CN104761991B - Environmental-protection type multi-element collaborative marine anti-fouling coating - Google Patents
Environmental-protection type multi-element collaborative marine anti-fouling coating Download PDFInfo
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- CN104761991B CN104761991B CN201410006285.XA CN201410006285A CN104761991B CN 104761991 B CN104761991 B CN 104761991B CN 201410006285 A CN201410006285 A CN 201410006285A CN 104761991 B CN104761991 B CN 104761991B
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Abstract
The invention discloses an environmental-protection type multi-element collaborative marine anti-fouling coating. The coating is composed of anti-fouling coating matrix resin containing an anti-fouling active group, a wetting and dispersing agent, a mixed organic solvent, a non-toxic anti-fouling agent, a pigment filler, a levelling agent, a defoaming agent and an anti-settling agent. The coating is non-toxic, does not pollute the environment, and is mainly applied in ship fouling resistance.
Description
Technical field
The present invention relates to a kind of environment-friendly type marine antifouling coating, more particularly to a kind of nontoxic, long-acting, wide spectrum environment-friendly type is more
Unit's collaboration marine antifouling coating, for the antifouling of foreign-going ship.
Background technology
China is greatly developing marine cause.And marine biofouling life-span of marine settings and military service performance are had compared with
Big negative effect.Sea organism attachment increases ship's navigation frictional resistance, affects the speed of a ship or plane, increases energy consumption.While pollution by sea living
Damage can accelerate film aging, and aggravation hull corruption endangers huge.Prevent the maximally effective means of biodeterioration be exactly brush it is antifouling
Coating, thus various anti-fouling ship paints just arise at the historic moment.In the past few decades, containing organotin（TBT）It is anti-from polishing
Dirty coating was once widely used.Organotin can reach at low concentrations wide spectrum, efficient antifouling purpose, but these materials are in water
In stable and easily accumulation, can cause some organisms deformities, and possibly into food chain, becoming affects human health and ecology
Potential safety hazard.Therefore International Maritime Organization（IMO）Affiliated Marine Environmental Protection Committee defines the antifouling painting containing organotin
The final useful life of material is on January 1st, 2008.
Since then, countries in the world all accelerate research and development new Nontoxic Antifouling Paint in succession.Wherein especially with the antifouling painting of tin-free self-polishing
Material and low surface energy anti-fouling paint are noticeable.At present, widely used Tin-free Spc Anti-fouling Paint is all imitated on market
One group of bactericidal properties antifouling paint of TBT copolymer coatings, its film forming binder is linear copolymer, with hydrolyzable side base but not
With bactericidal properties.Its Hydrolytic Mechanism is identical with TBT copolymers, so that anti-fouling agent is from coating surface controllable release, protects film
Hold smooth.Although Tin-free Spc Anti-fouling Paint excellent performance, have a problem that it is that static antifouling property is poor, the antifouling phase
Effect is short, can not show a candle to the self polishing copolymer antifouling paint containing TBT, and the anti-fouling agent Red copper oxide used by it can kill marine growth, to human body
Low toxicity.Low surface energy anti-fouling paint referred to by using the low-surface-energy feature of its anti-fouling material for preparing, and is difficult biology attached
, or attachment is loosely.Low-surface-energy nonpolluting coating does not have that the release of toxicant is lost and kills halobiontic,
But for current low-surface-energy nonpolluting coating, rely solely on the low surface property of coating can't be fully achieved it is thoroughly antifouling
Requirement.Simple low surface energy anti-fouling paint can only often be such that marine organisms adhere to loosely, need to periodically go up depressed place cleaning；Attachment life
Thing is once grown up and would become hard to remove, and scale removal process may destroy paint film, once damaging, antifouling property just will be substantially reduced.Together
When, low surface energy anti-fouling paint has selectivity to fouling organism, and it is invalid to diatom.At present, although the country have fluororesin and
The low surface energy coatings research of the types such as organosilicon, but due to due to starting evening and technical elements, mostly in primary research and development
In the stage, have no extensive application report.Although there are the application of low-surface-energy elastic coating in foreign countries, due to its elastomer, machinery is strong
The poor, hardness of degree is low, poor adhesive force, and construction is inconvenient and expensive, causes its application to there is significant limitations.In addition, research
Personnel have found that the small molecule silicone oil of the difficult degradation penetrated from low surface energy coat is enriched in a large number in ocean, has a strong impact on
Halobiontic normal growth, is just becoming a kind of new marine pollutant.According to estimates, with regard to the use of current low surface energy coatings
From the point of view of amount, 4000 tons of silicone oil are there are about every year and is discharged in ocean.
