CN113817108B - Hydroxy acrylic acid dispersoid and preparation method thereof, and water-based insulating baking varnish for metal shell of power battery module and preparation method thereof - Google Patents
Hydroxy acrylic acid dispersoid and preparation method thereof, and water-based insulating baking varnish for metal shell of power battery module and preparation method thereof Download PDFInfo
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- CN113817108B CN113817108B CN202111197877.0A CN202111197877A CN113817108B CN 113817108 B CN113817108 B CN 113817108B CN 202111197877 A CN202111197877 A CN 202111197877A CN 113817108 B CN113817108 B CN 113817108B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 239000002966 varnish Substances 0.000 title claims abstract description 38
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 60
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 38
- 239000003973 paint Substances 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- 239000012948 isocyanate Substances 0.000 claims description 27
- 150000002513 isocyanates Chemical class 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 229960002887 deanol Drugs 0.000 claims description 18
- 239000012972 dimethylethanolamine Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 239000002318 adhesion promoter Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920003180 amino resin Polymers 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 5
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 5
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- -1 modified dimethyl siloxane Chemical class 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 4
- JHRDMNILWGIFBI-UHFFFAOYSA-N 6-diazenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(N=N)=N1 JHRDMNILWGIFBI-UHFFFAOYSA-N 0.000 claims 1
- 229920000877 Melamine resin Polymers 0.000 claims 1
- 239000004640 Melamine resin Substances 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 20
- 239000012792 core layer Substances 0.000 abstract description 13
- 239000000839 emulsion Substances 0.000 abstract description 12
- 239000010410 layer Substances 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 7
- 238000009413 insulation Methods 0.000 abstract description 7
- 239000002985 plastic film Substances 0.000 abstract description 6
- 229920006255 plastic film Polymers 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 6
- 238000003618 dip coating Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 23
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 12
- 102100026735 Coagulation factor VIII Human genes 0.000 description 12
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 102100027391 Potassium/sodium hyperpolarization-activated cyclic nucleotide-gated channel 2 Human genes 0.000 description 7
- 101710088707 Potassium/sodium hyperpolarization-activated cyclic nucleotide-gated channel 2 Proteins 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 3
- 229920003270 Cymel® Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101001009083 Mus musculus Potassium/sodium hyperpolarization-activated cyclic nucleotide-gated channel 3 Proteins 0.000 description 3
- 102100027376 Potassium/sodium hyperpolarization-activated cyclic nucleotide-gated channel 1 Human genes 0.000 description 3
- 108050000102 Potassium/sodium hyperpolarization-activated cyclic nucleotide-gated channel 1 Proteins 0.000 description 3
- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical compound CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- 229920003275 CYMEL® 325 Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004021 metal welding Methods 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a hydroxy acrylic acid dispersoid and a preparation method thereof, and an aqueous insulating baking varnish for a metal shell of a power battery module and a preparation method thereof. The hydroxy acrylic dispersion has a core-shell structure in which the glass transition temperature (Tg 1) of the core layer is 15 ℃ to 25 ℃; the glass transition temperature (Tg 2) of the shell layer is 35-55 ℃; the glass transition temperature of the finally synthesized emulsion is (Tg 3) 20-30 ℃; the hydroxyl value of the hydroxy acrylic dispersion is from 100mgKOH/g to 150mgKOH/g. The hydroxyl acrylic acid dispersoid is used for preparing the water-based insulating baking varnish for the metal shell of the power battery module, and the prepared water-based insulating baking varnish for the metal shell of the power battery module has good insulativity, is convenient to construct, can be constructed in a spray coating or dip coating mode and the like, can coat and coat the inner wall and the outer wall of the metal shell of the power battery module and the hole, avoids the pasting insulation defect of the traditional pasting insulation plastic film, and becomes a better technological scheme.
Description
Technical Field
The invention relates to the field of coatings, in particular to a hydroxy acrylic acid dispersion and a preparation method thereof, and an aqueous insulating baking varnish for a metal shell of a power battery module and a preparation method thereof.
Background
The power battery shell is insulated by sticking a plastic film, and along with the integration, enlargement and complexity of the battery structure, such as the opening of a battery core on the outer wall of the battery shell, the positions of the holes are difficult to be insulated by coating the plastic film; for the insulation of the inner wall of the battery case cavity, the process is more difficult to realize if the plastic film is coated. In addition, the process of coating the insulating film has defects, such as bubbles, untight adhesion and the like, which affect the safety of the battery.
The water-based insulating baking varnish has good insulativity, is convenient to construct, can be constructed in a spray coating or dip coating mode and the like, and can be used for coating and cladding the inner wall, the outer wall and the holes of the metal shell of the power battery module.
The traditional solvent type insulating paint has the defects of high VOC content, large pollution, serious pungent smell, serious influence on physical and mental health of workers caused by harmful substances such as benzene series substances, formaldehyde and the like contained in the paint. The general water-based paint has the defects of small adhesive force on metal base materials, poor impact resistance, poor weather resistance and the like.
Disclosure of Invention
An object of the present invention is to provide a hydroxy acrylic dispersion for preparing an aqueous insulating varnish for a metal housing of a power battery module, which can improve the insulation, workability and adhesion of the aqueous varnish.
Further, the present invention also necessarily provides the above-mentioned hydroxyacrylic acid dispersion and a method for producing the same.
Further, the present invention also provides an aqueous insulating varnish for a metal housing of a power battery module.
Further, the invention also provides a preparation method of the water-based insulating baking varnish for the metal shell of the power battery module.
