CN102786871A - Nano antibacterial and anticorrosive paint and preparation method thereof - Google Patents
Nano antibacterial and anticorrosive paint and preparation method thereof Download PDFInfo
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- CN102786871A CN102786871A CN201210296452XA CN201210296452A CN102786871A CN 102786871 A CN102786871 A CN 102786871A CN 201210296452X A CN201210296452X A CN 201210296452XA CN 201210296452 A CN201210296452 A CN 201210296452A CN 102786871 A CN102786871 A CN 102786871A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003973 paint Substances 0.000 title abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 9
- 229920000767 polyaniline Polymers 0.000 claims abstract description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 36
- 230000001681 protective effect Effects 0.000 claims description 32
- 239000002121 nanofiber Substances 0.000 claims description 27
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004160 Ammonium persulphate Substances 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 12
- 150000002334 glycols Chemical class 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 230000003292 diminished effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 230000002421 anti-septic effect Effects 0.000 abstract description 5
- 239000003345 natural gas Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 239000004359 castor oil Substances 0.000 abstract 2
- 235000019438 castor oil Nutrition 0.000 abstract 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract 2
- 150000002009 diols Chemical class 0.000 abstract 1
- 239000008239 natural water Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 9
- 230000000845 anti-microbial effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000001680 brushing effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 241000295146 Gallionellaceae Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 235000021197 fiber intake Nutrition 0.000 description 4
- 230000000968 intestinal effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- 108010021006 Tyrothricin Proteins 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical class OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 description 1
- 229960002026 pyrithione Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- GSXRBRIWJGAPDU-BBVRJQLQSA-N tyrocidine A Chemical compound C([C@H]1C(=O)N[C@H](C(=O)N[C@@H](CCCN)C(=O)N[C@H](C(N[C@H](CC=2C=CC=CC=2)C(=O)N2CCC[C@H]2C(=O)N[C@@H](CC=2C=CC=CC=2)C(=O)N[C@H](CC=2C=CC=CC=2)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCC(N)=O)C(=O)N1)=O)CC(C)C)C(C)C)C1=CC=C(O)C=C1 GSXRBRIWJGAPDU-BBVRJQLQSA-N 0.000 description 1
- 229960003281 tyrothricin Drugs 0.000 description 1
Abstract
The invention discloses nano antibacterial and anticorrosive paint and a preparation method of the nano antibacterial and anticorrosive paint, which belong to the field of chemical materials. The antibacterial and anticorrosive paint consists of a component A and a component B. The component A is obtained by reacting polyether diols, castor oil, polyaniline nano fibres, toluene diisocynate and n-butyl alcohol; the component B comprises castor oil and stannous octoate; and the nano antibacterial and anticorrosive paint is obtained by mixing the components A and B according to the mass ratio of (2-5) to 1. The paint in stable in quality and easy to construct, has high-efficient antibiosis and antiseptic properties, and also has the characteristics of bactericidal broad-spectrum, good light and heat resistance stability, safety, environmental-protection, and the like; and the paint can be extensively applied to inner walls of the metal pipelines of long-distance petroleum, natural gas, water, and the like, in particular to the antibacterial and antiseptic fields of chemical oil storage tanks.
Description
Technical field
The present invention relates to a kind of nano-antibacterial protective system and preparation method thereof, belong to chemical material field.
Background technology
The corrosion of long defeated oil, Sweet natural gas, water metallic conduit and chemical industry oil depot metallic oil tank causes serious threat to the loss and the safety of resource.The method that metallic conduit or metallic oil tank inwall carry out coating can effectively reduce the threat that causes because of corrosion.Metallic conduit or metallic oil tank inwall carry out the selection of coating, have experienced brushing raw lacquer, epoxy resin from five sixties, develop into now generally the polyamine enamel paint of use, polyurethane paint, elastic polyurethane lacquer etc.But these coating all do not have the antimicrobial performance.Because long defeated oil, Sweet natural gas, water metallic conduit and oil storage tank inner-wall are prone to grow mushrooms such as tyrothricin, genus bacillus, pseudomonas.And after coating was by the mushroom corrosion, bonding strength descended, and the life-span shortens, and then influences the oil plant quality.The riverine band of coastal areas of southern China recurs oil plant by the bacterial contamination incident in recent years, has seriously disturbed normal storage of oil plant and supply.Therefore, development metallic conduit and the antibiotic protective system of inner wall of oil tank have great social significance and actual application value.
