CN104974640A - Preparation method of graphene-containing marine anticorrosive antifouling paint - Google Patents
Preparation method of graphene-containing marine anticorrosive antifouling paint Download PDFInfo
- Publication number
- CN104974640A CN104974640A CN201510428530.0A CN201510428530A CN104974640A CN 104974640 A CN104974640 A CN 104974640A CN 201510428530 A CN201510428530 A CN 201510428530A CN 104974640 A CN104974640 A CN 104974640A
- Authority
- CN
- China
- Prior art keywords
- graphene
- epoxy resin
- preparation
- coating
- paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Abstract
The invention discloses a preparation method of a graphene-containing marine anticorrosive antifouling paint. Graphene with antimicrobial function is used as a filler and added into an epoxy resin through surface modification, thereby preparing the nano composite antifouling paint with antimicrobial and anticorrosive properties. The graphene is added into the epoxy resin to obtain the marine antifouling paint, so that the favorable characteristics of the two materials can be sufficiently combined, and thus, the paint has the characteristics of fouling resistance and corrosion resistance. The graphene and epoxy resin are compounded, so that the antimicrobial property of the graphene and the anticorrosive property of the epoxy resin are organically combined, thereby developing the novel antifouling paint with corrosion resistance and fouling resistance.
Description
The present patent application is the divisional application of parent application " marine anticorrosion anti-pollution paint of a kind of graphene-containing and preparation method thereof ", and the application number of parent application is 2013105390377, and the applying date of parent application is on November 1st, 2013.
Technical field
The present invention relates to a kind of marine metal component antifouling paint and preparation method thereof, more particularly, ocean anti-pollution paint relating to graphene-containing and preparation method thereof.
Background technology
Biodeterioration is the significant problem of long-standing problem marine ship industrial development; Result of study shows, marine organisms adhere at marine surface roughness, the reduction speed of a ship or plane, the increase fuel consumption that the marime fouling caused can increase hull surface, and clean for later stage hull fouling the consumption causing substantial contribution and manpower.According to statistics, biodeterioration can increase the fuel oil consumption of steamer 40%; In addition, China at least reaches 90,000,000,000 yuans because corroding the financial loss that causes every year, and marine corrosion accounts for more than 30%, wherein adheres to relevant material corrosion with marine microorganism and destroys account for that marine material corrodes total amount about 30%.If can solve or alleviate hull fouling problem, economic and social benefit greatly will be brought.Knowhow according to mankind's centuries finds, applying coatings is easy and efficient antifouling strategy.Therefore, the anti-pollution paint that exploitation is excellent 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, is prevent a kind of tailor-(made) coating (Liu Dengliang, coating process, Beijing: Chemical Industry Press, 2010:1166) that marine attaching organism is stained, maintenance hull bottom is bright and clean, smooth.Marine antifouling coating, successively experienced by toxic material type and nontoxic type two developmental stage, has greatly promoted the fast development of the industry such as sea transport, sea farming.Traditional antifouling paint, normal employing Red copper oxide, organotin, organoaluminum, organoarsenic, organotin etc. are poison material, if International Paint company of Britain antifouling paint disclosed in European patent EP 0051930 is the composition of acrylic polymers, Red copper oxide, organotin.
Red copper oxide is one of antifouling pigment the earliest, itself is red, because this color limits the use range of Red copper oxide.So, also there are some researchists just to replace with the cuprous thiocyanate of white.But Red copper oxide has extremely strong toxicity, there is disadvantageous effect to ocean environment and human survival, so it has also little by little exited the arena of history.In Organotin antifouling paints, the most typical organo-tin compound is tributyl tin (TBT).As since the sterilant in anti-fouling ship paint from the sixties in 20th century, for shipping-trade brings huge profit.But TBT is the material that a kind of toxicity is very strong, it, in expeling or while killing as fouling organisms such as pipe worm, barnacle, mussel and algae, also constitutes a threat to nontarget organism.TBT can make the lethal or teratogenesis of marine organisms, destroy the eubiosis, make cultivation and the fish industry underproduction, can also at economic fish and shellfish body accumulation, indirectly harm is produced to human health, international community just prohibitted the use coating (L D Chambers, K R Stokes, F C Walsh containing TBT from 2003, et al.Modern approaches to marineantifouling coatings, Surf.Coat.Technol., 2006,201:3642-3652).
In order to control the rate of release of poison material, reduce the resistance on steamer surface, people have developed from polishing type antifouling paint.The working mechanism of this antifouling paint is: when coating is dipped in seawater, occur hydrolysis reaction, discharge poison material be dissolved among seawater, under the effect of current, paint film hydrolysis reaction constantly continues, exposes new surface, therefore, poison material rate of release very steady.Due to film, to fall in the little and hydrolysis rate of position flow action slow, thus cause film increasingly smooth.But containing highly toxic heavy metal ion or hypotoxicity but less metal ion (the Cao S of anti-soil scope in the type coating, 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.
Containing the coating of heavy metal oxide or ion, though there is higher anti-soil rate, but huge destruction is also created to environment.Therefore, people develop completely newly nontoxic low surface energy anti-fouling paint in succession.This coating is the low surface energy utilizing material, makes marine organisms be difficult to adhere to above, even if attachment is also insecure, easily comes off under current or other External Force Acting.At present, mainly concentrate on two fields: one is organic silicon antifouling paint to the research of this type of coating, another kind is organic fluorine antifouling paint.Organic silicon antifouling paint has worldwide been applied a lot of patent, as the relevant curable silicone coating patents of General Electric Corporation's application.Silicoorganic compound have hydrophobicity, and its surface tension is very low, and structure is extremely stable, even if soak for a long time in water, structural changes is also very little, can prevent marine organisms from adhering to, have good anti-fouling effect.The production and consumption of fluoropolymer mainly concentrates on the U.S., Japan and the Western European countries, disclosed in US Patent No. 4410363 disclosed in fluoro-resin, Japanese Patent Laid-Open 2003-261628 from polishing type organic fluorine acrylic polymers.The shortcoming of such coating is that cost is high, and not easily construct, film is excessively soft, is easily destroyed.
