CN106835093B - A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application - Google Patents
A kind of Q type POSS modified metal surface pretreating reagent and preparation method thereof, application Download PDFInfo
- Publication number
- CN106835093B CN106835093B CN201710104044.2A CN201710104044A CN106835093B CN 106835093 B CN106835093 B CN 106835093B CN 201710104044 A CN201710104044 A CN 201710104044A CN 106835093 B CN106835093 B CN 106835093B
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- CN
- China
- Prior art keywords
- parts
- metal surface
- acid
- silane
- pretreating reagent
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 100
- 239000002184 metal Substances 0.000 title claims abstract description 100
- 239000003153 chemical reaction reagent Substances 0.000 title claims description 60
- 238000002360 preparation method Methods 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 57
- 229910000077 silane Inorganic materials 0.000 claims abstract description 52
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 36
- -1 aminopropyl dimethylsiloxy Chemical group 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 27
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- 239000011737 fluorine Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000007921 spray Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 6
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 6
- 239000001630 malic acid Substances 0.000 claims description 6
- 235000011090 malic acid Nutrition 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 claims 1
- GTXWPZRNXZAPGM-UHFFFAOYSA-N NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCC[SiH](OC(OCC)(OCC)OCC)OC GTXWPZRNXZAPGM-UHFFFAOYSA-N 0.000 claims 1
- MEXATBHBIYUJGT-UHFFFAOYSA-N NCCNCCC[SiH](OCC(OCC)(OCC)OCC)OCC Chemical compound NCCNCCC[SiH](OCC(OCC)(OCC)OCC)OCC MEXATBHBIYUJGT-UHFFFAOYSA-N 0.000 claims 1
- NFCHYERDRQUCGJ-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[SiH](OC)CCCOCC1CO1 NFCHYERDRQUCGJ-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000008439 repair process Effects 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 3
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 abstract 1
- 238000001962 electrophoresis Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000013019 agitation Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 238000009501 film coating Methods 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000004017 vitrification Methods 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 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 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920002253 Tannate Polymers 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- MTKPOFJUULWZNU-UHFFFAOYSA-N ethoxysilicon Chemical compound CCO[Si] MTKPOFJUULWZNU-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000009182 swimming Effects 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 2
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical class CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 2
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 description 1
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 description 1
- OACPJIGCXFFIOJ-UHFFFAOYSA-N 3-silyloxypropan-1-amine Chemical compound NCCCO[SiH3] OACPJIGCXFFIOJ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- VLWUKSRKUMIQAX-UHFFFAOYSA-N diethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[SiH](OCC)CCCOCC1CO1 VLWUKSRKUMIQAX-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
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Abstract
本发明公开了一种Q型POSS改性的金属表面前处理剂，以水为溶剂，以硅烷作为主成膜剂，以氟锆酸盐和/或氟锆酸为第二种成膜剂，并添加八(氨丙基二甲基硅氧基)笼型八聚硅倍半氧烷(氨基Q型POSS)作为膜层封闭剂和修补剂，还可以包括酸、金属促进剂、稀土化合物、稳定剂。本发明所述Q型POSS改性的金属表面前处理剂在成膜时是硅烷成膜和氟锆酸盐陶化成膜同步进行，相互掺杂，形成致密的无机‑有机杂化膜，硅烷可以及时修补氟锆酸盐成膜过程中的缺陷，优化膜结构，而Q型POSS的多个氨基可以同时和膜层中多个位点发生作为，封闭效果会明显提升，实现了对膜层中缺陷的更好修补和封闭。The invention discloses a Q-type POSS-modified metal surface pretreatment agent. Water is used as a solvent, silane is used as a main film-forming agent, and fluorozirconate and/or fluorozirconic acid are used as the second film-forming agent. And add octa (aminopropyl dimethylsiloxy) cage octapolysilsesquioxane (amino Q-type POSS) as film sealer and repair agent, can also include acid, metal accelerator, rare earth compound, stabilizer. The Q-type POSS modified metal surface pretreatment agent of the present invention is formed by silane film formation and fluorozirconate ceramic film formation simultaneously, and doping with each other to form a dense inorganic-organic hybrid film. The defects in the fluorozirconate film formation process can be repaired in time, and the film structure can be optimized, and the multiple amino groups of Q-type POSS can act simultaneously with multiple sites in the film layer, and the sealing effect will be significantly improved. Better patching and closing of defects in the medium.
