CN109266075A - A method of improving the anti-marine organism corrsion of stainless steel plate and pollution - Google Patents
A method of improving the anti-marine organism corrsion of stainless steel plate and pollution Download PDFInfo
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- CN109266075A CN109266075A CN201810912201.7A CN201810912201A CN109266075A CN 109266075 A CN109266075 A CN 109266075A CN 201810912201 A CN201810912201 A CN 201810912201A CN 109266075 A CN109266075 A CN 109266075A
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- stainless steel
- functionalization
- radical polymerization
- transfer radical
- atom transfer
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 187
- 239000010935 stainless steel Substances 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000007797 corrosion Effects 0.000 claims abstract description 54
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 41
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 11
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000007306 functionalization reaction Methods 0.000 claims description 53
- 229920000642 polymer Polymers 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 210000004709 eyebrow Anatomy 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000002474 experimental method Methods 0.000 claims description 31
- 241000195493 Cryptophyta Species 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 229920006037 cross link polymer Polymers 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000013256 coordination polymer Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 241000894006 Bacteria Species 0.000 claims description 17
- 241000238586 Cirripedia Species 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920001690 polydopamine Polymers 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 12
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- 150000001347 alkyl bromides Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 10
- 230000001580 bacterial effect Effects 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000005956 quaternization reaction Methods 0.000 claims description 7
- 230000000844 anti-bacterial effect Effects 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000006557 surface reaction Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000004088 simulation Methods 0.000 claims description 3
- 241000894007 species Species 0.000 claims description 3
- -1 bromine isobutyl acylbromide Chemical class 0.000 claims 2
- 238000007872 degassing Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 claims 1
- 241000545067 Venus Species 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 229960003638 dopamine Drugs 0.000 abstract description 2
- 125000002008 alkyl bromide group Chemical group 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 241000589516 Pseudomonas Species 0.000 description 28
- 238000002073 fluorescence micrograph Methods 0.000 description 12
- 230000004083 survival effect Effects 0.000 description 12
- 239000012499 inoculation medium Substances 0.000 description 10
- 230000010287 polarization Effects 0.000 description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000012258 culturing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241001301450 Crocidium multicaule Species 0.000 description 2
- 238000002817 Miles and Misra method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000589540 Pseudomonas fluorescens Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 210000000887 face Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The present invention provides a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution.For this method using the modification of linear or crosslinked polymeric materials in stainless steel surface, which is polymethylacrylic acid dimethylamino second rouge (P (DMAEMA)) and its derivative for introducing quaternary ammonium group.Dopamine is in stainless steel surface auto polymerization to be anchored alkyl bromide atom transfer radical polymerization initiator, then dimethylaminoethyl acrylate methyl base ammonia second rouge carries out atom transfer radical polymerization in stainless steel surface, in stainless steel surface grafted linear or cross-linked poly-methyl methacrylate dimethylamino second rouge.The functionalized stainless steel has the function of good antifouling and anti-biological corrosion in marine environment.Compared with prior art, at low cost, long service life of the invention can carry out antifouling and anti-biological corrosion efficiently, environmentally friendly to stainless steel, and generate without any by-product, and the method for such functional modification stainless steel has a good application prospect in marine field.
Description
Technical field
The invention belongs to the antifouling and anti-biological corrosion fields of stainless steel, and in particular to a kind of stainless using functionalization of polymers
Steel is to reach the method for the antifouling and anti-biological corrosion in marine environment.
Background technique
Stainless steel (SS) is because its performance more erosion-resisting than other materials is most widely used engineering material in the application of ocean
Material.However, original stainless steel surface is still easy to be polluted by marine organisms attachment, the algae such as barnacle, bacterium and other seas
Foreign biology will form biomembrane in the easy fouling of stainless steel surface in the process, and biomembrane is once being formed, will cause stainless steel
The physical degradation and biodeterioration on surface.Biological corrosion is the thorny problem of ocean industry, and the serious structure of stainless steel is caused to be destroyed,
Increase fuel consumption and maintenance cost.Therefore, stainless steel is as the material being most widely used in the industry of ocean, improve its it is antifouling and
Antibiont corrosive nature contains the huge wealth of society, and the antifouling and anti-biological corrosion technology of stainless steel has become Now Domestic
The rising industry of outer ocean shipbuilding industry.
Currently, the method that the change of stainless steel watch surface properties is mainly modified by physics and chemical treatment or surface, wherein
Chemically treated method is mainly acid wash passivation.This method specifically: first wipe stainless steel surface grease clean；Then will
Acid-washing stainless steel passivation cream stirs evenly, and a protective layer is formed outside stainless steel, what the chromium usually in passivating solution was formed
Chromic salts.This method the problem is that: passivating solution contains the toxic reagents such as heavy metallic salt, and generates a large amount of acid-base waste fluid, such as
It does not use appropriate method to be handled, serious pollution and harm will be caused to ecological environment and human health.Surface is modified
Method in most common antifouling surface polymer be polyethylene glycol and its derivative, but polyethylene glycol holds in complex dielectrics
It is oxidizable, thus its prolonged application is restricted.
Therefore, the effective use for how carrying out surface functionalization and modification to stainless steel, realizing resource, is that human society faces
One of important problem.
Summary of the invention
The present invention is directed to the deficiency of above-mentioned existing stainless steel protection technology, provides a kind of in stainless steel surface graft polymerization
The modified method of object, this method has the advantages that safe and nontoxic, efficient and environmentally friendly.