Antibiotic paint is meant and in coating, adds antiseptic-germicide, makes coating have anti-microbial property.As the antiseptic-germicide of a kind of ideal metallic conduit and chemical industry tank inner wall coating, it must satisfy following various requirement: 1) high efficiency, promptly good anti-bacterial effect is only added the growth that bacterium just can killed or suppress to minor constituent.2) broad spectrum promptly has the various mushrooms that exist in the oil tank and kills or restraining effect.3) stability is promptly to Fails To Responds such as acid, alkali, light, heat.4) good dispersivity can be dispersed in the coating matrix.5) do not influence the performance index and the quality of oil plant.6) low toxicity, promptly safe, do not influence the health of human body during use, free from environmental pollution.Natural antiseptic-germicide such as chitin, horseradish etc., easy to use, but anti-microbial effect is limited, can not spectrum long-acting.Organic antibacterial agent such as quaternary ammonium salt, sulfurous cyanic acid compounds etc., their sterilization speed is fast, and exploitation and use technology are ripe, but stability and long-lasting poor.Inorganic metal and oxide compound; Like silver, copper, zinc, zinc oxide etc. mikrobe is had killing action in various degree, people adopt the powder material of these metals on carrier, to reduce cost; But these heavy metals or its ion come off from carrier easily, and product is caused heavy metal contamination.As having used triclosan and pyrithione antiseptic-germicide among the patent CN101250344A, prepared water anti-bacteria coating; Propose among the application CN1436820A to use commercially available with vitriol system, silicate be, oxide based inorganic materials adds in the commercially available trade sales coating as antimicrobial component as silver, copper, the zinc metal ion of carrier and prepares antibiotic paint; Patent CN100355839C is with white titanium pigment and T-ZnO whisker preparation of antimicrobial coating; Patent CN101353545B with silver suboxide as a kind of UV curing antibiotic coating of antibiotic preparation.From available data and applicable cases analysis revealed; Existing metallic conduit and the antibiotic protective system of chemical industry inner wall of oil tank are desirable not enough; Often exist the efficient of anti-microbial property low or unstable; There are heavy metal contamination oil product or water quality, have shortcomings such as antiseptic property difference, await researching and developing a kind of metallic conduit of new type ideal and the antibiotic paint of chemical industry tank inner wall coating.
Summary of the invention
The object of the invention is to overcome the shortcoming of existing metallic conduit or the antibiotic corrosion protection coating of metallic oil tank inwall, and the preparation method of the antibiotic protective system of a kind of novel nano is provided, and present method is carried out as follows:
(1) polyether Glycols, Viscotrol C and polyaniline nano fiber are joined in the reaction kettle mixes, stir and heat up, when temperature is raised to 40 ~ 60 ℃, drip tolylene diisocyanate, drip in the 1h; Then after 60 ℃ of insulations continue to stir 0.5 h; Add propyl carbinol and be warming up to 80 ℃ of insulated and stirred, after the end group nco value reaches 2.0 ~ 4.0%, be cooled to 40 ℃; And under this temperature vacuum outgas 0.5 h; Obtain A component---base polyurethane prepolymer for use as, wherein the mass ratio of polyether Glycols and Viscotrol C is 8:1 ~ 3:1, and the amount of tolylene diisocyanate is pressed isocyanate index NCO/OH=1:1 ~ 3:1 (mol ratio) and calculated; The propyl carbinol addition is 5 ~ 15% of a base polyurethane prepolymer for use as quality, and the polyaniline nano fiber addition is 1 ~ 10% of a base polyurethane prepolymer for use as quality;
(2) with Viscotrol C and the mixed B component that gets of stannous octoate, wherein the addition of stannous octoate is 0.1 ~ 0.8% of a base polyurethane prepolymer for use as quality, and the addition of Viscotrol C is to calculate by isocyanate index NCO/OH=1:1 ~ 3:1 (mol ratio);
(3) A component and B component are pressed mass ratio 2 ~ 5:1 mixing, promptly get the nano-antibacterial protective system.
