WO1997042823A1 - Use of organoboron compounds as antifouling agents - Google Patents

Use of organoboron compounds as antifouling agents Download PDF

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Publication number
WO1997042823A1
WO1997042823A1 PCT/US1997/007692 US9707692W WO9742823A1 WO 1997042823 A1 WO1997042823 A1 WO 1997042823A1 US 9707692 W US9707692 W US 9707692W WO 9742823 A1 WO9742823 A1 WO 9742823A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
methyldiphenylboron
halogen
independently
alkenyl
Prior art date
Application number
PCT/US1997/007692
Other languages
French (fr)
Inventor
Bomi Pilloo Patel
Mark Arthur Josepha Van Der Flaas
Jef F. E. Van Gestel
Original Assignee
American Cyanamid Company
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Filing date
Publication date
Application filed by American Cyanamid Company filed Critical American Cyanamid Company
Priority to AU29345/97A priority Critical patent/AU2934597A/en
Priority to JP9540933A priority patent/JP3034053B2/en
Publication of WO1997042823A1 publication Critical patent/WO1997042823A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

Definitions

  • fouling organisms such as bar ⁇ nacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidian ⁇ , tubeworms, Asiatic clams and the like can weigh down aquatic structures, hamper their hydrodynam- ics, reduce operating efficiency, increase susceptibility to corrosion, cause degradation and structural fractures, block or hamper water flow and water exchange and the like.
  • a common method of controlling the presence or at ⁇ tachment of fouling organisms is to coat or permeate the underwater structure with a composition which comprises a toxic metal-containing compound such as tri-n-butyl tin or cuprous oxide.
  • a composition which comprises a toxic metal-containing compound such as tri-n-butyl tin or cuprous oxide.
  • said compositions are some ⁇ what efficacious antifoulants, they degrade slowly in aquatic environments and are, therefore, ecologically harmful.
  • Diarylboron compounds are known to be effective in- secticidal, acaricidal and fungicidal agents useful in crop protection; said diarylboron compounds are described in U.S. patents 5,354,740, 5,354,741, 4,983,589 and 5,091,377. It is an object of this invention to provide an en ⁇ vironmentally and ecologically sound method of combatting or controlling marine and freshwater fouling organisms.
  • the antifoul- ing methods and compositions are free of heavy metal com ⁇ plexes.
  • he present invention provides a method for control ⁇ ling or combatting a marine or freshwater fouling organ ⁇ ism which comprises contacting said organism or the locus thereof with an antifouling-ef f ective amount of a diaryl ⁇ boron compound of formula I
  • R is Cx-Cc j alkyl , C 2 -C 8 a lkenyl or C 2 -C 8 alkynyl ;
  • W and Y are each independently halogen, Ci-C ⁇ alkyl or Cx-C ⁇ haloalkyl;
  • m and n are each independently 0 or an integer of l, 2 or 3;
  • X is NR 4 or S
  • Ri is H, halogen, Cj-C ⁇ alkyl, or C 2 -C 8 alkenyl
  • R 2 and R 3 are each independently H, Cj-C ⁇ alkyl, C j -Ce- haloalkyl, Ci-C ⁇ alkoxy, Ci-C ⁇ haloalkoxy, halogen, CN, N0 2 , C0R 5 or phenyl optionally substituted with one to three halogen or NR ⁇ R 7 groups or Rj and R 2 may be taken together with the atoms to which they are at ⁇ tached to form a saturated or unsaturated 6-membered carbocyclic ring optionally substituted with one to three halogen, N0 2 , C ⁇ -C 4 alkyl or Cx-C ⁇ alkoxy groups; R 4 is Ci-C ⁇ alkyl, C 2 -C 8 alkenyl or phenyl; and R 5 , R 6 and R 7 are each independently H or Ci-C ⁇ alkyl.
  • the present invention also provides a method for the protection of aquatic structures against fouling by a ma ⁇ rine or freshwater fouling organism and an antifoulant composition suitable for use therefor.