Antibiont corrosion and resistant to pollution side are improved using the stainless steel base of functionalization of polymers the present invention provides a kind of
Method.For this method using the modification of linear or crosslinked polymeric materials in stainless steel surface, which is poly- methyl-prop
Olefin(e) acid dimethylamino second rouge (P (DMAEMA)) and its derivative for introducing quaternary ammonium group.Dopamine is in stainless steel surface autohemagglutination
It shares to be anchored alkyl bromide atom transfer radical polymerization initiator, then dimethylaminoethyl acrylate methyl base ammonia second rouge is in stainless steel watch
Face carries out atom transfer radical polymerization, in stainless steel surface grafted linear or cross-linked poly-methyl methacrylate dimethylamino second rouge.
The functionalized stainless steel of the method has the function of good antifouling and anti-biological corrosion in marine environment.
A method of improving the anti-marine organism corrsion of stainless steel plate and pollution, which comprises the steps of:
(1) functionalization of polymers stainless steel is prepared
It is anchored alkyl bromide atom transfer radical polymerization initiator in the stainless steel surface of existing poly-dopamine coating first,
Then pass through atom transfer radical polymerization grafted linear or cross-linked poly-methyl methacrylate dimethylamino second rouge in stainless steel surface,
Obtain functionalization of polymers stainless steel；
(2) functionalization of polymers stainless steel simulation is applied to marine environment
Functionalization of polymers stainless steel obtained in step (1) is subjected to the double eyebrow algae attachment experiments of coffee, barnacle gold respectively
Star larva sedimentation experiment, to the antibacterial activity test of pseudomonad and the corrosion experiment of surface functionalization stainless steel；In bacterium
Culture solution used is all based on filtering sea in corrosion experiment.
A kind of method improving stainless steel plate anti-marine organism corrsion and pollution according to the present invention, in step (1)
After stainless steel surface is by atom transfer radical polymerization grafted linear or cross-linked poly-methyl methacrylate dimethylamino second rouge, into one
Step processing is to the stainless steel surface polymeric quartenary ammonium after functionalization of polymers.
Further, the method for functionalization of polymers stainless steel is prepared in step (1) are as follows:
1) it is anchored the process of alkyl bromide atom transfer radical polymerization initiator are as follows: poly-dopamine coating stainless steel SS-PDA
Matrix immerses in the 10-20mL methylene chloride containing 1.0-1.3mL (about 7.2mmol) triethylamine, cooling in mixture of ice and water；Contain
There is the 5mL methylene chloride of the 2- bromine isobutyl acylbromide of 0.9-1.2mL (about 7.2mmol) to be added dropwise in mixture；Later, instead
It answers mixture to be stirred at room temperature 24 hours, then is washed with a large amount of acetone, ethyl alcohol and deionized water, it is dry；
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization grafted linear polymethylacrylic acid diformazan
Base ammonia second rouge, process are as follows: [DMAEMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:1:0.2:1 is in high borosilicate
Surface is carried out in pipe causes atom transfer radical polymerization；After stirring and deaerate 20-40 minutes under the conditions of argon gas, SS-PDA-
Br substrate is introduced into reaction mixture；Reaction tube is sealed 24 hours under 35-40 DEG C of water bath condition, and linear polymerization is made
The functionalized stainless steel of object；
Or,
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization graft crosslinking polymethylacrylic acid diformazan
The process of base ammonia second rouge are as follows: carry out surface in high borosilicate tube and cause atom transfer radical polymerization, [DMAEMA]: [PEGDMA
Polyethylene glycol dimethacrylate]: [CuCl]: [CuCl2]: [Bpy2,2- bipyridyl] molar feed ratio 100:10:1:0.2:
1, it is reacted in 3-5mL methanol；After stirring and deaerate 20-40 minutes under the conditions of argon gas, SS-PDA-Br sample introduction to reaction
In mixture；Pipe is sealed 24 hours under 35-40 DEG C of water bath condition, so that it is functionalized stainless that cross-linked polymer is made
Steel.
Further, the preparation of quaternized linear or cross-linked polymer functionalization stainless steel: the high borosilicate tube at 70 DEG C
In, SS-g-P or SS-g-CP substrate is immersed in the 10- containing volume fraction 20% bromohexane and 0.1-0.3mL triethylamine
48 hours in 20mL2- propanol solution, SS-g-QP substrate or the surface SS-g-QCP is made；After quaternization reaction, with acetone and go
Ionized water rinses, dry, obtains quaternized linear or cross-linked polymer functionalization stainless steel.
A kind of method improving stainless steel plate anti-marine organism corrsion and pollution according to the present invention, the polymer
Linear or cross-linked poly-methyl methacrylate dimethylamino second rouge and they ring substitutive derivative or hetero atom replace derive
One of object also includes its quaternized products and derivative.
A kind of method improving stainless steel plate anti-marine organism corrsion and pollution according to the present invention, the anticorrosive reality
The bacterial species tested are unlimited, not only include the double eyebrow algaes of the coffee, barnacle cyprids and pseudomonad, to other marine bacterias
All have certain anticorrosive effect.
