CN102234251A - Benzisothiazolinone compound and application thereof - Google Patents

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

A kind of benzisothiazolone compound and its application

technical field

The invention relates to a marine biological inhibitor, in particular to a benzisothiazolinone compound and its application.

Background technique

In seawater or freshwater, aquatic organisms such as coelenterates (such as hydroids), shellfish, tube-dwelling polychaetes, algae, swarms, molluscs, etc. will attach to the bottom of boats or to fishing nets used for aquaculture . Once these aquatic organisms attach to the bottom of boats, fishing nets, etc., the boats and fishing nets are damaged, which may cause great economic losses. For example, if cirripedes attach to fishing nets, they will close the mesh and prevent the flow of tidal water, thereby causing a shortage of oxygen in the water, causing the cultured fish to die due to suffocation; it is difficult to operate due to the increase in weight when changing the net; and The resistance to big waves is relatively large, and NetEase is damaged when the typhoon hits. When these organisms adhere to the bottom of the ship, the propulsion efficiency of the ship decreases and fuel consumption increases. For the above reasons, these aquatic fouling organisms are called fouling organisms. In order to reduce the economic loss caused by fouling organisms, a lot of manpower and money have been invested in the maintenance of marine facilities that are prone to pollution.

Although effective, DDT and a range of organotin compounds are highly toxic and are currently banned. Therefore, the development of low-pollution antifouling agents and low-pollution antifouling coatings has an important demand in aquatic products, shipbuilding, marine military and other aspects. Japanese patent publication 10849/1976 discloses a kind of underwater antifouling paint containing benzothiazole compound as an active component; Stain agent, fishing net antifouling paint composition and antifouling solution in which tetraalkylthiuram disulfide compound is used in combination with other compounds; Japanese Patent Publication No. 50954/1986 discloses an antifouling agent for marine structures , which contains a 3-isothiazolone compound as an active ingredient; Japanese Patent Publications 20665/1989 and 24242/1990 and Japanese Laid-Open Patent Publications 9320/1978, 201804/1993, 100405/1994 and 100408/1994 disclose Antifouling coatings with imide compounds as active components.

As paints for ship bottoms, various antifouling paints have been studied, such as cuprous oxide, organotin, and thiourethane. However, these antifouling agents have only weak anti-adhesion effects on coelenterates (such as polyps), but do not show effect in sea areas where coelenterates frequently appear. The sea areas where coelenterates frequently appear mainly refer to the northeastern part of Japan and the coast of Hokkaido. In addition, in the East China Sea and the West Japan Sea, they showed only a limited effect on preventing the attachment of shellfish and tube-dwelling polychaetes, and therefore could not effectively prevent the attachment of these organisms. Copper is known to be effective against shellfish and copper-based antifoulants have also been shown to be effective against shellfish and tube-dwelling polychaetes. However, the use of heavy metal copper in copper antifouling agents has consequent detrimental effects on the environment.

The underwater objects refer to objects or products or structures that are in contact with or exposed to water, including ships, buoys, coastal factories, cooling water input channels for thermal or nuclear power stations, drilling rigs in subsea oil fields, port equipment and marine Marine facilities such as seawater anti-pollution strips of civil engineering facilities.

Many species of animals and plants living in the sea are known, and various organisms can often adhere to and adversely affect objects in water. Adhesion of such harmful aquatic organisms will cause slowed maintenance and increased ship fuel consumption, as well as reduced water delivery into cooling water input channels.

In order to control these adhering organisms, various antifouling agents such as cuprous oxide have hitherto been used, however, their effects are mostly not satisfactory.

Contents of the invention

The purpose of the present invention is to provide an application of benzisothiazolone compounds that can effectively prevent and inhibit the adhesion of various organisms to objects in water.

To achieve the above object, the technical solution adopted in the present invention is:

A benzisothiazolone compound: the benzisothiazolone compound is an N-acyl benzisothiazolone derivative as shown in the compound of formula (I):

Wherein: R is selected from H, C1-C10 alkyl, C2-C10 alkenyl, C6-C10 phenyl or phenyl substituent, the substituent is optionally substituted by halogen; said substituent is optionally substituted by halogen as Any substituent alkyl, alkenyl or phenyl in R can be substituted by halogen; X can be halogen, nitro, alkyl or alkoxy; m is an integer of 0-4. Said R is hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C6-C10 phenyl or substituted phenyl, and m is an integer of 0.

