CN102977744A - Nano-composite marine anti-fouling coating material and preparation method thereof - Google Patents
Nano-composite marine anti-fouling coating material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano-composite marine anti-fouling coating material and a preparation method of the nano-composite marine anti-fouling coating material. Nano-ZnO with an anti-bacterial function is taken as a filler to be added into epoxy resin by means of surface modification to prepare the nano-composite anti-fouling coating material with bacterium-resistant performance and corrosion-resistant performance. The invention aims at overcoming the defects in the prior art, and aiming at the practical difficulty of the current anti-fouling coating material, the nano-ZnO and the epoxy resin are composited with each other, and the good characteristics of the nano-ZnO and the epoxy resin are originally combined together, so that the novel anti-fouling coating material with the anti-corrosion performance and the anti-fouling performance can be developed.
Description
Technical field
The present invention relates to a kind of marine metal member antifouling paint and preparation method thereof, more particularly, relate to nano combined ocean anti-pollution paint and preparation method thereof.
Background technology
Biodeterioration is the significant problem that perplexs for a long time the marine ship industrial development; Result of study shows that the marime fouling that marine organisms cause in the boats and ships surface attachment can increase roughness, the reduction speed of a ship or plane, the increase fuel consumption of hull surface, and will cause the consumption of substantial contribution and manpower for later stage hull fouling cleaning.According to statistics, biodeterioration can increase the fuel oil consumption of steamer 40%; In addition, the financial loss that China causes because of corrosion every year reaches 90,000,000,000 yuans at least, and marine corrosion accounts for more than 30%, wherein adheres to relevant material corrosion destruction with marine microorganism and accounts for about 30% of ocean material corrosion total amount.If can solve or alleviate the hull fouling problem, will bring great economy and social benefit.Knowhow according to human centuries finds that applying coatings is easy and efficient antifouling strategy.Therefore, the excellent anti-pollution paint of exploitation is the emphasis of ocean protection industrial development.
Antifouling paint is commonly referred to ship bottom anti-fouling paint or is called for short antifouling varnish, be prevent that marine attaching organism is stained, keep bright and clean, the smooth a kind of tailor-(made) coating of hull bottom (Liu Dengliang, coating process, Beijing: Chemical Industry Press, 2010:1166).Marine antifouling coating has successively experienced two developmental stage of toxic material type and nontoxic type, has greatly promoted the fast development of the industries such as sea transport, sea farming.Traditional antifouling paint, normal Red copper oxide, organotin, organoaluminum, organoarsenic, the organotins etc. of adopting are the poison material, are the composition of acrylic polymers, Red copper oxide, organotin such as Britain International Paint company disclosed antifouling paint in European patent EP 0051930.
Red copper oxide is one of antifouling pigment the earliest, itself is red and since this limits of color the use range of Red copper oxide, so, also have some researchists just to replace with white cuprous thiocyanate.But Red copper oxide has extremely strong toxicity, and ocean environment and human survival are had disadvantageous effect, so it has also little by little withdrawed from the arena of history.
In the organotin antifouling paint, the most typical organo-tin compound is tributyl tin (TBT).Since the sixties in 20th century as the sterilant in the anti-fouling ship paint since, for shipping-trade has been brought huge profit.But TBT is the very strong material of a kind of toxicity, and it also constitutes a threat to nontarget organism when driving away or killing such as fouling organisms such as pipe worm, barnacle, mussel and algae.TBT can make marine organisms cause death or teratogenesis, destroy the eubiosis, make cultivation and the fish industry underproduction, can also be at economic fish and shellfish body accumulation, indirectly human health is produced harm, international community just banned use of coating (L.D.Chambers, K.R.Stokes, the F.C.Walsh that contains TBT from 2003, et al.Modernapproaches to marine antifouling coatings, Surf.Coat.Technol., 2006,201:3642-3652).