The present invention provides a kind of method for preparing functionalization of polymers stainless steel, includes the following steps:
1) it is anchored the process of alkyl bromide atom transfer radical polymerization initiator are as follows: poly-dopamine coating stainless steel SS-PDA
Matrix immerses in the 10-20mL methylene chloride containing 0.1-0.3mL (about 7.2mmol) triethylamine, cooling in mixture of ice and water；Contain
There is the 5-10mL methylene chloride of the 2- bromine isobutyl acylbromide of 0.9-1.3mL (about 7.2mmol) to be added dropwise in mixture；It
Afterwards, reaction mixture is stirred at room temperature 24 hours, then is washed with a large amount of acetone, ethyl alcohol and deionized water, dry；
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization grafted linear polymethylacrylic acid diformazan
Base ammonia second rouge, process are as follows: [DMAEMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:1:0.2:1 is in high borosilicate
Surface is carried out in pipe causes atom transfer radical polymerization；After stirring and deaerate 20-40 minutes under the conditions of argon gas, SS-PDA-
Br substrate is introduced into reaction mixture；Reaction tube is sealed 24 hours under 35-40 DEG C of water bath condition, and linear polymerization is made
The functionalized stainless steel of object；
Or,
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization graft crosslinking polymethylacrylic acid diformazan
The process of base ammonia second rouge are as follows: surface, which is carried out, in high borosilicate tube causes atom transfer radical polymerization, [DMAEMA]:
[PEGDMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:10:1:0.2:1 reacts in 4-6mL methanol；In argon
After stirring and deaerate 20-40 minutes under the conditions of gas, SS-PDA-Br sample introduction is into reaction mixture；Pipe is in 35-40 DEG C of water-bath
Under the conditions of be sealed 24 hours, thus be made the functionalized stainless steel of cross-linked polymer.
A kind of method preparing functionalization of polymers stainless steel according to the present invention, is further processed to polymer function
Stainless steel surface polymeric quartenary ammonium after change: in the high borosilicate tube at 70 DEG C, SS-g-P or SS-g-CP substrate, which is immersed in, to be contained
Have in the 10-20mL2- propanol solution of 20% bromohexane of volume fraction and 0.1-0.3mL triethylamine 48 hours, SS-g-QP is made
Substrate or the surface SS-g-QCP；After quaternization reaction, rinsed with acetone and deionized water, it is dry, obtain it is quaternized linear or
Cross-linked polymer is functionalized stainless steel.
The present invention also provides a kind of functionalization of polymers stainless steels, by the above-mentioned side for preparing functionalization of polymers stainless steel
Prepared by method.
The product of the end reaction of 1mg can modify 2*2cm in preparation method of the present invention2Stainless steel surface.
Detailed description of the invention:
A method of the anti-marine organism corrsion of stainless steel plate and pollution are improved, specifically includes the following steps:
(1) functionalization of polymers stainless steel is prepared
It is anchored alkyl bromide atom transfer radical polymerization initiator in the stainless steel surface of existing poly-dopamine coating first,
Then pass through atom transfer radical polymerization grafted linear or cross-linked poly-methyl methacrylate dimethylamino second rouge in stainless steel surface.
And being further processed is stainless steel surface polymeric quartenary ammonium to after functionalization of polymers.
(2) functionalized modification stainless steel simulation is applied to marine environment
Functionalization stainless steel obtained in step (1) is subjected to the double eyebrow algae attachment experiments of coffee, barnacle cyprids respectively
Sedimentation experiment, to the antibacterial activity test of pseudomonad and the corrosion experiment of surface functionalization stainless steel.In bacterial corrosion reality
It is simulating ocean environment in testing, and also to the antibiont corrosive effect of a certain bacterium of quantitative detection, culture solution used all bases
In filtering sea.Testing selected bacterium is the typical bacteria strain for being widely present while being also corrosion hull in ocean.
The polymer be linear or cross-linked poly-methyl methacrylate dimethylamino second rouge and they ring replace derive
One of object or heterosubstituted derivatives, including its quaternized products and derivative.
The bacterial species of the antibiont corrosion experiment are unlimited, not only include the double eyebrow algaes of the coffee, barnacle cyprids
And pseudomonad, certain anticorrosive effect is all had to other marine bacterias.
Prepare specific experiment step such as Fig. 7 of functionalization of polymers stainless steel:
1, alkyl bromide is introduced to stainless steel base as ATRP initiator
Poly-dopamine coating stainless steel (SS-PDA) matrix immerses the 10mL dichloro for containing 1.0mL (7.2mmol) triethylamine
In dichloromethane, 0 DEG C is cooled in mixture of ice and water.Then it will contain the 5mL of the 2- bromine isobutyl acylbromide of 0.9mL (7.2mmol)
Dichloromethane solution is added dropwise in mixture, and subsequent mixture is stirred at room temperature 24 hours.Alkyl bromide is modified not
Rust steel surface (SS-PDA-Br) is washed with a large amount of acetone, ethyl alcohol and deionized water.Finally, decompression is dry in a vacuum drying oven
It is dry.
2, methyl methacrylate (DMAEMA) atom transfer radical polymerization [DMAEMA]: [CuCl] is caused on surface:
[CuCl2]: [Bpy] molar feed ratio 100:1:0.2:1 carries out surface in high borosilicate tube and causes atom transfer radical polymerization.
It stirs and is evacuated after twenty minutes under the conditions of argon gas, SS-PDA-Br sample is added in reaction mixture.Reaction tube is in 35 DEG C of water
24 hours are sealed under the conditions of bath to cause DMAEMA in stainless steel surface graft polymerization.Product abbreviation SS-g-P.
3, SS-PDA-Br surfaces preparation crosslinking P (DMAEMA) brush
Polyethylene glycol dimethacrylate (PEGDMA) is used as crosslinking agent.Surface is carried out in high borosilicate tube to draw
Atom transfer radical polymerization is sent out, [DMAEMA]: [PEGDMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:10:
1:0.2:1 reacts in 4mL methanol.It stirs and is evacuated after twenty minutes under the conditions of argon gas, it is mixed that SS-PDA-Br is added to reaction
It closes in object.Reaction tube is sealed 24 hours under 35 DEG C of water bath conditions, so that the stainless of the crosslinking P in surface (DMAEMA) be made
Steel surface, the surface abbreviation SS-g-CP.
