CN102875765A - Method for preparing organic silicon and fluorine low surface energy antifouling coating agent with nano microstructure - Google Patents
Method for preparing organic silicon and fluorine low surface energy antifouling coating agent with nano microstructure Download PDFInfo
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Abstract
The invention relates to a method for preparing an organic silicon and fluorine low surface energy antifouling coating agent with a nano microstructure. The method comprises the following steps of: preparing organic fluorine modified polyacrylate well compounded with inorganic nanoparticles by an in-situ polymerization method; compounding and crosslinking the organic fluorine modified polyacrylate and organic silicon modified polyurethane terminated by isocyanate; and forming the organic silicon and fluorine low surface energy antifouling coating agent with the nano microstructure on the surface of a low surface energy coating by using the filling inorganic nanoparticles during curing and film forming. The surface energy of the antifouling coating agent is 5 to 10 mN/m, the contact angle of the antifouling coating agent and water is 110 to 130 degrees, the pencil hardness reaches 5 to 6H, the adhesion is grade 1, the shearing strength is 8 to 10 MPa, and the impact strength is 60 to 80 kg.cm. The coating agent is low in surface energy, the hydrophobicity of the antifouling coating can be obviously improved by the nano microstructure, the contact area of the surface of the coating and an attachment can be reduced to the maximum extent, and the antifouling performance of the coating is effectively improved.
Description
Technical field
The invention belongs to the chemistry painting industry field, be specifically related to the antifouling paint technology, relate in particular to the organic silicon-fluorine low surface energy antifouling coating agent preparation method with nano surface microstructure.
Background technology
As everyone knows, marine fouling organism brings very big harm to ship and maritime facilities.Various countries all are devoted to the research and development of marine anti-pollution for many years, and have obtained significant achievement.Yet, at present along with the growing interest of international community to environmental problem, the use because the release toxic substance is under an embargo of traditional marine antifouling coating.Thereby the development work of people's Efforts To Develop nontoxic antifouling paint, wherein low surface energy anti-fouling paint becomes one of research hot topic.
Low surface energy anti-fouling paint also claims not glue antifouling paint, usually is comprised of fluorocarbon resin, silicone resin, polytetrafluorethylepowder powder and special modified material etc., and its maximum characteristics are that not toxic material and surface energy are very low.Low surface energy anti-fouling paint is based on the physical action of coating surface, does not have the release of toxicant, can play long-term antifouling effect, and more common low surface energy anti-fouling paint peculiar to vessel mainly can be divided into organosilicon series and organic fluorine series two large classes at present.Organosilicon polymer has the Si-O skeleton and has unique performance, and such as low surface energy, thermostability lower glass transition temperatures etc., but that organosilicon series compound was filmed was soft, poor adhesive force, recoatability are poor.And organo-fluorine polymer has exactly remedied these defectives, also has simultaneously low surface energy characteristic and excellent weathering resistance, erosion resistance, high thermal resistance and chemical proofing.Therefore, organosilicon polymer and organo-fluorine polymer are carried out crosslinking curing prepare new low surface energy polymeric, had both common advantages concurrently.From environmental angle, the development of this coating and exploitation will become the main flow of following marine antifouling coating product development, because its fully not toxic material.In addition, be subject to the enlightenment of the antifouling mode of nature biotechnology, such as lotus leaf, shark skin etc., the approach that people begin the development of new antifouling paint always changes surfaceness and surface microstructure when reducing surface energy.
At present, really obtain research that the low surface energy organic silicon fluorine antifouling paint with nano-micro structure that Industry Promotion uses and coating thereof reach the international coatings industry at home also seldom, at present both at home and abroad also not about the patent application of low surface energy organic silicon fluorine antifouling coating with nano-micro structure and preparation method thereof.
Summary of the invention
The problem of first aspect to be solved by this invention is to overcome the defective of prior art, and a kind of good antifouling effect is provided, the preparation method of the organic silicon-fluorine low surface energy antifouling coating with nano-micro structure of nontoxic low surface energy.
The problem of second aspect to be solved by this invention is to provide a kind of organic silicon-fluorine low surface energy antifouling coating with nano-micro structure.
