JP3034053B2 - Use of organoboron compounds as antifouling agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Background of the Invention The constantly recurring growth of fouling organisms on underwater structures such as ships, docks, piers, piers, fish nets, heat exchangers, dams, piping structures, water absorption screens, cooling towers, and seawater And a costly and dangerous matter of great effort in both freshwater and freshwater.
The presence of fouling organisms such as wisteria, zebra purple shellfish, algae, diatoms, hydro worms, mosses, hoya, tubeworms (tubu worms), and Asian crumbs causes submerged structures to sink, impairing their hydrodynamics, It can reduce operating efficiency, make it more and more susceptible to corrosion, cause collapse and structural destruction, and can impede or impede water flow or water exchange.
A common method of controlling the presence or fouling of fouling organisms is to coat or impregnate underwater structures with compositions containing toxic metal-containing compounds such as tri-n-butyltin oxide or cuprous oxide. It is. Although the compositions are somewhat effective antifouling agents, they degrade slowly in an aquatic environment and are therefore ecologically harmful.

Diaryl boron compounds are known to be effective insecticides, acaricides and fungicides useful in crop protection; the diaryl boron compounds are disclosed in US Pat. No. 5,354,74.
0, 5,354,741, 4,983,599 and 5,091,377.

It is an object of the present invention to provide a method for controlling or controlling environmentally and ecologically sound seawater and freshwater fouling organisms.

Another object of the present invention is to provide an effective method for protecting underwater structures against contamination by seawater or freshwater fouling organisms.

Yet another object of the present invention is to provide an antifouling composition comprising a diaryl boron compound as an active agent.

It is a feature of the present invention that the antifouling method and composition do not include heavy metal complexes.

These and other features and objects of the present invention will become more apparent from the detailed description set forth below.

SUMMARY OF THE INVENTION The present invention provides antifouling-effective amounts of a formula I of seawater or freshwater fouling organisms or their habitat. Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C _8. 1 to haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, halogen, CN, NO _2, COR _5, or optionally
Phenyl which can be substituted by three halogens or NR ₆ R ₇ groups, or R ₁ and R ₂ together with the atoms to which they are attached are optionally 1 to 3 halogens R ₄ can form a saturated or unsaturated 6-membered carbocyclic ring which can be substituted by a NO ₂ , C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy group; C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl; R ₅ , R ₆ and R ₇ are each independently H or C ₁ -C ₄ alkyl]. A method for controlling or controlling seawater or freshwater fouling organisms, comprising the steps of:

The present invention also provides a method for protecting underwater structures against contamination by seawater or freshwater fouling organisms, and antifouling compositions suitable for use therefor.

DETAILED DESCRIPTION OF THE INVENTION Controlling or controlling fouling organisms in an aquatic environment without harming beneficial species or threatening the ecological balance of the environment is an ongoing scientific challenge. This time, Formula I Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C _8. 1 to haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, halogen, CN, NO _2, COR _5, or optionally
Phenyl which can be substituted by three halogens or NR ₆ R ₇ groups, or R ₁ and R ₂ together with the atoms to which they are attached are optionally 1 to 3 halogens , NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ - C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl; R _5, R ₆ and R ₇ Jiariruhou containing compound is H or C ₁ -C ₄ alkyl independently particularly effective antifoulant Was found.

Preferred antifouling agents suitable for use in the methods and compositions of the invention, R is a C ₁ -C ₄ alkyl or C ₂ -C ₄ alkenyl; X is located in the NR _4; m and n are 0 Yes; R ₄ is C ₁ −
R ₂ is hydrogen, halogen, C ₁ -C ₄ alkyl or phenyl; and R ₃ is hydrogen or methyl; diaryl boron compounds of formula I wherein C ₄ alkyl or C ₂ -C ₄ alkenyl;

In the description and in the claims, the term halogen refers to Cl, Br, I or F, and the term haloalkyl refers to any alkyl group C _n H _{2n + 1} having one halogen atom to _{2n + 1} halogen atoms. Also referred to herein as a halogen atom or the same or different. Similarly, haloalkoxy is OC _n H having one halogen atom to 2n + 1 halogen atoms.
_{Refers to 2n + 1} groups, where the halogen atoms are the same or different.

