CN117106354A - Water-based primer for thermoplastic polyolefin, and preparation method and application thereof - Google Patents
Water-based primer for thermoplastic polyolefin, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117106354A CN117106354A CN202311368510.XA CN202311368510A CN117106354A CN 117106354 A CN117106354 A CN 117106354A CN 202311368510 A CN202311368510 A CN 202311368510A CN 117106354 A CN117106354 A CN 117106354A
- Authority
- CN
- China
- Prior art keywords
- monomer
- shell
- emulsion
- thermoplastic polyolefin
- core layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002397 thermoplastic olefin Polymers 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 165
- 239000000839 emulsion Substances 0.000 claims abstract description 95
- 239000012792 core layer Substances 0.000 claims abstract description 48
- 239000010410 layer Substances 0.000 claims abstract description 47
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 31
- 229920000098 polyolefin Polymers 0.000 claims abstract description 24
- 230000009477 glass transition Effects 0.000 claims abstract description 21
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 13
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 93
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 22
- 238000004132 cross linking Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- -1 vinyl alkyl phosphate Chemical compound 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 8
- 230000001737 promoting effect Effects 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012875 nonionic emulsifier Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- NNQPQJLMERNWGN-UHFFFAOYSA-N 11-methyldodecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCOC(=O)C=C NNQPQJLMERNWGN-UHFFFAOYSA-N 0.000 claims description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 2
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 claims description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- JYFXWEZMAKLMME-UHFFFAOYSA-N N-carbamoyl-N-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCN(C(=O)N)C(C=C)=O JYFXWEZMAKLMME-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-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
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 claims description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical group 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- 229920001223 polyethylene glycol Polymers 0.000 claims 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- BEVBXDUWEHXAIF-UHFFFAOYSA-N C(C(=C)C)(=O)OCC.C(CC(=O)C)(=O)O Chemical group C(C(=C)C)(=O)OCC.C(CC(=O)C)(=O)O BEVBXDUWEHXAIF-UHFFFAOYSA-N 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YEQBHMVRNHTCPJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;3-oxobutanoic acid Chemical group CC(=C)C(O)=O.CC(=O)CC(O)=O YEQBHMVRNHTCPJ-UHFFFAOYSA-N 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PBZABDOXEJTBOB-UHFFFAOYSA-N ethyl 3-oxobutanoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)CC(C)=O PBZABDOXEJTBOB-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- 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
- C09D5/002—Priming paints
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a water-based primer for thermoplastic polyolefin, a preparation method and application thereof, wherein the water-based primer comprises acrylic resin emulsion and modified polyolefin emulsion, the acrylic resin has a core-shell structure of a core layer and a double shell layer, the double shell layer comprises a first shell layer and a second shell layer, the glass transition temperature of the core layer is greater than that of the first shell layer, and the glass transition temperature of the core layer is greater than that of the second shell layer; the functional monomers adopted by the first shell layer and the second shell layer are monomers with side acid groups and glass transition temperature lower than 40 ℃. The aqueous primer prepared by adopting the core-shell acrylate resin emulsion with the double-layer shell structure and the modified polyolefin emulsion can effectively improve the adhesion effect of the primer on the surface of thermoplastic polyolefin, has excellent post-coating effect, and can effectively improve the interlayer compatibility of the thermoplastic polyolefin waterproof coiled material and other coating materials.
Description
Technical Field
The invention belongs to the technical field of functional coatings, and particularly relates to a water-based primer for thermoplastic polyolefin, a preparation method and application thereof.
Background
The TPO waterproof coiled material, namely thermoplastic polyolefin waterproof coiled material, is a synthetic polymer waterproof coiled material prepared by taking synthetic resin which combines ethylene propylene rubber and polypropylene together by adopting an advanced polymerization technology as a base material and adding additives such as an antioxidant, an anti-aging agent and the like, has excellent weather resistance and ageing resistance of the ethylene propylene rubber and weldability of the polypropylene, is suitable for exposed or non-exposed roofs of buildings and underground waterproof of the buildings, and is one of the preferable waterproof materials of roofs of industrial plants, public buildings, photovoltaic integrated buildings and the like.
However, the application of a coating to the surface of TPOs has been a difficult task for TPOs to treat and modify due to their unique surface properties. Among them, solvent-based paints represented by epoxy resins and polyurethane are the main choice of the current paint for the surface treatment of TPO coiled materials, mainly because these two resins have good adhesion properties on low polarity surfaces.
Chinese patent CN 103820006B discloses a two-component solvent-based paint for surface treatment of TPO coiled material, wherein component a comprises epoxy resin, reactive diluent, functional auxiliary agent, polyolefin resin and functional filler, and component B comprises modified amine curing agent, coupling agent and curing accelerator, and the paint can be directly firmly adhered on the surface of the TPO coiled material and can overcome the defects of deformation, cracking and the like of the surface of the TPO coiled material. Chinese patent CN 115768812A discloses a composition in the form of a solution or dispersion as a TPO primer comprising an anhydride modified polyolefin, an anhydride modified styrenic block copolymer and an isocyanate-containing cross-linking agent, the solvent comprising a ketone and an alkylbenzene or alkane solvent, the coating being capable of adhering the TPO to the TPU, polyester or PU under heat and pressure to improve peel strength. Although the above patent discloses some coatings which can be used for enhancing the adhesion of TPO surfaces, the inherent insufficient toughness of epoxy resin often leads to aging, color change and cracking in the use process, and meanwhile, the organic solvent in the coating can generate volatile organic matters to cause certain toxicity and environmental problems, so that the development of the water-based coating for TPO surface treatment has practical significance.