In a word, antifouling paint must develop to low toxicity, nontoxic direction.And the antifouling painting of tin-free self-polishing simple at present
Material, static anti-fouling agent leaching rate is little, is not enough to kill the marine growth for attempting to be attached to hull, needs on resin copolymer main chain
Efficient sterilizing active group is introduced, is improved and is suppressed sea organism attachment ability；Simple low surface energy anti-fouling paint, can only make Hai Sheng
Thing adheres to loosely, and needs could realize the final cleaning to some aufwuches by external force.Therefore, rely solely on single antifouling
Approach can't reach nontoxic, long-acting, wide spectrum antifouling purpose.
The content of the invention
It is an object of the invention to overcoming, the antifouling approach of existing antifouling paint is single, environmentally harmful defect, and provide
A kind of environmental friendliness, surface energy be low, from polishing stable, the polynary synergetic marine antifouling coating of antifouling persistent.
To achieve these goals, the technical solution used in the present invention is：
The coating of the present invention, by the antifouling paint substrate resin containing antifouling activity group, wetting dispersing agent, mixes organic molten
Agent, nontoxic anti-fouling agent, color stuffing, levelling agent, defoamer and anti-settling agent composition.
The polynary collaboration marine antifouling coating of a kind of environment-friendly type, it is characterised in that coating is prepared by procedure below：
By free-radical polymerized, by acrylic compounds soft or hard monomer, Hydrophobic Ionic liquid monomer, esters of acrylic acid sulfonic acid potassium salt
Monomer carries out copolymerization in the presence of initiator, obtains the acrylic polymer containing bacteriostatic activity group, so with zinc hydroxide or
Copper, the mixture reaction of monovalence organic acid obtain the antifouling paint substrate resin containing antifouling activity group；
It is 30～55 parts of antifouling paint substrate resin, 0.5～1 part of wetting and dispersing containing antifouling activity group by parts by weight
Agent and 15～30 parts of mixed organic solvents after fully dispersed, add 0～10 part of nontoxic anti-fouling agent, 10～30 parts of color stuffings,
0.3 portion of levelling agent, 0.3 portion of defoamer, 1～3 portion of anti-settling agent, the wetting dispersing agent is polyether-modified polysiloxane, the moon
Ion-type wetting dispersing agent, low-molecular-weight unsaturation polycarboxylic acid polymers in one or more；Described is organic molten
Agent is the mixing liquid of dimethyl sulfoxide, glycol monoethyl ether and butyl acetate；Described nontoxic anti-fouling agent is copper pyrithione
Or Zinc Pyrithione；Described color stuffing is politef（PTFE）, iron oxide red, Zinc Oxide, titanium dioxide, in barium sulfate
At least three kinds；The levelling agent is in the Levaslip435 of De Qian Chemical Co., Ltd.s and the BYK300 of BYK companies of Germany
It is a kind of；Described defoamer is BYK052, the one kind in 066；Described anti-settling agent is BYK410, organobentonite, Pulvis Talci
Mixture；Dispersion is ground to coating fineness less than 50 m, obtains the polynary collaboration marine antifouling coating of non-toxic, environmental friendly.
Wetting dispersing agent of the present invention is that the modest chemistry of moral is limited selected from 103,104,161, the 163 of German BYK series
903, the 904 of company.
