CN104592851A - Biodegradable antifouling marine coating and preparation method thereof - Google Patents

Biodegradable antifouling marine coating and preparation method thereof Download PDF

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CN104592851A
CN104592851A CN201510002504.1A CN201510002504A CN104592851A CN 104592851 A CN104592851 A CN 104592851A CN 201510002504 A CN201510002504 A CN 201510002504A CN 104592851 A CN104592851 A CN 104592851A
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lactide
monomer
solvent
hydroxyethyl methylacrylate
antifouling coating
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CN104592851B (en
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郝红
闵江
陈琛
李卓
樊安
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Northwest University
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    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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Abstract

The invention relates to a biodegradable antifouling marine coating and a preparation method thereof. The synthetic antifouling marine coating is prepared from the following raw materials in percentage by weight: 65%-85% of copolymer, 10%-30% of a solvent, 1%-2% of nano SiO2, 1%-2% of nano TiO2, 1%-1.5% of KLE-333, 1%-2% of KF-64 and 0.5%-1% of KSL-52. The synthetic biodegradable antifouling marine coating can be hydrolyzed under the action of seawater and the like; the surface layer automatically falls off; the coating has self-polishing property; and the surface energy of a base material is reduced, so that the base material has dual characteristics of self-polishing property and low surface energy. The nano TiO2 is added to the coating as an antifouling agent; growth of planktons in sea and adhesion of the coating can be inhibited under the photo-catalysis action; and the problems that an existing single antifouling marine coating is poor in use effect and large in dosage, and generates secondary pollution to a marine environment are solved.

Description

A kind of biodegradation type marine antifouling coating and preparation method thereof
Technical field
The present invention relates to a kind of biodegradation type marine antifouling coating and preparation method thereof, belong to coating technology Application Areas.
Technical background
Since the mankind are engaged in Activities of Ocean, the control of marine biofouling is the important topic of research always.Marine biofouling not only produces corrosion to the surface of hull, harbour, marine oil pipeline and marine drilling platform, the surface of hull is made to produce roughness, bring very large friction resistance, hull weight also can be caused to increase, reduce ship's speed, need to consume more fuel, cause the increase of emissions figure.About the control of marime fouling, there is various solution in mankind's history of marine navigation.Wherein effective, the most most popular anti-fouling method is the tributyl tin self polishing copolymer antifouling paint (TBT-SPC) of the seventies research and development in last century, and the boats and ships in the whole world 70 percent use this coating, thus have very huge economic benefit.But TBT-SPC anti-fouling system pollution of marine environment, produces great effect to halobiontic growth and breeding.
What adopt from the skeleton of polishing or hydrolysis-type marine antifouling coating or base-material is the coating that the superpolymer being easy to be hydrolyzed is made, in the skeleton of these superpolymer or by adding some sterilants, stain control agent and disinfectant etc., or some heavy metal ion such as Sn, Zn, Cu are incorporated in molecular skeleton, make superpolymer (such as being polyacrylic ester, poly-aminoresin etc.) and play antifouling effect.Film prepared is thus under the souring of seawater, by carrying out ion-exchange with the ion in seawater, penetrate institute's metal ion, and then good antifouling property can be played, under the souring of seawater, constantly by the film polishing on surface, constantly expose new surface, make surface become smooth, while polishing, the marine fouling organism be attached on surface coatings also can be made to split away off, play antifouling effect.
Low surface energy antifouling coating for seas has low surface energy, and marine organisms are difficult in coating surface attachment, even if attachment is also insecure, easily comes off under the effect of current or other external force.At present, low surface energy anti-fouling paint mainly organic fluorine and organosilicon coating.Organic fluorine and organosilicon each tool relative merits: fluoro-resin critical surfaces can be lower, mechanical property is better, but due to fluoro-resin be rigid polymer, top layer fouling organism comes off and needs higher-energy, and expensive; The price of silicone resin lower than fluorine resin coating, but its antifouling property and mechanical property poor.
Summary of the invention
One of the object of the invention is to provide a kind of high-performance bio degraded type from polishing-low surface energy antifouling coating for seas.
Another object of the present invention is the preparation method providing above-mentioned biodegradation type from polishing-low surface energy antifouling coating for seas.