In order to solve the technical problem of above-mentioned first aspect, technical scheme of the present invention is: have the preparation method of the organic silicon-fluorine low surface energy antifouling coating of nano-micro structure, can be prepared by following step method:
(1) taking by weighing inorganic nano-particle is scattered in the acetone, vigorous stirring 10 ~ 60 minutes, adding hydrochloric acid soln adjusting PH is 1-3, at the uniform velocity drip the acetone soln that concentration is the coupling agent of 0.005 ~ 0.025g/mL after stirring, the backflow stirring reaction is 8 ~ 36 hours under 50 ~ 90 ℃ of conditions, takes out centrifugation, 90 ~ 110 ℃ of lower vacuum-dryings are more than 12 hours, obtain the inorganic nano-particle of coupling agent treatment, wherein, the weight ratio of the acetone soln of described inorganic nano-particle, coupling agent is 1:1 ~ 5;
(2) with the inorganic nano-particle ultra-sonic dispersion of above-mentioned coupling agent treatment in organic mixed solvent, under nitrogen protection, to electric mixer is housed, reflux condensing tube, add initiator in the there-necked flask of constant pressure funnel, temperature is elevated to 60 ~ 80 ℃ under the agitation condition, at the uniform velocity drip soft monomer, the mixed monomer solution of hard monomer and hydroxy acryl acid ester monomer, mixed monomer solution dropwises in 1.5 ~ 2.5h, the control temperature of reaction is constant, continue at the uniform velocity to drip fluorochemical monomer and initiator, fluorochemical monomer and initiator dropwise in 1.5 ~ 2.5h, be warming up to 80 ~ 90 ℃ and continue back flow reaction 2 ~ 4h, stopped heating, be cooled to below 60 ℃, namely obtain the organic fluorine modified polyacrylate that a kind of inorganic nano-particle is filled after the filtration, wherein, the inorganic nano-particle of described coupling agent treatment, initiator, soft monomer, hard monomer, hydroxy acryl acid ester monomer, the weight ratio of fluorochemical monomer and initiator is 5 ~ 15:0.03 ~ 1.5:10 ~ 30:10 ~ 60:5 ~ 20:5 ~ 20:0.015 ~ 0.075;
(3) under nitrogen protection, to electric mixer is housed, reflux condensing tube, add vulcabond in the there-necked flask of constant pressure funnel, polyester polyol, organotin catalysts and organic mixed solvent, keep 50 ~ 70 ℃ of temperature, at the uniform velocity drip hydroxy silicon oil, hydroxy silicon oil dropwises in 1 ~ 2h, after dropwising, be warming up to 70 ~ 90 ℃ and continue stirring reaction 2 ~ 4h, make reaction be tending towards finishing, namely obtain a kind of isocyanate-terminated organic silicon modified polyurethane, wherein vulcabond, polyester polyol, organotin catalysts, the weight ratio of organic mixed solvent and hydroxy silicon oil is 10 ~ 25:10 ~ 25:0.025 ~ 0.25:25 ~ 75:5 ~ 15;
(4) the organic fluorine modified polyacrylate solution that the inorganic nano-particle that step (2) is obtained is filled, isocyanate-terminated organic silicon modified polyurethane, chainextender, the organotin catalysts that step (3) obtains mix 50 ~ 90:60 ~ 100:1 ~ 10:0.05 ~ 0.5 by weight proportion, temperature is elevated to 60 ~ 90 ℃, stirring reaction 2 ~ 4h namely obtains a kind of organic silicon-fluorine low surface energy antifouling coating agent with nano-micro structure.
Preferably, inorganic nano-particle in the described step (1) is one or more mixture in nano silicon, nano titanium oxide, the nano ferriferrous oxide.
Preferably, coupling agent in the described step (1) is one or more the mixture in γ-(methacryloxy) propyl trimethoxy silicane, γ-(methacryloxy) propyl-triethoxysilicane, γ-(methacryloxy) propyl group three isopropoxy silane.
Preferably, organic mixed solvent is that non-polar solvent and polar solvent form in the described step (2), the volume ratio of non-polar solvent and polar solvent is 1:1 ~ 4:1, non-polar solvent is a kind of in toluene, the dimethylbenzene, and polar solvent is a kind of in dioxane, ethyl acetate, butylacetate, butanone, the pimelinketone.
Preferably, soft monomer in the described step (2) is one or more mixture in butyl acrylate, vinylformic acid heptyl ester, Octyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems and the vinylformic acid certain herbaceous plants with big flowers ester.
Preferably, hard monomer in the described step (2) is one or more mixture in methyl methacrylate, vinylbenzene or the vinyl cyanide.
Preferably, hydroxy acryl acid ester monomer in the described step (2) is one or more mixture in (methyl) senecioate-hydroxyl ethyl ester, (methyl) senecioate-hydroxypropyl acrylate, (methyl) glycidyl acrylate.