There are many biologies to have born stain resistance in ocean, have the anti-soil ability of this type of biology of scholar's research, have developed bionical anti-pollution paint.This coating imitates the organism in natural surroundings, and from surfacing, surface microstructure, the sink conditions of mimic biology body, to reach antifouling object.The one that Sweden develops antifouling paint peculiar to vessel, be made up of epoxy resin layer and layer of fibers two portions, epoxy resin applies that one deck is filled with electrostatic, extremely short compacted fibers, hull just as dolphin skin, with microvilli instability surface, prevent marine organisms from adhering to and strengthen the resistance to corrosion of hull.This ship coating not containing toxic substance, thus can not poison marine organisms completely, also can not polluted seawater.Hull coats this coating, can keep the higher speed of a ship or plane, and meanwhile, the work-ing life of this coating also reaches 3 ~ 5 years than general coating.The chemist of Washington, DC university also simulates microstructure and the mechanism of porpoise skin, has been developed into a kind of new antifouling paint.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 being cross-linked, and generate a kind of special coating.From nano-angle, this paint coatings has coarse surface, simulates the epidermis of dolphin, prevents marine organisms to 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 simulated ecological 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 the new antifouling paint that Mitsubishi heavy industry Co., Ltd. developed the nineties in 20th century.Its principle of work is be coated with layer of cloth on shell after, take conductive coating as anode, with shell other and contact with sea water part for negative electrode.When there being weak current by coating surface, neighbouring seawater generation electrolysis can be made, producing hypochlorite ion, covering hull surface, form protective membrane, so just can effectively prevent the halobiontic attachments such as microorganism, algae, shellfish.Because the concentration in produced chloranion concentration ratio tap water is in the seawater also low, so do not pollute the environment.But the application of this type of coating can produce many times chloranion, and then the corrosion of matrix metal is aggravated.
Have researchist to find, the seawater pH value of suitable marine organisms survival and reproduction is 7.5 ~ 8.0, and in the environment that acidity is stronger or alkalescence is stronger, marine organisms will be difficult to existence.It is found that the concrete structure underwater portion of new cast does not all have biological attachment within the time reaching 1 year.Therefore alkaline silicate is added in coating as nontoxic stain control agent, prevent sea organism attachment (Wang Huajin, Wang Xianming, Guan Chaoxiang, etc., silicate compound anti-fouling paint, CN1248599) by the method increasing coating surrounding seawater basicity.But the effective antifouling life of this kind of coating is not long, and physicochemical property is poor, still there is a segment distance (Wang Huajin, Wang Xianming, Guan Chaoxiang, etc., the development of marine antifouling coating, coatings industry, 2000,3:35-38) with practical application.The secretory product of microorganism adhering in metallic surface normally by self is used as medium; and these materials are often biologically active substances; they often can produce degraded under the effect of zymoprotein, therefore have researchist using proteolytic enzyme as additive to give coating antibiosis performance.Because the activity of enzyme is affected by environment, as temperature, pH value etc., so its anti-soil efficiency is different in different environments.In addition, enzyme catalysis has very strong specificity, antibacterial range will limited (JamesA.Callow, Maureen E.Callow.Trends in the development of environmentally friendlyfouling-resistant marine coatings, Nat.Commun., 2011,2:244).
Make a general survey of current anti-pollution paint current situation, although anti-soil technology presents the trend of diversification, from the situation of real world applications, mainly 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 also exists high environmental risk and the poor shortcoming of over-all properties.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, for the actual predicament of current anti-pollution paint, high anti-microbial property, the Graphene of low environment risk adds in epoxy resin will prepare excellent performance, the novel anticorrosion anti-soil composite coating that environmental effect is good, Graphene can be added in epoxy resin as marine antifouling coating, will fully in conjunction with the good characteristic of bi-material, coating is made to have antifouling and anticorrosion two large characteristics concurrently, compound is carried out by Graphene and epoxy resin, the anti-microbial property of Graphene and the antiseptic property of epoxy resin are organically combined, the novel anti-pollution paint having protection against corrosion and antifouling property concurrently is developed with this.
