NON-TIN-BASED, LOW TOXICITY ANTI-FOULING AGENTS

Abstract: Disclosed are marine anti-fouling compositions, such as coating compositions, of a thermoplastic or thermoset binder, solvent, and anti-fouling agent wherein the anti-fouling agent comprises a pesticide or herbicide having a chi value of between about 0.01 and 0.5, a Z parameter for vinyl or aromatic compounds of between about 0.01 and 0.08, and an LD50 value of greater than 200 mg/kg against rats and mice.

Description: NON-TIN-BASED, LOW TOXICITY ANTI-FOULING AGENTS Background of the Invention The present invention relates to anti-fouling marine coatings and more particularly to novel low toxicity anti-fouling agents therefor. 5 One of the earliest needs for performance-oriented coatings was in the marine environment. Early formulations were designed around known toxins, such as copper and mercury compounds. Nineteenth Century marine coatings typically used creosote and natural drying oil formulations bearing the toxins. For ship bottoms, presently, anti-fouling compounds based on ' ~~ copper and tin commonly are incorporated into somewhat water-sensitive binders to afford gradual break-down of the film to permit a sustained release of the "poison". This required self-erosion property necessitates frequent repainting of ship bottoms, depending upon location and severity of exposure conditions. 5 Today's anti-fouling coatings use two general leaching mechanisms, depending on the type of resin matrix selected, soluble or insoluble. The insoluble-matrix type leaves a resinous skeleton intact as the toxicant particles are removed by dissolving into solution in seawater. This also is called the contact type because it depends upon the toxicant migrating to 0 the surface and entering solution by making contact with seawater. Since the resins are somewhat water-permeable, the toxic particles may diffuse through the semi-permeable coating, and as one particle dissolves, another is exposed to seawater. The contact type contains several times more toxicant than the soluble type. The resulting thicker films of toxicant 5 provide a longer service life to the anti-fouling topcoats. As a general rule, the insoluble-matrix type of paint does not contain an extended pigment, and the geometry of the dry film requires high toxicant loadings (52 to 74% by volume) to ensure the CU2O particles will be in continuous contact with each other. Below the level of cubic packing (52%), the resin will encase 0 the CU2O particles and prevent solution; above the level of hexagonal packing (74%), the coating will be too-resin poor to maintain film integrity. These figures may vary somewhat in actual practice and it is common to adjust the leaching rate and the effective range of toxicant loading (e.g. by the addition of rosin or other natural resins). In common practice, both 5 natural resins and extender pigments are frequently used. When high levels SUBSTITUTE SHEET of rosin are used and high errosion might be expected, tougheners such as ester gum, ethyl cellulose, and modified rubbers are added. ("Paint Handbook", C.E. Weismantel, McGraw-Hill, New York, New York, pp 14-43 and 14-44, Chapter 14 "Marine Paints", authored by R.J. Dick). With respect to the toxins presently used, recent U.S. federal legislation has severely restricted the use of organo-tin anti-fouling agents. Toxicity concerns appear to be a prime motivation behind this recent legislation. Accordingly, there is a substantial need in the anti-fouling paint arena for new, low toxicity anti-fouling agents. Broad Statement of the Invention The present invention is addressed to a marine anti-fouling composition of a thermoplastic or thermosetting binder, solvent, anti- fouling agent, and optionally conventional additives, e.g. leaching agents, opacifying pigments, etc. More specifically, the present invention is addressed to new, low toxicity anti-fouling agents which comprise pesticide or herbicide compounds having a value of between about 0.01 and 3, a Z value for vinyl or aromatic compounds of between about 0.01 and 0.08, and an LD50 value of greater than 200 mg/kg against rats or mice. Such pesticide or algicide compounds broadly can be selected from heterocyclic compounds, aromatic compounds substituted with heteroatom substituents, various amino compounds, carbocyclic vinyl ether ketoπes, certain phospho compounds, certain poly chlorinated carbocyclic and acyclic compounds, certain chlorinated carbocyclic carboxylales, antimony tartrate, boric acid, and cupric oleate. Exemplary aromatic compounds include diaromatic compounds linked with a sigma bond or with a carbon or heteroatom linkage, fused aromatic rings, and mono-aromatic compounds. Another aspect of the present invention comprises the linking of the novel low toxicity anti-fouling agents into the composition for improved retention, e.g. their reaction with the binder. Advantages of the present invention include the ability to formulate marine anti-fouling coating compositions which contain low toxicity anti- fouling agents. Another advantage is the ability to formulate marine anti- fouling coating compositions wherein the low toxicity anti-fouling agents are better retained by their linking into the coating composition itself. These end other advantages will be readily apparent to those skilled in the art based upon the disclosure contained herein. SUBSTITUTE SHEET Detailed Description of the Invention With the curtailment in permissible use of organo-tin anti-foulin agents due to their human toxicity characteristics, the art truly needs t enable anti-fouling agents which exhibit low human toxicity characteristics 5 Once such agents are identified, they must be compatible with remainin formulation ingredients in marine coatings and other marine compositions Also, these low toxicity anti-fouling agents must display in situ activit and/or release characteristics making them practical. The non-tin anti-fouling agents of the present invention broadly ar '° selected from compounds which have exhibited terrestrial biologic activity e.g. known herbicides and pesticides. For present purposes, herbicides ar to be interpreted broadly as including not only compounds which selectivel and/or broadly kill various plant life, but also include various plant growt regulators, algicides, and the like. Pesticides, for present purposes, als 5 should be broadly interpreted as compounds which are selectively and/o broadly toxic or harmful plant infestations, such as acaricides. Thes compounds, however, must exhibit low toxicity to humans. For presen purposes, "low toxicity to hu ahs" is determined when the LD50 value i greater than 200 mg/kg against rats or mice. 0 Within the broad spectrum of biologically active compounds describe above, these compounds also must possess a )C factor of between about 0.01 and 3, and a Z value for vinyl or aromatic compounds of between 0.01 an 0.08. The " ^ factor is based upon the McGinniss predictive relationship a defined in Organic Coatings in Plastic Chemistry, vols. 39 and 46, pp 529 5 534 and 214-223, respectively (1978 and 1982, respectively). The McGinnis predictive relationship defines the /(-factor as a weight fraction o heteroatoms contained in the monomer or in the monomer repeat unit of a oligomer or polymer. The McGinniss predictive relationship defines the parameter as the weight fraction ofl l electrons contained in the monome 0 or in the monomer repeat unit of an oligomer or polymer (e.g. '^electron density of aromatic or vinyl compounds). Biologically-active compounds (as defined herein) that possess a ~X factor and Z parameter within the ranges defined herein, and possess the requisite LD50 value, will be compound which display anti-fouling characteristics in marine coatings. 