CN110358345A - A kind of microcapsule-type anti-fouling agent and preparation method thereof, a kind of antifouling paint and preparation method thereof - Google Patents
A kind of microcapsule-type anti-fouling agent and preparation method thereof, a kind of antifouling paint and preparation method thereof Download PDFInfo
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- CN110358345A CN110358345A CN201910772696.2A CN201910772696A CN110358345A CN 110358345 A CN110358345 A CN 110358345A CN 201910772696 A CN201910772696 A CN 201910772696A CN 110358345 A CN110358345 A CN 110358345A
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- microcapsule
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- fouling agent
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- chamaejasmine
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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Abstract
The present invention provides a kind of microcapsule-type anti-fouling agents and preparation method thereof, a kind of antifouling paint and preparation method thereof, belong to marine antifouling coating technical field.Microcapsule-type anti-fouling agent provided by the invention, wall material are poly-dopamine, and core material includes chamaejasmine and oil-based solvent.Chamaejasmine can be extracted from Chinese Stellera Root in microcapsule-type anti-fouling agent provided by the invention, environmentally friendly, and the microcapsule-type anti-fouling agent has slow-release function, when being used for antifouling paint, can extend antifouling phase effect.In addition, the present invention, using chamaejasmine as active constituent, gained anti-fouling agent has antifouling broad spectrum activity, there is good inhibiting effect to the growth of boat-shaped algae and purple ball algae, and the preparation method of the microcapsule-type anti-fouling agent is simple, is suitble to industrial applications.
Description
Technical field
The present invention relates to marine antifouling coating technical field more particularly to a kind of microcapsule-type anti-fouling agent and its preparation sides
Method, a kind of antifouling paint and preparation method thereof.
Background technique
Marine biofouling refers to that marine organisms (such as: bacterium, algae, mollusk) are enterprising on the surface for immersing seawater
The bad behavior colonized of row, can occur on any surface for immersing seawater.This behavior can be to the hair of ocean related fields
Exhibition causes totally unfavorable harm.For example, the attachment of fouling organism can accelerate the corrosion of hull surface；The boundary of ship and fluid
Resistance increases, and route speed reduces, and then the consumption of fuel is caused to increase；Furthermore the marine organisms of different genera are attached to hull
Surface can freely be migrated in different waters, certain threat is brought to the ecological balance in sea area.
A series of above-mentioned harm caused by avoid and mitigating because of marine fouling organism, in addition to science, rationally, safely
Outside design and construction artificial ocean facility, also needs economy, effectively selects and optimize anti-soil technology and means.60 years 20th century
In generation, begins to use doping tributyl tin (TBT) from the nonpolluting coating of polishing, and finds that it has stable and effective antifouling effect
Fruit, the mechanism of action are that tributyl tin can effectively discharge from coating and inhibit to be stained, and realize as long as five years effective anti-
Dirty effect.However, Ocean loading sex distortion is induced since organo-tin compound will affect the calcium metabolism of oyster, it is raw in ocean
It is accumulated in object, adverse effect is generated to human health by food chain, therefore in January, 2008, prohibite ship in the world
Oceangoing ship surface uses the nonpolluting coating containing organo-tin compound.Therefore, novel, efficient, less toxic, environment-friendly antifouling agent is developed to have become
For urgent problem in the world and research hotspot.
Although finding some substances with antifouling effect from marine organisms at present, these substances are in marine organisms
Comparision contents in body are few, and structure is relative complex, and inconvenience is deeply developed and is widely applied.It is anti-based on terrestrial plant chemistry
The enlightenment of imperial functional study is found from many kinds of, widely distributed, the convenient terrestrial plant resource of materials, to harmful organism
Efficiently, it is decomposed to non-target organism safety, easily, and the decomposition product anti-fouling composition harmless to environment will be that substitution TBT is fine
Selection.Such as the Chinese patent of Publication No. CN1709997A reports a kind of antifouling painting using capsaicine as anti-fouling agent
Material, has preferable anti-fouling effect, but the solubility of capsaicine in organic solvent is low, can not carry out slow release method processing, lead
Cause capsaicine rate of release fast, the antifouling time is short.Therefore, it is badly in need of finding new type natural antifouling activity substance, has with preparation slow
Release the anti-fouling agent of function.