Application of benzisothiazolone compounds: the benzisothiazolone compounds or benzisothiazolone compounds are mixed with resins as marine antifouling agents, and when the benzisothiazolone compounds are mixed with resins, benzene The isothiazolinone compound accounts for 0.2-40% by weight of the resin.

The benzisothiazolone compound and copper compound or metal copper are used as marine antifouling agent, wherein the copper compound or metal copper accounts for 5-35% of the total weight of the marine antifouling agent; or the benzisothiazolone compound Mixed with resin and benzisothiazolone compound according to weight percentage or benzisothiazolone compound mixed with resin and used as marine antifouling agent together with copper compound or metal copper, wherein copper compound or metal copper accounts for marine antifouling agent 5-35% of the total weight of the agent. The marine antifouling agent can prevent and inhibit harmful aquatic organisms from adhering to objects in water. The copper compound is copper thiocyanate, cuprous oxide, cuprous chloride, copper naphthenate, copper glycinate, 8-hydroxyquinoline-copper or cuprous carbonate. Described resin is vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, benzene Ethylene-butadiene copolymer, polyester resin, epoxy resin, phenolic resin, synthetic rubber, silicone rubber, silicone resin, petroleum resin, oleoresin, rosin ester resin, rosin soap or rosin. The resin is vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer or acrylic resin and styrene-butadiene copolymer. The marine antifouling agent can be directly or mixed with paint and applied to marine structures. The paint is a marine paint, and the marine paint is a solvent-based marine paint or a water-based marine paint.

The halogen is chlorine, fluorine, bromine or iodine; the C1-C10 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, tert-pentyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl, preferably C1-C5 alkyl; the C1-C10 alkoxy is methoxy, ethyl Oxygen, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, tert-amyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy Base, n-octyloxy, n-nonyloxy or n-decyloxy, preferably C1-C5 alkoxy; the C6-C10 phenyl and substituted phenyl are phenyl, tolyl, ethylphenyl, n- Propyl, cumyl, n-butylphenyl and isobutylphenyl.

The advantages that the present invention has:

The N-acyl substituted benzisothiazolone derivation of the present invention can be effectively used as an antifouling agent against attached aquatic organisms, and can be used to prevent the organisms that can cause fouling from adhering and growing on fishing nets that are cultured and fixed. Fouling agents, and antifouling agents that prevent the attachment and growth of fouling organisms on the bottom of boats, on materials used in fishing nets such as buoys and ropes, and on condensate channels in nuclear or thermal power plants. The marine antifouling agent of the present invention has no harmful effect on storage stability, does not cause viscosity increase and deterioration.

The N-acyl substituted benzisothiazolone derivatives of the present invention have the ability to prevent and inhibit harmful aquatic organisms from adhering to objects in water, and the harmful aquatic organisms are aquatic animals such as barnacles (Balanomorpha), skeletal genus ( Serpula), Polyzoa, Ascidiacea, Hydrozoa and Mollusca; aquatic plants such as Ulva, Enteromorpha, Ectocarpus and diatomaceae (Diatomaceae); and slime.

The underwater objects refer to objects or products or structures that are in contact with or exposed to water, including ships, buoys, coastal factories, cooling water input channels for thermal or nuclear power stations, drilling rigs in subsea oil fields, port equipment and marine Marine facilities such as seawater anti-pollution strips of civil engineering facilities.

Detailed ways

The benzisothiazolone compounds are N-acyl benzisothiazolone derivatives, as shown in the compound of formula (I), see Table 1:

R is selected from H, C1-C10 alkyl, C2-C10 alkenyl, C6-C10 phenyl or substituted phenyl, and the substituent is optionally substituted by halogen;

X can be halogen, nitro, alkyl or alkoxy; m is an integer of 0-4.

The compound of formula (I) can be prepared by common preparation methods usually used in the field of coatings, see (Fine Chemical Industry: 2008, 25(8):771-774.).