For the rate of release of controlling the poison material, the resistance that reduces the steamer surface, people have developed certainly polishing type antifouling paint.The working mechanism of this antifouling paint is: when coating is dipped in seawater, hydrolysis reaction occurs, discharge the poison material and be dissolved among the seawater, the paint film hydrolysis reaction constantly continues, exposes new surface under the effect of current, and therefore, poison material rate of release is very steady.Fall in the position flow action owing to film little and hydrolysis rate is slow, thereby it is increasingly smooth to cause filming.But contain highly toxic heavy metal ion or hypotoxicity in the type coating but the less metal ion (CaoS of anti-soil scope, Wang J D, Chen H S, et al.Progress of marine biofouling and antifouling technologies, Chinese Sci Bull., 2011,56:598-612), its application is also greatly limited.
Contain the coating of heavy metal oxide or ion, though higher anti-soil rate is arranged, environment has also been produced huge destruction.Therefore, people develop brand-new nontoxic low surface energy anti-fouling paint in succession.This coating is the low surface energy that utilizes material, makes marine organisms be difficult to adhere in the above, even adhere to also insecurely, easily comes off under current or other External Force Acting.At present, the research of this type of coating mainly concentrated on two fields: a kind of is organic silicon antifouling paint, and another kind is the organic fluorine antifouling paint.Organic silicon antifouling paint worldwide has been applied a lot of patents, such as the relevant curable silicone coating patent of General Electric Corporation's application.Silicoorganic compound have hydrophobicity, and its surface tension is very low, and structure is extremely stable, even in the medium-term and long-term immersion of water, structural changes is also very little, can prevent that marine organisms from adhering to, and good anti-fouling effect is arranged.The production and consumption of fluoropolymer mainly concentrates on the U.S., Japan and the Western European countries, as disclosed from polishing type organic fluorine acrylic polymers among disclosed fluoro-resin, the Japanese Patent Laid-Open 2003-261628 in the US Patent No. 4410363.The shortcoming of such coating is that cost is high, is difficult for construction, and it is soft to film, easily destroyed.
There are many biologies to have born stain resistance in the ocean, this type of biological anti-soil ability of scholar's research is arranged, developed bionical anti-pollution paint.Organism in this coating imitation natural surroundings, from surfacing, surface microstructure, the sink conditions of mimic biology body is to reach antifouling purpose.The antifouling paint a kind of peculiar to vessel that Sweden develops, formed by epoxy resin layer and layer of fibers two portions, apply the extremely short intensive fiber that one deck is filled with static at Resins, epoxy, hull just as dolphin skin with the unstable surface of microvilli, prevent that marine organisms from adhering to and strengthening the resistance to corrosion of hull.This ship coating does not contain toxic substance fully, thereby can not poison marine organisms, can polluted seawater yet.Hull is coated this coating, can keep the higher speed of a ship or plane, and simultaneously, also reach 3～5 years than general coating the work-ing life of this coating.The chemist of Washington, DC university has also simulated microstructure and the mechanism of porpoise skin, has been developed into a kind of novel antifouling coating.This coating is by two kinds of immiscible mixed with polymers, and a kind of is hyperbranched fluoropolymer, and another kind is linear polyvinyl chloride.These two kinds of polymkeric substance solidify by crosslinked, generate a kind of special coating.From the nanometer angle, this paint coatings has coarse surface, simulates the epidermis of dolphin, prevented marine organisms adhere to (Cao Ting, the up-to-date overview of anti-fouling ship paint, China's spark, 2005,6:60-62).Although the research of bionical coating makes some progress, its complicated process of preparation, technical requirements is very high, so its industrialization also needs for some time.
Seawater electrolysis conduction antifouling paint is that Mitsubishi heavy industry Co., Ltd. is in the novel antifouling coating of the exploitation nineties in 20th century.Its principle of work is after shell is coated with layer of cloth, take conductive coating as anode, take shell other and contact with sea water partly as negative electrode.When having weak current to pass through coating surface, near the seawater generation electrolysis can making produces the hypochlorite ion, covers the shell surface, forms protective membrane, so just can effectively prevent halobiontic the adhering to such as microorganism, algae, shellfish.Because the concentration in the concentration ratio tap water of chloranion in seawater that produces is also low, so do not pollute the environment.But this type of Application of coatings can produce many times chloranion, will make the corrosion aggravation of matrix metal.