However, because of the low surface energy of TPO, it is difficult for the aqueous component to reach less than the surface energy of TPO, so that the aqueous component does not wet TPO well, thereby forming effective adhesion. Related researches prove that materials such as waterborne polyurethane, waterborne acrylic acid and the like have poor adhesion to the TPO surface and cannot meet application requirements.
Foreign related researches show that the aqueous acrylic latex paint with special functions can be adhered to the surface of TPO subjected to surface modification by atmospheric oxidation and/or UV degradation to achieve the purpose of repairing, and the adhesion of the aqueous acrylic latex paint on the surface of aged TPO is obviously better. However, the process is complicated. There are few aqueous primer compositions available for TPO surface treatment to enhance the adhesion of the TPO surface. Therefore, how to design a suitable water-based primer for TPO surface treatment to enhance adhesion is a challenge and application prospect.
Disclosure of Invention
The invention aims to solve the technical problem of providing an aqueous primer capable of being applied to surface treatment of thermoplastic polyolefin coiled materials to enhance adhesive force aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aqueous primer for thermoplastic polyolefin, the aqueous primer comprising an acrylate resin emulsion and a modified polyolefin emulsion, the acrylate resin having a core-shell structure of a core layer and a double shell layer, the double shell layer comprising a first shell layer and a second shell layer, the first shell layer being located between the core layer and the second shell layer, wherein the core layer is obtained by polymerization of a core layer polymerization monomer, the first shell layer is obtained by polymerization of a first shell polymerization monomer, and the second shell layer is obtained by polymerization of a second shell polymerization monomer;
the glass transition temperature of the core layer is greater than the glass transition temperature of the first shell layer, and the glass transition temperature of the core layer is greater than the glass transition temperature of the second shell layer;
the first shell polymerization monomer comprises a room temperature self-crosslinking monomer, a functional monomer, a hard monomer and a soft monomer;
the second shell polymerization monomer comprises a room temperature self-crosslinking monomer, a functional monomer, a hard monomer and a hydrophilic monomer;
the functional monomer is a monomer with a side acid group and a glass transition temperature lower than 40 ℃.
According to the invention, the theoretical glass transition temperature of the core layer is-10 ℃, the theoretical glass transition temperature of the first shell layer is-25-0 ℃, the theoretical glass transition temperature of the second shell layer is-38-10 ℃, the theoretical glass transition temperatures of the core layer, the first shell layer and the second shell layer are obtained through Fox formula calculation, and the room temperature self-crosslinking monomer is not used as a first shell layer component or a second shell layer component during calculation.
In some embodiments, the pendant acid group is a pendant carboxylic acid or a pendant phosphoric acid.
In some embodiments, the functional monomer is one or a combination of several of beta-acryloxypropionic acid (beta-CEA), ethylene glycol monomethacrylate phosphate, methacrylate alkoxyphosphate, methacrylate alkyl phosphate, vinyl alkyl phosphate, lexomer TM 50.
In some embodiments, the functional monomer is one or a combination of several of Solvin Sipomer beta-CEA, solvin Sipomer PAM, lexomer TM 50. Specifically, the composition is one or a combination of several of Sorpe dimension Sipomer beta-CEA, sorpe dimension Sipomer Wam II, sorpe dimension Sipomer PAM-100, sorpe dimension Sipomer PAM-200, sorpe dimension Sipomer PAM-4000, sorpe dimension Sipomer PAM-5000 and Lexomer TM 50.
In the invention, the functional monomer has a side acid group, and compared with a common polymerization monomer, the functional monomer has a longer side chain, can give good flexibility to acrylate resin molecules, promotes more effective interaction between a shell layer and the surface of thermoplastic polyolefin, and improves the holding viscosity.
In some embodiments, the first shell polymerized monomer, the room temperature self-crosslinking monomer is one or a combination of several of hydroxyethyl acrylamide, N-methylolacrylamide and derivatives thereof, N-isobutoxymethyl acrylamide, N-N-butoxymethyl acrylamide and hydroxyethyl acryloylurea.
In some embodiments, in the second shell polymerized monomer, the room temperature self-crosslinking monomer is acetoacetate methacrylate.
In some embodiments, in the first shell polymerized monomer, the feed molar ratio of the room temperature self-crosslinking monomer, functional monomer, hard monomer, and soft monomer is 1: 2-8:7-12:8-12.
In some embodiments, in the second shell polymerization monomer, the feeding molar ratio of the room temperature self-crosslinking monomer, the functional monomer, the soft monomer and the hydrophilic monomer is 1:4-12:8-15:1-5.