  • R is Ci-C ⁇ alkyl, C 2 -C 8 alkenyl or C 2 -C 8 alkynyl; W and Y are each independently halogen, C ⁇ -C 8 alkyl or
  • Ci-C ⁇ haloalkyl m and n are each independently 0 or an integer of 1, 2
  • X is KR4 or S ;
  • R l is H, halogen, Ci-C ⁇ alkyl, or C 2 -C 8 alkenyl;
  • R 2 and R 3 are each independently H, Cj-C ⁇ alkyl, Cj-C ⁇ - haloalkyl, C !
  • Ri and R 2 may be taken together with the atoms to which they are at ⁇ tached to form a saturated or unsaturated 6-membered carbocyclic ring optionally substituted with one to three halogen, N0 2 , Ci ⁇ alkyl or C 1 -C 4 alkoxy groups;
  • R 4 is C ⁇ -C 8 alkyl, C 2 -C 8 alkenyl or phenyl; and R 5 , R 6 and R 7 are each independently H or C ! -C 4 alkyl.
  • Preferred antifoulant agents suitable for use in the methods and composition of the invention are those di ⁇ arylboron compounds of formula I wherein R is C ! -C 4 alkyl or C 2 -C 4 alkenyl; X is NR 4 ; m and n are 0; R 4 is or C 2 -C 4 alkenyl; R 2 is hydrogen, halogen, C 1 -C 4 alkyl or phenyl; and R 3 is hydrogen or methyl.
  • halogen designates Cl, Br, I or F and the term haloalkyl desig ⁇ nates any alkyl group C n H 2 n + i having from 1 halogen atom to 2n+l halogen atoms wherein the halogen atoms are the same or different.
  • haloalkoxy designates an 0C n H 2n+ ⁇ group having from 1 halogen atom to 2n+l halogen atoms wherein the halogen atoms are the same or differ ⁇ ent.
  • diarylboron compounds suitable for use in the methods and composition of the invention are: (3-vinylimidazolinio)vinyldiphenylboron; (3-methylpyridinio)methyldiphenylboron, • (4-phenylpyridinio)methyldiphenylboron; (4-isopropylpyridinio)methyldiphenylboron; (4-t-butylpyridinio)methyldiphenylboron; (3-isopropylimidazolinio)vinyldiphenylboron; (thiazolinio)methyldiphenylboron;
  • a fouling organism which may be combatted or con ⁇ trolled by the method of the invention can be any marine or freshwater organism which can attach to an inner or outer surface of a structure which is submerged or in continual contact with water.
  • Exemplary organisms in ⁇ clude algae, including members of the phyla Chlorophyta and Phaeophyta, microbes, tunicates, including members of the class Ascidiacea, such as Ciona intestinalis, Diplosoma listerianiu ⁇ i, and Botryllus sclosseri , members of the class Hydrozoa, including Ciava ⁇ quamata, Hy ⁇ dractinia echinata, Obelia geniculata, and Tubularia larnyx, bivalves, including Mytilu ⁇ edulis, Crasso ⁇ trea virginica, Ostrea edulis, Ostrea chilensia, and La ⁇ aea rubra, bryozoans, including Ectra pilo
  • Organisms of the genus Balanus are frequent foulers of aquatic structures. Spe ⁇ cific fouling organisms to which this invention is espe- cially directed include barnacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidians, tube worms and Asiatic clams.
  • the antifouling diarylboron com- 5 pound may be brought into contact with a fouling organism by: a) coating the aquatic structure to be protected with an antifouling-effective amount of said diarylboron compound such that the antifouling compound is released into the aquatic environment immediately adjacent the ex- Q ter ⁇ al surface of said structure, b) including an anti ⁇ fouling-effective amount of the diarylboron compound within material formed into an aquatic structure which then releases said compound, c) releasing an antifouling- effective amount of said compound directly into the 5 aquatic environment surrounding the structure to be pro ⁇ tected, or d) any other method wherein the diarylboron compound comes in contact with the fouling organism.
  • compositions of the invention comprise an aquatic- ally acceptable inert carrier and an antifouling- effective amount of a diarylboron compound of formula I.
  • preferred com ⁇ positions of the invention include a film-forming compo ⁇ s e nent such as a polymer resin solution.
