CN102311693A - Antifouling coating used for environmental protection type ship and preparation method thereof - Google Patents
Antifouling coating used for environmental protection type ship and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an antifouling coating used for an environmental protection type ship and a preparation method thereof. The coating comprises the following components in parts by weight: 15-30 parts of acrylic resin, 10-20 parts of silicate, 5-10 parts of rosin, 5-10 parts of zinc oxide, 0.5-5 parts of anti-settling agent, 2-10 parts of iron oxide red, 1-10 parts of isothiazolin-ketone, 0.5-10 parts of pyridine salt and 15-30 parts of solvent. The solvent is arranged in a reactor, the acrylic resin, the anti-setting agent, the rosin, the zinc oxide, the iron oxide red and the pyridine salt are added under stirring, obtained uniformly mixed materials are arranged in a grinder, then the isothiazolin-ketone and the silicate are added, and the mixture is ground to obtain a product. Compared with the prior art, the antifouling agent adopted in the antifouling coating is released into the environment to be naturally degraded and can not be accumulated, and in a better paint film performance state, a promoter truly realizes the environment protection of the coating.
Description
Technical field
The present invention relates to a kind of coating and preparation method thereof, especially relate to a kind of environment-friendly type boats and ships with antifouling paint and preparation method thereof.
Background technology
International Maritime Organizaton (IMO) has passed through new " international control boats and ships system's pact of harmful antifouling end " October calendar year 2001.New pact will forbid that boats and ships use deleterious antifouling end system, set up a kind of mechanism simultaneously, so that take control or denial measure when there is harm in system to environment or human health at the bottom of the marine antifouling of finding from now on to use.The purpose of this pact is to avoid the detrimentally affect of the harmful antifoulant of boats and ships with HUMAN HEALTH in order to protect the marine environment, and eliminates the antifoulant that uses organo-tin compound gradually, and sets up new mechanism and prevent to use in the later antifoulant other objectionable impurities.And this part pact is also formally effective on September 17th, 2008 in China.
On May 25 calendar year 2001, " Convention of Stockholm " that pass through at Stockholm, SWE is that international community takes the Finite control action to noxious chemical, and one has the pact of forcing to reduce discharging requirement.151 countries that comprise China have signed " about the Convention of Stockholm of persistence organic pollutant " jointly, are intended to make great efforts pollution superseded and the elimination persistence organic pollutant through the whole world, and protection human health and environment are avoided harm.And this part pact has formally come into force to China on November 11st, 2004, and this indicates each item basic obligations and conventional obligation that the pact defined will be fulfiled comprehensively by China.At first eliminate in the pact the 12 kinds POPs that the tool of human health and physical environment is endangered are: compound 118, Dieldrin-attapulgite mixture, endrin, DDT, heptachlor, Niran, mirex, toxaphene, Perchlorobenzene, polychlorobiphenyl, Dioxins and furans.Pact is stipulated simultaneously, and the POPs inventory of listing control in is open, expands by regulation screening procedure and standard in the future.Different with conventional pollutent, persistence organic pollutant is bigger to human health and physical environment harm: utmost point difficult degradation, long-distance migration in the world in physical environment; Taken in the back by organism and be difficult for decomposing, and amplify, the human and animal is endangered huge along food chain is concentrated.That a lot of persistence organic pollutants not only have is carcinogenic, teratogenesis, mutagenicity, but also has the internal secretion interference effect.Research shows that persistence organic pollutant can continue several generations to the mankind's influence, and human survival procreation and Sustainable development are constituted significant threat.
