CN105175615B - A kind of aqueous environment protection filmogen applied to steel fastener surface and preparation method and application - Google Patents
A kind of aqueous environment protection filmogen applied to steel fastener surface and preparation method and application Download PDFInfo
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- CN105175615B CN105175615B CN201510542857.0A CN201510542857A CN105175615B CN 105175615 B CN105175615 B CN 105175615B CN 201510542857 A CN201510542857 A CN 201510542857A CN 105175615 B CN105175615 B CN 105175615B
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- acid
- shell emulsion
- ester
- acrylate
- monomer
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 39
- 230000004224 protection Effects 0.000 title claims abstract description 39
- 239000010959 steel Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000839 emulsion Substances 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 49
- -1 alcohol ester Chemical class 0.000 claims abstract description 30
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 27
- 239000011258 core-shell material Substances 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 150000003014 phosphoric acid esters Chemical group 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 27
- 229910019142 PO4 Inorganic materials 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000004945 emulsification Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 16
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 claims description 6
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 235000003642 hunger Nutrition 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 230000037351 starvation Effects 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229940094933 n-dodecane Drugs 0.000 claims description 5
- GILMNGUTRWPWSY-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(O)COC(=O)C=C GILMNGUTRWPWSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000000295 complement effect Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- VICFASWPTIXXIR-UHFFFAOYSA-N ethenyl dihydrogen phosphate;sodium Chemical compound [Na].OP(O)(=O)OC=C VICFASWPTIXXIR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid 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
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical class COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 2
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 claims 1
- KJESGYZFVCIMDE-UHFFFAOYSA-N 1-chloroethanol Chemical compound CC(O)Cl KJESGYZFVCIMDE-UHFFFAOYSA-N 0.000 claims 1
- ZRIMDWRLVGDUBW-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid phosphoric acid Chemical group P(=O)(O)(O)O.OCCC=C(C(=O)O)C ZRIMDWRLVGDUBW-UHFFFAOYSA-N 0.000 claims 1
- QMRLJPVKZYHGRS-UHFFFAOYSA-N C(C(=C)C)(=O)N.[O] Chemical compound C(C(=C)C)(=O)N.[O] QMRLJPVKZYHGRS-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- MQVMJSWYKLYFIG-UHFFFAOYSA-N propane-1-sulfonic acid;sodium Chemical compound [Na].CCCS(O)(=O)=O MQVMJSWYKLYFIG-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 17
- 239000002585 base Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000003973 paint Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- MJYNUMNIZMSVQU-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid;sodium Chemical compound [Na].CCC(O)S(O)(=O)=O MJYNUMNIZMSVQU-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000006750 UV protection Effects 0.000 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 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 230000029219 regulation of pH Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- LPXFITACVAQQAL-UHFFFAOYSA-M sodium;prop-2-enoylazanide Chemical group [Na+].[NH-]C(=O)C=C LPXFITACVAQQAL-UHFFFAOYSA-M 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical class OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of aqueous environment protection filmogen applied to steel fastener surface and preparation method and application, specifically, the preparation method for being applied to the aqueous environment protection filmogen of steel fastener surface includes the synthesis of shell emulsion and the synthesis of core-shell emulsion, i.e., first uses ethylenic carboxylic acid, crosslinking functionality monomer and acrylic acid (C1‑C10) alcohol ester vinyl monomer I, shell emulsion is prepared；Acrylic acid (C is used to above-mentioned shell emulsion again1‑C10) alcohol ester, phosphoric acid ester function monomer, styrene one or more kinds of mixing vinyl monomer II synthesis core-shell emulsions, i.e. the aqueous environment protection filmogen applied to steel fastener surface；This be applied to steel fastener surface aqueous environment protection filmogen is high to base material adhesive force, corrosion-resistant, resistance to oxidation, wear-resisting.
Description
Technical field
The present invention relates to aqueous metal surface coating material technical field, and in particular to one kind is applied to steel fastener table
The aqueous environment protection filmogen in face and preparation method and application.
