CN117535021A - Electrolyte-resistant acrylate adhesive and preparation method and application thereof - Google Patents
Electrolyte-resistant acrylate adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN117535021A CN117535021A CN202311556916.0A CN202311556916A CN117535021A CN 117535021 A CN117535021 A CN 117535021A CN 202311556916 A CN202311556916 A CN 202311556916A CN 117535021 A CN117535021 A CN 117535021A
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- Prior art keywords
- acrylate
- parts
- electrolyte
- adhesive
- monomer
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000000853 adhesive Substances 0.000 title claims abstract description 73
- 239000003792 electrolyte Substances 0.000 title claims abstract description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 133
- 238000004132 cross linking Methods 0.000 claims abstract description 32
- -1 acrylic ester Chemical class 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 239000002390 adhesive tape Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000002994 raw material Substances 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 15
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 15
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003522 acrylic cement Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 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 7
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- YEQBHMVRNHTCPJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;3-oxobutanoic acid Chemical compound CC(=C)C(O)=O.CC(=O)CC(O)=O YEQBHMVRNHTCPJ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical group [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- WBZPMFHFKXZDRZ-UHFFFAOYSA-N ethenyl 6,6-dimethylheptanoate Chemical compound CC(C)(C)CCCCC(=O)OC=C WBZPMFHFKXZDRZ-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011888 foil Substances 0.000 abstract description 5
- 238000009413 insulation Methods 0.000 abstract description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000532 dioxanyl group Chemical group 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 12
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 7
- 150000004292 cyclic ethers Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920006395 saturated elastomer Chemical group 0.000 description 4
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FZHFLPZIOJBRGW-UHFFFAOYSA-N 3-(oxolan-2-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1CCCO1 FZHFLPZIOJBRGW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an electrolyte-resistant acrylic ester adhesive, and a preparation method and application thereof, and belongs to the technical field of adhesives. The electrolyte-resistant acrylate adhesive comprises, by mass, 30-40 parts of soft monomers, 5-10 parts of hard monomers, 3-8 parts of crosslinking monomers, 1-5 parts of oxygen-containing heterocyclic vinyl monomers, 0.2-0.5 part of initiators and 40-60 parts of organic solvents. The oxygen-containing heterocyclic vinyl monomer is selected from vinyl monomers containing one or more of epoxy group, dioxane group and tetrahydrofuran group. The electrolyte-resistant acrylic ester adhesive is matched with a curing agent, color paste and the like to prepare a termination adhesive tape, is adhered to an aluminum foil and is immersed in LiPF 6 In the electrolyte, the electrolyte resistance can be kept to be qualified for more than 4 hours in an environment of 85 ℃; the adhesive is stuck on an SUS plate and placed in the environment of 130 ℃, and can be kept to be peeled off for 30 minutes without adhesive residue; and has excellent insulating property, and can achieve leakage current<2mA, insulation resistance>1G omega, can be applied to the lithium battery and terminate the sticky tape field.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an electrolyte-resistant acrylic ester adhesive, and a preparation method and application thereof.
Background
Currently, with the rapid popularization of new energy automobiles and the continuous expansion of the scale of the power battery industry, the demand of lithium batteries is greatly increased, and the adhesive tape applied to the lithium battery industry has huge demand. In the PACK process of the lithium battery, one process is to wind the positive electrode plate, the diaphragm and the negative electrode plate into a battery core and then inject electrolyte, and the process needs to use an electrolyte-resistant termination adhesive tape for termination insulation fixation of lug positions and winding positions of the lithium battery such as a cylindrical shape or a square shape, thereby playing roles in termination and puncture prevention.
