CN104761991A - Environmental-protection type multi-element collaborative marine anti-fouling coating - Google Patents
Environmental-protection type multi-element collaborative marine anti-fouling coating Download PDFInfo
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- CN104761991A CN104761991A CN201410006285.XA CN201410006285A CN104761991A CN 104761991 A CN104761991 A CN 104761991A CN 201410006285 A CN201410006285 A CN 201410006285A CN 104761991 A CN104761991 A CN 104761991A
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Abstract
The invention discloses an environmental-protection type multi-element collaborative marine anti-fouling coating. The coating is composed of anti-fouling coating matrix resin containing an anti-fouling active group, a wetting and dispersing agent, a mixed organic solvent, a non-toxic anti-fouling agent, a pigment filler, a levelling agent, a defoaming agent and an anti-settling agent. The coating is non-toxic, does not pollute the environment, and is mainly applied in ship fouling resistance.
Description
Technical field
The present invention relates to a kind of environment-friendly type marine antifouling coating, particularly the polynary collaborative marine antifouling coating of a kind of environment-friendly type that is nontoxic, long-acting, wide spectrum, antifouling for oceangoing vessel.
Background technology
China greatly develops marine cause.And marine biofouling has larger negative impact to the life-span of marine settings and military service performance.Sea organism attachment makes ship's navigation friction resistance increase, and affects the speed of a ship or plane, increases energy consumption.Sea marine organism pollution can accelerate film aging simultaneously, and the corruption of aggravation hull, endangers huge.Prevent the most effective means of biodeterioration to be exactly brushing antifouling paint, thus various anti-fouling ship paint just arises at the historic moment.In the past few decades, the self polishing copolymer antifouling paint containing organotin (TBT) was once widely used.Organotin can reach wide spectrum, efficient antifouling object at low concentrations, but these materials are stablized and easily accumulated in water, can cause some organisms deformities, and may enter food chain, become and affect human health and ecological potential safety hazard.Therefore the final utilization time limit that the Marine Environmental Protection Committee belonging to International Maritime Organizaton (IMO) defines containing the antifouling paint of organotin is on January 1st, 2008.
Since then, countries in the world accelerate to research and develop new Nontoxic Antifouling Paint all in succession.Wherein especially with Tin-free Spc Anti-fouling Paint and low surface energy anti-fouling paint noticeable.At present, on market, widely used Tin-free Spc Anti-fouling Paint is all the one group of bactericidal properties antifouling paint imitating TBT copolymer coating, and its film forming binder is linear copolymer, does not but have microbe killing properties with hydrolyzable side base.Its Hydrolytic Mechanism is identical with TBT multipolymer, thus makes stain control agent from coatingsurface controllable release, makes film keep smooth.Although Tin-free Spc Anti-fouling Paint excellent performance, there is a problem is that effect of static antifouling property poor, antifouling phase is short, can not show a candle to the self polishing copolymer antifouling paint containing TBT, and its stain control agent Red copper oxide used can kill and wound marine life, to human body low toxicity.Low surface energy anti-fouling paint refers to the low surface energy feature of the anti-fouling material by utilizing it to prepare, and biology is not easily adhered to, or attachment loosely.There is not the release loss of toxicant and kill halobiontic problem in low surface energy antifouling coating, but with regard to current low surface energy antifouling coating, only relies on the low surface property of coating can't reach thoroughly antifouling requirement completely.Simple low surface energy anti-fouling paint often can only make marine organisms adhere to loosely, needs regularly upper depressed place cleaning; Settled organism is once grow up very difficult removing, and scale removal process may destroy paint film, once damage, antifouling property just will reduce greatly.Meanwhile, low surface energy anti-fouling paint has selectivity to fouling organism, and it is invalid to diatom.At present, there is although domestic the low surface energy coatings of the type such as fluoro-resin and organosilicon to study, due to evening and the technical elements of starting to walk, be mostly in elementary development, have no and widely apply report.Although there is the application of low surface energy elastic coating abroad, due to its elastomerics, bad mechanical strength, hardness are low, poor adhesive force, and construction is inconvenient, and expensive, cause its application to there is very large limitation.In addition, researchist finds, the small molecules silicone oil of the difficult degradation penetrated from low surface energy coat, is enriched in ocean in a large number, has had a strong impact on halobiontic normal growth, is just becoming a kind of new marine pollutants.According to estimates, just the usage quantity of current low surface energy coatings, about has 4000 tons of silicone oil to be discharged in ocean every year.