The season ammonification on the surface 4, SS-g-P and SS-g-CP
In high borosilicate tube at 70 DEG C, SS-g-P and SS-g-CP substrate is immersed in containing 20% bromohexane of volume fraction
With 48 hours in the 10mL2- propanol solution of 0.1mL triethylamine, be made quaternized stainless steel surface, abbreviation SS-g-QP respectively
With the surface SS-g-QCP.After quaternization reaction, sample is rinsed with a large amount of acetone and deionized water in order, is removed unreacted
Then bromohexane is dried overnight in a vacuum drying oven.
Compared with prior art, it is provided by the invention using the stainless steel base of functionalization of polymers improve antibiont corrosion and
Resistant to pollution method has the following beneficial effects:
(1) ability that antibiont corrosion is improved using the functionalized stainless steel base of modification, can be effective, incompetent
Consumption, with environmentally friendly protecting ocean and other waters hull surfaces stainless steel material；And it takes this polymer-modified
Stainless steel ground method, can effectively prevent bacterial micro-organism in ocean and lives away from home, there is antipollution effect well.
(2) synthetic method of polymers is simple, is easy for extensive mass production.
Detailed description of the invention
Fig. 1 is the double eyebrow algae fluorescence microscope images of each specimen surface coffee: (A) original stainless steel (B) SS-PDA-Br (C) SS-
g-P(D)SS-g-CP(E)SS-g-QP(F)SS-g-QCP。
Fig. 2 is original stainless steel surface and the relative extent for being functionalized the double eyebrow algae adherency of coffee on stainless steel surface.
Fig. 3 is the percentage of the sedimentation and dead cyprids on original and functionalized stainless steel surface.
Fig. 4 is each specimen surface pseudomonas fluorescence microscope images (living cells: a, c, e, g；Dead cell: b, d, f, h)
(a, b) original stainless steel, (c, d) SS-PDA-Br, (e, f) SS-g-QP, (g, h) SS-g-QCP.
Fig. 5 is the survival condition that pseudomonas is adhered to specimen surface.
Fig. 6 is Tafel polarization curve.
Fig. 7 prepares the flow diagram of functionalization of polymers stainless steel.
Specific embodiment
A kind of specific embodiment party for the method for improving the anti-marine organism corrsion of stainless steel plate and pollution of the present invention presented below
Formula.
Embodiment 1:
In the present embodiment, the preparation process of functionalized modification stainless steel is as follows:
(1) it is anchored the process of alkyl bromide atom transfer radical polymerization initiator are as follows: poly-dopamine coating stainless steel (SS-
PDA) matrix immerses in the 10mL methylene chloride containing 1.0mL (7.2mmol) triethylamine, cooling in mixture of ice and water.Contain
The 5mL methylene chloride of the 2- bromine isobutyl acylbromide of 0.9mL (7.2mmol) is added dropwise in mixture.Later, reaction mixture
It is stirred at room temperature 24 hours.Anchoring have a large amount of acetone of stainless steel (abbreviation SS-PDA-Br substrate) of initiator, ethyl alcohol and
Deionized water washing.Finally, being dried under reduced pressure in a vacuum drying oven.
(2) stainless steel surface in step (1) is passed through into atom transfer radical polymerization grafted linear polymethylacrylic acid two
Methyl ammonia second rouge, process are as follows: [DMAEMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:1:0.2:1 is in high boron
Surface is carried out in silicone tube causes atom transfer radical polymerization.It stirs and deaerates under the conditions of argon gas after twenty minutes, SS-PDA-Br
Substrate is introduced into reaction mixture.Reaction tube is sealed 24 hours under 35 DEG C of water bath conditions, and linear polymer official is made
The stainless steel surface (surface abbreviation SS-g-P) of energyization.
In order to verify the antifouling and anti-biological corrosive power of above-mentioned obtained linear polymer functionalization stainless steel, carry out as follows
Step (3)-(6):
(3) the double eyebrow algae culturing liquids of coffee preparation are filtered using the transmitting of exciter filter and 617nm equipped with 535nm
The microscope of piece obtains being immersed in the double eyebrow frustules of the coffee adhered on sample after 24 hours in algae suspension on sample
Fluorescence microscopy images.
(4) substrate of each precipitating in step (3) is transferred to ‰ salinity of 2mL30, in the seawater of 0.22 μm of filtering.Dipping
Ultrasonic bath 10 minutes to remove the double eyebrow algaes of the coffee settled.Then, the aliquot of 200 μ L 96 hole microplates are transferred to (to gather
Sulfuryl bottom).In the excitation wavelength (λ equipped with 440nmex) microplate reader on, the fluorescence in each hole is measured at 690nm
Intensity.The fluorescence intensity of 30 ‰ salinity, 0.22 μm of filtering sea is set as blank.Measurement is averaged in triplicate every time
Value.
The fluorescence microscope images of SS-g-P substrate surface in Fig. 1 are obtained in observation above-mentioned steps (3), it is glimmering with original stainless steel
Light microscope images comparison, the double eyebrow frustules of the coffee for the attachment that can visually see largely reduce.From this figure, it can be seen that SS-
The surface g-P adheres in which can efficiently reduce the double eyebrow frustules of coffee.
Above-mentioned steps (4) obtain the original stainless steel surface of Fig. 2 and are functionalized the double eyebrow algae adherency of coffee on stainless steel surface
Relative extent.Compared with original stainless steel surface, the double eyebrow algae adherency of SS-g-P substrate surface coffee are reduced to 38%.It is same from the figure
Sample can be seen that SS-g-P substrate surface and adhere to capable of efficiently reducing the double eyebrow frustules of coffee.