The preparation method of the antifouling paint substrate resin containing antifouling activity group of the present invention, specifically by 15 parts of quality
Than for 2:1 glycol monoethyl ether is added in reactor with n-butanol mixed solvent, 85 DEG C is warming up to, by 5 parts of acrylate
Class sulfonic acid potassium salt monomer and 5 parts of Hydrophobic Ionic liquid monomers are dissolved in 34 parts of mass ratioes for 1:1 dimethyl sulfoxide and dimethyl methyl
In amide mixed solvent, sequentially add 10 parts of methyl methacrylates, 10 parts of n-butyl acrylates, 4 parts of ethyl acrylate, 5
Part acrylic acid and 0.8 part of azodiisobutyronitrile, 0.5 part of lauryl mercaptan, above-mentioned mixed solution is added in reactor, and insulation 2 is little
When；Added in 0.5 hour again dissolved with 0.2 part of azodiisobutyronitrile 10 parts of mass ratioes be 1:1 dimethyl sulfoxide and ethylene glycol
Monomethyl ether mixed solution, continues to be incubated 1 hour, obtains the acrylic polymer containing antifouling activity group；Contain antifouling work by 65 parts
Property the acrylic polymer of group, 4 parts of zinc hydroxide or Copper hydrate, 15 parts of mass ratioes be 1:1:1 dimethylformamide, second
Glycol monomethyl ether is added in reactor with n-butyl acetate mixed solvent, and 5 parts of benzoic acid are dissolved in into 11 parts of mixed solvents, is added at 95 DEG C
Above-mentioned organic acid mixed solution, it is transparent to reactant liquor to maintain the reflux for state, after be warming up to 125 DEG C of dehydrations, until water is completely out,
Obtain the thick antifouling paint substrate resin containing antifouling activity group.
The preparation method of described Hydrophobic Ionic liquid monomer is, by the N- alkyl imidazoles of equimolar amountss, chloromethylbenzene second
Alkene is sufficiently stirred for generating micro- yellow thick liquid in room temperature, is dissolved in distilled water and adds the ammonium hexafluorophosphate or four of equimolar amountss
Sodium fluoroborate, filters after being sufficiently stirred for, and obtains white waxy solid product；Wherein described N- alkyl imidazoles be N- Methylimidazole .s, N-
Ethyl imidazol(e), or N- 1-Butyl-1H-imidazoles.
The polynary collaboration marine antifouling coating of environment-friendly type of the present invention, coating is had from polishing characteristic with low-surface-energy characteristic
Effect is combined, while the ionic liquid group with Efficient antibacterial activity is incorporated into into copolymer chain, strengthens antifouling phase effect, is a kind of
Environmental friendliness, surface energy be low, from polishing stable, the non-toxic, environmental friendly antifouling paint of antifouling persistent.In the seawater, the coating
Can realize that number of ways collaboration is antifouling, so as to show excellent long-acting and anti-fouling performance.Meanwhile, coating adheres to good with base material
Good, coating surface is smooth, easy construction, and the four seasons can use.
The polynary collaboration marine antifouling coating of environment-friendly type of the present invention, the traditional performance for being sprayed at tinplate is as follows：
1）Adhesive force： GB1720-79 （Draw circle method）, 1 grade；
2）Resistance to impact： GB1732-79,50 Kg.cm；
3）Hardness：GB6379-86,1H～2H levels；
4）Pliability： GB1731-79,1mm；
5）Coating surface energy：Less than 25 mJm-2；
6）The drying varniss time：GB1728-79,16～25 DEG C of room temperature, surface drying 2 hours, 12 hours actual drying time.
The polynary collaboration marine antifouling coating of environment-friendly type of the present invention, can be coated on epoxy and prevent by spraying or brushing mode
On the low carbon steel plate of rotten priming paint, epoxy anticorrosion primer build is 200 m or so, nonpolluting coating THICKNESS CONTROL in 150 m, i.e.,
Promising result is obtained.
