Marine compositions bearing preferentially concentrated domains of non-tin, organo anti-fouling agents

Abstract

The present invention is addressed to a curable, marine anti-fouling composition of a thermoplastic or thermosetting binder, solvent, non-tin, organo antifouling agent, and optionally conventional additives, e.g. leaching agents, opacifying pigments, etc. The anti-fouling agents are found in preferentially-concentrated domains (hereinafter, often referred to as "PCD") in the cured compositions. The PCDs can be termed non-homogeneous, phase-separated, or incompatible in the system. The art term used in describing the PCDs of anti-fouling agent is not limitative of the invention as the disclosure herein will demonstate. Preferably, PCDs are created by forming an oligomeric adduct of the anti-fouling agent which adduct is formed into PCDs upon the curing of the composition. Additional techniques for forming PCDs of anti-fouling agent are revealed herein. The present invention also is addressed to new, low toxicity anti-fouling agents which comprise pesticide or herbicide compounds having a X factor 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 ketones, certain phospho compounds, certain polychlorinated carbocyclic and acyclic compounds, certain chlorinated carbocyclic carboxylates, 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.

Description

BACKGROUND OF THE INVENTION

The present invention relates to anti-fouling marine coatings and more particularly to novel low toxicity anti-fouling agents therefor. 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.

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 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 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 Cu.sub.2 O particles will be in continuous contact with each other. Below the level of cubic packing (52%), the resin will encase the Cu.sub.2 O 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 natural resins and extender pigments are frequently used. When high levels of rosin are used and high erosion might be expected, tougheners such as ester gum, ethyl cellulose, and modified rubbers are added. (Paint Handbook, G. E. Weismantel, McGraw-Hill, New York, N.Y., pp 14-43 and 14-44; and R. J. Dick, Marine Paints, Chapter 14).

With respect to the toxins presently used in marine anti-fouling paints, 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. Prior proposals include, for example, Japanese Patents 56156202 and 52117425 report the use of a combination of a napthoquinone and a thiuram disulphide in order to obtain anti-fouling activity, while Japanese Patent 63243067 proposes the use of diphenylamines. Despite these proposals, there still is a substantial need in the anti-fouling arena for new, low toxicity anti-fouling coatings, caulks, and the like.

BROAD STATEMENT OF THE INVENTION

The present invention is addressed to a curable, marine anti-fouling composition of a thermoplastic or thermosetting binder, solvent, non-tin, organo antifouling agent, and optionally conventional additives, e.g. leaching agents, opacifying pigments, etc. The anti-fouling agents are found in preferentially-concentrated domains (hereinafter, often referred to as "PCD" or "PCDs") in the cured compositions. The PCDs can be termed non-homogeneous, phase-separated, or incompatible in the system. The art term used in describing the PCDs of anti-fouling agents is not limitative of the invention as the disclosure herein will demonstrate. Preferably, PCDs are created by forming an oligomeric adduct of the anti-fouling agent which adduct is formed into PCDs upon the curing of the composition. Additional techniques for forming PCDs of anti-fouling agent will be revealed herein.

The present invention also is addressed to the use of new, low toxicity anti-fouling agents which comprise pesticide or herbicide compounds having a X 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 ketones, certain phospho compounds, certain polychlorinated carbocyclic and acyclic compounds, certain chlorinated carbocyclic carboxylates, 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.

Advantages of the present invention include the ability to formulate marine anti-fouling compositions which contain low-toxicity antifouling agents. Another advantage is the ability to formulate marine antifouling coating compositions wherein the low-toxicity anti-fouling agents display improved effectiveness by virtue of being formed in PCDs. These and other advantages will be readily apparent to those skilled in the art based upon the disclosure contained herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a scanning electron micrograph (SEM) at 10,000 X of the cured epoxy resin composition of Example 16 containing an organo toxicant freely-dispersed therein;

FIG. 2 is an SEM at 10,000 X of a cured epoxy resin composition of Example 16 containing the same organo toxicant free-dispersed therein and a domain-forming polysulfide polymer;