In some embodiments, the hard monomer is one or a combination of several of acrylonitrile, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, cyclohexyl methacrylate, vinyl acetate, styrene; the soft monomer is one or a combination of more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl methacrylate, hydroxyethyl acrylate, isotridecyl acrylate, cetyl acrylate, ethoxyethoxyethyl acrylate, isodecyl methacrylate and methoxypolyethylene glycol methacrylate; the hydrophilic monomer is one or a combination of a plurality of acrylic acid, methacrylic acid, butenedioic acid, methylenesuccinic acid, acrylamide and glycidyl methacrylate.
In some embodiments, the core layer polymerized monomer, the first shell polymerized monomer, and the second shell polymerized monomer are fed in a molar ratio of 1:0.4-1.5.
In some embodiments, the core layer polymerization monomer comprises a hard monomer, a soft monomer and a hydrophilic monomer, and the feeding mole ratio of the soft monomer to the hard monomer to the hydrophilic monomer is 10-20: 10-20:1.
In some embodiments, the preparation method of the acrylate resin emulsion comprises the steps of respectively preparing a core layer polymerization monomer pre-emulsion, a first shell polymerization monomer pre-emulsion and a second shell polymerization monomer pre-emulsion, polymerizing the core layer polymerization monomer pre-emulsion to obtain a core layer polymer, adding the first shell polymerization monomer pre-emulsion to polymerize to obtain a first shell polymer, and adding the second shell polymerization monomer pre-emulsion to polymerize to obtain a second shell polymer.
In some embodiments, the method of preparing the acrylate resin emulsion includes the steps of:
step S1, mixing a core layer polymerization monomer, a composite emulsifier and water to prepare a core layer polymerization monomer pre-emulsion; mixing a first shell polymerization monomer, a composite emulsifier and water to prepare a first shell polymerization monomer pre-emulsion; mixing the second shell polymerized monomer, a composite emulsifier and water to prepare a second shell polymerized monomer pre-emulsion;
s2, adding 10-30% of core layer polymerization monomer pre-emulsion and 10-30% of initiator into a reaction kettle containing a buffering agent, a composite emulsifying agent and water, and initiating polymerization reaction to obtain seed emulsion;
step S3, dropwise adding 10-30% of initiator and residual core layer polymerization monomer pre-emulsion into the reaction kettle to perform core layer polymerization reaction;
step S4, dropwise adding 10-30% of initiator and first shell polymerization monomer pre-emulsion into the reaction kettle to perform a first shell polymerization reaction;
and S5, dropwise adding the residual initiator and the second shell polymerization monomer pre-emulsion into the reaction kettle, and performing a second shell polymerization reaction.
In some embodiments, the preparation method further comprises the steps of adding a pH regulator to the reaction kettle to regulate the pH to 7-8 after the step S5, and adding ethylenediamine to the reaction kettle.
Further, in the step S2, the temperature for initiating the polymerization reaction is 60-80 ℃; in the step S3, the temperature of the nuclear layer polymerization reaction is 60-80 ℃; and/or the number of the groups of groups,
in the step S4, the temperature of the first shell polymerization reaction is 70-90 ℃; in the step S5, the temperature of the second shell polymerization reaction is 75-95 ℃.
Further, the initiator is a peroxide thermal decomposition initiator, and the total amount of the initiator is 0.2-0.4% of the total amount of the core layer polymerization monomer, the first shell polymerization monomer and the second shell polymerization monomer.
The initiator is one or a combination of more of potassium persulfate, sodium persulfate, ammonium persulfate and the like.
Further, the composite emulsifier is a non-ionic emulsifier, a zwitterionic emulsifier and an anionic emulsifier which are compounded according to the mass ratio of 1-2:0.5-1.5:0.1-0.5, and the total dosage of the composite emulsifier is 2-4% of the total dosage of the core layer polymerized monomer, the first shell polymerized monomer and the second shell polymerized monomer.
The nonionic emulsifier is one of higher fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxypropylene ether type nonionic emulsifier and polyol ester type nonionic emulsifier; the zwitterionic emulsifier is one of polyoxyethylene nonyl phenyl ether phosphate, ammonium polyoxyethylene nonyl phenyl ether sulfate and sodium fatty alcohol ether sulfate; the anionic emulsifier is one of carboxylate, sulfate and sulfonate.
The solid content of the acrylic resin emulsion is 40-60%.
In some embodiments, the modified polyolefin emulsion is an aqueous maleic anhydride modified polyolefin emulsion, and the mass ratio of the acrylate resin emulsion to the aqueous maleic anhydride modified polyolefin emulsion is 80-90:1-10.
In some embodiments, the modified polyolefin emulsion is one or a combination of several of Advanbond 7418, advanbond 7419, advanbond 7424, advanbond 7426, advanbond 7251, eastman CP 310W from advanced polymers Inc.
In some embodiments, the aqueous primer further comprises an adhesion promoting resin that is a cationic polyethylenimine having a branched polymer structure, having a weight average molecular weight of 25000 or less.