Summary of the invention
The purpose of the present invention is to provide a kind of microcapsule-type anti-fouling agent and preparation method thereof, a kind of antifouling paint and its systems
Preparation Method, the active constituent of microcapsule-type anti-fouling agent provided by the invention are natural extract, and have slow-release function and antifouling
Broad spectrum activity.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of microcapsule-type anti-fouling agent, wall material are poly-dopamine, and core material includes chamaejasmine and oil-based solvent.
Preferably, the oil-based solvent is at least one of n-butanol, ethyl alcohol and ethylene glycol.
Preferably, the average grain diameter of the microcapsule-type anti-fouling agent is 150~400nm, and average wall thickness is 25~40nm, wolf
The load capacity of toxin is 70~80%.
The present invention also provides the preparation methods of the microcapsule-type anti-fouling agent described in above-mentioned technical proposal, including walk as follows
It is rapid:
Alkaline buffer solution and surfactant are mixed, water phase is obtained；
Chamaejasmine and oil-based solvent are mixed, oily phase is obtained；
After water phase and oil are mixed, dopamine hydrochloride is added, carries out oxidation auto polymerization reaction, it is anti-to obtain microcapsule-type
Dirty agent.
Preferably, the alkaline buffer solution is the Tris buffer solution that pH value is 8~9, and the surfactant is ten
At least one of six alkyl trimethyl ammonium chlorides and cetyl trimethylammonium bromide, the surfactant and alkaline buffer
The amount ratio of solution is 1g:45~55mL.
Preferably, the volume ratio of the water phase and oily phase is 10~30:1.
Preferably, the mass ratio of the chamaejasmine and dopamine hydrochloride is 1:5~20.
The present invention also provides a kind of antifouling paint, the component including following mass percent: acrylic compounds polish tree certainly
Rouge 30~60%, microcapsule-type anti-fouling agent 2~10%, organic solvent 20~40%, pigments and fillers 10~30%, auxiliary agent 1~3%,
The microcapsule-type anti-fouling agent is preparation side described in microcapsule-type anti-fouling agent described in above-mentioned technical proposal or above-mentioned technical proposal
The microcapsule-type anti-fouling agent that method obtains.
Preferably, the acrylic compounds include that acrylic acid zinc-type polishes the throwing certainly of resin, acrylic acid copper type certainly from polishing resin
Photopolymer resin and acrylic acid silicon type polish at least one of resin certainly.
The present invention also provides the preparation methods of antifouling paint described in above-mentioned technical proposal, which is characterized in that including as follows
Step:
By acrylic compounds from after polishing resin, organic solvent, pigments and fillers and auxiliary agent mixing, is ground, be then added micro-
Capsule-type anti-fouling agent, obtains antifouling paint.
The present invention provides a kind of microcapsule-type anti-fouling agent, wall material is poly-dopamine, and core material includes that chamaejasmine and oiliness are molten
Agent.Chamaejasmine can be extracted from Chinese Stellera Root in microcapsule-type anti-fouling agent provided by the invention, environmentally friendly, and microcapsule-type
Anti-fouling agent has slow-release function, when being used for antifouling paint, can extend antifouling phase effect.Prevent in addition, present invention gained anti-fouling agent has
Dirty broad spectrum activity has good inhibiting effect, and the preparation side of the microcapsule-type anti-fouling agent to the growth of boat-shaped algae and purple ball algae
Method is simple, is suitble to industrial applications.
The present invention also provides a kind of antifouling paint, the component including following mass percent: acrylic compounds polish tree certainly
Rouge 30~60%, microcapsule-type anti-fouling agent 2~10%, organic solvent 20~40%, pigments and fillers 10~30%, auxiliary agent 1~3%,
The microcapsule-type anti-fouling agent is preparation described in microcapsule-type anti-fouling agent described in above-mentioned technical proposal or above-mentioned technical proposal
The microcapsule-type anti-fouling agent that method obtains.Antifouling paint provided by the invention have antifouling broad spectrum activity, when be sprayed at containing
On the template of epoxy primer, when carrying out static panel experiment, place 8 months, surface still maintains clean, only have ooze stick in
Surface, is stained a little few, no large ocean fouling organism attachment, and anti-pollution is excellent.