Description
Technical field
The present invention relates to field of metal surface treatment, specifically a kind of Q type POSS modified metal surface pretreating reagent and
Preparation method, application.
Background technique
Metal material by surrounding medium effect and damage, referred to as metal erosion.When metal erosion, on the interface of metal
Chemistry or electrochemistry heterogeneous reaction has occurred in metal and empty gas and water etc., so that metal is transferred to oxidation (ion) state, this can significantly be dropped
The mechanical properties such as intensity, plasticity, the toughness of low metal material destroy the geometry of metal component, increase the abrasion between part,
Deteriorate the physical properties such as electrical and optical, shortens the service life of equipment.
The protection of application coating is the most common important method for preventing metal erosion on the metal surface.The work of coating
With being to keep apart metal product with surrounding medium, to prevent or reduce corrosion.Other than anticorrosion, there are also one for coating
Fixed dicoration or functionality.It is poor with the binding force of metal but since paint coatings belong to organic coating, it needs applying
Pre-treatment is carried out to metal surface before dress, increases by one layer of transition zone, enhances the binding force between metal surface and organic coating.
Traditional metal surface pre-treating method mainly has chemical conversion embrane method, and typical chemical conversion embrane method has at phosphatization
Reason, chromaking Passivation Treatment etc., but these traditional process for treating surface are faced with huge environmental pressure.Because of chromic acid passivation method
There are serious pollution of chromium, this method has limited use；And parco-lubrizing is polluted there are serious phosphorus, while also bringing an other huge sum of moneys
Belong to pollution, also belongs to the technology of being eliminated.For the pollution problem for solving conventional method, people more and more put the emphasis of research
In the technology that can substitute conventional surface treatment process.
Currently, novel metal surface pretreatment technology mainly has titanium salt conversion film (vitrification) technology, zirconates conversion film (pottery
Change) technology, tannate conversion membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology and silane conversion film etc..Titanium salt conversion
Film (vitrification) technology, tannate conversion membrane technology, Molybdate Conversion Film, cerium-based conversion coating technology are scarce since comprehensive performance has
It falls into, is only applied in certain special dimensions, fails to promote the use of on a large scale, and zirconates conversion film (vitrification) technology and silane
Conversion film is studied extensively due to haveing excellent performance, and obtains larger range application.
Zirconates conversion film (vitrification) technology refers to using fluozirconate as chemical composition coating active component, handles before metal
In the process, fluozirconate hydrolyzes to form zirconium dioxide film in metal surface.The advantage of this technology is that film layer is caused compared with phosphating coat
Close, required film layer is substantially reduced compared with phosphating coat, and its film-forming process process is similar with phosphatization, therefore can be produced in preceding processing
Phosphatization is directly substituted on line.But since the vitrification film layer still has more film forming defect, generally require addition sealer.
Silanization metal surface treatment technology overcomes the metals such as traditional phosphatization, chromaking as a kind of novel technology
Energy consumption is high in process for treating surface, pollutes the shortcomings that of itself can not overcoming such as big, oneself had been obtained extensive hair in recent years
Exhibition, has obtained actual application in industrial application.Silane is the hybrid object of a kind of silicon substrate, basic molecule
Formula are as follows: Y (CH2)nSiR2 x(OR3)3-x, wherein OR3It is hydrolyzable group, Y is organo-functional group.OR3Group promotes in hydrolysis
Under the action of agent, hydrolysis generate Si-OH group, with metal surface-Me-OH dehydrating condensation, formed Si-O-Me key, together
When Si-OH key itself occur dehydrating condensation formed space three-dimensional network structure.Y(CH2)nSubstituent group and organic coating compatibility
Good, corresponding chemical reaction can occur with the related functional group of organic coating for Y functional group when necessary, realize the molecule by silane
Bridge effect, realizes the effect between inorganic metal layer and organic layer, improves coating in the binding force of metal surface.