The polyethyleneimine of the adhesion promoting resin has a molecular structure similar to that of a thermoplastic polyolefin material, can be wetted on the surface of the thermoplastic polyolefin with low surface energy through similar compatible raw materials, and can be effectively adhered under the action of Van der Waals force, so that the adhesion between the primer layer and the thermoplastic polyolefin is further improved.
In some embodiments, the mass ratio of the acrylate resin emulsion to the adhesion promoting resin is 80-90: 0.1 to 2.
In some embodiments, the adhesion promoting resin is a Lupasol series surfactant. Specifically, the adhesion promoting resin is bafsf Lupasol SNA, lupasol SK, or the like.
The second technical scheme adopted by the invention is as follows: the application of the aqueous primer for thermoplastic polyolefin in thermoplastic polyolefin waterproof coiled materials.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the aqueous primer prepared by adopting the core-shell acrylate resin emulsion with the double-layer shell structure and the modified polyolefin emulsion can effectively improve the adhesion effect of the primer on the surface of thermoplastic polyolefin, has excellent post-coating effect, and can effectively improve the interlayer compatibility of the thermoplastic polyolefin waterproof coiled material and other coating materials.
Detailed Description
There are few aqueous primer compositions available for TPO surface treatment to enhance the adhesion of the TPO surface. According to the invention, the acrylate resin emulsion with a double-shell core-shell structure and the modified polyolefin emulsion with room temperature self-crosslinking property are used in a compounding way, the special molecular structure can generate multiple intermolecular interactions, the adhesive force of the aqueous primer on the surface of the low-surface-energy thermoplastic polyolefin is synergistically improved, an effective adhesive effect is generated, and the full aqueous primer is environment-friendly. Specifically, in the first aspect, the acrylate resin with the core-shell structure enables the bottom coating to have the performances of water resistance, bending resistance, anti-back adhesion, large extensibility and the like, the unique heterogeneous structure can improve the wettability on the surface with low surface energy, and meanwhile, the double shells all have room temperature self-crosslinking property, so that a compact polymer network film layer can be constructed, and effective adhesion is formed. In the second aspect, longer side chains in the molecular structure of the shell give the molecule good flexibility, promote more effective interaction between the shell and the surface of the thermoplastic polyolefin, and improve the holding viscosity. In a third aspect, the modified polyolefin emulsion has a molecular structure similar to that of a polyolefin material, can be wetted on the surface of a polyolefin with low surface energy by a similar principle of compatibility, and effectively adheres by van der Waals force. In the fourth aspect, the acrylic resin molecules and the polyolefin molecules form an interpenetrating structure through internal entanglement, the structure is well fixed after crosslinking, and the high adhesive force groups are further enhanced, and the adhesion and the holding viscosity are improved through the van der Waals force synergy based on the similar compatibility principle. The adhesion effect of the primer layer on the surface of the thermoplastic polyolefin can be effectively improved through the compounding of the acrylic resin emulsion and the modified polyolefin emulsion, the primer layer has an excellent post-coating effect, and the interlayer compatibility of the polyolefin and other coating materials is effectively improved.
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention.
Example 1
The aqueous primer provided in this example was obtained by stirring 80 parts of a room temperature self-crosslinking acrylate resin emulsion, 10 parts of a modified polyolefin emulsion Advabond 7418, and 0.1 part of Basoff Lupasol SNA for 30 minutes.
In this example, the room temperature self-crosslinking acrylate resin emulsion was prepared by the following method:
(1) Preparing a core layer polymerization monomer pre-emulsion: acrylic acid, butyl acrylate and isobutyl methacrylate are mixed according to a mole ratio of 1: after fully mixing 10:10, heating to 55 ℃, adding deionized water solution of a composite emulsifier (the mass ratio of the composite emulsifier to the deionized water is 1:30), and pre-emulsifying for 20min to obtain core layer polymerized monomer pre-emulsion, wherein the dosage of the composite emulsifier is 2% of that of the core layer polymerized monomer;
(2) Preparing a first shell polymerization monomer pre-emulsion: fully mixing N-methylol acrylamide, simer beta-CEA, methyl methacrylate and lauryl methacrylate according to a molar ratio of 1:4:10:10, heating to 55 ℃, adding deionized water solution of a composite emulsifier (the mass ratio of the composite emulsifier to the deionized water is 1:30), and pre-emulsifying for 20min to obtain a first shell polymerized monomer pre-emulsion, wherein the dosage of the composite emulsifier is 2% of that of the first shell polymerized monomer;
(3) Preparing a second shell polymerization monomer pre-emulsion: fully mixing ethyl acetoacetate methacrylate, simer beta-CEA, lauryl methacrylate and acrylic acid according to the molar ratio of 1:6:9:3, heating to 55 ℃, adding deionized water solution of a composite emulsifier (the mass ratio of the composite emulsifier to deionized water is 1:30), and pre-emulsifying for 20min to obtain second shell polymerized monomer pre-emulsion, wherein the dosage of the composite emulsifier is 2% of that of the second shell polymerized monomer;