Background technology
It is estimated that because direct economic loss caused by metal erosion accounts for the 3%~4% of gross national product.Anti-corrosion
Technology is most important in the fields such as chemical industry, oil, electric power, machinery, intermetallic composite coating, communications and transportation, nuclear energy and space flight.It is main at present
The anticorrosive measure wanted has from corrosion resistant material, cathodic protection, anodic protection, media processes, corrosion inhibiter, coating protection, oxidation
Processing etc., its floating coat Protection Code is most widely used, maximally effective measure.
Coating for metal surfaces guard method is a lot, and organic coating is such as coated in metal surface or applies coating, phosphatization, passivation
Deng.And traditional protection by metallic coating method, considerable influence to environment be present, as chromium passivating, phosphatization and organic solvent volatilize
Deng.
The development of waterborne polymeric brings opportunity to the development in anti-corrosion of metal field, and developing to arrive has solvent based coating
Performance water-base resin material, particularly have and endure water-base resin material such as water and salt corrosion harshness material, one
It all it has been the problem of anti-corrosion of metal antirust field is difficult to capture since straight.
The content of the invention
The defects of to overcome prior art, it is an object of the invention to provide a kind of corrosion resistance it is high be applied to steel it is tight
The aqueous environment protection filmogen on firmware surface.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of preparation method of aqueous environment protection filmogen applied to steel fastener surface, comprises the following steps：
1) synthesis of shell emulsion：Take the initiator, the molecule of 1-3 parts of vinyl monomer I, 0.5-1.5 part of 20-30 parts
Amount adjustments, the compound emulsifying agent of 0.5-1.5 parts, 1-3 parts pH adjusting agent and complement to 100 parts of water, the obtained shell of reaction
Emulsion；
2) synthesis of core-shell emulsion：The initiator of 1-2 parts, 50-90 parts are added in the shell emulsion obtained to step 1)
Vinyl monomer II, reaction obtain core-shell emulsion, i.e. the aqueous environment protection filmogen applied to steel fastener surface；
In step 1), the vinyl monomer I includes ethylenic carboxylic acid, crosslinking functionality monomer and acrylic acid (C1-C10) alcohol
Ester；
In step 2), the vinyl monomer II is acrylic acid (C1-C10) alcohol ester, phosphoric acid ester function monomer, styrene
One or more.
Preferably, the synthesis of step 1) the shell emulsion comprises the following steps：
I) add water rising temperature for dissolving to be passed through nitrogen deoxygenation initiator and obtain initiator solution；
Ii vinyl monomer I, molecular weight regulator, water and compound emulsifying agent) are mixed into pre-emulsification and obtain pre-emulsification solution；
Iii) pre-emulsification solution is added dropwise in initiator solution with " starvation method " at 80-85 DEG C and reacted, adds pH regulations
Agent adjusts pH to 7.5-8.0, obtains shell emulsion.
Preferably, the synthesis of the step 2) core-shell emulsion comprises the following steps：
I) initiator is added in the shell emulsion that step 1) obtains；
II vinyl monomer II) is added dropwise at 80-85 DEG C, continues to cure 60-90min after being added dropwise, is cooled to room temperature,
Filtering, obtains core-shell emulsion, i.e. the aqueous environment protection filmogen applied to steel fastener surface.
Preferably, in step 1),
The ethylenic carboxylic acid is fumaric acid, itaconic acid, maleic acid, methacrylic acid, acrylic acid and propyloic acrylic ester
One or both of more than；
The crosslinking functionality monomer is stupid divinyl, ethylene glycol diacrylate, diallyl maleate, Ji Wusi
Alcohol triallyl, terephthaldehyde's base diene acid ester, methylene-bisacrylamide, ethyoxyl trimethylolpropane trimethacrylate,
Triethylene glycol double methacrylate, N hydroxymethyl acrylamide, N- methoxymethyl propenamides, N- isobutoxy methyls acrylamide,
N- isopropoxymethyls acrylamide, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, methacrylic acid-β-hydroxypropyl acrylate,
Senecioate-hydroxypropyl acrylate, allyl glycidyl ether, GMA, glycidyl acrylate, methylol
It is more than one or both of DAAM, DAAM；
Acrylic acid (the C1-C10) ester monomer be methyl methacrylate, methyl acrylate, EMA,
One kind in ethyl acrylate, butyl methacrylate, butyl acrylate, EHMA, Isooctyl acrylate monomer or
It is two or more.