Technical purpose of the present invention is achieved by following technical proposals:
Marine anticorrosion anti-pollution paint of a kind of graphene-containing and preparation method thereof, the Graphene with antibacterial is added in epoxy resin as filler by surface modification, thus prepare there is nano combined anti-pollution paint that is antibacterial, corrosion resisting property, be prepared according to following step:
Step one: modification is carried out to Graphene (Graphene), obtains the Graphene of coupling modifier
Nano-substance has very high specific surface energy, so often can there is agglomeration, forms larger substance aggregate, and make Graphene be difficult to stably be scattered in epoxy-resin systems, this will seriously affect the performance of nano-substance performance.Therefore need to carry out surface modification to Graphene, reducing reunites occurs, and improve its stability in epoxy-resin systems, the present invention adopts surface hydroxylation and coupling method to carry out modification, and detailed process is as follows:
(1) graphenic surface hydroxylation:
Utilize the 98wt% vitriol oil and 65wt% concentrated nitric acid, press
proportions chloroazotic acid; Then m is pressed
graphene: V
chloroazotic acid=1g:(600 ~ 630) ratio of mL claims (amount) to get Graphene and chloroazotic acid.By the graphene dispersion that takes in chloroazotic acid, carry out after carrying out ultrasonic disperse being washed to neutrality, obtain the Graphene of surface hydroxylation after drying grinding, specifically carry out according to following step:
Utilize the 98wt% vitriol oil and 65wt% concentrated nitric acid, press
proportions chloroazotic acid; Then m is pressed
graphene: V
chloroazotic acid=1g:(600 ~ 630) ratio of mL claims (amount) to get Graphene and chloroazotic acid.By the graphene dispersion that takes in chloroazotic acid, and supersound process 30 minutes in a water bath.Then, system is placed in 60 DEG C of water-bath heated and stirred after 6 ~ 8 hours, and with distilled water, Graphene is washed till neutrality, 60 DEG C of oven for drying, grinding.
Described vitriol oil concentration is 98wt% (in sulphur aqueous acid the ratio of sulfuric acid and overall solution, mass percent), and described concentrated nitric acid concentration is 65wt% (in nitre aqueous acid the ratio of nitric acid and overall solution, mass percent).
(2) Graphene coupling
According to surface hydroxyl functionalized graphene and N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 1:(3 ~ 6) ratio of quality and the number of copies, by the Graphene of surface hydroxylation with N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (KH-602) is dissolved in deionized water, heated and stirred is carried out after ultrasonic disperse, washing is carried out dry after centrifugation, obtain the Graphene of coupling modifier after grinding, specifically carry out according to following step:
By modified Graphene and KH602 (N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane), by m
graphene: m
kH-602=1:(3 ~ 6) ratio of quality and the number of copies be dissolved in a small amount of deionized water; After stirring, ultrasonic disperse 30 minutes.System is used magnetic stirring apparatus heated and stirred 8 ~ 10 hours at 60 DEG C, and centrifugation goes out modified Graphene, distilled water wash 3 times, washing with alcohol 2 times, and in 60 DEG C of oven for drying, grinding.
Step 2: prepared and diluted agent, by dimethylbenzene and propyl carbinol according to ratio of quality and the number of copies m
dimethylbenzene: m
propyl carbinol=(2 ~ 5): mix after the ratio weighing of (5 ~ 9), for subsequent use as thinner
Step 3: preparation modified graphene slurry, Graphene after coupling modifier is added in the dimethylbenzene configured and propyl carbinol mixed diluent, in this, as modified graphene slurry, the add-on of the Graphene after described coupling modifier is 0.10% ~ 0.20% of film forming matter quality, and described filmogen is the total mass of epoxy resin and solidifying agent.
Step 4: preparation composite coating
After modified graphene slurry step 3 prepared adds to and stirs in epoxy resin, then add solidifying agent and stir, after leaving standstill slaking, namely obtain composite coating.
Described standing slaking is 40 ~ 60 minutes, to solvent evaporates, reacts between solidifying agent and epoxy resin, realizes the viscosity that coating needs.
The ratio of quality and the number of copies of described epoxy resin, solidifying agent, dimethylbenzene and propyl carbinol is 20:(8-12): (2 ~ 5): (5 ~ 9).
Described epoxy resin is bisphenol A type epoxy resin E-44, and its average epoxy value is 0.44; Described solidifying agent is low molecular polyamides solidifying agent 651, and its amine value is 380 ~ 420.
After preparing composite coating, brushing or spread coating can be utilized to carry out paint.After paint, after room temperature 20-25 degrees Celsius hangs 48h, then 2 ~ 3h need be toasted at 60 DEG C.
Utilize testing tool model: Bruker TENSOR 27 infrared spectrometer carries out the infrared line analysis of product, as shown in Figure 1, interpretation of result: can find from spectrogram, there is the 2933cm of silane coupling agent in modified Graphene
-1and 2835cm
-1characteristic peak, these characteristic peaks are-CH
2-charateristic avsorption band; In addition, the 1082cm of coupling agent
-1si-O-C characteristic peak, the 1261cm at place
-1the Si-CH at place
3characteristic peak and 767cm
-1-the NH at place
2characteristic peak also appears in modified Graphene, the charateristic avsorption band of these silane coupling agents just, above explanation Graphene modification success.
Compared with prior art, nano combined anticorrosion and antifouling coating of the present invention not only has higher antiseptic property, and has very high antifouling property, and required processing unit is simple, and cost is relatively low, easily realizes industrialization.Specific experiment data are as follows:
(1) antiseptic property: adopt identical formula, unmodified Graphene and epoxy resin is selected to carry out compound, to obtain unmodified Graphene and epoxy resin composite coating, and select identical epoxy resin as coating (bisphenol A type epoxy resin, its average epoxy value is 0.44).Adopt spread coating to be coated on Q235 steel disc respectively by epoxy resin, unmodified Graphene/epoxy resin and modified graphene/epoxypaint, coating film thickness is about 300 microns, cured at room temperature 3 days.Then three kinds of coatings are soaked in the 3.5wt%NaCl aqueous solution, Verstat 4 electrochemical workstation is utilized to measure the electrochemical impedance spectroscopy of each coating behind 1 day, 3 days and corrosion in 6 days, as Suo Shi Fig. 2-5 (herein indication " my god " be one day 24h), X-coordinate real part Zre reacts the size of equivalent electrical circuit middle impedance value, and ordinate zou imaginary part Zim reacts the frequency of disturbance voltage to the impact of equivalent electrical circuit middle impedance.Verstat 4 electrochemical workstation instrument designing parameter is as follows: disturbance voltage 20mV sinusoidal voltage; Start frequency 100000Hz; Limiting frequency 0.01Hz.Soak after 3 days, having there is the anti-arc feature of double volume in epoxy coating, shows that etchant solution has penetrated into matrix surface, plain steel there occurs corrosion; And two kinds of Graphene/epoxy coatings are still in single capacitive reactance arc feature, show that plain steel does not corrode.Soak after 6 days, unmodified Graphene/epoxy coating and modified graphene/epoxy coating all keep single capacitive reactance arc feature, and the impedance of modified graphene/epoxy coating (93M Ω) is higher than unmodified Graphene/epoxy resin (being about 40M Ω), illustrates that Graphene/epoxy resin has best corrosion resistance.