(4) Preparing an initiator solution: preparing potassium persulfate and deionized water into 10% potassium persulfate solution;
(5) Respectively taking a core layer polymerization monomer pre-emulsion, a first shell polymerization monomer pre-emulsion and a second shell polymerization monomer pre-emulsion according to the total molar ratio of the monomers of 1:0.8:1.2, and taking a potassium persulfate solution according to the amount of potassium persulfate accounting for 0.3% of the total amount of all the monomers;
(6) Adding 1/4 mass of core layer polymerization monomer pre-emulsion and 1/4 mass of potassium persulfate solution into a reaction kettle added with buffer solution under the nitrogen atmosphere, and performing condensation reflux reaction for 30min at 70 ℃ to obtain seed emulsion; slowly dropwise adding 1/4 mass of potassium persulfate solution and residual core layer polymerization monomer pre-emulsion into a reaction kettle at 70 ℃ for 2 hours, and continuing to react for 1.5 hours, wherein the buffer solution consists of water, a composite emulsifier and NaHCO 3 The emulsion comprises the components in a mass ratio of 1:0.01:0.01, and the solid content of the final acrylic resin emulsion is 50% by using water;
(7) Heating to 80 ℃, dropwise adding the first shell polymerization monomer pre-emulsion and 1/4 mass potassium persulfate solution into a reaction kettle, and keeping the temperature at 80 ℃ for continuous reaction for 2 hours after 2 hours of dropwise addition;
(8) Maintaining the temperature at 80 ℃, dropwise adding the second shell polymerization monomer pre-emulsion and 1/4 mass potassium persulfate solution into a reaction kettle, after 2h of dropwise adding, heating to 85 ℃ and reacting for 2h;
(9) Cooling to room temperature, regulating the pH to 7-8 by ammonia water, adding an ethylenediamine water solution with the mass concentration of 20%, wherein the consumption of ethylenediamine is 1/4 of the mass of acetoacetate methacrylate, stirring for 20min, and filtering to obtain the acrylic resin emulsion with the core-shell structure.
The composite emulsifier used in the example is a compound of alkylphenol ethoxylates, nonylphenol polyoxyethylene ether phosphate and sodium dodecyl sulfate according to the mass ratio of 1:0.5:0.5.
Example 2
The aqueous primer provided in this example differs from that in example 1 in that:
in the step (2), the molar ratio of the N-methylolacrylamide, the Sipomer beta-CEA, the methyl methacrylate and the lauryl methacrylate is 1:7.5:8:8.5;
in the step (3), the molar ratio of acetoacetate methacrylate, sipomer beta-CEA, lauryl methacrylate and acrylic acid is 1:11:15:5.
Example 3
The aqueous primer provided in this example differs from that in example 1 in that:
in the step (5), the core layer polymerization monomer pre-emulsion, the first shell polymerization monomer pre-emulsion and the second shell polymerization monomer pre-emulsion are respectively taken according to the total molar ratio of the monomers of 1:0.5:0.5.
Example 4
The aqueous primer provided in this example differs from that in example 1 in that:
in the step (1), the molar ratio of the acrylic acid to the butyl acrylate to the isobutyl methacrylate is 1:5:5.
In the step (2) and the step (3), the Sipomer beta-CEA is replaced by the Sorver Sipomer PAM-100.
Example 5
The aqueous primer provided in this example was obtained by stirring 85 parts of a room temperature self-crosslinking acrylate resin emulsion, 5 parts of a modified polyolefin emulsion Eastman CP 310W, and 1 part of Basoff Lupasol SNA for 30 minutes, wherein the room temperature self-crosslinking acrylate resin emulsion was prepared in the same manner as in example 1.
Comparative example 1
The aqueous primer provided in this comparative example differs from that of example 1 in that: the acrylate resin emulsion is prepared without adding the first shell polymerization monomer pre-emulsion.
Comparative example 2
The aqueous primer provided in this comparative example differs from that of example 1 in that: the functional monomer Sipomer beta-CEA is not added when the first shell polymerization monomer pre-emulsion and the second shell polymerization monomer pre-emulsion are prepared.
Comparative example 3
The aqueous primer provided in this comparative example differs from that of example 1 in that: n-methylol acrylamide is not added when the first shell polymerization monomer pre-emulsion is prepared, and acetoacetic acid ethyl ester methacrylate and ethylenediamine are not added when the second shell polymerization monomer pre-emulsion is prepared.
Comparative example 4
The aqueous primer provided in this comparative example differs from that of example 1 in that: no modified polyolefin emulsion was added.
And calculating theoretical glass transition temperatures of the core layer, the first shell layer and the second shell layer copolymers in the acrylate resin emulsions prepared in examples 1-5 and comparative examples 1-3 by adopting a Fox formula, wherein the room temperature self-crosslinking monomer in the first shell layer is not regarded as a component of the copolymer, and the room temperature self-crosslinking monomer in the second shell layer is not regarded as a component of the copolymer during calculation. As in example 1, the theoretical glass transition temperature of the first shell copolymer was calculated using only β -CEA, methyl methacrylate, lauryl methacrylate as the individual components of the first shell copolymer; when calculating the theoretical glass transition temperature of the second shell copolymer, only beta-CEA, lauryl methacrylate and acrylic acid are used as the components of the second shell copolymer. The results are shown in Table 1.