In a word, antifouling paint must to low toxicity, nontoxic future development.And Tin-free Spc Anti-fouling Paint simple at present, static stain control agent rate of release is little, is not enough to kill the marine life that attempt is attached to hull, needs to introduce efficient sterilizing active group on resin copolymer main chain, improves the sea organism attachment ability that suppresses; Simple low surface energy anti-fouling paint, can only make sea organism attachment loosely, needs the final cleaning that could realize some settled organismes by external force.Therefore, only rely on that single antifouling approach can't reach nontoxic, long-acting, the antifouling object of wide spectrum.
Summary of the invention
The object of the invention is to overcome single, the environmentally harmful defect of the antifouling approach of existing antifouling paint, and provide a kind of environmental friendliness, surface energy low, from the polynary synergetic marine antifouling coating of polishing stable, antifouling persistent.
To achieve these goals, the technical solution used in the present invention is:
Coating of the present invention, forms by containing the antifouling paint substrate resin of antifouling activity group, wetting dispersing agent, mixed organic solvents, nontoxic stain control agent, color stuffing, flow agent, defoamer and anti-settling agent.
The polynary collaborative marine antifouling coating of a kind of environment-friendly type, is characterized in that coating is prepared by following process:
By free-radical polymerized, acrylic acid or the like soft or hard monomer, Hydrophobic Ionic liquid monomer, esters of acrylic acid sulfonic acid potassium salt monomer are carried out copolymerization under initiator exists, obtain the acrylic polymer containing bacteriostatic activity group, and then obtain the antifouling paint substrate resin containing antifouling activity group with zinc hydroxide or copper, monovalence organic acid mixture reaction;
Be that 30 ~ 55 parts of antifouling paint substrate resins containing antifouling activity group, 0.5 ~ 1 part of wetting dispersing agent and 15 ~ 30 parts of mixed organic solvents are after fully disperseing by parts by weight, add 0 ~ 10 part of nontoxic stain control agent, 10 ~ 30 parts of color stuffings, 0.3 part of flow agent, 0.3 portion of defoamer, 1 ~ 3 portion of anti-settling agent, described wetting dispersing agent is one or more in polyether-modified organopolysiloxane, anionic wetting dispersing agent, the unsaturated polycarboxylic acid polymers of lower molecular weight; Described organic solvent is the mixing liquid of dimethyl sulfoxide (DMSO), ethylene glycol monomethyl ether and butylacetate; Described nontoxic stain control agent is copper pyrithione or Zinc Pyrithione; Described color stuffing is at least three kinds in polytetrafluoroethylene (PTFE), red iron oxide, zinc oxide, titanium dioxide, barium sulfate; Described flow agent is the one in the Levaslip435 of De Qian Chemical Co., Ltd. and the BYK300 of German BYK company; Described defoamer is the one in BYK052,066; Described anti-settling agent is BYK410, organobentonite, talcous mixture; Dispersion grinding is less than 50 μm to coating fineness, obtains the polynary collaborative marine antifouling coating of non-toxic, environmental friendly.
Wetting dispersing agent of the present invention is 903,904 of 103,104,161,163, the De Qian Chemical Co., Ltd.s being selected from German BYK series.
The preparation method of the antifouling paint substrate resin containing antifouling activity group of the present invention, be specifically that ethylene glycol monomethyl ether and the n-butanol mixed solvent of 2:1 joins in reactor by 15 parts of mass ratioes, be warming up to 85 DEG C, 5 parts of esters of acrylic acid sulfonic acid potassium salt monomers and 5 parts of Hydrophobic Ionic liquid monomers are dissolved in the dimethyl sulfoxide (DMSO) and dimethyl formamide mixed solvent that 34 parts of mass ratioes are 1:1, add 10 parts of methyl methacrylates more successively, 10 parts of n-butyl acrylates, 4 parts of ethyl propenoates, 5 parts of vinylformic acid and 0.8 part of Diisopropyl azodicarboxylate, 0.5 part of Dodecyl Mercaptan, above-mentioned mixing solutions is added in reactor, be incubated 2 hours, in 0.5 hour, add methyl-sulphoxide and ethylene glycol monomethyl ether mixing solutions that the 10 parts of mass ratioes being dissolved with 0.2 part of Diisopropyl azodicarboxylate are 1:1 again, continue insulation 1 hour, obtain the acrylic polymer containing antifouling activity group, by 65 parts containing the acrylic polymers of antifouling activity group, 4 parts of zinc hydroxides or copper hydroxide, 15 parts of mass ratioes be the dimethyl formamide of 1:1:1, ethylene glycol monomethyl ether and n-butyl acetate mixed solvent add in reactor, 5 parts of phenylformic acid are dissolved in 11 parts of mixed solvents, above-mentioned organic acid mixing solutions is added at 95 DEG C, keep reflux state transparent to reaction solution, after be warming up to 125 DEG C of dehydrations, until water is deviate from completely, obtain the thick antifouling paint substrate resin containing antifouling activity group.