Implementation procedure of the present invention is as follows:
A kind of marine antifouling coating, each composition weight percentage composition is:
Multipolymer 65% ~ 85%
Solvent 10% ~ 30%
Nano-meter SiO_2 21% ~ 2%
Nano-TiO 21% ~ 2%
KLE-333 1%～1.5%
KF-64 1%～2%
KSL-52 0.5%～1%
Described multipolymer is selected from vinylformic acid-copolymer of poly lactic acid, vinylformic acid-PGA multipolymer, vinylformic acid-poly-own lactide copolymers, vinylformic acid-poly (glycolide-lactide) multipolymer, vinylformic acid-poly-third own lactide copolymers;
Described solvent is the mixed solvent of ester class, alcohols, benzene-like compounds, wherein ester compound is selected from butylacetate, ethyl acetate, alcohol compound is selected from butanols, ethanol, benzene-like compounds is selected from dimethylbenzene, toluene, and in solvent, the mass ratio of ester class, alcohols, benzene-like compounds is 1:2:3 ~ 1:4:6.
Above-mentioned multipolymer obtains as follows: lactide mixes with hydroxyethyl methylacrylate by (1), add the sub-tin of octoate catalyst, first heating and melting, be warming up to 100 ~ 120 DEG C of reactions again, dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains hydroxyethyl methylacrylate-polylactide polymeric monomer, and described lactide is selected from glycollide, rac-Lactide, own lactide; (2) in hydroxyethyl methylacrylate-polylactide polymeric monomer and solvent, add methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, then add initiator, be obtained by reacting multipolymer at 45 ~ 85 DEG C; Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-polylactide polymeric monomer is function monomer.
Lactide described in above-mentioned steps (1) and the mol ratio of hydroxyethyl methylacrylate are 15 ~ 1.
Initiator described in above-mentioned steps (2) is selected from Diisopropyl azodicarboxylate, benzoyl peroxide, described soft monomer massfraction is 20 ~ 70%, hard monomer massfraction is 20 ~ 70%, and function monomer massfraction is the mass ratio of 10 ~ 20%, three kinds of monomers and solvent is 0.2 ~ 5.
The preparation method of above-mentioned marine antifouling coating, comprises the following steps:
(1) lactide is mixed with hydroxyethyl methylacrylate, add the sub-tin of octoate catalyst, first heating and melting, be warming up to 100 ~ 120 DEG C of reactions again, dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains hydroxyethyl methylacrylate-polylactide polymeric monomer, and described lactide is selected from glycollide, rac-Lactide, own lactide;
(2) in hydroxyethyl methylacrylate-polylactide polymeric monomer and solvent, add methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, then add initiator, be obtained by reacting multipolymer at 45 ~ 85 DEG C; Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-polylactide polymeric monomer is function monomer;
(3) by multipolymer and solvent, Nano-meter SiO_2 2, nano-TiO 2and KLE-333, KF-64, KSL-52 mixed grinding obtains marine antifouling coating.
Lactide described in above-mentioned steps (1) and the mol ratio of hydroxyethyl methylacrylate are 15 ~ 1; Soft monomer massfraction described in step (2) is 20 ~ 70%, and hard monomer massfraction is 20 ~ 70%, and function monomer massfraction is the mass ratio of 10 ~ 20%, three kinds of monomers and solvent is 0.2 ~ 5, and initiator is selected from Diisopropyl azodicarboxylate, benzoyl peroxide.
Advantage of the present invention and positively effect:
(1) marine antifouling coating of the present invention's synthesis hydrolyzable under the effects such as seawater, top layer meeting Automatic-falling, make coating have from polishing performance, and the surface energy of base-material is reduced, therefore base-material has from polishing and low surface energy dual nature;
(2) with nano-TiO 2for stain control agent, it can suppress planktonic growth and the attachment to coating in ocean under photocatalysis;
(3) instant invention overcomes that single type marine antifouling coating result of use is poor, consumption is large and ocean environment is produced to the deficiency of secondary pollution.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of hydroxyethyl methylacrylate-poly(lactic acid) polymeric monomer;
Fig. 2 is that hydroxyethyl methylacrylate-poly(lactic acid) polymeric monomer is with CDCl 3do solvent hydrogen nuclear magnetic resonance spectrogram ( 1h-NMR);
Fig. 3 is that hydroxyethyl methylacrylate-poly(lactic acid) polymeric monomer is with CDCl 3do solvent nuclear-magnetism carbon spectrogram ( 13c-NMR);
Fig. 4 is the infrared spectrum of vinylformic acid-copolymer of poly lactic acid;
Fig. 5 is the fungistatic effect of different ingredients composite ocean antifouling paint;
Fig. 6 is the photo that film soaks after 6 months in the seawater.