Detailed description of the invention
The SEM of 1 gained microcapsule-type anti-fouling agent of Fig. 1 embodiment schemes；
Fluorescent quenching figure of Fig. 2 chamaejasmine to boat-shaped algae and purple ball algae；
The fluorogram of the coating surface purple ball algae of 4 gained antifouling paint of Fig. 3 embodiment and blank control antifouling paint；
The template and epoxy blank template that Fig. 4 is coated with 4 gained antifouling paint of embodiment are in shallow sea static state panel experiment
Result figure.
Specific embodiment
The present invention provides a kind of microcapsule-type anti-fouling agent, wall material is poly-dopamine, and core material includes that chamaejasmine and oiliness are molten
Agent.In the present invention, the chamaejasmine has structure shown in formula I:
In the present invention, the chamaejasmine can be extracted from Chinese Stellera Root plant.Microcapsule-type provided by the invention is antifouling
The chamaejasmine being dissolved in oil-based solvent is wrapped in inside, in use, chamaejasmine as wall material by poly-dopamine in agent
Slow release, to achieve the purpose that extend antifouling phase effect.
In the present invention, the oil-based solvent is preferably at least one of n-butanol, ethyl alcohol and ethylene glycol.In the present invention
In, the oil-based solvent can dissolve chamaejasmine, to form oily phase.
In the present invention, the average grain diameter of the microcapsule-type anti-fouling agent is preferably 150~400nm, more preferably 200~
350nm, most preferably 250~300nm；Average wall thickness is preferably 25~40nm, more preferably 30~35nm, the load of chamaejasmine
Amount preferably 70~80%, more preferably 73~78%.
The present invention also provides the preparation methods of the microcapsule-type anti-fouling agent described in above-mentioned technical proposal, including walk as follows
It is rapid:
Alkaline buffer solution and surfactant are mixed, water phase is obtained；
Chamaejasmine and oil-based solvent are mixed, oily phase is obtained；
After water phase and oil are mixed, dopamine hydrochloride is added, carries out oxidation auto polymerization reaction, it is anti-to obtain microcapsule-type
Dirty agent.
The present invention mixes alkaline buffer solution and surfactant, obtains water phase.
In the present invention, the alkaline buffer solution is the Tris buffer solution that pH value is preferably 8~9, and the present invention is to institute
The preparation method for stating Tris buffer solution is not particularly limited, and obtains suitable pH value i.e. using the preparation method of this field routine
It can.In the present invention, Tris buffer solution can react for subsequent oxidation auto polymerization provides alkaline condition, so that dopamine hydrochloric acid
Salt can dehydrochlorination, with occur aoxidize self-polymeric reaction, formed poly-dopamine microcapsule wall.
In the present invention, the surfactant is preferably hexadecyltrimethylammonium chloride and cetyl trimethyl bromine
Change at least one of ammonium, the amount ratio of the surfactant and alkaline buffer solution is preferably 1g:45~55mL, more preferably
For 1g:50mL.
The present invention mixes chamaejasmine and oil-based solvent, obtains oily phase.
The present invention is not particularly limited the source of the chamaejasmine, in embodiments of the present invention, preferably passes through existing skill
Method disclosed in art extracts chamaejasmine from Chinese Stellera Root, such as the prior art " The Leaves And Stems of Stellera Chamaejasme chemical component and bioactivity
Research " extraction side disclosed in (Lu Liqin, Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences's master's thesis, 2013,06)
Method.
In the present invention, the amount ratio of the chamaejasmine and oil-based solvent is preferably 1g:90~110mL, more preferably 1g:
100mL。
After obtaining water phase and oily phase, after the present invention mixes water phase and oil, dopamine hydrochloride is added, aoxidize certainly
Polymerization reaction obtains microcapsule-type anti-fouling agent.In the present invention, after water phase and oil mix, under the action of surfactant,
The emulsion droplet of oil-in-water type is formed, after dopamine hydrochloride is added, in weakly alkaline environment, dopamine hydrochloride dehydrochlorination
Afterwards, oxidation auto polymerization reaction occurs, is wrapped in emulsion droplet surface, forms microcapsule wall.
In the present invention, the volume ratio of the water phase and oily phase is preferably 10~30:1, more preferably 15:1.
In the present invention, the mass ratio of the chamaejasmine and dopamine hydrochloride is preferably 1:5~20, more preferably 1:10
~15.