The technical scheme of the invention is as follows:
a hydroxy acrylic acid dispersoid for preparing water-based insulating baking varnish for a metal shell of a power battery module,
the hydroxy acrylic dispersion has a core-shell structure, wherein the glass transition temperature Tg1 of the core layer is 15-25 ℃; the glass transition temperature Tg2 of the shell layer is 35-55 ℃; the glass transition temperature of the finally synthesized emulsion is Tg3 and is 20-30 ℃; the hydroxyl value of the hydroxy acrylic dispersion is from 100mgKOH/g to 150mgKOH/g.
Preferably, the hydroxyacrylic acid dispersion has a core-shell structure, wherein the glass transition temperature Tg1 of the core layer is 17.4 ℃ to 23.3 ℃; the glass transition temperature Tg2 of the shell layer is 40-54 ℃; the final synthetic emulsion has a glass transition temperature Tg3 of 20.3-30deg.C and a hydroxyl value of the hydroxy acrylic dispersion of 118.3-133.6 mgKOH/g.
The preparation method of the hydroxy acrylic acid dispersoid comprises the following steps: firstly, synthesizing a core layer by taking an alcohol ether solvent as a base material, wherein the core layer comprises one or more hard monomers with high Tg, soft monomers with low Tg, functional monomers containing hydroxyl and a cross-linking agent; then synthesizing a shell layer which also comprises one or more of a hard monomer with high Tg, a soft monomer with low Tg, a functional monomer containing hydroxyl and a cross-linking agent; finally adding a cross-linking agent for curing, neutralizing the organic amine and dispersing the water.
The preferable solvent bottom material is propylene glycol monobutyl ether and trimethylbenzene; further preferred hard monomers are Methyl Methacrylate (MMA), isobornyl methacrylate (IBOMA), styrene (ST); a further preferred soft monomer is butyl methacrylate (BA); further preferred crosslinking agents are organic peroxides such as di-t-butyl peroxide (DTBP).
Preferably, the preparation method of the hydroxy acrylic acid dispersion used for preparing the water-based insulating baking varnish for the metal shell of the power battery module comprises the following steps:
step (a), adding a bottom material into a reaction kettle: 1-3 parts of propylene glycol monobutyl ether and 1-3 parts of trimethylbenzene, and heating to 150-160 ℃;
sequentially adding 2-4 parts of Methyl Methacrylate (MMA), 5-7 parts of isobornyl methacrylate (IBOMA), 2-3 parts of Styrene (ST), 8-10 parts of hydroxyethyl acrylate (HEMA), 11-13 parts of butyl methacrylate (BA) and 0.5-1 part of di-tert-butyl peroxide (DTBP) into a premixing barrel, dripping the premixing material drop into a reaction kettle bottom material at a constant speed through a peristaltic pump, and dripping for 3-5 h at 150-160 ℃;
step (c), sequentially adding 1-3 parts of monomer Acrylic Acid (AA), 1-3 parts of Methyl Methacrylate (MMA), 2-4 parts of hydroxyethyl acrylate (HEMA), 1-2 parts of butyl methacrylate (BA) and 0.1-0.5 of di-tert-butyl peroxide (DTBP);
step (d), adding 0.1-0.5 part of di-tert-butyl peroxide (DTBP), maintaining the temperature at 150-160 ℃, and preserving the temperature for 1-3 hours;
step (e) cooling to 100 ℃, adding 1-2 parts of Dimethylethanolamine (DMEA), and stirring for 30-60 min;
step (f) cooling to 90 ℃, dropwise adding 50-55 parts of water for dispersion, dropwise adding half of water by weight for 30min, dropwise adding the whole water for 40-60min, and maintaining the temperature at 80 ℃ for 20-30 min; cooling to 60 ℃, filtering and discharging to obtain the hydroxy acrylic acid dispersoid.
Further preferably, the preparation method of the hydroxy acrylic acid dispersion used for preparing the water-based insulating baking varnish for the metal shell of the power battery module comprises the following steps:
step (a), adding a bottom material into a reaction kettle: 1-2.5 parts of propylene glycol monobutyl ether and 2-3 parts of trimethylbenzene, and heating to 150-160 ℃;
sequentially adding 2-4 parts of Methyl Methacrylate (MMA), 5-7 parts of isobornyl methacrylate (IBOMA), 2-3 parts of Styrene (ST), 8-10 parts of hydroxyethyl acrylate (HEMA), 11-12 parts of butyl methacrylate (BA) and 0.5-1 part of di-tert-butyl peroxide (DTBP) into a premixing barrel, dripping the premixing material drop into a reaction kettle bottom material at a constant speed through a peristaltic pump, and dripping for 3-5 h at 150-160 ℃;
step (c) of sequentially adding 1-3 parts of monomer Acrylic Acid (AA), 1-2.9 parts of Methyl Methacrylate (MMA), 2-3.8 parts of hydroxyethyl acrylate (HEMA), 1-2 parts of butyl methacrylate (BA) and 0.1-0.5 part of di-tert-butyl peroxide (DTBP);
step (d), adding 0.1-0.5 part of di-tert-butyl peroxide (DTBP), maintaining the temperature at 150-160 ℃, and preserving the temperature for 1-3 hours;
step (e) cooling to 100 ℃, adding 1-2 parts of Dimethylethanolamine (DMEA), and stirring for 30-60 min;
cooling to 90 ℃, dropwise adding 50-55 water for dispersing, and keeping the temperature at 80 ℃ for 20-30min after 40-60min (30 min is half of water) is completed; cooling to 60 ℃, filtering and discharging to obtain the hydroxy acrylic acid dispersoid.