Preferably, in step 1), the compound emulsifying agent is acrylamido sodium isopropyl xanthate, the spy containing pi-allyl
Kind ether alcohol sulfate, double bond containing alcohol ether sulfenyl succinate sodium salt, vinyl phosphoric acid sodium, 2- allyl ether 3- hydroxy propanes-
1- sodium sulfonates, allyl ether hydroxypropanesulfonic acid sodium, branched alkyl alcohol APEO phosphate monoester, C12-C13Half Branched fatty
It is two or more in alcohol APEO and ethylene oxide/propylene oxide copolymer.
Preferably, the molecular weight regulator is primary DDM dodecyl mercaptan, tert-dodecyl mercaptan, acetic acid dodecyl sulphur
Alcohol ester, benzoic acid n-dodecyl mercaptan ester, 1- n-dodecane stream bases ethapon, beta-phenyl β-n-dodecane sulfenyl ethylo benzene
One kind in base ketone, two fragrant acyl disulphide or 3- mercaprols；The pH adjusting agent is alcamines organic amine or ammoniacal liquor.
Preferably, the vinyl monomer II be methyl methacrylate, methyl acrylate, EMA,
Ethyl acrylate, butyl methacrylate, butyl acrylate, EHMA, Isooctyl acrylate monomer, hydroxyethyl methyl
Acrylated phosphate, vinyl alkoxy phosphate, methacrylic acid ester group alkoxy phosphate, vinyl alkyl phosphate, nitrogen
It is one or more kinds of in heterocyclic methyl acrylate, isobornyl methacrylate, isobornyl acrylate or styrene.
Preferably, the initiator is ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
The second object of the present invention is to provide the water applied to steel fastener surface prepared by a kind of above-mentioned method
Property environment-friendly type filmogen.
The third object of the present invention is to provide the above-mentioned aqueous environment protection applied to steel fastener surface into membrane material
Expect the application in steel antirust.
Relative to prior art, there is following technique effect in the present invention：
1. the present invention is using self-cross linking type shell emulsion is first made, to improve to the adhesive force of metal, water resistance and weathering
Property；Again with phosphate ester monomer or other vinyl monomers, form core-shell emulsion, with improve corrosion resistance it is high to be applied to steel tight
Corrosion Protection and rust-preventing characteristic of the aqueous environment protection filmogen on firmware surface to metal；
2. the aqueous environment protection filmogen provided by the invention applied to steel fastener surface is shell-caryogram structure,
The hardness of its shell is high, and the big high temperature resistant of self-crosslinkable under normal temperature, i.e. intensity, not easy to crack or damaged；The hardness of its core can pass through
Adjust vinyl monomer II component and change, to obtain the shell core emulsion of different glass temperature；
3. preparation process of the present invention is simple to operate, operability is stable, suitable large-scale production；
4. product belongs to aqueous environment protection high-new technology productses, can be instructed by RoHS Directive 2002/95/EC and its
The limitation requirement of the 2011/65/EU annex two reformulated.Can be by being advised in Europe instruction 2009/48/EC and its order of subsequent amendments system
Fixed soluble elements content.Product and the technical support for meeting market demands are provided for the color aqueous environment-friendly coating of steel；
5. the aqueous environment protection filmogen provided by the invention applied to steel fastener surface has outstanding to metal
Adhesive force, anticorrosive property, anti-flash rusting, shielding, weatherability and water resistance, and can self-crosslinking under normal temperature；
6. the aqueous environment protection filmogen provided by the invention applied to steel fastener surface is applied to kind of a water-based painting
On material, there is the advantages of period of storage permanent, excellent in stability, high temperature resistant, water-fast, weather-proof, ambient self-crosslinking, and it is prepared
Process is simple, nontoxic, it is environmentally friendly the advantages that.
The present invention is described in further detail with reference to specific embodiment.