Embodiment
Embodiment 1
(1) be that the rac-Lactide of 15:1 mixes with hydroxyethyl methylacrylate by mol ratio, add the sub-tin of 0.1% octoate catalyst, at N 2the lower first heating and melting of protection, then be warming up to 100 DEG C, react 4 hours.Dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains the solid methyl Hydroxyethyl acrylate-poly(lactic acid) polymeric monomer of white.Its infrared spectrum is shown in Fig. 1,1759.1cm -1the strong absorption peak that place occurs is ester carbonyl group charateristic avsorption band, 3446.8cm -1place is the O-H stretching vibration of PLLA chain one end, and C-O stretching vibration peak appears at 1093.6cm -1and 1186.2cm -1place, this group appears in HEMA, PLLA, and the connection between HEMA and PLLA is also C-O; At 1653cm -1the absorption peak at place shows have-C=C-key to exist, and this double bond is present in the middle of HEMA; At 1384.9cm -1place and 1458.2cm -1place is respectively-CH-and-CH 3flexural vibration peak, at 3022-2900cm -1place is-CH-,-CH 2-and-CH 3stretching vibration peak; At 935.3cm -1place does not have ring skeleton peak, illustrates that L-rac-Lactide carries out ring-opening polymerization and generates poly(lactic acid) under the initiation of HEMA.Fig. 2 and Fig. 3 is that hydroxyethyl methylacrylate-poly(lactic acid) polymeric monomer is with CDCl respectively 3do solvent proton nmr spectra ( 1h-NMR) figure and nuclear-magnetism carbon spectrogram ( 13c-NMR), in hydrogen spectrogram, chemical shift δ is that occur near 1.57ppm and 5.23ppm is methyl-CH in PLLA repeating unit respectively 3with the proton uptake peak of methyne-CH-, the chemical shift in corresponding carbon spectrogram is respectively 16.9ppm and 69.8ppm.HEMA methylene-CH 2the absorption peak δ of-proton is at 4.35ppm, and-OCH 2cH 2the chemical shift of O-on carbon spectrogram greatly about 62.3ppm and 63.4ppm and document substantially identical, this also illustrates that poly(lactic acid) has been grafted on hydroxyethyl methylacrylate.
(2) N is used 2air in displacement apparatus, by mixed solvent, (mass ratio is the butylacetate of 1:2:3, butanols, dimethylbenzene mix) and hydroxyethyl methylacrylate-poly(lactic acid) polymeric monomer be loaded in four-hole boiling flask, drip methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, be rapidly heated 65 DEG C, then start to drip benzoyl peroxide, react 2 hours, drip 2/3, then 2 hours are incubated, again remaining benzoyl peroxide is dripped off, react 2 hours, finally be incubated 1 hour stopped reaction, obtain faint yellow, uniform viscous liquid is vinylformic acid-copolymer of poly lactic acid (base-material 1).Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-poly(lactic acid) polymeric monomer is function monomer; Mass ratio that is soft, hard, function monomer is 20:70:10, and the mass ratio of monomer and solvent is 0.2.
The infrared spectrum of base-material 1 is shown in Fig. 4, the 3460cm in spectrogram -1and 3550cm- 1the strong absorption peak at place shows containing-OH absorption peak in polymkeric substance, at 1750cm -1strong absorption peak then represent the stretching vibration of carbonyl, show in polymkeric substance containing carbonyl; At 2980cm -1and 2890cm -1there is the charateristic avsorption band that two groups strong, be respectively-CH 2-asymmetricly to cause with the stretching vibration of symmetry, at 1460cm -1there is corresponding-CH 2-flexural vibration absorption peak; 1660cm -1the absorption peak at place is carbon-carbon double bond peak residual in polymkeric substance, at 950cm -1with 880cm -1the absorption peak that place occurs, to represent in polymkeric substance also existence-CH=CH 2in C-H, the acrylic monomer also remaining and do not participate in reaction is described.
