CN102807651B - Method for preparing aqueous antirust polymer emulsion - Google Patents
Method for preparing aqueous antirust polymer emulsion Download PDFInfo
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- CN102807651B CN102807651B CN201210300054.0A CN201210300054A CN102807651B CN 102807651 B CN102807651 B CN 102807651B CN 201210300054 A CN201210300054 A CN 201210300054A CN 102807651 B CN102807651 B CN 102807651B
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- acid
- rust
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- antirust
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- 239000000839 emulsion Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 title abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000000178 monomer Substances 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 39
- 229920000180 alkyd Polymers 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 150000008065 acid anhydrides Chemical class 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 29
- 229920002521 macromolecule Polymers 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- -1 catalyzer Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 150000002632 lipids Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000003643 water by type Substances 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 6
- 235000019198 oils Nutrition 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007844 bleaching agent Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006040 2-hexenyl group Chemical group 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 239000000944 linseed oil Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims 4
- 238000005260 corrosion Methods 0.000 abstract description 45
- 230000007797 corrosion Effects 0.000 abstract description 44
- 239000003795 chemical substances by application Substances 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000012084 conversion product Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 abstract description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 26
- 229910000831 Steel Inorganic materials 0.000 description 21
- 239000010959 steel Substances 0.000 description 21
- 238000012545 processing Methods 0.000 description 14
- 239000003973 paint Substances 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000037452 priming Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QUBBAXISAHIDNM-UHFFFAOYSA-N ethyldimethylbenzene Natural products CCC1=CC=CC(C)=C1C QUBBAXISAHIDNM-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001648 tannin Chemical class 0.000 description 1
- 229920001864 tannin Chemical class 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a method for preparing an aqueous antirust polymer emulsion. The method comprises the following steps of: synthesizing a rust converting functional monomer; preparing an alcohol acid intermediate; and preparing an antirust high-polymer emulsion. The aqueous antirust polymer emulsion prepared by using the method can undergo a physical-biological reaction with iron rust on the surface of a metal substrate, and resin, a pigment, a filler, a stable rusty scale conversion product and molecules of the metal substrate are chelated together for forming a stable and firm compound shielding layer, so that oxidation ions are effective prevented from being dispersed towards a metal and blocking a corrosion channel; the adhesive force between the aqueous antirust high polymer emulsion and the metal substrate is higher than that of a general primer; and a phosphoric acid rust converting agent is not required to be added, so that metal corrosion possibly caused by residual phosphoric acid liquid is lowered. A single emulsion component is convenient to construct, and is dried rapidly; zinc phosphate serving as a primer can be added, can be applied to rusty construction and be taken as a general anti-rust primer, and has a high anti-rust function; and the aqueous antirust polymer emulsion can be taken as a primer-topcoat anti-rust aqueous coating, and has superior weather resistance.
Description
Technical field
The present invention relates to rust proof paint technical field, particularly the preparation method of the antirust macromolecule emulsion of a kind of aqueous rusty.
Background technology
Corrosion of metal is that metal is subject to the chemistry of surrounding medium or electrochemical action and destroyed phenomenon.Corrosion of metal spreads all over industry-by-industry field, and according to statistics, the whole world is about the more than 20% of its annual production because of the metal of rust corrosion every year, approximately 10,000 hundred million dollars of the financial losses of bringing thus.The financial loss that China causes because of metallic corrosion every year, up to more than 30,000,000,000 yuan, accounts for 4% of gross national product.Adopt anti-corrosion method can reduce by 20～30% loss.Anticorrosive coating application is exactly one of major measure of anticorrosive metal, large-scale steel structure, road and bridge high ferro engineering, ocean naval vessels, automobile chassis, motorway, civilian finishing the protection against corrosion work particularly important that seems, for the maintenance of these steel construction, can be directly on rust face application to play the demand that eliminates rust and have the environmental friendliness coating of antirust function be very urgent.
Rust-resisting coating is a kind of can be directly construction on the metallic surface of certain corrosion, and by making, rust is stable, passivation or conversion, makes active iron rust become harmless material, to reach the dual-purpose rust proof paint that not only eliminates rust but also protect.This early stage class coating products has mainly utilized stable and transformant principle, adopts phosphoric acid, Weibull etc. as turning rust agent, first corrosion is removed or passivation after apply again protection against corrosion priming paint, as USP 4880478, USP 5011551.The Corrosion Protection of this type coatings is subject to the impact of factors conventionally, the corrosion degree of the time of reacting with corrosion as the pH value of the kind of phosphoric acid, concentration, system, system, construction object etc.In addition, before applying protection against corrosion priming paint, need cleaning down fall the rust remover of metallic surface and turn rust agent, otherwise the acid solution that remains in metallic surface can corrode metal, and its protection against corrosion effect does not possess persistence.
At present, domestic Rust-resisting coating mostly is and adopts phosphoric acid, Weibull etc. as the solvent based coating kind that turns rust agent, in order to reach the object of long-acting antirust, mostly added zinc-chrome yellow etc. containing the rust-stabilising pigment of toxic heavy metal, if Chinese patent communique publication number is as described in the patent document of CN 101323726A, CN 1084906A, these coating products can not meet the requirement to the rust conversion coatings of the low VOC of high-performance at present.Application number is 200910110468.5 a kind of waterborne rust conversion polymer emulsion and coating and preparation method, mainly the Acrylic Acid Monomer with phosphate ester-containing participates in ACRYLIC EMULSION polymerization, utilize the combination of phosphoric acid functional group and metal base to eliminate rust, turn rust limited in one's ability.