At present, most of the stopping adhesive tapes on the market are of acrylic ester systems, on one hand, acrylic ester adhesives are attached to metal plates, and the problem of adhesive residue easily occurs when the adhesive tapes are peeled at high temperature; on the other hand, the acrylate adhesive is soaked in electrolyte, so that the viscosity is easy to lose, cohesive failure such as residual glue is generated, a metal belt of the battery cannot be effectively fixed, the battery is short-circuited, and the service life of the battery is shortened. Therefore, a special electrolyte-resistant acrylate adhesive needs to be developed to meet the requirements of an acrylate system for stopping the electrolyte resistance and the high temperature resistance of the adhesive tape.
Disclosure of Invention
In order to solve the technical problems, the invention provides an electrolyte-resistant acrylic ester adhesive, and a preparation method and application thereof.
The first object of the invention is to provide an electrolyte-resistant acrylate adhesive, which comprises, by mass, 30-40 parts of soft monomer, 5-10 parts of hard monomer, 3-8 parts of crosslinking monomer, 1-5 parts of oxygen-containing heterocycle vinyl monomer, 0.2-0.5 part of initiator and 40-60 parts of organic solvent.
In one embodiment of the present invention, the oxygen-containing heterocyclic vinyl monomer is selected from one or more of epoxy group, dioxane group and tetrahydrofuran group-containing vinyl monomers. The vinyl monomer containing saturated oxygen heterocycle belongs to cyclic ether substances with strong polarity, has strong adhesive force to most of base materials, especially to base materials such as metal, plastic and the like, and has poor solubility in organic solvents with low polarity. Compared with vinyl monomer containing aromatic ring, the vinyl monomer is easily oxidized into a quinone structure by complex factors such as acid, oxidant, light, heat and the like in the environment at the methyl substituted by the aromatic ring, so that pi-pi conjugated bond is formed. The vinyl monomer containing saturated oxygen heterocycle has stable chemical property, is not easy to oxidize, and has better acid and alkali resistance and water resistance.
LiPF 6 The electrolyte of the system mainly comprises ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, lithium hexafluorophosphate, phosphorus pentafluoride and hydrofluoric acid. The electrolyte-resistant acrylic acid ester adhesive disclosed by the invention adopts an oxygen-containing heterocyclic vinyl monomer to react with an acrylic acid monomer to form a block acrylic acid ester polymer, so that a strong-polarity cyclic ether group and a saturated ring structure are introduced into a polymer molecular chain. On one hand, the block structure design can provide good viscoelasticity and ion conductivity, and the carbonyl side group of the main chain midblock has stronger interaction with the carbonic ester solvent in the electrolyte to provide an ion conducting channel. On the other hand, the vinyl monomer containing saturated oxygen heterocycle has better mechanical strength and can provide mechanical support. The strong polar cyclic ether group can reduce the solubility of the acrylate adhesive in an organic solvent, is beneficial to improving the bonding strength and prolonging the electrolyte-resistant time; the saturated ring structure can increase the steric hindrance between molecules, enhance the thermal stability and facilitate the promotion of the acrylate adhesive at high temperatureThe adhesive property is very suitable for LiPF resistance 6 Electrolyte of the system.
In one embodiment of the present invention, the soft monomer is selected from one or more of isooctyl acrylate, n-octyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, vinyl neodecanoate, lauryl acrylate, and stearyl acrylate.
Further, the soft monomer is selected from one or more of isooctyl acrylate, ethyl acrylate, n-butyl acrylate, vinyl neodecanoate and stearyl acrylate.
In one embodiment of the present invention, the hard monomer is selected from one or more of vinyl acetate, styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl neononanoate, and isobornyl methacrylate.
Further, the hard monomer is selected from one or more of vinyl acetate, styrene, methyl methacrylate and isobornyl methacrylate.
In one embodiment of the present invention, the crosslinking monomer is selected from one or more of hydroxypropyl acrylate, acrylamide, methylolacrylamide, diacetone acrylamide, acetoacetate methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate, acrylic acid, and methacrylic acid.
Further, the crosslinking monomer is selected from one or more of hydroxypropyl acrylate, methylolacrylamide, 2-hydroxypropyl methacrylate, acrylic acid and methacrylic acid.