Among the diarylboron compounds suitable for use in the methods and compositions of the present invention are: (3-vinylimidazolinio) vinyldiphenylboron; (3-methylpyridinio) methyldihyphenylboron; (4-phenylpyridinio) (4-Isopropylpyridinio) methyldiphenylboron; (4-t-butylpyridinio) methyldiphenylboron; (3-isopropylimidazolinio) vinyldiphenylboron; (thiazolinio) methyldiphenylboron; (6,7,8-tetrahydroisoquinolinio) methyldiphenylboron; (isoquinolinio) methyldiphenylboron; (3-bromopyridinio) methyldiphenylboron; (4-acetylpyridinio) methyldiphenylboron; (4-cyanopyridinio) Methyldi Phenylboron; and (3-bromoisoquinolinio) methyldiphenylboron.

The diaryl boron compounds of formula I and their preparation are described in U.S. Patent Nos. 5,354,740, 5,091,377 and 4,983,589.

A fouling organism that can be controlled or controlled by the method of the present invention can be any seawater or freshwater organism that can be attached to the inner or outer surface of a structure submerged or in continuous contact. it can. Representative organisms include green plants (Chlorophyta) and algae, including members of the phyla phyta (Phaeophyta), microbes, chordates including members of ascidians, such as Ciona intestinalis, Diplosoma listerianium, Botryllus sclosseri, Clava
Mytilus edulis, Clair sulitis, Clilla squamata (Clava squamata), a member of hydroids including Myculus ezulis (Hydractinia echinata), Obelia geniculata, and Tubularia larnyx (Tubularia larnyx). virginica), Ostrea edulis, Ostrea edulis
Crustaceans including Ostrea chilensia and Lassea rubra, Ectra pilosa, Bugula nerica
itinia) and Bowerbankia Grasilis (Bowerban)
moss, including Hydroids norvegica, polychaetes including Hydroides norvegica, sponges, and Balanus amphitrite (Balanus a)
mphitrite, Lepas anatifer
a), Baranus baranus (Balanus balanus), Baranus baranoides (Balanus balanoides), Baranus hameri (Balanus hameri), Baranus crenatus (Balanus crenatus), Baranus improvisus (Balanus improvisus), Baranus galeatus (Balanus algalatus)
anus galeatus and Baranus ebruneus (Balanu)
s eburneus) and other members of the vines (Fujitsubo). Organisms of the genus Baranus are frequent contaminants of underwater structures. Particular fouling organisms of particular interest to the present invention include barnacles, zebra mussels, algae, diatoms, hydroids, mosses, hoya, tubeworms and asiatic clams.

Among the underwater structures that can be protected by the method of the present invention are mobile or fixed submerged or partially submerged structures, such as fishnets, boats, ships, piers, piers, Cooling towers, pipelines, stacks, heat exchangers,
Dams, water absorption screens, etc.

In practice: a) coating the underwater structure to be protected with an antifouling-effective amount of the diarylboron compound such that the antifouling compound is released into the aquatic environment immediately adjacent to the outer surface of the structure Or b) including an antifouling-effective amount of a diarylboron compound in the material forming the underwater structure, and the underwater structure then releasing the compound; or c) an antifouling-effective amount of the diarylboron compound. Release the compound directly into the aquatic environment around the structure to be protected, or d) by any other method by which the diaryl boron compound comes into contact with fouling organisms Can be contacted with fouling organisms.

The amount of the diaryl boron compound to be used in the method of the present invention will vary depending on the particular compound used, the identity of the fouling organism to be controlled, the extent of infestation of the surrounding aquatic environment, water temperature, mode of contact, etc. Will do. The compositions of the present invention comprise a water-acceptable inert carrier and an antifouling-effective amount of a diaryl boron compound of Formula I. For application on a structure surface, preferred compositions of the present invention include a film-forming component, such as a polymer resin solution. Representative polymer resins include: a) unsaturated acids or anhydrides, such as maleic anhydride, fumaric acid, itaconic acid, etc .; b) saturated acids or anhydrides, such as phthalic anhydride, isophthalic anhydride,
Terephthalic anhydride, tetrahydrophthalic anhydride, tetrahalophthalic anhydride, chlorendic acid, adipic acid, sebacic acid and the like; c) glycols such as ethylene glycol, 1,2 propylene glycol, dibromoneopentyl glycol; and d) vinyl Included are unsaturated polyester resins formed from monomers such as styrene, vinyl toluene, chlorostyrene, bromostyrene, methyl methacrylate, ethylene glycol dimethyl acrylate, and the like. Other suitable resins include vinyl esters, vinyl acetate and vinyl chloride based resins, elastomeric components, vulcanized rubbers, and urethane based resins.