Embodiment
The present invention provide a kind of aqueous environment protection filmogen applied to steel fastener surface and preparation method thereof with
Using the preparation method for the aqueous environment protection filmogen that should be applied to steel fastener surface comprise the following steps：
A kind of preparation method of aqueous environment protection filmogen applied to steel fastener surface, comprises the following steps：
1) synthesis of shell emulsion：Take the initiator, the molecule of 1-3 parts of vinyl monomer I, 0.5-1.5 part of 20-30 parts
Amount adjustments, the compound emulsifying agent of 0.5-1.5 parts, 1-3 parts pH adjusting agent and complement to 100 parts of water, the obtained shell of reaction
Emulsion；
2) synthesis of core-shell emulsion：The initiator of 1-2 parts, 50-90 parts are added in the shell emulsion obtained to step 1)
Vinyl monomer II, reaction obtain core-shell emulsion, i.e. the aqueous environment protection filmogen applied to steel fastener surface；
In step 1), the vinyl monomer I includes ethylenic carboxylic acid, crosslinking functionality monomer and acrylic acid (C1-C10) alcohol
Ester；
Wherein ethylenic carboxylic acid can effectively improve water paint to the adhesive force of base material, corrosion resistance and anti-flash rusting, improve breast
The stability of liquid system；Crosslinking functionality monomer promotes to form net formula cross-linked polymeric system, improves the stability and corrosion resistant of system
Corrosion；Acrylic acid (C1-C10) alcohol ester effectively improves the ultra-violet resistance of filmogen and the adhesive force to base material.
In step 2), the vinyl monomer II is acrylic acid (C1-C10) alcohol ester, phosphoric acid ester function monomer, styrene
One or more；
In core-shell emulsion, vinyl monomer I and vinyl monomer II weight ratio preferably 1：2.5-3.The nucleocapsid ratio
Design cause synthetic emulsion optimal protective coating is formed in metal surface.
Preferably, the synthesis of step 1) the shell emulsion comprises the following steps：
I) add water rising temperature for dissolving to be passed through nitrogen deoxygenation initiator and obtain initiator solution；
Ii vinyl monomer I, molecular weight regulator, water and compound emulsifying agent) are mixed into pre-emulsification and obtain pre-emulsification solution；
Iii) pre-emulsification solution is added dropwise in initiator solution with " starvation method " at 80-85 DEG C and reacted, adds pH regulations
Agent adjusts pH to 7.5-8.0, obtains shell emulsion.
Preferably, the synthesis of the step 2) core-shell emulsion comprises the following steps：
I) initiator is added in the shell emulsion that step 1) obtains；
II vinyl monomer II) is added dropwise at 80-85 DEG C, continues to cure 60-90min after being added dropwise, is cooled to room temperature,
Filtering, obtains core-shell emulsion, i.e. the aqueous environment protection filmogen applied to steel fastener surface.
Preferably, in step 1),
The ethylenic carboxylic acid is fumaric acid, itaconic acid, maleic acid, methacrylic acid, acrylic acid and propyloic acrylic ester
One or both of more than；
The crosslinking functionality monomer is stupid divinyl, ethylene glycol diacrylate, diallyl maleate, Ji Wusi
Alcohol triallyl, terephthaldehyde's base diene acid ester, methylene-bisacrylamide, ethyoxyl trimethylolpropane trimethacrylate,
Triethylene glycol double methacrylate, N hydroxymethyl acrylamide, N- methoxymethyl propenamides, N- isobutoxy methyls acrylamide,
N- isopropoxymethyls acrylamide, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, methacrylic acid-β-hydroxypropyl acrylate,
Senecioate-hydroxypropyl acrylate, allyl glycidyl ether, GMA, glycidyl acrylate, methylol
It is more than one or both of DAAM, DAAM；
Acrylic acid (the C1-C10) ester monomer be methyl methacrylate, methyl acrylate, EMA,
One kind in ethyl acrylate, butyl methacrylate, butyl acrylate, EHMA, Isooctyl acrylate monomer or
It is two or more.