The molecule of polyether Glycols described in the present invention is 1000 ~ 5000.
The preparation method is following for polyaniline nano fiber described in the present invention: with volumetric molar concentration is that the acid solution of 0.1 ~ 2.0 mol/L is divided into two equal portions, in a acid solution, adds aniline monomer, at room temperature stirs; Form a liquid, wherein the aniline monomer volumetric molar concentration is 0.1 ~ 2.0 mol/L, in another part acid solution, adds ammonium persulphate; The mol ratio of ammonium persulphate and aniline is 1:1 ~ 4, stirs, and forms b liquid; B liquid is at room temperature poured in a liquid fast, at room temperature left standstill 12 ~ 24h, filtration under diminished pressure then; And use zero(ppm) water, washing with acetone successively, till the pH=7 of filtrating, promptly obtain polyaniline nano fiber.
Acid solution described in the polyaniline nano fiber of the present invention preparation is a kind of in hydrochloric acid, sulfuric acid, nitric acid, acetate, the methylsulphonic acid.
Another purpose of the present invention provides a kind of nano-antibacterial protective system that makes according to the preparation method of above-mentioned nano-antibacterial protective system.
The present invention is with respect to the advantage and the technique effect of prior art:
(1) adopts polyaniline nano fiber among the present invention; Organic polyaniline nano fiber preparation method is simple, preparation cost is low, itself have the excellent antiseptic property and the anti-microbial property of broad-spectrum high efficacy; And can be in polyurethane matrix homodisperse, advantages such as consumption is few, nontoxic, excellent in stability.
(2) to have a raw materials cost low for this coating, and preparation technology is simple, and thinner toxicity is little, and environment is not impacted; And this coating is made up of A, B component, steady quality, and construction is simple, has high-efficiency antimicrobial, antiseptic property, and this coating has broad-spectrum sterilization property simultaneously, good fast light thermostability, and have characteristics such as security, environmentally safe.
(3) nano-antibacterial protective system provided by the invention can be widely used in inner-walls of duct such as long defeated oil, Sweet natural gas, water, is specially adapted to the antibiotic and corrosion-resistant field of chemical industry storage tank.
Embodiment
Through embodiment the present invention is described further below, but protection domain of the present invention is not limited to said content.
