CN106916477A - A kind of method of marine anti-pollution - Google Patents
A kind of method of marine anti-pollution Download PDFInfo
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- CN106916477A CN106916477A CN201510990763.XA CN201510990763A CN106916477A CN 106916477 A CN106916477 A CN 106916477A CN 201510990763 A CN201510990763 A CN 201510990763A CN 106916477 A CN106916477 A CN 106916477A
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- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a kind of method of marine anti-pollution, comprise the following steps：Epoxy polyamide anticorrosive paint is coated on antifouling object is needed；Tack coat is coated on the anticorrosive paint layer；The antifouling paint finish paint of low-surface-energy is coated on the tack coat, the method for the present invention employs low surface energy antifouling coating for seas using three road organic assembling coated bodies：I.e. using epoxy polyamide anticorrosive paint as priming paint, the interpenetrating networks tack coat of inter coat is styrene --- butyl acrylate --- polysiloxanes, followed by low-surface-energy nano inorganic silicon antifouling paint finish paint.Both the effect of forming a connecting link of adhesion property and inter coat that epoxy resin is excellent to base material had been make use of, and had preferably solved the problems, such as attachment, anti-pollution function and the difficult problem of environmental protection of steel substrate and anti-corrosion primer and antifouling paint.
Description
Technical field
The present invention relates to marine anti-pollution field, and in particular to a kind of method of marine anti-pollution.
Background technology
According to information, there are nearly more than 20,000 kinds of aufwuches in the marine site all over the world.The larva of these aufwuches and spore float in ocean, move about, and being developed when them will adhere on steel construction under the hull bottom of navigation ocean or sea, settle down and further breed to a certain extent.The attachment of these biologies can not only increase the surface roughness of steel construction, and the speed of a ship or plane for making ship declines, fuel consumption increases（Can reach 30%）, and cause structural material corrosion rate to be accelerated and endanger platform facility and aquaculture in water,
Such as：Cause cold water pipes to block, increase submarine pipeline transporting resistance etc..Due to the tension force produced by these biological growths, the organic protection coating-paint film of hull bottom or steel structure surface can be destroyed.Meanwhile, the organic acid that these bio secretions go out, the corrosion failure for making hull bottom steel plate and underwater facility aggravates, service life significantly shortens.To solve this problem, various marine antifouling coatings just arise at the historic moment.
At present, marine antifouling coating has evolved into the systemic technology for preventing marine organisms apposition growth.Wherein develop most fast with anti-fouling ship paint, be most widely used.The anti-fouling ship paint of early stage uses the compounds such as arsenic, mercury as the antifoulant additive of antifouling paint, is eliminated because toxicity is too big.It is therewith the soluble type anti-fouling ship paint with cuprous oxide as coating anti-fouling agent base-material, develops into the insoluble type of base-material of high-copper compounds content again afterwards（With high polymer as main base）The compound toxic agent type ship antifouling paint of anti-fouling ship paint, organotin and organotin --- cuprous oxide, then to the excellent tin-free self-polishing anti-fouling ship paint of high-performance, long-term effect, workability（SPC）, anti-fouling ship paint technology is constantly pushed ahead.
2nd, the development course of marine antifouling coating
Antifouling paint：With the coating for preventing adhesive performance of marine biology energy.Its composition is different from general coating, by poison, oozes out auxiliary agent, base-material, pigment, rib agent and solvent etc. and constitutes.It is antifouling using carrying out containing virose material always on history of marine navigation to prevent attachment of the marine organisms on ship or offshore steel structure, growth.The once compound such as used copper, arsenic, lead, mercury and tin, although can reduce or it is local eliminate marine organisms the surface of steel construction be stained, but harmful substance be released to ecological environment and human health also result in serious harm.The compounds such as early application arsenic, mercury prepare the countries such as the American and Britain of antifouling paint as anti-fouling agent, eliminate stop using already.After 20 century 70s, with the disabling of the anti-fouling agents such as mercury, arsenic, organotin can reach wide spectrum, efficient antifouling purpose and find and gradually use at low concentrations so that organo-tin compound turns into the representational anti-fouling agent of antifouling paint.The beginning of the eighties, research finds the accumulation because of organotin in fish, body of shellfish, can cause hereditary variation, but also be likely to enter food chain.To the end of the eighties, with growing to even greater heights for environmentally friendly cry, on the basis of world many countries have made considerable research to the toxicity problem of organotin, various countries make laws one after another, disable or limit the use of Organotin antifouling paints, International Maritime Organization（IMO）Propose by 2008 to completely forbid to use organotin in antifouling paint.