Have the researchist to find, the seawater pH value of suitable marine organisms survival and reproduction is 7.5 ~ 8.0, and in the stronger or alkaline stronger environment of acidity, marine organisms will be difficult to existence.The concrete structure underwater portion that it is found that new cast does not all have biological attachment reaching in the time in 1 year.Therefore alkaline silicate is added in the coating as nontoxic stain control agent, by increase coating on every side the method for alkalinity of seawater prevent marine life adhere to (Wang Huajin, Wang Xianming, Guan Chaoxiang, Liu Dengxin, Jin Gang, silicate compound anti-fouling paint, CN1248599).But the effective antifouling life of this kind coating is not long, and physicochemical property is poor, with practical application still have a segment distance (Wang Huajin, Wang Xianming, Guan Chaoxiang etc., the development of marine antifouling coating, coatings industry, 2000,3:35-38).Microorganism adhering in the metallic surface normally the secretory product by self be used as medium; and these materials often are biologically active substances; they often can produce degraded under the effect of zymoprotein, therefore have the researchist to give the coating antibiosis performance with proteolytic enzyme as additive.Because enzyme is active affected by environment, such as temperature, pH value etc., so its anti-soil efficient is different under different environment.In addition, enzyme catalysis has very strong specificity, antibacterial range will limited (James A.Callow, MaureenE.Callow.Trends in the development of environmentallyfriendly fouling-resistant marine coatings, Nat.Commun., 2011,2:244).
Making a general survey of current anti-pollution paint current situation, although the anti-soil technology presents the trend of diversification, from the situation of real world applications, mainly is that toxic filler and low surface energy coatings are in the principal status of public economy in world market at present.And this two classes coating exists high environmental risk and expensive shortcoming, and therefore, it is most important to research and develop the novel anti-soil composite coating cheap, that environmental effect is good.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, actual predicament for current anti-pollution paint, nano-ZnO and Resins, epoxy are carried out compound, both good characteristics are organically combined, develop the novel anti-pollution paint that has preservative property and antifouling property concurrently with this.
Technical purpose of the present invention is achieved by following technical proposals:
Nano combined ocean anti-pollution paint and preparation method thereof, the nano-ZnO that will have antibacterial is dosed in the Resins, epoxy by surface modification as filler, has nano combined anti-pollution paint antibiotic, corrosion resisting property thereby prepare.Specifically carry out according to following step:
Step 1, the modification of nano-ZnO
Nano-substance has very high specific surface energy, so often agglomeration can occur, forms larger material aggregation body, and this will seriously affect the performance of nano-substance performance, therefore, need to carry out surface modification to nano-ZnO, and reducing reunites occurs.This patent adopts the chemical method modification, and scheme is as follows:
m
Virahol: mHW201:m
Nano-ZnO=(3 ~ 6): (0.02 ~ 0.05): 1, i.e. the mass ratio of Virahol, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and nano zine oxide
Wherein, HW201 is sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, and the nano-ZnO particle diameter is about 20nm, and the purity of Virahol is 99.9%.
Successively be put in beaker according to the order of Virahol, HW201 the material of above mass ratio, after stirring, add corresponding nano-ZnO, then under room temperature 20-25 degree centigrade with magnetic stirring apparatus high speed 200-400 turn/min stirred 1 hour, again suction filtration, 80 ℃ of lower oven dry, grind.
Step 2, weighing and prepared and diluted agent
Usually the viscosity of Resins, epoxy is higher, is unfavorable for the coating of resin, therefore needs to add thinner and reduces its viscosity as auxiliary reagent.The preparation program of this patent is as follows:
m
E-44: m
651: m
Dimethylbenzene: m
Propyl carbinol=20:(8 ~ 12): (2 ~ 5): (5 ~ 9), the i.e. mass ratio of E-44,651, dimethylbenzene and propyl carbinol
Wherein, E-44 is bisphenol A type epoxy resin, and its average oxirane value is 0.44; 651 solidifying agent belong to the low molecular polyamides solidifying agent, and its amine value is 380 ~ 420; Dimethylbenzene and propyl carbinol are analytical pure.