(2) anti-microbial property: the streptococcus aureus liquid of 100 microlitres is dropped in respectively on epoxy coating, unmodified Graphene/epoxy coating and modified graphene/epoxy coating, then use the polyvinyl chloride film of 4cm × 4cm to be covered in coating, sample is cultivated 24 hours in the constant incubator of 37 DEG C.Afterwards, rinse film and coatingsurface with the 3.5%NaCl solution of 8ml, the washing fluid getting 200 microlitres is inoculated on solid medium, and by the coating of bacterium liquid evenly, in the constant incubator of 37 DEG C, cultivate counting after 24 hours, parallel sample is three groups.Get the average of three groups of numbers as net result, calculate antibiotic rate, the antibiotic rate of epoxy coating only has 29%, and the antibiotic rate of unmodified Graphene/epoxy coating is 81%, and the antibiotic rate of modified graphene/epoxy coating is 89%.Visible, add the antibiotic rate that can improve epoxy coat after Graphene, and Graphene modification can the antibiotic rate of epoxy coat further.
Accompanying drawing explanation
Fig. 1 is silane coupling agent KH602 and Graphene rear infrared spectrum before modified, and wherein 1 is KH602, and 2 is modified Graphene, and 3 is raw graphite alkene.
Fig. 2 is the electrochemical impedance spectrogram (1) of epoxy coating, and wherein ■ is 1 day.
Fig. 3 is the electrochemical impedance spectrogram (2) of epoxy coating, wherein ● be 3 days, ▲ be 6 days.
Fig. 4 is the electrochemical impedance spectrogram of unmodified Graphene/epoxy resin compound coating, and wherein ■ is 1 day; ● be 3 days; ▲ be 6 days.
Fig. 5 is the electrochemical impedance spectrogram of modified graphene of the present invention/epoxy resin compound coating, and wherein ■ is 1 day; ● be 3 days; ▲ be 6 days.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.Material therefor is respectively: E-44 bisphenol A type epoxy resin (Phoenix brand epoxy resin, Xingchen Synthetic Matrials Co., Ltd., Nantong), 651 polyamide curing agents (blue star chemical industry Wuxi fine chemistry industry institute), Graphene (Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences), dimethylbenzene, propyl carbinol, the vitriol oil and concentrated nitric acid are analytical pure (Tianjin Ke Wei chemical reagents corporation), silane coupling agent KH-602 (Hangzhou boiling point Chemical Co., Ltd.).
Embodiment one
Step one: graphenic surface hydroxylation
Utilize the 98wt% vitriol oil and 65wt% concentrated nitric acid, press
proportions chloroazotic acid; Then m:V is pressed
chloroazotic acidthe ratio of=1g:600mL claims (amount) to get Graphene and chloroazotic acid.By the graphene dispersion that takes in chloroazotic acid, and supersound process 30 minutes in a water bath.Then system is placed in 60 DEG C of water-bath heated and stirred after 6 hours, and with distilled water, Graphene is washed till neutrality, 60 DEG C of oven for drying, grinding.
Step 2: the coupling of Graphene
By step one gained Graphene and KH602 (N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane), by m
graphene: m
kH-602the mass ratio of=1mg:3mg is dissolved in a small amount of deionized water, after stirring, and ultrasonic disperse 30min.After this at 60 DEG C, use magnetic stirring apparatus heated and stirred 8h, centrifugation goes out modified Graphene, distilled water wash 3 times, washing with alcohol 2 times, in 60 DEG C of oven for drying, and grinding.
Step 3: prepared and diluted agent
According to m
e-44: m
651: m
dimethylbenzene: m
propyl carbinolthe ratio of=20g:8g:2g:5g, takes E-44 (bisphenol A type epoxy resin, its average epoxy value is 0.44), 651 solidifying agent (belong to low molecular polyamides solidifying agent, its amine value is 380 ~ 420), dimethylbenzene and propyl carbinol; And the dimethylbenzene weighed up and butanol solution are mixed, be mixed with thinner.
Step 4: prepare Graphene slurry
By Graphene modified for step 2, according to film forming matter (total mass of epoxy resin and solidifying agent) 0.15% ratio add in the dimethylbenzene and propyl carbinol mixed diluent that step 3 configures, in this, as slurry.
Step 5, the preparation of Graphene/epoxy resin composite coating
Graphene slurry step 4 prepared adds in the load weighted E-44 of step 3, stirs; And then add solidifying agent 651, stir, leave standstill slaking after 40 minutes, Graphene/epoxy resin composite coating can be obtained.