(5) the 0.5mL filtering sea that will contain about 40 barnacle cyprids is added separately to original or modifies stainless
In 2cm × 2cm sample of steel base.Room temperature cultivates 24 hours under dark.The total number of larva is settled down in observation under the microscope.
Detection is averaged three times.
Above-mentioned steps (5) obtain hundred of sedimentation and dead cyprids on the original and functionalized stainless steel surface of Fig. 3
Divide ratio.From this figure, it can be seen that about 68% barnacle cyprids are deposited in original stainless steel surface, show them to biological dirty
The sensibility of damage is very high.In contrast, the stainless steel surface sedimentation score after polymer grafting largely reduces, SS-g-P substrate
Surface is 15%.
(6) pseudomonad is used to observation antibacterial polymer coating bonding feature and bactericidal effect.False unicellular bacterium culture
In seawater full of nutrition.After hatching, bacterial suspension 2700 turns of centrifugations again, and separate supernatant.Bacterial cell is with artificial
Seawater is washed twice, and being resuspended in concentration is 107 cells every square centimeter.Each substrate is cut into 1cm × 1cm, is immersed in
Under static conditions then the bacteria suspension of 1mL is rushed with pure water three times to remove non-slime bacteria 4 hours at 37 DEG C.In order to determine official
The quantity that live bacterial cell on stainless steel surface can be changed carries out quantitative in-vitro antibacterial using expansion board method and measures.
Above-mentioned steps (6) obtain the survival condition that Fig. 5 pseudomonas is adhered to specimen surface, and survival rate is with every square li
Cell number on rice sample indicates.Original stainless steel surface viable count is every square centimeter to be higher than 106, and the surface SS-g-P subtracts
Less to 4 × 105.This shows to reduce in SS-g-P surface bacteria survival rate, so that biological corrosion can be effectively reduced.
It is found through experiments that the functionalized stainless steel of linear polymer has preferably anti-biological live away from home and anti-biological corrosion
Performance, applied to marine ship will effectively reduce Ship's corrosion loss, thus effectively save resource and maintenance cost.
Embodiment 2:
Functionalized stainless steel and embodiment 1 in the present embodiment use identical SS-PDA-Br substrate, the difference is that connecing
Branch cross-linked poly-methyl methacrylate dimethylamino second rouge, its step are as follows:
Pass through atom transfer radical polymerization graft crosslinking polymethylacrylic acid dimethylamino second rouge in stainless steel surface
Process are as follows: surface, which is carried out, in high borosilicate tube causes atom transfer radical polymerization, [DMAEMA]: [PEGDMA]: [CuCl]:
[CuCl2]: [Bpy] molar feed ratio 100:10:1:0.2:1 reacts in 4mL methanol.It stirs and deaerates under the conditions of argon gas
After twenty minutes, SS-PDA-Br sample introduction is into reaction mixture.It is small that reaction tube is sealed 24 under 35 DEG C of water bath conditions
When, so that the functionalized stainless steel of cross-linked polymer (abbreviation SS-g-CP substrate) be made.
In order to verify the antifouling and anti-biological corrosive power of above-mentioned obtained cross-linked polymer functionalization stainless steel, method and reality
Example 1 is identical.
Cross-linked polymer is functionalized stainless steel experiment in the double eyebrow algae culturing liquids of coffee and obtains SS-g-CP substrate table in Fig. 1
The fluorescence microscope images in face are compared with original stainless steel fluorescence microscope images, the double eyebrow algaes of the coffee for the attachment that can visually see
Cell largely reduces.From this figure, it can be seen that SS-g-CP substrate surface glues in which can also efficiently reduce the double eyebrow frustules of coffee
It is attached.
Cross-linked polymer is functionalized stainless steel and obtains original stainless steel surface in Fig. 2 in the experiment of the double eyebrow algae culturing liquids of coffee
With the relative extent of the double eyebrow algae adherency of coffee on functionalization stainless steel surface.Compared with original stainless steel surface, SS-g-CP substrate
Coffee double eyebrow algae adherency in surface are reduced to 33%.From this figure, it can be seen that SS-g-CP substrate surface can also efficiently reduce coffee
Adhere to the double eyebrow frustules of coffee.
Cross-linked polymer is functionalized stainless steel and obtains the original and functionalized stainless steel of Fig. 3 in the experiment of barnacle cyprids
The percentage of sedimentation and dead cyprids on surface.From this figure, it can be seen that heavy compared to about 68% barnacle cyprids
It forms sediment in original stainless steel surface, the stainless steel surface sedimentation score after cross-linked polymer grafted largely reduces, SS-g-CP base
Bottom surface is 4%.
Cross-linked polymer functionalization stainless steel obtains Fig. 5 pseudomonas in pseudomonas experiment and is adhered to sample table
The survival condition in face, survival rate are indicated with the cell number on sample every square centimeter.Original stainless steel surface viable count is every
Square centimeter is higher than 106, and SS-g-CP substrate surface is reduced to 2 × 105.This shows in SS-g-CP substrate surface bacteria living
Rate equally reduces, so that biological corrosion can be effectively reduced.
Embodiment 3:
SS-g-P substrate used is identical with step in embodiment 1 in the present embodiment.The difference is that then to SS-g-P
Substrate carried out it is quaternized, the specific steps of which are as follows:
(1) in the high borosilicate tube at 70 DEG C, SS-g-P substrate is immersed in containing 20% bromohexane of volume fraction and 0.1mL
48 hours in the 10mL2- propanol solution of triethylamine, SS-g-QP substrate is made respectively.After quaternization reaction, in order with a large amount of
Acetone and deionized water rinse sample, remove unreacted bromohexane, be then dried overnight in a vacuum drying oven.