Preferably, fluorochemical monomer in the described step (2) is one or more the mixture in (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) vinylformic acid ten trifluoro monooctyl esters, 2-(perfluoro hexyl) the ethyl-methyl acrylate.
Preferably, initiator in described step (2) and (3), a kind of in benzoyl peroxide, the Diisopropyl azodicarboxylate.
Preferably, organotin catalysts in the described step (3) is one or more the mixture in dibutyl tin laurate, two lauric acid dioctyl tins, dibutyltin diacetate, the stannous octoate.
Preferably, the chemical structural formula of the middle hydroxy silicon oil of described step (3) is as shown in Equation 1:
Formula 1
Wherein, R is C
1-C
5The straight or branched alkyl, n is the integer of 10-30.
In order to solve the technical problem of above-mentioned second aspect, provide a kind of organic silicon-fluorine low surface energy antifouling coating with nano-micro structure.
The present invention proposes has organic silicon-fluorine low surface energy antifouling coating agent of nano-micro structure and preparation method thereof, the method at first adopts situ aggregation method to prepare and the compound good organic fluorine modified polyacrylate of inorganic nano-particle, again it and isocyanate-terminated organic silicon modified polyurethane are carried out composite crosslinking, in film-forming, utilize the inorganic nano-particle of filling to form a kind of organic silicon-fluorine low surface energy antifouling coating with nano-micro structure on the low surface energy coat surface.
Advantage of the present invention is: 1. not only surface energy is lower in the organic silicon-fluorine low surface energy antifouling coating agent with nano-micro structure of the present invention, and the nano-micro structure on coating-forming agent surface can significantly improve again the hydrophobic nature of coating, effectively reduce the contact area of coatingsurface and dirt settling, good antifouling effect is a kind of wide spectrum, the agent of efficient, nontoxic low surface energy antifouling coating; 2. compare with common organic silicon-fluorine low surface energy anti-fouling paint, the surface energy that utilizes the organic silicon-fluorine low surface energy antifouling coating with nano-micro structure that the present invention prepares be 5 ~ 10mN/m, with water contact angle be 110 ~ 130 °, pencil hardness to reach 5H ~ 6H, sticking power be that 1 grade, shearing resistance are 8 ~ 10MPa, resistance to impact shock 60 ~ 80kgcm, obvious advantage is being arranged aspect hardness of film, sticking power, low surface energy, weathering resistance, erosion resistance, high thermal resistance and the chemical proofing; The advantages such as 3. preparation method of the present invention has that simple process is convenient, quality product is high, input-output ratio is high, with low cost and application prospect is extensive; the product that utilizes the present invention to prepare is wide spectrum of new generation, efficient, Non-Toxic Low Surface Energy Antifouling Coatings product; industrial applications has a extensive future, and can be applicable to the soiling protective in the fields such as harbour, buoy, fishing net, boats and ships and extra large lower basin.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples:
Fig. 1 is the preparation flow figure with organic silicon-fluorine low surface energy antifouling coating agent of nano-micro structure.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Describe the present invention in detail below in conjunction with embodiment, should be appreciated that described herein giving an example only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Taking by weighing the 15g nano silicon dioxide particles is scattered in the 125mL acetone, vigorous stirring 25 minutes, add 2mL hydrochloric acid soln (concentration is 1mol/L) and 8mL water, at the uniform velocity drip the acetone soln of the γ that 20g concentration is 0.015g/mL-(methacryloxy) propyl trimethoxy silicane after stirring, the backflow stirring reaction is 24 hours under 60 ℃ of conditions, take out centrifugation, 100 ℃ of lower vacuum-dryings obtained the nano silicon dioxide particles of coupling agent treatment more than 12 hours.
With the nano silicon dioxide particles ultra-sonic dispersion of the above-mentioned coupling agent treatment of 7.5g in the mixed solvent (volume ratio of toluene and butylacetate is 2:1) of 15mL toluene/butylacetate; under nitrogen protection; to electric mixer is housed; reflux condensing tube; add the 0.09g benzoyl peroxide in the there-necked flask of constant pressure funnel; temperature is elevated to 70 ℃ under the agitation condition; at the uniform velocity drip the 25g butyl acrylate; the 10g methyl methacrylate; the mixed monomer solution of 15g vinylbenzene and 12g methacrylic acid-beta-hydroxy ethyl ester; mixed monomer solution dropwises in 2h; the control temperature of reaction is constant; continue at the uniform velocity to drip 10g methacrylic acid ten trifluoro monooctyl esters and 0.035g benzoyl peroxide; methacrylic acid ten trifluoro monooctyl esters and benzoyl peroxide dropwise in 2h; be warming up to 85 ℃ and continue back flow reaction 2.5h; stopped heating; be cooled to below 60 ℃, namely obtain the organic fluorine modified polyacrylate that a kind of nano-silicon dioxide particle is filled after the filtration.