In the present invention, the temperature of the oxidation auto polymerization reaction is preferably room temperature, and the room temperature is preferably 10~40 DEG C,
Time is preferably 20~26h, more preferably 22~for 24 hours；Stirring is preferably maintained in the oxidation auto polymerization reaction process, it is described to stir
The revolving speed mixed is preferably 300~500r/min, more preferably 350~450r/min.In the present invention, above-mentioned revolving speed is conducive to
To the microcapsule-type anti-fouling agent of uniform particle diameter.
Aoxidize auto polymerization after the reaction was completed, the present invention is preferably centrifuged, by gained microcapsule-type anti-fouling agent crude product
It is successively washed and is dried, obtain microcapsule-type anti-fouling agent.
In the present invention, the revolving speed of the centrifuge separation is preferably 9000~11000r/min, more preferably 10000r/
min；Time is preferably 8~12min, more preferably 10min.In the present invention, the effect of the centrifuge separation is by microcapsules
Type anti-fouling agent is separated from mixed system.
In the present invention, the washing is preferably water with detergent, more preferably deionized water；The present invention is to the washing
Mode be not particularly limited, using conventional mode of washing, in embodiments of the present invention, the washing preferably will be from
Microcapsule-type anti-fouling agent crude product obtained by the heart is dispersed in water, then is centrifuged, and once washing, the number of the washing are completed
Preferably 3~5 times；The revolving speed of the centrifuge separation is preferably 9000~11000rpm, more preferably 10000rpm；Time is preferred
For 8~12min, more preferably 10min.
In the present invention, the drying is preferably dried in vacuo, and the vacuum drying temperature is preferably 40~60 DEG C, more
Preferably 45 DEG C.The present invention is not particularly limited the vacuum drying time, can obtain the product of constant weight.
The present invention also provides a kind of antifouling paint, the component including following mass percent: acrylic compounds polish tree certainly
Rouge 30~60%, microcapsule-type anti-fouling agent 2~10%, organic solvent 20~40%, pigments and fillers 10~30%, auxiliary agent 1~3%,
The microcapsule-type anti-fouling agent is preparation described in microcapsule-type anti-fouling agent described in above-mentioned technical proposal or above-mentioned technical proposal
The microcapsule-type anti-fouling agent that method obtains.
In the present invention, by percentage to the quality, the antifouling paint includes acrylic compounds polishing resin 30~60% certainly,
Preferably 40~50%；The acrylic compounds include that acrylic acid zinc-type polishes the throwing certainly of resin, acrylic acid copper type certainly from polishing resin
Photopolymer resin and acrylic acid silicon type polish at least one of resin certainly；The acrylic compounds from polishing resin solid content be preferably
45~55%, more preferably 50%.In the present invention, the acrylic compounds polish the base resin that resin is antifouling paint certainly,
Cementation is mainly played, while as surface layer resin, can slowly be hydrolyzed in the seawater, hydrophilic segment is formed, gradually from surface
It sloughs, realizes removing polishing layer by layer, be conducive to the anti-fouling effect for further increasing antifouling paint.
In the present invention, by percentage to the quality, the antifouling paint includes microcapsule-type anti-fouling agent 2~10%, preferably
It is 5~8%；The microcapsule-type anti-fouling agent is microcapsule-type anti-fouling agent described in above-mentioned technical proposal or above-mentioned technical proposal institute
The microcapsule-type anti-fouling agent that the preparation method stated obtains.
In the present invention, by percentage to the quality, the antifouling paint includes organic solvent 20~40%, preferably 25~
35%；The organic solvent is preferably the mixture of toluene and dimethylformamide, the matter of the toluene and dimethylformamide
Amount is than being preferably 1~2:1.
In the present invention, by percentage to the quality, the antifouling paint includes pigments and fillers 10~30%, preferably 15~
25%；The pigments and fillers are preferably at least three in zinc oxide, iron oxide red, organobentonite, blanc fixe and talcum powder
Kind.In the present invention, pigments and fillers play the role of enhancing the physicochemical properties such as paint film covering power, hardness, and three kinds of pigments and fillers cooperations can
To guarantee that paint film totality physicochemical property is good.
In the present invention, by percentage to the quality, the antifouling paint includes auxiliary agent 1~3%；The auxiliary agent is preferably moral
The coating additive of Guo Bike company, more preferably include BYK104S wetting dispersing agent, BYK354 levelling agent, BYK052 defoaming agent and
BYK410 anti-settling agent；The matter of the BYK104S wetting dispersing agent, BYK354 levelling agent, BYK052 defoaming agent, BYK410 anti-settling agent
Amount is than being preferably 2:1:1:1.