Experimental program two
Step one: graphenic surface hydroxylation
Utilize 98% vitriol oil and 65% concentrated nitric acid, press
proportions chloroazotic acid; Then m:V is pressed
chloroazotic acidthe ratio of=1g:610mL claims (amount) to get Graphene and chloroazotic acid.By the graphene dispersion that takes in chloroazotic acid, and supersound process 30 minutes in a water bath.Then system is placed in 60 DEG C of water-bath heated and stirred after 6 hours, and with distilled water, Graphene is washed till neutrality, 60 DEG C of oven for drying, grinding.
Step 2: the coupling of Graphene
By step one gained Graphene and KH602 (N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane), by m
graphene: m
kH-602the mass ratio of=1mg:4mg is dissolved in a small amount of deionized water, after stirring, and ultrasonic disperse 30min.After this at 60 DEG C, use magnetic stirring apparatus heated and stirred 9h, centrifugation goes out modified Graphene, distilled water wash 3 times, washing with alcohol 2 times, in 60 DEG C of oven for drying, and grinding.
Step 3: prepared and diluted agent
According to m
e-44: m
651: m
dimethylbenzene: m
propyl carbinolthe ratio of=20g:9g:3g:6g and the coating total amount of plan preparation, take E-44 (bisphenol A type epoxy resin, its average epoxy value is 0.44), 651 solidifying agent (belong to low molecular polyamides solidifying agent, its amine value is 380 ~ 420), dimethylbenzene and propyl carbinol; And the dimethylbenzene weighed up and butanol solution are mixed, be mixed with thinner.
Step 4: prepare Graphene slurry
By Graphene modified for step 2, according to film forming matter (total mass of epoxy resin and solidifying agent) 0.10% ratio add in the dimethylbenzene and propyl carbinol mixed diluent that step 3 configures, in this, as slurry.
Step 5, the preparation of Graphene/epoxy resin composite coating
Graphene slurry step 4 prepared adds in the load weighted E-44 of step 3, stirs; And then add solidifying agent 651, stir, leave standstill slaking after 50 minutes, Graphene/epoxy resin composite coating can be obtained.
Experimental program three
Step one: graphenic surface hydroxylation
Utilize 98% vitriol oil and 65% concentrated nitric acid, press
proportions chloroazotic acid; Then m:V is pressed
chloroazotic acidthe ratio of=1g:620mL claims (amount) to get Graphene and chloroazotic acid.By the graphene dispersion that takes in chloroazotic acid, and supersound process 30 minutes in a water bath.Then system is placed in 60 DEG C of water-bath heated and stirred after 6 hours, and with distilled water, Graphene is washed till neutrality, 60 DEG C of oven for drying, grinding.
Step 2: the coupling of Graphene
By step one gained Graphene and KH602 (N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane), by m
graphene: m
kH-602the mass ratio of=1mg:4mg is dissolved in a small amount of deionized water, after stirring, and ultrasonic disperse 30min.After this at 60 DEG C, use magnetic stirring apparatus heated and stirred 10h, centrifugation goes out modified Graphene, distilled water wash 3 times, washing with alcohol 2 times, in 60 DEG C of oven for drying, and grinding.
Step 3: prepared and diluted agent
According to m
e-44: m
651: m
dimethylbenzene: m
propyl carbinolthe ratio of=20g:10g:4g:8g and the coating total amount of plan preparation, take E-44 (bisphenol A type epoxy resin, its average epoxy value is 0.44), 651 solidifying agent (belong to low molecular polyamides solidifying agent, its amine value is 380 ~ 420), dimethylbenzene and propyl carbinol; And the dimethylbenzene weighed up and butanol solution are mixed, be mixed with thinner.
Step 4: prepare Graphene slurry
By Graphene modified for step 2, according to film forming matter (total mass of epoxy resin and solidifying agent) 0.20% ratio add in the dimethylbenzene and propyl carbinol mixed diluent that step 3 configures, in this, as slurry.
Step 5, the preparation of Graphene/epoxy resin composite coating
Graphene slurry step 4 prepared adds in the load weighted E-44 of step 3, stirs; And then add solidifying agent 651, stir, leave standstill slaking after 60 minutes, Graphene/epoxy resin composite coating can be obtained.
Experimental program four
Step one: graphenic surface hydroxylation
Utilize 98% vitriol oil and 65% concentrated nitric acid, press
proportions chloroazotic acid; Then m:V is pressed
chloroazotic acidthe ratio of=1g:630mL claims (amount) to get Graphene and chloroazotic acid.By the graphene dispersion that takes in chloroazotic acid, and supersound process 30 minutes in a water bath.Then system is placed in 60 DEG C of water-bath heated and stirred after 6 hours, and with distilled water, Graphene is washed till neutrality, 60 DEG C of oven for drying, grinding.
Step 2: the coupling of Graphene
By step one gained Graphene and KH602 (N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane), by m
graphene: m
kH-602the mass ratio of=1mg:6mg is dissolved in a small amount of deionized water, after stirring, and ultrasonic disperse 30min.After this at 60 DEG C, use magnetic stirring apparatus heated and stirred 9h, centrifugation goes out modified Graphene, distilled water wash 3 times, washing with alcohol 2 times, in 60 DEG C of oven for drying, and grinding.
Step 3: prepared and diluted agent
According to m
e-44: m
651: m
dimethylbenzene: m
propyl carbinolthe ratio of=20g:12g:5g:9g and the coating total amount of plan preparation, take E-44 (bisphenol A type epoxy resin, its average epoxy value is 0.44), 651 solidifying agent (belong to low molecular polyamides solidifying agent, its amine value is 380 ~ 420), dimethylbenzene and propyl carbinol; And the dimethylbenzene weighed up and butanol solution are mixed, be mixed with thinner.