It is the DDT of anti-fouling system, organotin that past is used always; Made very big contribution to marine antifouling, but the environmental pollution that thereupon produce to continue, the mankind's long-term survival has been brought tremendous influence; Caused worldwide great attention; All contract states are all adopted an effective measure, and the environmentally friendly antifouling driving agent of Development of New Generation is with this ocean environment of protecting the universe to depend on for existence.Mainly use Red copper oxide at present on the China market, bigger although Red copper oxide belongs to the lower toxicity compound to the toxicity of some fish, after long-term a large amount of the use, can separate out and be deposited in the permanent pollution of formation in the mud of seabed.The antifouling paint of usefulness all is based on Red copper oxide, and is bigger to the toxicity of some fish although Red copper oxide belongs to the lower toxicity compound, after long-term a large amount of the use, can separate out and be deposited in the permanent pollution of formation in the mud of seabed.And State Environmental Protection Administration is formulating and carry out the production and the use of restriction " high pollution, high ambient risk " product, and the coating that some of them have harm to people and environment also therein.Harmful heavy metal, organotin, DDT etc. will be limited or forbid in coating, using.Red copper oxide is transitional arrangement as toxic agent, can only use 2012 before.International Maritime Organizaton (IMO) forbade organo-tin antifouling paint in 2008 comprehensively, and forbade using in 2003.From 2003, tin-free self-polishing antifouling paint obtained extensive application.But its staple is a Red copper oxide, and its long-term a large amount of uses will impact ocean environment.Thereby the exploitation low toxicity, nontoxic, the antifouling varnish of no metal is the inexorable trend that develops in the future.Abroad, Holland has forbidden cleaning copper paint in its territorial waters; Claimed in United States Navy and Environmental Protection Agency and will control substance classes and the quantity that boats and ships possibly discharge on harbour and high sea, and copper is called as undesirable emission of substance in these standards of formulating the department that formulates emission standard.Can find out that the use of copper in stain control agent finally will be rejected.
Also can find out progressively perfect along with the environmental protection laws and regulations, research and development new generation of environment protection marine ship antifouling paint very urgent that seemed thus.
Summary of the invention
The object of the invention be exactly provide a kind of in order to overcome the defective that above-mentioned prior art exists and can not accumulate, protect the marine environment, environment-friendly type boats and ships that paint film property is preferable are with antifouling paint and preparation method thereof.
The object of the invention can be realized through following technical scheme:
A kind of environment-friendly type boats and ships are used antifouling paint, it is characterized in that, this coating comprises following component and weight part content:
Vinyl resin 15～30,
Silicate 10～20,
Rosin 5～10,
Zinc oxide 5～10,
Anti-heavy agent 0.5～5,
Red iron oxide 2～10,
RH-893 1～10,
Pyridinium salt 0.5～10,
Solvent 15～30.
The weight-average molecular weight of described vinyl resin is 20000～50000, comprises in TEB 3K, Jia Jibingxisuanyizhi or the NSC 20956 one or more.
Described silicate is the water glass particle of modulus 2.6～3.7, and particle diameter is 200 orders.
Described anti-heavy agent comprises in wilkinite, aerosil or the precipitated silica one or more.
Described pyridinium salt is pyridine triphenyl-boron or triphenyl pyridinium salt.
Described solvent comprises one or more in commercially available 200# solvent oil, commercially available 200# petroleum naphtha, sherwood oil, toluene, YLENE, acetone, butanone, pimelinketone, ETHYLE ACETATE, butylacetate, ethanol, butanols, gasoline or the coal tar.
A kind of environment-friendly type boats and ships is characterized in that with the preparation method of antifouling paint this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Vinyl resin 15～30,
Silicate 10～20,
Rosin 5～10,
Zinc oxide 5～10,
Anti-heavy agent 0.5～5,
Red iron oxide 2～10,
RH-893 1～10,
Pyridinium salt 0.5～10,
Solvent 15～30;
(2) solvent is placed reaction kettle, and open whipping appts and stir;
(3) in reaction kettle, progressively add vinyl resin and anti-heavy agent, continue to stir 0.5～2h;
(4) in reaction kettle, add rosin, zinc oxide, red iron oxide and pyridinium salt according to prescription, stir 1～2h, the material that obtains mixing;
(5) material that above-mentioned steps is obtained places shredder, and adds RH-893 and silicate according to prescription, opens to grind and stirs, and grinds 2～4h, promptly obtains product.