Tg is the glass transition temperature, and the glass transition temperature is approximately estimated according to the FOX equation according to the invention, and the specific calculation formula is as follows:
wherein T is g Is the glass transition temperature, K, of the copolymer;the glass transition temperature, K, of comonomer i; w (W) i For the mass fraction of comonomer i in the monomer problem, there should be +.>
The core layer of the hydroxy acrylic dispersion is prepared in step (b) and the glass transition temperature Tg1 of the core layer is calculated as mass fraction from the theoretical glass transition temperature values of Methyl Methacrylate (MMA), isobornyl methacrylate (IBOMA), styrene (ST), 8-10 parts of hydroxyethyl acrylate (HEMA) and butyl methacrylate (BA) added in step (b) according to the above formula.
Step (c) produces a shell layer of the hydroxy acrylic dispersion, and the glass transition temperature Tg2 of the core layer is calculated as mass fraction from the theoretical glass transition temperature values of the monomers Acrylic Acid (AA), methyl Methacrylate (MMA), hydroxyethyl acrylate (HEMA) and butyl methacrylate (BA) added in step (c) according to the above formula.
The glass transition temperature Tg3 of the final synthesized emulsion is calculated from all the monomers added in step (b) and step (c).
The invention also provides the water-based insulating baking varnish for the metal shell of the power battery module, which comprises the following components in parts by weight:
51 to 60 parts of the hydroxy acrylic dispersion having an aqueous core-shell structure according to claim 1;
1-5 parts of slurry;
6.5-7 parts of alcohol ether mixed solvent;
1-4 parts of an adhesion promoter;
1-4 parts of blocked isocyanate;
6-8 parts of amino resin;
0.1-0.5 part of wetting agent;
0.1-0.5 part of pH regulator;
24-40 parts of deionized water.
Wherein the blocked isocyanate is prepared by the following method: taking hexamethylene diisocyanate trimer, isophorone diisocyanate and diphenylmethane diisocyanate as raw materials, adding polyalcohol to carry out emulsification chain extension reaction, and then adding a sealing agent to seal to obtain the sealing isocyanate curing agent.
Preferably, the blocked isocyanate is prepared by the following method: taking 90-100 parts of hexamethylene diisocyanate trimer, 2-2.5 parts of isophorone diisocyanate, 2-2.5 parts of diphenylmethane diisocyanate and 25-30 parts of 1-methyl-2-pyrrolidone, uniformly mixing at 50 ℃, and stirring for 30 minutes; gradually adding 8-10 parts of polyethylene glycol, and preserving heat for 1 hour at 70 ℃; adding 4.5-5 parts of 2, 2-dimethylolpropionic acid, maintaining the temperature at 70 ℃, and stirring for 30 minutes; adding 0.5-1 part of hexanediol, and preserving the temperature at 70 ℃ for 1.5 hours; 3-3.5 parts of dimethylethanolamine is added, stirring is carried out for 10 minutes, 35-40 parts of 3, 5-dimethylpyrazole is added, and the mixture is stirred for 5 minutes at 70 ℃ to obtain the blocked isocyanate.
Preferably, the blocking temperature of the blocked isocyanate is 120 ℃ to 170 ℃.
Wherein the slurry is titanium dioxide slurry.
The slurry consists of 33-36 parts by weight of water, 0.05-0.15 part by weight of pH regulator, 1-3 parts by weight of dispersing agent, 0.05-0.1 part by weight of defoamer and 62-68 parts by weight of titanium dioxide.
Preferably, the preparation method of the slurry comprises the following steps: adding 33-36 parts of water, 0.05-0.15 part of pH regulator and 1-3 parts of dispersing agent in sequence at the rotating speed of 500-600rpm for dispersing for 10-15min; adjusting the rotating speed to 1200-1500rpm, adding 0.05-0.1 part of defoamer, and dispersing at high speed for 10-15min; adding 62-68 parts of titanium dioxide, and adjusting the rotating speed to 2500rpm-3500rpm for high-speed dispersion for 1 hour to prepare slurry;
the pH regulator used for preparing the slurry is selected from one of 2-amino-2-methyl-1-propanol, N-Dimethylethanolamine (DMEA) and triethylamine, the dispersing agent used for preparing the slurry is one of anionic or cationic or nonionic or amphoteric surfactants, and the defoaming agent used for preparing the slurry is one of mineral oil or organic silicon surfactants.
The alcohol ether mixed solvent is formed by mixing a solvent A, a solvent B and a solvent C, wherein the boiling point of the solvent A is less than 100 ℃; the boiling point of the solvent B is more than or equal to 100 ℃ and less than 200 ℃; the boiling point of the solvent C is more than 200 ℃.
Preferably, the solvent A is one or more of ethanol, propanol, isopropanol (IPA) and the like; the solvent B is one or more of n-butanol, dipropylene glycol methyl ether (DPM), propylene glycol methyl ether (PM), ethylene glycol butyl Ether (ETB), propylene glycol monobutyl ether (PnB) and the like; the solvent C is one or more of diethylene glycol monobutyl ether (BDG), dipropylene glycol butyl ether (DPnB), diethylene glycol propyl ether (DEP), tripropylene glycol butyl ether (TPNB) and the like.
Preferably, the adhesion promoter is one of phosphate esters or silane coupling agents. Further preferably, the adhesion promoter is a phosphate compound.
Preferably, the aqueous amino resin is a methyl etherified homoiminomelamine resin.
Preferably, the amino resin is one of CYMEL 325, CYMEL 303, CYMEL 327, BASF 072, and resumee 717.