Embodiment 1:The preparation method of this nano-antibacterial protective system, concrete operations are following:
(1) is that 1000 polyether Glycols, Viscotrol C, polyaniline nano fiber join in the reaction kettle and mix with molecular weight, stirs and heat up that when temperature rises to 40 ℃, drip tolylene diisocyanate, 50min adds; After 60 ℃ of insulations continue to stir 0.5 h, add propyl carbinol and be warming up to 80 ℃ of insulated and stirred then, the end group nco value is surveyed in sampling; After nco value reaches 2.0%; Be cooled to 40 ℃, and under this temperature vacuum outgas 0.5 h, promptly get the A component; Wherein the mass ratio of polyether Glycols and Viscotrol C is 8:1; The amount of tolylene diisocyanate is pressed isocyanate index (NCO/OH)=1:1 and is calculated, and the propyl carbinol addition is 5% of a base polyurethane prepolymer for use as quality, and the polyaniline nano fiber consumption is 1% of a base polyurethane prepolymer for use as quality;
(2) preparation process of used polyaniline nano fiber is following:
With volumetric molar concentration is that the hydrochloric acid soln of 0.1 mol/L is divided into two equal portions, in a hydrochloric acid soln, adds aniline monomer, at room temperature stirs; Form a liquid, wherein the aniline monomer volumetric molar concentration is 0.1 mol/L, in another part hydrochloric acid soln, adds ammonium persulphate; The mol ratio of ammonium persulphate and aniline is 1:1, stirs, and forms b liquid; B liquid is at room temperature poured in a liquid fast, at room temperature left standstill 12 h, filtration under diminished pressure then; And use zero(ppm) water, washing with acetone successively, till the pH=7 of filtrating, promptly obtain polyaniline nano fiber;
(3) with Viscotrol C and the mixed B component that gets of stannous octoate, wherein the addition of stannous octoate is 0.1% of a base polyurethane prepolymer for use as quality, and the addition of Viscotrol C is to calculate by isocyanate index NCO/OH=1:1;
(4) A component and B component are pressed mass ratio 2:1 mixing, promptly get the nano-antibacterial protective system.
(5) performance measurement of antibiotic protective system
Antibiotic protective system brushing on tinplate tin, behind room temperature held 48 h, is detected coating performance, and the result shows: 2 grades of sticking power (drawing the circle method); Cathodic disbonding (65 ℃, 48h)/mm, 3.0; Salt-fog test (1000 h), coating changes, and the intestinal bacteria bacteriostasis rate is greater than 86%; The streptococcus aureus bacteriostasis rate is greater than 89%, and the sulphate reducing bacteria bacteriostasis rate is greater than 82%, and the iron bacteria bacteriostasis rate is greater than 72%.
Embodiment 2:The preparation method of this nano-antibacterial protective system, concrete operations are following:
(1) preparation process of A component: with molecular weight is that 2000 polyether Glycols, Viscotrol C, polyaniline nano fiber join in the reaction kettle and mix, and stirs and heats up, and when temperature rises to 50 ℃, drips tolylene diisocyanate, and 45min adds; After 60 ℃ of insulations continue to stir 0.5 h, add propyl carbinol and be warming up to 80 ℃ of insulated and stirred then, the end group nco value is surveyed in sampling; After nco value reaches 2.5 %; Be cooled to 40 ℃, vacuum outgas 0.5 h promptly gets the A component under this temperature; Wherein the mass ratio of polyether Glycols and Viscotrol C is 6:1; The amount of tolylene diisocyanate is pressed isocyanate index (NCO/OH)=1.5:1 and is calculated, and the propyl carbinol consumption is 10 % of base polyurethane prepolymer for use as quality, and the polyaniline nano fiber consumption is 10 % of base polyurethane prepolymer for use as quality;
(2) preparation process of used polyaniline nano fiber is following:
With volumetric molar concentration is that the sulphuric acid soln of 0.2 mol/L is divided into two equal portions, in a sulphuric acid soln, adds aniline monomer, at room temperature stirs; Form a liquid, wherein the aniline monomer volumetric molar concentration is 0.3 mol/L, in another part sulphuric acid soln, adds ammonium persulphate; The mol ratio of ammonium persulphate and aniline is 1:1, stirs, and forms b liquid; B liquid is at room temperature poured in a liquid fast, at room temperature left standstill 12 h, filtration under diminished pressure then; And use zero(ppm) water, washing with acetone successively, till the pH=7 of filtrating, promptly obtain polyaniline nano fiber;
(3) with Viscotrol C and the mixed B component that gets of stannous octoate, wherein the addition of stannous octoate is 0.2% of a base polyurethane prepolymer for use as quality, and the addition of Viscotrol C is to calculate by isocyanate index NCO/OH=1.5:1;
(4) A component and B component are pressed mass ratio 3:1 mixing, promptly get the nano-antibacterial protective system.