Summary of the invention
The object of the present invention is to provide the preparation method of the antirust macromolecule emulsion of a kind of aqueous rusty, in the macromolecular chain of this emulsion, contain the group that can make corrosion passivation, do not need additional phosphoric acid class to turn rust agent, only depend on modified resin itself, produce physics-chemical reaction with metal base and iron rust, by resin, color stuffing, stable rusty scale conversion product and the molecule of metal base, be sequestered in together and form and stablize solid composite shielding layer, effectively stop oxidative ionic to spread to metal base, stop up corrosion passage; Due to the physics chemical action of itself and base material, the sticking power between itself and metal base is higher than general priming paint; Compare with current common on rust paint, it does not need additional phosphoric acid class to turn rust agent, has reduced the metallic corrosion that may cause due to residual phosphoric acid liquid.This emulsion single-component easy construction, rapidly dry, can add zinc phosphate as priming paint, not only can construct with becoming rusty but also can be used as general rust-proofing primer use, has good antirust function; It also can be used as bottom surface and unifies antirust water-borne coatings, has excellent weathering resistance.
Technical solution proposed by the invention is such: the preparation method of the antirust macromolecule emulsion of a kind of aqueous rusty comprises that the preparation of synthetic, the alkyd intermediate that turns rust function monomer is, three steps of preparation of band rust antirust emulsion, wherein:
(1) turn the synthetic of rust function monomer: in reactor, add solvent, unsaturated acid anhydride, polyphenolic substance and a small amount of catalyzer, import nitrogen and be warming up to reflux temperature; After question response thing bleach, be incubated 1 hour～2 hours, then reaction unit changed into water distilling apparatus, be cooled to 50～80 ℃, under 0.08～-0.1Mpa vacuum tightness, extract solvent;
The weight part consumption of each component described in building-up process is:
20～40 parts of unsaturated acid anhydrides;
50～70 parts of polyphenolic substances;
2～5 parts of catalyzer;
50～85 parts of solvents;
Described catalyzer is selected from any in tosic acid, tin protochloride, tin tetrachloride;
(2) preparation of alkyd intermediate: by with-SO
3the dicarboxylic acid of M group, polycarboxylic acid (acid anhydride) make alkyd intermediate mixture material with dibasic alcohol and fatty acid response, add with-SO in reactor
3the dicarboxylic acid of M group, polycarboxylic acid (acid anhydride), dibasic alcohol, lipid acid, catalyzer, solvent, deionized water, import nitrogen and heat up, and controlling temperature of reaction is 90 ℃～210 ℃ scopes, and the reaction times is 2～6 hours; When in reactor, mixture acid number is 0.2～5, stopped reaction;
The weight part consumption of each component described in building-up process is:
With-SO
35～12 parts of the dicarboxylic acid of M group;
15～25 parts of dibasic alcohol;
10～30 parts of polycarboxylic acids (acid anhydride);
20～35 parts, lipid acid;
5～10 parts of solvents;
0.2～0.8 part of catalyzer;
8～12 parts of deionized waters;
Described catalyzer is selected from any in Dibutyltin oxide, dibutyl tin dilaurate or monobutyl-tin-trichloride;
(3) preparation of band rust antirust emulsion: add appropriate amount of deionized water to being furnished with in the four-hole boiling flask of mechanical stirring device and nitrogen device, after mixing, alkyd intermediate prepared by step (2) and a small amount of acrylic monomer be added dropwise in reactor, be warming up to 80 ± 2 ℃, after temperature-stable, add a small amount of initiator solution, respectively by surplus acrylic ester monomer and through step (1), prepare turn rust function monomer slowly drop in reactor, add remaining initiator solution, at 1.5 hours～2.5 hours, with interior, dropwise; Be incubated 1 hour～2 hours;
The weight part consumption of each component described in building-up process is:
3～8 parts, alkyd intermediate;
70～100 parts of acrylic ester monomers;
Turn 2～6 parts of rust function monomers;
0.6～0.9 part of initiator;
30～55 parts of deionized waters;
The antirust macromolecule emulsion of aqueous rusty obtaining by preparation method of the present invention, pH value scope is 4.0～5.0, solid is divided into 40wt%～60wt%.
Compared with prior art, the present invention has following unusual effect:
(1) the antirust macromolecule emulsion of aqueous rusty that, the present invention makes is a kind of alkyd modified ACRYLIC EMULSION, this emulsion is passed through chemistry and two kinds of mode film forming of physics afterwards in construction, the surface drying time of filming has shortened, be about 10～15min, within 24 hours, do solid work, have advantages of that film forming is fast, easy construction.
(2), grafting can transform the functional group of corrosion on the antirust macromolecule emulsion macromolecular chain of aqueous rusty that makes of the present invention, emulsion turns rust agent without additional phosphoric acid, tannin acids, has avoided these additionally to turn the metal potential corrosion possibility that rust agent may bring.
(3), organic solvent content is about 0.7%～1.5% of emulsion total amount in the antirust macromolecule emulsion of aqueous rusty that makes of the present invention, its VOC content is low, environmental friendliness.