Coating total amount according to above ratio and plan preparation takes by weighing E-44,651 solidifying agent, dimethylbenzene and propyl carbinol; And with the dimethylbenzene and the butanol solution mixing that weigh up, be mixed with thinner.
Step 3, preparation nano-ZnO slurry
With the nano-ZnO after step 1 modification, add in the dimethylbenzene and propyl carbinol mixed diluent that step 2 configures according to 1% ~ 6% ratio of film forming matter (total mass of Resins, epoxy and solidifying agent), with this as slurry.
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of step 3 preparation is added among the load weighted E-44 of step 2, stir, and then add solidifying agent 651, stir, leave standstill slaking after 30 ~ 40 minutes, can apply.
Material therefor is respectively: E-44 bisphenol A type epoxy resin (Phoenix brand Resins, epoxy, Xingchen Synthetic Matrials Co., Ltd., Nantong), 651 polyamide curing agents (blue star chemical industry Wuxi fine chemistry industry institute), the nano-ZnO particle diameter is about 20nm(Beijing and receives occasion nanometer company), dimethylbenzene, propyl carbinol and Virahol all are analytical pure grade (Tianjin Ke Wei chemical reagents corporations), titanate coupling agent HW-201(Hangzhou boiling point chemical industry company limited).
Utilize the testing tool model: Bruker TENSOR 27 infrared spectrometers carry out the infrared line analysis of product, as shown in Figure 1, and interpretation of result: can find that from spectrogram the 2959cm of titanate coupling agent has appearred in the ZnO after the modification
-1, 2930cm
-1And 2866cm
-1Characteristic peak, these characteristic peaks are-CH
3,-CH
2-, the symmetrical stretching vibration charateristic avsorption band of-CH-; In addition, the 1461cm of coupling agent
-1, 1380cm
-1Characteristic peak also appears among the ZnO after the modification; At 1008cm
-1The P-O-Ti absorption peak occurred, this is the charateristic avsorption band of titanate coupling agent just, and parent peak is positioned at 1029cm
-1The place.More than explanation ZnO Modified success.The research of nano-ZnO was risen the nineties in 20th century, and people are more comprehensive to its performance study, and it has the good characteristics such as ultraviolet absorption ability, piezoelectricity, fluorescence and germ resistance, and in addition, it is to humans, to ocean environment without destruction.Resins, epoxy is existing historical for many years as the matrix of Heavy-duty Coatings In Ocean Chemical Industry, and its excellent performance has obtained the industry abundant affirmation.Therefore, technical solution of the present invention is added nano-ZnO to and is used as marine antifouling coating in the Resins, epoxy, will fully in conjunction with the good characteristic of bi-material, make coating have antifouling and anticorrosion two large characteristics concurrently.Compared with prior art, beneficial effect of the present invention is that nano combined anti-pollution paint not only has higher corrosion resisting property, and has good anti-army bacterium ability.Concrete experimental data is as follows:
(1) antiseptic property test: adopt spread coating respectively with Resins, epoxy, contain unmodified ZnO Resins, epoxy and contain modification ZnO Resins, epoxy and be coated on the Q235 steel disc, coating film thickness is about 300 microns, solidified 3 days under the room temperature, then they are soaked in the 3.5%NaCl solution respectively, behind 48h, 65h, 90h, utilize Verstat 4 electrochemical workstations to measure the electrochemical impedance value of each coating.Behind the corrosion 48h, the impedance of epoxy resin film is 22.4k Ω; Containing unmodified ZnO epoxy resin film is 19.4k Ω; Containing modification ZnO epoxy resin film is 114.9M Ω; Behind the 65h, be respectively 110k Ω, 23.3k Ω and 8.6M Ω; Behind the 90h, be respectively 32k Ω, 26.8k Ω and 701k Ω.Obviously, the impedance spectrum value that contains modification ZnO Resins, epoxy is the highest always, illustrates that it has best corrosion resistance.