Since beginning one's study silane being used for metal surface pre-treatment the eighties in last century, silane is dissolved in solvent by discovery
In, it with metal surface, works well, but solvent volatilizees in use will cause environmental pollution, and cost is very high.It is most ideal
Method be silane is molten in water, not only reduce cost, but also can be to avoid the pollution problem of organic solvent.But, people are in length
Phase practice, it is found that the organosilan that can be dissolved in water is mainly amino silane and epoxy radicals silicone hydride, but these silane hydrolyzates
Rear stability is bad, will generally be crosslinked in a few hours between a couple of days.In addition, pure silane pretreating reagent is when handling metal,
It is to be adsorbed by hydrogen bond in metal surface first, since dehydration needs certain item between Si-OH and Me-OH and Si-OH and Si-OH
Part is difficult quickly to form stable three-dimensional net structure under room temperature or 50 DEG C of the following conditions, therefore pure silane inorganic agent and chromic acid
Passivation, phosphatization are compared, and film forming speed is slow, generally require that stable silane film can be obtained by the process that is heating and curing together, and
It cannot be rinsed with water film before complete film forming, therefore cannot directly substitute phosphating process on existing phosphatization production line.Therefore, how
Obtaining stable aqueous silane and the fast silane finish of film forming speed is that silane technology is used in the pre-treatment of metal surface
Technical bottleneck.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of Q type POSS in view of the deficiency of the prior art
Modified metal surface pretreating reagent and preparation method thereof, application method, can be in cold-rolled steel, hot-rolled steel, stainless steel, aluminium alloy
Equal metal surfaces formed one layer of three-dimensional space network shape it is inorganic/organic hybrid composite membrane, the film have extremely strong compactness and, with
The extremely strong binding ability of metal, coating.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of metal surface pretreating reagent that Q type POSS is modified, takes water as a solvent, using silane as main film forming agent, with fluorine
Zirconates and/or fluorine zirconic acid are second of film forming agent, and add the poly- silicon sesquialter oxygen of eight (aminopropyl dimethylsilyl bis) cage modle eight
Alkane (referred to as amino Q type POSS or Q type POSS) is used as film layer sealer and healant.
It according to the above scheme, can also include acid, metal rush in above-mentioned Q type POSS modified metal surface pretreating reagent composition
Into agent, rare earth compound and organic stabilizer.
According to the above scheme, the Q type POSS modified metal surface pretreating reagent, its raw material components are according to the mass fraction
It include: 0.01-20 parts of silane, fluozirconate and/or 0.01-20 parts of fluorine zirconic acid, eight (aminopropyl dimethylsilyl bis) cage modles eight
It is 0.01-5 parts of oligomeric silsesquioxane, 0-10 parts sour, 0-1 parts of metallic promoter agent, 0-0.5 parts of rare earth compound, organic stabilizer 0-5
Part, 44-135 parts of water.
According to the above scheme, the silane is 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, N- ammonia second
Base -3- aminopropyl trimethoxysilane, N- aminoethyl -3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy dimethoxy silicon
Alkane, 3- aminopropyltriethoxy diethoxy silane, N- aminoethyl -3- aminopropyltriethoxy dimethoxysilane, N- aminoethyl -3- ammonia third
Ylmethyl diethoxy silane, epoxypropoxy triethoxysilane, glycidoxy-propyltrimethoxy silane, the third oxygen of epoxy
Hydroxypropyl methyl dimethoxysilane, glycidoxypropyl diethoxy silane, 1,2- bis- (trimethoxy silicon substrate) ethane, 1,
One of 2- bis- (triethoxy silicon substrate) ethane etc. or more than one mixture.
According to the above scheme, the fluozirconate is selected from one of ammonium fluozirconate, potassium fluorozirconate and sodium fluozirconate etc. or one
Kind or more mixture.
According to the above scheme, the structural formula difference of the amino Q type POSS is as follows:
Wherein, R1For 3- aminopropyl-dimethylsilyl bis (H2NC3H6(CH3)2SiO—)。
According to the above scheme, the acid is hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, malic acid, citric acid, tartaric acid, lactic acid, grass
One of acid etc. or more than one mixture.
According to the above scheme, the metallic promoter agent is one of manganese sulfate, manganese nitrate, copper sulphate, copper nitrate etc. or one
Kind or more mixture.
According to the above scheme, the rare earth compound is one of lanthanum nitrate, lanthanum chloride, cerous nitrate, cerous sulfate etc. or one
Kind or more mixture.