Step 4: prepare Graphene slurry
By Graphene modified for step 2, according to film forming matter (total mass of epoxy resin and solidifying agent) 0.15% ratio add in the dimethylbenzene and propyl carbinol mixed diluent that step 3 configures, in this, as slurry.
Step 5, the preparation of Graphene/epoxy resin composite coating
Graphene slurry step 4 prepared adds in the load weighted E-44 of step 3, stirs; And then add solidifying agent 651, stir, leave standstill slaking after 60 minutes, Graphene/epoxy resin composite coating can be obtained.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (5)
1. a preparation method for the marine anticorrosion anti-pollution paint of graphene-containing, is characterized in that, adds in epoxy resin, be prepared the Graphene with antibacterial according to following step as filler by surface modification:
Step one: carry out modification to Graphene, obtains the Graphene of coupling modifier
(1) graphenic surface hydroxylation
Utilize the 98wt% vitriol oil and 65wt% concentrated nitric acid, by V
h2SO4: V
hNO3the proportions chloroazotic acid of=3:1; Then m is pressed
graphene: V
chloroazotic acid=1g:(600 ~ 630) ratio of mL claims (amount) to get Graphene and chloroazotic acid, and by the graphene dispersion that takes in chloroazotic acid, carry out after carrying out ultrasonic disperse being washed to neutrality, after drying grinding, obtain the Graphene of surface hydroxylation;
(2) Graphene coupling
According to surface hydroxyl functionalized graphene and N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 1:(3 ~ 6) ratio of quality and the number of copies, by the Graphene of surface hydroxylation with N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane is dissolved in deionized water, heated and stirred is carried out after ultrasonic disperse, carry out washing after centrifugation dry, after grinding, obtain the Graphene of coupling modifier;
Step 2: prepared and diluted agent, by dimethylbenzene and propyl carbinol according to ratio of quality and the number of copies m
dimethylbenzene: m
propyl carbinol=(2 ~ 5): mix after the ratio weighing of (5 ~ 9), for subsequent use as thinner;
Step 3: preparation modified graphene slurry, Graphene after coupling modifier is added in the dimethylbenzene configured and propyl carbinol mixed diluent, in this, as modified graphene slurry, the add-on of the Graphene after described coupling modifier is 0.10% ~ 0.20% of film forming matter quality, and described filmogen is the total mass of epoxy resin and solidifying agent; The ratio of quality and the number of copies of described epoxy resin, solidifying agent, dimethylbenzene and propyl carbinol is 20:(8-12): (2 ~ 5): (5 ~ 9);
Step 4: preparation composite coating
After modified graphene slurry step 3 prepared adds to and stirs in epoxy resin, then add solidifying agent and stir, after leaving standstill slaking, namely obtain composite coating.
2. the preparation method of the marine anticorrosion anti-pollution paint of a kind of graphene-containing according to claim 1, it is characterized in that, in described step 4, described standing slaking is 40 ~ 60 minutes, to solvent evaporates, react between solidifying agent and epoxy resin, realize the viscosity that coating needs.
3. the preparation method of the marine anticorrosion anti-pollution paint of a kind of graphene-containing according to claim 1, is characterized in that, described epoxy resin is bisphenol A type epoxy resin E-44, and its average epoxy value is 0.44.
4. the preparation method of the marine anticorrosion anti-pollution paint of a kind of graphene-containing according to claim 1, is characterized in that, described solidifying agent is low molecular polyamides solidifying agent 651, and its amine value is 380 ~ 420.
5. the preparation method of the marine anticorrosion anti-pollution paint of a kind of graphene-containing according to claim 1, is characterized in that, after preparing composite coating, utilizes brushing or spread coating to carry out paint; After paint, after room temperature 20-25 degrees Celsius hangs 48h, then 2 ~ 3h need be toasted at 60 DEG C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310539037.7A CN103589282A (en) | 2013-11-01 | 2013-11-01 | Graphene-containing marine anticorrosion antifouling coating and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310539037.7A Division CN103589282A (en) | 2013-11-01 | 2013-11-01 | Graphene-containing marine anticorrosion antifouling coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104974640A true CN104974640A (en) | 2015-10-14 |
Family
ID=50079614
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510428530.0A Pending CN104974640A (en) | 2013-11-01 | 2013-11-01 | Preparation method of graphene-containing marine anticorrosive antifouling paint |
| CN201310539037.7A Pending CN103589282A (en) | 2013-11-01 | 2013-11-01 | Graphene-containing marine anticorrosion antifouling coating and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310539037.7A Pending CN103589282A (en) | 2013-11-01 | 2013-11-01 | Graphene-containing marine anticorrosion antifouling coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104974640A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969097A (en) * | 2016-05-12 | 2016-09-28 | 江苏永阳新材料科技有限公司 | High-performance antifouling paint |