FIG. 3 is a pictorial representation of the SEM results of FIG. 2;

FIG. 4 is an SEM at 250 X of a cured epoxy resin composition of Example 16 containing a polymer of the same organo toxicant and the polysulfide polymer of FIG. 2 which product forms discrete domains;

FIG. 5 is an Energy Dispersion Spectroscopy analysis for the chlorine content of the organo toxicant polymer domains of FIG. 4;

FIG. 6 is an Energy Dispersion Spectroscopy analysis for the sulfur content of the organo toxicant polymer domains of FIG. 4;

FIGS. 7 and 8 are SEMs at 500 X and 2,500 X, respectively, showing the domain structures formed in a continuous PVC binder by the domain creating acrylic polymers and organo toxicant monomer described in Example 17;

FIG. 9 is an optical micrograph (SEM) at 1,500 X of the sample of FIGS. 7 and 8;

FIG. 10 is an Energy Dispersion Spectroscopy analysis at 1,500 X for the oxygen content of the sample of FIGS. 7-9;

FIG. 11 is an optical micrograph at 2,000 X of the sample of FIGS. 7 and 8;

FIG. 12 is an Energy Dispersion Spectroscopy analysis at 2,000 X for the oxygen content of the sample of FIGS. 7-9;

FIG. 13 is an optical micrograph at 200 X showing the domain structures formed in a continuous epoxy resin by LP-32 polysulfide resin of Example 18; and

FIGS. 14-15 are Energy Dispersion Spectroscopy maps at 200 X for chlorine and sulfur, respectively, of the resin system of FIG. 13.

DETAILED DESCRIPTION OF THE INVENTION

With the curtailment in permissible use of organo-tin anti-fouling agents due to their human toxicity characteristics, the art truly needs to enable anti-fouling agents which exhibit low human toxicity characteristics. Once such agents are identified, they must be compatible with remaining formulation ingredients in marine coatings and other marine compositions. Also, these low toxicity anti-fouling agents must display efficacy characteristics making them practical. Use of the non-tin, organo anti-fouling agents in a marine composition will provide a modicum of protection to the substrate to which the composition is applied, yet enhanced, long-term protection is desired. Unexpectedly, it was discovered that enhanced activity for extended periods of time could be achieved by controlling the physical form in which the anti-fouling agents were presented in the cured marine compositions. Phase separation was the term initially used to define such physical form. Later, the term "preferentially-concentrated domains" was adopted due to the variety of techniques developed for achieving the desired physical form of the anti-fouling agents. Thus, islands, pools, or domains where the anti-fouling agents concentrate are created in the cured composition. Such domains typically will be the size of from about 0.3.mu. to 500.mu. (micrometers).

Techniques for achieving anti-fouling PCDs initially focused on chemically linking the anti-fouling agent with an oligomer or polymer that phase-separated in the cured composition. This technique has the additional advantage in preventing the anti-fouling agent from prematurely being leached from the cured composition resulting in loss of anti-fouling effectiveness. Other techniques envisioned include, for example, dispersing an anti-fouling agent soluble (or compatible) with a compound which compound itself is incompatible or domain-forming in the continuous phase of the composition. Such incompatible compound forms discrete domains in the cured composition which domains are enriched in the anti-fouling agent compared to the continuous phase of the cured composition. Besides chemically linking the anti-fouling agent with an oligomer or polymer, the anti-fouling agent could complex or otherwise associate with a compound incompatible with the continuous phase of the composition. So long as PCDs of the anti-fouling agent are formed in the cured composition, the precepts of the present invention have been practiced.

Conventional non-tin, organo anti-fouling agents may be used in the present invention for forming PCDs thereof. The preferred non-tin anti-fouling agents useful in the present invention, however, broadly are selected from compounds which have exhibited terrestrial biologic activity, e.g. known herbicides and pesticides. For present purposes, herbicides are to be interpreted broadly as including not only compounds which selectively and/or broadly kill various plant life, but also include various plant growth regulators, algicides, and the like. Pesticides, for present purposes, also should be broadly interpreted as compounds which are selectively and/or broadly toxic or harmful plant infestations, such as acaricides. These compounds, however, must exhibit low toxicity to humans. For present purposes, "low toxicity to humans" is determined when the LD50 value is greater than 200 mg/kg against rats or mice wherein LD50 is defined as the lethal oral dose which is expected to kill 50% of the population of a test group of adult male rats or mice.