This environmental protection type anti-pollution paint is coated on the low carbon steel plate of epoxy anticorrosion primer by spraying means（150×250
×2 mm）Model is made, after room temperature is fully dried, shallow sea board experiment is carried out.Select domestic conventional with Red copper oxide simultaneously
Based on anti-fouling agent tin-free self-polishing antifouling paint（It is hereinafter referred to as domestic）, and low-surface-energy anti-fouling paint（Surface energy is less than 17 mJ
m-2）Brush on same size steel plate respectively, used as control model, brushing thickness is identical with this coating.Select same control gauge simultaneously
Lattice steel plate does blank, a brushing epoxy anticorrosion primer.The experiment model for being painted with various antifouling paints is placed in into sea with blank plate
Lower 1 meter of depths carries out static real sea board experiment.Test period 2012,05,03～2012,08,29（The marine growth most productive period）,
Test site：Shenzhen Nan'ao marine site.Shown in experimental result picture 1-4：Wherein Fig. 1 is epoxy blank model, shallow sea static state link plate 118
Specimen surface adheres to all kinds of Macro-fouling Organismss after it, mainly based on barnacle, mussel, sponge, is stained serious.Fig. 2 is surface
The model static state link plate of brushing low surface energy anti-fouling paint result after 118 days, there are more diatom, barnacle attachment in its surface, antifouling
Poor-performing.Fig. 3 for the domestic anti-fouling paint of external coating model static state link plate result after 118 days, there is a small amount of barnacle children on its surface
Worm and diatom adhere to, and anti-fouling effect is preferable.Fig. 4 is the model of the polynary collaboration marine antifouling coating of external coating environment-friendly type of the present invention
Static link plate result after 118 days, specimen surface paint film is intact, and without bubbling, coming off, coating surface is more clean, is stained a little seldom,
Without the attachment of large ocean fouling organism, antifouling property is excellent.As can be seen that in probation, the environment-friendly type that we develop is polynary
Collaboration marine antifouling coating its antifouling property has surmounted the domestic self-polishing antifouling paint containing Red copper oxide, can substitute completely oxygen-containing
Change cuprous conventional composite type antifouling paint.
The polynary collaboration marine antifouling coating of environment-friendly type of the present invention, without Red copper oxide, asepsis environment-protecting, production technology is relative
Simply, raw material is easy to get, wide market.
The coating is nontoxic free from environmental pollution, is mainly used in the antifouling of ship.In the seawater, the low-surface-energy of the coating is special
Performance enough effectively suppress marine organisms attachment, meanwhile, coating surface acrylic copolymer is hydrolyzed, discharge organic acid zinc or
Copper and anti-fouling agent, realize coating surface from polishing, and the main polymer chain after hydrolyzing also is included with Efficient antibacterial performance
Antifouling activity group, makes coating continue to keep high-efficiency pollution-proof activity, suppresses marine organisms attachment, excellent long-acting so as to show
Antifouling property.
Description of the drawings
Fig. 1 is epoxy blank model shallow sea board experiment 118 days（Shenzhen Nan'ao marine site, 2012,05,03～2012,08,
29）As a result.
Fig. 2 is low surface energy anti-fouling paint shallow sea board experiment 118 days（Shenzhen Nan'ao marine site, 2012,05,03～2012,
08,29）As a result.
Fig. 3 is domestic anti-fouling paint shallow sea board experiment 118 days（Shenzhen Nan'ao marine site, 2012,05,03～2012,08,29）
As a result.
Fig. 4 is the polynary collaboration marine antifouling coating shallow sea board experiment of environment-friendly type of the present invention 118 days（Shenzhen Nan'ao marine site,
2012,05,03～2012,08,29）As a result.
Specific embodiment
The present invention is described further below by embodiment
The antifouling paint substrate resin containing antifouling activity group prepares as follows in the present invention：
It is 2 by 15 parts of mass ratioes:1 glycol monoethyl ether is added in reactor with n-butanol mixed solvent, is warming up to
85 DEG C, 5 parts of esters of acrylic acid sulfonic acid potassium salt monomers and 5 parts of Hydrophobic Ionic liquid monomers are dissolved in into 34 parts of mass ratioes for 1:The two of 1
In methyl sulfoxide and dimethylformamide mixed solvent, the positive fourth of 10 parts of methyl methacrylates, 10 parts of acrylic acid is sequentially added
Ester, 4 parts of ethyl acrylate, 5 parts of acrylic acid and 0.8 part of azodiisobutyronitrile, 0.5 part of lauryl mercaptan, above-mentioned mixed solution is added
In entering reactor, 2 hours are incubated；Added in 0.5 hour again dissolved with 0.2 part of azodiisobutyronitrile 10 parts of mass ratioes be 1:1
Dimethyl sulfoxide and glycol monoethyl ether mixed solution, continue to be incubated 1 hour, obtain the acrylic acid pre-polymerization containing antifouling activity group
Thing；It is 1 by 65 parts of acrylic polymers containing antifouling activity group, 4 parts of zinc hydroxide or Copper hydrates, 15 parts of mass ratioes:1:1
Dimethylformamide, glycol monoethyl ether and n-butyl acetate mixed solvent add in reactor, 5 parts of benzoic acid are dissolved in into 11 parts
Mixed solvent, in 95 DEG C plus above-mentioned organic acid mixed solution, it is transparent to reactant liquor to maintain the reflux for state, after be warming up to 125 DEG C and take off
Water, until water is completely out, obtains the thick antifouling paint substrate resin containing antifouling activity group.