2nd, 1 traditional and antifouling paint containing organic tin
This kind of antifouling paint, according to the evolution process of its mechanism of action, can be divided into erosion type, abrasion type and hydrolysis-type three types by traditional and material containing organic tin as the antifouling paint of anti-fouling agent.
2nd, 1,1 erosion type antifouling paint comes across the thirties in 20th century, its principle be with rosin and rosin derivative etc. can the adhesive of saponification in the seawater carry anti-fouling agent, in rosin soap dissolves in seawater, expose anti-fouling agent particle, reach antifouling purpose.But as coating surface gradually dissolves in the seawater, coating is also gradually thinning until failure.This kind of coating is only used for the ship of the relatively low speed of a ship or plane, and because antifouling agent content is small, effective antifouling life is only 12-15 month, but cheap.
2nd, 1,2 abrasion type antifouling paints result from the 40-50 ages in 20th century, and with polymer, such as chlorinated rubber and vinylite carries anti-fouling agent.This kind of polymer machinery intensity is higher, thicker coating is can obtain, so as to increase the load capacity of nonpolluting coating anti-fouling agent.Therefore, in seriously environment is stained, the antifouling time can also extend to 18-30 month.But the major drawbacks of this kind of coating are that shell coating surface becomes coarse after anti-fouling agent dissolves, headway is reduced, and the nonpolluting coating of failure is not easy to remove.
2nd, 1,3 hydrolysis-type（From polishing）Antifouling paint comes across the mid-1970s.Its film forming matter is（Itself has antifouling property）Tributyl（Methyl）Tin acrylic copolymer, then cuprous oxide, zinc oxide etc. are added as auxiliary anti-fouling agent.The coating is worked by the effect of current in ship's navigation, if shipping sail speed is too low, or the layover time is oversize, and its effect will also decrease, or even not work.Additionally, the various organo-tin compounds with TBT copolymers as representative, although using effect is good, but its degradability is small, it is easy to gathers in the environment, causes environmental pollution.Research shows that seawater of organic Theil indices higher than 0.1 × 10-6 will influence the marine eco-environment, has a strong impact on growth, the breeding of marine growth, also causes that marine growth occurs hereditary variation.
2nd, 2 cupric class low-toxicity anti-fouling coating
At present, commercially prevailing antifouling paint is the cupric antifouling paint of low release rate.I.e. with the less cuprous oxide of toxicity（Toxicity is the 2%-2.5% of TBT）It is the Tin-free Spc Anti-fouling Paint of anti-fouling agent with heterocyclic sterilization, mould inhibitor etc..
Japan develops with copper acrylate copolymer as matrix resin in nineteen ninety-five, the non-tin system hydrolysis-type self polishing copolymer antifouling paint with cuprous oxide as anti-fouling agent.Its mechanism of action is identical with hydrolysis-type tributyl tin acrylate copolymer.Afterwards, a series of self polishing colors with zinc acrylic copolymer as base-material are developed again, the copolymer carries out ion exchange and gradually dissolve by with the sodium in seawater, and while copolymer dissolves, the anti-fouling agent cuprous oxide for being carried also is discharged therewith.Therefore, it can the rate of release by controlling the dissolution velocity of copolymer to control cuprous ion.It is not totally nontoxic although such coating toxicity is smaller.Research shows：If it is invalid to diatom and other algae in anti-fouling agent that copper is used alone, it is necessary to add auxiliary toxic agent（Such as different thiophene, oxazoline ketone, the zinc of pyridine oxide mercaptan, copper complex heterocycle compound）, and the toxicity of copper+auxiliary toxic agent is nearly identical to organotin.Copper particularly can largely be gathered in ocean in harbour, cause the mortality of marine alga, and influence carp, salmon, shrimp, crab and various softwares, the embryo growth of tunicate destroy its haemocyte, so that the ecological balance is destroyed, therefore finally also will be disabled.