5 Though such compounds will exhibit anti-fouling characteristics, no all may be totally acceptable for some high performance marine coatings ET requirements, (ranging from submarine exterior coatings to anti-fouling polymer concrete). Nevertheless, the compounds will possess anti-fouling characteristics and low toxicity to humans which makes their identification significant in the arts efforts at replacing conventional organo-tin anti- fouling agents. Moreover, these new anti-fouling agents also possess functionality enabling them to be linked into a binder system and still exhibit anti-fouling activity. By linking the anti-fouling agent into the binder itself, unwanted leaching out of the anti-fouling agents over time will be minimized and longer term performance should result. Also, it is possible to complex some of the new anti-fouling agents with various non-tin metals and enhance the biologic activity thereof. Accordingly, the compounds disclosed herein are candidate reactants for synthesizing oligomeric/polymeric species having anti-fouling activity for inclusion in marine compositions for providing anti-fouling activity. The following biologically-active compounds illustrate the LD50 values, - factor, and Z parameter requirements possessed by the novel organo anti-fouling agents/reactants of the present invention and are offered as illustrative of the precepts of the present invention. TABLE 1 1. 4-allyl-2-methoxyphenol (Eugenol) LD50 Value X factor (O) of 0.195 Z parameter of 0.05 2. diphenylacetonitrile SUBSTITUTE SHEET LD50 Value of 3,500 mg/kg (rats) X factor (nitrogen) of 0.072 Z parameter of 0.062 3. 2,3-dichloro-l,4-napthoquinone X factor (Cl) of 0.313 X factor (O) of 0.141 Z parameter of 0.035 4. cetylpyridinium chloride LD50 Value of 200 mg/kg (rats) X factor (N) of 0.04 X factor (Cl) of 0.10 z parameter of 0.172 5. diphenylamine Low mammalian toxicity X factor (N) of 0.083 Z parameter of 0.071 .-mure βHS6T 6. boric acid B-(OH) 3 LD50 of 3,000 mg/kg (rats) X factor (O) of 0.777 X factor (B) of 0.175 7. 2-chloro-N,N-diallylacetamide LD50 value of 700 mg/kg (rats) X factor (Cl) of 0.205 X factor (O) of 0.092 X factor (N) of 0.081 Z parameter of 0.023 8. cetyltrimethylammonium bromide LD50 value of 500 mg/kg (rats) X factor (N) of 0.038 X factor (Br) of 0.22 9. 2-isopropylam ino-4-chloro-6-ethylamino triazine τ* - LD50 value of 1869 mg/kg (rats) X factor (N) of 0.325 X factor (Cl) of 0.244 Z parameter of 0.041 10. dimethoxythiophosphate derivative of diphenyl sulfide LD50 value of 2030 mg/kg (rats) X factor (O) of 0.21 X factor (S) of 0.21 X factor (P) of 0.13 Z parameter of 0.013 11. ethyl 4-chloro-alpha(4-chlorophenyl) alpha-hydroxy benzene acetate LD50 value of 5,000 mg/kg (rats) X factor (O) of 0.18 X factor (C) of 0.27 Z parameter of 0.022 12. methyl, diethylamino, dimethoxythiophosphate derivative of X factor (O) of 0.16 X factor (N) of 0.14 X factor (S) of 0.105 X factor (P) of 0.102 Z parameter of 0.007 13. ethoxylated nonylphenol LD50 value of 4,000 X factor (O) of 0.25 Z parameter of 0.0105 14. unsymmetrical hydrazine derivative of succinic acid LD50 value of 8400 X factor (O) of 0.30 X factor (N) of 0.175 15. allyl, methylhydroxy substituted cyclopententone ester of dimethyl- propenyl cyclopropane carboxylic acid SUBSTITUTE SHEET LD50 value of 1,000 X factor (O) of 0.11 Z parameter of 0.021 16. 2,5-dichloro,3-amino benzoic acid LD50 value X factor (O) of 0.155 X factor (N) of 0.068 X factor (Cl) of 0.345 10 Z parameter of 0.015 17. cinnamic acid X factor (O) of 0.216 Z parameter of 0.054 ~ * ~ - 18. 2,-6-dichloro, 4-nitroaniline LD50 value of 5,00 0 X factor (0) of 0.155 r ^ X factor (N) of 0.135 0 X factor (Cl) of 0.343 Z parameter of 0.029 SUBSTITUTE s HE 19. dichloro, isopropenyl anilide X factor (O) of 0.070 X factor (N) of 0.061 X factor (Cl) of 0.309 Z parameter of 0.035 20. dodecylguanidine monoaeetate LD50 value of 1,000 X factor (O) of 0.111 X factor (N) of 0.146 21. trichlorophenyl acetic acid LD50 value of 1,780 X factor (O) of 0.134 X factor (Cl) of 0.445 Z parameter of 0.025 22. diphenyl ether, chlorophenyl derivative of the isobutyric acid ester of hydroxyacetonitrile SUBSTITUTE SHEET LD50 value of 451 (toxic to fish) X factor (O) of 0.114 X factor (N) of 0.033 X factor (Cl) of 0.085 Z parameter of 0.043 Z parameter of 0.035 24. 3-indolacetic acid X factor (0) of 0.198 X factor (N) of 0.086 Z parameter of 0.037 25. 3,5-dichloro-N-(3,3-dimethylpropyne)benzamide LD50 value (dermal) of 8,350 X factor (0) of 0.063 X factor (N) of 0.055 X factor (Cl) of 0.278 Z parameter of 0.039 - E SHEET 26. dimethylphosphoramide ammonium salt LD50 value (dermal) of 2,400 X factor (O) of 0.276 X factor (N) of 0.165 X factor (P) of 0.182 27. napthalene acetamide LD50 value of 1,000 X factor (O) of 0.086 X factor (N) of 0.076 Z parameter of 0.065 28. dimethylethylphenoxy-cyclohexyl-2-propynyl sulfite X factor (0) of 0.146 X factor (S) of 0.098 ' Z parameter of 0.034 SUBSTITUTE SHEET 29. o-phenylphenol LD50 value of X factor (0) of 0.094 Z parameter of 0.071 30. phthalic acid X factor (O) of 0.386 Z parameter of 0.036 31. chlorophenyl-isopropyl, propynyl carbamate X factor (0) of 0.064 H* C= 14 X factor (N) of 0.112 X factor (Cl) of 0.142 Z parameter of 0.040 32. N-phenyl,N-butynyl chloroacetamide SUBSTITUTE SHEET LD50 value of 1,177 X factor (O) of 0.072 X factor (N) of 0.063 X factor (Cl) of 0.160 Z parameter of 0.045 33. amino, chloro, phenyl derivative of azacyclohexamine LD50 value of 3,030 X factor (O) of 0.073 X factor (N) of 0.190 X factor (Cl) of 0.161 Z parameter of 0.036 34. N,N-diallyl-2-chloroacetamide LD50 value of 750 X factor (0) of 0.092 X factor (N) of 0.081 X factor (Cl) of 0.205 Z parameter of 0.023 35. aminoacetic acid derivative of methylphosphonate o ? μo- -cH λ - jUM-£μ*- P-OM LD50 value of 4,300 O H X factor (O) of 0.473 X factor (N) of 0.083 x factor (P) of 0.183 β .BSTvτυTe β H* 36. 3,5-dinitro,4-N,N-dipropylamino benzene sulfonamide LD50 value of 10,000 X factor (O) of 0.277 X factor (N) of 0.162 X factor (S) of 0.092 Z parameter of 0.017 37. 