CN101564050B - Method for preparing Ulva pertusa Kjellm extract for marine antifoulant - Google Patents
Method for preparing Ulva pertusa Kjellm extract for marine antifoulant Download PDFInfo
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- CN101564050B CN101564050B CN2009100154742A CN200910015474A CN101564050B CN 101564050 B CN101564050 B CN 101564050B CN 2009100154742 A CN2009100154742 A CN 2009100154742A CN 200910015474 A CN200910015474 A CN 200910015474A CN 101564050 B CN101564050 B CN 101564050B
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Abstract
The invention relates to preparation of a biological antifoulant for preventing biofouling on the surface of an artificial material in the technical fields of marine environments and antifouling, in particular to a method for preparing an Ulva pertusa Kjellm extract for a marine antifoulant, which comprises the following steps: placing the fresh Ulva pertusa Kjellm which are dried in the air and crushed into a container, adding a solvent into the container till the fresh Ulva pertusa Kjellm are completely immersed in the solvent, heating the solution under reflux at a constant temperature of between 30 and 80 DEG C for 1 to 50 hours, and filtrating the solution to obtain a liquid solvent extractable matter; concentrating the liquid solvent extractable matter to remove the solvent to obtainan pasty extract A; and separating solvent extractable matter A by column chromatography, subjecting the separated solvent extractable matter A to gradient elution with sherwood oil, ethyl acetate an d ethanol respectively to obtain mixed separated product B sequentially, subjecting the separated product B to separation by column chromatography, and eluting the product of the separation by column chromatography with a mixed solution prepared from the ethyl acetate and the ethanol in weight ratio of from 1:20 to 20:1 to obtain a separated product C which is the Ulva pertusa Kjellm extract product. The Ulva pertusa Kjellm extract has the advantages of nontoxicity, environmental protection, readily available raw materials, simple preparation, high quality, high antifouling effect, and the like.
Description
Technical field:
The present invention relates to artificial material surface in a kind of marine environment and prevent and kill off the preparation of the bioantifouling agent that biodeterioration uses, particularly a kind of preparation method of Ulva pertusa Kjellm extract for marine antifoulant belongs to marine organisms anti-soil technology field.
Background technology:
Marine biofouling refers to the adverse effect that the biological attachment on marine structure surface causes soaking extra large material.This biology that is attached to the works surface is called marine fouling organism, comprises barnacle, mussel, Ascidian, bryozoan, hydra, sponge, green alga, diatom etc.Said structure thing surface comprises boats and ships, dock, harbour, oil platform, submarine cable, buoy, submarine mine, power plant's cooling pipe, fishing net etc.Marine biofouling causes serious harm, as causes ship resistance to increase, maritime pipeline obstruction, and the thermoelectric cooling apparatus thermal conductivity reduces, aquaculture catch reduction etc.And the most popular method that solves marine biofouling is the coating that brushing contains antifouling composition.The Britain international standard paint company has been invented a kind of antifouling paint (GB1457590) that contains triphenyltin, and the organotin antifouling paint is applied since then, and its anti-fouling effect can reach more than 5 years.Yet this antifouling paint is by discharging the mode of poisonous antifouling composition, killing fouling organism and reach antifouling purpose.Simultaneously other nontarget organism such as fish, shellfish etc. also there are strong toxicity, and easily accumulate in vivo with in seawater, mud, the marine eco-environment is caused have a strong impact on.International Maritime Organization (IMO) has forbidden the application of organotin in antifouling paint at present.In addition, other poisonous antifouling composition also because of the use that is under an embargo gradually of same problem, therefore needs the agent of invention novel antifouling as dichlorodiphenyl trichloroethane (DDT, dichlorodiphenyltrichloroethane) etc.Wherein extracting active substance from organism is the important channel of development of new antifouling composition.Some relevant patents of invention are disclosed both at home and abroad.
US Patent No. 2008/0095871 A1 discloses the cell extract that a kind of ocean replaces monad Alteromonas sp., and little algae of marime fouling, large-scale algae and invertebrate are had stronger growth inhibition effect.World patent WO0218500A1 discloses a kind of brown alga okamura ishige algae Ishige sinicola extract, has obvious inhibition active to marime fouling algae spore and mussel.US Patent No. 6346252 B1 disclose a kind of red algae Asparagopsis Armata extract, have good antibiotic and antifungal activity.
