CN105295631A - Fluorine-modified zinc acrylate antifouling coating material and preparation method thereof - Google Patents
Fluorine-modified zinc acrylate antifouling coating material and preparation method thereof Download PDFInfo
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- CN105295631A CN105295631A CN201510793679.9A CN201510793679A CN105295631A CN 105295631 A CN105295631 A CN 105295631A CN 201510793679 A CN201510793679 A CN 201510793679A CN 105295631 A CN105295631 A CN 105295631A
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Abstract
The present invention relates to a fluorine-modified zinc acrylate antifouling coating material and a preparation method thereof, wherein the base components comprise, by mass, 20-60 parts of a fluorine-modified zinc acrylate resin, 10-40 parts of an antifouling agent, 10-35 parts of a pigment filler, 1-10 parts of an auxiliary agent, and 10-35 parts of a solvent. According to the present invention, the prepared marine antifouling coating material has self-polishing property, wherein the coating gradually exposes the new surface layer so as to release the antifouling agent along with the new surface layer exposing; the coating material has low surface energy, such that marine microorganisms are difficult to adhere; and the required antifouling agent consumption is less than the antifouling agent consumption in other technologies, such that the harm on the environment is low.
Description
Technical field
The present invention relates to and a kind ofly have low surface energy concurrently and from fluorin modified crylic acid zinc antifouling paint of polishability and preparation method thereof.
Background technology
Ocean underwater facility and the boats and ships navigated by water in ocean all inevitably face the problem that marine fouling organism (animal, plant and microorganism) adheres to, this not only accelerates the corrosion of facility and boats and ships greatly, and then shorten its work-ing life, and significantly can increase energy expenditure for the boats and ships of navigation.Data show, when marine biofouling rate is 5%, ship resistance is just equivalent to 2 times of clean surface, and fuel consumption increases by 10%.
Since ancient times, the mankind just take various means to prevent halobiontic attachment, and through constantly attempting, the marine antifouling coating that application contains stain control agent has become effective, the most most economical and the most feasible method solving sea marine organism pollution.。In the past few decades, the antifouling paint containing organotin was once widely used.Organotin can reach wide spectrum, efficient antifouling object at low concentrations, but these materials are stablized and can be accumulated in water, can cause some organisms deformities, also likely enter food chain, become and affect human health and ecological potential safety hazard.A draft is adopted in the 42nd MEPC meeting November in 1998 unanimously, and this draft is decided to be on January 1st, 2003 using the final term of TBT, and after 1 day January in 2008, will forbid on shell, occur TBT marime fouling thing.Along with the enforcement of this ban, developing of environmental friendliness anti-fouling ship paint launches in the world, and wherein tin-free self-polishing coating and low surface energy decontamination type antifouling paint are two large main flow directions.
People in the process of research low surface energy anti-fouling paint, be all film is had more low surface energy is for pursuing a goal, reduce the surface energy of film by fair means or foul, seemingly surface energy is lower, and anti-fouling effect is better, but true really not so.Baier obtains famous Baier curve when studying the relation between surface energy and adhesion amount, points out when the surface energy of film is at 22-24mJ/m
2between time, the corresponding minimum value of adhesion amount.
At present, domestic about from polishing low surface energy type antifouling resin research report less, Chinese patent 103122188A discloses a kind of from polishing organic silicon-fluorine modification acrylate low surface energy anti-fouling paint, this coating has good in polishability and physical and mechanical properties, do not crack and other defect, there is very low surface energy simultaneously, realize collaborative antifouling with from polishing of low surface energy.Chinese patent CN1793247 discloses a kind of low surface energy fluorine carbon antifouling paint, this coating has very low surface energy and contact angle that is very high and water, and realize the collaborative antifouling of low surface energy and stain control agent, thus reach good effect preventing marine organisms from adhering to.Chinese patent CN102167774A discloses a kind of preparation method having fluorin modified crylic acid zinc antifouling resin from polishing and low surface energy character concurrently, this resin utilizes fluorinated acrylate to carry out modification to zinc acrylate resin, the obtained novel sea marine antifouling resin had concurrently from polishability and low surface energy, but the application of this resin at marine antifouling coating is not studied.
