalent chromium compound is a film-forming main salt of the trivalent chromium conversion film, and when the trivalent chromium compound is of the above type, formation of the trivalent chromium conversion film is facilitated.
In the present invention, the passivation solution includes 0.2 to 1.0 parts, preferably 0.5 to 0.8 parts of fluoride, based on 250 parts by mass of water. In the present invention, the fluoride preferably includes one or more of sodium fluoride, ammonium fluoride, and ammonium bifluoride, and more preferably sodium fluoride. In the present invention, the fluoride is capable of promoting the chemical conversion of trivalent chromium, and when the fluoride is of the above type, the formation of a trivalent chromium conversion film is more favored.
In the invention, the passivation solution comprises 0.2 to 1.0 parts, preferably 0.5 to 0.8 parts of ferricyanide based on 250 parts by weight of water. In the present invention, the ferricyanide is preferably potassium ferricyanide and/or sodium ferricyanide, more preferably potassium ferricyanide. In the present invention, the ferricyanide acts as a film-forming aid, shortening the time for the trivalent chromium conversion film to form on the surface of the aluminum foil, and when the ferricyanide is of the above type, the time for the trivalent chromium conversion film to form on the surface of the aluminum foil can be further shortened.
In the present invention, the passivation solution comprises 1.0 to 3.0 parts, preferably 2.0 to 3.0 parts of acid based on 250 parts by mass of water. In the present invention, the acid preferably includes one or more of hydrochloric acid, nitric acid, phosphoric acid and hydrofluoric acid, and more preferably phosphoric acid. The concentration of the acid is not particularly limited and may be adjusted as needed. In the invention, the acid is used for constructing an acidic environment to enable the surface of the aluminum foil to generate hydrogen evolution oxygen absorption corrosion, so that the oxide and hydroxide of trivalent chromium are deposited on the surface of the aluminum foil. In the invention, when the acid is phosphoric acid, hydroxyl groups in the phosphoric acid can react with hydroxyl groups on the surface of the aluminum foil to generate Al-O-P bonds, and can also react with metal ions Cr 3+ And the trivalent chromium conversion coating and the aluminum foil are firmly combined together by combining to generate a P-O-Cr bond.
In the invention, when the passivation solution is the components, a layer of compact trivalent chromium conversion film can be formed on the surface of the aluminum foil, so that the electrolyte corrosion resistance of the aluminum foil is improved; meanwhile, oxide and hydroxide of trivalent chromium in the conversion coating can interact with oxygen-containing functional groups of the inner layer hot melt adhesive in the modes of ionic bond, coordination bond and the like, so that the adhesive force of the aluminum foil is improved.
The invention preferably carries out cleaning and drying on the aluminum foil after the trivalent chromium chemical conversion in sequence to obtain the pretreated aluminum foil. In the present invention, the washing and drying can remove the passivation solution. The method is not particularly limited in the number of times of cleaning and the drying temperature, and the conventional adjustment is adopted, so that the passivation solution can be sufficiently removed and the surface of the aluminum foil can be dried. In the present invention, the reagent used for the washing is preferably water, and the drying temperature is preferably 50 ℃.
After the pretreated aluminum foil is obtained, nylon, an adhesive, the pretreated aluminum foil, an aluminum-plastic composite film hot melt adhesive and a polypropylene layer are sequentially stacked, and then hot pressing is carried out to obtain the aluminum-plastic composite film.
The thickness of nylon is not particularly limited, and commercially available products known to those skilled in the art may be used.
The kind of the adhesive is not particularly limited in the present invention, and an adhesive well known to those skilled in the art may be used. In the present invention, the adhesive is preferably an isocyanate-cured polyurethane-based adhesive. The amount of the adhesive is not particularly limited, and the nylon layer and the aluminum foil can be bonded by adjusting the amount according to the need.
In the invention, the aluminum-plastic composite film hot melt adhesive is the aluminum-plastic composite film hot melt adhesive according to the technical scheme or the aluminum-plastic composite film hot melt adhesive obtained by the preparation method according to the technical scheme.
The usage amount of the aluminum-plastic composite film hot melt adhesive is not particularly limited, and the aluminum foil and the polypropylene layer can be bonded by adjusting according to the needs.
The source of the polypropylene is not particularly limited and commercially available products known to those skilled in the art may be used. The thickness of the polypropylene layer is not particularly limited, and the polypropylene layer may be adjusted as needed.
In the present invention, the temperature of the hot pressing is preferably 100 to 300 ℃, more preferably 180 ℃; the time of the hot pressing is preferably 1 to 3 minutes, more preferably 2 minutes. In the invention, when the temperature and time of the hot pressing are in the above ranges, the aluminum-plastic composite film hot melt adhesive can be sufficiently melted, and the aluminum foil and the polypropylene layer can be sufficiently bonded.