Embodiment 2
Be that the glycollide of 10:1 mixes with hydroxyethyl methylacrylate by mol ratio, add the sub-tin of 0.08% octoate catalyst, at N 2the lower first heating and melting of protection, then be warming up to 110 DEG C, react 6 hours.Dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains the solid methyl Hydroxyethyl acrylate-PGA polymeric monomer of white.Use N 2air in displacement apparatus, by mixed solvent, (mass ratio is the ethyl acetate of 1:4:6, ethanol, toluene mix) and hydroxyethyl methylacrylate-PGA polymeric monomer be loaded in four-hole boiling flask, drip methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, be rapidly heated 45 DEG C, then start to drip Diisopropyl azodicarboxylate and react 2 hours, drip 2/3, then 2 hours are incubated, again remaining Diisopropyl azodicarboxylate is dripped off, react 2 hours, finally be incubated 1 hour stopped reaction, obtain faint yellow, uniform viscous liquid is vinylformic acid-PGA multipolymer (base-material 2).Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-PGA polymeric monomer is function monomer; Mass ratio that is soft, hard, function monomer is 40:40:20, and the mass ratio of monomer and solvent is 1.
Embodiment 3
Be that the own lactide of 5:1 mixes with hydroxyethyl methylacrylate by mol ratio, add the sub-tin of 0.05% octoate catalyst, at N 2the lower first heating and melting of protection, then be warming up to 110 DEG C, react 10 hours.Dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains the solid methyl Hydroxyethyl acrylate-poly-own lactide polymeric monomer of white.Use N 2air in displacement apparatus, by mixed solvent, (mass ratio is the butylacetate of 1:3:5, ethanol, toluene mixes) and hydroxyethyl methylacrylate-poly-own lactide polymeric monomer is loaded in four-hole boiling flask, drip methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, be rapidly heated 75 DEG C, then start to drip Diisopropyl azodicarboxylate 2 hours, drip 2/3, then 2 hours are incubated, again remaining Diisopropyl azodicarboxylate is dripped off, react 2 hours, finally be incubated 1 hour stopped reaction, obtain faint yellow, uniform viscous liquid is vinylformic acid-poly-own lactide copolymers (base-material 3).Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-poly-own lactide polymeric monomer is function monomer; Mass ratio that is soft, hard, function monomer is 70:20:10, and the mass ratio of monomer and solvent is 4.
Embodiment 4
Be that rac-Lactide, the glycollide of 1:1:1 mixes with hydroxyethyl methylacrylate by mol ratio, add the sub-tin of 0.01% octoate catalyst, at N 2the lower first heating and melting of protection, then be warming up to 120 DEG C, react 4 hours.Dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains the solid methyl Hydroxyethyl acrylate-poly (glycolide-lactide) polymeric monomer of white.Use N 2air in displacement apparatus, by mixed solvent, (mass ratio is the ethyl acetate of 1:4:6, butanols, dimethylbenzene mix) and hydroxyethyl methylacrylate-poly (glycolide-lactide) polymeric monomer be loaded in four-hole boiling flask, drip methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, be rapidly heated 85 DEG C, then start to drip benzoyl peroxide 2 hours, drip 2/3, then 2 hours are incubated, again remaining benzoyl peroxide is dripped off, react 2 hours, finally be incubated 1 hour stopped reaction, obtain faint yellow, uniform viscous liquid is vinylformic acid-poly (glycolide-lactide) multipolymer (base-material 4).Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-poly (glycolide-lactide) polymeric monomer is function monomer; Mass ratio that is soft, hard, function monomer is 60:25:15, and the mass ratio of monomer and solvent is 5.