Table 1

Compound No. Compound name substituent Physical and chemical properties 1 N-acetylbenzisothiazol-3-one R= _CH3 CDCl ₃ , δ: 7.26～8.03 (m, 4H, PhH), 3.33 (s, 3H, CH) 2 N-Trichloroacetylbenzisothiazol-3-one R= _CCl3 CDCl ₃ , δ: 7.26-8.03 (m, 4H, PhH), 3 N-propionylbenzisothiazol-3-one R _{= CH2CH3} CDCl ₃ , δ: 7.26～8.03(m, 4H, PhH), 3.17(q, 2H, CH), 1.28(t, 3H, CH) 4 N-(2-methylpropionyl)benzisothiazol-3-one R=CH(CH ₃ ) ₂ CDCl ₃ , δ: 7.26～8.03 (m, 4H, PhH), 3.57 (q, 1H, CH), 1.33 (d, 6H, CH) 5 N-(2-Methylhexanoyl)benzisothiazol-3-one R=CH(CH ₃ )CH ₂ CH ₂ CH ₂ CH ₂ CDCl ₃ , δ: 7.29～8.03(m, 4H, PhH), 3.46(m, 1H, CH), 2.43(m, 2H, CH), 2.23(m, 2H, CH), 2.19(m, 2H, CH ), 2.11(d, 3H, CH), 1.81(t, 3H, CH) 6 N-Chloroacetylbenzisothiazol-3-one R= _CH2Cl CDCl ₃ , δ: 7.25～8.02(m, 4H, PhH), 4.97(s, 2H, CH) 7 N-(2-Chloropropionyl)benzisothiazol-3-one R=CHClCH ₃ CDCl ₃ , δ: 7.26～8.04 (m, 4H, PhH), 4.89 (q, 1H, CH), 2.97 (d, 3H, CH) 8 N-(3-Chloropropionyl)benzisothiazol-3-one R _{= CH2CH2Cl} CDCl ₃ , δ: 7.26～8.04(m, 4H, PhH), 3.92(t, 2H, CH), 3.7(t, 2H, CH) 9 N-(2,3-dichloropropionyl)benzisothiazol-3-one R=CHClCH ₂ Cl CDCl ₃ , δ: 7.26～8.04(m, 4H, PhH), 4.93(t, 1H, CH), 4.15(d, 2H, CH) 10 N-benzoylbenzisothiazol-3-one R _{＝ C6H5} CDCl ₃ , δ: 7.21-8.05 (m, 4H, PhH), 7.44-8.11 (m, 5H, PhH) 11 N-(4-Chlorobenzoyl)benzisothiazol-3-one R = C ₆ H ₄ Cl CDCl ₃ , δ: 7.21-8.05 (m, 4H, PhH), 7.54-8.07 (m, 4H, PhH) 12 N-(4-Bromobenzoyl)benzisothiazol-3-one R = C ₆ H ₄ Br CDCl ₃ , δ: 7.21-8.05 (m, 4H, PhH), 7.61-7.97 (m, 4H, PhH) 13 N-(2-fluorobenzoyl)benzisothiazol-3-one R＝C ₆ H ₄ F CDCl ₃ , δ: 7.23-7.97 (m, 4H, PhH), 7.37-7.97 (m, 4H, PhH) 14 N-(2-methylbenzoyl)benzisothiazol-3-one R = C ₆ H ₄ CH ₃ CDCl ₃ , δ: 7.25-8.04 (m, 4H, PhH), 7.14-7.93 (m, 4H, PhH), 2.79 (s, 3H, CH) 15 N-(4-Ethylbenzoyl)benzisothiazol-3-one R = C ₆ H ₄ CH ₂ CH ₃ CDCl ₃ , δ: 7.23～8.01(m, 4H, PhH), 7.39～7.97(m, 4H, PhH), 2.83(q, 2H, CH), 2.04(t, 3H, CH) 16 N-(4-isopropylbenzoyl)benzisothiazol-3-one R＝C ₆ H ₄ CH(CH ₃ ) ₂ CDCl ₃ , δ: 7.23～8.01(m, 4H, PhH), 7.49～8.03(m, 4H, PhH), 2.83(m, 1H, CH), 2.04(q, 6H, CH) 17 N-(2-Methoxybenzoyl)benzisothiazol-3-one _{R ＝ C6H40CH3} CDCl ₃ , δ: 7.25-8.04 (m, 4H, PhH), 6.95-7.84 (m, 4H, PhH), 3.73 (s, 3H, CH) 18 N-(3-methoxybenzoyl)benziso R＝C ₆ H ₄ OCH ₃ CDCl ₃ , δ: 7.26-8.04 (m, 4H, PhH), 7.02-7.51 (m, 4H, PhH), 3.67 (s, 3H, CH) Thiazol-3-one 19 N-(4-Methoxybenzoyl)benzisothiazol-3-one _{R ＝ C6H40CH3} CDCl ₃ , δ: 7.26-8.04 (m, 4H, PhH), 6.95-7.84 (m, 