According to the above scheme, the organic stabilizer is in ethyl alcohol, methanol, glycerine, normal propyl alcohol, isopropanol, n-butanol etc.
Any one or more than one mixture.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) it after sour, fluozirconate and/or fluorine zirconic acid, metallic promoter agent and rare earth compound being added in water, stirs evenly
As component A；
2) amino Q type POSS, silane and organic stabilizer are added in water, is used as B component after mixing evenly；
3) B component obtained by step 2) is added in component A obtained by step 1), is stirred evenly to get modified to Q type POSS
Metal surface pretreating reagent.
According to the above scheme, it is respectively formed in the component A according to the mass fraction are as follows: 40-95 parts of water, fluozirconate and/or fluorine
It is 0.01-20 parts of zirconic acid, 0-10 parts sour, 0-1 parts of metallic promoter agent, 0-0.5 parts of rare earth compound.
According to the above scheme, it is respectively formed in the B component according to the mass fraction are as follows: 4-40 parts of water, 0.01-5 parts of Q type POSS,
0.01-20 parts of silane, 0-5 parts of organic stabilizer.
Q type POSS of the present invention modified metal surface pretreating reagent can be used for steel, galvanized sheet, aluminium alloy plate etc.
Metallic surface pre-treatment.Application method is: the modified metal surface pretreating reagent of the Q type POSS being diluted with water to and is contained admittedly
Amount is 0.001-1%, and adjusts pH to 3.8-5.0, carries out pre-treatment to metal using infusion method or spray process and obtains silane film
Layer.Wherein, it adjusts pH and generallys use the strong base-weak acid salts such as the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid or sodium carbonate or sodium hydroxide
Equal alkali.
Compared with prior art, the beneficial effects of the present invention are:
(1) Q type POSS of the present invention modified metal surface pretreating reagent is forming silane film and fluorine zirconic acid in film forming
Salt vitrification film forming is synchronous to be carried out, and is mutually adulterated, is formed fine and close inorganic-organic hybridization film, silane can repair fluorine zirconic acid in time
The defects of salt film forming procedure optimizes membrane structure, and multiple amino of Q type POSS can multiple sites occur simultaneously and in film layer
As sealing effect can be obviously improved, and realize more preferable repairing and closing to defect in film layer.
(2) Q type POSS of the present invention modified metal surface pretreating reagent is in film forming procedure, zirconium compounds (i.e. fluorine zirconic acid
Salt and/or fluorine zirconic acid) it can be used as crosslinked with silicane promotor, be conducive to accelerate forming silane film, make at of short duration metal surface
It manages in the time, water-soluble silane adsorbs and be crosslinked film forming without that can be dissolved in water in metal surface, and metal processing piece leaves silane
Treatment process can be washed at once, and realize silane film can quick water scrub function；
(3) present invention utilizes the introducing of silane complex technique and Q type POSS, ensure that the stability of aqueous silane systems,
And aqueous silane and fluozirconate can be re-dubbed uniform solution, and stability is very well, it can be achieved that the single group of user separates dilute make
With.
(4) Q type POSS of the present invention modified metal surface pretreating reagent can obtain fine and close hydridization in metal surface
Film, the film have excellent silane film (i.e. no upper outer protective paint, the lower naked mould of abbreviation) antirust ability and are coupled energy with coating
Power.
Q type POSS of the present invention modified metal surface pretreating reagent may be substituted for conventional phosphatizing processing technique,
Suitable for using various industrial circles of metal, such as automobile, household electrical appliances coating, hardware etc..