Within the broad spectrum of biologically active compounds described above, these compounds also must possess a X factor of between about 0.01 and 3, and a Z value for vinyl or aromatic compounds of between 0.01 and 0.08. The X factor is based upon the McGinniss predictive relationship as defined in Organic Coatings in Plastic Chemistry, Vols. 39 and 46, pp 529-543 and 214-223, respectively (1978 and 1982, respectively). The McGinniss predictive relationship defines the X factor as a weight fraction of heteroatoms contained in the monomer or in the monomer repeat unit of an oligomer or polymer. The McGinniss predictive relationship defines the Z parameter as the weight fraction of .pi. electrons contained in the monomer or in the monomer repeat unit of an oligomer or polymer (e.g. .pi. 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 compounds which display anti-fouling characteristics in marine coatings.

Though such compounds will exhibit anti-fouling characteristics, not all may be totally acceptable for all applications such as, for example, some high performance marine coatings requirements, e.g. submarine exterior coatings. Nevertheless, the compounds will possess anti-fouling characteristics and low toxicity to humans which makes their identification significant in the art's efforts at replacing conventional organo-tin anti-fouling agents.

The following biologically-active compounds illustrate the LD50 values, X factor, and Z parameter requirements possessed by the disclosed 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) ##STR1## LD50 Value of 2,000 mg/kg (rats) .chi. factor (O) of 0.195 Z parameter of 0.052. diphenylacetonitrile ##STR2## LD50 Value of 3,500 mg/kg (rats) .chi. factor (nitrogen) of 0.072 Z parameter of 0.0623. 2,3-dichloro-1,4-napthoquinone ##STR3## LD50 Value of 1500 mg/kg (rats) .chi. factor (Cl) of 0.313 .chi. factor (O) of 0.141 Z parameter of 0.0354. cetylpyridinium chloride ##STR4## LD50 Value of 200 mg/kg (rats) .chi. factor (N) of 0.04 .chi. factor (Cl) of 0.10 Z parameter of 0.1725. diphenylamine ##STR5## Low mammalian toxicity .chi. factor (N) of 0.083 Z parameter of 0.0716. boric acid B(OH).sub.3 LD50 of 3,000 mg/kg (rats) .chi. factor (O) of 0.777 .chi. factor (B) of 0.1757. 2-chloro-N,N-diallylacetamide ##STR6## LD50 value of 700 mg/kg (rats) .chi. factor (Cl) of 0.205 .chi. factor (O) of 0.092 .chi. factor (N) of 0.081 Z parameter of 0.0238. cetyltrimethylammonium bromide ##STR7## LD50 value of 500 mg/kg (rats) .chi. factor (N) of 0.038 .chi. factor (Br) of 0.229. 2-isopropylamino-4-chloro-6-ethylamino triazine ##STR8## LD50 value of 1869 mg/kg (rats) .chi. factor (N) of 0.325 .chi. factor (Cl) of 0.244 Z parameter of 0.04110. dimethoxythiophosphate derivative of diphenyl sulfide ##STR9## LD50 value of 2030 mg/kg (rats) .chi. factor (O) of 0.21 .chi. factor (S) of 0.21 .chi. factor (P) of 0.13 Z parameter of 0.01311. ethyl 4-chloro-alpha(4-chlorophenyl)alpha-hydroxy benzene acetate ##STR10## LD50 value of 5,000 mg/kg (rats) .chi. factor (O) of 0.18 .chi. factor (C) of 0.27 Z parameter of 