(4), letex polymerization of the present invention adopts sulfonic acid salinization alkyd intermediate as emulsifying agent, avoided common emulsifying agent to use the problems such as poor water resistance of bringing.The antirust macromolecule emulsion of aqueous rusty and metal substrate sticking power that the present invention makes are good, and the water tolerance of filming is good.
(5), the antirust macromolecule emulsion of aqueous rusty that makes of the present invention is slightly acidic, pH value approximately 4.0～5.0, is conducive to the wetting and reaction to corrosion, rust-proof effect is lasting.
The antirust macromolecule emulsion of aqueous rusty that the present invention makes can be used for the protection against corrosion of large-scale steel structure, road and bridge high ferro engineering, ocean naval vessels, automobile chassis, motorway etc. to be safeguarded; complex structure particularly, is difficult for carrying out protection and the decoration of thorough surface-treated metal substrate.Also can be used for historical relic's protection, building such as overhauls at the maintenance engineering.
Accompanying drawing explanation
Fig. 1 is respectively the embodiment of the present invention (5) and turns the x-ray photoelectron power spectrum that forward and backward corrosion steel plate is processed in rust agent; Wherein, (a) be full spectrum; (b) be near power spectrum ferro element; (c) be near power spectrum oxygen element.
Embodiment
By embodiment below, the present invention is further elaborated.
A preparation method for the antirust macromolecule emulsion of aqueous rusty, it comprises that the preparation of synthetic, the alkyd intermediate that turns rust function monomer is, three steps of preparation of band rust antirust emulsion, by each embodiment below, described three steps is elaborated.
Embodiment 1
:turn the synthetic of rust function monomer A
In building-up process, the weight part consumption of following each component is: 40 parts of unsaturated acid anhydrides; 50 parts of polyphenolic substances; 5 parts of catalyzer; 85 parts of solvents; Wherein unsaturated acid anhydride is chosen MALEIC ANHYDRIDE, and polyphenolic substance is chosen Gallic Acid, and catalyzer is chosen tosic acid, and solvent is chosen ethylene glycol; Every 1 weight part is got 0.5g; The concrete proportioning of each component is: MALEIC ANHYDRIDE 20g, Gallic Acid 25g, tosic acid 2.5g, ethylene glycol 42.5g; Said components material is joined in the reactor with condensing works and agitator arm, and limit passes into nitrogen limit and is warming up to reflux temperature, keeps temperature-resistant, the follow-up continuation of insurance temperature of question response thing bleach 2h; Then reaction unit is changed into water distilling apparatus, temperature is down to 80 ℃, extracts the about 34g of solvent under 0.09Mpa vacuum tightness, obtains product and is and turns rust function monomer A.
The rust function monomer A that turns making adopts following method to carry out performance characterization:
Turn the test of rust function monomer A molecular weight: adopt Waters 515 gel chromatographs of U.S. Waters company to measure;
Turn rust function monomer A and turn rust measure of merit: adopt the JSM-6700F field emission scanning electron microscope of NEC company to carry out pattern test;
Turn rust function monomer A and the composition analysis of corrosion conversion film: adopt FTIR-8300 infrared spectrometer.The preparation of liquid sample: the synthetic on a small quantity rust agent (turning rust function monomer) that turns is dissolved in to tetracol phenixin, is applied on kbr tablet after fully dissolving, test (sample 1) after its film forming; Corrosion on steel plate is scraped, fine ground, get 1～2 mg and mix with the pure KBr porphyrize of 200 mg, after being ground to granularity and meeting the demands, with test (sample 2) after pressing potassium bromide troche; Then remaining corrosion is poured in the container that turns the rust agent aqueous solution that is equipped with 10%, centrifugation after 3 days, get the vacuum-drying under 40 ℃ of conditions of its throw out, the black powder obtaining, gets that this powder of 1～2 mg mixes with the pure KBr of 200 mg, grinding, compressing tablet test (sample 3);
Turn the pH value test of rust function monomer A: adopt accurate pH test paper.
Prepared turns rust function monomer A technical indicator as table 1.
Table 1: the prepared rust function monomer A technical indicator that turns.
| Outward appearance | Reddish-brown viscous liquid |
| Molecular weight | Mw=580,Mn=470 |
| PH value (1:5 deionized water) | 3.0 |
Without the iron rust that turns the corrosion steel plate sample surface that rust agent processes, be mainly lumphy structure that some shape sizes differ and little grain pattern.Little grain pattern is amplified to analyze and can see that these small-particles are mushy, corrosion contains lepidocrocite and pyrrhosiderite, and wherein lepidocrocite is main component.
Through turning the corrosion surface of steel plate conversion film of rust agent processing, be mainly divided into Liang Ge district, clear zone and dark space, the possible cause that this phenomenon produces is that surface of steel plate corrosion is inhomogeneous.Wherein dark space is non-corroding position or the few position of corrosion on steel plate, and clear zone is the more part of corrosion.Clear zone is amplified and found that the corrosion in this district changes into the crystal of sheet structure under the effect that turns rust agent, and these sheet structure crystal are overlapped, cover closely metallic surface, can effectively prevent that outer corrosive medium from arriving metal base surface and producing corrosion.