| CN106047091A (en) * | 2016-07-05 | 2016-10-26 | 北京东方雨虹防水技术股份有限公司 | Waterproof and corrosion-resistant coating for coastal region |
| CN107417968A (en) * | 2017-04-12 | 2017-12-01 | 南京航空航天大学 | A kind of surface modifying method of powdered whiting and the method that high polymer composite material is prepared using this method |
| CN109423157A (en) * | 2017-06-29 | 2019-03-05 | 洛阳尖端技术研究院 | A kind of coating and preparation method thereof |
| WO2019178682A1 (en) | 2018-03-20 | 2019-09-26 | Graphite Innovation And Technologies Inc. | Multifunctional coatings for use in wet environments |
| CN110437662A (en) * | 2019-08-23 | 2019-11-12 | 江苏海晟涂料有限公司 | A method of preparing graphene composite material modified marine antifouling paint |
| EP3647375A1 (en) * | 2018-10-29 | 2020-05-06 | Ventus Engineering GmbH | Surface coating material, cured surface coating and use hereof |
| WO2021077502A1 (en) * | 2019-10-26 | 2021-04-29 | 维新制漆（江西）有限公司 | Nano silicon-carbon modified graphene special anti-corrosion coating and preparation method therefor |
| CN114702879A (en) * | 2022-04-02 | 2022-07-05 | 瑞格特新材料科技(佛山市)有限公司 | Anti-corrosion antifouling coating and preparation method thereof |
| US11679532B2 (en) | 2020-02-06 | 2023-06-20 | GM Global Technology Operations LLC | In-mold coating with improved flowability |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087126A (en) * | 2014-07-15 | 2014-10-08 | 南京航空航天大学 | Marine anticorrosive coating |
| CN104231815A (en) * | 2014-09-30 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Functionalized antifouling anticorrosive graphene paint as well as preparation method and painting method thereof |
| CN105647338B (en) * | 2014-11-28 | 2018-05-11 | 中国科学院金属研究所 | With high insulating graphene/epoxy resin composite anticorrosion coating and preparation method |
| CN104559669A (en) * | 2015-01-09 | 2015-04-29 | 上海大学 | Organic graphene anticorrosive paint applied to marine ship |
| CN105086663B (en) * | 2015-09-09 | 2017-07-14 | 河海大学常州校区 | The marine settings anti-corrosion hydrophobic treatment liquid of steel surface, preparation method and the usage |
| CN105131791A (en) * | 2015-09-30 | 2015-12-09 | 华东理工大学 | Preparation method of graphene-composited anticorrosive coating |
| CN105400374A (en) * | 2015-12-21 | 2016-03-16 | 深圳市嘉达高科产业发展有限公司 | Anticorrosive coating and preparation method thereof |
| CN106047077B (en) * | 2016-07-20 | 2018-03-06 | 太原理工大学 | Carbon nanomaterial composite conducting mica/epoxy radicals static conductive anticorrosion coating material and preparation method |
| CN106243943B (en) * | 2016-08-22 | 2018-07-20 | 广东纳路纳米科技有限公司 | A kind of modified white graphite alkene composite anticorrosion coating and its preparation |
| CN106752302A (en) * | 2016-12-01 | 2017-05-31 | 深圳市美信电子有限公司 | A kind of silane-modified Graphene ink and preparation method thereof |
| CN106871705A (en) * | 2017-02-21 | 2017-06-20 | 广东万家乐燃气具有限公司 | A kind of etch-proof heat exchanger preparation method with Graphene diaphragm of heat transfer efficient |
| CN109423158B (en) * | 2017-06-29 | 2022-03-29 | 洛阳尖端技术研究院 | Modified graphene and preparation method and application thereof |
| CN107459909A (en) * | 2017-08-31 | 2017-12-12 | 常州苏达欧包装材料有限公司 | A kind of Environment-friendlyanti-corrosive anti-corrosive paint peculiar to vessel and preparation method thereof |
| CN107974163A (en) * | 2017-11-21 | 2018-05-01 | 马鞍山天宇船舶制造有限公司 | A kind of preparation method of the composite modified wear-and corrosion-resistant type epoxy coating of nano-particle-hydridization Ludox |
| CN108841326B (en) * | 2018-05-24 | 2020-08-14 | 江苏昊科汽车空调有限公司 | Wear-resistant and corrosion-resistant air valve plate of air conditioner compressor and spraying method |
| CN109180051A (en) * | 2018-06-01 | 2019-01-11 | 湖南国盛石墨科技有限公司 | A kind of preparation method of the preservative of containing graphene |
| CN108929616B (en) * | 2018-07-16 | 2020-08-25 | 广东绿色大地化工有限公司 | Metal substrate graphene modified long-acting anticorrosive paint and preparation method thereof |
| CN109233558A (en) * | 2018-07-26 | 2019-01-18 | 广东鑫皇冠新材料有限公司 | A kind of ceramic coating and preparation method thereof |
| CN109179394B (en) * | 2018-09-26 | 2021-03-23 | 长飞光纤光缆股份有限公司 | Direct transfer device and method for graphene film |
| CN113039251B (en) * | 2018-11-29 | 2022-09-09 | 东丽先端材料研究开发（中国）有限公司 | Graphene anticorrosive paint |
| CN111117484A (en) * | 2019-12-27 | 2020-05-08 | 宁波知源新材料有限公司 | Anticorrosive composition containing sheet-like carbon material |
| CN113150628A (en) * | 2021-03-16 | 2021-07-23 | 赵青山 | Self-polishing graphene antifouling paint and preparation method thereof |
| CN113773723A (en) * | 2021-09-24 | 2021-12-10 | 深圳大学 | Marine anti-corrosion and anti-fouling composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265869A (en) * | 2013-06-04 | 2013-08-28 | 天津大学 | Hydrophobic nano composite ocean anti-staining coating and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604533A (en) * | 2012-03-14 | 2012-07-25 | 哈尔滨工程大学 | Polyaniline-graphene composite based anticorrosive paint and preparation method thereof |
| CN102977744A (en) * | 2012-12-13 | 2013-03-20 | 天津大学 | Nano-composite marine anti-fouling coating material and preparation method thereof |
| CN103254701B (en) * | 2013-05-02 | 2015-05-27 | 南京科孚纳米技术有限公司 | Novel anti-corrosion, anti-ultraviolet, anti-bacteria and wear-resistant paint and preparation method for same |