The oil on the surface of the aluminum foil is removed through oil removal; according to the invention, aluminum oxide or aluminum hydroxide on the surface of the aluminum foil is dissolved through acid activation, and as a small amount of iron is contained in the aluminum foil, an aluminum-iron compound on the surface of the aluminum foil can be exposed through acid activation, and a micro primary cell system is formed by the aluminum-iron compound and surrounding aluminum base in the trivalent chromium chemical conversion process, so that the deposition of trivalent chromium inorganic salt at the aluminum-iron compound is promoted; the passivation solution adopted by the invention adopts nontoxic trivalent chromium to replace the conventional toxic hexavalent chromium, and a compact trivalent chromium conversion film is formed on the surface of the aluminum foil through trivalent chromium chemical conversion, so that the electrolyte corrosion resistance of the aluminum foil is improved; according to the invention, the nylon, the adhesive, the pretreated aluminum foil, the aluminum-plastic composite film hot melt adhesive and the polypropylene layer are subjected to hot pressing to form the aluminum-plastic composite film, so that the electrolyte corrosion resistance of the aluminum-plastic composite film can be improved.
The invention also provides the aluminum-plastic composite film obtained by the preparation method according to the technical scheme, which comprises a nylon layer, an adhesive layer, an aluminum foil layer, a trivalent chromium conversion film layer, an aluminum-plastic composite film hot melt adhesive layer and a polypropylene layer which are sequentially arranged from bottom to top.
The structure of the aluminum-plastic composite film provided by the invention is shown in figure 1, and the aluminum-plastic composite film consists of a nylon layer 1, an adhesive layer 2, an aluminum foil layer 3, a trivalent chromium conversion film layer 4, an aluminum-plastic composite film hot melt adhesive layer 5 and a polypropylene layer 6 which are sequentially arranged from bottom to top.
In the invention, the trivalent chromium conversion film layer is formed in the pretreatment of the aluminum foil layer, so that the trivalent chromium conversion film layer is included in the aluminum-plastic composite film, and the existence of the trivalent chromium conversion film layer can not only improve the electrolyte corrosion resistance of the aluminum-plastic composite film, but also improve the adhesive strength of the aluminum foil layer and the polypropylene layer. According to the aluminum-plastic composite film provided by the invention, as the hot melt adhesive layer of the aluminum-plastic composite film is used as an adhesive, the adhesive strength of the aluminum foil and the polypropylene layer can be obviously improved, and the aluminum-plastic composite film can have excellent electrolyte corrosion resistance.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An aluminum-plastic composite film hot melt adhesive comprises the following raw materials:
propylene-based elastomer: vistamaxx 610250g (100 parts); and (3) an initiator: dicumyl peroxide 0.2g (0.4 part); grafting monomers: maleic anhydride 3g (6 parts); co-monomer: styrene 3.72g (7.44 parts).
The preparation method of the aluminum-plastic composite film hot melt adhesive comprises the following steps: adding the propenyl elastomer, the initiator, the grafting monomer and the comonomer into a torque rheometer at 180 ℃ for melt blending, wherein the rotating speed is 60r/min, the mixing time is 8min, cooling the obtained product to room temperature, dissolving in dimethylbenzene, then adding acetone, placing the precipitate into the acetone for soxhlet extraction, and then drying to obtain the aluminum-plastic composite film hot melt adhesive.
Example 2
The preparation method of the aluminum-plastic composite film comprises the following steps:
(1) Immersing the aluminum foil in alkaline washing degreasing fluid for 1min, degreasing, taking out, washing with water, and drying in a drying oven at 50 ℃; then immersing the dried aluminum foil in an acidic activating solution for 2min, performing acid activation, removing water, cleaning, and drying in a drying oven at 50 ℃; immersing the dried aluminum foil in passivation solution for 2min, taking out, washing with water, and drying in a drying oven at 50 ℃ to obtain pretreated aluminum foil;
the preparation method of the alkaline washing degreasing fluid comprises the following steps: dissolving 4g of sodium hydroxide, 2.5g of sodium carbonate and 2.5g of sodium silicate in water to constant volume to 250mL to obtain alkaline washing degreasing fluid;
the acidic activating solution comprises the following components: hydrofluoric acid aqueous solution with concentration of 12.27 mg/mL;
the passivation solution comprises the following components: chromium chloride hexahydrate 2.98g (2.98 parts), sodium fluoride 0.5g (0.5 parts), potassium ferricyanide 0.75g (0.75 parts), phosphoric acid 1.0g (1.0 parts), and water 250mL (250 parts);
(2) And (3) sequentially stacking nylon, an adhesive, the pretreated aluminum foil obtained in the step (1), the aluminum-plastic composite film hot melt adhesive and a polypropylene layer, and then carrying out hot pressing at 180 ℃ to obtain the aluminum-plastic composite film.