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Embodiment 1
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 54.89 parts of water, 10 according to the mass fraction
Part ammonium fluozirconate, 0.02 part of eight eight oligomeric silsesquioxane ((H of (3- aminopropyl-dimethylsilyl bis) cage type2NC3H6(CH3)2SiOSiO1.5)8) (molecular formula are as follows: C40H112Si16O20N8) (CAS registration number: 2046327-37-9), 20 parts of three second of 3- aminopropyl
Oxysilane, 2 parts of citric acids, 8 parts of malic acid, 0.02 part of cerous sulfate and 0.01 part of lanthanum nitrate.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 40 parts of water, 10 parts of ammonium fluozirconates are added under agitation, it is primary after being completely dissolved
2 parts of citric acids, 8 parts of malic acid, 0.02 part of cerous sulfate and 0.01 part of lanthanum nitrate is added, is uniformly mixing to obtain component A；
2) in 14.89 parts of water, 20 parts of 3- aminopropyl triethoxysilanes are added under agitation, after stirring and dissolving,
0.02 part of Q type-POSS is added, is used as B component after mixing evenly；
3) B component is added in component A, stirs evenly and obtain the modified metal surface pretreating reagent of Q type POSS, i.e.,
A kind of environment-friendly type silane coating metal surfaces pretreating reagent.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent is opened with pure water 1:39 it is dilute, open it is dilute after apparently
Solid content is 1.0%, and the pH value of dilute rear solution is opened with pH meter measurement, is maintained at 4.0 with sodium carbonate regulating solution pH；Then it uses
Infusion method after the cold-reduced sheet after degreasing is impregnated 30 seconds wherein, with twice of pure water rinsing, then uses 10421 electrophoretic paint of ippon
Electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
According to measurement cold-reduced sheet silane film (the cold rolling plate surface i.e. before electrophoresis of method as defined in GB/T10125 and GB/T6461
Film layer) resistance to Neutral Salt Spray Corrosion performance, according to method as defined in GB/T 1720 measurement cold-reduced sheet silane film adhesive force；
According to the flexibility of the measurement cold-reduced sheet silane film of method as defined in GB/T 1731；It is measured according to method as defined in GB/T 1732 cold
Roll the impact resistance of plate silane film.The resistance to Neutral Salt Spray Corrosion of cold rolling plate electrophoresis rear electrophoresis film is tested after the same method
Energy, adhesive force and flexibility.Test result is as shown in table 1.
Embodiment 2
A kind of Q type POSS modified metal surface pretreating reagent, composition include: according to the mass fraction 98.89 parts of water,
0.01 part of fluorine zirconic acid, 0.01 part of eight eight oligomeric silsesquioxane ((H of (3- aminopropyl-dimethylsilyl bis) cage type2NC3H6(CH3)2SiOSiO1.5)8) (molecular formula are as follows: C40H112Si16O20N8) (CAS registration number: 2046327-37-9), 0.08 part of third oxygen of epoxy third
Base trimethoxy silane, 0.9 part of N- aminoethyl -3- aminopropyl trimethoxysilane, 0.01 part of malic acid and 0.1 part of nitric acid.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) according to the mass fraction, in 74 parts of water, under agitation be added 0.01 part of malic acid, 0.1 part of nitric acid and
0.01 part of fluorine zirconic acid, obtains component A after being completely dissolved；
2) it is added 0.01 part of amino Q type POSS under agitation in 24.89 parts of water, after stirring and dissolving, adds
0.08 part of glycidoxy-propyltrimethoxy silane, 0.9 part of N- aminoethyl -3- aminopropyl trimethoxysilane, after mixing evenly
As B component；
3) B component is added in component A, is stirred evenly to get the metal surface pretreating reagent modified to Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent and pure water are diluted with volume ratio 1:1099,
And its pH value is measured with pH meter, and adjust pH with sodium hydroxide and be maintained at 4.0；Then use infusion method by the cold-reduced sheet after degreasing
After impregnating 3 minutes wherein, with twice of pure water rinsing, then with 10421 electrophoretic paint electrophoresis of ippon；With after pure water rinsing after electrophoresis,
Hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Embodiment 3
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 95.38 parts of water, 3 according to the mass fraction
Part fluorine zirconic acid, 0.5 part of Q type-POSS, 0.1 part of N- aminoethyl -3- aminopropyl trimethoxysilane, 1 part of tartaric acid, 0.01 part of nitre