The preparation method of described Hydrophobic Ionic liquid monomer is, the N-alkyl imidazole of equimolar amount, 1-chloro-4-methyl-benzene are fully stirred in room temperature and generates micro-yellow thick liquid, be dissolved in distilled water and added ammonium hexafluorophosphate or the sodium tetrafluoroborate of equimolar amount, filter after abundant stirring, obtain white waxy solid product; Wherein said N-alkyl imidazole is N-Methylimidazole, N-ethyl imidazol(e), or N-butyl imidazole.
The polynary collaborative marine antifouling coating of environment-friendly type of the present invention, being effectively combined coating with low surface energy characteristic from polishing characteristic, the ionic liquid group with Efficient antibacterial activity is incorporated into copolymer chain simultaneously, strengthen effect of antifouling phase, be a kind of environmental friendliness, surface energy low, from the non-toxic, environmental friendly antifouling paint of polishing stable, antifouling persistent.In the seawater, this coating can realize number of ways and work in coordination with antifouling, thus shows excellent long-acting and anti-fouling performance.Meanwhile, coating and base material adhere to well, and coating surface is smooth, easy construction, and the four seasons all can use.
The polynary collaborative marine antifouling coating of environment-friendly type of the present invention, the traditional performance being sprayed at tinplate is as follows:
1) sticking power: GB1720-79 (drawing circle method), 1 grade;
2) shock-resistance: GB1732-79,50 Kg.cm;
3) hardness: GB6379-86,1H ~ 2H level;
4) snappiness: GB1731-79,1mm;
5) coatingsurface energy: be less than 25 mJm
-2;
6) drying varniss time: GB1728-79, room temperature 16 ~ 25 DEG C, surface drying 2 hours, 12 hours actual drying time.
The polynary collaborative marine antifouling coating of environment-friendly type of the present invention, be coated on the mild steel plate of epoxy anticorrosion primer by spraying or brushing mode, epoxy anticorrosion primer build is about 200 μm, and antifouling coating gauge control, at 150 μm, can obtain promising result.
This environmental protection type anti-pollution paint is coated on (150 × 250 × 2 mm) on the mild steel plate of epoxy anticorrosion primer by spraying means and makes model, after the abundant drying of room temperature, carry out shallow sea board experiment.Select the domestic conventional tin-free self-polishing antifouling paint (hereinafter referred to as domestic) being main stain control agent with Red copper oxide simultaneously, and low surface energy antifouling varnish (surface energy is less than 17 mJm
-2) brush on same size steel plate respectively, model in contrast, brushing thickness is identical with this coating.Select same specification steel plate to do blank, a brushing epoxy anticorrosion primer simultaneously.Be placed in lower 1 meter of depths, sea with blank plate carry out the extra large board experiment of static state reality by being coated with the experiment model being brushed with various antifouling paint.Test period 2012,05,03 ~ 2012,08,29(marine growth most productive period), test site: marine site, Nan'ao, Shenzhen.Shown in experimental result picture 1-4: wherein Fig. 1 is the blank model of epoxy, the static link plate in shallow sea after 118 days specimen surface adhere to all kinds of Macro-fouling Organisms, mainly based on barnacle, mussel, sponge, seriously stained.Fig. 2 is the static link plate of model of external coating low surface energy anti-fouling paint result after 118 days, and there are more diatom, barnacle attachment in its surface, and antifouling property is poor.Fig. 3 is the static link plate of model of the domestic antifouling varnish of external coating result after 118 days, and there are a small amount of kentrogon and diatom attachment in its surface, and anti-fouling effect is better.Fig. 4 is the static link plate of model of the polynary collaborative marine antifouling coating of external coating environment-friendly type of the present invention result after 118 days, and specimen surface paint film is intact, without bubbling, coming off, coating surface is comparatively clean, stained point is few, and without the attachment of large ocean fouling organism, antifouling property is excellent.Can find out, in probation, polynary its antifouling property of collaborative marine antifouling coating of environment-friendly type of our development has surmounted the domestic self-polishing antifouling paint containing Red copper oxide, can substitute the conventional composite type antifouling paint containing Red copper oxide completely.