2-chloro-2-propenyl diethylcarbamodithioate LD50 value of 850 X factor (N) of 0.064 X factor (S) of 0.294 X factor (Cl) of 0.163 Z parameter of 0.0092 As the data will demonstrate, the foregoing biologically-active compounds all display efficacy as anti-fouling agents. Their diminished toxicity to humans is a decided benefit compared to conventional organo-tin anti-fouling agents. Broadly, the low toxicity anti-fouling agents of the present invention ran be described as biologically-active terrestrial compounds (e.g. pesticides and herbicides) that are heterocyclic, aromatic with heteroatomic substituents, amino compounds, and carbocyclic ketone vinyl ethers. The aromatic compounds can be further identified as mono-aromatic, fused aromatic ring compounds, and diaromatic compounds linked with a sigma bond or with a carbon or divalent heteroatomic substituent. In addition to the ring compounds, hetero-substituted aliphatic compounds that are biologically active and possess the requisite " f * . value and Z parameter also may find use as anti-fouling agents in accordance with the precepts of the SH SUBS ITUTE present invention. Additionally, compounds which do not quite fit any of the foregoing definitions also should be recognized as included within the scope of the anti-fouling agents of the present invention. These include boric acid which has been demonstrated to be quite active as an anti-fouling agent, as the data will testify. Additional compounds include, for example, antimony tartrate and cupric oleate. Illustrative of additional low toxicity anti- fouling agents/reactants of the present invention include those set forth in Table 2 below. TABLE 2 Additional candidate low toxicity anti-fouling agents include: Acrolein phenylhydrazone Alkyl dimethyl benzene ammonium saccharinate 2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one ester of 2,2-dimethyl-3-(2- methylpropenyl cyclopropanecarboxylic acid) 4-allyl-2-methoxyphenol o-(alIyloxy) phenyl methylcarbamate 2-(allylthio)-2-thiazoline l,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-2-πorbornene 4-ethylamino-6-isopropylamino-2-methylthio-l,3,5-triazine 2-amino-3-chloro-l,4-napthoquinone 3-am ino-5-n itr o-o-toluam Ide 3-amino-l,2,4-triazole ammonium sulfamate antimony potassium tartrate 2-chloro-4-ethylamino-6-isopropylamino-S-triazine 4-chloro-m-chlorocarbanilate 6-chloropiperonyl chrysanthemumate N-butyl-N-ethyl-c< j-,<λ-trifluoro-2-6-dinitro-p-toluidine bis (p-chlorophenyl)-3-pyridine methanol bis (dialkylphosphinothioyl) disulfide bis (4-hydroxyiminomethyI pyridinum-1-m ethyl) ether dichloride 2 , 4-bis ( 3-m ethoxylpr opylam ino)-6-m ethylthio-S-triazine bis (pentachloro-2,4-cyclopentadien-l-yl) SUBSTITUTE SHEET boric acid N-(4-bromo-3-chlorophenyl)-N'-methoxy-N'-methyl urea 5-(bromom ethyl)- l,2,3,4,7,7-hexachloro-2-norbornene S-(0,0-diisopropyl phosphoro-dithionate of N-(2-mercaptoethyl) benzenesulfonamide benzamidooxy-acetic acid 3-benzylideneamino-4-phenylthiazoline-2-thione bis (p-chlorophenoxy) methane bis (4-chlorophenyl) disulfide 1,1-bis (p-chlorophenyl) ethane 1,1-bis (p-chlorphenyl)-ethanol o,o-Dimethyl-o-2,5-dichloro-4-bromophenylthionophosphate 0 ,0-dim ethyl-2 , 2 ,2-tr ichloro- 1-n-butyryloxyethyl phosphonate N-butylacetanilide 2-tert-but lamino-4-chloro-6-ethyl amino-5-triazine 2-tert-butylamino-4-ethylamino-6methylmercapto-S-triazine 4-tert-butyl-2-chlorophenylm ethyl methylphosphoramidite o-(4-ter t-butyl-2-chlorophenyl)α-m ethyl phosphoram idothionate butyl 3,4-dihydro-2, 2-dimethyl-4-oxo-l,2h-pyran-6-carboxylate n-butyl-9-hydroxyfluorene-(9)-carboxylate 2-(p-tert-butylphenoxy) cyclohexyl 2-propynyl sulfite l-butyn-3-yl m-chlorophenyl-carbam te N-trichloro-m ethylthio-4-cyclohexene- 1 ,2-docarboxim ide 1-napththyl n-methylcarbamate S-[[(p-chlorophenyl) thiol] methyl] 0,0-diethylphosphorodithioate 2-chloro-N,N-diallyl-acetamide 2-chloroallyl diethyl-dithiocarbamate cetyldimethylethylammonium bromide cetyl pyridinium chloride tetrachloro-p-benzoquinone 2-chloro-4,6-bis(diethylamino)-s-triazine p-chlorobenzyl p-chlorophenyl sulfide 1,2,3,5,6,-7, 8, 8-octachloro-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene l-(3-chlorallyl)-3,5,7-triaza-l-azoniaadamantane chloride ethyl 4,4'-dichlorobenzylate 5-chloro-2-benzothiazolethiol zinc salt p-chlorobenzyl p-fluorophenyl sulfide SUBSTITUTE SHEET l-chloro-N'-(3,4-dichlorophenyl) N,N-dimethylformamidine 4-chloro-3,5-dimethyl henoxy-ethanol l,4-dichloro-2,5-dimethoxybenzene l-(ehloro-2-norbornyl)-3,3-dimethylurea S-(p-chloroτ_v.-phenylbenzyl) 0,0-diethyl phosphorodithioate p-chlorophenyl ester of benzene-sulfonϊc acid N-3-chlorophenyl-I-(isopropyl-carbamoyl-l)-ethyl carbamate 3-(p-chlorophenyl)-5-methyl rhodanine 4 (and 6)-chloro-2-phenylphenol sodium salt p-chlorophenyl phenyl sulfone 4-chlor ophenyl 2,4, 5-trichlor o-phenylaz osulf ide N-(5-chloro-5-thiazolyl) propionamide 2-[4-chloro-o-tolyl)oxy] propionanilide 2-chloro-l-(2,4,5-trichloro-phenyl) vinyl dimethyl phosphate N'-(4-chlorophenoxy) phenyl N,N-dimethylurea Isopropyl N-(3-chlorophenyl) carbamate Copper (cupric) oleate Copper 8-quinolinolate 2-(2,4-dihydroxyphenyl)-l-cyclohexene-l-carboxylic acid- -lactone 0,-Odiethylphosphorothioate 2-chloro-4-dimethylamino-6-methylpyrimidine 3-(2-cyclopenten-I-yl)-2-methyl-4-oxo-2-cyclopenten-l-yl chrysanthemunate o -cyclohexyl-Λ-phenyl-3-pyridyl-methanol, hydrochloride N'-cycIo-octyl-N j N-dimethylurea S'^'-dichlorocyclopropanecarboxanilide 2,4-dichlorophenoxyacetic acid 2,4-d,«^-chlorocrotyl ester 3,5-dimethyl-l,3,5,2H-tetrahydrothiadiazine-2-thione, tetra-hydro-3, 5-di m ethy 1-2 H- 1 , 3, 5-thiadiazin e-2-thione 4-(2,4-dichlorophenoxy) butyric acid Dim ethyl 2,3,5, 6-tetra-chlor o ter ephthalate uecyltriphenylphosphonium-bromochlorotriphenylstannate dehydroacetic acid (and its sodium salt) Tris and Bis(2,4-dichlorophenoxyethyl) phosphite 2-methyi-thio-4-isopropylamino-6-methylamino-s-triazine S-2,3-dichloroallyI N,N-diisopropylthiolcarbamate l,3-diaza-2, 4-cyclopentadiene SUBS ^ N,N-di-n-butyl-p-chlorobenzene-sulfonamide 3,6-dichloro-o-anisic acid 0-(2-chloro-4-nitrophenyl) 0,0-dimethyl phosphorothioate 2, 6-di chlorobenzon itr ile 2,3-dichloro-l, 4-naphthoquinone l,3-bis(l-hydroxy-2,2,2-trichloroethyl) urea 3,4-dichlorobenzyl methylcarbamate (80%) mixture with 2,3-dichlorobenzyl methylcarbamate (20%) 1, l-dichloro-2,2-bis (p-ethylphenyl)ethane 2,4-dichloro-6-(o-chloro-anilino)-s-triazine N-(dichlorofluoromethylthio)-N'N'-dimethyl-n-phenyl sulfamide 4,4'-dichloro-N-methylbenzene-sulfoanilide 2,3-dichloro-2-methylpropionic acid sodium salt 2,6-dichloro-4-nitroaniline 2,5-dichloro-3-nitrobenzoic acid 5,2'-dichloro-4'-nitro-salicylanilide ethanolamine salt 2',5'-dichloro-4'-nitrososalicylanilide 2,2'-dihydroxy-5,5'-dichlorophenylmethane l-(2,4-dichlorophenoxyacetyl)-3,5-dimethyl pyrazole N-3,4-dichlorophenyl N'-5-chloro-2-(2-sodium sulfonyl-4-chlorophenoxy) phenyl urea 2,4-dichlorophenyl ester of benzene sulfonic acid 2,4-dichlorophenyl methanesulfonate 2,4-dichlorophenyl 4-nitrophenyl ether 4-dichlorotetrahydrothiophene 1,1-dioxide 4,4'-dichloro-alpha-trichloromethylbenzhydrol 3 , ,4'-dichloro-2-methacrylanilide (Diethoxyphosphinothioylthio) gamma-butyrolactone 0,0-diethyl s-carboethoxy methyl phosphorothioate 0,0-diethyl O-naphthylamido phosphorothioate 0,0-diethyl 0-3,5, 6-trichloro-2-pyridyl phosphorothioate 2,2 ! -dihydroxy-3,5,3',5*,4"-pentachlorotriphenylmethane 