CN102234251A - Benzisothiazolinone compound and application thereof - Google Patents
Benzisothiazolinone compound and application thereof Download PDFInfo
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Abstract
The invention relates to a marine organism inhibitor, and concretely relates to a benzisothiazolinone compound and an application thereof. The benzisothiazolinone compound or a mixture of the benzisothiazolinone compound and a resin is treated as a marine antifouling agent. An N-acyl benzisothiazolinone derivative of the invention can be effectively treated as the antifouling agent for preventing aquatics from adhering to organisms, a fishing net antifouling agent for preventing the organisms which can cause fouling from adhering to and growing on the fixedly arranged fishing net for culture, and the antifouling agent for preventing the fouled organisms from adhering to and growing on bottoms of ships, materials used in fishing nets (buoys and ropes for example), and condensate water channels in nuclear energy/heat energy power plants. The marine antifouling agent of the present invention has no detrimental effect on the storage stability, and does not allow the viscosity to be increased and deterioration to be carried out.
Description
Technical field
The present invention relates to the marine organisms inhibitor, a kind of specifically benzisothiazole ketone compounds and application thereof.
Background technology
In seawater or fresh water, aquatic organism, for example coelenterates (as hydrozoans), shellfish, the pipe fishing net that polychetes annelid, algae, Polyzoa animal, mollusk etc. can be attached to hull bottom or be used to culture of dwelling.In case these aquatic organisms are attached on hull bottom, the fishing net etc., ship and fishing net suffer damage, and this may cause very big financial loss.For example, when being attached on the fishing net as if the cirrus class, it can seal mesh, stops tidal water flow, thereby causes oxygen shortage under water, and the fish of breed is died owing to being choked to death; When draping because weight increases operational difficulty; And since bigger to the resistance of billow, Netease's breakage when typhoon attacks.When if these organisms stick to hull bottom, the puopulsion efficiency of ship reduces, and fuel consumption increases.For above-mentioned reasons, these periphytons are called the fouling organism body.Financial loss for reducing to be caused by fouling organism has dropped into the maritime facilities that very big manpower and fund are safeguarded vulnerable to pollution.
Although dichlorodiphenyl trichloroethane and a series of organo-tin compound are effective,, these they have strong toxicity, application at present has been under an embargo.Therefore, exploitation low pollution stain control agent and oligosaprobic antifouling paint have important need at aspects such as aquatic products, shipbuilding, ocean military affairs.Japan's special permission communique 10849/1976 discloses a kind of underwater antifouling coating that contains benzothiazole compound as active ingredient; Day disclosure special permission communique 38303/1985,284275/1988 speciallys permit communique 11606/1989 with Japan discloses various fishing net anti-fouling agents, ANTI-FOULING PAINT FOR FISHING NET composition and antifouling solution, wherein thiuram disulfide compound and other compound is used in combination; Japan's special permission communique 50954/1986 discloses a kind of stainproofing agent that is used for marine works, wherein contains a kind of 3-isothiazolone compounds as active ingredient; Japan special permission communique 20665/1989 and 24242/1990 and a day disclosure special permission communique 9320/1978,201804/1993,100405/1994 and 100408/1994 disclose and contained the antifouling paint of maleimide compound as active ingredient.
As the coating that is used for hull bottom, various antifouling paints had once been studied, for example Red copper oxide, organotin and thiocarbamate.But these stain control agents have only more weak anti-adhesion effect for coelenterates (for example hydrozoans), then can not show effect in the frequent marine site that occurs of coelenterates.The frequent marine site that occurs of coelenterates is local and Hokkaido bank in this northeast in a few days mainly.In addition, in the East Sea and western Japanese marine site, they only to preventing shellfish and the pipe annelidan demonstration limited action that adheres to of polychetes of dwelling, therefore can not prevent adhering to of these organisms effectively.Known copper is effective to the control shellfish, and has confirmed that copper class stain control agent can resist shellfish and the pipe polychetes annelid that dwells really effectively.But, in the copper stain control agent, use heavy metal copper to produce harmful effect to environment thereupon.