4H, PhH), 3.69 (s, 3H, CH) 20 N-(2,4-dichlorobenzoyl)benzisothiazol-3-one R = C ₆ H ₃ Cl ₂ CDCl ₃ , δ: 7.22-8.03 (m, 4H, PhH), 6.33-7.82 (m, 3H, PhH) twenty one N-(2,6-dichlorobenzoyl)benzisothiazol-3-one R = C ₆ H ₃ Cl ₂ CDCl ₃ , δ: 7.26-7.99 (m, 4H, PhH), 6.33-7.82 (m, 3H, PhH) twenty two N-(2,4,6-trichlorobenzoyl)benzisothiazol-3-one R = C ₆ H ₂ Cl ₃ CDCl ₃ , δ: 7.24～7.97 (m, 4H, PhH), 7.34 (m, 2H, PhH) twenty three N-(2,3,4,5,6-pentachlorobenzoyl)benzisothiazol-3-one R = C ₆ Cl ₅ CDCl ₃ , δ: 7.24～8.01 (m, 4H, PhH) twenty four N-(2,4-Dimethylbenzoyl)benzisothiazol-3-one R＝C ₆ H 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, CH), 2.30(s, 3H, CH) 25 N-(3,4-Dimethylbenzoyl)benzisothiazol-3-one R＝C ₆ H 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, CH), 2.27(s, 3H, CH) 26 N-(2,6-Dimethylbenzoyl)benzisothiazol-3-one R＝C ₆ H 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, CH) 27 N-(2,4,6-trimethylbenzoyl)benzisothiazol-3-one R＝C ₆ H ₂ (CH ₃ ) ₃ CDCl ₃ , δ: 7.24～8.09(m, 4H, PhH), 6.85(s, 2H, PhH), 2.29(s, 9H, CH) 28 N-(3,4-dimethoxybenzoyl)benzisothiazol-3-one R＝C ₆ H 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, CH), 3.67(s, 3H, CH) 29 N-(3,5-dimethoxybenzoyl)benzisothiazol-3-one R＝C ₆ H 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, CH) 30 N-(3,4,5-trimethoxybenzoyl)benzisothiazol-3-one R＝C ₆ H ₂ (OCH ₃ ) ₃ CDCl ₃ , δ: 7.25～8.03(m, 4H, PhH), 6.97(s, 2H, PhH), 3.75(s, 9H, CH) 31 N-(2-Chloro-4-methylbenzoyl)benzisothiazol-3-one R=C ₆ H ₃ Cl(CH ₃ ) CDCl ₃ , δ: 7.35-8.05 (m, 4H, PhH), 7.22-7.97 (m, 3H, PhH), 2.45 (s, 3H, CH) 32 N-(2-fluoro-4-chlorobenzoyl)benzisothiazol-3-one R = C ₆ H ₃ ClF CDCl ₃ , δ: 7.25-7.97 (m, 4H, PhH), 7.25-7.97 (m, 3H, PhH) 33 5-Chloro-N-benzoylbenzisothiazole R _{= C6H5X} =Cl CDCl ₃ , δ: 7.35-8.01 (m, 3H, PhH), 7.45-8.07 (m, 5H, PhH) -3-one 34 5-Bromo-N-benzoylbenzisothiazol-3-one R= _{C6H5X =} Br CDCl ₃ , δ: 7.35-8.11 (m, 3H, PhH), 7.45-8.07 (m, 5H, PhH) 35 5-Methyl-N-benzoylbenzisothiazol-3-one R=C ₆ H 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, CH) 36 6-Ethyl-N-benzoylbenzisothiazol-3-one R=C ₆ H ₅ X=CH ₂ CH ₃ CDCl ₃ , δ: 7.39～7.97(m, 3H, PhH), 7.47～8.07(m, 5H, PhH), 2.51(t, 3H, CH), 1.27(q, 2H, CH) 37 5-Methoxy-N-benzoylbenzisothiazol-3-one R＝ _{C6H5X ＝ OCH3} CDCl ₃ , δ: 7.05-8.01 (m, 3H, PhH), 7.35-7.98 (m, 5H, PhH), 3.87 (s, 3H, CH) 38 6-Chloro-N-(4-chlorobenzoyl)benzisothiazol-3-one R= _{C6H4ClX =} Cl CDCl ₃ , δ: 7.36-7.91 (m, 3H, PhH), 7.51-8.13 (m, 4H, PhH)