  • Exemplary polymer resins include unsaturated polyester resins formed from: a) unsaturated acids or anhydrides, such as maleic anhy ⁇ dride, fumaric acid, itaconic acid and the like; b) satu ⁇ rated acids or anhydrides, such as phthalic anhydride, 20 isophthalic anhydride, terephthalic anhydride, tetrahy- drophthalic anhydride, tetrahalophthalic anhydride, chlorendic acid, adipic acid, subacic acid, and the like; c) glycols, such as ethylene glycol, 1,2 propylene gly ⁇ col, dibromoneo-pentyl glycol, and the like; or d) vinyl 5 monomers, such as styrene, vinyl toluene, chlorostyrene, bromostyrene, methylmethacrylate, ethylene glycol dimeth- acrylate and the like.
  • Other suitable resins include vi
  • the crustaceous marine animal Artemia salina is use d as a model organism for other marine animal foulers (e.g. barnacles) in this laboratory assay.
  • Test compounds are dissolved in dimethylsulfoxide at a concentration of 4,000 ppm, diluted to a concentration of 200 ppm with wa ⁇ ter and further diluted with Probst artificial seawater to a concentration of 10 ppm.
  • Approximately 30 Artemia salina instar II larvae are incubated in microwell plates in 2 ml of Probst artificial seawater containing 10 ppm of the test compound. Survival of the organism is evalu ⁇ ated after 24 hours, and test compounds are rated accord ⁇ ing to the scale shown below. Test results are shown in Table I.
  • test compounds are dissolved in cyclohexanone.
  • the solution is treated with vinylite (manufactured by Union Carbide) to obtain a final concen ⁇ tration of 26% in the dried coating.
  • PVC boards (100x20x5mm) are degreased by washing with ethanol and coated with the test formulation by brushing (2 coats) .
  • the total thickness of the test film is approximately 50 ⁇ M.
  • the exact quantity of test compound on each board is determined by comparing the initial and final weights.
  • the test sample boards are placed in a frame and immersed to a depth of IM in the North Sea.
  • the frames are sus ⁇ pended from the bottom of a raft and are intermittently raised to evaluate the surface fouling.
  • the rating sys ⁇ tem used is shown below. The data are shown in Table II.
  • test panels (100x10x5mm) are prepared.
  • test panels are placed in 80 ml artifi ⁇ cial sea water which is renewed weekly.
  • Arteraia is added to each treatment.
  • the activity of the test com ⁇ pound is expressed as the number of weeks during which the leaching is sufficient to cause a toxic effect, i.e. a rating of at least 2.
  • the results are shown in Table III.

Abstract

There is provided a method for controlling or combatting the attachment of a fouling organism to an underwater surface which comprises contacting said organism with an antifouling-effective amou of a diarylboron compound of formula (I). A method for protecting aquatic structures against fouling by a marine or freshwater fouling organism and antifoulant compositions therefor are also provided.

Description

DSE OF ORGANOBORON COMPOUNDS ΛS ANTIFOULING AGENTS
BACKGROUND OF THE INVENTION The ever recurring growth of fouling organisms on underwater structures such as ships, docks, piers, pil¬ ings, fishnets, heat exchangers, dams, piping structures, intake screens, cooling towers and the like is a costly and hazardous problem in both marine and freshwater en¬ deavors. The presence of fouling organisms such as bar¬ nacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidianε, tubeworms, Asiatic clams and the like can weigh down aquatic structures, hamper their hydrodynam- ics, reduce operating efficiency, increase susceptibility to corrosion, cause degradation and structural fractures, block or hamper water flow and water exchange and the like. A common method of controlling the presence or at¬ tachment of fouling organisms is to coat or permeate the underwater structure with a composition which comprises a toxic metal-containing compound such as tri-n-butyl tin or cuprous oxide. Although said compositions are some¬ what efficacious antifoulants, they degrade slowly in aquatic environments and are, therefore, ecologically harmful.
Diarylboron compounds are known to be effective in- secticidal, acaricidal and fungicidal agents useful in crop protection; said diarylboron compounds are described in U.S. patents 5,354,740, 5,354,741, 4,983,589 and 5,091,377. It is an object of this invention to provide an en¬ vironmentally and ecologically sound method of combatting or controlling marine and freshwater fouling organisms.