(5) performance measurement of antibiotic protective system
Antibiotic protective system brushing on tinplate tin, behind 48 h, is detected coating performance under the room temperature, and the result shows: 1 grade of sticking power (drawing the circle method); Cathodic disbonding (65 ℃, 48h)/mm, 2.8; Salt-fog test (1000 h), the coating no change, the intestinal bacteria bacteriostasis rate is greater than 90%; The streptococcus aureus bacteriostasis rate is greater than 89%, and the sulphate reducing bacteria bacteriostasis rate is greater than 87%, and the iron bacteria bacteriostasis rate is greater than 83%.
Embodiment 3:The preparation method of this nano-antibacterial protective system, concrete operations are following:
(1) polyether Glycols, Viscotrol C, the polyaniline nano fiber of molecular weight 3000 joined in the reaction kettle mix, stir and heat up, when temperature rises to 60 ℃, drip tolylene diisocyanate, 55min adds; After 60 ℃ of insulations continue to stir 0.5 h, add propyl carbinol and be warming up to 80 ℃ of insulated and stirred then, the end group nco value is surveyed in sampling; After nco value reaches 3.0%; Be cooled to 40 ℃, vacuum outgas 0.5 h promptly gets the A component under this temperature; Wherein the mass ratio of polyether glycol and Viscotrol C is 5:1; The amount of tolylene diisocyanate is pressed isocyanate index (NCO/OH)=1.8:1 and is calculated, and the propyl carbinol consumption is 15 % of base polyurethane prepolymer for use as quality, and the polyaniline nano fiber consumption is 3 % of base polyurethane prepolymer for use as quality.
(2) preparation process of used polyaniline nano fiber is following:
With volumetric molar concentration is that the salpeter solution of 1.0 mol/L is divided into two equal portions, in a salpeter solution, adds aniline monomer, at room temperature stirs; Form a liquid, wherein the aniline monomer volumetric molar concentration is 1.0 mol/L, in another part salpeter solution, adds ammonium persulphate; Ammonium persulphate/aniline volumetric molar concentration is 1:4, stirs, and forms b liquid; B liquid is at room temperature poured in the A liquid fast, at room temperature left standstill 24h, filtration under diminished pressure then; And use zero(ppm) water, washing with acetone successively, till the pH=7 of filtrating, promptly obtain polyaniline nano fiber;
(3) with Viscotrol C and the mixed B component that gets of stannous octoate, wherein the addition of stannous octoate is 0.3% of a base polyurethane prepolymer for use as quality, and the addition of Viscotrol C is to calculate by isocyanate index NCO/OH=1.8:1;
(4) A component and B component are pressed mass ratio 3:1 mixing, promptly get the nano-antibacterial protective system.
(5) performance measurement of antibiotic protective system
Antibiotic protective system brushing on tinplate tin, behind 48 h, is detected coating performance under the room temperature, and its main result is: 0 grade of sticking power (drawing the circle method); Cathodic disbonding (65 ℃, 48h)/mm, 2.0; Salt-fog test (1000 h), the coating no change, the intestinal bacteria bacteriostasis rate is greater than 99%; The streptococcus aureus bacteriostasis rate is greater than 99%, and the sulphate reducing bacteria bacteriostasis rate is greater than 99%, and the iron bacteria bacteriostasis rate is greater than 99%.