Chinese patent CN200710092627 discloses a kind of biological anti-fouling paint that contains plant extracts vegetable tannin and Tea Polyphenols, and the release by natural anti-fouling agent reaches anti-fouling effect.Chinese patent CN200510013553.1 discloses a kind of capsaicin antifouling paint, and the bioactivator that extracts from natural capsicum as driving agent, prevents that marine growth from adhering to.Chinese patent CN1238447C discloses a kind of ocean Zostera marina extract and sponge extract as the antifouling paint of antifouling composition, as active component, prevents halobiontic adhere in conjunction with the fluororesin of low-surface-energy with alkaloid and peptides.Chinese patent CN1820603A discloses a kind of pyrethrum flowers extract, as marine antifoulant, the Macro-fouling Organisms barnacle is had stronger inhibition ability.Above-mentioned existing natural extract uses as marine antifoulant and the preparation extractive technique, all fails to reach the antifouling property of organotin antifouling composition, and larger on the marine environment impact, and anti-fouling effect is poor, and extraction process is complicated, and cost is high.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, problem for the heavy damage environment such as marine antifoulant such as organotin, DDT, urgent need environment-friend substitution product, design provides a kind of method of utilizing natural marine green alga hole sea lettuce extract preparation antifouling composition, can suppress well adhering to of the marine growths such as diatom, mussel, reach the antifouling purpose of asepsis environment-protecting.Hole sea lettuce (Ulvapertusa) is a kind of large ocean green alga, be commonly called as sea lettuce, extra large spinach, Hai Geba etc., genus Chlorophyta stone medicine section Ulva, its young green, the adult aquamarine is lived in the intertidal zone, is distributed widely in the Western Pacific coastal, resource is very abundant in wild algae, is a kind of green alga of output maximum.
To achieve these goals, the present invention prepares solvent extractable matter and column chromatography for separation product take marine green algae hole sea lettuce as raw material; Solvent extractable matter is the product that the finger-hole sea lettuce obtains after solvent extraction, solvent refers to water, methyl alcohol, ethanol, ethyl acetate, chloroform, toluene, benzinum etc., extraction refers to soaked in solvent certain hour at a certain temperature, then filters, and obtains product after the concentrated desolventizing of filtrate; Adopt single solvent extraction, or multi-solvents extracts in turn; The column chromatography for separation product is that finger-hole sea lettuce solvent extractable matter is through the isolated product of chromatographic column, fixing silica gel, aluminium oxide, polyamide, the ion exchange resin etc. of comprising mutually of chromatographic column, mobile phase is water, methyl alcohol, ethanol, ethyl acetate, chloroform, toluene, benzinum equal solvent, carry out single solvent or the mode wash-outs such as mixed solvent or gradient, eluent is collected, can be obtained the column chromatography for separation product after concentrating.
The preparation method of the hole sea lettuce extract that the present invention relates to, first with fresh hole sea lettuce after air-dry, fragmentation, take a certain amount of container of putting into, solubilizer is to submergence fully, add hot reflux 1～50 hour under 30～80 ℃ of constant temperatures, then filter and obtain filtrate, be solvent extractable matter liquid; Again extract liquid is obtained paste extract A after concentrated desolventizing; Again with extract A through column chromatography for separation, carry out gradient elution with benzinum, ethyl acetate and ethanol respectively, obtain successively the hybrid separation product B, with separated product B again through column chromatography for separation, carry out wash-out with ethyl acetate and ethanol by the mixed solution of the part by weight of 1: 20 to 20: 1, obtain separated product C, be hole sea lettuce extract product.
Solvent for use of the present invention is polar organic solvent or non-polar organic solvent, uses separately or multiple mixing use; Polar organic solvent comprises: distilled water, methyl alcohol, ethanol, chloroform, acetone, acetonitrile, oxolane, DMF and dimethyl sulfoxide (DMSO) and two or more mixed solvents thereof; Non-polar organic solvent comprises benzene, toluene, n-hexane, cyclohexane, carbon tetrachloride, benzinum and ethyl acetate; The preferred organic solvent that uses is chloroform, ethyl acetate, ethanol, distilled water, more preferably uses ethyl acetate, ethanol; Concentrated mode comprises rotary evaporation, freeze drying, atomized drying.