In one embodiment of the invention, the initiator is selected from acyl peroxides and/or azo compounds.
Further, the acyl peroxide is selected from benzoyl peroxide and/or lauroyl peroxide.
Further, the azo compound is selected from azobisisobutyronitrile.
In one embodiment of the present invention, the organic solvent is selected from one or more of ethyl acetate, toluene, butanone, and methyl acetate.
In one embodiment of the invention, the electrolyte resistant acrylate adhesive has a solids content of 40% -50%, a rotational viscosity of 1000cps-3000cps and a glass transition temperature of-35 ℃ to-45 ℃.
Further, the solid content of the electrolyte-resistant acrylate adhesive is 45% -48%, the rotational viscosity is 1500cps-2500cps, and the glass transition temperature is-38 ℃ to-43 ℃.
The second object of the invention is to provide a preparation method of the electrolyte-resistant acrylic ester adhesive, which comprises the following steps,
s1, uniformly stirring a soft monomer, a hard monomer, a crosslinking monomer and an organic solvent in an inert atmosphere, adding 1/4-1/2 amount of an initiator, and reacting at 76-80 ℃ for 1-2 h to obtain a first reaction solution;
s2, adding an oxygen-containing heterocyclic vinyl monomer and 1/4-1/2 amount of initiator into the first reaction solution in the S1, and reacting for 2-3 hours at the temperature of 80-83 ℃ to obtain a second reaction solution;
s3, adding the rest initiator into the second reaction solution in the step S2, and reacting for 1-2 hours at 83-86 ℃ to obtain the electrolyte-resistant acrylate adhesive.
In one embodiment of the present invention, in S1, the temperature of the stirring is 70 ℃ to 75 ℃ for 30min to 40min.
In one embodiment of the invention, the initiator is added in 3 portions, the reaction temperature is increased stepwise from 76 ℃ to 86 ℃.
The third object of the invention is to provide a termination adhesive tape, which comprises a release film layer, an acrylic adhesive layer and a substrate layer which are sequentially laminated, wherein the preparation raw materials of the acrylic adhesive layer comprise the acrylic adhesive.
In one embodiment of the present invention, the raw materials for preparing the acrylate adhesive layer further include a curing agent, color paste and a solvent.
In one embodiment of the invention, the mass ratio of the acrylate adhesive to the curing agent to the color paste to the solvent is 100:0.8-1.2:4-8:20-40.
Further, the mass ratio of the acrylic adhesive to the curing agent to the color paste to the solvent is 100:0.9-1.1:5-6:25-35.
In one embodiment of the present invention, the curing agent is selected from one or more of epoxy resin curing agents, amino resin curing agents and isocyanate curing agents; the color paste is selected from phthalocyanine blue color paste; the solvent is selected from one or more of ethyl acetate and methyl acetate.
In one embodiment of the invention, the material of the substrate layer is PET, and the PET has excellent physical and mechanical properties in a wider temperature range, the service temperature can reach 120 ℃, the electrical insulation is excellent, and even at high temperature and high frequency, the electrical insulation and the dimensional stability are excellent.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The electrolyte-resistant acrylic acid ester adhesive disclosed by the invention adopts an oxygen-containing heterocyclic vinyl monomer to react with an acrylic acid monomer to form a block acrylic acid ester polymer, so that a strong-polarity cyclic ether group and a saturated ring structure are introduced into a polymer molecular chain. On one hand, the block structure design can provide good viscoelasticity and ion conductivity, and the carbonyl side group of the main chain midblock has stronger interaction with the carbonic ester solvent in the electrolyte to provide an ion conducting channel. On the other hand, the vinyl monomer containing saturated oxygen heterocycle has better mechanical strength and can provide mechanical support. The strong polar cyclic ether group can reduce the solubility of the acrylate adhesive in an organic solvent, is beneficial to improving the bonding strength and prolonging the electrolyte-resistant time; the saturated ring structure can increase the steric hindrance between molecules, enhance the thermal stability and facilitate the improvement of the bonding performance of the acrylate adhesive at high temperature.