Embodiment 2: turn the synthetic of rust function monomer B
In building-up process, the weight part consumption of following each component is: 30 parts of unsaturated acid anhydrides; 70 parts of polyphenolic substances; 3 parts of catalyzer; 50 parts of solvents; Wherein unsaturated acid anhydride is chosen 2-hexenyl Succinic anhydried, and polyphenolic substance is chosen xitix, also can choose gallic acid, and catalyzer is chosen tin protochloride, and solvent is chosen propyl carbinol and Virahol; Every 1 weight part get 0.5g the concrete proportioning of each component be: 2-hexenyl Succinic anhydried 15g, xitix 35g, tin protochloride 1.5g, propyl carbinol 10g, Virahol 15g; Said components material is joined in the reactor with condensing works and agitator arm, and limit passes into nitrogen limit and is warming up to reflux temperature, keeps temperature-resistant, the follow-up continuation of insurance temperature of question response thing bleach 1.5h; Then reaction unit is changed into water distilling apparatus, temperature is down to 70 ℃, extracts the about 25g of solvent under 0.1Mpa vacuum tightness, obtains product and is and turns rust function monomer B.
To turn rust function monomer B and deionized water composite with 1:10 ratio, and be coated on the surface of steel plate with corrosion after mixing, drying at room temperature is to be measured after 3 days.
To turning the corrosion steel plate sample of rust agent processing front and back, carry out x-ray photoelectron power spectrum (XPS) analysis, obtain Fig. 1 (in figure, I line represents the spectral line before processing, and II line is the spectral line after processing).From Fig. 1 a, after turning rust agent processing, the absorption peak of C1s, O1s all relative I line significantly increases, and the absorption peak of Fe2p significantly reduces.By XPS, its surface-element is analyzed, the surface-element that acquisition turns rust agent processing front and back corrosion steel plate sample forms in Table 2 simultaneously.
Table 2: process the surface composition of front and back corrosion steel plate sample and the electron binding energy of element through turning rust agent.
From table 2, C content (the massfraction of surface of steel plate after turning rust agent processing, lower same) by 73.82%, be increased to 75.02%, O content is increased to 23.95% by 22.96%, and Fe content is also decreased to 1.02% by 3.23%, this is mainly to make surface of steel plate produce conversion film owing to turning rust agent processing, and the investigation depth of XPS only has 5 nm left and right, so the content of Fe element reduces, and the content of C element increases.Fig. 1 b is for processing the electron binding energy variation diagram of front and back oxygen element through turning rust agent.As can be seen from Figure, before processing, the electron binding energy of oxygen element is 532.41 eV, after processing, increase by 0.42 eV and become 532.83 eV, this shows to turn rust agent and forms Fe-O-C key at steel surface, because the electronegativity of C reduces than the strong O of causing of Fe electron density around, shielding effect is corresponding to be reduced, and causes the electron binding energy of O element to increase.Fig. 1 c is the electron binding energy variation diagram on two tracks through turning the Fe2p of rust agent before and after processing, as seen from the figure after turning rust agent and processing, in conjunction with can peak position move from low to high, process front Fe2p
3/2, Fe2p
1/2peak position is 709.96 eV and 723.16 eV, is increased to 713.99 eV and 728.55 eV after processing, and this explanation turns in the reaction process of rust agent and corrosion and is accompanied by part ferrous iron to ferric transformation.
Fig. 1 a is full spectrum, and Fig. 1 b is Fe2p part collection of illustrative plates, and Fig. 1 c is O1s collection of illustrative plates; In Fig. 1, I is to turn the photoelectron spectrum figure that front corrosion steel plate is processed in the agent of becoming rusty, and II is to turn the photoelectron spectrum that rear corrosion steel plate is processed in rust agent.
Embodiment 3: turn the synthetic of rust function monomer C
In building-up process, the weight part consumption of following each component is: 20 parts of unsaturated acid anhydrides; 60 parts of polyphenolic substances; 2 parts of catalyzer; 70 parts of solvents; Wherein unsaturated acid anhydride is chosen dodecenylsuccinic acid acid anhydride, and polyphenolic substance is chosen 2,3-resorcylic acid, and catalyzer is chosen tin tetrachloride, and solvent is chosen propylene glycol monomethyl ether; Every 1 weight part is got 0.5g; The concrete proportioning of each component is: dodecenylsuccinic acid acid anhydride 10g, 2,3-resorcylic acid 30g, tin tetrachloride 1.0g, propylene glycol monomethyl ether 35g; Said components material is joined in the reactor with condensing works and agitator arm, and limit passes into nitrogen limit and is warming up to reflux temperature, keeps temperature-resistant, the follow-up continuation of insurance temperature of question response thing bleach 1h; Then reaction unit is changed into water distilling apparatus, temperature is down to 50 ℃, extracts the about 35g of solvent under 0.08Mpa vacuum tightness, obtains product and is and turns rust function monomer C.