It is another object of this invention to provide an effective method for protecting aquatic structures against fouling by marine or freshwater fouling organ¬ isms.
It is a further object of this invention to provide antifoulant compositions which comprise diarylboron com¬ pounds as the active agents.
It is a feature of this invention that the antifoul- ing methods and compositions are free of heavy metal com¬ plexes.
These and other features and objects of the inven¬ tion will become more apparent from the detailed descrip¬ tion set forth hereinbelow.
SUMMARY OF THE INVENTION The present invention provides a method for control¬ ling or combatting a marine or freshwater fouling organ¬ ism which comprises contacting said organism or the locus thereof with an antifouling-ef f ective amount of a diaryl¬ boron compound of formula I
Figure imgf000004_0001
( I )
wherein R is Cx-Ccjalkyl , C2-C8a lkenyl or C2-C8alkynyl ; W and Y are each independently halogen, Ci-Cβalkyl or Cx-Cβhaloalkyl; m and n are each independently 0 or an integer of l, 2 or 3;
Figure imgf000005_0001
X is NR4 or S;
Ri is H, halogen, Cj-Cβalkyl, or C2-C8alkenyl;
R2 and R3 are each independently H, Cj-Cβalkyl, Cj-Ce- haloalkyl, Ci-Cβalkoxy, Ci-Cβhaloalkoxy, halogen, CN, N02, C0R5 or phenyl optionally substituted with one to three halogen or NRβR7 groups or Rj and R2 may be taken together with the atoms to which they are at¬ tached to form a saturated or unsaturated 6-membered carbocyclic ring optionally substituted with one to three halogen, N02, Cι-C4alkyl or Cx-Cήalkoxy groups; R4 is Ci-Cβalkyl, C2-C8alkenyl or phenyl; and R5, R6 and R7 are each independently H or Ci-Cήalkyl.
The present invention also provides a method for the protection of aquatic structures against fouling by a ma¬ rine or freshwater fouling organism and an antifoulant composition suitable for use therefor.
DETAILED DESCRIPTION OF THE INVENTION Controlling or combatting fouling organisms in aquatic environments without harming beneficial species or threatening the ecological balance of said environment is a continuing scientific challenge. It has now been found that particularly effective antifouling agents are those diarylboron compounds of formula I
Figure imgf000006_0001
Q
( I )
wherein R is Ci-Cβalkyl, C2-C8alkenyl or C2-C8alkynyl; W and Y are each independently halogen, Cι-C8alkyl or
Ci-Cβhaloalkyl; m and n are each independently 0 or an integer of 1, 2
Figure imgf000006_0002
X is KR4 or S ;
Rl is H, halogen, Ci-Cβalkyl, or C2-C8alkenyl; R2 and R3 are each independently H, Cj-Cβalkyl, Cj-Cβ- haloalkyl, C!-C8alkoxy, Ci-Cβhaloalkoxy, halogen, CN, N02, C0R5 or phenyl optionally substituted with one to three halogen or NR6R7 groups or Ri and R2 may be taken together with the atoms to which they are at¬ tached to form a saturated or unsaturated 6-membered carbocyclic ring optionally substituted with one to three halogen, N02, Ci^alkyl or C1-C4alkoxy groups; R4 is Cι-C8alkyl, C2-C8alkenyl or phenyl; and R5, R6 and R7 are each independently H or C!-C4alkyl.
Preferred antifoulant agents suitable for use in the methods and composition of the invention are those di¬ arylboron compounds of formula I wherein R is C!-C4alkyl or C2-C4alkenyl; X is NR4; m and n are 0; R4 is
Figure imgf000006_0003
or C2-C4alkenyl; R2 is hydrogen, halogen, C1-C4alkyl or phenyl; and R3 is hydrogen or methyl. In the specification and claims the term halogen designates Cl, Br, I or F and the term haloalkyl desig¬ nates any alkyl group CnH2n+i having from 1 halogen atom to 2n+l halogen atoms wherein the halogen atoms are the same or different. Similarly haloalkoxy designates an 0CnH2n+ι group having from 1 halogen atom to 2n+l halogen atoms wherein the halogen atoms are the same or differ¬ ent.