Embodiment 1
By 30 parts of antifouling paint substrate resins containing antifouling activity group, 1 part of wetting dispersing agent BYK163 and 26 parts of mixing
Organic solvent（Dimethyl sulfoxide：Glycol monoethyl ether：Butyl acetate=1:1:1）Add dispersion cylinder in, it is fully dispersed and successively plus
Enter 10 parts of copper pyrithiones, 30 parts of color stuffings（6 parts of politef, 8 parts of iron oxide red, 8 parts of Zinc Oxide, barium sulfate 8
Part）, 0.3 portion of levelling agent BYK300,0.3 portion of defoamer BYK052,2.4 portions of anti-settling agents（Wherein, 0.4 part of BYK410,1 part it is organic
Bentonite, 1 part of Pulvis Talci）, disperse and be ground to coating fineness at a high speed less than 50 m, obtain the polynary collaboration marine anti-pollution of environment-friendly type
Coating.Finally pack.The polynary collaboration marine antifouling coating of this example environment-friendly type, the traditional performance for being sprayed at tinplate is as follows：
Adhesive force：1 grade；Resistance to impact：50 Kg.cm；Hardness：1H levels；Pliability：1mm；Coating surface energy：Less than 24 mJm-2；Paint
Film drying time：Room temperature surface drying 2 hours, does solid work 8 hours.
Embodiment 2
By 30 parts of antifouling paint substrate resins containing antifouling activity group, 1 part of wetting dispersing agent BYK163 and 26 parts of mixing
Organic solvent is added in dispersion cylinder, fully dispersed and sequentially add 5 parts of copper pyrithiones, 5 parts of Zinc Pyrithione, 30 parts of color stuffings
（5 parts of politef, 8 parts of iron oxide red, 8 parts of Zinc Oxide, 9 parts of barium sulfate）, 0.3 part of levelling agent Levaslip435,0.3
Part defoamer BYK052,2.4 portions of anti-settling agents（Wherein, 0.4 part of BYK410,1 part of organobentonite, 1 part of Pulvis Talci）, disperse at a high speed
And coating fineness is ground to less than 50 m, obtain the polynary collaboration marine antifouling coating of environment-friendly type.Finally pack.This example environment-friendly type
Polynary collaboration marine antifouling coating, the traditional performance for being sprayed at tinplate is as follows：Adhesive force：1 grade；Resistance to impact：50
Kg.cm；Hardness：1H levels；Pliability：1mm；Coating surface energy：Less than 24 mJm-2；The drying varniss time：Room temperature surface drying 2 is little
When, do solid work 8 hours.
Embodiment 3
40 parts of antifouling paint substrate resins containing antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 22 parts are mixed
Close organic solvent to add in dispersion cylinder, it is fully dispersed and sequentially add 4 parts of copper pyrithiones, 3.5 parts of Zinc Pyrithione, 27 parts of face
Filler（5 parts of politef, 8 parts of iron oxide red, 7 parts of Zinc Oxide, 7 parts of barium sulfate）, 0.3 part of levelling agent
Levaslip435,0.3 portion of defoamer BYK052,2.1 portions of anti-settling agents（Wherein, 0.3 part of BYK410,0.9 part of organobentonite,
0.9 part of Pulvis Talci）, disperse and be ground to coating fineness at a high speed less than 50 m, obtain the polynary collaboration marine antifouling coating of environment-friendly type.
Finally pack.The polynary collaboration marine antifouling coating of this example environment-friendly type, the traditional performance for being sprayed at tinplate is as follows：Attachment
Power：1 grade；Resistance to impact：50 Kg.cm；Hardness：1H levels；Pliability：1mm；Coating surface energy：Less than 25 mJm-2；Paint film is done
The dry time：Room temperature surface drying 2 hours, does solid work 8 hours.