Embodiment 4: the preparation of alkyd intermediate A
In building-up process, the weight part consumption of following each component is: with-SO
38 parts of the dicarboxylic acid of M group; 15 parts of dibasic alcohol; 30 parts of polycarboxylic acids (acid anhydride); 28 parts, lipid acid; 5 parts of solvents; 0.5 part of catalyzer; 10 parts of deionized waters; Wherein with-SO
3the dicarboxylic acid monomer of M group is aromatic monomer, and M is sodium Metal 99.5 ion, with-SO
3the connected group of M is chosen 5-sodium sulfo isophthalate, and dibasic alcohol is chosen neopentyl glycol (2,2-dimethyl-1, ammediol, NPG), polycarboxylic acid (acid anhydride) is chosen m-phthalic acid, lipid acid is chosen soy(a)-bean oil fatty acid, and solvent is chosen dimethylbenzene, and catalyzer is chosen monobutyl-tin-trichloride; Every 1 weight part is got 10g; The concrete proportioning of each component is: 5-sodium sulfo isophthalate 80g, neopentyl glycol (2,2-dimethyl-1, ammediol, NPG) 150g, m-phthalic acid 300g, soy(a)-bean oil fatty acid 280g, dimethylbenzene 50g, monobutyl-tin-trichloride 5.0g, deionized water 100g join in the reactor bottle with agitator arm, condensing works, thermopair and nitrogen inlet, logical nitrogen, temperature is risen to 160 ℃ while stirring, be incubated half an hour.Then controlling temperature rise rate is that 10 ℃/30min is further warming up to 200 ℃, continues reaction until final product (alkyd intermediate mixture) acid number is at 3 o'clock, and stopped reaction, obtains alkyd intermediate A, lowers the temperature standby.
Embodiment 5: the preparation of alkyd intermediate B
In building-up process, the weight part consumption of following each component is: with-SO
35 parts of the dicarboxylic acid of M group; 20 parts of dibasic alcohol; 10 parts of polycarboxylic acids (acid anhydride); 35 parts, lipid acid; 10 parts of solvents; 0.2 part of catalyzer; 12 parts of deionized waters; Wherein with-SO
3the dicarboxylic acid monomer of M group is aromatic monomer, and M is sodium Metal 99.5 ion, with-SO
3the connected group of M is chosen dimethyl terephthalate (DMT)-5-sodium sulfonate, and dibasic alcohol is chosen ethylene glycol and 1,3-PD, polycarboxylic acid (acid anhydride) is chosen terephthalic acid, lipid acid is chosen ready denier oil acid, and solvent is chosen 1-Methoxy-2-propyl acetate, and catalyzer is chosen dibutyl tin dilaurate; Every 1 weight part is got 10g; The concrete proportioning of each component is: dimethyl terephthalate (DMT)-5-sodium sulfonate 50g, ethylene glycol 90g, 1, ammediol 110g, terephthalic acid 100g, ready denier oil acid 350g, 1-Methoxy-2-propyl acetate 100g, dibutyl tin dilaurate 2.0g, deionized water 120g join in the reactor bottle with agitator arm, condensing works, thermopair and nitrogen inlet, logical nitrogen, temperature is risen to 90 ℃ while stirring, be incubated half an hour.Then controlling temperature rise rate is that 10 ℃/30min is further warming up to 145 ℃, continues reaction until final product alkyd intermediate mixture acid number is at 0.2 o'clock, and stopped reaction, obtains alkyd intermediate B, lowers the temperature standby.
Embodiment 6: the preparation of alkyd intermediate C
In building-up process, the weight part consumption of following each component is: with-SO
312 parts of the dicarboxylic acid of M group; 25 parts of dibasic alcohol; 20 parts of polycarboxylic acids (acid anhydride); 20 parts, lipid acid; 8 parts of solvents; 0.8 part of catalyzer; 8.5 parts of deionized waters; Wherein with-SO
3the dicarboxylic acid monomer of M group is aromatic monomer, and M is sodium Metal 99.5 ion, with-SO
3the connected group of M is chosen terephthalic acid 5 sodium sulfonates, dibasic alcohol chooses 1,2-propylene glycol and 1,6-hexylene glycol (1,6-HDO), polycarboxylic acid (acid anhydride) is chosen toxilic acid (acid anhydride) and phthalic acid (acid anhydride), and lipid acid is chosen linseed oil fatty acid, solvent is chosen propylene-glycol ethyl ether and dimethylbenzene, and catalyzer is chosen Dibutyltin oxide; Every 1 weight part is got 10g; The concrete proportioning of each component is: terephthalic acid-5-sodium sulfonate 120g, 1,2-propylene glycol 125g, 1,6-hexylene glycol (1,6-HDO) 125g, toxilic acid (acid anhydride) 90g, phthalic acid (acid anhydride) 110g, linseed oil fatty acid 200g, propylene-glycol ethyl ether 50g, dimethylbenzene 30g, Dibutyltin oxide 8.0g, deionized water 85g join in the reactor bottle with agitator arm, condensing works, thermopair and nitrogen inlet, logical nitrogen, temperature is risen to 160 ℃ while stirring, be incubated half an hour.Then controlling temperature rise rate is that 10 ℃/30min is further warming up to 210 ℃, continues reaction until final product alkyd intermediate mixture acid number is at 5 o'clock, and stopped reaction, obtains alkyd intermediate C, lowers the temperature standby.
Embodiment 7: the preparation of band rust antirust emulsion A
In building-up process, the weight part consumption of following each component is: 6 parts, alkyd intermediate; 70 parts of acrylic ester monomers; Turn 6 parts of rust function monomers; 0.8 part of initiator; 55 parts of deionized waters; Wherein alkyd intermediate is chosen alkyd intermediate A, and acrylic ester monomer is chosen methyl methacrylate, vinylbenzene and vinylformic acid pentyl ester, turns rust function monomer and chooses and turn rust function monomer A, and initiator is chosen Potassium Persulphate; Every 1 weight part is got 8g; Concrete proportioning of each group is: alkyd intermediate A 48g, methyl methacrylate 200g, vinylbenzene 112g, vinylformic acid pentyl ester 248g, turn rust function monomer A 48g, Potassium Persulphate 6.4g, deionized water 440g.