Summary of the invention
An object of the present invention is to provide a kind of fluorin modified crylic acid zinc antifouling paint.This coating have effect length of antifouling phase, good antifouling effect, sticking power good, do not contain organotin, the advantage such as environmentally friendly, has broad application prospects.
Two of object of the present invention is the preparation method providing this antifouling paint.
A kind of fluorin modified crylic acid zinc antifouling paint, is characterized in that the composition of this antifouling paint and mass fraction are:
Fluorin modified crylic acid zinc resin 20 ~ 60 parts,
Stain control agent 10 ~ 40 parts,
Filler 10 ~ 35 parts,
Auxiliary agent 1 ~ 10 part,
Balance of solvent.
Above-mentioned stain control agent has: Red copper oxide, zinc oxide, 2,3,5,6 one four chloro 1 (sulfonyloxy methyl) pyridines, 2 monomethyl sulfo-1 monobutylamine (MBA) base 1 cyclopropylamine one s mono-triazines, the zinc complex, 4 of 2 one coloured glaze yl pyridines 1 monoxide, 5 one dichloro-1 n-octyl 1 isothiazoline 1 ketone, pyridinium triphenylboron complex compound, 2,4,5,6 one four chloro m-dicyanobenzene or 3 one (3,4 one dichloro-phenyl)-1,1 one Dimethylureas.
Above-mentioned filler is color stuffing and common fillers, and described color stuffing is: titanium white, iron oxide black, red iron oxide or zinc oxide; Described common fillers is calcium carbonate, wollastonite powder, diatomite, silicon powder, barium sulfate, ground barium sulfate, zinc sulphide, zinc sulfide white, mica powder, magnesium oxide, silica powder or talcum powder.
Above-mentioned solvent is the mixed solvent that dimethylbenzene and propyl carbinol form by the mass ratio of 4:1.
Prepare a method for above-mentioned fluorin modified crylic acid zinc antifouling paint, it is characterized in that the concrete steps of the method are:
A. the composition of reaction monomers and mass percent are:
Vinylformic acid 1 ~ 8%, fluorinated acrylate monomer 2 ~ 10%, acrylate hard monomer 6 ~ 20%, vinylformic acid soft monomer 3 ~ 15%, radical initiator 1 ~ 5% and solvent 40 ~ 60%;
B. at a reflux temperature, acrylate soft or hard monomer, Acrylic Acid Monomer, fluorinated acrylate monomer are added drop-wise in solvent, stirring reaction 1.5 hours; Drip initiator solution again, react 1 hour, then add zinc hydroxide and acetic acid solution (ratio of the amount of zinc hydroxide, acetic acid and acrylic substance is 1:1:1), continue stirring reaction 1 hour, after distillation dehydration, obtain fluorin modified crylic acid zinc resin; This resin number-average molecular weight is 28000 ~ 40000, and after film forming, contact angle is 98 ~ 115 °, has certain hydrolysis rate, has from polishability.
C. above-mentioned each component is mixed rear shredder to grind, reach less than 60 μm to fineness, namely obtain fluorin modified crylic acid zinc antifouling paint.
Above-mentioned above-mentioned fluorinated acrylate monomer is dodecafluoroheptyl methacrylate; Described acrylate hard monomer is methyl methacrylate; Described vinylformic acid soft monomer is butyl acrylate; Described initiator is Diisopropyl azodicarboxylate; Described solvent is the mixed solvent of dimethylbenzene and propyl carbinol.
Innovative point of the present invention and advantage: zinc acrylate resin has from polishing performance, stain control agent dissolution rate is in the seawater controlled, effect of antifouling phase can be extended like this, the character of low surface energy that made resin have again after fluorine richness, marime fouling thing is difficult to attachment, and antifouling property further improves.And the antifouling dosage that the stain control agent of required interpolation uses than other technologies is few, less to the harm of environment.