Among the diarylboron compounds suitable for use in the methods and composition of the invention are: (3-vinylimidazolinio)vinyldiphenylboron; (3-methylpyridinio)methyldiphenylboron,• (4-phenylpyridinio)methyldiphenylboron; (4-isopropylpyridinio)methyldiphenylboron; (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)methyldiphenylboron.
Said formula I diarylboron compounds and methods to prepare same are described in U.S. patents 5,354,740, 5,091,377 and 4,983,589.
A fouling organism which may be combatted or con¬ trolled by the method of the invention can be any marine or freshwater organism which can attach to an inner or outer surface of a structure which is submerged or in continual contact with water. Exemplary organisms in¬ clude algae, including members of the phyla Chlorophyta and Phaeophyta, microbes, tunicates, including members of the class Ascidiacea, such as Ciona intestinalis, Diplosoma listerianiuπi, and Botryllus sclosseri , members of the class Hydrozoa, including Ciava εquamata, Hy~ dractinia echinata, Obelia geniculata, and Tubularia larnyx, bivalves, including Mytiluε edulis, Crassoεtrea virginica, Ostrea edulis, Ostrea chilensia, and Laεaea rubra, bryozoans, including Ectra piloεa, Bugula nerit- inia, and Bowerbankia gracilis, polychaete worms, includ¬ ing Hydroideε norvegica, sponges and members of the class Cirripedia (barnacles) , such as Balanus amphitrite, Lepas anatifera, Balanus balanus, Balanus balanoideε, Balanus hameri , Balanus crenatuε, Balanuε improvisuε, Balanus galeatuε, and Balanus eburneus . Organisms of the genus Balanus are frequent foulers of aquatic structures. Spe¬ cific fouling organisms to which this invention is espe- cially directed include barnacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidians, tube worms and Asiatic clams.
Among the aquatic structures which may be protected by the method of invention are any submerged or partially o submerged structure, either mobile or stationary, such as a fishnet, boat, ship, piling, pier, cooling tower, pipe¬ line, standpipe, heat exchanger, dam, intake screen or the like.
In actual practice the antifouling diarylboron com- 5 pound may be brought into contact with a fouling organism by: a) coating the aquatic structure to be protected with an antifouling-effective amount of said diarylboron compound such that the antifouling compound is released into the aquatic environment immediately adjacent the ex- Q terπal surface of said structure, b) including an anti¬ fouling-effective amount of the diarylboron compound within material formed into an aquatic structure which then releases said compound, c) releasing an antifouling- effective amount of said compound directly into the 5 aquatic environment surrounding the structure to be pro¬ tected, or d) any other method wherein the diarylboron compound comes in contact with the fouling organism.
The amount of diarylboron compound to be used in the _ method of invention will vary according to the specific compound used, the identity of the fouling organism to be controlled, degree of infestation of the surrounding aquatic environment, the water temperature, the mode of contact and the like. 10 Compositions of the invention comprise an aquatic- ally acceptable inert carrier and an antifouling- effective amount of a diarylboron compound of formula I. For application onto structural surfaces, preferred com¬ positions of the invention include a film-forming compo¬ se nent such as a polymer resin solution. Exemplary polymer resins include unsaturated polyester resins formed from: a) unsaturated acids or anhydrides, such as maleic anhy¬ dride, fumaric acid, itaconic acid and the like; b) satu¬ rated acids or anhydrides, such as phthalic anhydride, 20 isophthalic anhydride, terephthalic anhydride, tetrahy- drophthalic anhydride, tetrahalophthalic anhydride, chlorendic acid, adipic acid, subacic acid, and the like; c) glycols, such as ethylene glycol, 1,2 propylene gly¬ col, dibromoneo-pentyl glycol, and the like; or d) vinyl 5 monomers, such as styrene, vinyl toluene, chlorostyrene, bromostyrene, methylmethacrylate, ethylene glycol dimeth- acrylate and the like. Other suitable resins include vi¬ nyl ester-, vinyl acetate-, and vinyl chloride-based res¬ ins, elastomeric components, vulcanized rubbers, and ure-
30 thane-based resins.