2"-sodium sulfonate 0,0-diisopropyl s-diethyldithiocarbamoyl phosphorodithioate 2,4-dimethylbenzyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropane- carboxylate 0,0-dimethyl-S-2-(acetylamino)-ethyl dithiophosphate N-dimethylamino succinamic acid l,l-dimethyl-3-[3-(n n--tιeerrtt--bDuuttyylι--ccaarrbDaammooyyliooxxyy);pphneeιιιιyι Ilurea SUBSTITUTE SHEE 0,0-dimethyl s-carboethoxy ethyl phosphorothioate 0,0-dimethyl 0-(3-chloro-4-nitrophenyl) phosphorothioate 0,0-dimethyl-o-p-eyanopheπyl phosphorothioate o,o-dimethyl-s-[5-ethoxy-l,3,4-thiadiazol-2(3H)-onyl-(3)-methyI] phosphorodithioate N,N-dimethyl-N'-(2-methyl-4-chlorophenyl)-formamidine hydrochloride 0,0-dimethyl o-(4-nitro-m-tolyl) phosphorothioate o,s-dim ethyl tetrachloro thiotere-phthalate 4'-dimethyltriazenoacetanilide dinitrocyclohexylphenol 2,4'-dinitro-4-trifIuoromethyl diphenylether 2-(l-methyl-n-heptyl)-4,6-dinitrophenyl crotonate N,N-dimethyl-2,2-diphenylacetamide diphenylacetonitrile diphenylam ine 2,6-dinitro-N,N-di-n-propyl-p-toluidine Di-n-propyl-2,5-pyridine-dicarboxylate l,l'-ethylene-2,2 , -dlpyridinium dibromide 2,3-dieyano-l,4-dithia-anthraquinone 3-(3,4-dichlorphenyl)-l, 1-dimethyl-urea n-dodecyl thiocyanate n-dodecylguanidine acetate Ethyl N,N-dipropylthiolcarbamate 2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate ethoxymethylbis (p-chlorophenyl) carbinol l,2-dihydro-6-ethoxy-2,2,4-trimethylquinone ethyl-N,N-diisobutyl thiolcarbamate ethylenebis (dithiocarbamato) zinc 3-phenyl-l, 1-dimethylurea trichloroacetate ferric dimethyl-dithiocarbamate 0,0-dimethyl S-(N-formyl-N-methylcarbamoyI-methyl)phosphorodithioate 2-formyl-4-chlorophenoxyacetic acid 3-furfuryl-2-methyl-4-oxo-2-cyclopenten-l-yl chrysanthemunate 2-heptadecyl-2-imidazoline 7-chloro-4,6-dimethoxycoumaran-3-one-2-spiro-r-(2'-methoxy-6'-methylcycl hex-2'-en-4'-one) l,l,l,3,3,3,-hexachloro-2-propanone l,5a,6,9,9a,9b-hexahydro-4a(4H)-dibenzofuran-carboxaldehyde 9-(p-n-hexyloxyphenyl)-10-methyl-acridinium chloride 2-hydroxymethyl-4-chloro-phenoxyacetic acid N-hydroxy-methyl-2,6-dichlorothiobenzamide Isopropyl N-phenylcarbamate isobornyl thiocyanoacetate isobutyl triphenylmethylamine 5-bromo-3-isopropyl-6-methyluraeil isopropyl-4,4'-diboromobenzilate isopropyl 4,4'-dichlorobenzilate isorpropyl mercaptophenyl-acetate, 0,0-dimethyl phosphorodithioate 3-cyclohexyl-6,7-dihydro-lH-cyclopentapyrimidine-2,4(3H,5H)-dione 3-(3,4-dichlorophenyl)-l-methoxy-l-methylurea S-[l,2-bis(ethoxy-carbonyl)ethyl] 0,0-dimethyl phosphorodithioate manganese ethylenebisdithiocarbamate 4-chloro-2-methylphenoxyacetic acid 2-(4-chloro-2-methylphenoxy) propionic acid sec-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate s-[(4, 6-diam ino-s-tr iazine-2-yl)m ethy 0 ,0-dim ethyl phosphorodithioate 2-isopropylam ino-4-(3-methoxypropylamino)-6-methylthio-s-triazine l,l,l-trichloro-2,2-bis(p-methoxyphenyl) ethane 2-methoxy-4-isopropylamino-6-diethylamino-s-triazine S-(N-methoxymethylcarbamoylmethyl) dimethyl phosphorothiolothiononate alpha-met hylbenzyl 3-(dimethoxy-phosphinyloxy)-cis-crotonate m-(l -methyl butyl) phenyl methyl-carbarn ate methyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate 3,3'-methylenebis (4-hydroxycoumarin) 2,2'-methylenebis (3,4,6-trichlorophenol) 6-m e thyl-2-oxo- 1 , 3-dithio(4, 5-b)quinoxaline 0,0-dimethyl S-(2,5-dichlorophenyl-thio)-methyl phosphorodithioate 3(2-methylpiperidino)propyl-3,4-dichlorobenzoate 4-(methylsulfonyl)-2,6-dinitro-n,n-dipropylaniline m ethy 1-2, 3,5 ,6-tetrachloro-n-m ethoxy-n-m ethylter ephthalamate O-m ethyl 0-(2,4,5-trichloro-phenyl) amidophosphorothiomate 3-(p-bromophenyl)-l-methyl-l-methoxyurea 1 ,2-dihydropyridazine-3,6-dione 3,3'-ethylenebis-(tetrahydro-4,6-dimethyl-2H-l,3,5-thiadiazone-2-thione) SUBSTITUTE SHEET S-ethyl hexahydro-lH-azepine-1-carbothioate 3-(p-chlorphenyl)-l , 1-dim ethylurea 3-(p-chlorophenyl)-l , 1-dimethylurea trichloroacetate disodium ethylene bisdithiocarbamate l,2-dibromo-2,2-dichloroethyl dimethyl phosphate beta-naphthoxyacetic acid 3-(3,4-dichlorophenyl)-l-methyl-l-n-butylurea 3-(hexahydro-4,7-methanoindan-5-yl)-l, 1-dimethylurea N-1-πaphthyl-phthalamic acid p-chlorophenyl p-phenyl 4-chlorobenzenesulfonate s-propylbutyl-ethylthiocarbamate phenothiazine ethyl mercapto-phenylacetate 0,0-dimethyl-phosphorodithioate n-phenyl-l-(ethylcarbamo l-l) ethylcarbamate (d isomer) phosphoric acid, 2-chloro-l-(2,4,5-trichlorophenyl)vinyl dimethyl ester 4-amino-3,5,6-trichloropicolinic acid piperony l-bis(2-[2'-n-butoxyethoxy] ethyl) acetal piperonyl butoxide alpha[2-(2-n-butoxyethoxy)-ethoxy]4,5-methylenedioxy- 2-propyltoluene piperonyl cyclonene polychlorobenzoic acid, dimethylamine salt 2,4-bis-(isopropylamino)-6-methoxy-s-triazine 2-methyl-mercapto-4,6-bis(isopropylamino)-s-triazine 2-chloro-n-isopropylacetanilide 3',4'-dichloropropionalide 2-chloro-4,6-bis(isopropyl-amino)-s-triazine di-n-propyl-3-methyl-6,7-methylenedioxy-l,2,3,4-tetra-hydronaphthalene-l,2- dicarboxylate 5-amino-4-chloro-2-phenyl-3(2H) pyridazinone pyrethrin I 8-quinolinol dimethyl 2,4,5-trichlorophenyl phosphorothionate salicylanilide l-(3,4-methylene-dioxyphenoxy)-3,6,9-trioxoundecane sodium 2-(2,4-dichlorophenoxy)ethyl sulfate i-(2-methyl-cyclohexyl)-3-phenylurea l-(2,4,5-trichlorophenoxy) propionic acid SUBSTITUTE SHEET N'-chlor-2-methyl-p-valerotoluidide 1 ,2-methylenedioxy-4-[2-(octylsulf inyDpropyl] benzene methyl 3,4-dichlorocarbanilate 2,4,5-trichlorophenoxyacetic acid trichlorobenzyl chloride 2,2-bis(p-chlorophenyl)-l,l-dichloroethane ethylene-l,2-bis (thiocarbamoyldimethylthio-carbamoyldisulfide) 3-tert-butyl-5-chloro-6-methyluracil 2,6-di-tert-butyl-p-tolylmethylcarbamate 2,3,6,7-tetrachloro-4a,8a-epoxy-l,2,3,4,4a,8a-hexahydro-l,4- m ethanonaphthalene-5 ,8-dione N-(l,l,2,2-tetrachloro-ethyl-sulfenyl)-cisτj -4-cyclohexene-l,2-dicarboximid 2,4,5,6-tetrachloroiso-phthalonitrile l,2,4,5-tetrachloro-3-nitrobenzene p-chlorophenyl 2,4,5-trichlorophenyl sulfone 5,6,7,8-tetrahydro-l-naphthyl methylcarbamate 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropanecarboxylate 0,0,0', O'-tetram ethyl 0,0'-thiodi-p-phenylene phosphorothioate 1,3,6,8-tetranitrocarbazole 2-(4-thiazolyl) benzimidazole 2,2'-thiobis(4,6-dichlorophenol) 2-thiocyanoethyl dodecanoate 2,3-quinoxaline-dithiol cyclic trithiocarbonate tetramethylthiuram disulfide N-meta-tolyl phthalamic acid S-2,3,3-trichloroallyl N,N-di-isopropyl-thiolcarbamate 0,0-dimethyl (l-hydroxy-2,2,2-trichloroethyl)phosphonate 2,3,6-trichlorobenzoic acid trichlorobenoic acid, dimethylamine salt 4,5,7-trichlorobenzthiadiazole-2,l,3 2,3,6-trichlorobenzyloxypropanol N-trichloromethylthio-benzothiazolone N-trichloromethylthiobenzoxazolone 2,2,2-trichloro-n-(pentachloro-phenyl)acetimidoyl chloride 2-(2,4,5-trichlorophenoxy)ethyl sulfate, sodium salt N,N'-N"-trichloro-2,4,6-triamine-l,3,5-triazine SUBSTITUTE SHEET 2-chloro-4-(di-ethylamino)-6-(ethylamino)-s-triazine tert-butyl 4(or 5)-chloro-2rmethylcyclohexanecarboxylate S-propyldipropylthiocarbamate zinc ethylene bisdithiocarbamate zinc dimethyldithiocarbamate 3,5-dinitro-o-toluamide As noted above, the