Sour copper, 0.01 part of glycerine.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 91.38 parts of water, under agitation be added 3 parts of fluorine zirconic acids, 1 part of tartaric acid and
0.01 part of copper nitrate, is uniformly mixing to obtain component A；
2) in 4 parts of water, 0.01 part of glycerine and 0.1 part of three second of N- aminoethyl -3- aminopropyl are added under agitation
Oxysilane after stirring and dissolving, adds 0.5 part of Q type-POSS, is used as B component after mixing evenly；
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent is opened with pure water 1:49 it is dilute, open it is dilute after apparently
Solid content is 0.09%, and the pH value of dilute rear solution is opened with pH meter measurement, pH value of solution is adjusted with nitric acid, pH value of solution is made to be maintained at 4.0,
Using spray process, after the cold-reduced sheet after degreasing is sprayed 3 minutes, with twice of pure water rinsing, using ippon 10421 electrophoretic paint electricity
Swimming, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Embodiment 4
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 89.3 parts of water, 0.2 according to the mass fraction
Part fluorine zirconic acid, 5 parts of Q type-POSS, 1 part of 1,2- bis- (front three oxygen silicon base) ethane, 1 part of 2- aminoethyl trimethoxy silane, 1 part of ring
The third oxygen propyl trimethoxy silicane of oxygen, 0.5 part of hydrochloric acid, 1 part of n-butanol and 1 part of isopropanol.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 80 parts of water, 0.2 part of fluorine zirconic acid is added under agitation, it is primary after being completely dissolved
0.5 part of hydrochloric acid is added, is uniformly mixing to obtain component A；
2) in 9.3 parts of water, 1 part of 1,2- bis- (front three oxygen silicon base) ethane, 1 part of 2- ammonia second are sequentially added under agitation
Base trimethoxy silane and 1 part of glycidoxy-propyltrimethoxy silane, after stirring and dissolving, add 1 part of isopropanol, 1 part just
Butanol and 5 parts of Q type-POSS are used as B component after mixing evenly；
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent being opened with pure water 1:199 dilute, opens dilute table afterwards
Seeing solid content is 0.044%, protects pH value of solution with sodium hydrate regulator solution pH with the pH value that dilute rear solution is opened in pH meter measurement
It holds 4.0, using infusion method, after the cold-reduced sheet after degreasing is impregnated 3 minutes, with twice of pure water rinsing, using 10421 electricity of ippon
Swimming paint electrophoresis, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Embodiment 5
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 75 parts of water, 1 part of fluorine according to the mass fraction
Sodium zirconate, 0.01 part of potassium fluorozirconate, 0.9 part of Q type-POSS, 10 parts of aminomethyl triethoxysilanes, 5 parts of (trimethoxy silicon of 1,2- bis-
Base) ethane, 3 parts of nitric acid, 0.01 part of copper nitrate, 0.02 part of lanthanum nitrate, 0.06 part of cerous sulfate, 5 parts of isopropanols.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 40 parts of water, 1 part of sodium fluozirconate and 0.01 part of fluorine zirconic acid are added under agitation
Potassium, it is primary after being completely dissolved that 3 parts of nitric acid, 0.01 part of copper nitrate, 0.02 part of lanthanum nitrate, 0.06 part of cerous sulfate are added, it stirs evenly
Obtain component A；
2) in 35 parts of water, 5 parts of isopropanols, 10 parts of aminomethyl triethoxysilanes and 5 part 1 are added under agitation,
2- bis- (front three oxygen silicon base) ethane after stirring and dissolving, adds 0.9 part of Q type-POSS, is used as B component after mixing evenly；
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent being opened with pure water 1:599 dilute, opens dilute table afterwards
Seeing solid content is 0.03%, keeps pH value of solution with sodium hydrate regulator solution pH with the pH value that dilute rear solution is opened in pH meter measurement
4.0, using infusion method, after the cold-reduced sheet after degreasing is impregnated 3 minutes, with twice of pure water rinsing, using 10421 electrophoresis of ippon
Electrophoresis is painted, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Embodiment 6
A kind of metal surface pretreating reagent that Q type POSS is modified, composition includes: 67 parts of water, 20 parts according to the mass fraction
Fluorine zirconic acid, 4 parts of Q type-POSS, 1 part of 1,2- bis- (three ethoxy silicon substrates) ethane, 1 part of 3- aminopropyltriethoxy diethoxy silane, 3 parts
98% sulfuric acid, 2 parts of citric acids, 0.5 part of copper sulphate, 0.5 part of manganese nitrate, 1 part of n-butanol.