Preferably, the wetting agent is one of polyether modified dimethyl siloxane or organosilicon gemini structure surfactant or fluorine-containing surface active polymer.
Preferably, the dispersant is one of an anionic or cationic or nonionic or amphoteric surfactant.
Preferably, the dispersing agent is one of Dow OROTAN 731A, BYK-190, BYK-192 and Additol VXW 6208/60.
Preferably, the defoamer is one of a mineral oil or a silicone surfactant.
Further preferably, the defoamer is one of Tego-840, surfynol MD20, BYK-011, BYK-020, BYK-019.
Preferably, the pH adjustor is an organic amine, and further preferably, the pH adjustor used is one of 2-amino-2-methyl-1-propanol or N, N-dimethylethanolamine or triethylamine.
The preparation method of the water-based insulating baking varnish for the metal shell of the power battery module comprises the following steps:
1) Sequentially adding titanium dioxide, a wetting agent, a dispersing agent, a defoaming agent and water according to a proportion, and carrying out high-speed dispersion grinding to obtain slurry for later use;
2) Sequentially adding the hydroxy acrylic acid dispersoid, the prepared slurry, the alcohol ether mixed solvent, the amino resin, the blocked isocyanate, the adhesion promoter and the wetting agent according to a proportion, and uniformly stirring; and adding a pH regulator and water to regulate the viscosity to obtain the water-based insulating baking paint.
The preparation method of the water-based insulating baking varnish for the metal shell of the power battery module is carried out by using a common high-speed dispersing machine.
Furthermore, the application method of the water-based insulating baking varnish for the metal shell of the power battery module can be used for construction by adopting a spray coating or dip coating method, and insulating varnish with different thickness can be sprayed according to the requirements of insulating properties in different application scenes.
Compared with the prior art, the invention has the following advantages:
(1) The water-based insulating baking varnish has good insulativity, is convenient to construct, can be constructed in a spray coating or dip coating mode and the like, and can be used for coating and cladding the inner wall, the outer wall and the holes of the metal shell of the power battery module. Can replace the traditional technological scheme of adhering insulating plastic film.
(2) The water-based insulating baking varnish can be solidified into a film at 140 ℃, and the metal shell and the metal welding accessory of the battery module cannot deform due to overhigh baking temperature.
(3) The water-based hydroxyl acrylic emulsion, the water-based closed polyurethane and the proper adhesion promoter are effectively matched, so that the paint film has excellent insulating strength and adhesion on the metal shell of the power battery module.
(4) The resin adopted by the invention is all water-based resin, and the used auxiliary agent is also an environment-friendly solvent, so that the resin has low VOC content and is safe and environment-friendly.
(5) The aqueous hydroxyl acrylic emulsion prepared by the invention has a special aqueous core-shell structure, wherein the glass transition temperature of the core layer is lower than that of the shell layer, and the paint film has good flexibility and certain rigidity.
(6) The waterborne closed polyurethane prepared by the invention has a composite structure with three functional groups, so that the mechanical property of a paint film and the resistance of the paint film under high temperature and high humidity are improved.
(7) The ternary alcohol ether solvent system used in the invention has the advantages of ladder-type specific volatilization, difficult occurrence of defects such as pinholes, bubbles and the like in the film curing and forming process of a paint film, and improved insulation reliability.
Detailed Description
The technical solution of the present invention will be further described with reference to the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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. The parts indicated in the examples are parts by weight unless otherwise indicated.
The starting materials in examples and comparative examples were synthesized by themselves or obtained commercially, and the specific sources are as follows
Experimental example 1: preparation of hydroxy acrylic Dispersion HAC-1
Step (a), adding a bottom material into a reaction kettle: 2.5 parts of propylene glycol monobutyl ether and 2.5 parts of trimethylbenzene, and heating to 150 ℃;
sequentially adding 3 parts of Methyl Methacrylate (MMA), 6 parts of isobornyl methacrylate (IBOMA), 3 parts of Styrene (ST), 9 parts of hydroxyethyl acrylate (HEMA), 12 parts of butyl methacrylate (BA) and 0.96 part of di-tert-butyl peroxide (DTBP) into a premixing barrel, dripping the premixing material drop into a reaction kettle bottom material at a constant speed through a peristaltic pump, and dripping for 5 hours at 150 ℃;
step (c) is sequentially added with 1.3 parts of monomer Acrylic Acid (AA), 2.9 parts of Methyl Methacrylate (MMA), 3.8 parts of hydroxyethyl acrylate (HEMA), 2 parts of butyl methacrylate (BA) and 0.2 part of di-tert-butyl peroxide (DTBP);
step (d), after 0.1 part of di-tert-butyl peroxide (DTBP) is added, maintaining the temperature at 150 ℃ and preserving the temperature for 1h;
step (e) cooling to 100 ℃, adding 1.4 parts of Dimethylethanolamine (DMEA), and stirring for 30min;
step (f) cooling to 90 ℃, dropwise adding 50 parts of water for dispersion, and keeping the temperature at 80 ℃ for 20min after 40-60min of dripping (30 min of dripping half of water); cooling to 60 ℃, filtering and discharging. This hydroxy acrylic dispersion was designated as HAC-1 for use.
According to calculation, the core layer Tg1 of the polymer HAC-1 is 20.3 ℃, the shell layer Tg2 is 40.7 ℃, the polymer HAC-1Tg3 is 24.8 ℃, and the hydroxyl value of the polymer is 128.5mgKOH/g.