The present invention also provides the preparation methods of antifouling paint described in above-mentioned technical proposal, include the following steps:
By acrylic compounds from after polishing resin, organic solvent, pigments and fillers and auxiliary agent mixing, is ground, be then added micro-
Capsule-type anti-fouling agent, obtains antifouling paint.
In the present invention, in slurry obtained by the grinding partial size of particulate matter preferably≤30 μm.
The present invention is not particularly limited the parameter of the grinding, can obtain the material of required partial size.
After microcapsule-type anti-fouling agent is added, the present invention is preferably stirred.The present invention is to the condition of the stirring without spy
It is different to limit, uniformly mixed antifouling paint can be obtained.
Below with reference to embodiment to a kind of microcapsule-type anti-fouling agent provided by the invention and preparation method thereof, a kind of antifouling painting
Material and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
150mL pH value is mixed for 8.5 Tris buffer solution and 3g hexadecyltrimethylammonium chloride, obtains water phase；
10mL n-butanol and 0.1g chamaejasmine are mixed, oily phase is obtained；
After the water phase and oil are mixed, 1g dopamine hydrochloride is added, in room temperature (25 DEG C) with the revolving speed of 400rpm
Stirring for 24 hours, is then centrifuged 10min under the revolving speed of 10000rpm, obtains microcapsule-type anti-fouling agent crude product, then use deionized water
It is dry in 45 DEG C of progress vacuum after washing centrifugation gained microcapsule-type anti-fouling agent crude product 3 times, obtain microcapsule-type anti-fouling agent.
Using ultraviolet-uisible spectrophotometer, the ultraviolet absorptivity of chamaejasmine in microcapsule-type anti-fouling agent is tested, wolf is passed through
The ultraviolet absorptivity of toxin obtains its concentration, and the absorbance of chamaejasmine, obtains about chamaejasmine specially under test various concentration
Concentration and absorbance standard curve, then test obtain microcapsules release chamaejasmine absorbance, pass through standard curve
Its concentration is obtained, the quality of chamaejasmine is then calculated, then its load is obtained divided by the quality of microcapsules by the quality of chamaejasmine
Amount is 73%.
The pattern of microcapsule-type anti-fouling agent obtained by the present embodiment is characterized, as a result as shown in Figure 1.As shown in Figure 1, originally
It is the uniform particle diameter of microcapsule-type anti-fouling agent obtained by embodiment, average grain diameter 255nm.
As transmissioning electric mirror test obtain the present embodiment obtained by microcapsule-type anti-fouling agent average wall thickness be 30nm.
Embodiment 2
Microcapsule-type anti-fouling agent is prepared according to the method for embodiment 1, the difference is that, the dosage of dopamine hydrochloride is
2g。
The method in embodiment 1 is used to detect the load capacity of chamaejasmine as 75%.
The average grain diameter of microcapsule-type anti-fouling agent as obtained by sem test the present embodiment is 270nm, passes through transmission
Electronic Speculum test is originally that the average wall thickness of microcapsule-type anti-fouling agent obtained by embodiment is 34nm.
Embodiment 3
Microcapsule-type anti-fouling agent is prepared according to the method for embodiment 1, the difference is that, the dosage of n-butanol is 20mL,
The dosage of chamaejasmine is 0.2g.
The method in embodiment 1 is used to detect the load capacity of chamaejasmine as 75%.
The average grain diameter of microcapsule-type anti-fouling agent as obtained by sem test the present embodiment is 260nm, passes through transmission
Electronic Speculum test is originally that the average wall thickness of microcapsule-type anti-fouling agent obtained by embodiment is 32nm.
Embodiment 4
The zinc acrylate resin that 50g solid content is 50% is polished into resin, 15g pigments and fillers (wherein zinc oxide, organobentonite certainly
(wherein BYK104S wetting dispersing agent 0.6g, BYK354 levelling agent 0.3g, BYK052 disappears with each 5g of iron oxide red), 1.5g auxiliary agent
Infusion 0.3g, BYK410 anti-settling agent 0.3g), 18.5g toluene and the mixing of 10g dimethylformamide, said mixture is placed in planet
It is ground 5 hours in formula ball mill, discharges after checking fineness less than 30 μm, 1 gained capsule-type anti-fouling agent of 5g embodiment is added, with
1000rpm revolving speed stirs 20min, obtains antifouling paint.
The antifouling broad spectrum activity test of chamaejasmine
Inhibiting effect of the test chamaejasmine to boat-shaped algae: it disperses chamaejasmine in the solution containing boat-shaped algae, wherein molten
The initial fluorescent intensity of liquid is 655, prepares the ethanol solution of the chamaejasmine containing various concentration, when 12h is placed in test, boat-shaped algae
Fluorescence intensity, as a result as shown in A in Fig. 2, the fluorescence intensity of boat-shaped algae is significantly reduced with the increase of chamaejasmine concentration.
Chamaejasmine is tested to the inhibiting effect of purple ball algae: using the above method, boat-shaped algae is replaced with into purple ball algae, tests wolf
Behavior is quenched to purple ball algae in toxin, as a result as shown in B in Fig. 2.
As shown in Figure 2, when there is no chamaejasmine addition (0mg/mL), the fluorescence intensity of solution is higher, illustrates the dense of algae
Degree is high, and after chamaejasmine is added, with the increase of chamaejasmine concentration, the fluorescence intensity of boat-shaped algae and purple ball algae is gradually reduced, explanation
Chamaejasmine all has inhibiting effect to boat-shaped algae and purple ball algae, illustrates its anti-fouling effect with wide spectrum.
The sustained release performance of microcapsule-type anti-fouling agent is tested:
It disperses 1 gained microcapsule-type anti-fouling agent of embodiment in the mixed liquor of ethyl alcohol and Tris buffer solution, wherein second
The volume ratio of pure and mild Tris buffer solution is 3:7, and the pH value of Tris buffer solution is 8.4, microcapsule-type in obtained mixed liquor
The concentration of anti-fouling agent is 0.02mg/mL, per at regular intervals, tests the concentration of the chamaejasmine in mixed liquor.As a result such as 1 institute of table
Show.
The sustained release performance test result of 1 microcapsule-type anti-fouling agent of table
As shown in Table 1 with the extension of time, the radix euphorbiae lantu concentration in mixed liquor slowly increases, illustrate provided by the present invention
Microcapsule-type anti-fouling agent has slow-release function, is able to extend antifouling phase effect.
The anti-pollution of antifouling paint is tested:
Blank control antifouling paint: according to the method for embodiment 4, it is added without microcapsule-type anti-fouling agent, prepares antifouling paint.
(1) embodiment 4 and blank control antifouling paint are sprayed on glass slide respectively, room temperature curing 12h.Then by this
Two kinds of coatings are placed in purple ball algae solution, for 24 hours after fluorescence microscopy under the microscope its surface amount of algae, as a result such as Fig. 3 institute
Show, wherein a is blank control nonpolluting coating surface, and b is 4 gained nonpolluting coating surface of embodiment, and the bright spot in figure is purple ball algae.
From the figure 3, it may be seen that the nonpolluting coating surface algae density of embodiment 4 is significantly smaller relative to blank control nonpolluting coating.Thus it says
Antifouling paint provided by bright embodiment 4 is inhibited to the growth of purple ball algae.
(2) 4 gained antifouling paint of embodiment is sprayed on the low carbon steel plate of epoxy anticorrosion primer (150 × 250 ×
Template 2mm) is made, after room temperature is sufficiently dried, carries out shallow sea static state board experiment；The same specification steel plate of simultaneous selection does blank
(being denoted as epoxy blank) coats epoxy anticorrosion primer on its surface.Two templates are placed in 1 meter of depths of undersea and carry out static real sea
Board experiment, test period in October, 2018~2019 year 06 month, experimental field are as follows: Shenzhen waters.
It respectively at static hanging plate 4 months and 8 months, takes pictures to two templates, observes the surface shape of two templates
State, as a result as shown in Figure 4.Epoxy blank template shallow sea static state hanging plate all kinds of Macro-fouling Organismss of specimen surface attachment after 4 months,
It mainly based on barnacle, mussel, lime worm, is stained seriously, and is coated with the template static state hanging plate of 4 gained antifouling paint of embodiment
After 4 months, specimen surface paint film is intact, and without blistering, falling off, surface of the paint film is clean；After hanging plate 8 months, epoxy blank template table
Face, which is stained, to be further aggravated, and there are many fouling organisms to adhere to, and forms fouling community, and is coated with 4 gained antifouling paint of embodiment
Surface remain unchanged cleaning, only there is ooze to stick in surface, be stained a little few, no large ocean fouling organism adheres to, anti-pollution
It is excellent.It can be seen that antifouling paint anti-pollution provided by the invention is very excellent in probation, the anti-of wide spectrum is shown
Dirty effect, and it is entirely free of cuprous oxide.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of microcapsule-type anti-fouling agent, which is characterized in that wall material is poly-dopamine, and core material includes chamaejasmine and oil-based solvent.
2. microcapsule-type anti-fouling agent according to claim 1, which is characterized in that the oil-based solvent is n-butanol, ethyl alcohol
At least one of with ethylene glycol.
3. microcapsule-type anti-fouling agent according to claim 1 or 2, which is characterized in that the microcapsule-type anti-fouling agent is put down
Equal partial size is 150~400nm, and average wall thickness is 25~40nm, and the load capacity of chamaejasmine is 70~80%.
4. the preparation method of the described in any item microcapsule-type anti-fouling agents of claims 1 to 3, which is characterized in that including walking as follows
It is rapid:
Alkaline buffer solution and surfactant are mixed, water phase is obtained；
Chamaejasmine and oil-based solvent are mixed, oily phase is obtained；
After water phase and oil are mixed, dopamine hydrochloride is added, carries out oxidation auto polymerization reaction, it is antifouling to obtain microcapsule-type
Agent.
5. the preparation method according to claim 4, which is characterized in that the alkaline buffer solution is that pH value is 8~9
Tris buffer solution, the surfactant be in hexadecyltrimethylammonium chloride and cetyl trimethylammonium bromide extremely
The amount ratio of few one kind, the surfactant and alkaline buffer solution is 1g:45~55mL.
6. preparation method according to claim 4 or 5, which is characterized in that the volume ratio of the water phase and oily phase is 10~
30:1。
7. the preparation method according to claim 4, which is characterized in that the mass ratio of the chamaejasmine and dopamine hydrochloride
For 1:5~20.
8. a kind of antifouling paint, which is characterized in that the component including following mass percent: acrylic compounds from polishing resin 30~
60%, microcapsule-type anti-fouling agent 2~10%, organic solvent 20~40%, pigments and fillers 10~30%, auxiliary agent 1~3% is described micro-
Capsule-type anti-fouling agent is described in the described in any item microcapsule-type anti-fouling agents of claim 2~4 or any one of claim 5~7
The obtained microcapsule-type anti-fouling agent of preparation method.
9. antifouling paint according to claim 8, which is characterized in that the acrylic compounds include acrylic acid from resin is polished
Zinc-type is from resin, acrylic acid copper type is polished from resin and acrylic acid silicon type is polished from least one of polishing resin.
10. the preparation method of the antifouling paint of claim 8 or 9, which comprises the steps of:
By acrylic compounds from after polishing resin, organic solvent, pigments and fillers and auxiliary agent mixing, is ground, microcapsules are then added
Type anti-fouling agent, obtains antifouling paint.
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| CN114085563A (en) * | 2021-12-28 | 2022-02-25 | 广东美涂士建材股份有限公司 | Green environment-friendly capsule release type antifouling paint and preparation method thereof |
| CN116463004A (en) * | 2023-04-22 | 2023-07-21 | 西安石油大学 | Preparation method of microcapsule type anti-fouling agent suitable for seawater environment |
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| CN105670565A (en) * | 2014-11-18 | 2016-06-15 | 中国科学院兰州化学物理研究所 | Self-clean material having self-repair function and preparation method thereof |
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| CN105295655A (en) * | 2015-11-25 | 2016-02-03 | 中国科学院兰州化学物理研究所 | Super-hydrophobic repairable aqueous coating material and preparation method thereof |
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| CN114085563A (en) * | 2021-12-28 | 2022-02-25 | 广东美涂士建材股份有限公司 | Green environment-friendly capsule release type antifouling paint and preparation method thereof |
| CN116463004A (en) * | 2023-04-22 | 2023-07-21 | 西安石油大学 | Preparation method of microcapsule type anti-fouling agent suitable for seawater environment |
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