Embodiment 4:The preparation method of this nano-antibacterial protective system, concrete operations are following:
(1) polyether Glycols, Viscotrol C, the polyaniline nano fiber of molecular weight 4000 joined in the reaction kettle mix, stir and heat up, when temperature rises to 60 ℃, drip tolylene diisocyanate, 55min adds; After 60 ℃ of insulations continue to stir 0.5 h, add propyl carbinol and be warming up to 80 ℃ of insulated and stirred then, the end group nco value is surveyed in sampling, after nco value reaches 4.0%, is cooled to 40 ℃, and vacuum outgas 0.5 h promptly gets the A component under this temperature; Wherein polyether glycol is 3:1 with the ratio of the massfraction of Viscotrol C; The amount of tolylene diisocyanate is pressed isocyanate index (NCO/OH)=3:1 and is calculated; The propyl carbinol consumption is 10% of a base polyurethane prepolymer for use as, and the polyaniline nano fiber consumption is 6 % of base polyurethane prepolymer for use as;
(2) preparation process of used polyaniline nano fiber is following:
With volumetric molar concentration is that the acetic acid soln of 2.0 mol/L is divided into two equal portions, in a acetic acid soln, adds aniline monomer, at room temperature stirs; Form a liquid, wherein the aniline monomer volumetric molar concentration is 2.0 mol/L, in another part acetic acid soln, adds ammonium persulphate; Ammonium persulphate/aniline volumetric molar concentration is 1:3, stirs, and forms b liquid; B liquid is at room temperature poured in the A liquid fast, at room temperature left standstill 20h, filtration under diminished pressure then; And use zero(ppm) water, washing with acetone successively, till the pH=7 of filtrating, promptly obtain polyaniline nano fiber;
(3) with Viscotrol C and the mixed B component that gets of stannous octoate, wherein the addition of stannous octoate is 0.8% of a base polyurethane prepolymer for use as quality, and the addition of Viscotrol C is to calculate by isocyanate index NCO/OH=3:1;
(4) A component and B component are pressed mass ratio 5:1 mixing, promptly get the nano-antibacterial protective system.
(5) performance measurement of antibiotic protective system
Antibiotic protective system brushing on tinplate tin, behind 48 h, is detected coating performance under the room temperature, and its main result is: 1 grade of sticking power (drawing the circle method); Cathodic disbonding (65 ℃, 48h)/mm, 2.9; Salt-fog test (1000 h), coating changes, and the intestinal bacteria bacteriostasis rate is greater than 99%; The streptococcus aureus bacteriostasis rate is greater than 99%, and the sulphate reducing bacteria bacteriostasis rate is greater than 99%, and the iron bacteria bacteriostasis rate is greater than 99%.
In sum, although the present invention is described in detail through specific embodiment.Persons skilled in the art should be understood that; The foregoing description only is to the prepared a kind of antibiotic preparation method of anticorrosion paint of the present invention and the description of application; But not to the restriction of protection domain of the present invention; The variation that persons skilled in the art can be expected in the technical scope that the present invention disclosed easily is all within protection scope of the present invention.
Claims (5)
1. the preparation method of a nano-antibacterial protective system is characterized in that carrying out as follows:
(1) polyether Glycols, Viscotrol C and polyaniline nano fiber are joined in the reaction kettle mixes, stir and heat up, when temperature is raised to 40 ~ 60 ℃, drip tolylene diisocyanate, drip in the 1h; After 60 ℃ of insulations continue to stir 0.5 h, add propyl carbinol and be warming up to 80 ℃ of insulated and stirred then, the end group nco value is surveyed in sampling; After the end group nco value reaches 2.0 ~ 4.0%; Be cooled to 40 ℃, and under this temperature vacuum outgas 0.5 h, obtain A component---base polyurethane prepolymer for use as; Wherein the mass ratio of polyether Glycols and Viscotrol C is 8:1 ~ 3:1; The amount of tolylene diisocyanate is pressed isocyanate index NCO/OH=1:1 ~ 3:1 and is calculated, and the propyl carbinol addition is 5 ~ 15% of a base polyurethane prepolymer for use as quality, and the polyaniline nano fiber addition is 1 ~ 10% of a base polyurethane prepolymer for use as quality;
(2) with Viscotrol C and the mixed B component that gets of stannous octoate, wherein the addition of stannous octoate is 0.1 ~ 0.8% of a base polyurethane prepolymer for use as quality, and the addition of Viscotrol C is to calculate by isocyanate index NCO/OH=1:1 ~ 3:1;
(3) A component and B component are pressed mass ratio 2 ~ 5:1 mixing, promptly get the nano-antibacterial protective system.