The preparation process of band rust antirust emulsion A is as follows: in the reactor that is equipped with condensing works and agitator arm, add 400g deionized water; Get 48g and mix from alkyd intermediate A and 72g methyl methacrylate, the 136g vinylformic acid pentyl ester of embodiment 4 preparations, with the speed of 15 per second, be added dropwise in reactor, be warming up to 80 ℃; , 6.4 g Potassium Persulphates are dissolved in 40g deionized water meanwhile, treat that temperature-stable is 80 ℃, adds 2/3 persulfate aqueous solution in reactor.Then by 128g methyl methacrylate, 112g vinylbenzene, 112g vinylformic acid pentyl ester and slowly drop to reactor from the prepared rust function monomer A 48g that turns of embodiment 1, add remaining initiator solution, within approximately 2 hours, dropwise, insulation 1.5h, filters discharging.
The band the making antirust macromolecule emulsion A that becomes rusty adopts following method to carry out performance characterization:
Solid content test: with reference to GB 1725-79 standard;
PH value test: adopt accurate pH test paper;
Viscosity test: adopt NDJ-1 type Rotary Viscosimeter to measure;
Film resistance to salt water according to standard GB/T/10834-89 test;
Hardness test is with reference to GB/T6739-2006 < < hardness of film pencil assay method > >;
Shock resistance test is with reference to the shock-resistant assay method > > of GB/T1732-93 < < paint film;
Sticking power test is measured > > with reference to the lattice of drawing of GB/T9286-1998 < < paint and varnish paint film;
Snappiness test is with reference to GB/T1731-93 < < paint film flexibility assay method > >;
Water resistance test is with reference to first method in GB/T1733-1993 < < paint film water tolerance assay method > >;
Acidproof, alkali resistance is tested with reference to GB/T1763-89 < < paint film chemical reagent resistance assay method > >.
The technical indicator of prepared band rust antirust emulsion A is as table 3, and corrosion steel plate is processed rear film performance as table 4.
The technical indicator of the prepared band rust of table 3: embodiment 7 antirust emulsion A.
| Test item | Performance index |
| Outward appearance | The partially yellow emulsion of white |
| Emulsion film forming | Room temperature film-forming, without shrinkage cavity |
| Solid content | 52.3% |
| pH | 5.5 |
| 25 ℃ of viscosity (mPas) | 700mpa. s |
| Mechanical stability | Centrifugal 3000 revs/min (15 minutes without breakdown of emulsion) |
| Storage stability/moon | 50 ℃ of baking ovens (> 6) |
The test of the prepared band rust of table 4: embodiment 7 antirust emulsion A film performance.
| Test event | Result |
| Surface drying h | 0.5 |
| Do solid work the time (h) | 6 |
| Sticking power (cross-hatching) | 0 grade |
| Impact resistance cm | 50 |
| Hardness | B |
| Snappiness mm | 1 |
| Resistance to salt water (72h) | Without bubbling, without coming off, without variable color |
| Alkali resistance (24h) | Without foaming, variable color |
| Turn the antirust degree of rust | 20 μ m rusty scales are converted into black densification and film, and ground non-corroding is residual, soak 3 months non-corrodings in water and produce |
Embodiment 8: the preparation of band rust antirust emulsion B
In building-up process, the weight part consumption of following each component is: 3 parts, alkyd intermediate; 90 parts of acrylic ester monomers; Turn 4 parts of rust function monomers; 0.6 part of initiator; 45 parts of deionized waters; Wherein alkyd intermediate is chosen alkyd intermediate B, and acrylic ester monomer is chosen methyl methacrylate, butyl acrylate and vinylbenzene, turns rust function monomer and chooses and turn rust function monomer B, and initiator is chosen ammonium persulphate; Every 1 weight part is got 8g; Concrete proportioning of each group is: alkyd intermediate B 24g, methyl methacrylate 320g, butyl acrylate 336g, vinylbenzene 64g, ammonium persulphate 4.8g, turn rust function monomer B 32g, deionized water 360g.
The preparation process of band rust antirust emulsion B is as follows: in the reactor that is equipped with condensing works and agitator arm, add 320g deionized water; Get 24g and mix from alkyd intermediate B and 120g methyl methacrylate, the 96g butyl acrylate of embodiment 5 preparations, with the speed of per second ten, be added dropwise in reactor, be warming up to 80 ℃; , 4.8 g ammonium persulphates are dissolved in 40g deionized water meanwhile, treat that temperature-stable is 80 ℃, adds 2/3 ammonium persulfate aqueous solution in reactor.Then by 200g methyl methacrylate, 64g vinylbenzene, 240g butyl acrylate and slowly drop to reactor from the prepared rust function monomer B 32g that turns of embodiment 2, add remaining initiator solution, within approximately 1.5 hours, dropwise, insulation 1.0h, filters discharging.Prepared band rust antirust emulsion technical indicator is as table 5, and corrosion steel plate is processed rear film performance as table 6.