ability to polymerize an anti-fouling agent into the coating backbone has the apparent advantage of retaining the anti- fouling agent within the coating with concomitant prevention of its being leached out of the coating by the sea water at an unacceptable rate. Activity of the anti-fouling agent, though, must be preserved following its reaction. Based upon the data as set forth in the examples, it appears that coupling of anti-fouling agents with coupling agents (monomers, oligomers, or polymers) which are relatively high in molecular weight (e.g. above about 300 molecular weight) and substantially deplete in heteroatom content (especially nitrogen and sulfur atoms) dilutes the activity of the anti-fouling agent to such a level that its " performance is substantially compromised. Lower molecular weight coupling agents, even those deficient in heteroatom content, can be tolerated providing that the resulting structure (oligomer or polymer) retains its " Λ value and Z parameter as defined above.. It is desirable, however, that the coupling agents contain significant heteroatom content, especially nitrogen and sulfur atoms, in order to maintain the anti- fouling activity of the anti-fouling agent being converted into oligomeric or polymeric form. While not all anti-fouling agents disclosed herein can provide acceptable polymeric derivatives, the anti-fouling agents of the present invention are candidates suitable for being evaluated with respect to incorporation into an oligom eric/polymeric structure for formulating marine compositions devoid of tin content, yet displaying anti-fouling activity. The formulation of the marine coatings containing the anti-fouling agents of the present invention is practiced in conventional fashion as those skilled in the art appreciate utilizing conventional film-forming binders appropriate for marine environments. Marine compositions broadly for present purposes include coatings, elastomers, sealants, caulks, grout, and like polymeric structures appropriate for the marine environment. The form of the marine composition can be as a coating, as rigid or elastomeric (including foamaceous) objects, as a sealant, as a gel for cementitious and SUBSTITUTE SHEET plastic surfaces, as polymer concrete, or as a three-dimensional configured structure such as villous trailing fingers in the exterior of marine vessels. In addition, the anti-fouling agents of the present invention may be chemically or physically incorporated into cementitious surfaces. Conventional additives, organic solvents (including reactive solvents or diluents), and the like are incorporated into the formulation. The proportion of anti-fouling agent generally is between about 1 and 20 weight percent by weight of the formulation. The following examples show how the present invention has been practiced but should not be construed as limiting. In this application, all percentages and proportions are by weight and all units are in the metric system, unless otherwise expressly indicated. Also, all citations are expressly incorporated herein by reference. EXAMPLES EXAMPLE 1 Test panels were 15.24 cm x 30.48 cm (6 in x 12 in) in dimension and constructed of white plastic top surface and a black plastic bottom surface. The test coating sample utilized 20 weight parts of the anti-fouling agent incorporated into a resinous vinyl binder (80 weight parts of a vinyl chloride polymer, VAGH, Union Carbide Carbide Corporation, New York, New York) reduced in methyl ethyl ketone solvent to 50% solids content. The coating sample was applied to both surfaces of the test panels at a film thickness of about 5 mils dry. The test panels then were exposed horizontally with the white surface upward and the black surface downward in the ocean at Daytona Beach, Florida, U.S.A. Control panels (uncoated) also were tested. The panels were viewed one month and four months after immersion exposure and rated visually for the presence of hard or soft marine life (primarily barnacles and grass). A rating of 10 is perfect (no marine organisms) and a rating of 0 indicates a complete failure of the panel to resist marine organisms. The following results were recorded: SUBSTITUTE SHEET TABLE 3 General Rating Panel No. Anti-Fouling Agent 1 mo. 4 mos. Avg. of top and bottom of the panel readings 13-A1 Eugenol, 99% (4-allyl-2- methoxyphenol) 13-A2 Eugenol, 99% (4-allyl-2- methoxyphenol) The above-tabulated results show that all of the candidate anti-fouling agents displayed anti-fouling properties at the end of one month immersion. Moreover, anti-fouling properties still are exhibited by the anti-fouling agents after four months immersion. EXAMPLE 2 In order to bind an organic anti-fouling agent into a polymeric structure, a three-neck reaction flask fitted with a mechanical stirrer, thermometer, and reflux condenser was charged with a polysulfide polymer (200 g of LP-3 polysulfide polymer, Thiokol), 1,2-dicyano, tetrachlorobenzene (100 g of Nopocide brand, Diamond Shamrock), SUBSTITUTE SHEET potassium hydroxide (80 g), and dimethyl sulfoxide (100 ml). The reaction mixture was heated for three hours to a temperature of 105°C, cooled to room temperature, washed, and subjected to vacuum for removal of solvent. The resulting polymeric structure 38159-23 can be represented conventionally as follows: An anti-fouling agent-modified adduct was synthesized in accordance with the following reaction scheme. Toluene (100 ml) was added to a round- bottomed flask followed by the addition of hydroxyethyl methacrylate (14 ml) and toluene diisocyanate (17 ml). This mixture was stirred for one hour at room temperature followed by the addition of triethylamine catalyst (three drops). After two hours, 3,4-dichloroanaline (16 ml) was added to the solution which then was heated to 50°C and held for 10 hours. The resulting solid product was filtered through number 40 filter paper and washed with additional alliquots of toluene and hexane. Infrared analysis showed the expected urethane-amide structures consistent with the desired reaction product 38159-33 which is illustrated conventionally below. EXAMPLE 4 A pressure reactor fitted with a pressure gauge was loaded with 3- (3,4-dichlorophenyl)-l,l-dimethyl urea (45g) and propylene oxide (150 ml). The reactor was sealed and heated to 80° C (a pressure reading of 50 psi) and held for 20 hours. The sample removed from the reactor was analyzed by IR SUBSTITUTE SHEET and showed broadening of the NH bands and the presence of hydroxyl functionality and some polyether functionality (1100 cm"*). Preparation of this material is similar to that preparation described in J. Polymer Science, vol. 15, 427-446 (1955). Reaction production 38159-32 can be represented conventionally below. It will be observed that the reaction product contains a hydroxyl group which could be reacted with isocyanate or other functionality for its incorporation into a curable resin. OH EXAMPLE 5 To l,4,5,6,7,7-hexachloro-5-norborene-2,3-dicarboxylic anhydride (37 g) was added hydroxyethyl methacrylate (37 ml). This reaction mixture was heated