(2) The electrolyte-resistant acrylic ester adhesive is prepared by modifying an oxygen-containing heterocyclic vinyl monomer, matching with a curing agent, color paste and the like to prepare a termination adhesive tape, and pasting the termination adhesive tape on an aluminum foil and immersing the termination adhesive tape in LiPF 6 In the electrolyte, the electrolyte resistance can be kept to be qualified for more than 4 hours in an environment of 85 ℃; the adhesive is stuck on an SUS plate and placed in the environment of 130 ℃, and can be kept to be peeled off for 30 minutes without adhesive residue; and has excellent insulating property, and can achieve leakage current<2mA, insulation resistance>1G omega, can be applied to the lithium battery and terminate the sticky tape field.
Detailed Description
The present invention will be further described in conjunction with the specific embodiments described below so that those skilled in the art may better understand the present invention and practice it, and it is evident that the described embodiments are only some, but not all, of the embodiments of the present invention. It should be understood that the detailed description is intended to illustrate the invention, but is not intended to limit the invention to the particular embodiments disclosed.
In the present invention, unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present invention, the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, unless otherwise indicated.
In the present invention, unless otherwise indicated, all the experimental methods used in the examples of the present invention are conventional methods, and materials, reagents and the like used, unless otherwise indicated, are commercially available.
In the present application, unless otherwise indicated, the terms "comprises" and/or "comprising" when used in the present specification specify the presence of stated features, integers, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof.
The invention relates to experimental raw materials:
isooctyl acrylate, ethyl acrylate, stearyl acrylate, methyl methacrylate, isobornyl methacrylate, vinyl acetate, acrylamide, hydroxypropyl acrylate, acrylic acid, available from bard rich industries, inc;
4-t-butylcyclohexyl acrylate (TBCHA), available from Shanghai Poly (R) Utility Co., ltd;
methyl (5-ethyl-1, 3-dioxan-5-yl) acrylate (CTFA), available from Shandong Jiapeng fine chemical Co., ltd;
glycidyl Methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA) are available from Shanghai and invasive chemistry inc;
the initiator Azobisisobutyronitrile (AIBN), available from alaa Ding Shiji (Shanghai) limited, analytically pure;
ethyl acetate and toluene were purchased from sigma aldrich (Shanghai) trade limited, commercially pure;
the curing agent is purchased from Korsche Polymer (China) Co., ltd, and the model is Desmodur L-75;
the color paste was purchased from Shanghai Sehong Material technology Co., ltd, model 6153-SA.
The substrate PET and the release film are purchased from Dongguan Zhonglian electronic materials, inc., the thickness of the substrate can be selected according to the actual requirement, and the PET with the thickness of 25 μm and the release film with the thickness of 30 μm are selected in the following examples.
Example 1
(1) The electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of soft monomer isooctyl acrylate, 5 parts of soft monomer ethyl acrylate, 5 parts of soft monomer stearyl acrylate, 4 parts of hard monomer methyl methacrylate, 3 parts of hard monomer vinyl acetate, 3 parts of cross-linking monomer hydroxypropyl acrylate, 2 parts of cross-linking monomer acrylic acid, 3 parts of tetrahydrofuran acrylate (THFA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate;
the method specifically comprises the following steps:
s1, at N 2 Under the atmosphere, weighing soft monomer, hard monomer, crosslinking monomer, ethyl acetate and toluene according to the formula amount, stirring for 35min at 73 ℃, adding 1/3 of the total initiator amount of initiator, and reacting for 1h at 78 ℃ to obtain a first reaction solution;
s2, adding an oxygen-containing heterocyclic vinyl monomer and an initiator with 1/3 total initiator amount into the first reaction solution of the S1, and reacting at 82 ℃ for 2.5 hours to obtain a second reaction solution;
s3, adding the rest initiator into the second reaction solution of the S2, reacting for 1.5 hours at the temperature of 85 ℃, cooling after the reaction is finished, and discharging to obtain the electrolyte-resistant acrylic ester adhesive.