Preferably, in step 1), the compound emulsifying agent is acrylamido sodium isopropyl xanthate, the spy containing pi-allyl
Kind ether alcohol sulfate, double bond containing alcohol ether sulfenyl succinate sodium salt, vinyl phosphoric acid sodium, 2- allyl ether 3- hydroxy propanes-
1- sodium sulfonates, allyl ether hydroxypropanesulfonic acid sodium, branched alkyl alcohol APEO phosphate monoester, C12,C13Half Branched fatty
It is two or more in alcohol APEO and ethylene oxide/propylene oxide copolymer.
Preferably, the molecular weight regulator is primary DDM dodecyl mercaptan, tert-dodecyl mercaptan, acetic acid dodecyl sulphur
Alcohol ester, benzoic acid n-dodecyl mercaptan ester, 1- n-dodecane stream bases ethapon, beta-phenyl β-n-dodecane sulfenyl ethylo benzene
One kind in base ketone, two fragrant acyl disulphide or 3- mercaprols；Described pH adjusting agent is alcamines organic amine or ammoniacal liquor.
Preferably, the vinyl monomer II be methyl methacrylate, methyl acrylate, EMA,
Ethyl acrylate, butyl methacrylate, butyl acrylate, EHMA, Isooctyl acrylate monomer, hydroxyethyl methyl
Acrylated phosphate, vinyl alkoxy phosphate, methacrylic acid ester group alkoxy phosphate, vinyl alkyl phosphate, nitrogen
It is one or more kinds of in heterocyclic methyl acrylate, isobornyl methacrylate, isobornyl acrylate or styrene.
Preferably, the initiator is ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate, wherein, ammonium persulfate is optimal.
Embodiment 1：
1) synthesis of shell emulsion：
I) add 1158 grams of water dissolvings to be warming up to 83 DEG C 8 grams of ammonium persulfates, be passed through nitrogen 30min deoxygenations, obtain initiator
Solution；
Ii 500 grams of deionized waters, 2 grams of acrylamido sodium isopropyl xanthates, 8 grams of branched alkyls) are added in head tank
Alcohol APEO phosphate monoester, 272 grams of methyl methacrylates, 48 grams of N hydroxymethyl acrylamides, 40 grams of methacrylic acids,
50 grams of butyl methacrylates, 50 grams of senecioate-hydroxypropyl acrylates, 20 grams of 3- mercaprols carry out pre-emulsification, and it is molten to obtain pre-emulsification
Liquid；
Iii) pre-emulsification solution is added dropwise in initiator solution in 90min with " starvation method " at 80-85 DEG C and reacted, is added
Enter ammoniacal liquor regulation pH to 7.5-8.0, be incubated 30min, obtain shell emulsion；
2) synthesis of core-shell emulsion：
I) 12 grams of ammonium persulfates are dissolved in 50g deionized waters, added in the shell emulsion that step 1) obtains；
II 220 grams of Isooctyl acrylate monomers, 100 grams of azacyclo- methacrylates) are added dropwise in 120min at 80-85 DEG C
With 372 grams of styrene, continue to cure 90min after being added dropwise, be cooled to room temperature, filter, obtain core-shell emulsion A, that is, be applied to
The aqueous environment protection filmogen of steel fastener surface.
Embodiment 2：
1) synthesis of shell emulsion：
I) add 1158 grams of water dissolvings to be warming up to 83 DEG C 8 grams of ammonium persulfates, be passed through nitrogen 30min deoxygenations, obtain initiator
Solution；
Ii 500 grams of deionized waters, 4 grams of alkenyl sodium phosphates, 6 grams of branched alkyl alcohol APEOs) are added in head tank
Phosphate monoester, 272 grams of methyl methacrylates, 48 grams of (methyl) glycidyl acrylates, 40 grams of propyloic acrylic esters (β-
CEA), 50 grams of butyl methacrylates, 50 grams of methacrylic acid-β-hydroxypropyl acrylates, 20 grams of 3- mercaprols carry out pre-emulsification, obtain
Pre-emulsification solution；
Iii) pre-emulsification solution is added dropwise in initiator solution in 90min with " starvation method " at 80-85 DEG C and reacted, is added
Enter ammoniacal liquor regulation pH to 7.5-8.0, be incubated 30min, obtain shell emulsion；
2) synthesis of core-shell emulsion：
I) 12 grams of ammonium sulfate are dissolved in 50g deionized waters, added in the shell emulsion that step 1) obtains；
II 220 grams of Isooctyl acrylate monomers, 100 grams of azacyclo- methacrylates) are added dropwise in 120min at 80-85 DEG C
With 372 grams of styrene, continue to cure 90min after being added dropwise, be cooled to room temperature, filter, obtain core-shell emulsion B, that is, be applied to
The aqueous environment protection filmogen of steel fastener surface.