The marine antifouling agent of the present invention can be used to inhibit the growth of marine organisms when coated on or added to marine structures. Capable of protecting marine structures, the marine antifouling agent of the present invention can be directly added to marine structures, directly coated on marine structures or added to coatings, and then coated on marine structures. Coating can be done by any conventional method such as dipping, spraying or coating. In addition, the marine antifouling agent of the present invention can be loaded into a carrier and applied to wood used as stakes by pressure treatment or vacuum impregnation. These compositions can also be added to the fishnet fibers during the manufacturing process.

The marine coatings of the present invention generally contain binders, solvents and other optional components. The solvent can be an organic solvent, water or a mixture thereof. The marine antifouling agent of the present invention is suitable for solvent-based marine coatings and water-based marine coatings, and solvent-based marine coatings are preferred.

The marine antifouling agent of the present invention may further contain various additives commonly used in conventional compositions, such as plasticizers such as chlorinated paraffin and tris(p-cresyl phosphate); coloring pigments such as red iron oxide and titanium dioxide; extender pigments such as zinc oxide and silica powder; and organic solvents such as xylene and methyl isobutyl ketone. And the marine antifouling agent of the present invention can also contain other commonly used antifouling agents, the example of this type of antifouling agent is the antifouling agent proposed on the 209th seminar of Japan Shipbuilding Research Association (Japan Shipbuilding Research Association), such as Zinc dimethyldithiocarbamate, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n-octyl-4-isothiazole -3-one, N-(fluorodichloromethylthio)phthalimide and tetraphenylboryl pyridinium salt, etc.

Example 2

Antibacterial efficacy of N-acylbenzisothiazolone derivatives such as formula (I) compounds against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, etc.

The preparation of the test solution is to dissolve the compounds in Table 1 in water, make them into different concentrations, and carry out the antibacterial test. These test solutions are moved to centrifuge tubes with a pipette and cultivated for 24 hours, and then further diluted with different concentrations with sterile distilled water. Take a certain amount in a petri dish, add the medium, after cooling, the medium is cultivated with the following yeast or bacteria:

Escherichia coli (A); Staphylococcus aureus (B); Bacillus subtilis (C); Enterobacteriaceae (G).

After adequate growth of untreated cultures, the compounds were evaluated using the following scoring system:

The scores for the antibacterial and antifouling efficacy evaluations of the compounds of the present invention are listed in Table 1 below. A "one" indicates that the compound was not tested.

When testing against bacteria A:

When testing against bacteria B:

When tested against bacteria C:

When tested against bacteria D:

When tested against bacteria E:

When tested against bacteria F:

When tested against bacteria G:

Synthetic benzothiazolinone compounds have better bactericidal effect and higher bacteriostatic rate. Efficacy of Example 3 N-acyl benzisothiazolone derivatives such as formula (I) compounds against marine algae

Experiments were carried out to determine the toxicity of the marine antifouling agent of the present invention to Amphora. Amphites represent soft-living fouling organisms.