The electrolyte-resistant acrylate adhesive prepared in this example had a solid content of 47%, a rotational viscosity of 2100cps and a glass transition temperature of-40 ℃.
(2) The invention relates to a termination adhesive tape and a preparation method thereof, which specifically comprise the following steps:
the acrylic ester adhesive, the curing agent, the color paste and the ethyl acetate are mixed according to the mass ratio of 100:0.9:5:30, uniformly stirring and mixing, coating the mixture on a PET substrate layer with the thickness of 25 mu m by using a scraper, baking for 5min at 100 ℃, curing for 72h in a 50 ℃ environment to form an acrylate adhesive layer with the thickness of 20 mu m, and finally attaching a release film layer with the thickness of 30 mu m to prepare the termination adhesive tape.
Example 2
Substantially the same as in example 1, the difference is that: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
22 parts of soft monomer isooctyl acrylate, 3 parts of soft monomer ethyl acrylate, 5 parts of soft monomer stearyl acrylate, 4 parts of hard monomer methyl methacrylate, 3 parts of hard monomer vinyl acetate, 3 parts of cross-linking monomer hydroxypropyl acrylate, 2 parts of cross-linking monomer acrylic acid, 3 parts of (5-ethyl-1, 3-dioxane-5-yl) methyl acrylate (CTFA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this example had a solids content of 45%, a rotational viscosity of 1500cps and a glass transition temperature of-43 ℃.
Example 3
Substantially the same as in example 1, the difference is that: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
28 parts of soft monomer isooctyl acrylate, 5 parts of soft monomer ethyl acrylate, 3 parts of soft monomer stearyl acrylate, 4 parts of hard monomer methyl methacrylate, 3 parts of hard monomer vinyl acetate, 3 parts of cross-linking monomer hydroxypropyl acrylate, 2 parts of cross-linking monomer acrylic acid, 3 parts of Glycidyl Methacrylate (GMA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this example had a solids content of 49%, a rotational viscosity of 2800cps and a glass transition temperature of-35 ℃.
Example 4
Substantially the same as in example 1, the difference is that: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of isooctyl acrylate as a soft monomer, 5 parts of ethyl acrylate as a soft monomer, 5 parts of stearyl acrylate as a soft monomer, 3 parts of methyl methacrylate as a hard monomer, 3 parts of isobornyl methacrylate as a hard monomer, 5 parts of acrylic acid as a crosslinking monomer, 1 part of Glycidyl Methacrylate (GMA), 3 parts of methyl (5-ethyl-1, 3-dioxane-5-yl) acrylate (CTFA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in the embodiment has a solid content of 48%, a rotational viscosity of 2300cps and a glass transition temperature of-38 ℃.
Example 5
Substantially the same as in example 1, the difference is that: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of isooctyl acrylate as a soft monomer, 5 parts of ethyl acrylate as a soft monomer, 5 parts of stearyl acrylate as a soft monomer, 3 parts of methyl methacrylate as a hard monomer, 5 parts of vinyl acetate as a hard monomer, 3 parts of acrylamide as a crosslinking monomer, 2 parts of hydroxypropyl acrylate as a crosslinking monomer, 1.5 parts of methyl (5-ethyl-1, 3-dioxane-5-yl) acrylate (CTFA), 2.5 parts of tetrahydrofuran acrylate (THFA), 0.35 parts of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in the embodiment has a solid content of 48%, a rotational viscosity of 2500cps and a glass transition temperature of-35 ℃.