Compared with prior art, the present invention has the following advantages:
(1) adopt 4,5-two chloro-2 n-octyls-3-RH-893 and pyridine triphenyl-boron (TPBP) or triphenyl pyridinium salt are the antifouling driving agent combinations of a kind of novel environment friendly as driving agent, in the development and use of environment-friendly antifouling agent, have explored a new direction.Not only abandoned banned substance in the Convention of the International Maritme Organization fully; And rejected the use of Red copper oxide on antifouling paint first; Antifouling driving agent more than the employing, in being discharged into environment after, can be through mode natural degradations such as photodissociation, hydrolysis; Can not accumulate, thereby reach the purpose of protecting the marine environment;
(2) adopt the base-material of active crylic acid resin as this system; Can reach ionic bond with antifouling group; In briny environment, slowly discharge, reach long-term antifouling effect, control the zone of reasonableness of PEMULEN TR2 molecular weight simultaneously; Reach the paint film property optimum regime, be fit to the application of naval vessel, fishing boat;
(3) used other auxiliary agent all takes into full account environmental requirement, adds country, international all the other that have banned use of are added auxiliary agents, have really realized the feature of environmental protection of coating.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
The present invention relates to anti-fouling ship paint, is a kind of antifouling combined system based on environment-friendly type.This coating is with 4; 5-two chloro-2 n-octyls-3-RH-893 and pyridine triphenyl-boron (TPBP) or triphenyl pyridinium salt are as driving agent; Cooperating other effective auxiliary agent, is base-material with the active crylic acid resin, through vinyl resin slowly-releasing principle in seawater; Slowly discharge driving agent, reach antifouling and drive the effect that mikrobe is being covered.
4,5-two chloro-2 n-octyls-3-RH-893 is characterized in that its structural formula is:
Pyridine triphenyl-boron (TPBP) is characterized in that its structural formula is:
The triphenyl pyridinium salt is characterized in that its structural formula is:
A kind of preparation method of environmental protection anti-fouling ship paint, this method comprises following process step:
With TEB 3K, Bing Xisuandingzhi, methylacrylic acid hydroxyl propyl ester, NSC 20956, be 50: 40: 5 according to weight ratio: 5 mix, and obtain mix monomer; In reaction kettle, add 15 parts of propyl carbinols and 15 parts of YLENE, 2 parts of Lucidols are heated to be incubated about 50 ℃ and stir; And unlatching condenser system; Then 100 parts of mix monomers are added dropwise to reaction kettle, the control dropping time is 3h, keeps reflux state 30 minutes with continued; Add 0.5 part of Lucidol again, keep backflow 2h.Last naturally cooling had both got the active crylic acid resin monomer.
Formulation for coating material: the water glass particle of 25g active crylic acid resin, 14g modulus 2.6, water glass particle grain size are 200 orders, 8g rosin, 10g zinc oxide, 2g wilkinite as the commercially available 20# solvent oil of antiager, 8g red iron oxide, 7g RH-893,2g triphenyl pyridinium salt, 24g as solvent.
(1), whole required solvent oil 24g is dropped in the reaction kettle, and begin to stir according to prescription;
(2) according to aequum, progressively add vinyl resin multipolymer 25g, and then add wilkinite 2g, continue to stir 1h;
(3) once progressively add rosin 8g, zinc oxide 10g, red iron oxide 8g, triphenyl pyridinium salt 2g according to aequum, stir 1h;
(4) close stirring, be discharged to shredder, and, open to grind and stir, grind 3h according to the required RH-893 7g water glass particle 14g of prescription;
(5) viscosity of sampling and measuring coating, fineness and solid content, qualified back weighing and bagging promptly obtains product.
The antifouling actual effect of this antifouling paint can reach 1 year.
Embodiment 2
A kind of environmental protection anti-fouling ship paint and preparation method thereof, this method comprises following process step:
Formulation for coating material: the 20g weight-average molecular weight is that 40000 active crylic acid resin, 16g modulus are 3.7 water glass particle, 10g rosin, 6g zinc oxide, 3g wilkinite, 6g red iron oxide, 10g RH-893 10g, 8g pyridine triphenyl-boron (TPBP), and the mixture of 15g 20# solvent oil and 6g butylacetate is as mixed solvent.
(1), whole required 20# solvent oil 15g and butylacetate 6g are dropped in the reaction kettle, and begin to stir according to prescription;
(2) according to aequum, progressively add vinyl resin multipolymer 20g, and then add wilkinite 3g, continue to stir 0.5h;
(3) once progressively add rosin 10g, zinc oxide 6g, red iron oxide 6g, pyridine triphenyl-boron (TPBP) 8g according to aequum, stir 2h;
(4) close stirring, be discharged to shredder, and, open to grind and stir, grind 2h according to required RH-893 10g of prescription and water glass 16g;
(5) viscosity of sampling and measuring coating, fineness and solid content, qualified back weighing and bagging promptly obtains product.