Embodiment 4
50 parts of antifouling paint substrate resins containing antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 18 parts are mixed
Close organic solvent to add in dispersion cylinder, it is fully dispersed and sequentially add 3 parts of copper pyrithiones, 2.5 parts of Zinc Pyrithione, 23 parts of face
Filler（5 parts of politef, 6 parts of iron oxide red, 6 parts of Zinc Oxide, 6 parts of barium sulfate）, 0.3 part of levelling agent
Levaslip435,0.3 portion of defoamer BYK052,2.1 portions of anti-settling agents（Wherein, 0.3 part of BYK410,0.9 part of organobentonite,
0.9 part of Pulvis Talci）, disperse and be ground to coating fineness at a high speed less than 50 m, obtain the polynary collaboration marine antifouling coating of environment-friendly type.
Finally pack.The polynary collaboration marine antifouling coating of this example environment-friendly type, the traditional performance for being sprayed at tinplate is as follows：Attachment
Power：1 grade；Resistance to impact：50 Kg.cm；Hardness：1H levels；Pliability：1mm；Coating surface energy：Less than 25 mJm-2；Paint film is done
The dry time：Room temperature surface drying 2 hours, does solid work 10 hours.
Embodiment 5
55 parts of antifouling paint substrate resins containing antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 15 parts are mixed
Close organic solvent to add in dispersion cylinder, it is fully dispersed and sequentially add 3 parts of copper pyrithiones, 2.5 parts of Zinc Pyrithione, 21 parts of face
Filler（4 parts of politef, 6 parts of iron oxide red, 5 parts of Zinc Oxide, 6 parts of barium sulfate）, 0.3 part of levelling agent BYK300,0.3
Part defoamer BYK052,2.1 portions of anti-settling agents（Wherein, 0.3 part of BYK410,0.9 part of organobentonite, 0.9 part of Pulvis Talci）, at a high speed
Disperse and be ground to coating fineness less than 50 m, obtain the polynary collaboration marine antifouling coating of environment-friendly type.Finally pack.This example ring
The polynary collaboration marine antifouling coating of guarantor's type, the traditional performance for being sprayed at tinplate is as follows：Adhesive force：1 grade；Resistance to impact：50
Kg.cm；Hardness：2H levels；Pliability：1mm；Coating surface energy：Less than 25 mJm-2；The drying varniss time：Room temperature surface drying 2 is little
When, do solid work 10 hours.
Embodiment 6
By 50 parts of antifouling paint substrate resins containing antifouling activity group, 0.8 part of wetting dispersing agent BYK163 and 15.5 parts
Mixed organic solvents are added in dispersion cylinder, fully dispersed and sequentially add 10 parts of Zinc Pyrithione, 21 parts of color stuffings（Polytetrafluoroethyl-ne
4 parts of alkene, 6 parts of iron oxide red, 5 parts of Zinc Oxide, 6 parts of barium sulfate）, 0.3 part of levelling agent BYK300,0.3 part of defoamer
BYK052,2.1 portions of anti-settling agents（Wherein, 0.3 part of BYK410,0.9 part of organobentonite, 0.9 part of Pulvis Talci）, disperse at a high speed and grind
Coating fineness is milled to less than 50 m, the polynary collaboration marine antifouling coating of environment-friendly type is obtained.Finally pack.This example environment-friendly type is polynary
Collaboration marine antifouling coating, the traditional performance for being sprayed at tinplate is as follows：Adhesive force：1 grade；Resistance to impact：50 Kg.cm；Firmly
Degree：2H levels；Pliability：1mm；Coating surface energy：Less than 25 mJm-2；The drying varniss time：Room temperature surface drying 2 hours, does solid work 10
Hour.
Embodiment 7
By 45 parts of antifouling paint substrate resins containing antifouling activity group, 1 part of wetting dispersing agent BYK163 and 21 parts of mixing
Organic solvent is added in dispersion cylinder, fully dispersed and sequentially add 30 parts of color stuffings（6 parts of politef, iron oxide red 8
Part, 6 parts of Zinc Oxide, 8 parts of barium sulfate, 2 parts of titanium dioxide）, 0.3 part of levelling agent BYK300,0.3 part of defoamer BYK052,2.4
Part anti-settling agent（Wherein, 0.4 part of BYK410,1 part of organobentonite, 1 part of Pulvis Talci）, disperse and be ground to coating fineness at a high speed little
In 50 m, the polynary collaboration marine antifouling coating of environment-friendly type is obtained.Finally pack.The polynary collaboration marine anti-pollution of this example environment-friendly type is applied
Material, the traditional performance for being sprayed at tinplate is as follows：Adhesive force：1 grade；Resistance to impact：50 Kg.cm；Hardness：2H levels；It is flexible
Property：1mm；Coating surface energy：Less than 24 mJm-2；The drying varniss time：Room temperature surface drying 2 hours, does solid work 10 hours.