(2) anti-microbial property test: in the triangular flask that 3 capacity are 100mL, install the 20mL substratum, then with intestinal bacteria or streptococcus aureus, and modification/unmodified ZnO powder add wherein.Under 37 ℃, 200rpm/min concussion condition, cultivate 24h, and then analyze the absorbance OD600 that determinator is measured bacterium liquid with protein nucleic acid, and then come the bacteriostasis rate of Calculating material with the light absorption value that do not contain the powder body material substratum and the light absorption value that contains powder body material.Experimental result shows, unmodified ZnO powder is respectively 61.61%, 86.46% to the antibiotic rate of intestinal bacteria or streptococcus aureus, and modification ZnO powder is respectively 86.46% and 90.12% to the antibiotic rate of intestinal bacteria or streptococcus aureus, obviously, the anti-microbial property of modification ZnO is better than unmodified ZnO powder.
Description of drawings
The infrared spectrum of the nano combined ocean of Fig. 1 the present invention anti-pollution paint (Bruker TENSOR 27 infrared spectrometers), a are sec.-propyl three (dioctyl phosphoric acid acyloxy) titanate coupling agent, and b is nano-ZnO, and c is modified nano-ZnO
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.Material therefor is respectively E-44 bisphenol A type epoxy resin (Phoenix brand Resins, epoxy, Xingchen Synthetic Matrials Co., Ltd., Nantong), 651 polyamide curing agents (blue star chemical industry Wuxi fine chemistry industry institute), the nano-ZnO particle diameter is about 20nm(Beijing and receives occasion nanometer company), dimethylbenzene, propyl carbinol and Virahol all are analytical pure grade (Tianjin Ke Wei chemical reagents corporations), titanate coupling agent HW-201(Hangzhou boiling point chemical industry company limited).
Embodiment one
Step 1, the modification of nano-ZnO
Virahol, HW201 and nano-ZnO usage ratio are 6:0.04:1, successively be put in beaker according to the order of Virahol, HW201 the material of above mass ratio, after stirring, add corresponding nano-ZnO, then at room temperature use magnetic stirring apparatus high-speed stirring 1 hour, again suction filtration, 80 ℃ times oven dry, grinding.
Step 2, weighing and prepared and diluted agent
Preparation program is such as m
E-44: m
651: m
Dimethylbenzene: m
Propyl carbinol=20:10:3:7
Coating total amount according to above ratio and plan preparation takes by weighing E-44,651 solidifying agent, dimethylbenzene and propyl carbinol; And with the dimethylbenzene and the butanol solution mixing that weigh up, be mixed with thinner.
Step 3, preparation nano-ZnO slurry
With the nano-ZnO after the modification, add in the dimethylbenzene and propyl carbinol mixed diluent that configures according to 3% ratio of film forming matter (total mass of Resins, epoxy and solidifying agent), with this as slurry.
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of preparation is added among the load weighted E-44, stir, and then add solidifying agent 651, stir, leave standstill slaking and apply after 30 minutes.
Experimental program two
Step 1, the modification of nano-ZnO
Virahol, HW201 and nano-ZnO usage ratio are 5:0.03:1, successively be put in beaker according to the order of Virahol, HW201 the material of above mass ratio, after stirring, add corresponding nano-ZnO, then at room temperature use magnetic stirring apparatus high-speed stirring 1 hour, again suction filtration, 80 ℃ times oven dry, grinding.
Step 2, weighing and prepared and diluted agent
Preparation program is such as m
E-44: m
651: m
Dimethylbenzene: m
Propyl carbinol=20:12:7:3
Coating total amount according to above ratio and plan preparation takes by weighing E-44,651 solidifying agent, dimethylbenzene and propyl carbinol; And with the dimethylbenzene and the butanol solution mixing that weigh up, be mixed with thinner.
Step 3, preparation nano-ZnO slurry
With the nano-ZnO after the modification, add in the dimethylbenzene and propyl carbinol mixed diluent that configures according to 4% ratio of film forming matter (total mass of Resins, epoxy and solidifying agent), with this as slurry.