Object refers to contact with water or exposes object or goods or structure in water to the open air in the described water, comprising the maritime facilitieies such as the antifouling band of seawater of boring tower, port facilities and the ocean civil engineering facility of the water coolant input canal of naval vessel, buoy, seashore factory, heat or nuclear power plant, submarine oil field.
Known many kinds are lived in marine animal and plant, and various organisms usually can adhere in the water and cause disadvantageous effect on the object and to it.The adhesion of harmful aquatic organism like this will cause the increase of slowing down of maintenance speed and naval vessel fuel consumption, and the carrying capacity reduction that enters water coolant input canal.
Adhere to organism in order to control these, used various stain control agents such as Red copper oxide so far, yet its effect is mostly not ideal enough.
Content of the present invention
The object of the invention is to provide a kind of and prevents effectively and suppress the application that various organisms adhere to the benzisothia sulfinpyrazone compound of object in the water.
For achieving the above object, the technical solution used in the present invention is:
A kind of benzisothia sulfinpyrazone compound: described benzisothia sulfinpyrazone compound be N-acyl group benzisothia trazodone derivative suc as formula shown in (I) compound:
Wherein: R is selected from H, the C1-C10 alkyl, and the C2-C10 thiazolinyl, C6-C10 phenyl or phenyl substituent, substituting group is randomly replaced by halogen; Described substituting group randomly is substituted by among the R by halogen and all can be replaced by halogen on substituting group alkyl, thiazolinyl or the phenyl arbitrarily; X can be halogen, nitro, alkyl or alkoxyl group; M is the integer of 0-4.Described R thinks hydrogen, the C1-C10 alkyl, and C2-C10 thiazolinyl, C6-C10 phenyl or substituted-phenyl, m are integers 0.
The application of benzisothia sulfinpyrazone compound: described benzisothia sulfinpyrazone compound or benzisothia sulfinpyrazone compound and mixed with resin be as marine antifoulant, and to account for the weight of resin be 0.2-40% to the benzisothiazole ketone compounds when described benzisothia sulfinpyrazone compound and mixed with resin.
Described benzisothia sulfinpyrazone compound and copper compound or metallic copper are as marine antifoulant, and wherein copper compound or metallic copper account for the 5-35% of marine antifoulant gross weight; Perhaps described benzisothia sulfinpyrazone compound with mixed with resin and benzisothia sulfinpyrazone compound with according to after weight percent or benzisothia sulfinpyrazone compound and the mixed with resin with copper compound or metallic copper as marine antifoulant, wherein copper compound or metallic copper account for the 5-35% of marine antifoulant gross weight.Described marine antifoulant can prevent and suppress harmful aquatic organism and adhere in the water on the object.Described copper compound is cupric thiocyanide, Red copper oxide, cuprous chloride, copper naphthenate, glycocoll-copper, oxine-copper or cuprous carbonate.Described resin is a vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene base isobutyl ether multipolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene, acrylic resin, styrene-butadiene copolymer, vibrin, Resins, epoxy, resol, synthetic rubber, silicon rubber, silicone resin, petroleum resin, oleo-resinous, rosin ester resin, rosined soap or rosin.Described resin is a vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene base isobutyl ether multipolymer or acrylic resin and styrene-butadiene copolymer.Described marine antifoulant can be directly or is mixed with coating and to be applied to marine structure.Described coating is ocean coating, and ocean coating is solvent base ocean coating and water base ocean coating.
Described halogen is chlorine, fluorine, bromine or iodine; Described C1-C10 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, tert-pentyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or positive decyl, preferably C1-C5 alkyl; Described C1-C10 alkoxyl group be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, sec-butoxy, uncle's pentyloxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base or n-decyloxy, preferably C1-C5 alkoxyl group; Described C6-C10 phenyl and substituted-phenyl are phenyl, tolyl, ethylbenzene base, n-proplbenzene base, cumyl, n-butyl benzene base misfortune isobutylphenyl.