Embodiment 5
Be the rac-Lactide of 3:1:1 by mol ratio, own lactide mixes with hydroxyethyl methylacrylate, add the sub-tin of 0.1% octoate catalyst, at N 2the lower first heating and melting of protection, then be warming up to 120 DEG C, react 4 hours.Dissolve with chloroform, methyl alcohol separates out precipitation, and oven drying obtains solid methyl Hydroxyethyl acrylate-poly-(rac-Lactide-own lactide) polymeric monomer of white.Use N 2air in displacement apparatus, by mixed solvent, (mass ratio is the butylacetate of 1:2:3, butanols, dimethylbenzene mixes) and hydroxyethyl methylacrylate-poly-(rac-Lactide-own lactide) polymeric monomer is loaded in four-hole boiling flask, drip methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, be rapidly heated 85 DEG C, then start to drip benzoyl peroxide 2 hours, drip 2/3, then 2 hours are incubated, again remaining benzoyl peroxide is dripped off, react 2 hours, finally be incubated 1 hour stopped reaction, obtain faint yellow, uniform viscous liquid is vinylformic acid-poly-(rac-Lactide-own lactide) multipolymer (base-material 5).Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-poly-(rac-Lactide-own lactide) polymeric monomer is function monomer; Mass ratio that is soft, hard, function monomer is 70:20:10, and the mass ratio of monomer and solvent is 3.
Embodiment 6
Get 1% polyether-modified polydimethylsiloxane (KLE-333) and the vinylformic acid-copolymer of poly lactic acid (base-material 1) of 78 %, KLE-333 is joined rapid stirring in base-material 1, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes.Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 16 %, nano-TiO 2with Nano-meter SiO_2 2get 1 % simultaneously, disperseed with mixed solvent, then join in colloidal mill respectively, grind 2 ~ 4 hours; Finally add 2% unsaturated polycarboxylic acid and join organic siloxane solution (KF-64) and 1% acrylic acid modified broken bubble polymkeric substance (KSL-52), grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y1).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, the results are shown in Table 1, Fig. 5-6.
Embodiment 7
Get the vinylformic acid-copolymer of poly lactic acid (base-material 2) of 1.2%KLE-333 and 72 %, KLE-333 is joined rapid stirring in base-material 2, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes; Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 21.8 %, TiO 2with SiO 2(≤40nm) gets 1.5% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add 1%KF-64 and 1%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y2).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, the results are shown in Table 1, Fig. 5-6.
Embodiment 8
Get the vinylformic acid-copolymer of poly lactic acid (base-material 3) of 1.4%KLE-333 and 66 %, KLE-333 is joined rapid stirring in base-material 3, mix, then base-material is placed in colloidal mill grinding 10 ~ 30 minutes; Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 26.6 %, TiO 2with SiO 2(≤40nm) gets 2% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add 1.5%KF-64 and 0.5%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y3).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, result is respectively in table 1, Fig. 5-6.
Embodiment 9
Get the vinylformic acid-copolymer of poly lactic acid (base-material 4) of 1.5%KLE-333 and 65 %, KLE-333 is joined rapid stirring in base-material 4, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes; Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 29 %, TiO 2with SiO 2(≤40nm) gets 1% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add 1.5%KF-64 and 1%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y4).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, result is respectively in table 1, Fig. 5-6.
Embodiment 10
Get the vinylformic acid-copolymer of poly lactic acid (base-material 5) of 1 %KLE-333 and 65 %, KLE-333 is joined rapid stirring in base-material 5, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes; Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 30 %, TiO 2with SiO 2(≤40nm) gets 1% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add 1.2%KF-64 and 0.8%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y5).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, result is respectively in table 1, Fig. 5-6.
Embodiment 11
Get the vinylformic acid-copolymer of poly lactic acid (base-material 6) of 1.2%KLE-333 and 71%, KLE-333 is joined rapid stirring in base-material 6, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes; 21.8%, TiO got by mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) 2with SiO 2(≤40nm) gets 2% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add 1%KF-64 and 1%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y6).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, result is respectively in table 1, Fig. 5-6.
Embodiment 12
Get the vinylformic acid-copolymer of poly lactic acid (base-material 7) of 1.5%KLE-333 and 85 %, KLE-333 is joined rapid stirring in base-material 7, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes; Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 10 %, TiO 2with SiO 2(≤40nm) gets 1% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add 1%KF-64 and 0.5%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y7).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, result is respectively in table 1, Fig. 5-6.
Embodiment 13
Get the vinylformic acid-copolymer of poly lactic acid (base-material 8) of 1%KLE-333 and 80 %, KLE-333 is joined rapid stirring in base-material 8, mix, be then placed in colloidal mill grinding 10 ~ 30 minutes; Mixed solvent (mass ratio be the butylacetate of 1:2:3, the mixing of butanols, dimethylbenzene) gets 14 %, TiO 2with SiO 2(≤40nm) gets 1.5% simultaneously, is disperseed with mixed solvent, then joins in colloidal mill, grinds 2 ~ 4 hours; Finally add appropriate 1%KF-64 and 1%KSL-52, grind discharging in 1 ~ 3 hour, obtained composite ocean antifouling paint (Y8).Analyze the fundamental property of film, antibacterial and real extra large link plate effect, result is respectively in table 1, Fig. 5-6.