Example 6
Substantially the same as in example 1, the difference is that: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of soft monomer isooctyl acrylate, 5 parts of soft monomer ethyl acrylate, 5 parts of soft monomer stearyl acrylate, 3 parts of hard monomer methyl methacrylate, 2 parts of hard monomer isobornyl methacrylate, 3 parts of cross-linking monomer acrylamide, 5 parts of cross-linking monomer acrylic acid, 1.5 parts of tetrahydrofuran acrylate (THFA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this example had a solid content of 46%, a rotational viscosity of 2000cps and a glass transition temperature of-43 ℃.
Example 7
Substantially the same as in example 1, the difference is that: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of isooctyl acrylate as a soft monomer, 5 parts of ethyl acrylate as a soft monomer, 5 parts of stearyl acrylate as a soft monomer, 3 parts of methyl methacrylate as a hard monomer, 4 parts of vinyl acetate as a hard monomer, 2 parts of acrylamide as a crosslinking monomer, 3 parts of hydroxypropyl acrylate as a crosslinking monomer, 5 parts of Glycidyl Methacrylate (GMA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this example had a solids content of 49%, a rotational viscosity of 3000cps and a glass transition temperature of-36 ℃.
Comparative example 1
Substantially as in example 1, except that tetrahydrofuran acrylate (THFA) was not added: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of soft monomer isooctyl acrylate, 5 parts of soft monomer ethyl acrylate, 5 parts of soft monomer stearyl acrylate, 4 parts of hard monomer methyl methacrylate, 3 parts of hard monomer vinyl acetate, 3 parts of cross-linking monomer hydroxypropyl acrylate, 2 parts of cross-linking monomer acrylic acid, 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this comparative example has a solids content of 42%, a rotational viscosity of 1200cps and a glass transition temperature of-40 ℃.
Comparative example 2
Substantially as in example 1, except that tetrahydrofuran acrylate (THFA) was replaced with 4-t-butylcyclohexyl acrylate (TBCHA): the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of isooctyl acrylate as a soft monomer, 5 parts of ethyl acrylate as a soft monomer, 5 parts of stearyl acrylate as a soft monomer, 4 parts of methyl methacrylate as a hard monomer, 3 parts of vinyl acetate as a hard monomer, 3 parts of hydroxypropyl acrylate as a crosslinking monomer, 2 parts of acrylic acid as a crosslinking monomer, 3 parts of 4-tert-butylcyclohexyl acrylate (TBCHA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in the comparative example has a solid content of 48%, a rotational viscosity of 2300cps and a glass transition temperature of-39 ℃.
Comparative example 3
Substantially as in example 1, except that the amount of Tetrahydrofuranacrylate (THFA) used was: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of isooctyl acrylate as a soft monomer, 5 parts of ethyl acrylate as a soft monomer, 5 parts of stearyl acrylate as a soft monomer, 4 parts of methyl methacrylate as a hard monomer, 3 parts of vinyl acetate as a hard monomer, 3 parts of hydroxypropyl acrylate as a crosslinking monomer, 2 parts of acrylic acid as a crosslinking monomer, 8 parts of tetrahydrofuran acrylate (THFA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this comparative example had a solid content of 50%, a rotational viscosity of 3100cps and a glass transition temperature of-34 ℃.
Comparative example 4
Substantially as in example 1, except that the hard monomer is different: the electrolyte-resistant acrylic ester adhesive comprises the following raw materials in parts by mass:
25 parts of soft monomer isooctyl acrylate, 5 parts of soft monomer ethyl acrylate, 5 parts of soft monomer stearyl acrylate, 6 parts of hard monomer methyl methacrylate, 6 parts of hard monomer isobornyl methacrylate, 3 parts of cross-linking monomer hydroxypropyl acrylate, 2 parts of cross-linking monomer acrylic acid, 3 parts of tetrahydrofuran acrylate (THFA), 0.35 part of azobisisobutyronitrile, 13 parts of toluene and 39 parts of ethyl acetate.