Table 1 theoretical glass transition temperatures of the acrylate resin emulsions of examples 1 to 4 and comparative examples 1 to 3
The aqueous primer compositions of examples 1 to 5 and comparative examples 1 to 4 were tested for adhesion to TPO surfaces by cross-hatch with reference to GBT9286-2021, and the results are shown in tables 2 and 3.
The specific method comprises the following steps: firstly, a 50 mu m wire rod is used for coating an aqueous primer on the surface of TPO, and after curing for 7 days under the curing conditions specified by the standard, a 200 mu m wire rod is used for coating the anti-pollution five-in-one white paint of the Libang bamboo charcoal on the surface of TPO.
Table 2 adhesion test results of the Water-borne base coating of examples 1 to 5 on TPO
Table 3 adhesion test results of the Water-borne base coating of comparative examples 1 to 4 on TPO
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (17)
1. An aqueous primer for thermoplastic polyolefin, characterized in that: the aqueous primer comprises an acrylic resin emulsion and a modified polyolefin emulsion, wherein the acrylic resin has a core-shell structure of a core layer and a double-shell layer, the double-shell layer comprises a first shell layer and a second shell layer, the first shell layer is positioned between the core layer and the second shell layer, the core layer is obtained by polymerizing a core layer polymerization monomer, the first shell layer is obtained by polymerizing a first shell polymerization monomer, and the second shell layer is obtained by polymerizing a second shell polymerization monomer;
the glass transition temperature of the core layer is greater than the glass transition temperature of the first shell layer, and the glass transition temperature of the core layer is greater than the glass transition temperature of the second shell layer;
the first shell polymerization monomer comprises a room temperature self-crosslinking monomer, a functional monomer, a hard monomer and a soft monomer;
the second shell polymerization monomer comprises a room temperature self-crosslinking monomer, a functional monomer, a soft monomer and a hydrophilic monomer;
the functional monomer is a monomer with a side acid group and a glass transition temperature lower than 40 ℃.
2. The aqueous primer for thermoplastic polyolefin according to claim 1, wherein: the pendant acid group is a pendant carboxylic acid or a pendant phosphoric acid.
3. The aqueous primer for thermoplastic polyolefin according to claim 1, wherein: the functional monomer is one or a combination of a plurality of beta-acryloxypropionic acid, polyethylene glycol monomethacrylate phosphate, methacrylate alkoxyl phosphate, methacrylic acid alkyl phosphate, vinyl alkyl phosphate and Lexomer TM 50.
4. The aqueous primer for thermoplastic polyolefin according to claim 3, wherein: the functional monomer is one or a combination of more of Sipomer beta-CEA, sipomer PAM and Lexomer TM 50.
5. The aqueous primer for thermoplastic polyolefin according to claim 1, wherein: in the first shell polymerization monomer, the room temperature self-crosslinking monomer is one or a combination of more of hydroxyethyl acrylamide, N-methylolacrylamide and derivatives thereof, N-isobutoxymethyl acrylamide, N-N-butoxymethyl acrylamide and hydroxyethyl acryloylurea; and/or, in the second shell polymerization monomer, the room temperature self-crosslinking monomer is acetoacetic acid ethyl methacrylate.
6. The aqueous primer for thermoplastic polyolefin according to claim 1, wherein: in the first shell polymerization monomer, the feeding mole ratio of the room temperature self-crosslinking monomer to the functional monomer to the hard monomer to the soft monomer is 1: 2-8:7-12:8-12; and/or in the second shell polymerization monomer, the feeding mole ratio of the room temperature self-crosslinking monomer to the functional monomer to the soft monomer to the hydrophilic monomer is 1:4-12:8-15:1-5.
7. The aqueous primer for thermoplastic polyolefin according to claim 1 or 6, characterized in that: the hard monomer is one or a combination of a plurality of acrylonitrile, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, cyclohexyl methacrylate, vinyl acetate and styrene; and/or the soft monomer is one or a combination of more than one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl methacrylate, hydroxyethyl acrylate, isotridecyl acrylate, cetyl acrylate, ethoxyethoxyethyl acrylate, isodecyl methacrylate and methoxy polyethylene glycol methacrylate; and/or the hydrophilic monomer is one or a combination of a plurality of acrylic acid, methacrylic acid, butenedioic acid, itaconic acid, acrylamide and glycidyl methacrylate.
8. The aqueous primer for thermoplastic polyolefin according to claim 1, wherein: the feeding mole ratio of the core layer polymerization monomer to the first shell polymerization monomer to the second shell polymerization monomer is 1:0.4-1.5.
9. The aqueous primer for thermoplastic polyolefin according to claim 1 or 8, characterized in that: the core layer polymerization monomer comprises a hard monomer, a soft monomer and a hydrophilic monomer, wherein the feeding mole ratio of the hard monomer to the soft monomer to the hydrophilic monomer is 10-20: 10-20:1.