Example 3
An aluminum-plastic composite film hot melt adhesive comprises the following raw materials:
propylene-based elastomer: vistamaxx 610250g (100 parts); and (3) an initiator: dicumyl peroxide 0.2g (0.4 part); grafting monomers: 3g (6 parts) of bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride; co-monomer: styrene 2.56g (5.12 parts).
The preparation method of the aluminum-plastic composite film hot melt adhesive comprises the following steps: adding the propenyl elastomer, the initiator, the grafting monomer and the comonomer into a torque rheometer at 180 ℃ for melt blending, wherein the rotating speed is 60r/min, the mixing time is 8min, cooling the obtained product to room temperature, dissolving in dimethylbenzene, then adding acetone, placing the precipitate into the acetone for soxhlet extraction, and then drying to obtain the aluminum-plastic composite film hot melt adhesive.
Example 4
The difference from example 2 is that the aluminum-plastic composite film hot melt adhesive used in step (2) is the aluminum-plastic composite film hot melt adhesive prepared in example 3, and the remaining steps are the same as in example 2.
Example 5
The difference from example 2 is that the acidic activation solution used in step (1) is an aqueous hydrofluoric acid solution having a concentration of 28.8 mg/mL; the remaining steps were the same as in example 2.
Example 6
Step (1) was consistent with example 5; step (2) was consistent with example 4; the remaining steps were the same as in example 2.
Example 7
Step (1) is different from example 2 in that the time of immersion in the acidic activating solution is 4min; step (2) was consistent with example 2; the remaining steps were the same as in example 2.
Example 8
The difference from example 7 is that the aluminum-plastic composite film hot melt adhesive used in step (2) is the aluminum-plastic composite film hot melt adhesive prepared in example 3; the remaining steps were the same as in example 7.
Example 9
The difference from example 2 is that the acidic activating solution used in step (1) is: hydrochloric acid solution with concentration of 30 mg/mL; the remaining steps were the same as in example 2.
Example 10
The difference from example 9 is that the aluminum-plastic composite film hot melt adhesive used in the step (2) is the aluminum-plastic composite film hot melt adhesive prepared in example 3; the remaining steps were the same as in example 8.
Comparative example 1
The difference from example 2 is that the trivalent chromium conversion treatment was directly carried out in step (1) without acid washing activation after degreasing, and the rest of the steps were the same as in example 2.
Comparative example 2
The difference from example 4 is that the trivalent chromium conversion treatment was directly carried out in step (1) without acid washing activation after degreasing, and the rest of the steps were the same as in example 4.
Comparative example 3
The difference from example 5 is that the aluminum plastic composite film hot melt adhesive used in the step (2) is a commercial SAG A material, and the rest steps are the same as example 5.
Comparative example 4
The difference from example 5 is that the aluminum-plastic composite film hot melt adhesive used in step (2) is commercially available Dupont 739, and the remaining steps are the same as in example 5.
Comparative example 5
The difference from example 5 is that the aluminum-plastic composite film hot melt adhesive used in step (2) is commercially available Dupont 739, and the remaining steps are the same as in example 5.
Test case
In order to test the adhesive force of the aluminum-plastic composite film hot melt adhesive prepared by the invention, the aluminum-plastic composite film semi-finished products prepared by the invention examples 2, 4-10 and the comparative examples 1 and 2 are cut into 15mm wide strips, soaked in electrolyte at 85 ℃, subjected to stripping test according to GB/T8808-1988, and tested for residual adhesive force after the aluminum-plastic film is soaked in the electrolyte, wherein the stripping speed is 300 mm/min. The test results are shown in Table 1.
TABLE 1T-Peel test results between aluminum foil and inner layer adhesive for different aluminum-plastic composite film semi-finished products
As can be seen from Table 1, the bond strength of oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride modified propylene-based elastomers is generally higher than that of maleic anhydride modified propylene-based elastomers because oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride contains two anhydride groups, which have better electron donating ability than maleic anhydride and can form more coordination chemical bonds with metal oxides on the aluminum foil surface.
As is clear from comparison of examples 2 and 5, and examples 4 and 6, increasing the concentration of hydrofluoric acid in the acid-washing activating solution at a constant pretreatment time can effectively improve the adhesion strength of the trivalent chromium conversion coating and the electrolyte resistance.