Embodiment 3：
1) synthesis of shell emulsion：
I) add 1158 grams of water dissolvings to be warming up to 83 DEG C 8 grams of ammonium persulfates, be passed through nitrogen 30min deoxygenations, obtain initiator
Solution；
Ii) in head tank add 500 grams of deionized waters, 2 grams of alkene 2- allyl ether 3- hydroxy propane -1- sodium sulfonates, 8 grams
Branched alkyl alcohol APEO phosphate monoester, 272 grams of methyl methacrylates, 48 grams of (methyl) glycidyl acrylates,
48 grams of N- isopropoxymethyls acrylamides, 40 grams of propyloic acrylic esters (β-CEA), 50 grams of butyl methacrylates, 50 grams of first
Base senecioate-hydroxypropyl acrylate, 20 grams of 3- mercaprols carry out pre-emulsification, obtain pre-emulsification solution；
Iii) pre-emulsification solution is added dropwise in initiator solution in 90min with " starvation method " at 80-85 DEG C and reacted, is added
Enter ammoniacal liquor regulation pH to 8.5, be incubated 30min, obtain shell emulsion；
2) synthesis of core-shell emulsion：
I) 12 grams of ammonium sulfate are dissolved in 50g deionized waters, added in the shell emulsion that step 1) obtains；
II 220 grams of Isooctyl acrylate monomers, 100 grams of methacrylic acid ester group alcoxyls) are added dropwise in 120min at 80-85 DEG C
Base phosphate and 372 grams of styrene, continue to cure 90min after being added dropwise, be cooled to room temperature, filter, obtain core-shell emulsion C,
It is applied to the aqueous environment protection filmogen of steel fastener surface.
Detect embodiment
By core-shell emulsion A, B and C, formula is modulated into water paint I, II, III as described in table 1 respectively,
1 water-based paint formula of table
By three after overpickling the clean firm part of steel screw in surface entered respectively using water paint I, II, III dip-coating
Row coating test, its result is as shown in table 2,
The water paint coating test of table 2
Note：A) GB/T 10125-1997 standards are used, carry out resistance to misty rain test in 72 hours；
B) tested using GB/T13303-1991 standards,
C) paint film is carried out to test after water soaks 48 hours；
D) tested using GB/T 9286-1998 standards.
As can be seen from Table 2, properties of water paint I, II, the III coated on steel screw fastener are all qualified.Pass through
Water paint I and II results contrast understand that water paint II spalling resistance test result is good compared with water paint I, add olefinic carboxylic
Acid monomers propyloic acrylic ester, this can be effectively improved applied to the aqueous environment protection filmogen of steel fastener surface to carrying
The adhesive force of body, ethylenic carboxylic acid's monomer propyloic acrylic ester (β-CEA) are extremely easily integrated into polymer emulsion system, and it is outstanding
Vertical carboxyl functional group can assist to improve emulsion intercalation method, improve the adhesive force to base material；Due to its relatively low vitrifying temperature
Characteristic is spent, also has obvious contribution to the low temperature bonding and low temperature flexibility for improving adhesive and coating；
By water paint II and III results contrast, water paint III spalling resistance test result is compared with water paint II
It is good, i.e., when synthesizing core-shell emulsion, add phosphate ester monomer methacrylic acid ester group alkoxy phosphate, this can be effectively improved
Aqueous environment protection filmogen applied to steel fastener surface is to the adhesive force of carrier.