2nd, 3 marine antifouling coating of additive kind containing natural biological
Traditional antifouling paint is oozing out by anti-fouling agent, and carrying out poisoning to aufwuch reaches antifouling purpose.Due to making anti-fouling agent using containing virose material, such as copper, arsenic, lead, mercury and tin hazardous compound be released to ecological environment and human health causes serious harm, therefore people's trial develops antifouling paint from new mentality of designing：On the one hand macromolecule anti-fouling material is found, some biological sink conditions is imitated；On the other hand suitable natural anti-fouling agent is found, biological attachment is prevented on the premise of not welding.Such as：The material with bioactivity is extracted from plant as anti-fouling agent.I.e. with powdered capsicim（Come from pepper, capsicum or onion）For the low-surface-energy nontoxic antifouling paint that natural anti-fouling agent is made, the attachment of bacterium and marine growth can be resisted, and have good adhesive force to metal, timber and cement etc..Sodium Benzoate and tannic acid can also be extracted from chestnut, sensitive plant, yaruru as preparing antifouling paint anti-fouling agent.The bioassay in laboratory shows：Sodium Benzoate and tannic acid have anesthetic effect to the larva of beetle, and as these compound concentrations increase, anesthetic effect is accelerated, but as long as being placed in fresh seawater, they can come to life again.These new approaches, new product by anti-corrosion material due to being originated, cost, and being confined in popularization and application for the aspect such as application property is as one wishes not to the utmost.
The content of the invention
For there is above-mentioned deficiency in the prior art, the invention provides a kind of method of marine anti-pollution, using epoxy polyamide anticorrosive paint as priming paint, the interpenetrating networks tack coat of inter coat is styrene --- butyl acrylate --- polysiloxanes, followed by low-surface-energy nano inorganic silicon antifouling paint finish paint.Both the effect of forming a connecting link of adhesion property and inter coat that epoxy resin is excellent to base material had been make use of, and had preferably solved the problems, such as attachment, anti-pollution function and the difficult problem of environmental protection of steel substrate and anti-corrosion primer and antifouling paint.
The technical scheme is that, a kind of method of marine anti-pollution is comprised the following steps：
Epoxy polyamide anticorrosive paint is coated on antifouling object is needed；
Tack coat is coated on the anticorrosive paint layer；
The antifouling paint finish paint of low-surface-energy is coated on the tack coat.
The method of above-mentioned marine anti-pollution, wherein, described that tack coat is coated in the step on the anticorrosive paint layer, the interpenetrating networks tack coat that the tack coat is made up of styrene, butyl acrylate, polysiloxanes.
The method of above-mentioned marine anti-pollution, wherein, described that the antifouling paint finish paint of low-surface-energy is coated in the step on the tack coat, the antifouling paint finish paint of the low-surface-energy includes following composition：Fluorochemical and nano inorganic silicon.
A kind of method of marine anti-pollution that the present invention is provided, comprises the following steps：Epoxy polyamide anticorrosive paint is coated on antifouling object is needed；Tack coat is coated on the anticorrosive paint layer；The antifouling paint finish paint of low-surface-energy is coated on the tack coat, the method for the present invention employs low surface energy antifouling coating for seas using three road organic assembling coated bodies：I.e. using epoxy polyamide anticorrosive paint as priming paint, the interpenetrating networks tack coat of inter coat is styrene --- butyl acrylate --- polysiloxanes, followed by low-surface-energy nano inorganic silicon antifouling paint finish paint.Both the effect of forming a connecting link of adhesion property and inter coat that epoxy resin is excellent to base material had been make use of, and had preferably solved the problems, such as attachment, anti-pollution function and the difficult problem of environmental protection of steel substrate and anti-corrosion primer and antifouling paint.
Specific embodiment
In the following description, a large amount of concrete details are given to provide more thorough understanding of the invention.It is, however, obvious to a person skilled in the art that the present invention can be carried out without one or more of these details.In other examples, in order to avoid obscuring with the present invention, it is not described for some technical characteristics well known in the art.
In order to thoroughly understand the present invention, detailed step and detailed structure will be proposed in following description, to explain technical scheme.Presently preferred embodiments of the present invention is described in detail as follows, but in addition to these detailed descriptions, the present invention can also have other embodiment.
In the introduction, it has been mentioned that the situation of current marine anti-pollution, following several approach are mainly taken in the exploitation of novel non-toxic marine antifouling coating：（1）Change the physical and chemical performance of coating surface；（2）Using the bionics techniques of biomaterial；（3）Using coating from polishing mechanism；（4）Reduce the free energy on surface.Marine organisms adhesion mechanism is extremely complex, and the anti-fouling effect of antifouling paint is also restricted by factors.Influence the factor of antifouling paint anti-fouling effect a lot, mainly have it is following some：（1）Surface tension（Surface energy）；（2）Elastic modulus E；（3）Coating thickness；（4）Polarity；（5）Surface smoothness；（6）Surface molecular mobility.