The advantage that the present invention had:
N-acyl substituted benzisothia oxazolone of the present invention is derived and can be effective as the stain control agent of antagonism periphyton body; can be used for preventing the fishing net anti-fouling agent that can cause stained organism on the fishing net of culturing and fixedly installing, to adhere to and grow, and stop the fouling organism body alow, on the material of fishing net use (as buoy and rope) and the stain control agent that on the condensation water channel of nuclear energy or heat energy power plant, adheres to and grow.Marine antifoulant of the present invention does not have harmful effect to package stability, can not make viscosity increase and rotten.
N-acyl substituted benzisothia trazodone derivative of the present invention has preventing and suppresses harmful aquatic organism and adheres in the water on the object, described harmful aquatic organism be hydrocoles such as barnacle (Balanomorpha), the dragon cyprid belongs to (Serpula), the bright worm (Polyzoa) of tongue, Ascidicea (Ascidiacea), Hydrozoa (Hydrozoa) and mollusk (Mollusca); Waterplant such as stone garden (Ulva), Enteromorpha (Enteromorpha), Ectocarpus (Ectocarpus) and diatoms (Diatomaceae); And foundry loam.
Object refers to contact with water or exposes object or goods or structure in water to the open air in the described water, comprising the maritime facilitieies such as the antifouling band of seawater of boring tower, port facilities and the ocean civil engineering facility of the water coolant input canal of naval vessel, buoy, seashore factory, heat or nuclear power plant, submarine oil field.
Embodiment
Described benzisothia sulfinpyrazone compound be N-acyl group benzisothia trazodone derivative suc as formula shown in (I) compound referring to table 1:
R is selected from H, the C1-C10 alkyl, and the C2-C10 thiazolinyl, C6-C10 phenyl or substituted-phenyl, substituting group is randomly replaced by halogen;
X can be halogen, nitro, alkyl or alkoxyl group; M is the integer of 0-4.
Formula (I) compound can be made by the common compound method that is generally used for paint field, referring to (fine chemistry industry: 2008,25 (8): 771-774.).
Table 1
| Compound number | The compound title | Substituting group | Physicochemical characteristic |
| 1 | N-ethanoyl benzo isothiazole-3-ketone | R＝CH 3 | CDCl 3，δ：7.26～8.03(m，4H，PhH)，3.33(s，3H，C-H) |
| 2 | N-tribromo-acetyl base benzisothiazole-3-ketone | R＝CCl 3 | CDCl 3，δ：7.26～8.03(m，4H，PhH)， |
| 3 | N-propionyl benzisothiazole-3-ketone | R＝CH 2CH 3 | CDCl 3，δ：7.26～8.03(m，4H，PhH)， 3.17(q，2H，C-H)，1.28(t，3H，C-H) |