The polynary collaborative marine antifouling coating of environment-friendly type of the present invention, oxygen-freeization is cuprous, asepsis environment-protecting, and production technique is relatively simple, raw material is easy to get, wide market.
This coating is nontoxic free from environmental pollution, is mainly used in the antifouling of boats and ships.In the seawater, the low surface energy characteristic of this coating can effectively suppress marine organisms to adhere to, simultaneously, coatingsurface acrylic copolymer is hydrolyzed, and discharges organic acid zinc or copper and stain control agent, realizes coatingsurface from polishing, and the main polymer chain after hydrolysis also comprises the antifouling activity group with Efficient antibacterial performance, make coating continue to keep high-efficiency pollution-proof active, suppress marine organisms attachment, thus show excellent long-acting and anti-fouling performance.
Accompanying drawing explanation
Fig. 1 is the blank model shallow sea board experiment of epoxy 118 days (marine site, Nan'ao, Shenzhen, 2012,05,03 ~ 2012,08,29) results.
Fig. 2 is low surface energy anti-fouling paint shallow sea board experiment 118 days (marine site, Nan'ao, Shenzhen, 2012,05,03 ~ 2012,08,29) result.
Fig. 3 is domestic antifouling varnish shallow sea board experiment 118 days (marine site, Nan'ao, Shenzhen, 2012,05,03 ~ 2012,08,29) result.
Fig. 4 is environment-friendly type of the present invention polynary collaborative marine antifouling coating shallow sea board experiment 118 days (marine site, Nan'ao, Shenzhen, 2012,05,03 ~ 2012,08,29) results.
Embodiment
Below by embodiment, the present invention is described further
Antifouling paint substrate resin containing antifouling activity group in the present invention is prepared as follows:
Be that ethylene glycol monomethyl ether and the n-butanol mixed solvent of 2:1 joins in reactor by 15 parts of mass ratioes, be warming up to 85 DEG C, 5 parts of esters of acrylic acid sulfonic acid potassium salt monomers and 5 parts of Hydrophobic Ionic liquid monomers are dissolved in the dimethyl sulfoxide (DMSO) and dimethyl formamide mixed solvent that 34 parts of mass ratioes are 1:1, add 10 parts of methyl methacrylates, 10 parts of n-butyl acrylates, 4 parts of ethyl propenoates, 5 parts of vinylformic acid and 0.8 part of Diisopropyl azodicarboxylate, 0.5 part of Dodecyl Mercaptan more successively, above-mentioned mixing solutions is added in reactor, is incubated 2 hours; In 0.5 hour, add methyl-sulphoxide and ethylene glycol monomethyl ether mixing solutions that the 10 parts of mass ratioes being dissolved with 0.2 part of Diisopropyl azodicarboxylate are 1:1 again, continue insulation 1 hour, obtain the acrylic polymer containing antifouling activity group; By 65 parts containing the acrylic polymers of antifouling activity group, 4 parts of zinc hydroxides or copper hydroxide, 15 parts of mass ratioes be the dimethyl formamide of 1:1:1, ethylene glycol monomethyl ether and n-butyl acetate mixed solvent add in reactor, 5 parts of phenylformic acid are dissolved in 11 parts of mixed solvents, above-mentioned organic acid mixing solutions is added at 95 DEG C, keep reflux state transparent to reaction solution, after be warming up to 125 DEG C of dehydrations, until water is deviate from completely, obtain the thick antifouling paint substrate resin containing antifouling activity group.