Marine organisms attachment on a surface of an is a kind of mucus of secretion first, this mucus is soaked to body surface, and disperse thereon, then combined by one or several mechanism of several mechanism of chemical bonding, electrostatic interaction, mechanical interlocking and diffusion and adhered to.Therefore, effective measures are：Marine organisms wetting is prevented to be attached to thing and prevent it from disperseing.All factors of attachment are caused due to that can not possibly eliminate, actually all coating surfaces will all produce attachment.So only allow to form a relatively weak attachment interface, and design is convenient to clean the coating system of pollutant based on this.The mechanism that waste comes off from coating surface can be divided into three types：Stripping comes off, plane shear comes off comes off with on-plane surface shearing.Stripping comes off to be come off than shearing needs less energy.Surface energy（Tension force）：Surface can be that a surface forms the ability being connected with another surface, and it is one of critically important condition that antifouling paint should meet that surface energy is sufficiently low.Because the initial stage of sea organism attachment is attached to surface to realize by secreting mucus wetting, mucus is poor to the wellability of lower-surface-free-energy surface, so that contact angle is big, it is difficult to which attachment or attachment are loosely.So for low-surface-energy ship antifouling paint, its surface can 97 ° of ﹤ 2.2mN ㎝, contact angle ﹥ it is more suitable.
Surface molecular mobility：Marine adhesive thing may induce the molecular motion for being attached to thing surface, produce instantaneous hole, promote mucus to permeate.It is to this method for being eliminated that acts on：Assemble orientation, compact arranged functional group on the surface, crosslinking fixation is carried out to it, so as to stop invasion and the thing followed molecular rearrangement of mucus.And coating keeps a certain amount of low-energy liquid after hardening, they can be continuously replenished the surface for repairing abrasion.Reach has good adhesive force and matching with anti-corrosion primer.
Nano inorganic silicon is employed, without toxic agent, environmental requirement is complied fully with.Nano inorganic silicon self property influences very big to anti-fouling effect.Research shows, to reach good anti-fouling effect, it is therefore desirable to meet following condition：（1）Low-surface-energy, can prevent the initial attachment of marine organisms；（2）Low elastic modulus, can make waste tend to come off in peel way, it is necessary to less external force；（3）Suitable thickness, with the fracture of control interface；（4）Smooth surface；（5）Poor molecular mobility, enough side chain surface active groups.And nano inorganic silicon molecular structure can meet all conditions above.
Biodeterioration can have very big internal relation with surface, Solid Surface Free Energy is lower, adhesive force is smaller, the contact angle of surface of solids liquid is also bigger, can with very low surface, marine organisms are just difficult to adhere to above, even if attachment is also insecure, are easy to come off under current or the effect of other external force.Traditional toxicity anti-fouling ship paint is general only to have inhibitory action to some marine growths, and with the continuous release of toxicant, its antifouling paint effect also progressively declines, my company's nanometer low surface energy antifouling coating for seas（Alternatively referred to as non-toxic foul comes off type antifouling paint）It is the physical action based on surface, the release in the absence of toxicant is lost problem, because its attachment interface is very weak, attachment can be easily removed completely using the impact of current in deadweight, navigation or the cleaning of auxiliary equipment.And long-term anti-fouling ship paint can be played a part of.Nano inorganic silicon block copolymer in nanometer low surface energy antifouling coating for seas is carried out from conformation so as to very low surface energy is presented in atmosphere, thus as the best candidate of development type antifouling paint easy to fall off.But, only surface can be low not enough, also needs to meet other following conditions.
For the anti-pollution function of enhanced coating, the appropriate fluorochemical of compatibility in nanometer low surface energy antifouling coating for seas is designed in formula, fluorochemical is assembled automatically on one-liquid of gas interface in aqueous medium, under conditions of solvent or heating is lost, fluorochemical forms covalent cross-linking, so as to lose ionic charge, CF3 end groups are in surface close-packed arrays and are orientated.Because the crosslink density of coating is high, the fluorine-containing end group of orientation is strictly fixed, and can both resist the infiltration of adhesion molecule, and the induced molecular rearrangement of adhesion can be resisted again.Make adhesion molecule permeate and reset to be restricted, simultaneously because the interface between the advantage coating and bur of low-surface-energy is loosely, so as to form interface that is clearly demarcated, easily departing from.The anti-pollution function of coating is enhanced, makes the coating prevent marine organisms from adhering to than other current coating more effectively.
The invention provides a kind of method of marine anti-pollution, comprise the following steps：
Step S1：Epoxy polyamide anticorrosive paint is coated on antifouling object is needed, using the adhesion property that epoxy resin is excellent to base material.