2. according to the preparation method of the said nano-antibacterial protective system of claim 1, it is characterized in that: the molecule of polyether Glycols is 1000 ~ 5000.
3. according to the preparation method of the said nano-antibacterial protective system of claim 1, it is characterized in that the polyaniline nano fiber preparation method is following: with volumetric molar concentration is that the acid solution of 0.1 ~ 2.0 mol/L is divided into two equal portions, in a acid solution, adds aniline monomer; At room temperature stir, form a liquid, wherein the aniline monomer volumetric molar concentration is 0.1 ~ 2.0 mol/L; In another part acid solution, add ammonium persulphate, the mol ratio of ammonium persulphate and aniline is 1:1 ~ 4, stirs; Form b liquid, b liquid is at room temperature poured in a liquid fast, at room temperature leave standstill 12 ~ 24h then; Filtration under diminished pressure; And use zero(ppm) water, washing with acetone successively, till the pH=7 of filtrating, promptly obtain polyaniline nano fiber.
4. according to the preparation method of the said nano-antibacterial protective system of claim 3, it is characterized in that: acid solution is a kind of in hydrochloric acid, sulfuric acid, nitric acid, acetate, the methylsulphonic acid.
5. the nano-antibacterial protective system that the preparation method of each said nano-antibacterial protective system makes among the claim 1-3.
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| CN103232597A (en) * | 2013-04-28 | 2013-08-07 | 同济大学 | 2-mercapto benzimidazole/polyaniline anticorrosion composite material and preparation method thereof |
| CN104312241A (en) * | 2014-11-11 | 2015-01-28 | 合肥不老传奇保健科技有限公司 | Sterilizing, anti-algae and anti-aging water-based exterior wall coating and preparation method thereof |
| CN104747817A (en) * | 2014-07-28 | 2015-07-01 | 李莹 | Anti-corrosion sterilizing metal pipe |
| CN109294447A (en) * | 2018-10-29 | 2019-02-01 | 湖北工业大学 | A kind of composite coating and its preparation method and application for preventing mussel from adhering to |
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| CN101353545A (en) * | 2008-08-26 | 2009-01-28 | 苏州市明大高分子科技材料有限公司 | UV curing antibiotic coating and preparation thereof |
| CN101585980A (en) * | 2008-05-21 | 2009-11-25 | 中国科学院金属研究所 | Antibacterium paint and preparation method thereof |
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| CN1436820A (en) * | 2002-02-06 | 2003-08-20 | 云南大学 | Antibacterial paint |
| CN101250344A (en) * | 2008-03-26 | 2008-08-27 | 中国印钞造币总公司 | Antibiotic paint and method for preparing the same |
| CN101585980A (en) * | 2008-05-21 | 2009-11-25 | 中国科学院金属研究所 | Antibacterium paint and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103232597A (en) * | 2013-04-28 | 2013-08-07 | 同济大学 | 2-mercapto benzimidazole/polyaniline anticorrosion composite material and preparation method thereof |
| CN103232597B (en) * | 2013-04-28 | 2015-07-29 | 同济大学 | 2-mercaptobenzimidazole/polyaniline anticorrosion matrix material and preparation method thereof |
| CN104747817A (en) * | 2014-07-28 | 2015-07-01 | 李莹 | Anti-corrosion sterilizing metal pipe |
| CN104312241A (en) * | 2014-11-11 | 2015-01-28 | 合肥不老传奇保健科技有限公司 | Sterilizing, anti-algae and anti-aging water-based exterior wall coating and preparation method thereof |
| CN109294447A (en) * | 2018-10-29 | 2019-02-01 | 湖北工业大学 | A kind of composite coating and its preparation method and application for preventing mussel from adhering to |
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| CN102786871B (en) | 2014-07-02 |
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