In order to verify the antifouling and anti-biological corrosive power of above-mentioned obtained cross-linked polymer functionalization stainless steel, the reality of front
Proved recipe method is identical as example 1, is not uniquely both to detect its Ta Feier polarization song after the exposure of pseudomonas inoculation medium
Line obtains Tafel slope (βcAnd βa), corrosion potential (Ecorr) and corrosion electric current density (icorr) value, analysis result see
Table 1.
The experiment in the double eyebrow algae culturing liquids of coffee of quaternized linear polymer functionalization stainless steel obtains SS-g- in Fig. 1
The fluorescence microscope images of CP substrate surface compare, the coffee for the attachment that can visually see with original stainless steel fluorescence microscope images
The double eyebrow frustules of coffee largely reduce.From this figure, it can be seen that SS-g-QP substrate surface can also efficiently reduce the double eyebrow algaes of coffee
Adhere to cell.
Quaternized linear polymer functionalization stainless steel the experiment of the double eyebrow algae culturing liquids of coffee obtain in Fig. 2 it is original not
Steel surface of becoming rusty and the relative extent for being functionalized the double eyebrow algae adherency of coffee on stainless steel surface.Compared with original stainless steel surface, SS-
The double eyebrow algae adherency of g-QP substrate surface coffee are reduced to 24%.From this figure, it can be seen that SS-g-QP substrate surface also can be effective
Ground adheres to reducing the double eyebrow frustules of coffee.
Quaternized linear polymer functionalization stainless steel obtains that Fig. 3 is original and functionalization in the experiment of barnacle cyprids
Stainless steel surface on sedimentation and dead cyprids percentage.From this figure, it can be seen that compared to about 68% barnacle gold
Star larva is deposited in original stainless steel surface, and the stainless steel surface sedimentation score after cross-linked polymer grafted largely reduces,
SS-g-QP substrate surface is 8%.
Quaternized linear polymer functionalization stainless steel obtains the adherency of Fig. 4 pseudomonas in pseudomonas experiment
In the fluorescence microscope images of specimen surface.It can visually see in figure, SS-g-QP substrate surface living cells largely reduces,
Dead cell increases.Show that quaternized linear polymer functionalization stainless steel can effectively prevent bacterium and live away from home.
Quaternized linear polymer functionalization stainless steel obtains the adherency of Fig. 5 pseudomonas in pseudomonas experiment
In the survival condition of specimen surface, survival rate is indicated with the cell number on sample every square centimeter.Original stainless steel surface is living
Cell number is every square centimeter to be higher than 106, and SS-g-QP substrate surface is reduced to 4 × 104.This shows in SS-g-QP substrate surface
Survival probability of bacteria equally reduces, so that biological corrosion can be effectively reduced.
Obtain that Fig. 6 is original and surface functionalization sample is exposed to sterile and pseudomonas in pseudomonas experiment
Tafel polarization curve in inoculation medium, analysis obtain Tafel slope (βcAnd βa), corrosion potential (Ecorr) and corrosion electricity
Current density (icorr) value, analysis the results are shown in Table 1.The corrosion potential of original sample is protected with the exposure duration in aseptic culture medium
Hold relative constant, and in pseudomonas inoculation medium, negative sense direction occurs actively to be displaced, this usual attribution of phenomenon
Anodic dissolution processes in mixed potential theory.For macromolecular grafted sample, relative in inoculation pseudomonas
Original sample, corrosion potential experienced one to be changed significantly.Corrosion potential is strengthened, and shows that resistance to corrosion enhances.By
In the passivation of skin covering of the surface, the corrosion electric current density (i of original samplecorr) still very little, even slightly decline in sterile media.
However, corrosion electric current density (the i of original stainless steel samplecorr) value gradually increases with the exposure duration in inoculation medium,
Exposure reached about 12.85 μ Acm after 35 days-2, show under the action of pseudomonas, the significant raising of corrosion rate.As for poly-
Object coating sample is closed, corrosion electric current density significantly reduces.This again shows that the corrosion resistance of stainless steel is strengthened very well.With
Original sample after the exposure of pseudomonas inoculation medium 21 days is compared, the i of SS-g-QP samplecorrMagnitude drop respectively
Low about 6 times.The result shows that polymer coating has good protective value to the biological corrosion of pseudomonas.In exposure 21 days
Afterwards, the inhibition efficiency (IE) of SS-g-QP sample is higher than 83%.
Embodiment 4:
SS-g-CP substrate used is identical with step in embodiment 2 in the present embodiment.The difference is that then to SS-g-
CP substrate carried out it is quaternized, the specific steps of which are as follows:
(1) in the high borosilicate tube at 70 DEG C, SS-g-CP substrate be immersed in containing 20% bromohexane of volume fraction and
48 hours in the 10mL2- propanol solution of 0.1mL triethylamine, the surface SS-g-QCP is made respectively.After quaternization reaction, in order
Sample is rinsed with a large amount of acetone and deionized water, unreacted bromohexane is removed, is then dried overnight in a vacuum drying oven.
In order to verify the antifouling and anti-biological corrosive power of above-mentioned obtained cross-linked polymer functionalization stainless steel, the reality of front
Proved recipe method is identical as example 2, is not uniquely both to detect its Ta Feier polarization song after the exposure of pseudomonas inoculation medium
Line obtains Tafel slope (βcAnd βa), corrosion potential (Ecorr) and corrosion electric current density (icorr) value, analysis result see
Table 1.