Under nitrogen protection; the mixed solvent (volume ratio of toluene and butylacetate is 2:1) that adds the different Buddhist ketone of 18g vulcabond, 15g polyester polyol, 0.05g dibutyl tin dilaurate and 25mL toluene/butylacetate in the there-necked flask that electric mixer, reflux condensing tube, constant pressure funnel are housed; keep temperature 60 C, at the uniform velocity drip 12.5g hydroxy silicon oil (HOC
2H
5-(Si (CH
3)
2O-)
18-C
2H
5OH), hydroxy silicon oil dropwises in 1.5h, after dropwising, is warming up to 80 ℃ and continues stirring reaction 2.5h, makes reaction be tending towards finishing, and namely obtains a kind of isocyanate-terminated organic silicon modified polyurethane.
The organic fluorine modified polyacrylate that above-mentioned nano-silicon dioxide particle is filled, the organic silicon modified polyurethane of above-mentioned cyanate end-blocking, quadrol, dibutyl tin dilaurate by weight proportion 60:80:6:0.1 mix, temperature is elevated to 85 ℃, stirring reaction 3h namely obtains a kind of organic silicon-fluorine low surface energy antifouling coating agent of nano-micro structure.
At last organic silicon-fluorine low surface energy antifouling coating obtained above agent being coated on metal iron block surface, is to dry 2h under the condition of 95 ° of C in temperature, namely obtains a kind of organic silicon-fluorine low surface energy antifouling coating with nano-micro structure.
Embodiment 2
Identical with embodiment 1, but the consumption of the nano silicon dioxide particles of step (2) coupling agent treatment becomes 12.5g by 7.5g, and other are constant.
Embodiment 3
Identical with embodiment 1, but step (2) methacrylic acid ten trifluoro monooctyl esters become methacrylic acid octafluoro pentyl ester, its consumption becomes 15g by 10g, and other are constant.
Embodiment 4
Identical with embodiment 1, but the consumption of step (3) hydroxy silicon oil becomes 10g by 12.5g, and other are constant.
Embodiment 5
Identical with embodiment 1, but the part by weight of the organic fluorine modified polyacrylate that the above-mentioned nano-silicon dioxide particle of step (4) is filled, the organic silicon modified polyurethane of above-mentioned cyanate end-blocking, quadrol, dibutyl tin dilaurate becomes 50:90:8:0.25 by 60:80:6:0.1, and other are constant.
Table 1 is surface energy, water contact angle and the conventional mechanical property etc. with organic silicon-fluorine low surface energy antifouling coating agent of nano-micro structure of the present invention.
Table 1 has the salient features of the organic silicon-fluorine low surface energy antifouling coating agent of nano-micro structure
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (12)
1. have the preparation method of the organic silicon-fluorine low surface energy antifouling coating of nano-micro structure, prepared by following step method:
(1) taking by weighing inorganic nano-particle is scattered in the acetone, vigorous stirring 10 ~ 60 minutes, adding hydrochloric acid soln adjusting PH is 1-3, at the uniform velocity drip the acetone soln that concentration is the coupling agent of 0.005 ~ 0.025g/mL after stirring, the backflow stirring reaction is 8 ~ 36 hours under 50 ~ 90 ℃ of conditions, takes out centrifugation, 90 ~ 110 ℃ of lower vacuum-dryings are more than 12 hours, obtain the inorganic nano-particle of coupling agent treatment, wherein, the weight ratio of the acetone soln of described inorganic nano-particle, coupling agent is 1:1 ~ 5;
(2) with the inorganic nano-particle ultra-sonic dispersion of above-mentioned coupling agent treatment in organic mixed solvent, under nitrogen protection, to electric mixer is housed, reflux condensing tube, add initiator in the there-necked flask of constant pressure funnel, temperature is elevated to 60 ~ 80 ℃ under the agitation condition, at the uniform velocity drip soft monomer, the mixed monomer solution of hard monomer and hydroxy acryl acid ester monomer, mixed monomer solution dropwises in 1.5 ~ 2.5h, the control temperature of reaction is constant, continue at the uniform velocity to drip fluorochemical monomer and initiator, fluorochemical monomer and initiator dropwise in 1.5 ~ 2.5h, be warming up to 80 ~ 90 ℃ and continue back flow reaction 2 ~ 4h, stopped heating, be cooled to below 60 ℃, namely obtain the organic fluorine modified polyacrylate that a kind of inorganic nano-particle is filled after the filtration, wherein, the inorganic nano-particle of described coupling agent treatment, initiator, soft monomer, hard monomer, hydroxy acryl acid ester monomer, the weight ratio of fluorochemical monomer and initiator is 5 ~ 15:0.03 ~ 1.5:10 ~ 30:10 ~ 60:5 ~ 20:5 ~ 20:0.015 ~ 0.075;