The electrolyte-resistant acrylate adhesive prepared in this comparative example has a solids content of 48%, a rotational viscosity of 2500cps and a glass transition temperature of-38 ℃.
Comparative example 5
Substantially the same as in example 1, except that the amount of the curing agent used was different: the mass ratio of the raw materials of the acrylic adhesive layer in the termination adhesive tape is as follows:
acrylate adhesive, curing agent, color paste and ethyl acetate according to the mass ratio of 100:0.5:5:30.
comparative example 6
Substantially the same as in example 1, except that the amount of the curing agent used was different: the mass ratio of the raw materials of the acrylic adhesive layer in the termination adhesive tape is as follows:
acrylate adhesive, curing agent, color paste and ethyl acetate according to the mass ratio of 100:1.5:5:30.
test case
The terminated tapes prepared in examples 1 to 7 and comparative examples 1 to 6 were subjected to performance test, and the related performance test methods were as follows:
(1) 180 ° peel force test: the measurement was carried out in accordance with GB/T2792-1998 standard (SUS plate, peeling speed: 300 mm/min), which requires: 3-10N/25mm;
(2) Initial tack test: the measurement is carried out according to the GB/T4852-2002 standard, and the requirements are that: initial adhesion ball >4#;
(3) And (3) testing the holding power: the measurement was carried out according to GB/T4851-1998 (80 ℃ C., 1 h), requiring: displacement <0.20mm;
(4) High temperature resistance test: flatly sticking a steel plate, baking at 130 ℃ for 30min, cooling to room temperature, and stripping, wherein the following requirements are that: the adhesive is free from deformation, shrinkage, fading and viscosity;
(5) Electrolyte resistance test: flatly attaching an aluminum foil, immersing the aluminum foil in electrolyte of LiPF6, standing at 85 ℃, taking out the termination adhesive tape, cooling to room temperature, and uncovering the termination adhesive tape from the aluminum foil, wherein the following steps are as follows: the color is not lost, the displacement is not caused, the falling is not caused, the viscosity is realized, and the adhesive residue is not caused. Preparing a large number of parallel test samples in advance, and testing for 1 time every 4 hours until the test samples are unqualified;
(6) Insulation performance test: under 500VDC,60s conditions, the following requirements are: the insulation resistance is more than 1G omega;
(7) High pressure resistance test: under 1500vdc@60s conditions, no breakdown is required: leakage current < 2mA;
(8) Tape thickness (excluding release film) test: after drying, the thickness of the tape was (45.+ -.2). Mu.m.
The test results are shown in table 1 below:
TABLE 1
As is clear from Table 1, in examples 1 to 7, the 180 DEG peel force was 6 to 9N/25mm, the peel force was moderate, the initial adhesion and the holding adhesion were acceptable, and the adhesive was applicable to most of the terminated bonding processes, and the adhesive was acceptable in terms of high temperature resistance, electrolyte resistance and electrical insulation properties. Examples 1, 2 and 5 have excellent electrolyte resistance and better comprehensive performance. This suggests that THFA monomers are more beneficial in improving electrolyte resistance of acrylates.
Compared with the above examples, the comparative example 1 has no oxygen-containing heterocyclic vinyl monomer added, and the adhesive composition is pure propylene resin, and has poor high temperature resistance and electrolyte resistance, and is unqualified. The vinyl monomer having an alicyclic ring added thereto in comparative example 2 had poor solvent resistance and failed electrolyte resistance. While the THFA monomer containing oxygen heterocycle is added in comparative examples 3-4, the electrolyte resistance and the high temperature resistance are qualified. However, the THFA monomer content in comparative example 3 is too high, and the hard monomer content in comparative example 4 is too high, which results in a large peeling force and a small initial adhesion, which is not beneficial to the current adhesive tape attaching and producing process, and is not acceptable.