Embodiment 1
30 parts are contained the antifouling paint substrate resin of antifouling activity group, 1 part of wetting dispersing agent BYK163 and 26 part mixed organic solvents (dimethyl sulfoxide (DMSO): ethylene glycol monomethyl ether: butylacetate=1:1:1) adds in dispersion cylinder, abundant dispersion also adds 10 parts of copper pyrithiones successively, 30 parts of color stuffing (tetrafluoroethylene 6 parts, red iron oxide 8 parts, 8 parts, zinc oxide, 8 parts, barium sulfate), 0.3 part of flow agent BYK300, 0.3 part of defoamer BYK052, 2.4 portions of anti-settling agents (wherein, 0.4 part of BYK410, 1 part of organobentonite, 1 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 1H level; Snappiness: 1mm; Coatingsurface energy: be less than 24 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 8 hours.
Embodiment 2
30 parts are contained the antifouling paint substrate resin of antifouling activity group, 1 part of wetting dispersing agent BYK163 and 26 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 5 parts of copper pyrithiones successively, 5 parts of Zinc Pyrithione, 30 parts of color stuffing (tetrafluoroethylene 5 parts, red iron oxide 8 parts, 8 parts, zinc oxide, 9 parts, barium sulfate), 0.3 part of flow agent Levaslip435, 0.3 part of defoamer BYK052, 2.4 portions of anti-settling agents (wherein, 0.4 part of BYK410, 1 part of organobentonite, 1 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 1H level; Snappiness: 1mm; Coatingsurface energy: be less than 24 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 8 hours.
Embodiment 3
40 parts are contained the antifouling paint substrate resin of antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 22 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 4 parts of copper pyrithiones successively, 3.5 parts of Zinc Pyrithione, 27 parts of color stuffing (tetrafluoroethylene 5 parts, red iron oxide 8 parts, 7 parts, zinc oxide, 7 parts, barium sulfate), 0.3 part of flow agent Levaslip435, 0.3 part of defoamer BYK052, 2.1 portions of anti-settling agents (wherein, 0.3 part of BYK410, 0.9 part of organobentonite, 0.9 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 1H level; Snappiness: 1mm; Coatingsurface energy: be less than 25 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 8 hours.
Embodiment 4
50 parts are contained the antifouling paint substrate resin of antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 18 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 3 parts of copper pyrithiones successively, 2.5 parts of Zinc Pyrithione, 23 parts of color stuffing (tetrafluoroethylene 5 parts, red iron oxide 6 parts, 6 parts, zinc oxide, 6 parts, barium sulfate), 0.3 part of flow agent Levaslip435, 0.3 part of defoamer BYK052, 2.1 portions of anti-settling agents (wherein, 0.3 part of BYK410, 0.9 part of organobentonite, 0.9 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 1H level; Snappiness: 1mm; Coatingsurface energy: be less than 25 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 10 hours.
Embodiment 5
55 parts are contained the antifouling paint substrate resin of antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 15 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 3 parts of copper pyrithiones successively, 2.5 parts of Zinc Pyrithione, 21 parts of color stuffing (tetrafluoroethylene 4 parts, red iron oxide 6 parts, 5 parts, zinc oxide, 6 parts, barium sulfate), 0.3 part of flow agent BYK300, 0.3 part of defoamer BYK052, 2.1 portions of anti-settling agents (wherein, 0.3 part of BYK410, 0.9 part of organobentonite, 0.9 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 2H level; Snappiness: 1mm; Coatingsurface energy: be less than 25 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 10 hours.
Embodiment 6
50 parts are contained the antifouling paint substrate resin of antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 15.5 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 10 parts of Zinc Pyrithione successively, 21 parts of color stuffing (tetrafluoroethylene 4 parts, red iron oxide 6 parts, 5 parts, zinc oxide, 6 parts, barium sulfate), 0.3 part of flow agent BYK300, 0.3 part of defoamer BYK052, 2.1 portions of anti-settling agents (wherein, 0.3 part of BYK410, 0.9 part of organobentonite, 0.9 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 2H level; Snappiness: 1mm; Coatingsurface energy: be less than 25 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 10 hours.
Embodiment 7
45 parts are contained the antifouling paint substrate resin of antifouling activity group, 1 part of wetting dispersing agent BYK163 and 21 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 30 parts of color stuffings (tetrafluoroethylene 6 parts successively, red iron oxide 8 parts, 6 parts, zinc oxide, 8 parts, barium sulfate, titanium dioxide 2 parts), 0.3 part of flow agent BYK300, 0.3 part of defoamer BYK052, 2.4 portions of anti-settling agents (wherein, 0.4 part of BYK410, 1 part of organobentonite, 1 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 2H level; Snappiness: 1mm; Coatingsurface energy: be less than 24 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 10 hours.