To provide a clearer understanding of the invention, specific embodiments of the invention are set forth below. These examples are merely illustrative and should not be understood as limiting in any way the scope of the invention and the principles upon which it is based. fact,
In addition to the invention shown and described herein, various modifications of the invention will be made from the following examples and the foregoing description.
It will be apparent to those skilled in the art.
Such modifications are intended to fall within the scope of the appended claims.

Example 1 Evaluation of Seawater Antifouling Activity of Test Compounds In this laboratory assay, the crustacean marine animal, Artemia salina, is used as a model organism for other contaminated marine animals (eg, Fujitsubo). . The test compound is dissolved in dimethylsulfoxide at a concentration of 4,000 ppm, diluted with water to a concentration of 200 ppm, and further diluted with Probst artificial seawater to a concentration of 10 ppm. Approximately 30 Artemina salina II larvae are incubated in 2 ml of Probst artificial seawater containing 10 ppm of test compound in microwell plates. The survival of the organism is assessed after 24 hours and the test compounds are graded according to the scale given below. The test results are shown in Table I.

Example 2 Field Evaluation of Seawater Antifouling Activity of Test Compound (Raft Exposure) In this evaluation, the test compound is dissolved in cyclohexanone. Solution is vinylite (manufactured by Union Carbide)
And obtain a final concentration of 26% in the dried coating. The PVC board (100x20x5mm) is degreased by washing with ethanol, and the test preparation is coated by brushing (2 coats). The total thickness of the test film is about 50 μM. The exact amount of test compound on each board is determined by comparison of the initial and final weights. Place the test sample board in the frame and submerge it to a depth of 1M in the North Sea. The frame is hung from the bottom of the raft and raised occasionally to assess surface contamination. The grading system used is shown below. The data is shown in Table II.

Example 3 Evaluation of Leachability of Test Compound A test panel (100 × 10 × 5 mm) is prepared using essentially the same method as described in Example 2. In this evaluation, the test panels are placed in 80 ml of artificial seawater, and the seawater is refreshed weekly. At two week intervals, Artemia is added to each treatment immediately after the seawater is refreshed. Three days after the addition of Artena, the experiment is evaluated using the following grading scale. The activity of the test compound is expressed as the number of weeks during which leaching is sufficient to cause a toxic effect, ie at least a grade of 2. The results are shown in Table III.

The main features or aspects of the present invention are as follows.

1. Antifouling organisms or their habitats-an effective amount of formula I Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C ₈ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkyl, halogen, CN, NO _2, COR _5, or optionally 1 to 3
Halogen or phenyl, which can be substituted with an NR ₆ R ₇ group, or R ₁ and R ₂ together with the atom to which they are attached, optionally 1-3 halogens, NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl; R _5, R ₆ and R ₇ comprises contacting the compound of independently H or C ₁ -C ₄ alkyl, in water surface For suppressing or controlling the adhesion of fouling organisms.

2. m and n are 0; R is C ₁ -C ₄ alkyl or C ₂ -C ₄ alkenyl; The method of claim 1, wherein

3.Fouling organisms, whales, zebra purple shellfish, algae, diatoms,
Hydroworms, mosses, hoya, tube worms
2. The method of claim 1 selected from the group consisting of s) and Asian crumb.

4. Compounds of formula I are (3-methylpyridinio) methyldiphenylboron, (4-fail-pyridinio) methyldiphenylboron, (4-t-butylpyridinio) methyldiphenylboron, (4-isopropylpyridinio) methyl-diphenylboron (3-bromopyridinio) methyldiphenylboron, (4-acetylpyridinio) methyldiphenylboron, (4-cyanopyridinio) methyldiphenylboron, (isoquinolinio) methyldiphenylboron, (3-bromoisoquinolinio) methyldiphenylboron And the (5,6,7,8-tetrahydrisoquinolinio) methyldiphenylboron.

5. Antifouling-Effective amount of formula I Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C _8. 1 to haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, halogen, CN, NO _2, COR _5, or optionally
Phenyl which can be substituted by three halogens or NR ₆ R ₇ groups, or R ₁ and R ₂ together with the atoms to which they are attached are optionally 1 to 3 halogens , NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ - or R _5, R ₆ and R ₇ applies the compounds of each independently H or C ₁ -C ₄ alkyl on the underwater structure; C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl Or a method for protecting underwater structures against contamination by seawater or freshwater fouling organisms, including penetrating therethrough.