The antifouling actual effect of this antifouling paint can reach 3 years.
Embodiment 3
A kind of environment-friendly type boats and ships are with the preparation method of antifouling paint, and this method may further comprise the steps:
(1) get the raw materials ready according to following component: the 15g weight-average molecular weight is that 20000 TEB 3K, 10g particle diameter are 200 purpose water glass, and modulus is 3.0,5g rosin, 5g zinc oxide, 0.5g aerosil, 2g red iron oxide, 5g RH-893,5g pyridine triphenyl-boron, 15g sherwood oil is as solvent;
(2) the solvent sherwood oil is placed reaction kettle, and open whipping appts and stir;
(3) in reaction kettle, progressively add TEB 3K and anti-heavy agent aerosil, continue to stir 0.5h;
(4) in reaction kettle, add rosin, zinc oxide, red iron oxide and pyridine triphenyl-boron according to prescription, stir 1h, the material that obtains mixing;
(5) material that above-mentioned steps is obtained places shredder, and adds RH-893 and water glass according to prescription, opens to grind and stirs, and grinds 2h, promptly obtains product.
Embodiment 4
A kind of environment-friendly type boats and ships are with the preparation method of antifouling paint, and this method may further comprise the steps:
(1) get the raw materials ready according to following component: the 15g weight-average molecular weight is that 30000 Jia Jibingxisuanyizhi and 15g weight-average molecular weight are that 50000 NSC 20956,20g particle diameter are 200 purpose water glass, modulus is 3.0, the mixture of 10g rosin, 10g zinc oxide, 2g aerosil and 3g precipitated silica as anti-heavy agent, 10g red iron oxide, 10g RH-893,10g triphenyl pyridinium salt, 15g pimelinketone and 15g ethanol as mixed solvent;
(2) mixed solvent pimelinketone and ethanol are placed reaction kettle, and open whipping appts and stir;
(3) progressively methylate ethyl propenoate, NSC 20956, aerosil and precipitated silica in reaction kettle continue to stir 2h;
(4) in reaction kettle, add rosin, zinc oxide, red iron oxide and triphenyl pyridinium salt according to prescription, stir 2h, the material that obtains mixing;
(5) material that above-mentioned steps is obtained places shredder, and adds RH-893 and water glass according to prescription, opens to grind and stirs, and grinds 4h, promptly obtains product.
Claims (7)
1. environment-friendly type boats and ships are used antifouling paint, it is characterized in that, this coating comprises following component and weight part content:
Vinyl resin 15～30,
Silicate 10～20,
Rosin 5～10,
Zinc oxide 5～10,
Anti-heavy agent 0.5～5,
Red iron oxide 2～10,
RH-893 1～10,
Pyridinium salt 0.5～10,
Solvent 15～30.
2. a kind of environment-friendly type boats and ships according to claim 1 are used antifouling paint; It is characterized in that; The weight-average molecular weight of described vinyl resin is 20000～50000, comprises in TEB 3K, Jia Jibingxisuanyizhi or the NSC 20956 one or more.
3. a kind of environment-friendly type boats and ships according to claim 1 are used antifouling paint, it is characterized in that, described silicate is the water glass particle of modulus 2.6～3.7, and particle diameter is 200 orders.
4. a kind of environment-friendly type boats and ships according to claim 1 are used antifouling paint, it is characterized in that, described anti-heavy agent comprises in wilkinite, aerosil or the precipitated silica one or more.
5. a kind of environment-friendly type boats and ships according to claim 1 are used antifouling paint, it is characterized in that, described pyridinium salt is pyridine triphenyl-boron or triphenyl pyridinium salt.
6. a kind of environment-friendly type boats and ships according to claim 1 are used antifouling paint; It is characterized in that described solvent comprises one or more in commercially available 200# solvent oil, commercially available 200# petroleum naphtha, sherwood oil, toluene, YLENE, acetone, butanone, pimelinketone, ETHYLE ACETATE, butylacetate, ethanol, butanols, gasoline or the coal tar.