Embodiment 8
45 parts are contained the antifouling paint substrate resin of antifouling activity group, 1 part of wetting dispersing agent BYK163 and 21 part mixed organic solvents adds in dispersion cylinder, abundant dispersion also adds 5 parts of copper pyrithiones successively, 3 parts of Zinc Pyrithione, 22 parts of color stuffing (tetrafluoroethylene 5 parts, red iron oxide 6 parts, 4 parts, zinc oxide, 6 parts, barium sulfate, titanium dioxide 1 part), 0.3 part of flow agent BYK300, 0.3 part of defoamer BYK052, 2.4 portions of anti-settling agents (wherein, 0.4 part of BYK410, 1 part of organobentonite, 1 part of talcum powder), high speed dispersion is also ground to coating fineness and is less than 50 μm, obtain the polynary collaborative marine antifouling coating of environment-friendly type.Finally pack.The polynary collaborative marine antifouling coating of this example environment-friendly type, the traditional performance being sprayed at tinplate is as follows: sticking power: 1 grade; Shock-resistance: 50 Kg.cm; Hardness: 2H level; Snappiness: 1mm; Coatingsurface energy: be less than 25 mJm
-2; The drying varniss time: room temperature surface drying 2 hours, do solid work 10 hours.
Claims (4)
1. the polynary collaborative marine antifouling coating of environment-friendly type, is characterized in that coating is prepared by following process:
By free-radical polymerized, acrylic acid or the like soft or hard monomer, Hydrophobic Ionic liquid monomer, esters of acrylic acid sulfonic acid potassium salt monomer are carried out copolymerization under initiator exists, obtain the acrylic polymer containing bacteriostatic activity group, and then obtain the antifouling paint substrate resin containing antifouling activity group with zinc hydroxide or copper, monovalence organic acid mixture reaction;
Be that 30 ~ 55 parts of antifouling paint substrate resins containing antifouling activity group, 0.5 ~ 1 part of wetting dispersing agent and 15 ~ 30 parts of mixed organic solvents are after fully disperseing by parts by weight, add 0 ~ 10 part of nontoxic stain control agent, 10 ~ 30 parts of color stuffings, 0.3 part of flow agent, 0.3 portion of defoamer, 1 ~ 3 portion of anti-settling agent, described wetting dispersing agent is one or more in polyether-modified organopolysiloxane, anionic wetting dispersing agent, the unsaturated polycarboxylic acid polymers of lower molecular weight; Described organic solvent is the mixing liquid of dimethyl sulfoxide (DMSO), ethylene glycol monomethyl ether and butylacetate; Described nontoxic stain control agent is copper pyrithione or Zinc Pyrithione; Described color stuffing is at least three kinds in polytetrafluoroethylene (PTFE), red iron oxide, zinc oxide, titanium dioxide, barium sulfate; Described flow agent is the one in the Levaslip435 of De Qian Chemical Co., Ltd. and the BYK300 of German BYK company; Described defoamer is the one in BYK052,066; Described anti-settling agent is BYK410, organobentonite, talcous mixture; Dispersion grinding is less than 50 μm to coating fineness, obtains the polynary collaborative marine antifouling coating of non-toxic, environmental friendly.
2. coating as claimed in claim 1, is characterized in that described wetting dispersing agent is 903,904 of 103,104,161,163, the De Qian Chemical Co., Ltd.s being selected from German BYK series.