Experimental example 2: preparation of hydroxy acrylic Dispersion HAC-2
Step (a), adding a bottom material into a reaction kettle: 1 part of propylene glycol monobutyl ether and 3 parts of trimethylbenzene, and heating to 160 ℃;
sequentially adding 2 parts of Methyl Methacrylate (MMA), 7 parts of isobornyl methacrylate (IBOMA), 2 parts of Styrene (ST), 10 parts of hydroxyethyl acrylate (HEMA), 11 parts of butyl methacrylate (BA) and 1 part of di-tert-butyl peroxide (DTBP) into a premixing barrel, dripping the premixing material drop into a reaction kettle bottom material at a constant speed through a peristaltic pump, and dripping for 3 hours at 160 ℃;
step (c) is sequentially added with 3 parts of monomer Acrylic Acid (AA), 2.5 parts of Methyl Methacrylate (MMA), 3 parts of hydroxyethyl acrylate (HEMA), 1.5 parts of butyl methacrylate (BA) and 0.5 part of di-tert-butyl peroxide (DTBP);
step (d), maintaining the temperature at 150 ℃ after adding 0.25 part of di-tert-butyl peroxide (DTBP), and preserving the temperature for 1h;
step (e) cooling to 100 ℃, adding 1 part of Dimethylethanolamine (DMEA), and stirring for 30min;
cooling to 90 ℃, dropwise adding 51 parts of water for dispersion, and keeping the temperature at 80 ℃ for 20min after 40-60min of water is completely dripped (30 min of half water is dripped); cooling to 60 ℃, filtering and discharging. This hydroxy acrylic dispersion was designated as HAC-2 for use.
According to calculation, the core layer Tg1 of the polymer HAC-1 is 23.3 ℃, the shell layer Tg2 is 54 ℃, the polymer HAC-2Tg3 is 30 ℃, and the hydroxyl value of the polymer is 133.6mgKOH/g.
Experimental example 3: preparation of hydroxy acrylic Dispersion HAC-3
Step (a), adding a bottom material into a reaction kettle: 2 parts of propylene glycol monobutyl ether and 2 parts of trimethylbenzene, and heating to 155 ℃;
sequentially adding 4 parts of Methyl Methacrylate (MMA), 5 parts of isobornyl methacrylate (IBOMA), 2.5 parts of Styrene (ST), 8 parts of hydroxyethyl acrylate (HEMA), 12 parts of butyl methacrylate (BA) and 0.5 part of di-tert-butyl peroxide (DTBP) into a premixing barrel, dripping the premixing material drop into a reaction kettle bottom material at a constant speed through a peristaltic pump, and dripping for 3 hours at 150 ℃;
step (c) is sequentially added with 1 part of monomer Acrylic Acid (AA), 1 part of Methyl Methacrylate (MMA), 2 parts of hydroxyethyl acrylate (HEMA), 1 part of butyl methacrylate (BA) and 0.1 part of di-tert-butyl peroxide (DTBP);
step (d), after adding 0.5 part of di-tert-butyl peroxide (DTBP), maintaining 155 ℃ and preserving heat for 4 hours;
step (e) cooling to 100 ℃, adding 2 parts of Dimethylethanolamine (DMEA), and stirring for 30min;
step (f) cooling to 90 ℃, dropwise adding 55 parts of water for dispersing, and keeping the temperature at 80 ℃ for 20min after 40-60min of water is completely dripped (30 min of half water is dripped); cooling to 60 ℃, filtering and discharging. This hydroxy acrylic dispersion was designated as HAC-3 for use.
According to calculation, the core layer Tg1 of the polymer HAC-1 is 17.4 ℃, the shell layer Tg2 is 40 ℃, the polymer HAC-2Tg3 is 20.3 ℃, and the polymer hydroxyl value is 118.3mgKOH/g.
Experimental example 4: preparation of blocked isocyanates A-1
100 parts of hexamethylene diisocyanate trimer, 2.5 parts of isophorone diisocyanate, 2.5 parts of diphenylmethane diisocyanate and 30 parts of 1-methyl-2-pyrrolidone are taken, uniformly mixed at 50 ℃ and stirred for 30 minutes; gradually adding 10 parts of polyethylene glycol and preserving heat for 1 hour at 70 ℃; 5 parts of 2, 2-dimethylolpropionic acid is added, and the temperature is maintained at 70 ℃ and stirred for 30 minutes; 1 part of hexanediol is added, and the temperature is kept at 70 ℃ for 1.5 hours; 3.5 parts of dimethylethanolamine are added, stirring is carried out for 10 minutes, 40 parts of 3, 5-dimethylpyrazole are added, and the mixture is stirred at 70 ℃ for 5 minutes to obtain the blocked isocyanate, which is named A-1.
Experimental example 5: preparation of blocked isocyanates A-2
Taking 90 parts of hexamethylene diisocyanate trimer, 2.5 parts of isophorone diisocyanate, 2.5 parts of diphenylmethane diisocyanate and 30 parts of 1-methyl-2-pyrrolidone, uniformly mixing at 50 ℃, and stirring for 30 minutes; gradually adding 8 parts of polyethylene glycol and preserving heat for 1 hour at 70 ℃; 4.5 parts of 2, 2-dimethylolpropionic acid are added, and the temperature is maintained at 70 ℃ and stirred for 30 minutes; 0.5 part of hexanediol is added, and the temperature is kept at 70 ℃ for 1.5 hours; adding 3 parts of dimethylethanolamine and stirring for 10 minutes; 35 parts of 3, 5-dimethylpyrazole are added and the mixture is stirred at 70℃for 5 minutes to give the blocked isocyanate, designated A-2.