| 4 | N-(2-methylpropionyl) benzisothiazole-3-ketone | R＝CH(CH 3) 2 | CDCl 3，δ：7.26～8.03(m，4H，PhH)， 3.57(q，1H，C-H)，1.33(d，6H，C-H) |
| 5 | N-(2-methyl caproyl) benzisothiazole-3-ketone | R＝CH(CH 3)CH 2CH 2CH 2CH 2 | CDCl 3，δ：7.29～8.03(m，4H，PhH)， 3.46(m，1H，C-H)，2.43(m，2H，C-H)，2.23(m，2H，C-H)， 2.19(m，2H，C-H)，2.11(d，3H，C-H)，1.81(t，3H，C-H) |
| 6 | N-chloracetyl benzisothiazole-3-ketone | R＝CH 2Cl | CDCl 3，δ：7.25～8.02(m，4H，PhH)，4.97(s，2H，C-H) |
| 7 | N-(2-chlorine propionyl) benzisothiazole-3-ketone | R＝CHClCH 3 | CDCl 3，δ：7.26～ 8.04(m，4H，PhH)，4.89(q，1H，C-H)，2.97(d，3H，C-H) |
| 8 | N-(3-chlorine propionyl) benzisothiazole-3-ketone | R＝CH 2CH 2Cl | CDCl 3，δ：7.26～8.04(m，4H，PhH)， 3.92(t，2H，C-H)，3.7(t，2H，C-H) |
| 9 | N-(2,3-dichloro propionyl) benzisothiazole-3-ketone | R＝CHClCH 2Cl | CDCl 3，δ：7.26～8.04(m，4H，PhH)， 4.93(t，1H，C-H)，4.15(d，2H，C-H) |
| 10 | N-benzoyl benzo isothiazole-3-ketone | R＝C 6H 5 | CDCl 3，δ：7.21～8.05(m，4H，PhH)，7.44～ 8.11(m，5H，PhH) |
| 11 | N-(4-chlorobenzene formacyl) benzisothiazole-3-ketone | R＝C 6H 4Cl | CDCl 3，δ：7.21～8.05(m，4H，PhH)，7.54～ 8.07(m，4H，PhH) |
| 12 | N-(4-benzoyl bromide) benzisothiazole-3-ketone | R＝C 6H 4Br | CDCl 3，δ：7.21～8.05(m，4H，PhH)，7.61～ 7.97(m，4H，PhH) |
| 13 | N-(2-fluoro benzoyl) benzisothiazole-3-ketone | R＝C 6H 4F | CDCl 3，δ：7.23～7.97(m，4H，PhH)，7.37～ 7.97(m，4H，PhH) |
| 14 | N-(2-methyl benzoyl) benzisothiazole-3-ketone | R＝C 6H 4CH 3 | CDCl 3，δ：7.25～8.04(m，4H，PhH)，7.14～ 7.93(m，4H，PhH)，2.79(s，3H，C-H) |
| 15 | N-(4-ethylamino benzonitrile acyl group) benzisothiazole-3-ketone | R＝C 6H 4CH 2CH 3 | CDCl 3，δ：7.23～8.01(m，4H，PhH)，7.39～ 7.97(m，4H，PhH)，2.83(q，2H，C-H)，2.04(t，3H，C-H) |
| 16 | N-(4-isopropyl benzene formyl radical) benzisothiazole-3-ketone | R＝C 6H 4CH(CH 3) 2 | CDCl 3，δ：7.23～8.01(m，4H，PhH)，7.49～ 8.03(m，4H，PhH)，2.83(m，1H，C-H)，2.04(q，6H，C-H) |
| 17 | N-(2-anisoyl) benzisothiazole-3-ketone | R＝C 6H 40CH 3 | CDCl 3，δ：7.25～8.04(m，4H，PhH)，6.95～ 7.84(m，4H，PhH)，3.73(s，3H，C-H) |
| 18 | N-(3-anisoyl) benzisoxa | R＝C 6H 4OCH 3 | CDCl 3，δ：7.26～8.04(m，4H，PhH)，7.02～ 7.51(m，4H，PhH)，3.67(s，3H，C-H) |
| Thiazole-3-ketone | |||
| 19 | N-(4-anisoyl) benzisothiazole-3-ketone | R＝C 6H 40CH 3 | CDCl 3，δ：7.26～8.04(m，4H，PhH)，6.95～ 7.84(m，4H，PhH)，3.69(s，3H，C-H) |
| 20 | N-(2,4 dichloro benzene formyl radical) benzisothiazole-3-ketone | R＝C 6H 3Cl 2 | CDCl 3，δ：7.22～8.03(m，4H，PhH)，6.33～ 7.82(m，3H，PhH) |
| 21 | N-(2,6-dichloro-benzoyl base) benzisothiazole-3-ketone | R＝C 6H 3Cl 2 | CDCl 3，δ：7.26～7.99(m，4H，PhH)，6.33～ 7.82(m，3H，PhH) |
| 22 | N-(2,4,6-trichlorobenzene formyl radical) benzisothiazole-3-ketone | R＝C 6H 2Cl 3 | CDCl 3，δ：7.24～7.97(m，4H，PhH)，7.34(m，2H，PhH) |
| 23 | N-(2,3,4,5,6-pentachlorobenzene formyl radical) benzisothiazole-3-ketone | R＝C 6Cl 5 | CDCl 3，δ：7.24～8.01(m，4H，PhH) |