Comparative examples 5 and 6 changed the amount of curing agent compared to the terminated adhesive tape prepared in example 1, resulting in a change in the crosslinking density of the system and an influence on the cohesive force. The comparative example 5 uses a smaller amount of curing agent, has low crosslinking density and small cohesion, and causes poor holding power, high temperature resistance and electrolyte resistance. The curing agent used in comparative example 6 has a large amount, isocyanate reacts with-OH and part-COOH in the system thoroughly, so that the adhesive film is hard, the adhesive force is reduced, the stripping force is low, the adhesive is easy to lose after electrolyte resistance, and the adhesive film is unqualified.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The electrolyte-resistant acrylate adhesive is characterized by comprising, by mass, 30-40 parts of a soft monomer, 5-10 parts of a hard monomer, 3-8 parts of a crosslinking monomer, 1-5 parts of an oxygen-containing heterocycle vinyl monomer, 0.2-0.5 part of an initiator and 40-60 parts of an organic solvent.
2. The electrolyte resistant acrylate adhesive of claim 1 wherein said oxygen-containing heterocyclic vinyl monomer is selected from the group consisting of epoxy-, dioxane-and tetrahydrofuranyl-containing vinyl monomers.
3. The electrolyte resistant acrylate adhesive of claim 1 wherein the soft monomer is selected from one or more of isooctyl acrylate, n-octyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, vinyl neodecanoate, lauryl acrylate, and stearyl acrylate;
the hard monomer is one or more selected from vinyl acetate, styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl neononanoate and isobornyl methacrylate;
the crosslinking monomer is selected from one or more of hydroxypropyl acrylate, acrylamide, methylolacrylamide, diacetone acrylamide, acetoacetate methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate, acrylic acid and methacrylic acid;
the initiator is selected from acyl peroxides and/or azo compounds;
the organic solvent is one or more selected from ethyl acetate, toluene, butanone and methyl acetate.
4. The electrolyte-resistant acrylate adhesive according to claim 1, wherein the electrolyte-resistant acrylate adhesive has a solid content of 40% -50%, a rotational viscosity of 1000cps-3000cps, and a glass transition temperature of-35 ℃ to-45 ℃.
5. A method for preparing an electrolyte-resistant acrylate adhesive according to any one of claims 1 to 4, comprising the steps of,
s1, uniformly stirring a soft monomer, a hard monomer, a crosslinking monomer and an organic solvent in an inert atmosphere, adding 1/4-1/2 amount of an initiator, and reacting at 76-80 ℃ for 1-2 h to obtain a first reaction solution;
s2, adding an oxygen-containing heterocyclic vinyl monomer and 1/4-1/2 amount of initiator into the first reaction solution in the S1, and reacting for 2-3 hours at the temperature of 80-83 ℃ to obtain a second reaction solution;
s3, adding the rest initiator into the second reaction solution in the step S2, and reacting for 1-2 hours at 83-86 ℃ to obtain the electrolyte-resistant acrylate adhesive.
6. The method for preparing an electrolyte-resistant acrylate adhesive according to claim 5, wherein in S1, the stirring temperature is 70-75 ℃ and the stirring time is 30-40 min.
7. A termination adhesive tape comprising a release film layer, an acrylic adhesive layer and a substrate layer which are sequentially laminated, wherein the preparation raw material of the acrylic adhesive layer comprises the acrylic adhesive as claimed in any one of claims 1 to 4.
8. The termination tape of claim 7, wherein the acrylate adhesive layer is prepared from a raw material further comprising a curing agent, color paste, and a solvent.
9. The termination tape of claim 8, wherein the mass ratio of the acrylate adhesive, the curing agent, the color paste and the solvent is 100:0.8-1.2:4-8:20-40.
10. The termination tape of claim 8, wherein the curing agent is selected from one or more of epoxy curing agents, amino curing agents, and isocyanate curing agents; the color paste is selected from phthalocyanine blue color paste; the solvent is selected from one or more of ethyl acetate and methyl acetate.
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