10. The aqueous primer for thermoplastic polyolefin according to any one of claims 1 to 6 or 8, characterized in that: the preparation method of the acrylic resin emulsion comprises the steps of respectively preparing a core layer polymerization monomer pre-emulsion, a first shell polymerization monomer pre-emulsion and a second shell polymerization monomer pre-emulsion, polymerizing the core layer polymerization monomer pre-emulsion to obtain a core layer polymer, adding the first shell polymerization monomer pre-emulsion to polymerize to obtain a first shell polymer, and adding the second shell polymerization monomer pre-emulsion to polymerize to obtain a second shell polymer.
11. The aqueous primer for thermoplastic polyolefin according to claim 10, wherein: the preparation method of the acrylic resin emulsion comprises the following steps:
step S1, mixing a core layer polymerization monomer, a composite emulsifier and water to prepare a core layer polymerization monomer pre-emulsion; mixing a first shell polymerization monomer, a composite emulsifier and water to prepare a first shell polymerization monomer pre-emulsion; mixing the second shell polymerized monomer, a composite emulsifier and water to prepare a second shell polymerized monomer pre-emulsion;
s2, adding 10-30% of core layer polymerization monomer pre-emulsion and 10-30% of initiator into a reaction kettle containing a buffering agent, a composite emulsifying agent and water, and initiating polymerization reaction to obtain seed emulsion;
step S3, dropwise adding 10-30% of initiator and residual core layer polymerization monomer pre-emulsion into the reaction kettle to perform core layer polymerization reaction;
step S4, dropwise adding 10-30% of initiator and first shell polymerization monomer pre-emulsion into the reaction kettle to perform a first shell polymerization reaction;
and S5, dropwise adding the residual initiator and the second shell polymerization monomer pre-emulsion into the reaction kettle, and performing a second shell polymerization reaction.
12. The aqueous primer for thermoplastic polyolefin according to claim 11, wherein:
in the step S2, the temperature for initiating the polymerization reaction is 60-80 ℃; and/or the number of the groups of groups,
in the step S3, the temperature of the nuclear layer polymerization reaction is 60-80 ℃; and/or the number of the groups of groups,
in the step S4, the temperature of the first shell polymerization reaction is 70-90 ℃; and/or the number of the groups of groups,
in the step S5, the temperature of the second shell polymerization reaction is 75-95 ℃; and/or the number of the groups of groups,
the initiator is a peroxide thermal decomposition initiator, and the total amount of the initiator is 0.2-0.4% of the total amount of the core layer polymerization monomer, the first shell polymerization monomer and the second shell polymerization monomer; and/or the number of the groups of groups,
the composite emulsifier is a compound of a nonionic emulsifier, a zwitterionic emulsifier and an anionic emulsifier according to a mass ratio of 1-2:0.5-1.5:0.1-0.5; and/or the number of the groups of groups,
the preparation method further comprises the steps of adding a pH regulator into the reaction kettle to regulate the pH to 7-8 after the step S5, and adding ethylenediamine into the reaction kettle.
13. The aqueous primer for thermoplastic polyolefin according to any one of claims 1 to 6 or 8, characterized in that: the modified polyolefin emulsion is aqueous maleic anhydride modified polyolefin emulsion, and the mass ratio of the acrylic resin emulsion to the aqueous maleic anhydride modified polyolefin emulsion is 80-90:1-10.
14. The aqueous primer for thermoplastic polyolefin according to claim 13, wherein: the modified polyolefin emulsion is one or the combination of a plurality of Advanbond 7418, advanbond 7419, advanbond 7414, advanbond 7426, advanbond 7251 and Eastman CP 310W.
15. The aqueous primer for thermoplastic polyolefin according to claim 13, wherein: the aqueous primer further comprises an adhesion promoting resin which is a cationic polyethyleneimine having a branched polymer structure, and has a weight average molecular weight of 25000 or less.
16. The aqueous primer for thermoplastic polyolefin according to claim 15, wherein: the mass ratio of the acrylic resin emulsion to the adhesion promoting resin is 80-90: 0.1-2; and/or the adhesion promoting resin is Lupasol series surfactant.