| 24 | N-(2, the 4-dimethylbenzoyl) benzisothiazole-3-ketone | R＝C 6H 3(CH 3) 2 | CDCl 3，δ：7.32～8.04(m，4H，PhH)，7.04～ 7.73(m，3H，PhH)，2.35(s，3H，C-H)，2.30(s，3H，C-H) |
| 25 | N-(3, the 4-dimethylbenzoyl) benzisothiazole-3-ketone | R＝C 6H 3(CH 3) 2 | CDCl 3，δ：7.34～8.11(m，4H，PhH)，7.12～ 7.69(m，3H，PhH)，2.33(s，3H，C-H)，2.27(s，3H，C-H) |
| 26 | N-(2, the 6-dimethylbenzoyl) benzisothiazole-3-ketone | R＝C 6H 3(CH 3) 2 | CDCl 3，δ：7.34～8.09(m，4H，PhH)，7.05～ 7.47(m，3H，PhH)，2.31(s，6H，C-H) |
| 27 | N-(2,4, the 6-trimethylbenzoyl) benzisothiazole-3-ketone | R＝C 6H 2(CH 3) 3 | CDCl 3，δ：7.24～ 8.09(m，4H，PhH)，6.85(s，2H，PhH)，2.29(s，9H，C-H) |
| 28 | N-(3,4-dimethoxy benzoyl) benzisothiazole-3-ketone | R＝C 6H 3(OCH 3) 2 | CDCl 3，δ：7.30～8.02(m，4H，PhH)，7.04～ 7.35(m，3H，PhH)，3.75(s，3H，C-H)，3.67(s，3H，C-H) |
| 29 | N-(3,5-dimethoxy benzoyl) benzisothiazole-3-ketone | R＝C 6H 3(OCH 3) 2 | CDCl 3，δ：7.25～8.07(m，4H，PhH)，6.83～ 7.32(m，3H，PhH)，3.77(s，6H，C-H) |
| 30 | N-(3,4,5-trimethoxy benzoyl) benzisothiazole-3-ketone | R＝C 6H 2(OCH 3) 3 | CDCl 3，δ：7.25～ 8.03(m，4H，PhH)，6.97(s，2H，PhH)，3.75(s，9H，C-H) |
| 31 | N-(2-chloro-4-methyl benzoyl) benzisothiazole-3-ketone | R＝C 6H 3Cl(CH 3) | CDCl 3，δ：7.35～8.05(m，4H，PhH)，7.22～ 7.97(m，3H，PhH)，2.45(s，3H，C-H) |
| 32 | N-(2-fluoro-4-chlorobenzene formacyl) benzisothiazole-3-ketone | R＝C 6H 3ClF | CDCl 3，δ：7.25～7.97(m，4H，PhH)，7.25～ 7.97(m，3H，PhH) |
| 33 | 5-chloro-N-benzoyl benzo isothiazole | R＝C 6H 5 X＝Cl | CDCl 3，δ：7.35～8.01(m，3H，PhH)，7.45～ 8.07(m，5H，PhH) |
| -3-ketone | |||
| 34 | 5-bromo-N-benzoyl benzo isothiazole-3-ketone | R＝C 6H 5 X＝Br | CDCl 3，δ：7.35～8.11(m，3H，PhH)，7.45～ 8.07(m，5H，PhH) |
| 35 | 5-methyl-N-benzoyl benzo isothiazole-3-ketone | R＝C 6H 5 X＝CH 3 | CDCl 3，δ：7.25～7.99(m，3H，PhH)，7.45～ 8.03(m，5H，PhH)，2.47(s，3H，C-H) |
| 36 | 6-ethyl-N-benzoyl benzo isothiazole-3-ketone | R＝C 6H 5 X＝CH 2CH 3 | CDCl 3，δ：7.39～7.97(m，3H，PhH)，7.47～ 8.07(m，5H，PhH)，2.51(t，3H，C-H)，1.27(q，2H，C-H) |
| 37 | 5-methoxyl group-N-benzoyl benzo isothiazole-3-ketone | R＝C 6H 5 X＝OCH 3 | CDCl 3，δ：7.05～8.01(m，3H，PhH)，7.35～ 7.98(m，5H，PhH)，3.87(s，3H，C-H) |
| 38 | 6-chloro-N-(4-chlorobenzene formacyl) benzisothiazole-3-ketone | R＝C 6H 4Cl X＝Cl | CDCl 3，δ：7.36～7.91(m，3H，PhH)，7.51～ 8.13(m，4H，PhH) |
Marine antifoulant of the present invention is applied on the marine structure or is added to and can be used to suppress halobiontic growth in the marine structure.Can protect marine structure, marine antifoulant of the present invention can directly be added in the marine structure, is coated directly onto on the marine structure or is added in the coating, and then be applied on the marine structure.Be coated with available any traditional method such as dip-coating, spraying or coating.Can marine antifoulant of the present invention be loaded on the timber that is applied in the carrier as timber by pressure treatment or vacuum impregnation in addition.Also can in manufacturing processed, these compositions be added in the fishing net fiber.