-
2013
- 2013-11-01 CN CN201510428530.0A patent/CN104974640A/en active Pending
- 2013-11-01 CN CN201310539037.7A patent/CN103589282A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265869A (en) * | 2013-06-04 | 2013-08-28 | 天津大学 | Hydrophobic nano composite ocean anti-staining coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王耀文: "聚苯胺与石墨烯在防腐涂料中的应用", 《中国优秀硕士论文集工程科技I辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969097B (en) * | 2016-05-12 | 2018-08-03 | 江苏永阳新材料科技有限公司 | A kind of pollution resisting coating |
| CN105969097A (en) * | 2016-05-12 | 2016-09-28 | 江苏永阳新材料科技有限公司 | High-performance antifouling paint |
| CN106047091A (en) * | 2016-07-05 | 2016-10-26 | 北京东方雨虹防水技术股份有限公司 | Waterproof and corrosion-resistant coating for coastal region |
| CN107417968A (en) * | 2017-04-12 | 2017-12-01 | 南京航空航天大学 | A kind of surface modifying method of powdered whiting and the method that high polymer composite material is prepared using this method |
| CN107417968B (en) * | 2017-04-12 | 2019-12-20 | 南京航空航天大学 | Surface modification method of heavy calcium carbonate and method for preparing high polymer composite material by adopting method |
| CN109423157A (en) * | 2017-06-29 | 2019-03-05 | 洛阳尖端技术研究院 | A kind of coating and preparation method thereof |
| WO2019178682A1 (en) | 2018-03-20 | 2019-09-26 | Graphite Innovation And Technologies Inc. | Multifunctional coatings for use in wet environments |
| EP3647375A1 (en) * | 2018-10-29 | 2020-05-06 | Ventus Engineering GmbH | Surface coating material, cured surface coating and use hereof |
| CN110437662A (en) * | 2019-08-23 | 2019-11-12 | 江苏海晟涂料有限公司 | A method of preparing graphene composite material modified marine antifouling paint |
| WO2021077502A1 (en) * | 2019-10-26 | 2021-04-29 | 维新制漆（江西）有限公司 | Nano silicon-carbon modified graphene special anti-corrosion coating and preparation method therefor |
| US11679532B2 (en) | 2020-02-06 | 2023-06-20 | GM Global Technology Operations LLC | In-mold coating with improved flowability |
| CN114702879A (en) * | 2022-04-02 | 2022-07-05 | 瑞格特新材料科技(佛山市)有限公司 | Anti-corrosion antifouling coating and preparation method thereof |
| CN114702879B (en) * | 2022-04-02 | 2023-03-14 | 瑞格特新材料科技(佛山市)有限公司 | Anti-corrosion antifouling coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103589282A (en) | 2014-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104974640A (en) | Preparation method of graphene-containing marine anticorrosive antifouling paint | |
| CN102977744A (en) | Nano-composite marine anti-fouling coating material and preparation method thereof | |
| CN103265869A (en) | Hydrophobic nano composite ocean anti-staining coating and preparation method thereof | |
| CN108997889A (en) | A kind of ocean naval vessel graphene heavy antisepsis priming paint and preparation method thereof | |
| CN110305580B (en) | Graphene-based hydrophobic anticorrosive coating and preparation method and application thereof | |
| CN105295585A (en) | Novel paint for anti-fouling and anti-corrosion treatment on marine metal component and preparation method of novel paint | |
| CN110041807A (en) | A kind of preparation method of marine anticorrosion composite coating | |
| CN102206848A (en) | Cathode electrophoresis protective coating modified by silicane and application thereof | |
| Liu et al. | Review on formation of biofouling in the marine environment and functionalization of new marine antifouling coatings | |
| CN109385630A (en) | A kind of Zn-based plating layer super hydrophobic functional surface one-step preparation process | |
| CN104693970A (en) | Contact type inshore fishing boat anti-fouling paint and preparation method thereof | |
| CN110358396A (en) | A kind of long-acting controlled release marine antifouling coating | |
| CN104403448A (en) | Nano cuprous oxide and nano silver compounded sea anti-fouling paint | |
| CN110330865A (en) | Modified anti-corrosion primer of a kind of graphene and preparation method thereof | |
| Liu | Development of anti-fouling coating using in marine environment | |
| CN102642356B (en) | Non-toxic biological anti-fouling resistance reducing composite coating, preparation method for composite coating and anti-fouling resistance reducing treatment method for base material | |
| CN107541129A (en) | A kind of nano combined antifouling paint and preparation method thereof | |
| CN102732106B (en) | Antifouling coating composition for marine structures, coating preparation method and obtained coating | |
| CN106479353B (en) | A kind of hydrophobic chromium-free Dyclo paint | |
| CN102399486A (en) | Nano marine anti-fouling coating | |
| Subbaiyan et al. | Bioprospecting and Exploration of the Natural Antifouling Approaches against Marine Foulers. | |
| CN108795267B (en) | Graphene modified electrostatic antifouling paint and preparation method and application thereof | |
| Chaudhari | Adhesion of Fouling Organisms and its Prevention Technique | |
| CN115572516A (en) | Water-soluble high polymer composite anti-drag coating, preparation method and application of coating | |
| CN114410151B (en) | Super-infiltrated metal net film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151014 |
|
| RJ01 | Rejection of invention patent application after publication |