to 87° C for three hours to produce reaction product 38159-34 which can be represented conventionally as follow: SUBSTITUTE SHEET EXAMPLE 6 Addition of a 10% solution of CuCl2 in ethanol to a 10% solution of 8- hydroxyquinaldine formed a dark brown complex immediately. This complex 38159-35/37 was washed with hexane and dried without further purification. The structure of the complex can be represented conventionally as follows: EXAMPLE 7 The procedure of Example 3 was repeated using 2,5-dichloroanaline instead of 3,4-dichloroanaline. Reaction product 38159-43 is illustrated below: SUBSTITUTE SHEET EXAMPLE 8 1,5-napthalene diisocyanate (25 g) was reacted with l,3-diaza-2,4- cyclopentadiene (14 g) using the urethane reaction procedure as set forth in EXAMPLE 9 To DER 331 epoxy resin (Dow epoxy resin, about 300 molecular weight, epoxide equivalent of 150, 33 g) was added 35 ml of toluene and phenothiazine (40 g). This mixture was heated to 90° C for three hours until a clear solution was obtained. " The product was used without any further purification. Reaction product 83159-51 can be illustrated conventionally below: EXAMPLE 10 Two different modified polymeric structures were prepared. Polymeric structure 38159-41 was prepared by adding DER 331 resin (11 g) to 2-mercaptobenzothiazole (10 g) dissolved in toluene solvent (35 ml). This reaction mixture was heated to 90° C for three hours until a clear solution was obtained. The second polymeric structure identified as 38159-42 was SUBSTIT prepared by the same reaction procedure utilizing morpholine in place of 2- mercaptobenzothiazole. Both structures can be represented conventionally below. EXAMPLE 11 Marine coating compositions were formulated with the polymeric and oligomeric anti-fouling modified structures of Examples 2-10, d-trans allerthrin, and Kerb 50-W herbicide (Pronamide or 3,5-dichloro-N-(3,3- dimethylpropyne) benzamide, Rohm and Haas Co., Philadelphia, Pa.) Immersion testing was conducted for 0.5 months between late July and early August at Nagasaki Bay, Japan. The fouling ratings are the percentage of coverage with barnacle and tube worm on the panels. The coating composition formulations and anti-fouling performance are set forth below. SUBSTITUTE SHEET TABLE 4: Amount (wt-Parts) Ingredient BCL-1 BCL-2 BCL-3 BCL-4 BCL-5 BCL-6 BCL-7 BCL-8 BCL-9 BL-10 BCL-11 Laroflex MP-45 copolymer of 3 3 3 3 3 3 3 3 3 3 3 vinyl chloride and vinyl isobutyl ether (75/25), BASF Wyandotte 10 15 20 25 The above-tabulated data shows that samples BCL-2, 3, 5, 8, and 10 provided quite acceptable anti-fouling performance. Samples BCL-4, 9, and 11, however, did not appear to provide acceptable performance, i.e. at least 50% protection to the panel. The negative results for samples BCL-6 and 11 are expected considering the enormous dilution of the anti-fouling agent by virtue of the epoxy compound used in the synthesis of the polymer. The results for BCL-9 were unexpected since only a positional difference of the chlorine atoms exists between the adduct in this sample and sample BCL-3. Based upon sample 3CL-3 and the results of Example 12, it is believed that the results for sample BCL-9 comprise anomalous results. EXAMPLE 12 Additional marine coating compositions were formulated with the polymeric and oligomeric anti-fouling-modified structures of Examples 2 and 3 as follows: TABLE 5 Amount (wt-Parts) Ingredient BCL-1 BCL-3 Laroflex MP-45 copolymer of vinyl chloride and vinyl isobutyl ether (75/25), BASF Wyandotte 10 0.1 5 30 10 SUBSTITUTE SHEET Panels as described in connection with Example 1 were coated with the two formulations and then subjected to Florida immersion testing as described in connection with Example 1 along with the control panel detailed above. The following results were recorded. Wpanel coated with 12% triphenyl tin hydroxide in VAGH vinyl binder of Example 1. (^Rating for day 399 The above-tabulated results clearly show that the polymeric and oligomeric structures modified with a low toxicity, organic anti-fouling agent displayed quite acceptable anti-fouling properties, even compared to the organo-tin-containing control paint. These results are especially encouraging considering the extended time period involved in the immersion testing. Clearly, the ability to incorporate low toxicity, organic anti- foulling agents into an oligomeric/polymeric structure in marine compositions is demonstrated. SHEE STITUTE SUB

Claims: CLAIMS 1. In a marine anti-fouling composition of a thermoplastic or thermoset binder, solvent, and anti-fouling agent, the improvement wherein said anti-fouling agent comprises a pesticide or herbicide compound having a value of between about 0.01 and 0.5, a Z parameter for vinyl or aromatic compounds of between about 0.01 and 0.08, and an LD50 value of greater than 200 mg/kg against rats or mice. 2. The composition of claim 1 wherein the value is established ' by said agent containing heteroatoms selected from the group consisting of sulfur, oxygen, nitrogen, halogen, and mixtures thereof. 3. The composition of claim 1 wherein said anti-fouling agent is selected from the group consisting of heterocyclic compounds, aromatic compounds containing heteroatomic substituents, amino compounds, and carbocyclic ketone vinyl ethers. 4. The composition of claim 3 wherein said aromatic compound with heteroatomic substituents is selected from the group consisting of monoaromatic compounds; fused aromatic rings; and di-aromatic compounds linked with a sigma bond, a dialkylene group, or a divalent heteroatomic group; and mixtures thereof. 5. The composition of claim 1 wherein said anti-fouling agent is selected from the group consisting of: 4-allyl-2-methoxyphenol diphenylacetonitrile 2,3-dichloro-l,4-napthoquinone cetylpyridinium chloride diphenylamine boric acid 2-chloro-N ,N-diallylacetam ide cetyltrimethylammonium bromide 2-isopropylam ino-4-chlor o-6-ethy lam ino triazine dimethoxythiophosphate derivative of diphenyl sulfide ethyl 4-chloro-alpha(4-chlorophenyl) alpha-hydroxy benzene acetate methyl, diethylamino, dimethoxythiophosphate derivative of pyrimidine ethoxylated nonylphenol unsymmetrical hydrazine derivative of succinic acid allyl, methylhydroxy substituted cyclopententone ester of dimethyl- propenyl cyclopropane carboxylic acid 2,5-dichloro,3-amino benzoic acid cinnamic acid 2,-6-dichloro, 4-nitroaniline dichloro, isopropenyl an ilide dodecylguanidine monoaeetate trichlorophenyl acetic acid diphenyl ether, chlorophenyl derivative of the isobutyric acid ester of hydroxylacetonitrile trihydroxybenzoic acid 3-indolacetic acid 3 , 5-dichlor o-N-(3 , 3-dim ethylpr opyne)benzam ide dimethylphosphoramide ammonium salt napthalene acetamide dimethylethylphenoxy-cyclohexyl-2-propynyl sulfite o-phenylphenol phthalic acid chlorophenyl-isopropyl, propynyl carbamate N-phenyl,N-butynyl chloroacetam ide amino, chloro, phenyl derivative of azacyclohexamine N,N-diallyl-2-chloroacetamide aminoacetic acid derivative of methylphosphonate 3,5-dinitro,4-N,N-dipropylamino benzene sulfonamide 2-chloro-2-propenyl diethylcarbamodithioate and mixtures thereof. 