Can be separately when hole of the present invention sea lettuce extract product uses as antifouling composition or composite with other antifouling composition, or add in the antifouling paint system, all can prepare antifouling composition or antifouling paint under marine environment; The preparation of antifouling paint defer to conventional coating production technology or
Process, comprise the preparation of resin or select, the adding and disperse, prepare coating, repeatedly grind and obtain antifouling paint at last of the grinding distribution of the solid material such as face (filling out) material, antifouling composition; Wherein resin refers to that asphalt series commonly used, acrylic resin, vinylite, chlorinated rubber are resin, phenolic resins etc., different resin binders need use different solvents to dissolve, and selects appropriate solvent according to the consumption of resin, the dissolution degree of resin, the requirement of coating application; The consumption of hole sea lettuce extract accounts for 5% to 80% percentage by weight of antifouling paint, and is preferred 20% to 60%, and the consumption of face (filling out) material accounts for the 5%-50% of coating weight, and the consumption of resin is 2-70%, all is weight percentage.
The present invention as the novel antifouling agent, shows to the inhibition test result of common fouling organism diatom and mussel in the laboratory that with hole sea lettuce extract diatom and mussel are had stronger growth inhibition effect, and effectively inhibition concentration is less than 1mg/ml; Real extra large static link plate shows to have obvious anti-fouling effect; Compare with prior art products and have asepsis environment-protecting, raw material is easily got, and preparation is simple, good product quality, the advantage such as antifouling effect is strong.
Embodiment:
Be described further below by embodiment.
Embodiment 1: the preparation of a kind of hole sea lettuce extract A
Gather fresh hole sea lettuce from the intertidal zone, natural air drying is pulverized into about 1cm with cracker
2Size, take 250g and put into flask, add ethyl acetate submergence hole sea lettuce extremely fully, 50 ℃ of heating of water-bath, soaked 48 hours, filter, filter residue still is deposited in flask, then adds ethyl acetate to submergence fully, repeat to extract three times, filtrate obtains black paste through the rotary evaporation desolventizing, is hole sea lettuce solvent extractable matter A.
Embodiment 2: the preparation of a kind of hole sea lettuce extract B
Get 60g 200 order silica gel in baking oven 110 ° the activation 2 hours, then with benzinum wet method dress post, get the hole sea lettuce extract A 0.5g that embodiment 1 makes, be dissolved in a small amount of ethyl acetate, the wet method loading, carry out gradient elution with benzinum, ethyl acetate, ethanol respectively, collect efflux according to the layering color, collect according to this and obtain 6 kinds of separated products, after wherein the 5th kind of separated product collected, through revolving evaporation, after desolventizing, namely obtain hole sea lettuce extract B.
Embodiment 3: the preparation of a kind of hole sea lettuce extract C
Get 50g 300 order silica gel in baking oven 110 ° the activation 2 hours, then with benzinum wet method dress post, get the hole sea lettuce extract B 0.5g that embodiment 2 makes, be dissolved in a small amount of ethyl acetate, the wet method loading, carry out wash-out with ethyl acetate and alcohol mixed solution (mixed proportion is 1: 20), collect efflux according to the layering color, collect according to this and obtain 4 kinds of separated products, after wherein the 2nd kind of separated product collected, through revolving evaporation, after desolventizing, namely obtain hole sea lettuce extract C.
Embodiment 4: prepare antifouling paint as the antifouling composition conventional method separately with hole sea lettuce extract.
Each raw material shared percentage by weight in coating is:
M133 acrylic resin 30%
Hole sea lettuce extract A or B or C 10%
Limed rosin 15%
Zinc oxide 16%
Iron oxide red 10%
Rilanit special (anti-settling agent) 2%
Bentonite 2%
N-butanol 5%
Dimethylbenzene 10%
Described acrylic resin dissolves with dimethylbenzene and n-butanol, zinc oxide joins in acrylic resin soln, repeatedly grinding distribution evenly after, the solution that adds respectively again hand-hole sea lettuce extract A, B and C, limed rosin, rilanit special, further grind, form homodisperse coating, namely obtain respectively three kinds of hole sea lettuce extract antifouling paints.