Embodiment 8
By 45 parts of antifouling paint substrate resins containing antifouling activity group, 1 part of wetting dispersing agent BYK163 and 21 parts of mixing
Organic solvent is added in dispersion cylinder, fully dispersed and sequentially add 5 parts of copper pyrithiones, 3 parts of Zinc Pyrithione, 22 parts of color stuffings
（5 parts of politef, 6 parts of iron oxide red, 4 parts of Zinc Oxide, 6 parts of barium sulfate, 1 part of titanium dioxide）, 0.3 part of levelling agent
BYK300,0.3 portion of defoamer BYK052,2.4 portions of anti-settling agents（Wherein, 0.4 part of BYK410,1 part of organobentonite, 1 part of Talcum
Powder）, disperse and be ground to coating fineness at a high speed less than 50 m, obtain the polynary collaboration marine antifouling coating of environment-friendly type.Finally pack.
The polynary collaboration marine antifouling coating of this example environment-friendly type, the traditional performance for being sprayed at tinplate is as follows：Adhesive force：1 grade；Resistance to punching
Hitting property：50 Kg.cm；Hardness：2H levels；Pliability：1mm；Coating surface energy：Less than 25 mJm-2；The drying varniss time：Room temperature
Surface drying 2 hours, does solid work 10 hours.
Claims (3)
1. the polynary collaboration marine antifouling coating of a kind of environment-friendly type, it is characterised in that coating is prepared by procedure below：
By free-radical polymerized, by acrylic compounds soft or hard monomer, Hydrophobic Ionic liquid monomer, esters of acrylic acid sulfonic acid potassium salt monomer
Copolymerization is carried out in the presence of initiator, the acrylic polymer containing bacteriostatic activity group is obtained, so with zinc hydroxide or copper, one
The mixture reaction of valency organic acid obtains the antifouling paint substrate resin containing antifouling activity group；
By parts by weight be 30～55 parts containing the antifouling paint substrate resins of antifouling activity group, 0.5～1 part of wetting dispersing agent and
15～30 parts of mixed organic solvents after fully dispersed, add 0～10 part of nontoxic anti-fouling agent, 10～30 parts of color stuffings, 0.3 part
Levelling agent, 0.3 portion of defoamer, 1～3 portion of anti-settling agent, the wetting dispersing agent is polyether-modified polysiloxane, anion
Type wetting dispersing agent, low-molecular-weight unsaturation polycarboxylic acid polymers in one or more；Described organic solvent is
The mixing liquid of dimethyl sulfoxide, glycol monoethyl ether and butyl acetate；Described nontoxic anti-fouling agent is copper pyrithione or pyrrole
Pyridine thioketone zinc；Described color stuffing is at least three in politef, iron oxide red, Zinc Oxide, titanium dioxide, barium sulfate
Kind；The levelling agent is the one kind in the Levaslip435 of De Qian Chemical Co., Ltd.s and the BYK300 of BYK companies of Germany；Institute
The defoamer stated is BYK052, the one kind in 066；Described anti-settling agent is BYK410, organobentonite, talcous mixing
Thing；Dispersion is ground to coating fineness less than 50 m, obtains the polynary collaboration marine antifouling coating of non-toxic, environmental friendly；
The preparation method of the antifouling paint substrate resin containing antifouling activity group, be by 15 parts of mass ratioes be 2:1 ethylene glycol list
Methyl ether is added in reactor with n-butanol mixed solvent, 85 DEG C is warming up to, by 5 parts of esters of acrylic acid sulfonic acid potassium salt monomers and 5
Part Hydrophobic Ionic liquid monomer is dissolved in 34 parts of mass ratioes for 1:In 1 dimethyl sulfoxide and dimethylformamide mixed solvent, then
Sequentially add 10 parts of methyl methacrylates, 10 parts of n-butyl acrylates, 4 parts of ethyl acrylate, 5 parts of acrylic acid and 0.8 part of idol