Embodiment
Embodiment 1
Agitator is being housed, reflux exchanger, constant pressure funnel, 70g dimethylbenzene is added in the four-hole bottle of thermometer, 18g propyl carbinol, stir and be warming up to 85 DEG C, then 50g methyl methacrylate is weighed, 30g butyl acrylate, 10g vinylformic acid, 10g dodecafluoroheptyl methacrylate, the mixed solution of 5g Diisopropyl azodicarboxylate, drip off at 2.5h with constant pressure funnel, continue insulation 1.5 hours, weigh 50g dimethylbenzene again, 14g propyl carbinol, 1g Diisopropyl azodicarboxylate, drip off in 0.5h, be incubated 1h again, then 60 ~ 80 DEG C are cooled to, weigh 50g dimethylbenzene again, 18g propyl carbinol, 13.75g zinc hydroxide, 8.33g acetic acid, add successively in 15 minutes, insulation 1h, be warming up to 100 ~ 110 DEG C again, room temperature is down to when steaming without moisture again, discharging, obtain fluorin modified crylic acid zinc resin.
Sample prepared by the present embodiment is analyzed after tested, and number-average molecular weight is 31225, and molecular weight distribution is 2.9, and second-order transition temperature is 26 DEG C, and surveying its film to the contact angle of water is 100.3 °, has certain hydrolysis rate, has from polishability.
Embodiment 2
Fluorin modified crylic acid zinc resin prepared by 40 mass parts embodiments 1,5 mass parts Red copper oxide, 5 mass parts 2,4,5,6 one four chloro m-dicyanobenzene (m-tetrachlorophthalodinitrile), 9 mass parts iron oxide reds, 6 mass parts zinc oxide, 7 mass parts talcum powder, 2 mass parts multifunctional type auxiliary agents, 21 mass parts dimethylbenzene, 5 quality divide propyl carbinol mixing and stirring, grinding distribution to granularity is less than 60 microns, obtained coating 1, after tested, its sticking power is 4 grades, and hardness is H.
Embodiment 3
Agitator is being housed, reflux exchanger, constant pressure funnel, 70g dimethylbenzene is added in the four-hole bottle of thermometer, 18g propyl carbinol, stir and be warming up to 85 DEG C, then 50g methyl methacrylate is weighed, 30g butyl acrylate, 10g vinylformic acid, 20g dodecafluoroheptyl methacrylate, the mixed solution of 5g Diisopropyl azodicarboxylate, drip off at 2.5h with constant pressure funnel, continue insulation 1.5 hours, weigh 50g dimethylbenzene again, 14g propyl carbinol, 1g Diisopropyl azodicarboxylate, drip off in 0.5h, be incubated 1h again, then 60 ~ 80 DEG C are cooled to, weigh 50g dimethylbenzene again, 18g propyl carbinol, 13.75g zinc hydroxide, 8.33g acetic acid, add successively in 15 minutes, insulation 1h, be warming up to 100 ~ 110 DEG C again, room temperature is down to when steaming without moisture again, discharging, obtain fluorin modified crylic acid zinc resin.
Sample prepared by the present embodiment is analyzed after tested, and number-average molecular weight is 30823, and molecular weight distribution is 3.1, and second-order transition temperature is 27 DEG C, and surveying its film to the contact angle of water is 105.4 °, has certain hydrolysis rate, has from polishability.
Embodiment 4
With embodiment 2, adopt resin prepared by embodiment 3, obtained coating 2, after tested, its sticking power is 4 grades, and hardness is H.
Embodiment 5
By obtained for 40 mass parts embodiments 3 fluorin modified crylic acid zinc resin, 5 mass parts Red copper oxide, 5 mass parts 3 one (3,4 one dichloro-phenyl)-1,1 one Dimethylureas (Diuron Tech), 9 mass parts iron oxide reds, 6 mass parts zinc oxide, 7 mass parts talcum powder, 2 mass parts multifunctional type auxiliary agents, 21 mass parts dimethylbenzene, 5 quality divide propyl carbinol mixing and stirring, grinding distribution to granularity is less than 60 microns, obtained coating 3, after tested, its sticking power is 4 grades, and hardness is H.