3. coating as claimed in claim 1, it is characterized in that the preparation method of the antifouling paint substrate resin containing antifouling activity group, be that the ethylene glycol monomethyl ether of 2:1 and n-butanol mixed solvent join in reactor by 15 parts of mass ratioes, be warming up to 85 DEG C, 5 parts of esters of acrylic acid sulfonic acid potassium salt monomers and 5 parts of Hydrophobic Ionic liquid monomers are dissolved in the dimethyl sulfoxide (DMSO) and dimethyl formamide mixed solvent that 34 parts of mass ratioes are 1:1, add 10 parts of methyl methacrylates more successively, 10 parts of n-butyl acrylates, 4 parts of ethyl propenoates, 5 parts of vinylformic acid and 0.8 part of Diisopropyl azodicarboxylate, 0.5 part of Dodecyl Mercaptan, above-mentioned mixing solutions is added in reactor, be incubated 2 hours, in 0.5 hour, add methyl-sulphoxide and ethylene glycol monomethyl ether mixing solutions that the 10 parts of mass ratioes being dissolved with 0.2 part of Diisopropyl azodicarboxylate are 1:1 again, continue insulation 1 hour, obtain the acrylic polymer containing antifouling activity group, by 65 parts containing the acrylic polymers of antifouling activity group, 4 parts of zinc hydroxides or copper hydroxide, 15 parts of mass ratioes be the dimethyl formamide of 1:1:1, ethylene glycol monomethyl ether and n-butyl acetate mixed solvent add in reactor, 5 parts of phenylformic acid are dissolved in 11 parts of mixed solvents, above-mentioned organic acid mixing solutions is added at 95 DEG C, keep reflux state transparent to reaction solution, after be warming up to 125 DEG C of dehydrations, until water is deviate from completely, obtain the thick antifouling paint substrate resin containing antifouling activity group.
4. the coating as described in claim 1 or 3, it is characterized in that the preparation method of Hydrophobic Ionic liquid monomer is, the N-alkyl imidazole of equimolar amount, 1-chloro-4-methyl-benzene are fully stirred in room temperature and generates micro-yellow thick liquid, be dissolved in distilled water and added ammonium hexafluorophosphate or the sodium tetrafluoroborate of equimolar amount, filter after abundant stirring, obtain white waxy solid product; Wherein said N-alkyl imidazole is N-Methylimidazole, N-ethyl imidazol(e), or N-butyl imidazole.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106675294A (en) * | 2016-12-20 | 2017-05-17 | 海洋化工研究院有限公司 | Copper-free and environment-friendly self-polishing ocean antifouling paint |
| CN108148488A (en) * | 2017-12-30 | 2018-06-12 | 常州市阿曼特化工有限公司 | A kind of control release type marine antifouling coating |
| CN108610449A (en) * | 2017-01-14 | 2018-10-02 | 浙江省海洋开发研究院 | P-chloromethyl styrene/acrylic resin grafting methyl nicotinate pyridiniujm and its novel sea antifouling paint obtained |
| CN113004752A (en) * | 2021-04-02 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Transparent marine antifouling paint and preparation method and application thereof |
| CN113981689A (en) * | 2021-12-16 | 2022-01-28 | 中国纺织信息中心 | Moisture-sensitive self-adaptive breathable fabric |
| CN114716684A (en) * | 2022-03-31 | 2022-07-08 | 吴晓金 | Self-polishing antifouling resin with degradation and hydrolysis performances and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255291A (en) * | 2015-11-25 | 2016-01-20 | 蓬莱蔚阳新材料有限公司 | Poly(ionic liquid) broad-spectrum antifouling compound containing environment-friendly marine antifouling coating and preparation process thereof |
| CN106675294A (en) * | 2016-12-20 | 2017-05-17 | 海洋化工研究院有限公司 | Copper-free and environment-friendly self-polishing ocean antifouling paint |
| CN106675294B (en) * | 2016-12-20 | 2019-04-19 | 海洋化工研究院有限公司 | No copper ring is protected from polishing marine antifouling coating |
| CN108610449A (en) * | 2017-01-14 | 2018-10-02 | 浙江省海洋开发研究院 | P-chloromethyl styrene/acrylic resin grafting methyl nicotinate pyridiniujm and its novel sea antifouling paint obtained |
| CN108610449B (en) * | 2017-01-14 | 2021-03-12 | 浙江省海洋开发研究院 | Para-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and novel marine antifouling paint prepared from same |
| CN108148488A (en) * | 2017-12-30 | 2018-06-12 | 常州市阿曼特化工有限公司 | A kind of control release type marine antifouling coating |
| CN113004752A (en) * | 2021-04-02 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Transparent marine antifouling paint and preparation method and application thereof |
| CN113981689A (en) * | 2021-12-16 | 2022-01-28 | 中国纺织信息中心 | Moisture-sensitive self-adaptive breathable fabric |
| CN114716684A (en) * | 2022-03-31 | 2022-07-08 | 吴晓金 | Self-polishing antifouling resin with degradation and hydrolysis performances and preparation method thereof |
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