The experiment in the double eyebrow algae culturing liquids of coffee of quaternized cross-linked polymer functionalization stainless steel obtains SS-g- in Fig. 1
The fluorescence microscope images of CQP substrate surface compare, the coffee for the attachment that can visually see with original stainless steel fluorescence microscope images
The double eyebrow frustules of coffee largely reduce.From this figure, it can be seen that SS-g-CQP substrate surface can also efficiently reduce the double eyebrows of coffee
Adhere to frustule.
Quaternized cross-linked polymer functionalization stainless steel the experiment of the double eyebrow algae culturing liquids of coffee obtain in Fig. 2 it is original not
Steel surface of becoming rusty and the relative extent for being functionalized the double eyebrow algae adherency of coffee on stainless steel surface.Compared with original stainless steel surface, SS-
The double eyebrow algae adherency of g-CQP substrate surface coffee are reduced to 20%.From this figure, it can be seen that SS-g-CQP substrate surface can also have
Effect ground adheres to reducing the double eyebrow frustules of coffee.
Quaternized cross-linked polymer functionalization stainless steel obtains that Fig. 3 is original and functionalization in the experiment of barnacle cyprids
Stainless steel surface on sedimentation and dead cyprids percentage.From this figure, it can be seen that compared to about 68% barnacle gold
Star larva is deposited in original stainless steel surface, and the stainless steel surface sedimentation score after cross-linked polymer grafted largely reduces,
SS-g-CQP substrate surface is 0%.
Quaternized linear polymer functionalization stainless steel obtains the adherency of Fig. 4 pseudomonas in pseudomonas experiment
In the fluorescence microscope images of specimen surface.It can visually see in figure, SS-g-QP substrate surface living cells largely reduces,
And dead cell does not increase.Show that quaternized linear polymer functionalization stainless steel can effectively prevent bacterium and live away from home, and right
Environment is without influence.
Quaternized cross-linked polymer functionalization stainless steel obtains the adherency of Fig. 5 pseudomonas in pseudomonas experiment
In the survival condition of specimen surface, survival rate is indicated with the cell number on sample every square centimeter.Original stainless steel surface is living
Cell number is every square centimeter to be higher than 106, and SS-g-CQP substrate surface is reduced to 103.This shows thin in SS-g-CQP substrate surface
Bacterium survival volume largely reduces, so that biological corrosion can be effectively reduced.
Obtain that Fig. 6 is original and surface functionalization sample is exposed to sterile and pseudomonas in pseudomonas experiment
Tafel polarization curve in inoculation medium, analysis obtain Tafel slope (βcAnd βa), corrosion potential (Ecorr) and corrosion electricity
Current density (icorr) value, analysis the results are shown in Table 1.The corrosion potential of original sample is protected with the exposure duration in aseptic culture medium
Hold relative constant, and in pseudomonas inoculation medium, negative sense direction occurs actively to be displaced, this usual attribution of phenomenon
Anodic dissolution processes in mixed potential theory.For macromolecular grafted sample, relative in inoculation pseudomonas
Original sample, corrosion potential experienced one to be changed significantly.Corrosion potential is strengthened, and shows that resistance to corrosion enhances.By
In the passivation of skin covering of the surface, the corrosion electric current density (i of original samplecorr) still very little, even slightly decline in sterile media.
However, corrosion electric current density (the i of original stainless steel samplecorr) value gradually increases with the exposure duration in inoculation medium,
Exposure reached about 12.85 μ Acm after 35 days-2, show under the action of pseudomonas, the significant raising of corrosion rate.As for poly-
Object coating sample is closed, corrosion electric current density significantly reduces.This again shows that the corrosion resistance of stainless steel is strengthened very well.With
Original sample after the exposure of pseudomonas inoculation medium 21 days is compared, the i of SS-g-CQP samplecorrMagnitude drop respectively
Low about 12 times.The result shows that polymer coating has good protective value to the biological corrosion of pseudomonas.In exposure 21
After it, the inhibition efficiency (IE) of SS-g-CQP sample is higher than 92%.Quaternized cross-linked polymer functionalization stainless steel it is antifouling and
Anti-biological corrosive effect is very significant, has great use value and huge commercial value, is on the other hand also beneficial to resource
Saving and marine environmental protection.
βc: the Tafel slope of cathodic polarization curve.
βa: the Tafel slope of anodic polarization curves.
Ecorr: corrosion potential when polarization current is zero.
CR: corrosion rate.
IE: inhibit efficiency
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to limit the present invention, all any modifications made in spirit of the invention, supplement
Or similar fashion substitution etc., it should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution, which comprises the steps of:
(1) functionalization of polymers stainless steel is prepared
It is anchored alkyl bromide atom transfer radical polymerization initiator in the stainless steel surface of existing poly-dopamine coating first, then
In stainless steel surface by atom transfer radical polymerization grafted linear or cross-linked poly-methyl methacrylate dimethylamino second rouge, obtain
Functionalization of polymers stainless steel；
(2) functionalization of polymers stainless steel simulation is applied to marine environment
Functionalization of polymers stainless steel obtained in step (1) is subjected to the double eyebrow algae attachment experiments of coffee, barnacle Venus children respectively
Worm sedimentation experiment, to the antibacterial activity test of pseudomonad and the corrosion experiment of surface functionalization stainless steel；In bacterial corrosion
Culture solution used is all based on filtering sea in experiment.
2. a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution according to claim 1, which is characterized in that
Pass through atom transfer radical polymerization grafted linear or cross-linked poly-methyl methacrylate dimethylamino in stainless steel surface in step (1)
After second rouge, it is further processed to the stainless steel surface polymeric quartenary ammonium after functionalization of polymers.