In order to present a more clear understanding of the invention, specific examples thereof are set forth below. These examples are merely illustrative and are not to be understood as limiting the scope and underlying
35 principles of the invention in any way. Indeed, various modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the following examples and the foregoing description. Such modifications are also in¬ tended to fall within the scope of the appended claims.
EXAMPLE 1
Figure imgf000011_0001
The crustaceous marine animal Artemia salina is used as a model organism for other marine animal foulers (e.g. barnacles) in this laboratory assay. Test compounds are dissolved in dimethylsulfoxide at a concentration of 4,000 ppm, diluted to a concentration of 200 ppm with wa¬ ter and further diluted with Probst artificial seawater to a concentration of 10 ppm. Approximately 30 Artemia salina instar II larvae are incubated in microwell plates in 2 ml of Probst artificial seawater containing 10 ppm of the test compound. Survival of the organism is evalu¬ ated after 24 hours, and test compounds are rated accord¬ ing to the scale shown below. Test results are shown in Table I.
RATING SCALE
Rating Definition 1 No activity, 0% - <20% mortality 2 Toxic effect, 20%-80% mortality 3 Completely active, >80% mortality
Table I
Test Compound Art-
(3-vinylimidazolinio)vinyldiphenylboron 3
(4-isopropylpyridinio)methyldiphenylboron 3
(3-methylpyridinio)methyldiphenylboron 3
(3-isopropylimidazolinio)vinyldiphenylboron 1
(thiazolinio)methyldiphenylboron 1
(3-bromoisoquinolinio)methyldiphenylboron 1
(3-bromopyridinio)methyldiphenylboron 1
(4-phenylpyridinio)methyldiphenylboron 1
(4-cyanopyridinio)methyldiphenylboron 1
Artemia
EXAMPLE 2 Field Evaluation Of Marine Antifouling Activity Of Teat Compounds (Raft Exposure)
In this evaluation, test compounds are dissolved in cyclohexanone. The solution is treated with vinylite (manufactured by Union Carbide) to obtain a final concen¬ tration of 26% in the dried coating. PVC boards (100x20x5mm) are degreased by washing with ethanol and coated with the test formulation by brushing (2 coats) . The total thickness of the test film is approximately 50μM. The exact quantity of test compound on each board is determined by comparing the initial and final weights. The test sample boards are placed in a frame and immersed to a depth of IM in the North Sea. The frames are sus¬ pended from the bottom of a raft and are intermittently raised to evaluate the surface fouling. The rating sys¬ tem used is shown below. The data are shown in Table II.
RATING SCALE
Rating
0 No growth on the panel
1 1-20% of the surface covered by animal foulers
2 21-40% of the surface covered by animal foulers
3 41-60% of the surface covered by animal foulers
4 61-80% of the surface covered by animal foulers
5 81-100% of the surface covered by animal foulers Table II
Weeks after tτaatmor.+-
Test Compound 6 i£ M 22 31
(3-vinylimidazolinio)vinyldiphenylboron 0 0 0 0 0 (3-methylpyridinio)methyldiphenylboron 0 0 1 2 1 (3-isopropylpyridinio)vinyldiphenylboron 0 1 5 5 4 (thiazolinio)methyldiphenylboron 0 0 1 2 2 (3-bromoisoquinolinio)methyldiphenylboron 0 3 5 5 5 (3-brαmopyridinio)methyldiphenylboron 0 2 5 3* 5 (4-aσetylpyridinio)methyldiphenylboron 0 1 2 2* 3 (4-phenylpyridinio)methyldiphenylboron 0 1 2 2 2 (4-cyanopyridinio)methyldiphenylboron 0 2 5 4 3
17 27
(isoquinolinio)methyldiphenylboron 0 1 4 5 5
(4-t-butylpyridinio)methyldiphenylboron 0 2 4 5 4
(4-isopropylpyridinio)methyldiphenylboron 0 0 1 1* 1
(5,6,7,8-tetxahydroiscquinolinio)methy1- 0 2 4 5 * 3 dipheπylboron
Cuprous Oxide 0 0 1 3 3
Tri (n-butyl) Tin Oxide 0 1 2 4 4
Control
*no barnacles
EXAMPLE 3 Evaluation Of Leaching Properties Of Test Compounds
Using essentially the same procedure described in Example 2, test panels (100x10x5mm) are prepared. In this evaluation test panels are placed in 80 ml artifi¬ cial sea water which is renewed weekly. At two week in¬ tervals, just after the sea water is refreshed, Arteraia is added to each treatment. Three days after the addi¬ tion of Artejnia, the experiment is evaluated using the rating scale shown below. The activity of the test com¬ pound is expressed as the number of weeks during which the leaching is sufficient to cause a toxic effect, i.e. a rating of at least 2. The results are shown in Table III.
Rating System
Rating
1 No activity, comparable to control
2 Toxic effect, but not 100% mortality (20-<80%)
3 Completely active (80-100% mortality)
Table III
Weeks Of
Test Compound Effective Leaching
(3-vinylimidazolinio)vinyldiphenylboron >32
(3-methylpyridinio)methyldiphenylboron >32
(3-isopropylpyridinio)vinyldiphenylboron 0
(thiazolinio)methyldiphenylboron 24
(3-bromoisoquinolinio)methyldiphenylboron 0
(3-bromopyridinio)methyldiphenylboron 0
(4-aσetylpyridinio)methyldiphenylboron 0
(4-phenylpyridinio)methyldiphenylboron >32
(4-cyanopyridinio)methyldiphenylboron 0
(isoquinolinio)methyldiphenylboron 20
(4-t-butylpyridinio)methyldiphenylboron >28
(4-isopropylpyridinio)methyldiphenylboron >28
(5,6,7,8-tetrahydroisoquinolinio)methy1- 0 diphenylboron
Cuprous Oxide 0
Tri(n-butyl)Tin Oxide 28
Control

Claims

WE CLAIM:
1. A method for controlling or combatting the attachment of a fouling organism to an underwater surface which comprises contacting said organism or the locus thereof with an antifouling effective amount of a compound of formula I
Figure imgf000017_0001
wherein R is C|-C8alkyl, C2-C8alkenyl or C2-C8alkynyl; W and Y are each independently halogen, CrC8alkyl or
C,-C8haloalkyl; m and n are each independently 0 or an integer of 1 , 2 or 3;
Figure imgf000017_0002
X is NR4 or S;
R] is H, halogen, CrC8alkyl, or C2-C8alkenyl;
R2 and R3 are each independently H, C,-C8alkyl, Cι-C8-haloalkyl, CrC8alkoxy, Cr C8haloalkoxy, halogen, CN, NO2, COR5 or phenyl optionally substituted with one to three halogen or NR6R7 groups or R] and R2 may be taken together with the atoms to which they are attached to form a saturated or unsaturated 6- membered carbocyclic ring optionally substituted with one to three halogen, NO2, CrC4alkyl or CrC4alkoxy groups;
R4 is CrCgalkyl, C2-C8alkenyl or phenyl; and
R5, R6 and R7 are each independently H or C,-C4alkyl.
2. The method according to claim 1 wherein m and n are 0; R is CrC4alkyl or C2-C4alkenyl; and Q is
Figure imgf000018_0001
R„
3. The method according to claim 1 wherein the fouling organism is selected from the group consisting of barnacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidians, tubeworms and Asiatic clams.
4. The method according to claim 1 wherein the formula I compound is selected from the group consisting of (3-methylpyridinio)methyldiphenylboron, (4- phenyl-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 (5,6,7, 8-tetrahydroisoquinolinio)methyldiphenylboron).
5. A method for protecting an aquatic structure against fouling by a marine or freshwater fouling organism which comprises applying onto or permeating into said structure an antifouling-effective amount of a compound of formula I
Figure imgf000018_0002
wherein R is CrC8alkyl, C2-C8alkenyl or C2-C8alkynyl; W and Y are each independently halogen, C,-C8alkyl or C,-C8haloalkyl; m and n are each independently 0 or an integer of 1 , 2 or 3;
Figure imgf000019_0001
X is NR4 or S;
R, is H, halogen. CrC8alkyl, or C2-C8alkenyl;
R2 and R3 are each independently H, C,-C8alkyl, C,-C8-haloalkyl, CrC8alkoxy, Cr Cghaloalkoxy, halogen, CN, NO2, COR5 or phenyl optionally substituted with one to three halogen or NR^R-? groups or Rj and R2 may be taken together with the atoms to which they are attached to form a saturated or unsaturated 6- membered carbocyclic ring optionally substituted with one to three halogen, NO2, C,-C4alkyl or CrC4alkoxy groups;
R4 is CrC8alkyl, C2-C8alkenyl or phenyl; and
R5, Rβ and R7 are each independently H or CrC4alkyl.