7. environment-friendly type boats and ships is characterized in that with the preparation method of antifouling paint this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Vinyl resin 15～30,
Silicate 10～20,
Rosin 5～10,
Zinc oxide 5～10,
Anti-heavy agent 0.5～5,
Red iron oxide 2～10,
RH-893 1～10,
Pyridinium salt 0.5～10,
Solvent 15～30;
(2) solvent is placed reaction kettle, and open whipping appts and stir;
(3) in reaction kettle, progressively add vinyl resin and anti-heavy agent, continue to stir 0.5～2h;
(4) in reaction kettle, add rosin, zinc oxide, red iron oxide and pyridinium salt according to prescription, stir 1～2h, the material that obtains mixing;
(5) material that above-mentioned steps is obtained places shredder, and adds RH-893 and silicate according to prescription, opens to grind and stirs, and grinds 2～4h, promptly obtains product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618137A (en) * | 2012-04-01 | 2012-08-01 | 海洋化工研究院 | Green and environment-friendly antifouling paint for fishing boats, and fouling-panel testing method |
| CN103059682A (en) * | 2013-01-16 | 2013-04-24 | 北海光谷纳米科技研发中心 | Nano silver composited antifouling paint for underwater equipment, and preparation method of same |
| CN103265858A (en) * | 2013-05-24 | 2013-08-28 | 苏州市德莱尔建材科技有限公司 | Acrylic resin fireproof paint for wood material |
| CN105949398A (en) * | 2016-05-18 | 2016-09-21 | 巢湖市翔宇渔具有限公司 | Antifouling paint for fishing gear |
| CN106632262A (en) * | 2016-11-28 | 2017-05-10 | 江苏师范大学 | Triarylpyridine derivatives containing carbazole frameworks and preparation method and application thereof |
| CN107286794A (en) * | 2017-08-03 | 2017-10-24 | 厦门双瑞船舶涂料有限公司 | A kind of drag reduction antifouling paint of not cupric class anti-fouling agent and preparation method thereof |
| CN111364428A (en) * | 2018-12-25 | 2020-07-03 | 深圳市百安百科技有限公司 | Method for preventing marine organism fouling of underwater structure of active marine facility |
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| CN101550304A (en) * | 2008-04-02 | 2009-10-07 | 上海海悦涂料有限公司 | Environment-friendly marine antifouling coating for finishing boat |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618137A (en) * | 2012-04-01 | 2012-08-01 | 海洋化工研究院 | Green and environment-friendly antifouling paint for fishing boats, and fouling-panel testing method |
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| CN103059682A (en) * | 2013-01-16 | 2013-04-24 | 北海光谷纳米科技研发中心 | Nano silver composited antifouling paint for underwater equipment, and preparation method of same |
| CN103265858A (en) * | 2013-05-24 | 2013-08-28 | 苏州市德莱尔建材科技有限公司 | Acrylic resin fireproof paint for wood material |
| CN103265858B (en) * | 2013-05-24 | 2015-08-12 | 苏州市德莱尔建材科技有限公司 | A kind of Acrylic resin fireproof paint for wood material |
| CN105949398A (en) * | 2016-05-18 | 2016-09-21 | 巢湖市翔宇渔具有限公司 | Antifouling paint for fishing gear |
| CN106632262A (en) * | 2016-11-28 | 2017-05-10 | 江苏师范大学 | Triarylpyridine derivatives containing carbazole frameworks and preparation method and application thereof |
| CN106632262B (en) * | 2016-11-28 | 2019-05-31 | 江苏师范大学 | Triaryl pyridine derivate and the preparation method and application thereof of the one kind containing carbazole skelton |
| CN107286794A (en) * | 2017-08-03 | 2017-10-24 | 厦门双瑞船舶涂料有限公司 | A kind of drag reduction antifouling paint of not cupric class anti-fouling agent and preparation method thereof |
| CN111364428A (en) * | 2018-12-25 | 2020-07-03 | 深圳市百安百科技有限公司 | Method for preventing marine organism fouling of underwater structure of active marine facility |
| CN111364428B (en) * | 2018-12-25 | 2021-08-06 | 深圳市百安百科技有限公司 | Method for preventing marine organism fouling of underwater structure of active marine facility |
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Application publication date: 20120111 |