6.m and n is 0; R is the method described in the item 5 is C ₁ -C ₄ alkyl or C ₂ -C ₄ alkenyl.

7. The method according to claim 5, wherein the underwater structure is a fishnet, board, ship, pier, pier, intake screen, cooling tower, pipeline or upright.

8. The method according to the above item 5, wherein the seawater or freshwater fouling organism is selected from the group consisting of a barnacle, a zebra mussel, an algae, a diatom, a hydroid, a moss, a firefly, a tubeworm and an asian crumb.

9. An inert carrier or diluent that can be permitted with water, and an antifouling-effective amount of Formula I Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C _8. 1 to haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, halogen, CN, NO _2, COR _5, or optionally
Phenyl which can be substituted by three halogens or NR ₆ R ₇ groups, or R ₁ and R ₂ together with the atoms to which they are attached are optionally 1 to 3 halogens , NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ - C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl; R _5, R ₆ and R ₇ are seawater or freshwater antifoulant composition comprising a compound of independently H or C ₁ -C ₄ alkyl] Stuff.

10. The compound of formula I is (3-vinylimidazolinio) vinyldiphenylboron, (3-methyl-pyridinio) methyldiphenylboron, (4-phenylpyridinio) methyldiphenylboron, (4-isopropylpyridinio)
Methyl-diphenylboron, (4-t-butylpyridinio) methyldiphenylboron, (3-isopropylimidazolinio) vinyldiphenylboron, (thiazolinio) methyldiphenylboron, (5,6,7,8-tetrahydroisoquinolinio) Methyldiphenylboron, (isoquinolinio) methyldiphenylboron, (3-bromopyridinio) methyldiphenylboron, (4-acetylpyridinio) methyldiphenylboron, (4-cyanopyridinio) methyldiphenylboron, and (3-bromoisoquinolinio) 10. The composition according to the above item 9, wherein the composition is selected from the group consisting of methyldiphenylboron.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A01N 55/08 CA (STN)

Claims (3)

(57) [Claims] Claims: 1. An antifouling-effective amount of a formula I of a fouling organism or its habitat. Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C ₈ haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkyl, halogen, CN, NO _2, COR _5, or optionally 1 to 3
Halogen or phenyl, which can be substituted with an NR ₆ R ₇ group, or R ₁ and R ₂ together with the atom to which they are attached, optionally 1-3 halogens, NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl; R _5, R ₆ and R ₇ comprises contacting the compound of independently H or C ₁ -C ₄ alkyl, in water surface For suppressing or controlling the adhesion of fouling organisms. 2. An antifouling-effective amount of formula I. Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C _8. 1 to haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, halogen, CN, NO _2, COR _5, or optionally
Phenyl which can be substituted by three halogens or NR ₆ R ₇ groups, or R ₁ and R ₂ together with the atoms to which they are attached are optionally 1 to 3 halogens , NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ - or R _5, R ₆ and R ₇ applies the compounds of each independently H or C ₁ -C ₄ alkyl on the underwater structure; C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl Or a method for protecting underwater structures against contamination by seawater or freshwater fouling organisms, including penetrating therethrough. 3. An inert carrier or diluent which is acceptable with water and an antifouling-effective amount of the formula I. Wherein R is C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl or C ₂
-C ₈ alkynyl; W and Y are each independently halogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ haloalkyl; m and n are each independently 0 or 1, 2 or 3,
Is an integer of X is NR ₄ or S; R ₁ is H, halogen, C ₁ -C ₈ alkyl or C ₂ -C ₈ alkenyl; R ₂ and R ₃ are each independently H, C _1-. C ₈ alkyl, C ₁ −
C _8. 1 to haloalkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkoxy, halogen, CN, NO _2, COR _5, or optionally
Phenyl which can be substituted by three halogens or NR ₆ R ₇ groups, or R ₁ and R ₂ together with the atoms to which they are attached are optionally 1 to 3 halogens , NO _2, C ₁ -C ₄ alkyl or C ₁ -C ₄ can be substituted with an alkoxy group can form a saturated or unsaturated 6-membered carbocyclic ring; R ₄ is C ₁ - C ₈ alkyl, C ₂ -C ₈ alkenyl or phenyl; R _5, R ₆ and R ₇ are seawater or freshwater antifoulant composition comprising a compound of independently H or C ₁ -C ₄ alkyl] Stuff.