3. a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution according to claim 1, which is characterized in that
The method of functionalization of polymers stainless steel is prepared in step (1) are as follows:
1) it is anchored the process of alkyl bromide atom transfer radical polymerization initiator are as follows: poly-dopamine coating stainless steel SS-PDA matrix
It immerses in the 10-20mL methylene chloride containing 1.0-1.3mL triethylamine, it is cooling in mixture of ice and water；2- containing 0.9-1.2mL
The 5mL methylene chloride of bromine isobutyl acylbromide is added dropwise in mixture；Later, it is small to be stirred at room temperature 24 for reaction mixture
When, then washed with a large amount of acetone, ethyl alcohol and deionized water, it is dry；
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization grafted linear polymethylacrylic acid dimethylamino
Second rouge, process are as follows: [DMAEMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:1:0.2:1 is in high borosilicate tube
It carries out surface and causes atom transfer radical polymerization；After stirring and deaerate 20-40 minutes under the conditions of argon gas, SS-PDA-Br base
Bottom is introduced into reaction mixture；Reaction tube is sealed 24 hours under 35-40 DEG C of water bath condition, and linear polymer official is made
The stainless steel of energyization；
Or,
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization graft crosslinking polymethylacrylic acid dimethylamino
The process of second rouge are as follows: surface, which is carried out, in high borosilicate tube causes atom transfer radical polymerization, [DMAEMA]: [PEGDMA]:
[CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:10:1:0.2:1 reacts in 3-5mL methanol；It is stirred under the conditions of argon gas
After mixing and stirring degassing 20-40 minutes, SS-PDA-Br sample introduction is into reaction mixture；Pipe seals under 35-40 DEG C of water bath condition
It saves 24 hours, so that the functionalized stainless steel of cross-linked polymer be made.
4. a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution according to claim 2, which is characterized in that
The preparation of quaternized linear or cross-linked polymer functionalization stainless steel: in the high borosilicate tube at 70 DEG C, SS-g-P or SS-g-
It is small that CP substrate is immersed in the 10-20mL2- propanol solution containing 20% bromohexane of volume fraction and 0.1-0.3mL triethylamine 48
When, SS-g-QP substrate or the surface SS-g-QCP is made；After quaternization reaction, rinsed with acetone and deionized water, it is dry, it obtains
Quaternized linear or cross-linked polymer is functionalized stainless steel.
5. a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution according to claim 1, which is characterized in that
The polymer is linear or cross-linked poly-methyl methacrylate dimethylamino second rouge and their ring substitutive derivative or miscellaneous
One of atom substitutive derivative also includes its quaternized products and derivative.
6. a kind of method for improving stainless steel plate anti-marine organism corrsion and pollution according to claim 1, which is characterized in that
The bacterial species of the anticorrosive experiment are unlimited, right not only including the double eyebrow algaes of the coffee, barnacle cyprids and pseudomonad
Other marine bacterias all have certain anticorrosive effect.
7. a kind of method for preparing functionalization of polymers stainless steel, which comprises the steps of:
1) it is anchored the process of alkyl bromide atom transfer radical polymerization initiator are as follows: poly-dopamine coating stainless steel SS-PDA matrix
It immerses in the 10-20mL methylene chloride containing 0.1-0.3mL triethylamine, it is cooling in mixture of ice and water；2- containing 0.9-1.3mL
The 5-10mL methylene chloride of bromine isobutyl acylbromide is added dropwise in mixture；Later, reaction mixture is stirred at room temperature 24
Hour, then washed with a large amount of acetone, ethyl alcohol and deionized water, it is dry；
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization grafted linear polymethylacrylic acid dimethylamino
Second rouge, process are as follows: [DMAEMA]: [CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:1:0.2:1 is in high borosilicate tube
It carries out surface and causes atom transfer radical polymerization；After stirring and deaerate 20-40 minutes under the conditions of argon gas, SS-PDA-Br base
Bottom is introduced into reaction mixture；Reaction tube is sealed 24 hours under 35-40 DEG C of water bath condition, and linear polymer official is made
The stainless steel of energyization；
Or,
2) stainless steel surface in step 1) is passed through into atom transfer radical polymerization graft crosslinking polymethylacrylic acid dimethylamino
The process of second rouge are as follows: surface, which is carried out, in high borosilicate tube causes atom transfer radical polymerization, [DMAEMA]: [PEGDMA]:
[CuCl]: [CuCl2]: [Bpy] molar feed ratio 100:10:1:0.2:1 reacts in 4-6mL methanol；It is stirred under the conditions of argon gas
After mixing and stirring degassing 20-40 minutes, SS-PDA-Br sample introduction is into reaction mixture；Pipe seals under 35-40 DEG C of water bath condition
It saves 24 hours, so that the functionalized stainless steel of cross-linked polymer be made.
8. a kind of method for preparing functionalization of polymers stainless steel according to claim 7, which is characterized in that be further processed
To the stainless steel surface polymeric quartenary ammonium after functionalization of polymers: in the high borosilicate tube at 70 DEG C, SS-g-P or SS-g-CP
Substrate is immersed in the 10-20mL2- propanol solution containing 20% bromohexane of volume fraction and 0.1-0.3mL triethylamine 48 hours,
SS-g-QP substrate or the surface SS-g-QCP is made；After quaternization reaction, rinsed with acetone and deionized water, it is dry, obtain quaternary ammonium
The linear or cross-linked polymer changed is functionalized stainless steel.
9. a kind of functionalization of polymers stainless steel, by the method for preparing functionalization of polymers stainless steel of claim 7 or 8
It is prepared.
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| CN111116958A (en) * | 2020-01-01 | 2020-05-08 | 西北大学 | Construction method of crosslinked stable polymer brush coating |
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