Experimental example 6: preparation of blocked isocyanates A-3
100 parts of hexamethylene diisocyanate trimer, 2 parts of isophorone diisocyanate, 2 parts of diphenylmethane diisocyanate and 25 parts of 1-methyl-2-pyrrolidone are taken, uniformly mixed at 50 ℃ and stirred for 30 minutes; gradually adding 9 parts of polyethylene glycol and preserving heat for 1 hour at 70 ℃; 5 parts of 2, 2-dimethylolpropionic acid is added, and the temperature is maintained at 70 ℃ and stirred for 30 minutes; 1 part of hexanediol is added, and the temperature is kept at 70 ℃ for 1.5 hours; adding 3 parts of dimethylethanolamine and stirring for 10 minutes; 40 parts of 3, 5-dimethylpyrazole are added and the mixture is stirred at 70℃for 5 minutes to give the blocked isocyanate, designated A-3.
Example 1
Preparing slurry: at 600rpm, 35 parts of water, 0.1 part of 2-amino-2-methyl-1-propanol and 1.2 parts of Dow OROTAN 731A are added in sequence for dispersion for 10 minutes; adjusting the rotating speed to 1500rpm, adding 0.05 part of Tego-840, and dispersing at a high speed for 10 minutes; 63 parts of titanium dioxide is added, the rotating speed is adjusted to 2500rpm, and the slurry SLU-1 is prepared for standby.
Mixing paint: 60 parts of HAC-1 and 5 parts of SLU-1 are sequentially added into a cylinder according to the proportion of each component in the formula table of the table 1 at 500rpm, and stirred for 10min; 2 parts of isopropanol, 4 parts of n-butanol, 1 part of dipropylene glycol butyl ether, 8.5 parts of CYMEL 325, 1 part of blocked isocyanate A-1 and 4 parts of Dow Corning Z6040 are continuously added and stirred for 15 minutes; adding 0.5 part of 2-amino-2-methyl-1-propanol and 0.5 part of Tego-4100 13 parts of deionized water, and uniformly stirring to obtain the water-based insulating baking paint.
Example 2
Preparing slurry: 33 parts of water, 0.15 part of N, N-dimethylethanolamine and 1.5 parts of BYK-190 are added in sequence at a rotation speed of 600rpm for dispersion for 10 minutes; adjusting the rotating speed to 1500rpm, adding 0.1 part of Surfynol MD20, and dispersing at a high speed for 10 minutes; 68 parts of titanium dioxide is added, the rotating speed is adjusted to 2500rpm, and the slurry SLU-2 is prepared for standby.
Mixing paint: at 500rpm, 55 parts of HAC-2 and 3 parts of SLU-2 are sequentially added into a cylinder according to the proportion of each component in the formula table in the table 1, and stirring is carried out for 10min; the rotational speed is increased to 1000rpm, 3 parts of propanol, 3 parts of propylene glycol monobutyl ether, 1 part of diethylene glycol monobutyl ether, 7.5 parts of CYMEL 327, 2.5 parts of blocked isocyanate A-2 and 2.5 parts of Lubrizol 2063H are added and stirred for 15 minutes; adding 0.3 part of Tego-510, 0.3 part of N, N-dimethylethanolamine and 23 parts of deionized water, and uniformly stirring to obtain the water-based insulating baking paint.
Example 3
Preparing slurry: 34 parts of water, 0.13 part of triethylamine and 1.4 parts of BYK-192 dispersant are added in sequence for 10 minutes at a rotation speed of 600 rpm; adjusting the rotating speed to 1500rpm, adding 0.07 part of BYK-011, and dispersing at a high speed for 10 minutes; adding 65 parts of titanium dioxide, regulating the rotating speed to 2500rpm, and dispersing for 1 hour at high speed to prepare slurry SLU-3 for later use.
Mixing paint: 51 parts of HAC-3 and 3 parts of SLU-3 are sequentially added into a cylinder according to the proportion of each component in the formula table in the table 1 at 500rpm, and stirred for 10min; the rotational speed is increased to 1000rpm, and then 1 part of ethanol, 2.5 parts of dipropylene glycol methyl ether, 3 parts of tripropylene glycol butyl ether, 6 parts of BASF 072, 4 parts of blocked isocyanate A-3 and 1 part of Dow Corning Z6040 are added and stirred for 15 minutes; adding 0.5 part of Tego-245, 0.1 part of triethylamine and 30 parts of deionized water, and uniformly stirring to obtain the water-based insulating baking paint.
Example 4
The composition of the aqueous insulating varnish for the metal shell of the power battery module is shown in table 1, raw materials are added according to the composition of table 1 during preparation, and the rest preparation methods are the same as in example 1.
Example 5
The composition of the aqueous insulating varnish for the metal shell of the power battery module is shown in table 1, raw materials are added according to the composition of table 1 during preparation, and the rest preparation methods are the same as in example 2.
Example 6
The composition of the aqueous insulating varnish for the metal shell of the power battery module is shown in table 1, raw materials are added according to the composition of table 1 during preparation, and the rest of preparation methods are the same as in example 3.
Example 7
The composition of the aqueous insulating varnish for the metal shell of the power battery module is shown in table 1, raw materials are added according to the composition of table 1 during preparation, and the rest preparation methods are the same as in example 1.
Comparative example 1
The raw materials were added in the compositions shown in Table 2, and the preparation method was the same as in example 1 except that the selection of the hydroxy acrylic resin was different.
Comparative example 2
The raw materials were added in the compositions shown in Table 2, and the preparation method was the same as in example 2 except that the selection of the alcohol ether mixed solvent was different.