6. The composition of claim 1 wherein said anti-fouling agent is selected from the group consisting of: acrolein phenylhydrazone alkyl dimethyl benzene ammonium saccharinate 2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one ester of 2,2-dimethyl-3-(2- methylpropenyl cyclopropanecarbox lic acid) 4-ally 1-2-m ethoxyphenol o-(allyloxy) phenyl methylcarbamate 2-(allylthio)-2-thiazoline l,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-2-norbornene 4-ethylam ino-6-isoprop lam ino-2-m ethylthio- 1,3, 5-tr iazine 2-amino-3-chloro-l,4-napthoquinone 3-amino-5-nitro-o-toluamide 3-amino-l,2,4-triazole ammonium sulfamate antimony potassium tartrate 2-chloro-4-ethylamino-6-isopropylamino-S-triazine 4-chloro-m-chlorocarbanilate 6-chloropiperonyl chrysanthemumate N-butyl-N-ethyl- ,^ ^trifluoro-2-6-dinitro-p-toluidine bis (p-chlorophenyl)-3-pyridine methanol bis (dialkylphosphinothioyl) disulfide bis (4-hydroxyiminomethyl pyridinum-1-methyl) ether dichloride 2,4-bis (3-methoxylpropylamino)-6-methylthio-S-triazine bis (pentachloro-2,4-cyclopentadien-l-yl) boric acid N-(4-bromo-3-chlorophenyD-N'-methoxy-N'-methyl urea 5-(bromomethyl)-l,2,3,4,7,7-hexachloro-2-norbornene S-(0,0-di isopropyl phosphoro-dithionate of N-(2-mercaptoethyl) benzenesulfonamide benzamidooxy-acetic acid 3-benzylideneamino-4-phenylthiazoline-2-thione bis (p-chlorophenoxy) methane bis (4-chlorophenyl) disulfide 1,1-bis (p-chlorophenyl) ethane 1,1-bis (p-chlorphenyl)-ethanol o,o-dimethyl-o-2,5-dichloro-4-bromophenylthionophosphate 0,0-dimethyl-2,2,2-trichloro-l-n-butyryloxyethyl phosphonate N-butylacetanilide 2-tert-butylamino-4-chloro-6-ethyl amino-5-triazine 2-tert-butylamino-4-ethylamino-6methylmercapto-S-triazine 4-tert-butyl-2-chlorophenylmethyl ethylphosphoramidite o-(4-tert-butyl-2-chlorophenyl)o-m ethyl phosphoramidothionate SUBSTITUTE SHEET butyl 3,4-dihydro-2, 2-dimethyl-4-oxo-l,2h-pyran-6-carboxylate n-butyl-9-hydroxyfluorene-(9)-carboxylate 2-(p-tert-butylphenoxy) cyclohexyl 2-propynyl sulfite l-butyn-3-yl m-chlorophenyl-carbamate N-trichloro-m ethylthio-4-cyclohexene- 1 ,2-docarboxim ide 1-napththyl n-methylcarbamate S-[[(p-chlorophenyl) thiol] methyl] 0,0-diethylphosphorodithioate 2-chloro-N,N-diallyl-acetamide 2-chloroallyl diethyl-dithiocarbamate cetyldim ethy lethy lam monium bromide cetyl pyridinium chloride tetrachloro-p-benzoquinone 2-chloro-4,6-bis(diethylamino)-s-triazine p-chlorobenzyl p-chlorophenyl sulfide l,2,3,5,6,-7,8,8-octachloro-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene l-(3-chlorallyl)-3,5,7-triaza-l-azoniaadamantane chloride ethyl 4,4'-dichlorobenzylate 5-chloro-2-benzothiazolethiol zinc " salt p-chlorobenzyl p-fluorophenyl sulfide l-chloro-N'-(3,4-dichlorophenyl) N,N-dimethylformamidine 4-chloro-3,5-dimethyl phenoxy-ethanol l,4-dichloro-2,5-dimethoxybenzene l-(chloro-2-norbornyl)-3,3-dimethylurea S-(p-chloro — phenylbenzyl) 0,0-diethyl phosphorodithioate p-chlorophenyl ester of benzene-sulfonic acid N-3-chlorophenyl-l-(isopropyl-carbamoyl-l)-ethyl carbamate 3-(p-chlorophenyl)-5-methyl rhodanine 4 (and 6)-chloro-2-phenylphenol sodium salt p-chlorophenyl phenyl sulfone 4-chlorophenyl 2,4,5-trichloro-phenylazosulfide N-(5-chloro-5-thiazolyl) propionamide 2-[4-chloro-o-tolyl)oxy] propionanilide 2-chloro-l-(2,4,5-trichloro-phenyl) vinyl dimethyl phosphate N*-(4-chlorophenoxy) phenyl N,N-dimethylurea isopropyl N-(3-chlorophenyl) carbamate copper (cupric) oleate copper 8-quinolinolate SUBSTITUTE SHEET 2-(2,4-dihydroxyphenyl)-l-cyclohexene-l-carboxylic acid- -lactone 0,-Odiethylphosphorothioate 2-chloro-4-dimethylamino-6-methylpyrimidine 3-(2-cyclopenten- 1 -yl)-2-m ethyl-4-oxo-2-cyclopenten- 1 -yl chrysanthemunate ov-cyclohexyl-Λ-phenyl-3-pyridyl-methanol, hydrochloride N'-cyclo-octyl-N,N-dimethylurea 3',4'-dichlorocyclopropanecarboxanilide 2,4-diehlorophenoxyacetic acid 2,4-d,ø(-chlorocrotyl ester 3,5-dimethyl-l,3,5,2H-tetrahydrothiadiazine-2-thione, tetra-hydro-3, 5-dimethyl-2H-l,3,5-thiadiazine-2-thione 4-(2,4-dichlorophenoxy) butyric acid dimethyl 2,3,5,6-tetra-chloroterephthalate decyltriphenylphosphonium-bromochlorotriphenylstannate dehydroacetic acid (and its sodium salt) tris and bis(2,4-dichlorophenoxyethyl) phosphite 2-methyl-thio-4-isopropylamino-6-methylamino-s-triazine S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate l,3-diaza-2, 4-cyclopentadiene N,N-di-n-butyl-p-chlorobenzene-sulfonamide 3,6-dichloro-o-anisic acid 0-(2-chloro-4-nitrophenyl) 0,0-dimethyl phosphorothioate 2,6-dichlorobenzonitrile 2,3-dichloro-l, 4-naphthoquinone l,3-bis(l-hydroxy-2,2,2-trichloroethyl) urea 3,4-dichlorobenzyl methylcarbamate (80%) mixture with 2,3-dichlorobenzyl methylcarbamate (20%) l,l-dichloro-2,2-bis (p-ethylphenyl)ethane 2,4-dichloro-6-(o-chloro-anilino)-s-triazine N- dichlorofluoromethylthioJ-N'N'-dimethyl-n-phenyl sulfamide 4,4'-dichloro-N-methylbenzene-sulfoanilide 2,3-dichloro-2-methylpropionic acid sodium salt 2,6-dichloro-4-nitroaniline 2,5-dichloro-3-nitrobenzoic acid 5,2'-dichloro-4'-nitro-salicylanilide ethanolamine salt 2',5'-dichloro-4'-nitrososalicylanilide 2,2'-dihydroxy-5,5'-dichlorophenylmethane SUBSTITUTE SHEET l-(2,4-dichlorophenoxyacetyl)-3,5-dimethyl pyrazole N-3,4-dichlorophenyl N'-5-chloro-2-(2-sodium sulfonyl-4-chlorophenoxy) phenyl urea 2,4-dichlorophenyl ester of benzene sulfonic acid 2,4-dichlorophenyl methanesulfonate 2,4-dichlorophenyl 4-nitrophenyl ether 4-dichlorotetrahydrothiophene 1,1-dioxide 4, 4'-dichloro-alpha-trichlor om ethy lbenzhydrol 3 , ,4'-dichloro-2-methacrylanilide c^Diethoxyphosphinothioylthio) gamma-butyrolactone 0,0-diethyl s-carboethoxy methyl phosphorothioate 0,0-diethyl O-naphthylamido phosphorothioate 0,0-diethyl 0-3,5, 6-trichloro-2-pyridyl phosphorothioate 2,2 , -dihydroxy-3,5,3 , ,5 , ,4"-pentachlorotriphenylmethane 2"-sodium sulfonate 0,0-diisopropyl s-diethyldithiocarbamoyl phosphorodithioate 2,4-dimethylbenzyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropane- carboxylate 0,0-dimethyl-S-2-(acetylamino)-ethyl dithiophosphate N-dimethylamino succinamic acid l,l-dimethyl-3-[3-(n-tert-butyl-carbamoyloxy)phenyI]urea 0,0-dimethyl s-carboethoxymethyl phosphorothioate 0,0-dimethyl 0-(3-chloro-4-nitrophenyl) phosphorothioate 0,0-dimethyl-o-p-cyanophenyl phosphorothioate o,o-dimethyl-s-[5-ethoxy-l,3,4-thiadiazol-2(3H)-onyl-(3)-methyIl phosphorodithioate N,N-dimethyl-N'-(2-methyl-4-chlorophenyl)-formamidine hydrochloride 0,0-dimethyl o-(4-nitro-m-tolyl) phosphorothioate o,s-dimethyl tetrachloro thiotere-phthalate 4'-dimethyltriazenoacetanilide dinitrocyclohexylphenol 2,4'-dinitro-4-trifluoromethyl diphenylether 2-( l-methyl-n-heptyl)-4,6-dinitrophenyl crotonate N ,N-dimethyl-2 ,2-diphenylacetam ide diphenylacetonitrile diphenylamine 2,6-dinitro-N,N-di-n-propyl-p-toluidine di-n-propyl-2,5-pyridine-dicarboxylate l,l'-ethylene-2,2 , -dipyridinium dibromide SUBSTITUTE SHEET 2,3-dicyano-l,4-dithia-anthraquinone 3-(3,4-dichlorphenyl)-l, 1-dimethyl-urea n-dodecyl thiocyanate n-dodecylguanidine acetate ethyl N,N-dipropylthiolcarbamate 2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate ethoxy ethylbis (p-chlorophenyl) carbinol l,2-dihydro-6-ethoxy-2,2,4-trimethylquinone ethyl-N,N-diisobutyl thiolcarbamate ethylenebis (dithiocarbamato) zinc 3-phenyl-l, 1-dimethylurea trichloroacetate ferric dimethyl-dithiocarbamate 0,0-dimethyl S-(N-formyl-N-methylcarbamoyl-methyl)phosphorodithioate 2-formyl-4-chlorophenoxyacetic acid 3-furfuryl-2-methyl-4-oxo-2-cyclopenten-l-yl chrysanthemunate 2-heptadecyl-2-imidazoline 7-chloro-4,6-dimethoxycoumaran-3-one-2-spiro- -(2 l -methoxy-6'-methylcyclo hex-2'-en-4'-one) l,l,l,3,3,3,-hexachloro-2-propanone l,5a,6,9,9a,9b-hexahydro-4a(4H)-dibenzofuran-carboxaldehyde 9-(p-n-hexyloxyphenyl)-10-methyl-acridinium chloride 2-hydroxymethyl-4-chloro-phenoxyacetic acid N-hydroxy-methyl-2,6-dichlorothiobenzamide Isopropyl N-phenylcarbamate isobornyl thiocyanoacetate isobutyl triphenylm ethy lam ine 5-bromo-3-isopropyl-6-methyluracil isopropyl-4,4'-diboromobenzilate isopropyl 4,4'-dichlorobenzilate isorpropyl mercaptophenyl-aeetate, 0,0-dimethyl phosphorodithioate 3-cyclohexyl-6,7-dihydro-lH-cyclopentapyrimidine-2,4(3H,5H)-dione 3-(3,4-dichlorophenyl)-l-methoxy-l-methylurea S-[l,2-bis(ethoxy-carbonyl)ethyl] 0,0-dimethyl phosphorodithioate manganese ethylenebisdithiocarbamate 4-ehloro-2-methylphenoxyacetic acid 2-(4-chloro-2-methylphenoxy) propionic acid sec-butyl 4(or 5)-chloro-2-methylcyelohexanecarboxylate SUBSTITUTE SHEET s-[(4,6-diamino-s-triazine-2-yl)methyl] 0,0-dimethyl phosphorodithioate 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthϊo-s-triazine 1,1, 1-tr ichloro-2 ,2-bis(p-m ethoxyphenyl) ethane 2-methoxy-4-isopropylamino-6-diethylamino-s-triazine S-(N-methoxymethylcarbamoylmethyl) dimethyl phosphorothiolothiononate alpha-methylbenzyl 3-(dimethoxy-phosphinyloxy)-cis-crotonate m-(l-methyl butyl) phenyl methyl-carbamate methyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate 3 ,3'-m ethyleneb is (4-hydroxycoumarin) 2,2'-methylenebis (3,4,6-trichlorophenol) 6-methyl-2-oxo-l,3-dithio(4,5-b)quinoxaline 0,0-dimethyl S-(2,5-dichlorophenyl-thio)-methyl phosphorodithioate 3(2-methylpiperidino)propyl-3,4-dichlorobenzoate 4-(methylsulfonyl)-2,6-dinitro-n,n-dipropylaniline methyl-2,3,5,6-tetrachloro-n-methoxy-n-methylterephthalamate O-methyl 0-(2,4,5-trichloro-phenyl) amidophosphorothiomate 3-(p-bromophenyl)-l-methyl-l-methoxyurea l,2-dihydropyridazine-3,6-dione 3,3'-ethylenebis-(tetrahydro-4,6-dimethyl-2H-l,3,5-thiadiazone-2-thione) S-ethyl hexahydro-lH-azepine-1-carbothioate 3-(p-chlorphenyl)-l, 1-dimethylurea 3-(p-chlorophenyl)-l, 1-dimethylurea trichloroacetate disodium ethylene bisdithiocarbamate l,2-dibromo-2,2-dichloroethyl dimethyl phosphate beta-naphthoxyacetic acid 3-(3,4-dichlorophenyl)-l-methyl-l-n-butylurea 3-(hexahydro-4,7-methanoindan-5-yl)-l, 1-dimethylurea N-1-naphthyl-phthalamic acid p-chlorophenyl p-phenyl 4-chlorobenzenesulfonate s-propylbutyl-ethylthiocarbamate phenothiazine ethyl mercapto-phenylacetate 0,0-dimethyl-phosphorodithioate n-phenyl-l-(ethylcarbamoyl-l) ethylcarbamate (d isomer) phosphoric acid, 2-chloro-l-(2,4,5-trichlorophenyl)vinyl dimethyl ester 4-amino-3,5,6-trichloropicolinic acid piperonyl-bis(2-[2'-n-butoxyethoxy] ethyl) acetal piperonyl butoxide alpha[2-(2-n-butoxyethoxy)-ethoxy] 4,5-methylenedioxy- SUBSTITUTE SHEET 2-propyltoluene piperonyl cyclonene polychlorobenzoic acid, dim ethy lam ine salt 2,4-bis-(isopropylamino)-6-methoxy-s-triazine 2-methyl-mercapto-4,6-bis(isopropylamino)-s-triazine 2-chloro-n-isopropylacetanilide S'^'-dichloropropionalide 2-chloro-4,6-bis(isopropyl-amino)-s-triazine di-n-propyl-3-methyl-6,7-methylenedioxy-l,2,3,4-tetra-hydronaphthalene-l,2- dicarboxylate 5-amino-4-chloro-2-phenyl-3(2H) pyridazinone pyrethrin I 8-quinolinol dimethyl 2,4,5-trichlorophenyl phosphorothionate salicylanilide l-(3,4-methylene-dioxyphenoxy)-3,6,9-trioxoundecane sodium 2-(2,4-dichlorophenoxy)ethyl sulfate l-(2-methyl-cyclohexyl)-3-phenylurea l-(2,4,5-trichlorophenoxy) propionic acid N'-chlor-2-methyl-p-valerotoluidide i,2-methylenedioxy-4-[2-(octylsulfinyl)propyIJ benzene methyl 3,4-dichlorocarbanilate 2,4,5-trichlorophenoxyacetic acid trichlorobenzyl chloride 2,2-bis(p-chlorophenyl)-l,l-dichloroethane ethylene-l,2-bis (thiocarbamoyldimethylthio-carbamoyldisulfide) 3-tert-butyl-5-chloro-6-methyluracil 2,6-di-tert-butyl-p-tolylmethylcarbamate 2,3,6, 7-tetrachloro-4a,8a-epoxy-l,2,3,4,4a,8a-hexahydro-l,4-methano- naphthalene-5,8-dione N-( 1 , 1 , 2 , 2-te trachlor o-ethyl-sulf enyl)-cis — 4-cyclohexene- 1 ,2-dicarboxi m ide 2,4,5, 6-tetrachloroiso-phthalonitrile l,2,4,5-tetrachloro-3-nitrobenzene p-chlorophenyl 2,4,5-trichlorophenyl sulfone 5,6,7, 8-tetrahydro-l-naphthyl methylcarbamate 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropanecarboxylate 0,0,0',0'-tetramethyl 0,0'-thiodi-p-phenylene phosphorothioate SUBSTITUTE SHEET 1,3,6, 8-tetranitr ocar bazole 2-(4-thiazolyl) benzimidazole 2,2'-thiobis(4,6-dichlorophenol) 2-thiocyanoethyl dodecanoate 2,3-quinoxaline-dithiol cyclic trithiocarbonate tetramethylthiuram disulfide N-meta-tolyl phthalamic acid S-2,3,3-trichloroallyl N,N-di-isopropyl-thiolcarbamate 0,0-dimethyl (l-hydroxy-2,2,2-trichloroethyl)phosphonate 2,3,6-trichlorobenzoic acid trichlorobenoic acid, dimethylamine salt 4,5,7-trichlorobenzthiadiazoIe-2,l,3 2,3,6-trichlorobenzyloxypropanol N-trichloromethylthio-benzothiazolone N-trichloromethylthiobenzoxazolone 2,2,2-trichloro-n-(pentachloro-phenyl)acetimidoyl chloride 2-(2,4,5-trichlorophenoxy)ethyl sulfate, sodium salt N,N'-N"-trichloro-2,4,6-triamine-l,3,5-triazine 2-chloro-4-(di-ethylamino)-6-(ethylamino)-s-triazine tert-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate S-propyldipropylthiocarbamate zinc ethylene bisdithiocarbamate zinc dimethyldithiocarbamate 3,5-diπitro-o-toluamide and mixtures thereof. 7. The composition of claim 1 wherein said anti-fouling agent is reacted with a coupling agent containing functionality for further reaction to form an oligomer or polymer bearing said anti-fouling agent. 8. The composition of claim 7 wherein said coupling agent has a molecular weight of less than about 300. 9. The composition of claim 7 wherein said coupling agent contains heteroatomic substituents selected from the group consisting of nitrogen, sulfur, or both. SUBSTITUTE SHEET 10. The composition of claim 1 which comprises a film-forming coating composition. 11. The composition of claim 5 wherein said anti-fouling agent is reacted with a coupling agent containing functionality for further reaction to form an oligomer or polymer bearing said anti-fouling agent. 12. The composition of claim 6 wherein said anti-fouling agent is reacted with a coupling agent containing functionality for further reaction to form an oligomer or polymer bearing said anti-fouling agent. 13. The composition of claim 1 wherein said anti-fouling agent is chemically or physically incorporated into cementitious surfaces. SUBST I TUTE SHEET

Inventors: DICK RICHARD J, MCGINNISS VINCENT D, DICK, RICHARD, J., MCGINNISS, VINCENT, D.
Applicants: BATTELLE MEMORIAL INSTITUTE
Application year: 1989
Main classification: C09D5
IPC codes: C09D5