The preparation method of above-mentioned Q type POSS modified metal surface pretreating reagent, mainly includes the following steps:
1) as mass fraction, in 45 parts of water, 3 part of 98% sulfuric acid, 2 parts of citric acids, 20 parts are added under agitation
Fluorine zirconic acid, 0.5 part of copper sulphate and 0.5 part of manganese nitrate, are uniformly mixing to obtain component A；
2) in 22 parts of water, 1 part of n-butanol and 1 part of 3- aminopropyltriethoxy diethoxy silane, 1 are added under agitation
Part 1,2- bis- (three ethoxy silicon substrates) ethane after stirring and dissolving, adds 4 parts of Q type-POSS, is used as B component after mixing evenly；
3) B component is added in component A, stirs evenly and obtains the modified metal surface pretreating reagent of Q type POSS.
Application method: above-mentioned Q type POSS modified metal surface pretreating reagent being opened with pure water 1:639 dilute, opens dilute table afterwards
Seeing solid content is 0.05%, keeps pH value of solution with sodium hydrate regulator solution pH with the pH value that dilute rear solution is opened in pH meter measurement
4.0, using infusion method, the cold-reduced sheet after degreasing is impregnated after five minutes, with twice of pure water rinsing, using 10421 electrophoresis of ippon
Electrophoresis is painted, with after pure water rinsing after electrophoresis, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Comparative example 1
A kind of metal surface pretreating reagent, composition includes: 95 parts of water, 3 parts of fluorine zirconic acids, 1 part of epoxy according to the mass fraction
Third oxygen propyl trimethoxy silicane, 1 part of citric acid.
The preparation method of above-mentioned metal surface pretreating reagent mainly includes the following steps: as mass fraction, in 75 parts of water
In, 3 parts of fluorine zirconic acids are added under agitation, is stirring evenly and then adding into 1 part of citric acid, is uniformly mixing to obtain component A；At 20 parts
In water, 1 part of glycidoxy-propyltrimethoxy silane is added under agitation, is used as B component after mixing evenly；By B component
It is added in component A, stirs evenly and obtain metal surface pretreating reagent.
Application method: above-mentioned metal surface pretreating reagent is opened with pure water 1:99 it is dilute, open it is dilute after apparent solid content be
0.05%, so that pH value of solution is maintained at 3.8 with sodium hydroxide solution pH with the pH value that dilute rear solution is opened in pH meter measurement, using spray
Method, after five minutes by the cold-reduced sheet spray after degreasing, with twice of pure water rinsing, using 10421 electrophoretic paint electrophoresis of ippon, after electrophoresis
After pure water rinsing, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Comparative example 2
A kind of metal surface pretreating reagent, composition includes: 95 parts of water, 3 parts of fluorine zirconic acids, 1 part of 3- ammonia according to the mass fraction
Propyl trimethoxy silicane, 1 part of 60% concentrated nitric acid.
The preparation method of above-mentioned metal surface pretreating reagent, mainly includes the following steps:
As mass fraction, in 75 parts of water, 3 parts of fluorine zirconic acids is added under agitation, are stirring evenly and then adding into 1 part of nitre
Acid is uniformly mixing to obtain component A；In 20 parts of water, 1 part of 3- aminopropyl trimethoxysilane, stirring are added under agitation
B component is used as after uniformly；B component is added in component A, stirs evenly and obtains metal surface pretreating reagent.
Application method: above-mentioned metal surface pretreating reagent is opened with pure water 1:99 it is dilute, open it is dilute after apparent solid content be
0.05%, so that pH value of solution is maintained at 3.8 with sodium hydroxide solution pH with the pH value that dilute rear solution is opened in pH meter measurement, using spray
Method, after five minutes by the cold-reduced sheet spray after degreasing, with twice of pure water rinsing, using 10421 electrophoretic paint electrophoresis of ippon, after electrophoresis
After pure water rinsing, hot blast drying.
The resistance to Neutral Salt Spray Corrosion performance of silane film and electrocoating film, adhesive force and flexible are measured according to the method for embodiment 1
Property.Test result is as shown in table 1.