Comparative example 3
The raw materials were added in the composition shown in Table 2, and the preparation method was the same as in example 3 except that the selection of the alcohol ether mixed solvent was different.
Comparative example 4
The raw materials were added in the composition shown in Table 2, and the preparation method was the same as in example 4 except that the materials for the blocked isocyanate were selected differently.
Comparative example 5
The raw materials were added in the composition shown in Table 2, and the preparation method was the same as in example 5 except that the materials for the blocked isocyanate were selected differently.
Comparative example 6
The raw materials were added in the composition shown in Table 2, and the preparation method was the same as in example 6 except that the materials for the blocked isocyanate were selected differently.
Comparative example 7
Raw materials were added in the composition shown in Table 2, and the other preparation methods were the same as in example 7.
TABLE 1 composition of aqueous insulating paints of examples 1-7
TABLE 2 composition of aqueous insulating paints of comparative examples 1 to 7
The aqueous insulating paints prepared in examples 1 to 7 and comparative examples 1 to 7 were tested, and the test standards and test results are shown in tables 3 and 4.
Table 3 test results for examples 1-7
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Table 4 comparative examples 1-7 test results
The insulating property, voltage breakdown resistance and high-temperature storage property of the examples 1-7 and the comparative examples 1-7 are that the base material is aluminum material, and the dry film thickness of the paint film is 90-110 mu m; other properties were tested and the thickness of the paint film was in accordance with the test standards. The paint film is prepared by spraying for 2-3 times and baking for 2-3 times at 140 ℃ for 20-30min.
From the test results in Table 3, it is clear that the aqueous insulating stoving varnish prepared with the self-synthesized aqueous hydroxy acrylic emulsion and the self-synthesized blocked isocyanate has smooth and no defect in appearance; the adhesive force on the metal shell is of the level 0; the bonding strength between the coating and the substrate and between the coating and the Jitai adhesive is more than 5MPa; the coating is not broken down at a voltage of AC3540V for 60 seconds at a thickness of 100 μm; the adhesive force, the insulation and the pressure resistance are not attenuated under the storage adjustment of high temperature and high humidity.
From comparative example 1, it can be seen that the difference is that comparative example 1 uses a commercially available hydroxy propylene emulsion, example 1 uses a self-synthesized HAC-1 emulsion, and the paint film of comparative example 1 is not acceptable in terms of high temperature and high humidity storage properties;
as can be seen from comparative examples 2-3 and examples 2-3, the difference is that comparative examples 2-3 use the same alcohol ether solvent, whereas examples 2-3 use a combination of A, B and C three alcohol ether solvents with different boiling points. The paint film of comparative example 2 had the disadvantage of foaming and failed to break down at an AC3540V voltage; the paint film of the comparative example 3 has only HB, and the electrical property of the paint film is reduced under high-temperature and high-humidity storage;
from the commercial blocked isocyanates used in comparative examples 4 to 6, and the self-synthesized blocked isocyanates used in examples 4 to 6, it can be seen that the paint films of comparative examples 4 to 6 have an impact resistance of only 40cm, an adhesion of only 1 grade, a bonding strength with the substrate and the adhesive tape of less than 5MPa, and a deterioration in electrical properties after high-temperature and high-humidity storage.
As can be seen from comparative example 7 and example 7, comparative example 7, in which the A-1 blocked isocyanate was not added, example 7, in which A-1 was added, had an impact resistance of only 30cm, a flexibility of 2mm, an adhesion of only 2 grades, and a deterioration in high-temperature high-humidity storage performance.
The test results show that the aqueous hydroxyl acrylic emulsion prepared by the invention is used in water paint, is used for the inner wall and the outer wall of a metal shell of a power battery module, and can improve the insulativity, the processability and the adhesive force of baking varnish.
The water-based insulating baking varnish prepared by the invention has good insulativity under the effective collocation of self-made water-based hydroxyl acrylic emulsion, water-based closed polyurethane and proper adhesion promoter, is convenient to construct, and can be used for coating and cladding the inner wall, the outer wall and the holes of a metal shell of a power battery module in a spray coating or dip coating mode. Can replace the traditional technological scheme of adhering insulating plastic film.