Step S2：Tack coat is coated on anticorrosive paint layer as intermediate layer, the interpenetrating networks tack coat of inter coat is styrene --- butyl acrylate --- polysiloxanes, the interpenetrating networks tack coat that tack coat is made up of styrene, butyl acrylate, polysiloxanes.
Step S3：The antifouling paint finish paint of low-surface-energy is coated on the tack coat, the antifouling paint finish paint of low-surface-energy includes following composition：Fluorochemical and nano inorganic silicon, the method of the present invention, both the effect of forming a connecting link of adhesion property and inter coat that epoxy resin is excellent to base material had been make use of, and had preferably solved the problems, such as attachment, anti-pollution function and the difficult problem of environmental protection of steel substrate and anti-corrosion primer and antifouling paint.
In sum, a kind of method of marine anti-pollution that the present invention is provided, comprises the following steps：Epoxy polyamide anticorrosive paint is coated on antifouling object is needed；Tack coat is coated on the anticorrosive paint layer；The antifouling paint finish paint of low-surface-energy is coated on the tack coat, the method for the present invention employs low surface energy antifouling coating for seas using three road organic assembling coated bodies：I.e. using epoxy polyamide anticorrosive paint as priming paint, the interpenetrating networks tack coat of inter coat is styrene --- butyl acrylate --- polysiloxanes, followed by low-surface-energy nano inorganic silicon antifouling paint finish paint.Both the effect of forming a connecting link of adhesion property and inter coat that epoxy resin is excellent to base material had been make use of, and had preferably solved the problems, such as attachment, anti-pollution function and the difficult problem of environmental protection of steel substrate and anti-corrosion primer and antifouling paint.
Presently preferred embodiments of the present invention is described above.It is to be appreciated that the present invention is not limited to the above specific embodiments, wherein the equipment and structure that do not describe in detail to the greatest extent are construed as being practiced with the common mode in this area；Any those of ordinary skill in the art, in the case where technical solution of the present invention ambit is not departed from, many possible variations and modification are all made to technical solution of the present invention using the methods and techniques content of the disclosure above, or the Equivalent embodiments of equivalent variations are revised as, this has no effect on substance of the invention.Therefore, every content without departing from technical solution of the present invention, according to technical spirit of the invention to any simple modification, equivalent variation and modification made for any of the above embodiments, still falls within the range of technical solution of the present invention protection.
Claims (3)
1. a kind of method of marine anti-pollution, it is characterised in that comprise the following steps：
Epoxy polyamide anticorrosive paint is coated on antifouling object is needed；
Tack coat is coated on the anticorrosive paint layer；
The antifouling paint finish paint of low-surface-energy is coated on the tack coat.
2. a kind of method of marine anti-pollution as claimed in claim 1, it is characterised in that described that tack coat is coated in the step on the anticorrosive paint layer, the interpenetrating networks tack coat that the tack coat is made up of styrene, butyl acrylate, polysiloxanes.
3. a kind of method of marine anti-pollution as claimed in claim 1, it is characterised in that described that the antifouling paint finish paint of low-surface-energy is coated in the step on the tack coat, the antifouling paint finish paint of the low-surface-energy includes following composition：Fluorochemical and nano inorganic silicon.
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| CN108047881A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山起劲磁塑科技有限公司 | A kind of method for promoting magnechuck bottom plate anti-pollution characteristic |
| CN114394856A (en) * | 2022-01-06 | 2022-04-26 | 天津大学 | Concrete anti-corrosion coating based on tannic acid and polyamide and preparation method thereof |
| CN116120750A (en) * | 2023-04-04 | 2023-05-16 | 中国海洋大学 | Composite elastomer integrating resistance and killing, preparation method and antifouling application |
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| CN108047881A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山起劲磁塑科技有限公司 | A kind of method for promoting magnechuck bottom plate anti-pollution characteristic |
| CN114394856A (en) * | 2022-01-06 | 2022-04-26 | 天津大学 | Concrete anti-corrosion coating based on tannic acid and polyamide and preparation method thereof |
| CN114394856B (en) * | 2022-01-06 | 2023-08-29 | 天津大学 | Concrete anti-corrosion coating based on tannic acid and polyamide and preparation method thereof |
| CN116120750A (en) * | 2023-04-04 | 2023-05-16 | 中国海洋大学 | Composite elastomer integrating resistance and killing, preparation method and antifouling application |
| CN116120750B (en) * | 2023-04-04 | 2023-10-27 | 中国海洋大学 | Anti-killing composite elastomer, preparation method and anti-fouling application |
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