Ocean of the present invention coating contains tackiness agent, solvent and other optional components usually.Solvent can be organic solvent, water or its mixture.Marine antifoulant of the present invention is applicable to solvent base ocean coating and water base ocean coating, and solvent base ocean coating is preferred.
Marine antifoulant of the present invention can further contain various additives commonly used in conventional compositions, for example softening agent such as clorafin and tricresyl phosphate (to the toluene ester); Tinting pigment such as red iron oxide and titanium dioxide; Extender pigment such as zinc oxide and silicon dioxide powder; And organic solvent such as dimethylbenzene and methyl iso-butyl ketone (MIBK).And also can contain other stain control agent commonly used in the marine antifoulant of the present invention, the example of this class stain control agent is the stain control agent that proposes in the 209th symposial of Japan shipbuilding EASD (Japan Shipbuilding ResearchAssociation), ziram for example, 2-methylthio group-uncle's 4-fourth amino-6-cyclopropylamino-s-triazine, 4,5-two chloro-2-n-octyls-4-isothiazole-3-ketone, N-(fluorine dichloromethane sulfenyl) Phthalimide and tetraphenyl borane pyridinium salt etc.
Embodiment 2
N-acyl group benzisothia trazodone derivative is suc as formula the antibiotic effect of (I) compound to intestinal bacteria, streptococcus aureus, subtilis etc.
The preparation of testing liquid be the compound dissolution in the table 1 in water, be made into different concns, carry out bacteriostatic test, these testing liquids move to pipettor and cultivate 24h in the centrifuge tube, further dilute different concns again, get a certain amount ofly in culture dish, add substratum with sterile distilled water, after the cooling, this substratum is cultivated with following yeast or bacterium:
Intestinal bacteria (A); Streptococcus aureus (B); Subtilis (C); Cereus fungi shape bacillus (D); Pseudomonas aeruginosa (E); Streptomyces albus (F); Enteroaerogen (G).
After the culture that is untreated is fully grown, assess these compounds with following scoring system:
The mark of the antibiotic and antifouling effect evaluation of The compounds of this invention is listed in the table below in 1." one " number represents that this compound tests.