The water-based insulating baking varnish prepared by the invention can be solidified into a film at 140 ℃, and the metal shell and the metal welding accessory of the battery module can not deform due to overhigh baking temperature. The paint film has excellent insulating strength and adhesive force on the metal shell of the power battery module. The resin adopted by the invention is all water-based resin, and the used auxiliary agent is also an environment-friendly solvent, so that the resin has low VOC content and is safe and environment-friendly. The aqueous hydroxyl acrylic emulsion prepared by the invention has a special aqueous core-shell structure, wherein the glass transition temperature of the core layer is lower than that of the shell layer, and the paint film has good flexibility and certain rigidity. The waterborne closed polyurethane prepared by the invention has a composite structure with three functional groups, so that the mechanical property of a paint film and the resistance of the paint film under high temperature and high humidity are improved. The ternary alcohol ether solvent system used in the invention has the advantages of ladder-type specific volatilization, difficult occurrence of defects such as pinholes, bubbles and the like in the film curing and forming process of a paint film, and improved insulation reliability.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The water-based insulating baking varnish for the metal shell of the power battery module comprises the following components in parts by weight:
51-60 parts of a hydroxy acrylic dispersion having an aqueous core-shell structure;
1-5 parts of slurry;
6.5-7 parts of alcohol ether mixed solvent;
1-4 parts of an adhesion promoter;
1-4 parts of blocked isocyanate;
6-8 parts of amino resin;
0.1-0.5 part of wetting agent;
0.1-0.5 part of pH regulator;
24-40 parts of deionized water;
wherein, the hydroxy acrylic acid dispersion with the water-based core-shell structure is prepared by the following method:
step (a), adding a bottom material into a reaction kettle: 1-3 parts of propylene glycol monobutyl ether and 1-3 parts of trimethylbenzene, and heating to 150-160 ℃;
sequentially adding 2-4 parts of Methyl Methacrylate (MMA), 5-7 parts of isobornyl methacrylate (IBOMA), 2-3 parts of Styrene (ST), 8-10 parts of hydroxyethyl methacrylate (HEMA), 11-13 parts of Butyl Methacrylate (BMA) and 0.5-1 part of di-tert-butyl peroxide (DTBP) into a premixing barrel, dripping the premix into a reaction kettle bottom material through a peristaltic pump, and dripping for 3-5 h at 150-160 ℃;
step (c) of sequentially adding 1-3 parts of monomer Acrylic Acid (AA), 1-3 parts of Methyl Methacrylate (MMA), 2-4 parts of hydroxyethyl methacrylate (HEMA), 1-2 parts of Butyl Methacrylate (BMA) and 0.1-0.5 part of di-tert-butyl peroxide (DTBP);
step (d) adding 0.1-0.5 part of di-tert-butyl peroxide (DTBP), maintaining the temperature at 150-160 ℃, and preserving the temperature for 1-3 hours;
step (e) cooling to 100 ℃, adding 1-2 parts of Dimethylethanolamine (DMEA), and stirring for 30-60 min;
step (f) cooling to 90 ℃, dropwise adding 50-55 parts of water for dispersion, dropwise adding half of water by weight for 30min, dropwise adding the whole water for 40-60min, and maintaining the temperature at 80 ℃ for 20-30 min; cooling to 60 ℃, filtering and discharging to obtain a hydroxy acrylic acid dispersoid;
the blocked isocyanate is prepared by the following method: taking 90-100 parts of hexamethylene diisocyanate trimer, 2-2.5 parts of isophorone diisocyanate, 2-2.5 parts of diphenylmethane diisocyanate and 25-30 parts of 1-methyl-2-pyrrolidone, uniformly mixing at 50 ℃, and stirring for 30 minutes; gradually adding 8-10 parts of polyethylene glycol, and preserving heat for 1 hour at 70 ℃; adding 4.5-5 parts of 2, 2-dimethylolpropionic acid, maintaining the temperature at 70 ℃, and stirring for 30 minutes; adding 0.5-1 part of hexanediol, and preserving the temperature at 70 ℃ for 1.5 hours; adding 3-3.5 parts of dimethylethanolamine, stirring for 10 minutes, adding 35-40 parts of 3, 5-dimethylpyrazole, and stirring the mixture at 70 ℃ for 5 minutes to obtain closed isocyanate;
the alcohol ether mixed solvent is formed by mixing a solvent A, a solvent B and a solvent C, wherein the boiling point of the solvent A is less than 100 ℃; the boiling point of the solvent B is more than or equal to 100 ℃ and less than 200 ℃; the boiling point of the solvent C is more than 200 ℃;
the slurry is titanium dioxide slurry.
2. The aqueous insulating varnish for a metal housing of a power battery module according to claim 1, wherein:
the slurry consists of 33-36 parts by weight of water, 0.05-0.15 part by weight of pH regulator, 1-3 parts by weight of dispersing agent, 0.05-0.1 part by weight of defoamer and 62-68 parts by weight of titanium dioxide.
3. The aqueous insulating varnish for a metal housing of a power battery module according to claim 1, wherein:
the adhesion promoter is one of phosphate esters or silane coupling agents.
4. The aqueous insulating varnish for a metal housing of a power battery module according to claim 1, wherein:
the amino resin is methyl etherified high imino melamine resin.
5. The aqueous insulating varnish for a metal housing of a power battery module according to claim 1, wherein:
the wetting agent is one of polyether modified dimethyl siloxane or fluorine-containing surface active polymer.
6. The aqueous insulating varnish for a metal housing of a power battery module according to claim 2, wherein:
the dispersing agent is one of anionic or cationic or nonionic or amphoteric surfactant.
7. The aqueous insulating varnish for a metal housing of a power battery module according to claim 2, wherein: the defoaming agent is one of mineral oil or organic silicon surfactant.
8. The aqueous insulating varnish for a metal housing of a power battery module according to claim 1 or 2, wherein:
the pH regulator is one of 2-amino-2-methyl-1-propanol or N, N-dimethylethanolamine or triethylamine.
9. A method for preparing the aqueous insulating varnish for the metal shell of the power battery module according to any one of claims 1 to 8, which is characterized by comprising the following steps:
1) And (3) preparing slurry: adding 33-36 parts of water, 0.05-0.15 part of pH regulator and 1-3 parts of dispersing agent in sequence at the rotating speed of 500-600rpm for dispersing for 10-15min; adjusting the rotating speed to 1200-1500rpm, adding 0.05-0.1 part of defoamer, and dispersing at high speed for 10-15min; adding 62-68 parts of titanium dioxide, and adjusting the rotating speed to 2500rpm-3500rpm for high-speed dispersion for 1 hour to prepare slurry;
2) Sequentially adding the hydroxy acrylic acid dispersoid, the prepared slurry, the alcohol ether mixed solvent, the amino resin, the blocked isocyanate, the adhesion promoter and the wetting agent according to a proportion, and uniformly stirring; and adding a pH regulator and deionized water to regulate the viscosity to obtain the water-based insulating baking paint.
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