Application Example
Core-shell emulsion A, B, C of 10 times of volumes are added into black water environmental protection mill base respectively, after being dispersed with stirring uniformly, is obtained
To water-based steel blackened solution.Steel construction fastener after overpickling, heat treatment step is immersed into 5-20 in blackened solution
Second, the workpiece after salvaging is wrapped up by black coating uniform, after workpiece residual temperature evaporates surface liquid boiling (5-10 seconds), work
Part is presented the black of high glaze, wear-resisting, anticorrosion, water-fast, ultra-violet resistance, alkali resistance, acid resistance, excellent aft-loaded airfoil and
Storage stability.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to the scope of protection of the invention is limited with this,
The change and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed scope.
Claims (9)
1. a kind of preparation method of aqueous environment protection filmogen applied to steel fastener surface, comprises the following steps：
1) synthesis of shell emulsion：The initiator of vinyl monomer I, 0.5-1.5 part of 20-30 parts, the molecular weight of 1-3 parts is taken to adjust
Agent, the compound emulsifying agent of 0.5-1.5 parts, 1-3 parts pH adjusting agent and complement to 100 parts of water, react and shell emulsion be made；
2) synthesis of core-shell emulsion：The initiator, the ethene of 50-90 parts of 1-2 parts are added in the shell emulsion obtained to step 1)
Base monomer II, reaction obtain core-shell emulsion, i.e. the aqueous environment protection filmogen applied to steel fastener surface；
In step 1), the vinyl monomer I includes ethylenic carboxylic acid, crosslinking functionality monomer and (methyl) acrylic acid C1-C10 alkane
Base ester；
In step 2), the vinyl monomer II is (methyl) acrylic acid C1-C10 Arrcostabs, phosphoric acid ester function monomer and benzene
Ethene；
(methyl) the acrylic acid C1-C10 Arrcostabs be selected from methyl methacrylate, methyl acrylate, EMA,
Ethyl acrylate, butyl methacrylate, butyl acrylate, EHMA, Isooctyl acrylate monomer, methacrylic acid
Isobornyl thiocyanoacetate, isobornyl acrylate；
The phosphoric acid ester function monomer is selected from hydroxyethyl methacrylic acid phosphate, vinyl alkoxy phosphate, methyl-prop
Olefin(e) acid ester group alkoxy phosphate, vinyl alkyl phosphate.
2. the method as described in claim 1, it is characterised in that the synthesis of step 1) the shell emulsion comprises the following steps：
I) add water rising temperature for dissolving to be passed through nitrogen deoxygenation initiator and obtain initiator solution；
Ii vinyl monomer I, molecular weight regulator, water and compound emulsifying agent) are mixed into pre-emulsification and obtain pre-emulsification solution；
Iii) pre-emulsification solution is added dropwise in initiator solution with " starvation method " at 80-85 DEG C and reacted, pH adjusting agent is added and adjusts
PH to 7.5-8.0 is saved, obtains shell emulsion.
3. the method as described in claim 1, it is characterised in that the synthesis of the step 2) core-shell emulsion comprises the following steps：
I) initiator is added in the shell emulsion that step 1) obtains；
II vinyl monomer II) is added dropwise at 80-85 DEG C, continues to cure 60-90min after being added dropwise, is cooled to room temperature, mistake
Filter, obtains core-shell emulsion, i.e. the aqueous environment protection filmogen applied to steel fastener surface.
4. the method as described in claim 1, it is characterised in that in step 1),
The ethylenic carboxylic acid is in fumaric acid, itaconic acid, maleic acid, methacrylic acid, acrylic acid and propyloic acrylic ester
It is one or more kinds of；
The crosslinking functionality monomer is divinylbenzene, ethylene glycol diacrylate, diallyl maleate, pentaerythrite three
Allyl ester, terephthaldehyde's base diene acid ester, methylene-bisacrylamide, ethyoxyl trimethylolpropane trimethacrylate, three second
Diol acrylate, N hydroxymethyl acrylamide, N- methoxymethyl propenamides, N- isobutoxy methyls acrylamide, N- are different
Third oxygen Methacrylamide, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, propylene
Acid-β-hydroxypropyl acrylate, allyl glycidyl ether, GMA, glycidyl acrylate, methylol double third
It is more than one or both of ketone acrylamide, DAAM；
(methyl) the acrylic acid C1-C10 alkyl ester monomers are methyl methacrylate, methyl acrylate, methacrylic acid second
Two kinds in ester, ethyl acrylate, butyl methacrylate, butyl acrylate, EHMA, Isooctyl acrylate monomer
More than.