Embodiment 6
Agitator is being housed, reflux exchanger, constant pressure funnel, 70g dimethylbenzene is added in the four-hole bottle of thermometer, 18g propyl carbinol, stir and be warming up to 85 DEG C, then 50g methyl methacrylate is weighed, 40g butyl acrylate, 10g vinylformic acid, 25g dodecafluoroheptyl methacrylate, the mixed solution of 7g Diisopropyl azodicarboxylate, drip off at 2.5h with constant pressure funnel, continue insulation 1.5 hours, weigh 50g dimethylbenzene again, 14g propyl carbinol, 1g Diisopropyl azodicarboxylate, drip off in 0.5h, be incubated 1h again, then 60 ~ 80 DEG C are cooled to, weigh 50g dimethylbenzene again, 18g propyl carbinol, 13.75g zinc hydroxide, 8.33g acetic acid, add successively in 15 minutes, insulation 1h, be warming up to 100 ~ 110 DEG C again, room temperature is down to when steaming without moisture again, discharging, obtain fluorin modified crylic acid zinc resin.
Sample prepared by the present embodiment is analyzed after tested, and number-average molecular weight is 32022, and molecular weight distribution is 2.8, and second-order transition temperature is 20 DEG C, and surveying its film to the contact angle of water is 110.6 °.
Embodiment 7
By obtained for 40 mass parts embodiments 6 fluorin modified crylic acid zinc resin, 5 mass parts Red copper oxide, 5 mass parts 2,4,5,6 one four chloro m-dicyanobenzene (m-tetrachlorophthalodinitrile), 9 mass parts iron oxide reds, 6 mass parts zinc oxide, 7 mass parts talcum powder, 2 mass parts multifunctional type auxiliary agents, 21 mass parts dimethylbenzene, 5 quality divide propyl carbinol mixing and stirring, grinding distribution to granularity is less than 60 microns, obtained coating 4, after tested, its sticking power is 3 grades, and hardness is H.
Embodiment 8
By obtained for 40 mass parts embodiments 6 fluorin modified crylic acid zinc resin, 5 mass parts Red copper oxide, 5 mass parts 3 one (3,4 one dichloro-phenyl)-1,1 one Dimethylureas (Diuron Tech), 9 mass parts iron oxide reds, 6 mass parts zinc oxide, 7 mass parts talcum powder, 2 mass parts multifunctional type auxiliary agents, 21 mass parts dimethylbenzene, 5 quality divide propyl carbinol mixing and stirring, grinding distribution to granularity is less than 60 microns, obtained coating 5, after tested, its sticking power is 4 grades, and hardness is H.
Claims (6)
1. a fluorin modified crylic acid zinc antifouling paint, is characterized in that the composition of this antifouling paint and mass fraction are:
Fluorin modified crylic acid zinc resin 20 ~ 60 parts,
Stain control agent 10 ~ 40 parts,
Filler 10 ~ 35 parts,
Auxiliary agent 1 ~ 10 part,
Balance of solvent.
2. fluorin modified crylic acid zinc antifouling paint according to claim 1, it is characterized in that described stain control agent has: Red copper oxide, zinc oxide, 2,3,5,6 one four chloro 1 (sulfonyloxy methyl) pyridines, 2 monomethyl sulfo-1 monobutylamine (MBA) base 1 cyclopropylamine one s mono-triazines, the zinc complex, 4 of 2 one coloured glaze yl pyridines 1 monoxide, 5 one dichloro-1 n-octyl 1 isothiazoline 1 ketone, pyridinium triphenylboron complex compound, 2,4,5,6 one four chloro m-dicyanobenzene or 3 one (3,4 one dichloro-phenyl)-1,1 one Dimethylureas.
3. fluorin modified crylic acid zinc antifouling paint according to claim 1, it is characterized in that described filler is color stuffing and common fillers, described color stuffing is: titanium white, iron oxide black, red iron oxide or zinc oxide; Described common fillers is calcium carbonate, wollastonite powder, diatomite, silicon powder, barium sulfate, ground barium sulfate, zinc sulphide, zinc sulfide white, mica powder, magnesium oxide, silica powder or talcum powder.