6. The method according to claim 5 wherein m and n are 0; and R is Cr C4alkyl or C2-C4alkenyl.
7. The method according to claim 5 wherein the aquatic structure is a fishnet, boat, ship, piling, pier, intake screen, cooling tower, pipeline or standpipe.
8. The method according to claim 5 wherein the marine or freshwater fouling organism is selected from the group consisting of barnacles, zebra mussels, algae, diatoms, hydroids, bryozoa, ascidians, tubeworms and Asiatic clams.
9. A marine or freshwater antifoulant composition which comprises an aquatically acceptable inert carrier or diluent and an antifouling-effective amount of a compound of formula I
Figure imgf000020_0001
wherein R is C,-C8alkyl, C2-C8alkenyl or C2-C8alkynyl; W and Y are each independently halogen, C,-C8alkyl or
C,-C8haloalkyl; m and n are each independently 0 or an integer of 1 , 2 or 3;
Figure imgf000020_0002
X is NR4 or S;
R! is H, halogen, CrC8alkyl, or C2-C8alkenyl; R2 and R3 are each independently H, C,-C8alkyl, C,-C8-haloalkyl, C,-C8alkoxy, Cr C8haloalkoxy, halogen, CN, NO2, COR5 or phenyl optionally substituted with one
10. The composition according to claim 9 wherein the formula I compound is selected from the group consisting of (3 -vinylimidazolinio)viny ldipheny lboron, (3- methyl-pyridinio)methyldiphenylboron, (4-phenylpyridinio)-methyldiphenylboron, (4- isopropylpyridinio)methyl-diphenylboron, (4-t-butylpyridinio)methyldiphenylboron, (3-isopropylimidazolinio)vinyldiphenylboron, (thiazo-linio)methyldiphenylboron, (5,6,7,8-tetrahydroiso-quinolinio)methyldiphenylboron, (isoquinolinio)methyl- diphenylboron, (3 -bromopyridinio)methyldipheny lboron, (4-acetylpyridinio)methyl - diphenylboron, (4-cyanopyridinio)-methyldiphenylboron, and (3-bromoisoquinolinio)- methyldiphenylboron.
PCT/US1997/007692 1996-05-13 1997-05-07 Use of organoboron compounds as antifouling agents WO1997042823A1 (en)

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WO2007116051A1 (en) * 2006-04-10 2007-10-18 Janssen Pharmaceutica N.V. Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and biocidal compounds
US8399506B2 (en) 2006-08-07 2013-03-19 Janssen Pharmaceutica, Nv Combinations of 4 bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile and oxidizing agents
US8512763B2 (en) 2006-02-01 2013-08-20 Janssen Pharmaceutica, Nv Combinations of 4 bromo 2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile and metal compounds
US8841338B2 (en) 2001-11-08 2014-09-23 Janssen Pharmaceutica N.V. Synergistic antifouling compositions comprising 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile

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JP4592153B2 (en) * 2000-06-01 2010-12-01 ケイ・アイ化成株式会社 Diarylborane-primary amine complex compound and water-fouling biofouling agent
JP2005060510A (en) * 2003-08-12 2005-03-10 Nof Kansai Marine Coatings Co Ltd Coating material composition, antifouling coating film, antifouling underwater structure, and antifouling method

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US8841338B2 (en) 2001-11-08 2014-09-23 Janssen Pharmaceutica N.V. Synergistic antifouling compositions comprising 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
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US8512763B2 (en) 2006-02-01 2013-08-20 Janssen Pharmaceutica, Nv Combinations of 4 bromo 2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile and metal compounds
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JPH11500457A (en) 1999-01-12

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