Amphora coffeea eformis var. perpusilla was isolated from natural biofilm and cultured aseptically in Guillard's F2 medium. Dilute the log culture of Amphitheater sp. with F2 medium to obtain a chlorophyll a concentration of 0.25 µg/mL. Chlorophyll a was determined by passing a measured volume (FV) of the cell culture through a nitrocellulose filter with a pore size of 3 μm and a diameter of 25 mm. Transfer the filter together with the collected algal cells into a glass tube. A measured volume (SV) of DMSO solvent was added to the glass tube. The tube was incubated in the dark for 1.5 hours. After incubation, the absorbance of the samples was read on a spectrophotometer at 630 and 664 nm against a DMSO/filter blank. The concentration of chlorophyll a can be calculated by the following equation:

Chlorophyll a (μg/mL)＝11.47×Abs ₆₆₄ -0.4×Abs ₆₃₀ ×SV/FV

Pipette 10 mL of the diluted culture into a glass tube. Add 10 µL of marine antifouling agent or, in comparative examples, 10 µL of DMF to each glass tube. The tubes were incubated for 96 hours in a lighted, 20° C. tunnel shaker before the chlorophyll a concentration of each tube was measured. Each treatment was repeated three times. The dose effect of the marine antifouling agent was evaluated by the average inhibition percentage of the control sample. _EC50 is the dose effect that prevents 50% of algae growth. EC ₁₀₀ is the dose effect that prevents 100% algae growth. The experimental results are listed below.

Table 3 Activity (ppm) to Amphitheater

compound _{EC50 EC100} 1 2.5 17 2 1.3 4 3 3 19 6 2.1 15 7 2.7 twenty one 11 1.6 17 18 2.3 15 33 1.5 10

Compounds exhibiting activity in the low ppm range can be considered active against soft polluting organisms. These results indicate that the compounds of the present invention are effective against soft fouling organisms at low concentrations.

Example 4 Efficacy against Artemia

Fifteen second-instar larvae of the genus Artemia were added to 1 mL of artificial seawater containing the compound of Example 1 tested in different quantities. The test was evaluated after 24 hours of static incubation with continuous lighting. Compounds 2, 6, 7, 10, 11, 12, 33 in Table 1 caused 100% mortality at concentration levels equal to or lower than 1 ppm.

Example 5

Add the components shown in Table 4 to compounds (1), (2), (3), (6), (7), (11), (18) and (33) in Table 1 of Examples. These materials were mixed independently and dispersed with a paint conditioner to obtain the compositions of Experimental Examples 1-9 in Table 4. In the same manner, the composition of Comparative Example 1 was obtained. The trade names of the components used are as follows:

LAROFLEX MP-45: Vinyl chloride-vinyl isobutyl ether copolymer manufactured by BASF A.G., Germany.

PLIOLITE S-5B: Styrene-butadiene copolymer manufactured by The Goodyear Company in the United States.

AEROZIL# 200: Silica powder manufactured by Degsa A.G., Germany.

Table 4

With each kind of coating that experimental examples 1-5 and comparative example 1 gained in table 4, be coated with the 300 * 100 * 3.2mm sandblasting steel plate that has been coated with one layer of commercially available primer and vinyl tar type anticorrosion coating with air spray method On, its dry film thickness is 100μm. After the test panel was dried for 7 days, it was immersed in seawater and tested for adhesion of harmful aquatic animals and plants and adhesion of slime. The results are listed in Table 5. The amount of harmful aquatic animals and plants adhered in the table is evaluated by the percentage (%) of their adhered area, while the amount of adhered slime in the table is evaluated by the following criteria:

0: no adhesion; 1: slight adhesion; 2: slight adhesion; 3: moderate adhesion; 4: moderate to substantial adhesion; and 5: substantial adhesion.

table 5

As described above, the compound of formula (I) of the present invention has an excellent effect on preventing and inhibiting harmful aquatic organisms from adhering to underwater objects, and this effect can be maintained for a long time. Accordingly, the compounds of the formula (I) according to the invention can be used in various applications as inhibitors against harmful aquatic organisms or in the form of antifouling compositions.

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.