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of preparation is added among the load weighted E-44, stir, and then add solidifying agent 651, stir, leave standstill slaking and apply after 30 minutes.
Experimental program three
Step 1, the modification of nano-ZnO
Virahol, HW201 and nano-ZnO usage ratio are 4:0.05:1, successively be put in beaker according to the order of Virahol, HW201 the material of above mass ratio, after stirring, add corresponding nano-ZnO, then at room temperature use magnetic stirring apparatus high-speed stirring 1 hour, again suction filtration, 80 ℃ times oven dry, grinding.
Step 2, weighing and prepared and diluted agent
Preparation program is such as m
E-44: m
651: m
Dimethylbenzene: m
Propyl carbinol=18:12:4:7
Coating total amount according to above ratio and plan preparation takes by weighing E-44,651 solidifying agent, dimethylbenzene and propyl carbinol; And with the dimethylbenzene and the butanol solution mixing that weigh up, be mixed with thinner.
Step 3, preparation nano-ZnO slurry
With the nano-ZnO after the modification, add in the dimethylbenzene and propyl carbinol mixed diluent that configures according to 5% ratio of film forming matter (total mass of Resins, epoxy and solidifying agent), with this as slurry.
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of preparation is added among the load weighted E-44, stir, and then add solidifying agent 651, stir, leave standstill slaking and apply after 40 minutes.
Experimental program four
Step 1, the modification of nano-ZnO
Virahol, HW201 and nano-ZnO usage ratio are 3:0.04:1, successively be put in beaker according to the order of Virahol, HW201 the material of above mass ratio, after stirring, add corresponding nano-ZnO, then at room temperature use magnetic stirring apparatus high-speed stirring 1 hour, again suction filtration, 80 ℃ times oven dry, grinding.
Step 2, weighing and prepared and diluted agent
Preparation program is such as m
E-44: m
651: m
Dimethylbenzene: m
Propyl carbinol=20:12:4:7
Coating total amount according to above ratio and plan preparation takes by weighing E-44,651 solidifying agent, dimethylbenzene and propyl carbinol; And with the dimethylbenzene and the butanol solution mixing that weigh up, be mixed with thinner.
Step 3, preparation nano-ZnO slurry
With the nano-ZnO after the modification, add in the dimethylbenzene and propyl carbinol mixed diluent that configures according to 4% ratio of film forming matter (total mass of Resins, epoxy and solidifying agent), with this as slurry.
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of preparation is added among the load weighted E-44, stir, and then add solidifying agent 651, stir, leave standstill slaking and apply after 40 minutes.
More than the present invention has been done exemplary description; should be noted that; in the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (8)
1. a nano combined ocean anti-pollution paint is characterized in that, the nano-ZnO that will have antibacterial is dosed in the Resins, epoxy by surface modification as filler, specifically is prepared according to following step:
Step 1, the modification of nano-ZnO
Mass ratio (3～6) according to Virahol, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and nano zine oxide: (0.02～0.05): 1, take by weighing respective substance, then Virahol, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester order successively are put in the beaker, after stirring, add nano-ZnO, then room temperature 20-25 degree centigrade of lower the stirring 1 hour, again suction filtration, 80 ℃ of lower oven dry, grind
Step 2, weighing and prepared and diluted agent
Mass ratio 20 according to Resins, epoxy, polyamide curing agent, dimethylbenzene and propyl carbinol: (8～12): (2～5): (5～9), take by weighing respective substance, and dimethylbenzene and butanol solution are mixed, be mixed with thinner
Step 3, preparation nano-ZnO slurry
Nano-ZnO after step 1 modification is joined in the dimethylbenzene and propyl carbinol mixed diluent that step 2 configures, and as slurry, the add-on of nano-ZnO is 1%～6% of Resins, epoxy and polyamide curing agent total mass with this
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of step 3 preparation is added in the load weighted Resins, epoxy of step 2, stir, and then add polyamide curing agent, stir, leave standstill slaking after 30～40 minutes, can obtain nano combined ocean anti-pollution paint.