Nitrogen bis-isobutyronitrile, 0.5 part of lauryl mercaptan, above-mentioned mixed solution is added in reactor, is incubated 2 hours；Mended in 0.5 hour again
Plus dissolved with 0.2 part of azodiisobutyronitrile 10 parts of mass ratioes be 1:1 dimethyl sulfoxide and glycol monoethyl ether mixed solution, continue
Insulation 1 hour, obtains the acrylic polymer containing antifouling activity group；By 65 parts of acrylic acid pre-polymerizations containing antifouling activity group
Thing, 4 parts of zinc hydroxide or Copper hydrate, 15 parts of mass ratioes are 1:1:1 dimethylformamide, glycol monoethyl ether and acetic acid fourth
Ester mixed solvent is added in reactor, and 5 parts of benzoic acid are dissolved in into 11 parts of mixed solvents, adds above-mentioned organic acid mixing molten at 95 DEG C
Liquid, it is transparent to reactant liquor to maintain the reflux for state, after be warming up to 125 DEG C of dehydrations, until water is completely out, obtain thick containing antifouling
The antifouling paint substrate resin of active group.
2. coating as claimed in claim 1, it is characterised in that described wetting dispersing agent be selected from German BYK series 103,
104th, 161, the 903 of 163, De Qian Chemical Co., Ltd.s, 904.
3. coating as claimed in claim 1, it is characterised in that the preparation method of Hydrophobic Ionic liquid monomer is, by equimolar amountss
N- alkyl imidazoles, 1-chloro-4-methyl-benzene be sufficiently stirred for generating micro- yellow thick liquid in room temperature, be dissolved in distilled water and add
The ammonium hexafluorophosphate or sodium tetrafluoroborate of equimolar amountss, filters after being sufficiently stirred for, and obtains white waxy solid product；Wherein described N-
Alkyl imidazole is N- Methylimidazole .s, N- ethyl imidazol(e)s, or N- 1-Butyl-1H-imidazoles.
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| CN105255291B (en) * | 2015-11-25 | 2016-11-23 | 蓬莱蔚阳新材料有限公司 | A kind of environment-friendly marine antifouling coating containing polyion liquid broad spectrum type anti-fouling agent and preparation technology thereof |
| CN106675294B (en) * | 2016-12-20 | 2019-04-19 | 海洋化工研究院有限公司 | No copper ring is protected from polishing marine antifouling coating |
| CN108610449B (en) * | 2017-01-14 | 2021-03-12 | 浙江省海洋开发研究院 | Para-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and novel marine antifouling paint prepared from same |
| CN108148488A (en) * | 2017-12-30 | 2018-06-12 | 常州市阿曼特化工有限公司 | A kind of control release type marine antifouling coating |
| CN113004752A (en) * | 2021-04-02 | 2021-06-22 | 中国科学院兰州化学物理研究所 | Transparent marine antifouling paint and preparation method and application thereof |
| CN113981689A (en) * | 2021-12-16 | 2022-01-28 | 中国纺织信息中心 | Moisture-sensitive self-adaptive breathable fabric |
| CN114716684B (en) * | 2022-03-31 | 2023-07-18 | 吴晓金 | Self-polishing antifouling resin with degradation and hydrolysis performances and preparation method thereof |
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| CN103122187A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院兰州化学物理研究所 | Ionic liquid modified marine antifouling paint |
| CN103274955A (en) * | 2013-05-23 | 2013-09-04 | 华南理工大学 | Synthesis method for betaine-type amphoteric ion compound containing reactive group |
| WO2013187311A1 (en) * | 2012-06-12 | 2013-12-19 | 三井化学株式会社 | Modified hydrophilic acrylic resin film |
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| CN103122187A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院兰州化学物理研究所 | Ionic liquid modified marine antifouling paint |
| WO2013187311A1 (en) * | 2012-06-12 | 2013-12-19 | 三井化学株式会社 | Modified hydrophilic acrylic resin film |
| CN103274955A (en) * | 2013-05-23 | 2013-09-04 | 华南理工大学 | Synthesis method for betaine-type amphoteric ion compound containing reactive group |
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