As is clear from comparison of examples 5 and 7, examples 6 and 8, increasing the acid-washing activation time of hydrofluoric acid at a constant concentration of hydrofluoric acid in the acid-washing activation liquid can also effectively improve the adhesion strength and electrolyte resistance of the trivalent chromium conversion coating.
As is clear from comparison of examples 5 and 9, examples 6 and 10, the adhesion strength of the trivalent chromium conversion coating after the hydrofluoric acid pretreatment was higher than that after the hydrochloric acid pretreatment when the concentration of the acid in the acid-washing activating solution was constant for a certain pretreatment time.
As is clear from comparative examples 1 and 2, the trivalent chromium conversion film that was not subjected to the acid washing activation treatment had little electrolyte resistance.
When the concentration of hydrofluoric acid is 28.8mg/mL and the pickling activation time is 4min, the adhesion strength of the trivalent chromium conversion coating is optimal. The electrolyte resistance of examples 4-8 and 10 is higher than the standard that the peel strength between aluminum foil and CPP is more than 12N/15mm after the electrolyte specified in the aluminum-plastic film industry is soaked for 1 day. After 5 days of electrolyte soaking, the adhesion of examples 6 to 8 was not greatly reduced.
From the data, the aluminum-plastic composite film hot melt adhesive provided by the invention can obviously improve the adhesive strength between the aluminum foil and the polypropylene layer and can improve the electrolyte corrosion resistance. Therefore, when the polymer composite film is used for preparing the aluminum-plastic composite film, the aluminum-plastic composite film can be endowed with better electrolyte corrosion resistance. In addition, after the aluminum-plastic composite film hot melt adhesive provided by the invention is used, the corrosion resistance of the aluminum-plastic composite film can be further improved through pretreatment of the aluminum foil.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The aluminum-plastic composite film hot melt adhesive is prepared from the following raw materials in parts by weight:
the grafting monomer comprises one or more of maleic anhydride, maleic acid, itaconic acid, acrylic acid, norbornene anhydride, glycidyl methacrylate and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride.
2. The aluminum-plastic composite film hot melt adhesive of claim 1, wherein the propylene-based elastomer comprises elkson mobil Vistamaxx6102, elkson mobil Vistamaxx 8380, or elkson mobil Vistamaxx 7020.
3. The aluminum-plastic composite film hot melt adhesive according to claim 1, wherein the initiator comprises one or more of dicumyl peroxide, dibenzoyl peroxide, t-butyl peroxylaurate, t-butyl peroxybenzoate and t-butyl peroxyacetate.
4. The aluminum-plastic composite film hot melt adhesive of claim 1, wherein the comonomer comprises one or more of styrene, diallyl phthalate, and triallyl isocyanurate.
5. The method for preparing the aluminum-plastic composite film hot melt adhesive according to any one of claims 1 to 4, comprising the following steps: and (3) carrying out melt blending on the propenyl elastomer, the initiator, the grafting monomer and the comonomer to obtain the aluminum-plastic composite film hot melt adhesive.
6. The method for preparing the aluminum-plastic composite film hot melt adhesive according to claim 5, wherein the temperature of melt blending is 100-250 ℃; the time of melt blending is 4-12 min.
7. The preparation method of the aluminum-plastic composite film comprises the following steps:
(1) Sequentially carrying out degreasing, acid activation and trivalent chromium chemical conversion on the aluminum foil to obtain a pretreated aluminum foil; the passivation solution for the chemical conversion of trivalent chromium comprises the following components in parts by weight:
(2) Sequentially stacking nylon, an adhesive, the pretreated aluminum foil obtained in the step (1), an aluminum-plastic composite film hot melt adhesive and a polypropylene layer, and then carrying out hot pressing to obtain an aluminum-plastic composite film; the aluminum-plastic composite film hot melt adhesive is prepared by the aluminum-plastic composite film hot melt adhesive according to any one of claims 1 to 4 or the preparation method according to any one of claims 5 to 6.
8. The method of producing an aluminum-plastic composite film according to claim 7, wherein the agent used for degreasing in the step (1) is an alkaline degreasing solution.
9. The method of producing an aluminum plastic composite film according to claim 7, wherein the hot pressing in the step (2) is performed at a temperature of 100 to 300 ℃ for 1 to 3 minutes.
10. The aluminum-plastic composite film prepared by the preparation method of any one of claims 7 to 9, which comprises a nylon layer, an adhesive layer, an aluminum foil layer, a trivalent chromium conversion film layer, an aluminum-plastic composite film hot melt adhesive layer and a polypropylene layer which are sequentially arranged from bottom to top.
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2023
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