17. Use of the aqueous primer for thermoplastic polyolefin according to any one of claims 1 to 16 for thermoplastic polyolefin waterproof rolls.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311368510.XA CN117106354B (en) | 2023-10-23 | 2023-10-23 | Water-based primer for thermoplastic polyolefin, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311368510.XA CN117106354B (en) | 2023-10-23 | 2023-10-23 | Water-based primer for thermoplastic polyolefin, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117106354A true CN117106354A (en) | 2023-11-24 |
| CN117106354B CN117106354B (en) | 2024-01-05 |
Family
ID=88795055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311368510.XA Active CN117106354B (en) | 2023-10-23 | 2023-10-23 | Water-based primer for thermoplastic polyolefin, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117106354B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160280932A1 (en) * | 2013-11-15 | 2016-09-29 | Arkema France | Aqueous dispersion of polymer made from multistructured particles for aqueous wall coatings resistant to dirt and wet abrasion |
| US20160289489A1 (en) * | 2013-11-15 | 2016-10-06 | Arkema France | Aqueous dispersion of polymer made from multistructured particles for aqueous coatings having improved blocking and fingerprint resistance and hardness |
| CN109824818A (en) * | 2019-01-18 | 2019-05-31 | 郑州中科新兴产业技术研究院 | A kind of core-shell structure ambient self cross-linkable acrylic emulsion of multiple cross-linked modification and preparation method thereof |
| CN112778470A (en) * | 2020-12-30 | 2021-05-11 | 优美特（北京）环境材料科技股份公司 | Single-component water-based resin for high-barrier bottom surface combination and preparation method thereof |
| CN114940728A (en) * | 2022-07-26 | 2022-08-26 | 江苏凯伦建材股份有限公司 | Acrylic emulsion for thermoplastic polyolefin and preparation method and application thereof |
| CN116769114A (en) * | 2023-07-18 | 2023-09-19 | 浙江辉柯纸塑制品有限公司 | Multilayer core-shell acrylate emulsion and preparation method and application thereof |
-
2023
- 2023-10-23 CN CN202311368510.XA patent/CN117106354B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160280932A1 (en) * | 2013-11-15 | 2016-09-29 | Arkema France | Aqueous dispersion of polymer made from multistructured particles for aqueous wall coatings resistant to dirt and wet abrasion |
| US20160289489A1 (en) * | 2013-11-15 | 2016-10-06 | Arkema France | Aqueous dispersion of polymer made from multistructured particles for aqueous coatings having improved blocking and fingerprint resistance and hardness |
| CN109824818A (en) * | 2019-01-18 | 2019-05-31 | 郑州中科新兴产业技术研究院 | A kind of core-shell structure ambient self cross-linkable acrylic emulsion of multiple cross-linked modification and preparation method thereof |
| CN112778470A (en) * | 2020-12-30 | 2021-05-11 | 优美特（北京）环境材料科技股份公司 | Single-component water-based resin for high-barrier bottom surface combination and preparation method thereof |
| CN114940728A (en) * | 2022-07-26 | 2022-08-26 | 江苏凯伦建材股份有限公司 | Acrylic emulsion for thermoplastic polyolefin and preparation method and application thereof |
| CN116769114A (en) * | 2023-07-18 | 2023-09-19 | 浙江辉柯纸塑制品有限公司 | Multilayer core-shell acrylate emulsion and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117106354B (en) | 2024-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107522821B (en) | Acrylic acid modified polyester water-based resin for coil coating and preparation method thereof | |
| CN103045113B (en) | Preparation method of self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive | |
| CN109651551B (en) | Acrylate emulsion for building interior wall coating, preparation method thereof and coating | |
| CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
| CN110627950A (en) | Aqueous fluorine modified acrylic emulsion and preparation method and application thereof | |
| CN110818828B (en) | Self-retardant fuel alcohol polyether-2 phosphate modified waterborne acrylic acid anticorrosive resin and preparation method thereof | |
| CN1919889A (en) | Organosilicon epoxide acrylate water dispersion, preparation method and application thereof | |
| CN113105571B (en) | Low-temperature self-crosslinking waterborne epoxy modified acrylic resin and preparation method and application thereof | |
| CN114015307B (en) | Single-component water-based acrylic acid strippable paint and preparation method and application thereof | |
| CN114316854B (en) | Acrylic acid adhesive with high solid content and low viscosity and preparation method thereof | |
| CN107383269B (en) | Preparation method of room-temperature-cured water-based acrylic resin secondary dispersion | |
| CN111073445B (en) | Water-based two-component paint with high impact resistance and application thereof | |
| CN113980187B (en) | Water-based matte core-shell emulsion and preparation method and application thereof | |
| CN117106354B (en) | Water-based primer for thermoplastic polyolefin, and preparation method and application thereof | |
| CN113563503A (en) | Preparation method of environment-friendly water-resistant yellowing-resistant copolymer emulsion | |
| CN110922540B (en) | Polyether amine derivative modified waterborne acrylic resin and preparation method thereof | |
| CN109942742A (en) | A kind of water dispersion glass coated polymeric and preparation method thereof | |
| CN110527031B (en) | Water-based acrylic emulsion for quick-drying sealant and preparation method thereof | |
| CN114891166A (en) | Organic silicon oil composite acrylic latex and preparation method thereof | |
| CN114989362A (en) | Functional multifunctional siloxane prepolymer acrylate emulsion and preparation method thereof | |
| CN114316160A (en) | Acrylic emulsion polymer and preparation method of water-based paint based on polymer | |
| CN117362506B (en) | Self-crosslinking acrylic emulsion and preparation method and application thereof | |
| JPH11343449A (en) | Coating resin composition | |
| CN116836657B (en) | Water-based optical adhesive and preparation method thereof | |
| CN115010867B (en) | Water-based wood lacquer emulsion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |