CN109082193A - It is a kind of with anti-corrosion and antifouling difunctional coatings and preparation method thereof - Google Patents
It is a kind of with anti-corrosion and antifouling difunctional coatings and preparation method thereof Download PDFInfo
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
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Abstract
本发明属于海洋防腐防污技术领域。具体涉及一种具有防腐和防污双功能的自修复涂层及其制备方法。所述方法包括：首先制备同时负载有环保防污剂和自修复试剂的高分子微胶囊，通过加入分散助剂，将微胶囊分散至树脂中，制得自修复涂层。涂层出现损伤时，微胶囊破裂释放其中的自修复试剂和环保防污剂，一方面修复微裂纹，一方面阻止微裂纹处微生物的附着。相比于传统自修复防腐涂层，该类自修复涂层通过一种微胶囊的高附加值作用可以同时实现自修复防腐和防污功能，负载的防污剂环境友好且高效广谱；本发明涉及到的原料便宜易得，合成过程易控，无须特设条件和设备，产率较高，自修复防腐和防污效果显著。
The invention belongs to the technical field of marine anticorrosion and antifouling. In particular, it relates to a self-repairing coating with dual functions of anticorrosion and antifouling and a preparation method thereof. The method includes: first preparing polymer microcapsules loaded with an environmental protection antifouling agent and a self-repairing agent, and dispersing the microcapsules into a resin by adding a dispersing aid to prepare a self-repairing coating. When the coating is damaged, the microcapsules rupture to release the self-repairing agent and environmental protection antifouling agent, which can repair the micro-cracks on the one hand and prevent the attachment of microorganisms at the micro-cracks on the other hand. Compared with traditional self-healing anti-corrosion coatings, this type of self-healing coating can realize self-healing anti-corrosion and anti-fouling functions at the same time through the high value-added function of microcapsules. The loaded anti-fouling agent is environmentally friendly and efficient and broad-spectrum; The raw materials involved in the invention are cheap and easy to obtain, the synthesis process is easy to control, no special conditions and equipment are required, the yield is high, and the self-repairing anticorrosion and antifouling effects are remarkable.
Description
Technical field
The invention belongs to marine anticorrosion anti-soil technology fields, and in particular, to a kind of with anti-corrosion and antifouling difunctional
Coatings and preparation method thereof coat environment-friendly antifouling agent and selfreparing reagent using microcapsules more particularly to a kind of simultaneously
Selfreparing anticorrosion and antifouling coating and preparation method thereof.
Background technique
Marine corrosion, biodeterioration problem are the significant threats that ocean development faces in the process.As caused by marine corrosion
Catastrophic failure case it is very much, cause extremely huge loss.And biodeterioration increases hull ship resistance and fuel disappears
Consumption blocks sea water conveying pipelines, increases operating cost etc., is the technology bottle for restricting marine economy and developing and maintaining coast defence safety
Neck.The common method for solving metal erosion and biodeterioration is coating macromolecule protective coating, such as epoxy resin, polyurethane tree
Rouge, polyaniline, resin with low surface energy etc..But coating is in complicated marine environment, usually due to external force and aging action
It cracks, the metallic substrates of breakage directly and contact with sea water, cause to corrode rapidly.In addition, breakage loses anti-pollution function,
Marine growth largely adheres to and grows, and leads to serious biodeterioration problem.
In recent years, people are more and more for the research of Smart self-repairing corrosion-inhibiting coating, and the early stage micro-crack of coating is reviewed one's lessons by oneself
Recovering technology is at present by very big concern.When coating is damaged, self-repairing microcapsule dispersed therein can discharge inside
The selfreparing reagent of cladding occurs further reaction and forms new protective layer, realizes the self-regeneration of breakage, prevent or slow down
Corrosion process improves the life cycle of anticorrosive paint.Common renovation agent such as vegetable oil (CN102719184A,
CN102390147A), epoxy resin (CN107777905A CN104772086B, CN106334503A, CN105056853B,
CN106215826A, CN106118367A), isocyanates analog derivative (CN105080442B, CN102702838A).
However, the coatings developed at present often only have antiseptic property, and it is antifouling for caused by coating damage
Disabler is helpless.By the way that load is added simultaneously into coating, to have the high molecular functional microballoon of fungicide and load to have slow
The nano container of erosion agent can prepare the selfreparing corrosion-inhibiting coating with anti-pollution function by the collective effect of two kinds of functional particles
(CN107760163A).But currently, simpler efficient mode prepares and has both reviewing one's lessons by oneself for anti-corrosion and anti-pollution function not yet
Overcoating layer.
Summary of the invention
It is an object of the invention to provide a kind of with anti-corrosion and antifouling difunctional coatings and preparation method thereof, the party
Method is prepared for high molecule microcapsule that is a kind of while loading environment-friendly antifouling agent and selfreparing reagent, distributes it in coating, applies
When layer rupture, selfreparing reagent, which is discharged and reacted, fills breakage, and substrate is avoided to corrode；In addition release environmental protection is anti-
Dirty agent resists the attachment of breakage microorganism, realizes anti-pollution function.Microcapsules synthetic route prepared by the present invention is simple, and raw material is easy
, the coating of preparation has both efficient selfreparing anti-corrosion and anti-pollution function, has potential using value.
The specific technical solution of the present invention is as follows:
The present invention relates to a kind of with anti-corrosion and the preparation method of antifouling difunctional coatings, including following step
It is rapid:
1) 10~80g emulsifier is added in 120mL water, obtains emulsifier solution.
2) 2.5~50g urea, 0.25~5g ammonium chloride, between 0.25~5g are added into emulsifier solution described in step 1)
Benzenediol adjusts pH of mixed to 2.0~4.5, forms stable emulsion；
3) 1~99g environment-friendly antifouling agent is added in 1~99g selfreparing reagent and is mixed, obtain mixed solution；
4) mixed solution that step 3) obtains is added to pre- mixed stable emulsion in step 2), is emulsified；
5) formalin that 10~90g is added into the reaction solution after step 4) emulsification is reacted, and is dropped after reaction
To room temperature, after washed, suction filtration, vacuum drying, microscapsule powder is obtained；
6) microscapsule powder is distributed in diluent, dispersing aid is added, resin and corresponding curing agent, system is then added
Derived from reparation.
In the above-mentioned selfreparing Tu layer preparation method of the present invention, the microcapsules prepared further include wall material structure, described micro-
The wall material structure of capsule is Lauxite single-wall structure.
Further, the preparation method the present invention relates to another kind with anti-corrosion and antifouling difunctional coatings,
The following steps are included:
1) 10~80g emulsifier is added in 120mL water, obtains emulsifier solution；
2) 2.5~50g urea, 0.25~5g ammonium chloride, between 0.25~5g are added into emulsifier solution described in step 1)
Benzenediol adjusts pH of mixed to 2.0~4.5, forms stable emulsion；
3) 1~99g environment-friendly antifouling agent is added in 1~99g selfreparing reagent, obtains mixed solution；
3 ') 4~25g polyurethane prepolymer is mixed under protective atmosphere with 4~15mL organic solvent；
4) mixed solution in step 3) is added to 3 ') in mixed solution, then add pre- in step 2)
Mixed stable emulsion, is emulsified；
5) formalin that 10~90g is added into the reaction solution after step 4) emulsification is reacted, and is dropped after reaction
To room temperature, after washed, suction filtration, vacuum drying, microscapsule powder is obtained；
6) microscapsule powder is distributed in diluent, dispersing aid is added, resin and curing agent is then added, be made certainly
Reparation.
In the preparation method of another kind selfreparing Tu layer of the present invention, the microcapsules prepared further include wall material knot
Structure, due to increasing step 3 ') so that the wall material structure for preparing microcapsules is Lauxite-polyurethane double-walled construction.
According to the preparation method of the coatings, wherein preferably, the Lauxite mainly by urea and
Formaldehyde reacts to obtain.
According to the preparation method of the coatings, wherein preferably, step 3 ') polyurethane is by isocyanates
Analog derivative reacts to obtain with polyalcohol or polyamine.
According to the preparation method of the coatings, wherein preferably, step 3 ') described in polyurethane prepolymer packet
Include toluene diisocyanate prepolymer (TDI), hexamethylene diisocyanate (HDI) prepolymer, diphenylmethane diisocyanate
The one or more of ester (MDI) prepolymer and isophorone diisocyanate (IPDI) prepolymer.
According to the preparation method of the coatings, wherein preferably, step 3 ') used in organic solvent include acetic acid
Ethyl ester, one or more of cyclohexanone, toluene, hexane, hexamethylene and acetone.
According to the preparation method of the coatings, wherein preferably, emulsifier described in step 1) includes: polyoxy
Ethylene sorbierite lanolin derivative, polyvinyl alcohol, soap, neopelex, lauryl sodium sulfate, polyoxyethylene
Cetyl ether, alkylaryl sulfonates, Emulphor FM, N- cetyl-N-ethylmorpholine base sodium ethylsulfate, oil
Sour potassium, gum arabic, gelatin, lecithin, lanolin, glycerine monofatty ester, sucrose ester, sorbose alcohol ester, soybean lecithin,
One or more of lauric monoglyceride and propylene glycol fatty acid.
According to the preparation method of the coatings, wherein preferably, environment-friendly antifouling agent described in step 3) includes
Capsaicine, shogaol, di-terpene formamide, homarine, homopiperony lamine, halogeno indole, nancoin, Osthole are high recessed
Push up algae alcohol, protease, halogenated furan ketone, p- meat silicic acid sulfuric acid ester, tannic acid, tannic acid copper, tannic acid zinc, 4,5- dichloro-s-
Kathon (DCOIT), 1,2-benzisothiazolin-3-one (BIT), 2- (rubigan) -3- cyanogen
Base -4- bromo -5- trifluoromethyl-pyrroles, sodium benzoate, Bravo, dichlorophenyl dimethyl urea, dichlofluanid, the tertiary fourth ammonia of 2-
Base -4- cyclopropylamino -6- methylthio-s-triazine, one or more of pyrithione zinc and triphenylboron pyridine alkane.
According to the preparation method of the coatings, wherein preferably, selfreparing reagent described in step 3) includes
One or more of isocyanates analog derivative, tung oil, linseed oil and octadecyl trimethoxysilane.
According to the preparation method of the coatings, wherein preferably, the step 3) environment-friendly antifouling agent and review one's lessons by oneself
10~50g environment-friendly antifouling agent is preferably added in 50~90g selfreparing reagent and mixes by retrial agent.
According to the preparation method of the coatings, wherein preferably, to emulsifier described in step 1) in step 2)
It is added defoaming agent in solution, the defoaming agent includes that soya-bean oil, corn oil, rape oil, fish oil, octanol, higher alcohols, glycerol trihydroxy are poly-
The one or more of ether and dimethyl silicone polymer.
According to the preparation method of the coatings, wherein preferably, step 3 ') described in protective atmosphere include nitrogen
One or more of gas and inert gas.
According to the preparation method of the coatings, wherein preferably, step 4) is emulsified in 500~2000rpm
10~30min.
According to the preparation method of the coatings, wherein preferably, the mass fraction of formalin in step 5)
For 36.5wt%-50.5wt%.
According to the preparation method of the coatings, wherein preferably, step 5) isothermal reaction 3 at 45~65 DEG C
~6h.
According to the preparation method of the coatings, wherein preferably, the reaction after emulsification described in step 5)
Formalin is added in liquid to be reacted, 5~15min of ice-bath ultrasonic.
According to the preparation method of the coatings, the step 6) microcapsules, curing agent, resin, dispersing agent add
Enter amount is microcapsules according to the mass fraction: curing agent: resin: dispersing aid: the mass ratio of diluent is 0.6~90:2~200:
10~100:1~50:0.5~50.
According to the preparation method of the coatings, wherein preferably, diluent described in step 6) includes water, neighbour
Dibatyl phithalate, dioctyl phthalate, styrene, dially phthalate, toluene, dimethylbenzene, acrylic shrink
Glycerin ether, butyl glycidyl ether and phenyl glycidyl ether are one or more of.
According to the preparation method of the coatings, wherein preferably, dispersing aid described in step 6) includes benzene
Ethylene-melamine class, polyacrylic, modified alkyd resin, polyester resin, derivative of fatty acid, lecithin lipid and hydramine
Esters product is one or more of.
According to the preparation method of the coatings, wherein preferably, curing agent described in step 6) includes fat
Amine, aliphatic cyclic amine, aromatic amine, phenolic aldehyde amine, anhydride, imidazoles, thio-alcohol, polyetheramine, polyamide, triethylene tetramine, isophthalic two
Methylamine and alkyl alcoholamine, isocyanates, pyridine, amino resins, band epoxy group resin and tetraisopropoxy titanium are a kind of or several
Kind.
According to the preparation method of the coatings, wherein preferably, resin described in step 6) includes asphalt mixtures modified by epoxy resin
One or more of rouge, polyurethane, acrylic resin, aqueous epoxy resins, aqueous polyurethane and water-based acrylic resin.
According to the preparation method of the coatings, wherein preferably, water used in step 1) include go from water or
Distilled water.
The present invention also provides a kind of with anti-corrosion and antifouling difunctional coatings, and the coatings are by above-mentioned
The preparation method of any coatings is made.Microcapsules Size prepared by the present invention ranges preferably between 1-500 μm.
Compared with prior art, present invention has an advantage that
(1) a kind of microcapsules prepared can discharge self repairing agent and environment-friendly antifouling agent simultaneously, realize selfreparing anti-corrosion and prevent
Dirty function；It is good with a variety of coating system conformabilities, it is applied widely；
(2) the self repairing agent reactivity of microcapsule coated is high, and film forming is excellent after release, effectively realizes that selfreparing is anti-
It is rotten；The anti-fouling agent of load is environmental-friendly and high-efficiency broad spectrum；
(3) in order to improve the mechanical property of microcapsule wall material, the present invention additionally uses uramit-polyurethane bilayer shell
Layer structure, increases the mechanical stability of microcapsules；
(4) the present invention relates to raw material it is cheap and easily-available, synthesis process is easily-controllable, without ad hoc condition and equipment, yield compared with
Height, selfreparing anti-corrosion and anti-fouling effect are significant.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the microcapsules of the load environment-friendly antifouling agent obtained of embodiment 1 and selfreparing reagent.
Fig. 2 is coating made from coatings made from embodiment 1 and control group 1, the comparison after salt water impregnates
Photo.
Fig. 3 be using coating as 3 days bacteriums of substrate culture after, at scratch particle-bound bacteria attachment state laser co-focusing comparison
Photo.(a) with (b) embodiment 1 made from coatings；(c) with (d) control group 2 made from coating.(a) it is shown and lives
The quantity of dead bacterium (b) is shown in the quantity of bacterium, it can be observed that the bacterium that lives at scratch after coatings immersion 3 days
Quantity be significantly more than the quantity of dead bacterium；(c) quantity of bacterium living is shown in picture, and (d) dead bacterium is shown in picture
Quantity said it can be observed that scratch puts to death the quantity of bacterium and is significantly more than the quantity of bacterium living after control group coating impregnates 3 days
Microcapsules made from bright the present embodiment have significant bactericidal effect.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
At room temperature, 120mL distilled water is added in 500mL flask, 13.5g gum arabic emulsifier, 500rpm is added
Mechanical stirring 4 hours then sequentially adds 2.5g urea to upper foam lower layer clear state, 0.25g ammonium chloride, between 0.25g
Benzenediol adjusts pH of mixed to 3.5；Meanwhile 2.7g DCOIT being dissolved in 27g isophorone diisocyanate, ultrasound point
It dissipates uniformly, then, 4g Bayer Desmodur L75 is added in 500mL two mouth flask, it is equal with 4mL ethyl acetate under nitrogen atmosphere
Even stirring 10min, then addition 27g isophorone diisocyanate, which is stirred to the two, uniformly mixes, then by pre- mixed cream
Agent mixed liquor is poured slowly into flask, and 1100rpm emulsifies 10min, and it is water-soluble that the formaldehyde that 6.33g mass fraction is 37% is added
Liquid is warming up to 55 DEG C, reacts 3 hours, cool to room temperature after reaction, clear separation of inclining, in triplicate with distilled water, room temperature is dried in the air
Dry, then weighing is sieved, is sealed in vacuum desiccator.
Microscapsule powder after drying and screening is distributed in dilution with toluene agent, DISPERBYK dispersing aid is added, is added
In polyetheramine epoxy curing agent, 500rpm stirs 10min, and epoxy resin E-44 is then added, and 500rpm stirs 10min,
Microcapsules: curing agent: epoxy resin: dispersing aid: diluent=10:30:60:12:18 prepares selfreparing using knife coating procedure
Coating.
Control group 1
It will be uniformly mixed with epoxy resin E-44 according to the mass ratio of 3:6 in polyetheramine epoxy curing agent, using scraping
Coating method prepares epoxy coating.
Control group 2
At room temperature, 120mL distilled water is added in 500mL flask, 13.5g gum arabic emulsifier, 500rpm is added
Mechanical stirring 4 hours then sequentially adds 2.5g urea to upper foam lower layer clear state, 0.25g ammonium chloride, between 0.25g
Benzenediol adjusts pH of mixed to 3.5；Then, 4g Bayer Desmodur L75, nitrogen atmosphere are added in 500mL two mouth flask
Lower and 4mL ethyl acetate uniform stirring 10min is enclosed, then addition 27g isophorone diisocyanate, which is stirred to the two, uniformly mixes
It closes, then pre- mixed emulsifier mixed liquor is poured slowly into flask, 1100rpm emulsifies 10min, and 6.33g mass point is added
The formalin that number is 37% is warming up to 55 degree, reacts 3 hours, cool to room temperature, clear separation of inclining, with distillation after reaction
Water in triplicate, dry by room temperature, then weighing is sieved, is sealed in vacuum desiccator.
Microscapsule powder after drying and screening is distributed in dilution with toluene agent, DISPERBYK dispersing aid is added, is added
In polyetheramine epoxy curing agent, 500rpm stirs 10min, and epoxy resin E-44 is then added, and 500rpm stirs 10min,
Microcapsules: curing agent: epoxy resin: dispersing aid: diluent=10:30:60:12:18 prepares selfreparing using knife coating procedure
Corrosion-inhibiting coating.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.
Fig. 1 is microcapsules made from this example, and capsule size is uniform, and encystation is good.Fig. 2 and Fig. 3 is respectively corrosion situation
With the attachment of bacterium.In Fig. 2 as it can be seen that compared with blank sample, after the microcapsules of preparation are added, anti-corrosion effects at scratch
Significantly, corrosion can be inhibited to spread.In Fig. 3 as it can be seen that compared with the blank sample of (a) control group 2, load, which is added, has environmental protection antifouling
After the microcapsules of agent, bacterium attachment is seldom at scratch.
Embodiment 2
At room temperature, in 500mL flask be added 120mL distilled water, be added 15g polyvinyl alcohol, 90 DEG C mechanical stirring 4 hours
To pellucidity, 2.5g urea, 0.25g ammonium chloride are then sequentially added, 0.25g resorcinol adjusts pH of mixed to 3.5；
Meanwhile 10g DCOIT being dissolved in 20g isophorone diisocyanate, ultrasonic disperse is uniform, then, in 500mL two mouth flask
Then above-mentioned different Buddhist is added with 4mL acetone uniform stirring under nitrogen atmosphere in middle addition 4g hexamethylene diisocyanate prepolymer
The mixed liquor of that ketone diisocyanate and DCOIT are stirred until homogeneous mixing, and pre- mixed emulsifier is then poured slowly into flask
In, 1100rpm emulsifies 10min, and the formalin that 6.5g mass fraction is 37% is added, is warming up to 55 DEG C, reacts 3 hours,
Cool to room temperature after reaction, clear separation of inclining, in triplicate with distilled water, room temperature is dried, and is then sieved, close in vacuum desiccator
Envelope saves.
Microscapsule powder after drying and screening is distributed in styrene diluent, polyacrylic dispersing aid is added,
Polyetheramine epoxy curing agent and epoxy resin E-51, microcapsules: curing agent: epoxy resin: dispersing aid: diluent are added
Mass ratio is 0.6:2:10:1:1, prepares coatings, room temperature curing using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 3
At room temperature, 120mL distilled water is added in 500mL flask, 20g neopelex is added, stirs to complete
Fully dissolved, then sequentially adds 2.5g urea, 0.25g ammonium chloride, and 0.25g resorcinol adjusts pH of mixed to 3.5；Meanwhile
10g Bravo is dissolved in 20g 4, in 4'- dicyclohexyl methyl hydride diisocyanate, ultrasonic disperse is uniform, then that emulsifier is molten
Liquid is slowly added to above-mentioned isocyanates and the mixed liquor of DCOIT, is stirred until homogeneous mixing, and 900rpm emulsifies 10min, and 10g is added
The formalin that mass fraction is 37%, ice-bath ultrasonic 15min are warming up to 55 DEG C, react 4 hours, after reaction it is cool extremely
Room temperature, clear separation of inclining, in triplicate with distilled water, room temperature is dried, and is then sieved, and is sealed in vacuum desiccator.
Microcapsules are dispersed in a certain amount of distilled water, a certain amount of DISPERBYK dispersing aid is added after being uniformly dispersed,
It is sufficiently mixed, is subsequently poured into aqueous epoxy resins aqueous epoxy curing agent, stirs evenly, microcapsules: curing agent: water-base epoxy
Resin: water: dispersing aid mass ratio is 90:200:100:25:25, prepares coatings, room temperature curing using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 4
At room temperature, 120mL distilled water is added in 500mL flask, 80g neopelex is added, stirs to complete
Fully dissolved, then sequentially adds 10g urea, 1g ammonium chloride, and 1g resorcinol adjusts pH of mixed to 4.5；Meanwhile by 50g bis-
Chlorphenyl dimethyl urea is dissolved in 10g isophorone diisocyanate, and ultrasonic disperse is uniform, then, is added in 500mL two mouth flask
Enter 20g biphenyl methane diisocyanate prepolymer, with 8mL hexamethylene uniform stirring under nitrogen atmosphere, is then added above-mentioned different
The mixed liquor of cyanate and dichlorophenyl dimethyl urea is stirred until homogeneous mixing, then emulsifier solution is poured slowly into flask,
900rpm emulsifies 10min, and the formalin that 32g mass fraction is 37% is added, is warming up to 55 DEG C, reacts 4 hours, reaction knot
Cool to room temperature after beam, clear separation of inclining, in triplicate with distilled water, room temperature is dried, and is then sieved, and sealing is protected in vacuum desiccator
It deposits.
Microscapsule powder after drying and screening is distributed in ethyl acetate, the dispersion of acrylic acid dimethylethanolamine ester is added
Auxiliary agent is stirred evenly with dropper, and pure acrylic resin is then added, and stirs evenly stand-by, microcapsules: acrylic resin: second
Acetoacetic ester: dispersing aid mass ratio is 10:90:10:2, prepares coatings, room temperature curing using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 5
At room temperature, 120mL distilled water is added in 500mL flask, 15g gum arabic is added, mechanical stirring 3 hours is extremely
Pellucidity, then sequentially adds 2.5g urea, 0.25g ammonium chloride, and 0.25g resorcinol adjusts pH of mixed to 3.0；Together
When, it takes 9.45g octadecyl trimethoxysilane and 17.55g isophorone diisocyanate to mix and shakes up, 5.4g BIT is molten
In above-mentioned mixed liquor, ultrasonic disperse is uniform, then, it is pre- that 4g hexamethylene diisocyanate is added in 500mL two mouth flask
Then above-mentioned isophorone diisocyanate, octadecyl is added with 4mL ethyl acetate uniform stirring under nitrogen atmosphere in polymers
Trimethoxy silane, BIT mixed liquor be stirred until homogeneous mixing, then pre- mixed emulsifier is poured slowly into flask,
1400rpm emulsifies 20min, and the formalin that 6.33g mass fraction is 37% is added, is warming up to 55 DEG C, reacts 3 hours, instead
Cool to room temperature after answering, clear separation of inclining, in triplicate with distilled water, room temperature is dried, and is then sieved, sealing in vacuum desiccator
It saves.
Microscapsule powder after drying and screening is distributed in 103 epoxy resin diluents, DISPERBYK dispersion is added and helps
Then bisphenol A epoxide resin and polyetheramine epoxy curing agent is added, microcapsules in agent: curing agent: epoxy resin: diluent:
Dispersing aid mass ratio is 2:2.36:13.6:4.08:5.44, prepares coatings, room temperature curing using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 6
Microscapsule powder 2.36g obtained in embodiment 4 is distributed in 103 epoxide diluent of 5.4g, is added
In 5.4gDISPERBYK epoxy dispersing aid, 500rpm stirs 10min, is then added in 13.6g bisphenol A epoxide resin, stirring
Uniformly, 4.6g polyethers amine hardener is added, prepares coatings, 80 DEG C of solidifications using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 7
The microcapsules 1g that Example 3 obtains, the microcapsules 5g that embodiment 4 obtains, is distributed in 5g water, and the poly- carboxylic of 3g is added
The derivative alcohol diluent of acid, is then added 10g aqueous polyurethane coating and 5g polyisocyanate curing agent, and 500rpm stirs 10min,
Coatings, room temperature curing are prepared using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 8
Microscapsule powder 2g obtained in example 5 is distributed in 2.5g water, 5g acrylic acid dimethylethanolamine ester is added
Then 10g water-based acrylic resin is added in dispersing aid, 500rpm stirs 10min, reviews one's lessons by oneself overcoating using knife coating procedure preparation
Layer, room temperature curing.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 9
At room temperature, 120mL distilled water is added in 500mL flask, 80g gum arabic emulsifier, 500rpm machine is added
Tool stirs 4 hours to upper foam lower layer clear state, then sequentially adds 50g urea, 3g ammonium chloride, 4g resorcinol is adjusted
PH of mixed is saved to 2.0；Meanwhile 1g DCOIT being dissolved in 99g isophorone diisocyanate, ultrasonic disperse is uniform, with
Afterwards, 25g Bayer Desmodur L75 is added in 500mL two mouth flask, under nitrogen atmosphere with 15mL ethyl acetate uniform stirring
Then the mixture of isophorone diisocyanate and DCOIT is added in 10min, stirring to the two uniformly mixing will be pre- mixed
Emulsifier mixed liquor is poured slowly into flask, and 1100rpm emulsifies 10min, and it is water-soluble that the formaldehyde that 70g mass fraction is 37% is added
Liquid is warming up to 50 DEG C, reacts 6 hours, cool to room temperature after reaction, clear separation of inclining, in triplicate with distilled water, room temperature is dried in the air
Dry, then weighing is sieved, is sealed in vacuum desiccator.
Microscapsule powder after drying and screening is distributed in acetone, high molecular weight alkyl ammonium salt copolymer point is then added
Auxiliary agent is dissipated, 500rpm stirs 10min, is then added in epoxy resin E-44 and polyetheramine epoxy curing agent, 500rpm is stirred
Mix 10min, microcapsules: curing agent: epoxy resin=1.2:3:10:5:5 prepares coatings using knife coating procedure.
Embodiment 10
At room temperature, 120mL distilled water is added in 500mL flask, 20g neopelex is added, stirs to complete
Fully dissolved, then sequentially adds 50g urea, 5g ammonium chloride, and 5g resorcinol adjusts pH of mixed to 3.5；Meanwhile by 99g hundred
Bacterium is dissolved in clearly 20g 4, and in 4'- dicyclohexyl methyl hydride diisocyanate, ultrasonic disperse is uniform, then slowly adds emulsifier solution
Enter above-mentioned isocyanates and the mixed liquor of DCOIT, be stirred until homogeneous mixing, 900rpm emulsifies 10min, and 90g mass fraction is added
For 37% formalin, ice-bath ultrasonic 5min is warming up to 65 DEG C, reacts 4 hours, cool to room temperature after reaction, inclines clear
Separation, in triplicate with distilled water, room temperature is dried, and is then sieved, and is sealed in vacuum desiccator.
Microcapsules are dispersed in a certain amount of distilled water, a certain amount of DISPERBYK dispersing aid is added after being uniformly dispersed,
It is sufficiently mixed, is subsequently poured into aqueous epoxy resins, polyamine aqueous epoxy resin curing agent is added, stirs evenly, microcapsules:
Curing agent: aqueous epoxy resins: water: dispersing aid mass ratio is 90:100:100:50:35, is reviewed one's lessons by oneself using knife coating procedure preparation
Overcoating layer, room temperature curing.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Embodiment 11
At room temperature, in 500mL flask be added 120mL distilled water, be added 15g polyvinyl alcohol, 90 DEG C mechanical stirring 4 hours
To pellucidity, 2.5g urea, 0.25g ammonium chloride are then sequentially added, 0.25g resorcinol adjusts pH of mixed to 3.5；
Meanwhile 99g DCOIT being dissolved in 20g isophorone diisocyanate, ultrasonic disperse is uniform, then, in 500mL two mouth flask
Then middle addition 20g hexamethylene diisocyanate prepolymer is added above-mentioned different with 10mL acetone uniform stirring under nitrogen atmosphere
The mixed liquor of isophorone diisocyanate and DCOIT are stirred until homogeneous mixing, and pre- mixed emulsifier is then poured slowly into burning
In bottle, 2000rpm emulsifies 30min, and the formalin that 10g mass fraction is 50.5% is added, and is warming up to 55 DEG C, reaction 3 is small
When, cool to room temperature after reaction, clear separation of inclining, in triplicate with distilled water, room temperature is dried, and is then sieved, vacuum desiccator
Inside it is sealed.
Microscapsule powder after drying and screening is distributed in dilution with toluene agent, DISPERBYK dispersing aid is added, then
Epoxy resin E-51 and polyetheramine epoxy curing agent, microcapsules: curing agent: epoxy resin: diluent: dispersing aid are added
Mass ratio is 54:80:100:30:50, prepares coatings, room temperature curing using knife coating procedure.
It with the standardized scratch of blade, is dipped in 3.5% sodium chloride solution, observes corrosion situation.With the standardized scratch of blade
Antibacterial experiment is carried out, attachment of the bacterium at scratch is observed.Experimental result is the same as embodiment 1.
Certainly, the present invention can also there are many embodiments, without deviating from the spirit and substance of the present invention, are familiar with
Those skilled in the art can disclosure according to the present invention make various corresponding changes and modifications, but these it is corresponding change and
Deformation all should belong to scope of protection of the claims of the invention.
Claims (11)
1. a kind of with anti-corrosion and the preparation method of antifouling difunctional coatings, comprising the following steps:
1) 10~80g emulsifier is added in 120mL water, obtains emulsifier solution；
2) 2.5~50g urea, 0.25~5g ammonium chloride, 0.25~5g isophthalic two are added into emulsifier solution described in step 1)
Phenol adjusts pH of mixed to 2.0~4.5, forms stable emulsion；
3) 1~99g environment-friendly antifouling agent is added in 1~99g selfreparing reagent and is mixed, obtain mixed solution；
4) mixed solution that step 3) obtains is added to pre- mixed stable emulsion in step 2), is emulsified；
5) formalin of 10~90g is added into the reaction solution after step 4) emulsification, is reacted, is down to room after reaction
Temperature after vacuum dried, obtains microscapsule powder；
6) microscapsule powder is distributed in diluent, dispersing aid is added, resin and corresponding curing agent is then added, be made certainly
Reparation.
2. a kind of with anti-corrosion and the preparation method of antifouling difunctional coatings, comprising the following steps:
1) 10~80g emulsifier is added in 120mL water, obtains emulsifier solution；
2) 2.5~50g urea, 0.25~5g ammonium chloride, 0.25~5g isophthalic two are added into emulsifier solution described in step 1)
Phenol adjusts pH of mixed to 2.0~4.5, forms stable emulsion；
3) 1~99g environment-friendly antifouling agent is added in 1~99g selfreparing reagent, obtains mixed solution；
3 ') 4~25g polyurethane prepolymer is mixed under protective atmosphere with 4~15mL organic solvent；
4) mixed solution in step 3) is added to 3 ') in mixed solution, then add pre- mixed in step 2)
Stable emulsion, emulsified；
5) formalin that 10~90g is added into the reaction solution after step 4) emulsification is reacted, and is down to room after reaction
Temperature obtains microscapsule powder after washed, suction filtration, vacuum drying；
6) microscapsule powder is distributed in diluent, dispersing aid is added, resin and corresponding curing agent is then added, be made certainly
Reparation.
3. the preparation method of coatings according to claim 1 or 2, which is characterized in that emulsification described in step 1)
Agent includes: polyoxyethylene sorbitol lanolin derivative, polyvinyl alcohol, soap, neopelex, dodecyl sulphate
Sodium, polyoxyethylene cetyl ether, alkylaryl sulfonates, Emulphor FM, N- cetyl-N-ethylmorpholine base second
Base sodium sulphate, potassium oleate, gum arabic, gelatin, lecithin, lanolin, glycerine monofatty ester, sucrose ester, D-sorbite
One or more of rouge, soybean lecithin, lauric monoglyceride and propylene glycol fatty acid.
4. the preparation method of coatings according to claim 1 or 2, which is characterized in that environmental protection described in step 3)
Anti-fouling agent includes capsaicine, shogaol, di-terpene formamide, homarine, homopiperony lamine, halogeno indole, nancoin, cnidium monnieri
Sub- element, elatol, protease, halogenated furan ketone, p- meat silicic acid sulfuric acid ester, tannic acid, tannic acid copper, tannic acid zinc, 4,
5- dichloro--Kathon, 1,2-benzisothiazolin-3-one, 2- (rubigan) -3- cyano -
4- bromo -5- trifluoromethyl-pyrroles, sodium benzoate, Bravo, dichlorophenyl dimethyl urea, dichlofluanid, the tertiary fourth amino -4- of 2-
Cyclopropylamino -6- methylthio-s-triazine, one or more of pyrithione zinc and triphenylboron pyridine alkane；The selfreparing
Reagent includes one or more of isocyanates analog derivative, tung oil, linseed oil and octadecyl trimethoxysilane.
5. the preparation method of coatings according to claim 1 or 2, which is characterized in that step 3) is by 10~50g ring
It protects anti-fouling agent to be added in 50~90g selfreparing reagent, obtains mixed solution.
6. the preparation method of coatings according to claim 1 or 2, which is characterized in that step 1) in step 2)
It is added defoaming agent in the emulsifier solution, the defoaming agent includes soya-bean oil, corn oil, rape oil, fish oil, octanol, higher alcohols, sweet
The one or more of oily trihydroxy polyethers and dimethyl silicone polymer.
7. the preparation method of coatings according to claim 2, which is characterized in that step 3 ') described in protection gas
Atmosphere includes one or more of nitrogen and inert gas；The polyurethane prepolymer includes toluene di-isocyanate(TDI) pre-polymerization
Object, hexamethylene diisocyanate prepolymer, biphenyl methane diisocyanate prepolymer and isophorone diisocyanate are pre-
The one or more of polymers；The organic solvent includes ethyl acetate, and one in cyclohexanone, toluene, hexane, hexamethylene and acetone
Kind is several.
8. the preparation method of coatings according to claim 1 or 2, which is characterized in that step 4) 500~
Emulsified 10~the 30min of 2000rpm；And step 5) 3~6h of isothermal reaction at 45~65 DEG C.
9. the preparation method of coatings according to claim 1 or 2, which is characterized in that the step 6) microcapsules,
Curing agent, resin, dispersing aid and diluent additional amount are microcapsules according to the mass fraction: curing agent: resin: dispersing aid:
The mass ratio of diluent is 0.6~90:2~200:10~100:1~50:0.5~50.
10. the preparation method of coatings according to claim 1 or 2, which is characterized in that dilution described in step 6)
Agent includes water, dibutyl phthalate, dioctyl phthalate, styrene, dially phthalate, toluene, dimethylbenzene,
Acrylic glycidol ether, butyl glycidyl ether and phenyl glycidyl ether are one or more of；The dispersing aid includes
Styrene-melamine class, polyacrylic, modified alkyd resin, polyester resin, derivative of fatty acid, lecithin lipid and alcohol
Amine esters product is one or more of；The curing agent include fatty amine, aliphatic cyclic amine, aromatic amine, phenolic aldehyde amine, anhydride, imidazoles,
Thio-alcohol, polyetheramine, polyamide, triethylene tetramine, m-xylene diamine and alkyl alcoholamine, isocyanates, pyridine, amino resins,
Band epoxy group resin and tetraisopropoxy titanium are one or more of；The resin includes epoxy resin, polyurethane, acrylic acid
One or more of resin, aqueous epoxy resins, aqueous polyurethane and water-based acrylic resin.
11. a kind of with anti-corrosion and antifouling difunctional coatings, which is characterized in that the coatings are wanted by right
Any preparation method in 1-10 is asked to be made.
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Application publication date: 20181225 |