Having prepared a certain amount of artificial seawater, is then that film prepared by ground with steel plate, they is placed in artificial seawater environment to simulate real extra large panel experiment, checks their stability finally by measurement hardness.
the fundamental property of film prepared by table 1 different ingredients composite ocean antifouling paint
As seen from Table 1, the film that generates of Y1-Y8 level and smooth, without be full of cracks or trickle be full of cracks; Time of drying is substantially between 35 ~ 45 hours; Hardness is up to standard; Sticking power is substantially all identical, is all between 0 ~ 1 grade.
The circle footpath antibacterial to intestinal bacteria to different coating (Y1-Y8) is analyzed, and they all have fungistatic effect as can be seen from Figure 5, and effectiveness ranking is: Y5 → Y2 → Y1 → Y4 → Y7 → Y8 → Y6 → Y3.
Fig. 6 is the concrete change of the film of different ingredients when soaking 6 months in artificial seawater.The effect that painting Y1-Y8 shows is desirable, only occurs occurring bubble on a small quantity, show lasting sticking power, and top layer also keeps essentially smooth state to ground always.

Claims (9)

1. a marine antifouling coating, is characterized in that each composition weight percentage composition is:
Multipolymer 65% ~ 85%
Solvent 10% ~ 30%
Nano-meter SiO_2 21% ~ 2%
Nano-TiO 21% ~ 2%
KLE-333 1%～1.5%
KF-64 1%～2%
KSL-52 0.5%～1%
Described multipolymer is selected from vinylformic acid-copolymer of poly lactic acid, vinylformic acid-PGA multipolymer, vinylformic acid-poly-own lactide copolymers, vinylformic acid-poly (glycolide-lactide) multipolymer, vinylformic acid-poly-third own lactide copolymers;
Described solvent is the mixed solvent of ester class, alcohols, benzene-like compounds, and wherein ester compound is selected from butylacetate, ethyl acetate, and alcohol compound is selected from butanols, ethanol, and benzene-like compounds is selected from dimethylbenzene, toluene.
2. marine antifouling coating according to claim 1, is characterized in that: in described solvent, the mass ratio of ester class, alcohols, benzene-like compounds is 1:2:3 ~ 1:4:6.
3. marine antifouling coating according to claim 1, is characterized in that described multipolymer obtains as follows,
(1) lactide is mixed with hydroxyethyl methylacrylate, add the sub-tin of octoate catalyst, first heating and melting, be warming up to 100 ~ 120 DEG C of reactions again, dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains hydroxyethyl methylacrylate-polylactide polymeric monomer, and described lactide is selected from glycollide, rac-Lactide, own lactide;
(2) in hydroxyethyl methylacrylate-polylactide polymeric monomer and solvent, add methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, then add initiator, be obtained by reacting multipolymer at 45 ~ 85 DEG C; Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-polylactide polymeric monomer is function monomer.
4. marine antifouling coating according to claim 3, is characterized in that: the lactide described in step (1) and the mol ratio of hydroxyethyl methylacrylate are 15 ~ 1.
5. marine antifouling coating according to claim 3, is characterized in that: the initiator described in step (2) is selected from Diisopropyl azodicarboxylate, benzoyl peroxide.
6. marine antifouling coating according to claim 3, it is characterized in that: the soft monomer massfraction described in step (2) is 20 ~ 70%, hard monomer massfraction is 20 ~ 70%, and function monomer massfraction is the mass ratio of 10 ~ 20%, three kinds of monomers and solvent is 0.2 ~ 5.