When bacterium A is tested:
When bacterium B is tested:
When bacterium C is tested:
When bacterium D is tested:
When bacterium E is tested:
When bacterium F is tested:
When bacterium G is tested:
The sterilization effect of synthetic benzothiazolinone compounds is better, and bacteriostasis rate is higher.Example 3N-acyl group benzisothia trazodone derivative is suc as formula the effect of the anti-marine algae of (I) compound
Experimentize to measure the toxicity of marine antifoulant of the present invention to two eyebrow algaes (Amphora).Two eyebrow algaes are represented soft living dirt biology.
Isolate (Amphora coffea eformis var.perpusilla) two eyebrow algaes and Guillard ' s F2 substratum, carry out sterile culture from natural biological film.With the log culture of the two eyebrow algaes of F2 substratum dilution, to obtain the chlorophyll-a concentration of 0.25 μ g/mL.Chlorophyll a is that to pass a hole by the cell culture that will measure volume (FV) be that 3 μ m, diameter are that the nitrocellulose strainer of 25mm is measured.Strainer is moved in the Glass tubing with the frustule of collecting.The DMSO solvent that to measure volume (SV) adds in this Glass tubing.This pipe in the dark carried out 1.5 hours cultivation.After the cultivation, contrast DMSO/ strainer check sample is in 630 and the 664nm light absorption ratio of reading sample on spectrophotometer.The concentration of chlorophyll a can be used following Equation for Calculating:
Chlorophyll a (μ g/mL)=11.47 * Abs
664-0.4 * Abs
630* SV/FV
The culture of 10mL dilution is moved in the Glass tubing with dropper.With 10 μ L marine antifoulants or in Comparative Examples 10 μ L DMF are added in each Glass tubing.Before measuring the chlorophyll-a concentration of each pipe, these Guan Zaiyi are illuminated, 20 ℃ hold in the oscillator and cultivated 96 hours.Each triplicate of handling.Average in the same old way inhibition percentage ratio is estimated the dose effect of marine antifoulant.EC
50It is the dose effect that prevents 50% algal grown.EC
100It is the dose effect that prevents 100% algal grown.Experimental result is listed following.
The activity (ppm) of table 3 pair two eyebrow algaes
| Compound | EC 50 | EC 100 |
| 1 | 2.5 | 17 |
| 2 | 1.3 | 4 |
| 3 | 3 | 19 |
| 6 | 2.1 | 15 |
| 7 | 2.7 | 21 |
| 11 | 1.6 | 17 |
| 18 | 2.3 | 15 |
| 33 | 1.5 | 10 |
Compound can think that to showing activity soft pollution organism is had activity in low ppm scope.These results show that compound of the present invention is effectively biological to soft living dirt in lower concentration.
The effect of example 4 anti-genus artemias (Artemia)
In containing the artificial seawater of embodiment 1 compound of different quantities test, 1mL adds 15 genus artemia two instar larvaes.After 24 hours, assess this test in the continuous illumination static cultivation.Compound 2,6,7,10,11,12,33 causes 100% mortality ratio at the concentration level that is equal to or less than 1ppm in the table 1.
Embodiment 5
Compound in embodiment table 1 (1), (2), (3), (6), (7) add the component shown in the table 4 respectively in (11) (18) and (33).These materials are mixed independently and paint setter and disperse, and obtain the composition of experimental example 1-9 in the table 4.In the same way, obtain the composition of comparative example 1.The trade(brand)name of used component is as follows:
LAROFLEX MP-45: the vinyl chloride-ethylene base isobutyl ether multipolymer that German BASF A.G. makes.
PLIOLITE S-5B: the styrene-butadiene copolymer that U.S. The Goodyear company makes.
AEROZIL# 200: the silicon dioxide powder that German Degsa A.G. makes.