The technical indicator of the prepared band rust of table 5: embodiment 8 antirust emulsion B.
| Test item | Performance index |
| Outward appearance | Blue-fluorescence emulsion |
| Emulsion film forming | Room temperature film-forming, without shrinkage cavity |
| Solid content | 57.8% |
| pH | 5.0 |
| 25 ℃ of viscosity (mPas) | 650mpa. s |
| Mechanical stability | Centrifugal 3000 revs/min (15 minutes without breakdown of emulsion) |
| Storage stability/moon (50 ℃ of baking ovens) | ＞1 |
The test of the prepared band rust of table 6: embodiment 8 antirust emulsion B film performance.
| Test event | Result |
| Surface drying h | 0.75 |
| Do solid work the time (h) | 12 |
| Sticking power (cross-hatching) | 1 grade |
| Impact resistance cm | 50 |
| Hardness | B |
| Snappiness mm | 1 |
| Resistance to salt water (72h) | Nothing is bubbled, nothing comes off, micro-variable color |
| Alkali resistance (24h) | Without foaming, variable color |
| Turn the antirust degree of rust | 20 μ m rusty scales are converted into black densification and film, and ground non-corroding is residual, soak 3 months non-corrodings in water and produce |
Embodiment 9: the preparation of band rust antirust emulsion C
In building-up process, the weight part consumption of following each component is: 8 parts, alkyd intermediate; 100 parts of acrylic ester monomers; Turn 2 parts of rust function monomers; 0.9 part of initiator; 30 parts of deionized waters; Wherein alkyd intermediate is chosen alkyd intermediate C, and acrylic ester monomer is chosen methyl methacrylate, isobornyl methacrylate, butyl acrylate and isobutyl acrylate, turns rust function monomer and chooses and turn rust function monomer C, and initiator is chosen Sodium Persulfate; Every 1 weight part is got 8g; Concrete proportioning of each group is: alkyd intermediate C 64g, methyl methacrylate 264g, isobornyl methacrylate 72g, butyl acrylate 176g, isobutyl acrylate 288g, turn rust function monomer C 16g, Sodium Persulfate 7.2g, deionized water 240g.
The preparation process of band rust antirust emulsion C is as follows:
In the reactor that is equipped with condensing works and agitator arm, add 200g deionized water; Get 64g and mix from alkyd intermediate C and 80g methyl methacrylate, 136g butyl acrylate, the 80g isobutyl acrylate of embodiment 6 preparations, with the speed of 12 per second, be added dropwise in reactor, be warming up to 80 ℃; , 7.2 g Sodium Persulfates are dissolved in 40g deionized water meanwhile, treat that temperature-stable is 80 ℃, adds 2/3 sodium persulfate aqueous solution in reactor.Then 184g methyl methacrylate, 72g isobornyl methacrylate, 208g isobutyl acrylate, 40g butyl acrylate and 16g are slowly dropped in reactor from turning rust function monomer C mixes of embodiment 3 preparations, add remaining initiator solution, within approximately 2.5 hours, dropwise, insulation 2.0h obtains aqueous rusty antirust emulsion C.
The technical indicator of the prepared band rust of table 7: embodiment 9 antirust emulsion C.
| Test item | Performance index |
| Outward appearance | Milky emulsion |
| Emulsion film forming | Room temperature film-forming, without shrinkage cavity |
| Solid content | 53.9% |
| pH | 4.5 |
| 25 ℃ of viscosity (mPas) | 550mpa. s |
| Mechanical stability | Centrifugal 3000 revs/min (15 minutes without breakdown of emulsion) |
| Storage stability/moon | 50 ℃ of baking ovens (> 6) |
The test of the prepared band rust of table 8: embodiment 9 antirust emulsion C film performance.
| Test event | Result |
| Surface drying h | 0.5 |
| Do solid work the time (h) | 8 |
| Sticking power (cross-hatching) | 0 grade |
| Impact resistance cm | 50 |
| Hardness | B |
| Snappiness mm | 1 |
| Resistance to salt water (72h) | Nothing is bubbled, nothing comes off, micro-variable color |
| Alkali resistance (24h) | Without foaming, variable color |
| Turn the antirust degree of rust | 20 μ m rusty scales are converted into black densification and film, and ground non-corroding is residual, soak 3 months non-corrodings in water and produce |
The technical indicator of aqueous rusty antirust emulsion C is as table 7, and corrosion steel plate is processed rear film performance as table 8.