4. fluorin modified crylic acid zinc antifouling paint according to claim 1, is characterized in that described solvent is the mixed solvent that dimethylbenzene and propyl carbinol form by the mass ratio of 4:1.
5. prepare a method for the fluorin modified crylic acid zinc antifouling paint according to any one of Claims 1 to 4, it is characterized in that the concrete steps of the method are:
A. the composition of reaction monomers and mass percent are:
Vinylformic acid 1 ~ 8%, fluorinated acrylate monomer 2 ~ 10%, acrylate hard monomer 6 ~ 20%, vinylformic acid soft monomer 3 ~ 15%, radical initiator 1 ~ 5% and solvent 40 ~ 60%;
B. at a reflux temperature, acrylate soft or hard monomer, Acrylic Acid Monomer, fluorinated acrylate monomer are added drop-wise in solvent, stirring reaction 1.5 hours; Drip initiator solution again, react 1 hour, then add zinc hydroxide and acetic acid solution, wherein zinc hydroxide, acetic acid and acrylic acid mol ratio are 1:1:1, continue stirring reaction 1 hour, obtain fluorin modified crylic acid zinc resin after distillation dehydration;
C. above-mentioned each component is mixed rear shredder to grind, reach less than 60 μm to fineness, namely obtain fluorin modified crylic acid zinc antifouling paint.
6. method according to claim 5, is characterized in that described above-mentioned fluorinated acrylate monomer is dodecafluoroheptyl methacrylate; Described acrylate hard monomer is methyl methacrylate; Described vinylformic acid soft monomer is butyl acrylate; Described initiator is Diisopropyl azodicarboxylate; Described solvent is the mixed solvent of dimethylbenzene and propyl carbinol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141942A (en) * | 2017-05-15 | 2017-09-08 | 岭东核电有限公司 | Coastal Power Plant water tunnel drag reduction antifouling paint and preparation method thereof |
| CN113880996A (en) * | 2021-10-27 | 2022-01-04 | 大连理工大学 | Multifunctional marine antifouling coating resin and preparation method thereof |
| CN117384522A (en) * | 2023-11-08 | 2024-01-12 | 青岛海泰科瑞化学科技有限公司 | Zinc acrylate resin marine antifouling coating repair paint and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550306A (en) * | 2008-04-02 | 2009-10-07 | 上海海悦涂料有限公司 | Universal ship bottom antifouling coating |
| CN101555374A (en) * | 2008-04-11 | 2009-10-14 | 上海海悦涂料有限公司 | Aluminum boat antifouling paint |
| CN102167774A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Method for preparing fluorine modified zinc acrylate antifouling resin |
-
2015
- 2015-11-18 CN CN201510793679.9A patent/CN105295631A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550306A (en) * | 2008-04-02 | 2009-10-07 | 上海海悦涂料有限公司 | Universal ship bottom antifouling coating |
| CN101555374A (en) * | 2008-04-11 | 2009-10-14 | 上海海悦涂料有限公司 | Aluminum boat antifouling paint |
| CN102167774A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Method for preparing fluorine modified zinc acrylate antifouling resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141942A (en) * | 2017-05-15 | 2017-09-08 | 岭东核电有限公司 | Coastal Power Plant water tunnel drag reduction antifouling paint and preparation method thereof |
| CN113880996A (en) * | 2021-10-27 | 2022-01-04 | 大连理工大学 | Multifunctional marine antifouling coating resin and preparation method thereof |
| CN113880996B (en) * | 2021-10-27 | 2024-02-13 | 大连理工大学 | Multifunctional marine antifouling paint resin and preparation method thereof |
| CN117384522A (en) * | 2023-11-08 | 2024-01-12 | 青岛海泰科瑞化学科技有限公司 | Zinc acrylate resin marine antifouling coating repair paint and preparation method thereof |
| CN117384522B (en) * | 2023-11-08 | 2024-03-19 | 青岛海泰科瑞化学科技有限公司 | Zinc acrylate resin marine antifouling coating repair paint and preparation method thereof |
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Application publication date: 20160203 |