7. the preparation method of marine antifouling coating described in claim 1, is characterized in that:
(1) lactide is mixed with hydroxyethyl methylacrylate, add the sub-tin of octoate catalyst, first heating and melting, be warming up to 100 ~ 120 DEG C of reactions again, dissolve with chloroform, methyl alcohol separates out precipitation, and drying obtains hydroxyethyl methylacrylate-polylactide polymeric monomer, and described lactide is selected from glycollide, rac-Lactide, own lactide;
(2) in hydroxyethyl methylacrylate-polylactide polymeric monomer and solvent, add methyl methacrylate, vinylbenzene, ethyl propenoate, butyl acrylate, hydroxyethyl acrylate monomers, then add initiator, be obtained by reacting multipolymer at 45 ~ 85 DEG C; Wherein, methyl methacrylate, vinylbenzene are hard monomer, and ethyl propenoate, butyl acrylate are soft monomer, and Hydroxyethyl acrylate, hydroxyethyl methylacrylate-polylactide polymeric monomer is function monomer;
(3) by multipolymer and solvent, Nano-meter SiO_2 2, stain control agent nano-TiO 2and KLE-333, KF-64, KSL-52 mixed grinding obtains marine antifouling coating.
8. the preparation method of marine antifouling coating according to claim 7, is characterized in that: the lactide described in step (1) and the mol ratio of hydroxyethyl methylacrylate are 15 ~ 1.
9. the preparation method of marine antifouling coating according to claim 7, it is characterized in that: the soft monomer massfraction described in step (2) is 20 ~ 70%, hard monomer massfraction is 20 ~ 70%, function monomer massfraction is 10 ~ 20%, the mass ratio of three kinds of monomers and solvent is 0.2 ~ 5, and initiator is selected from Diisopropyl azodicarboxylate, benzoyl peroxide.
CN201510002504.1A 2015-01-06 2015-01-06 Biodegradable antifouling marine coating and preparation method thereof Expired - Fee Related CN104592851B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106752935A (en) * 2016-12-04 2017-05-31 西北大学 A kind of low surface energy antifouling coating for seas of polishing certainly and preparation method thereof
CN107446402A (en) * 2017-08-30 2017-12-08 深圳先进技术研究院 Charge transfer type autoxidation reduced nano material, its preparation method and application and marine antifoulant and marine antifouling coating
CN109180885A (en) * 2018-08-03 2019-01-11 常州大学 A kind of preparation method of water polyacrylic acid lotion

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032301A (en) * 2008-08-08 2011-02-17 Nippon Bee Chemical Co Ltd Lactic acid-based polymer and use thereof
CN102203195A (en) * 2008-10-31 2011-09-28 帝斯曼知识产权资产管理有限公司 Antifouling coating composition comprising functionalized nanoparticules
CN102532559A (en) * 2011-12-30 2012-07-04 中国船舶重工集团公司第七二五研究所 Comb type acrylic resin of lateral chain grafting polyester resin and preparation method and application thereof
CN102731745A (en) * 2012-06-29 2012-10-17 华南理工大学 Degradation type marine anti-fouling material, preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032301A (en) * 2008-08-08 2011-02-17 Nippon Bee Chemical Co Ltd Lactic acid-based polymer and use thereof
CN102203195A (en) * 2008-10-31 2011-09-28 帝斯曼知识产权资产管理有限公司 Antifouling coating composition comprising functionalized nanoparticules
CN102532559A (en) * 2011-12-30 2012-07-04 中国船舶重工集团公司第七二五研究所 Comb type acrylic resin of lateral chain grafting polyester resin and preparation method and application thereof
CN102731745A (en) * 2012-06-29 2012-10-17 华南理工大学 Degradation type marine anti-fouling material, preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KIYOAKI ISHIMIOTO等: "Biobased Polymers: Synthesis of Graft Copolymers and Comb Polymers Using Lactic Acid Macromonomer and Properties of the Product Polymers", 《BIOMACROMOLECULES》 *
沈丽霞: "纳米材料在海洋无毒防污涂料中的应用", 《电镀与精饰》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106752935A (en) * 2016-12-04 2017-05-31 西北大学 A kind of low surface energy antifouling coating for seas of polishing certainly and preparation method thereof
CN107446402A (en) * 2017-08-30 2017-12-08 深圳先进技术研究院 Charge transfer type autoxidation reduced nano material, its preparation method and application and marine antifoulant and marine antifouling coating
CN109180885A (en) * 2018-08-03 2019-01-11 常州大学 A kind of preparation method of water polyacrylic acid lotion
CN109180885B (en) * 2018-08-03 2020-11-24 常州大学 Preparation method of water-based polyacrylate emulsion

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