Claims (8)
1. a preparation method for the antirust macromolecule emulsion of aqueous rusty, is characterized in that, it comprises that the preparation of synthetic, the alkyd intermediate that turns rust function monomer is, three steps of preparation of band rust antirust emulsion, wherein:
(1) turn the synthetic of rust function monomer: in reactor, add solvent, unsaturated acid anhydride, polyphenolic substance and a small amount of catalyzer, import nitrogen and be warming up to reflux temperature; After question response thing bleach, be incubated 1 hour～2 hours, then reaction unit changed into water distilling apparatus, be cooled to 50～80 ℃, under 0.08～-0.1Mpa vacuum tightness, extract solvent;
In building-up process, the weight part consumption of each component is:
20～40 parts of unsaturated acid anhydrides;
50～70 parts of polyphenolic substances;
2～5 parts of catalyzer;
50～85 parts of solvents;
Described polyphenolic substance is selected from any in 2,3-resorcylic acid, Gallic Acid;
Described catalyzer is selected from any in tosic acid, tin protochloride, tin tetrachloride;
(2) preparation of alkyd intermediate: by with-SO
3the aromatic monomer of M group, polycarboxylic acid and/or polybasic acid anhydride and dibasic alcohol and fatty acid response make alkyd intermediate mixture material; In reactor, add with-SO
3the aromatic monomer of M group, polycarboxylic acid and/or polybasic acid anhydride, dibasic alcohol, lipid acid, catalyzer, solvent, deionized water, import nitrogen and heat up, and controlling temperature of reaction is 90 ℃～210 ℃ scopes, and the reaction times is 2～6 hours; When in reactor, alkyd intermediate mixture material acid number is 0.2～5, stopped reaction;
In building-up process, the weight part consumption of each component is:
With-SO
35～12 parts of the aromatic monomers of M group;
15～25 parts of dibasic alcohol;
10～30 parts of polycarboxylic acid and/or polybasic acid anhydrides;
20～35 parts, lipid acid;
5～10 parts of solvents;
0.2～0.8 part of catalyzer;
8～12 parts of deionized waters;
Wherein, M is sodium Metal 99.5 ion;
Described catalyzer is selected from any in Dibutyltin oxide, dibutyl tin dilaurate or monobutyl-tin-trichloride; With-SO
3the aromatic monomer of M group is any in 5-sodium sulfo isophthalate, terephthalic acid-5-sodium sulfonate;
(3) preparation of band rust antirust emulsion: add appropriate amount of deionized water to being furnished with in the four-hole boiling flask of mechanical stirring device and nitrogen device, after mixing, alkyd intermediate prepared by step (2) and a small amount of acrylic monomer be added dropwise in reactor, be warming up to 80 ± 2 ℃, after temperature-stable, add a small amount of initiator solution, respectively by surplus acrylic ester monomer and through step (1), prepare turn rust function monomer slowly drop in reactor, add remaining initiator solution, at 1.5 hours～2.5 hours, with interior, dropwise; Be incubated 1 hour～2 hours;
In building-up process, the weight part consumption of each component is:
3～8 parts, alkyd intermediate;
70～100 parts of acrylic ester monomers;
Turn 2～6 parts of rust function monomers;
0.6～0.9 part of initiator;
30～55 parts of deionized waters;
Wherein acrylic ester monomer is selected from the arbitrary combination of following one or more: vinylformic acid pentyl ester, butyl acrylate, isobutyl acrylate.
2. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, in described step (1), solvent is selected from the arbitrary combination of one or more following solvents:
Ethylene glycol, Virahol, propyl carbinol, propylene glycol monomethyl ether.
3. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, in described step (1), unsaturated acid anhydride is selected from any in following acid anhydrides:
MALEIC ANHYDRIDE, 2-hexenyl Succinic anhydried, dodecenylsuccinic acid acid anhydride.
4. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, the dibasic alcohol in described step (2) is one or more the arbitrary combination in following dibasic alcohol:
Ethylene glycol, 1,2-PD, 1,3-PD, neopentyl glycol (2，2-dimethyl-1，3-propanediol, NPG), 1,6-hexylene glycol (1,6-HDO).
5. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, the arbitrary combination of one or more that the polycarboxylic acid in described step (2) and/or polybasic acid anhydride are selected from following polycarboxylic acid:
M-phthalic acid, terephthalic acid, toxilic acid.
6. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, in described step (2), lipid acid is selected from any following lipid acid:
Ready denier oil acid, linseed oil fatty acid, soy(a)-bean oil fatty acid.
7. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, solvent is selected from following one or more arbitrary combination in described step (2):
1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether, dimethylbenzene.
8. the preparation method of the antirust macromolecule emulsion of aqueous rusty according to claim 1, is characterized in that, in described step (3), initiator is selected from any in following initiator:
Potassium Persulphate, Sodium Persulfate, ammonium persulphate.
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| CN103849862A (en) * | 2014-03-05 | 2014-06-11 | 山东科技大学 | Rust transforming agent and preparation method thereof, water-based iron rust conversion coating and preparation method thereof |
| CN104561977B (en) * | 2015-01-29 | 2015-12-02 | 贵州电网公司输电运行检修分公司 | A kind of band rust treatment solution being applicable to high humidity area and preparation method thereof |
| CN105153346A (en) * | 2015-09-29 | 2015-12-16 | 南通瑞普埃尔生物工程有限公司 | Special waterborne anti-corrosion emulsion for multi-component copolymerization rust converting primer and preparation method of emulsion |
| KR20180066947A (en) * | 2016-12-09 | 2018-06-20 | 변상준 | Aqueous paints composition for rust prevention and rust removing and method therof |
| CN109971266A (en) * | 2019-04-26 | 2019-07-05 | 河南青山环保科技有限公司 | A kind of synthetic method of band rust antirust resin emulsion |
| CN110144146A (en) * | 2019-04-26 | 2019-08-20 | 河南青山环保科技有限公司 | A kind of synthetic method of band rust antirust styrene-acrylic emulsion |
| CN110577761A (en) * | 2019-09-28 | 2019-12-17 | 东台市明山石涂料有限公司 | Water-based rusty antirust paint and preparation method thereof |
| CN111925680A (en) * | 2020-07-28 | 2020-11-13 | 德爱威（中国）有限公司 | Water-based primer for rusty coating and preparation method thereof |
| CN113652131A (en) * | 2021-09-28 | 2021-11-16 | 西北永新涂料有限公司 | Water-based acrylic primer-topcoat integrated coating suitable for rusty steel structure and steel structure renovation coating, and preparation method and application method thereof |
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