(3) under nitrogen protection, to electric mixer is housed, reflux condensing tube, add vulcabond in the there-necked flask of constant pressure funnel, polyester polyol, organotin catalysts and organic mixed solvent, keep 50 ~ 70 ℃ of temperature, at the uniform velocity drip hydroxy silicon oil, hydroxy silicon oil dropwises in 1 ~ 2h, after dropwising, be warming up to 70 ~ 90 ℃ and continue stirring reaction 2 ~ 4h, make reaction be tending towards finishing, namely obtain a kind of isocyanate-terminated organic silicon modified polyurethane, wherein vulcabond, polyester polyol, organotin catalysts, the weight ratio of organic mixed solvent and hydroxy silicon oil is 10 ~ 25:10 ~ 25:0.025 ~ 0.25:25 ~ 75:5 ~ 15;
(4) the organic fluorine modified polyacrylate solution that the inorganic nano-particle that step (2) is obtained is filled, isocyanate-terminated organic silicon modified polyurethane, chainextender, the organotin catalysts that step (3) obtains mix 50 ~ 90:60 ~ 100:1 ~ 10:0.05 ~ 0.5 by weight proportion, temperature is elevated to 60 ~ 90 ℃, stirring reaction 2 ~ 4h namely obtains a kind of organic silicon-fluorine low surface energy antifouling coating agent with nano-micro structure.
2. preparation method according to claim 1 is characterized in that, inorganic nano-particle in the described step (1) is one or more mixture in nano silicon, nano titanium oxide, the nano ferriferrous oxide.
3. preparation method according to claim 1, it is characterized in that, coupling agent in the described step (1) is one or more the mixture in γ-(methacryloxy) propyl trimethoxy silicane, γ-(methacryloxy) propyl-triethoxysilicane, γ-(methacryloxy) propyl group three isopropoxy silane.
4. preparation method according to claim 1, it is characterized in that, organic mixed solvent is that non-polar solvent and polar solvent form in the described step (2), the volume ratio of non-polar solvent and polar solvent is 1:1 ~ 4:1, non-polar solvent is a kind of in toluene, the dimethylbenzene, and polar solvent is a kind of in dioxane, ethyl acetate, butylacetate, butanone, the pimelinketone.
5. preparation method according to claim 1 is characterized in that, soft monomer in the described step (2) is one or more mixture in butyl acrylate, vinylformic acid heptyl ester, Octyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems and the vinylformic acid certain herbaceous plants with big flowers ester.
6. preparation method according to claim 1 is characterized in that, hard monomer in the described step (2) is one or more mixture in methyl methacrylate, vinylbenzene or the vinyl cyanide.
7. preparation method according to claim 1, it is characterized in that, hydroxy acryl acid ester monomer in the described step (2) is one or more mixture in (methyl) senecioate-hydroxyl ethyl ester, (methyl) senecioate-hydroxypropyl acrylate, (methyl) glycidyl acrylate.
8. preparation method according to claim 1, it is characterized in that, fluorochemical monomer in the described step (2) is one or more the mixture in (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) vinylformic acid ten trifluoro monooctyl esters, 2-(perfluoro hexyl) the ethyl-methyl acrylate.
9. preparation method according to claim 1 is characterized in that, initiator in described step (2) and (3), a kind of in benzoyl peroxide, the Diisopropyl azodicarboxylate.
10. preparation method according to claim 1, it is characterized in that, organotin catalysts in the described step (3) is one or more the mixture in dibutyl tin laurate, two lauric acid dioctyl tins, dibutyltin diacetate, the stannous octoate.
11. preparation method according to claim 1 is characterized in that, the chemical structural formula of hydroxy silicon oil is as shown in Equation 1 in the described step (3):
Formula 1
Wherein, R is C
1-C
5The straight or branched alkyl, n is the integer of 10-30.
12. a kind of organic silicon-fluorine low surface energy antifouling coating with nano-micro structure that preparation method according to claim 1-11 obtains.
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