5. the method as described in claim 1, it is characterised in that in step 1), the compound emulsifying agent is that acrylamido is different
Propyl sulfonic acid sodium, the extraordinary ether alcohol sulfate containing pi-allyl, double bond containing alcohol ether sulfenyl succinate sodium salt, vinyl phosphoric acid
Sodium, 2- allyl ether 3- hydroxy propane -1- sodium sulfonates, branched alkyl alcohol APEO phosphate monoester, the side chain fat of C12, C13 half
It is two or more in fat alcohol APEO and ethylene oxide/propylene oxide copolymer.
6. the method as described in claim 1, it is characterised in that in step 1), the molecular weight regulator is 12 carbon sulphur of uncle
Alcohol, tert-dodecyl mercaptan, acetic acid n-dodecyl mercaptan ester, benzoic acid n-dodecyl mercaptan ester, 1- n-dodecanes sulfenyl three
One kind in chlorethanol, beta-phenyl β-n-dodecane sulfenyl ethyl phenyl ketone, two fragrant acyl disulphide or 3- mercaprols；It is described
PH adjusting agent be alcamines organic amine or ammoniacal liquor.
7. the method as described in claim 1, it is characterised in that the initiator is ammonium persulfate, sodium peroxydisulfate or persulfuric acid
Potassium.
8. the aqueous environment protection film forming applied to steel fastener surface prepared by the method as described in claim any one of 1-7
Material.
9. the aqueous environment protection filmogen applied to steel fastener surface is in steel antirust as claimed in claim 8
Using.
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| CN107163180B (en) * | 2017-06-15 | 2019-08-06 | 陕西科技大学 | A kind of preparation method of anticorrosion core-shell polyacrylate emulsion |
| CN107603301B (en) * | 2017-10-27 | 2020-05-12 | 青岛科技大学 | Preparation method of special resin for water metal paint |
| CN108250877B (en) * | 2017-12-19 | 2020-07-17 | 吉力水性新材料科技（珠海）有限公司 | Phosphate modified acrylic water-based industrial coating |
| CN110922823A (en) * | 2019-12-18 | 2020-03-27 | 南通达克罗新材料科技有限公司 | Flame-retardant coating for fastener and preparation method thereof |
| CN111363444A (en) * | 2020-05-11 | 2020-07-03 | 龙海市大华涂料有限公司 | A kind of preparation method of high-adhesion self-crosslinking water-based paint |
| CN113698831A (en) * | 2021-09-09 | 2021-11-26 | 哈尔滨工业大学无锡新材料研究院 | High-oxygen barrier coating |
| CN113698652A (en) * | 2021-09-09 | 2021-11-26 | 哈尔滨工业大学无锡新材料研究院 | High-oxygen barrier coating film and preparation method thereof |
| CN113698525A (en) * | 2021-09-09 | 2021-11-26 | 哈尔滨工业大学无锡新材料研究院 | High-oxygen-barrier coating |
| CN113698820A (en) * | 2021-09-09 | 2021-11-26 | 哈尔滨工业大学无锡新材料研究院 | High-oxygen barrier coating, preparation method and use method thereof |
| CN113604116A (en) * | 2021-09-09 | 2021-11-05 | 哈尔滨工业大学无锡新材料研究院 | High-oxygen barrier coating and preparation method and coating method thereof |
| CN114316113A (en) * | 2022-01-06 | 2022-04-12 | 上海广沣科技有限公司 | A kind of water-based acrylic emulsion resin and preparation method thereof |
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| CN105175615A (en) | 2015-12-23 |
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