2. a kind of nano combined ocean according to claim 1 anti-pollution paint is characterized in that described Resins, epoxy is bisphenol A type epoxy resin, and its average oxirane value is 0.44; Described polyamide curing agent is the low molecular polyamides solidifying agent, and its amine value is 380～420.
3. a kind of nano combined ocean according to claim 1 anti-pollution paint is characterized in that described dimethylbenzene and propyl carbinol are analytical pure, and the purity of Virahol is 99.9%.
4. a kind of nano combined ocean according to claim 1 anti-pollution paint is characterized in that described nano-ZnO particle diameter is 20nm.
5. the preparation method of a nano combined ocean anti-pollution paint is characterized in that, the nano-ZnO that will have antibacterial is dosed in the Resins, epoxy by surface modification as filler, specifically is prepared according to following step:
Step 1, the modification of nano-ZnO
Mass ratio (3～6) according to Virahol, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester and nano zine oxide: (0.02～0.05): 1, take by weighing respective substance, then Virahol, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester order successively are put in the beaker, after stirring, add nano-ZnO, then room temperature 20-25 degree centigrade of lower the stirring 1 hour, again suction filtration, 80 ℃ of lower oven dry, grind
Step 2, weighing and prepared and diluted agent
Mass ratio 20 according to Resins, epoxy, polyamide curing agent, dimethylbenzene and propyl carbinol: (8～12): (2～5): (5～9), take by weighing respective substance, and dimethylbenzene and butanol solution are mixed, be mixed with thinner
Step 3, preparation nano-ZnO slurry
Nano-ZnO after step 1 modification is joined in the dimethylbenzene and propyl carbinol mixed diluent that step 2 configures, and as slurry, the add-on of nano-ZnO is 1%～6% of Resins, epoxy and polyamide curing agent total mass with this
Step 4 is added Resins, epoxy and is realized compound
The nano-ZnO slurry of step 3 preparation is added in the load weighted Resins, epoxy of step 2, stir, and then add polyamide curing agent, stir, leave standstill slaking after 30～40 minutes, can obtain nano combined ocean anti-pollution paint.
6. the preparation method of a kind of nano combined ocean according to claim 5 anti-pollution paint is characterized in that described Resins, epoxy is bisphenol A type epoxy resin, and its average oxirane value is 0.44; Described polyamide curing agent is the low molecular polyamides solidifying agent, and its amine value is 380～420.
7. the preparation method of a kind of nano combined ocean according to claim 5 anti-pollution paint is characterized in that described dimethylbenzene and propyl carbinol are analytical pure, and the purity of Virahol is 99.9%.
8. the preparation method of a kind of nano combined ocean according to claim 5 anti-pollution paint is characterized in that described nano-ZnO particle diameter is 20nm.
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| CN103694743A (en) * | 2013-11-27 | 2014-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Zinc oxide surface modification method by titanate coupling agent |
| CN105802281A (en) * | 2016-03-17 | 2016-07-27 | 安徽颖达锌业发展有限公司 | Method for modifying nano-zinc oxide powder |
| CN108676491A (en) * | 2018-05-04 | 2018-10-19 | 砺剑防务技术集团有限公司 | For the anticorrosive paint of metal base, preparation method and metallic substrate surface processing method |
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| CN103265869A (en) * | 2013-06-04 | 2013-08-28 | 天津大学 | Hydrophobic nano composite ocean anti-staining coating and preparation method thereof |
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| CN109306230A (en) * | 2018-10-10 | 2019-02-05 | 广州市修米德科技有限公司 | A kind of strong adhesive force environmental protection coating material that anti-pollution is excellent |
| CN116042071A (en) * | 2022-10-25 | 2023-05-02 | 苏州红旭新材料科技有限公司 | Infrared stealth coating and preparation method thereof |
| CN116891668A (en) * | 2023-06-28 | 2023-10-17 | 青岛科技大学 | Epoxy resin antifouling paint based on double-strategy antibacterial property and preparation method thereof |
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