Embodiment 5: indoor antifouling activity test
Get the hole sea lettuce extract A 36mg of embodiment 1, add 6ml ethanol ultrasonic dissolution, get respectively in 50,100,150,200,250,300,350,400,450,500 μ l to 24 well culture plates, after ethanol is removed in volatilization, add 2.8ml nutrient solution and 0.2ml diatom solution in each hole; Be configured to the liquid that concentration is respectively 0.1～1.0mg/ml concentration gradient; Be 12h in 20 ℃, 1900lux illumination, light and shade cycle: cultivate under the 12h condition; To Bottomattached diatom counting, adhere to number according to the bottom diatom after 7 days, calculate diatom is got the growth inhibition situation, result shows, hole sea lettuce extract A is 0.5mg/ml to the minimal inhibitory concentration of diatom.
Claims (3)
1. the preparation method of a Ulva pertusa Kjellm extract for marine antifoulant, it is characterized in that first fresh hole sea lettuce is put into container after air-dry, fragmentation, solubilizer is to submergence fully, added hot reflux 1～50 hour under 30～80 ℃ of constant temperatures, then filter and obtain filtrate, be solvent extractable matter liquid; Again extract liquid is obtained paste extract A after concentrated desolventizing; Again with extract A through column chromatography for separation, carry out gradient elution with benzinum, ethyl acetate and ethanol respectively, obtain successively the hybrid separation product B, with separated product B again through column chromatography for separation, carry out wash-out with ethyl acetate and ethanol by the mixed solution of the part by weight of 1: 20 to 20: 1, obtain separated product C, be hole sea lettuce extract product.
2. the preparation method of Ulva pertusa Kjellm extract for marine antifoulant according to claim 1, is characterized in that solvent for use comprises ethyl acetate.
3. Ulva pertusa Kjellm extract for marine antifoulant according to claim 1, the consumption that it is characterized in that hole sea lettuce extract accounts for 5% to 80% percentage by weight of antifouling paint, the consumption of pigment or filler accounts for the 5%-50% of coating weight, the consumption of resin is 2-70%, all is weight percentage.
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| CN2009100154742A CN101564050B (en) | 2009-05-23 | 2009-05-23 | Method for preparing Ulva pertusa Kjellm extract for marine antifoulant |
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| CN101564050B true CN101564050B (en) | 2013-06-19 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102040909A (en) * | 2010-10-23 | 2011-05-04 | 中国船舶重工集团公司第七二五研究所 | Preparation method of low-elasticity modulus organic silicon antifouling material |
| CN102807797B (en) * | 2012-05-23 | 2014-10-15 | 浙江省海洋开发研究院 | Efficient marine antifouling coating and broad-spectrum controlled-release antifouling agent for same |
| CL2015002602A1 (en) * | 2015-09-11 | 2016-07-08 | Univ Concepcion | Antifouling bio-paint comprising a two-barrier protection system, which includes extracts of macroalgae attractants of epibiont bacteria and active extracts of bacteria with antifouling characteristics. |
| CN105670446B (en) * | 2016-03-22 | 2018-03-27 | 佛山市顺德区绅教合成剂有限公司 | A kind of preparation method of organosilicon marine antifouling coating |
Citations (2)
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| CN1850631A (en) * | 2006-05-26 | 2006-10-25 | 中国海洋大学 | Method for preparing inhibitor of skeletonema costatum (greville) cleve |
| CN101336940A (en) * | 2008-08-14 | 2009-01-07 | 中国科学院南海海洋研究所 | Thalassia hemprichii extract and preparation method and use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850631A (en) * | 2006-05-26 | 2006-10-25 | 中国海洋大学 | Method for preparing inhibitor of skeletonema costatum (greville) cleve |
| CN101336940A (en) * | 2008-08-14 | 2009-01-07 | 中国科学院南海海洋研究所 | Thalassia hemprichii extract and preparation method and use thereof |
Non-Patent Citations (2)
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| 南春容等.孔石莼水溶性抽提液抑制3种海洋赤潮藻的生长.《环境科学学报》.2004,第24卷(第4期),703-706. * |
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