Table 1
As it can be seen from table 1 metal surface pretreating reagent Q type POSS modified in each embodiment is formed in cold rolling plate surface
Silane film there is good adhesive force, flexibility and impact resistance, with the anti-corruption in extraordinary room temperature atmospheric environment
Erosion ability, and without addition Q type POSS compound in comparative example, resulting cold-reduced sheet silane film is rapid in room temperature atmospheric environment
It gets rusty；Through electrophoresis after cold-reduced sheet silane film painting on surface film, in embodiment 1-6 paint film all have extraordinary adhesive force,
Flexibility, impact resistance and excellent resistance to neutral salt spray performance, comprehensive performance are more than joint auto vendor to body paint
It is required that and the impact resistance of electrodeposited paint film does not reach requirement in comparative example, corrosion resistance is also very poor, and joint multiply far is not achieved
Requirement with vehicle enterprise to body paint.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (7)
1. a kind of Q type POSS modified metal surface pretreating reagent, it is characterised in that the raw material of the metal surface pretreating reagent
Component includes: 0.01-20 parts of silane according to the mass fraction, fluozirconate and/or 0.01-20 parts of fluorine zirconic acid, eight (aminopropyl diformazans
Base siloxy) 0.01-5 parts of eight oligomeric silsesquioxane of cage modle, it is 0-10 parts sour, 0-1 parts of metallic promoter agent, rare earth compound 0-0.5
Part, 0-5 parts of organic stabilizer, 44-135 parts of water.
2. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the silane is 3-
Aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, N- aminoethyl -3- aminopropyl trimethoxysilane, N- ammonia second
Base -3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy dimethoxysilane, 3- aminopropyltriethoxy diethoxy silane, N-
Aminoethyl -3- aminopropyltriethoxy dimethoxysilane, N- aminoethyl -3- aminopropyltriethoxy diethoxy silane, the third oxygen of epoxy third
Ethyl triethoxy silicane alkane, glycidoxy-propyltrimethoxy silane, glycidoxypropyl dimethoxysilane, the third oxygen of epoxy
One of hydroxypropyl methyl diethoxy silane, 1,2- bis- (tri-alkoxy silicon substrate) ethane or more than one mixture；Work as institute
When to state silane be more than one mixture, wherein must have amino silane.
3. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the eight (ammonia third
Base dimethylsilyl bis) cage modle eight oligomeric silsesquioxane be amino Q type POSS, structural formula is as follows:
Wherein, R1For 3- aminopropyl-dimethylsilyl bis.
4. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the acid is hydrogen fluorine
One of acid, hydrochloric acid, sulfuric acid, nitric acid, malic acid, citric acid, tartaric acid, lactic acid, oxalic acid or more than one mixture；Institute
State organic stabilizer be ethyl alcohol, it is methanol, glycerine, normal propyl alcohol, isopropanol, any one or more than one mixed in n-butanol
Close object.
5. Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that the metal promoted
Agent is one of manganese sulfate, manganese nitrate, copper sulphate, copper nitrate or more than one mixture；The rare earth compound is nitre
One of sour lanthanum, lanthanum chloride, cerous nitrate, cerous sulfate or more than one mixture.
6. a kind of preparation method of Q type POSS modified metal surface pretreating reagent, it is characterised in that mainly include the following steps:
1) it after fluozirconate and/or fluorine zirconic acid, acid, metallic promoter agent and rare earth compound being added in water, stirs evenly as A
Component；
2) add eight oligomeric silsesquioxane of organic stabilizer, silane and eight (aminopropyl dimethylsilyl bis) cage modles, stirring in water
B component is used as after uniformly；
3) B component obtained by step 2) is added in component A obtained by step 1), is stirred evenly to get the gold modified to Q type POSS
Metal surface pretreating reagent；
It is respectively formed in the component A according to the mass fraction are as follows: 40-95 parts of water, fluozirconate and/or 0.01-20 parts of fluorine zirconic acid, acid
0-10 parts, 0-1 parts of metallic promoter agent, 0-0.5 parts of rare earth compound；It is respectively formed in the B component according to the mass fraction are as follows: water 4-
40 parts, eight 0.01-5 parts of eight oligomeric silsesquioxanes of (aminopropyl dimethylsilyl bis) cage modles, 0.01-20 parts of silane, organic stabilizers
0-5 parts of agent.
7. the application method of Q type POSS according to claim 1 modified metal surface pretreating reagent, it is characterised in that will
It is 0.001-1% that the Q type POSS modified metal surface pretreating reagent, which is diluted with water to solid content, and adjusts pH to 3.8-
In the range of 5.0, pre-treatment is carried out to metal using infusion method or spray process.
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| CN102140634A (en) * | 2011-03-09 | 2011-08-03 | 东北大学 | Composite aqueous passivation solution and preparation method thereof for hot galvanizing surface treatment |
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