Table 4
With every kind of coating of experimental example 1-5 in the table 4 and comparative example 1 gained, be coated on 300 * 100 * 3.2mm sandblast steel plate that scribbles commercially available priming paint of one deck and vinyl tar oil type protective system with the air-atomizing method, its dried film thickness is 100 μ m.Behind dry 7 days of the test piece, soak and place seawater and the harmful hydrocoles of check and the adhesion of plant and the adhesion of foundry loam, the results are shown in Table 5 for it.The amount of adherent harmful hydrocoles and plant is estimated with the per-cent (%) of their adherent areas in the table, and the amount of adhesion foundry loam is estimated with following standard in the table:
0: do not have adhesion; 1: the slight adhesion; 2: a small amount of adhesion; 3: medium adhesion; 4: medium to a large amount of adhesions; With 5: a large amount of adhesion.
Table 5
As mentioned above, formula of the present invention (I) compound is preventing and is suppressing to have superior effect aspect the object in harmful aquatic organism adhesion water, and this effect can keep for a long time.Therefore, formula of the present invention (I) compound can be used as the inhibitor of anti-harmful aquatic organism or the form of antifouling composition is done various application.
Claims (9)
1. benzisothia sulfinpyrazone compound, it is characterized in that: described benzisothia sulfinpyrazone compound be N-acyl group benzisothia trazodone derivative suc as formula shown in (I) compound: wherein: R is selected from H, the C1-C10 alkyl, the C2-C10 thiazolinyl, C6-C10 phenyl or phenyl substituent, substituting group is randomly replaced by halogen; X can be halogen, nitro, alkyl or alkoxyl group; M is the integer of 0-4;
2. by the described benzisothia sulfinpyrazone compound of claim 1, it is characterized in that: described R thinks hydrogen, the C1-C10 alkyl, and C2-C10 thiazolinyl, C6-C10 phenyl or substituted-phenyl, m are integers 0.
3. application by the described benzisothia sulfinpyrazone compound of claim 1, it is characterized in that: described benzisothia sulfinpyrazone compound or benzisothia sulfinpyrazone compound and mixed with resin be as marine antifoulant, and to account for the weight of resin be 0.2-40% to the benzisothiazole ketone compounds when described benzisothia sulfinpyrazone compound and mixed with resin.
4. press the application of the described benzisothia sulfinpyrazone compound of claim 3, it is characterized in that: described benzisothia sulfinpyrazone compound and copper compound or metallic copper are as marine antifoulant, and wherein copper compound or metallic copper account for the 5-35% of marine antifoulant gross weight; Perhaps described benzisothia sulfinpyrazone compound with mixed with resin and benzisothia sulfinpyrazone compound with according to after weight percent or benzisothia sulfinpyrazone compound and the mixed with resin with copper compound or metallic copper as marine antifoulant, wherein copper compound or metallic copper account for the 5-35% of marine antifoulant gross weight.
5. by the application of the described benzisothia sulfinpyrazone compound of claim 3, it is characterized in that: described marine antifoulant can prevent and suppress harmful aquatic organism and adhere in the water on the object.
6. by the application of the described benzisothia sulfinpyrazone compound of claim 3, it is characterized in that: described copper compound is cupric thiocyanide, Red copper oxide, cuprous chloride, copper naphthenate, glycocoll-copper, oxine-copper or cuprous carbonate.
7. press the application of the described benzisothia sulfinpyrazone compound of claim 3, it is characterized in that: described resin is a vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene base isobutyl ether multipolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene, acrylic resin, styrene-butadiene copolymer, vibrin, Resins, epoxy, resol, synthetic rubber, silicon rubber, silicone resin, petroleum resin, oleo-resinous, rosin ester resin, rosined soap or rosin.
8. press the application of the described benzisothia sulfinpyrazone compound of claim 7, it is characterized in that: described resin is a vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene base isobutyl ether multipolymer or acrylic resin and styrene-butadiene copolymer.
9. by the application of the described benzisothia sulfinpyrazone compound of claim 3, it is characterized in that: described marine antifoulant can be directly or is mixed with coating and to be applied to marine structure.
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