0.02212. methyl, diethylamino, dimethoxythiophosphate derivative of pyrimidine ##STR11## LD50 value of 2,000 mg/kg (rats) .chi. factor (O) of 0.16 .chi. factor (N) of 0.14 .chi. factor (S) of 0.105 .chi. factor (P) of 0.102 Z parameter of 0.00713. ethoxylated nonylphenol ##STR12## LD50 value of 4,000 .chi. factor (O) of 0.25 Z parameter of 0.010514. unsymmetrical hydrazine derivative of succinic acid ##STR13## LD50 value of 8400 .chi. factor (O) of 0.30 .chi. factor (N) of 0.17515. allyl, methylhydroxy substituted cyclopententone ester of dimethylpropenyl cyclopropane carboxylic acid ##STR14## LD50 value of 1,000 .chi. factor (O) of 0.11 Z parameter of 0.02116. 2,5-dichloro,3-amino benzoic acid ##STR15## LD50 value of 5,620 .chi. factor (O) of 0.155 .chi. factor (N) of 0.068 .chi. factor (Cl) of 0.345 Z parameter of 0.01517. cinnamic acid ##STR16## .chi. factor (O) of 0.216 Z parameter of 0.05418. 2,-6-dichloro, 4-nitroaniline ##STR17## LD50 value of 5,000 .chi. factor (O) of 0.155 .chi. factor (N) of 0.135 .chi. factor (Cl) of 0.343 Z parameter of 0.02919. dichloro, isopropenyl anilide ##STR18## .chi. factor (O) of 0.070 .chi. factor (N) of 0.061 .chi. factor (Cl) of 0.309 Z parameter of 0.03520. dodecylguanidine monoacetate ##STR19## LD50 value of 1,000 .chi. factor (O) of 0.111 .chi. factor (N) of 0.14621. trichlorophenyl acetic acid ##STR20## LD50 value of 1,780 .chi. factor (O) of 0.134 .chi. factor (Cl) of 0.445 Z parameter of 0.02522. diphenyl ether, chlorophenyl derivative of the isobutyric acid ester of hydroxyacetonitrile ##STR21## LD50 value of 451 (toxic to fish) .chi. factor (O) of 0.114 .chi. factor (N) of 0.033 .chi. factor (Cl) of 0.085 Z parameter of 0.04323. trihydroxybenzoic acid ##STR22## .chi. factor (O) of 0.471 Z parameter of 0.03524. 3-indolacetic acid ##STR23## .chi. factor (O) of 0.198 .chi. factor (N) of 0.086 Z parameter of 0.03725. 3,5-dichloro-N-(3,3-dimethylpropyne)benzamide ##STR24## LD50 value (dermal) of 8,350 .chi. factor (O) of 0.063 .chi. factor (N) of 0.055 .chi. factor (Cl) of 0.278 Z parameter of 0.03926. dimethylphosphoramide ammonium salt ##STR25## LD50 value (dermal) of 2,400 .chi. factor (O) of 0.276 .chi. factor (N) of 0.165 .chi. factor (P) of 0.18227. napthalene acetamide ##STR26## LD50 value of 1,000 .chi. factor (O) of 0.086 .chi. factor (N) of 0.076 Z parameter of 0.06528. dimethylethylphenoxy-cyclohexyl-2-propynyl sulfite ##STR27## LD50 value of 2,200 .chi. factor (O) of 0.146 .chi. factor (S) of 0.098 Z parameter of 0.03429. o-phenylphenol ##STR28## LD50 value of 2,700 .chi. factor (O) of 0.094 Z parameter of 0.07130. phthalic acid ##STR29## .chi. factor (O) of 0.386 Z parameter of 0.03631. chlorophenyl-isopropyl, propynyl carbamate ##STR30## .chi. factor (O) of 0.064 .chi. factor (N) of 0.112 .chi. factor (Cl) of 0.142 Z parameter of 0.04032. N-phenyl,N-butynyl chloroacetamide ##STR31## LD50 value of 1,177 .chi. factor (O) of 0.072 .chi. factor (N) of 0.063 .chi. factor (Cl) of 0.160 Z parameter of 0.04533. amino, chloro, phenyl derivative of azacyclohexamine ##STR32## LD50 value of 3,030 .chi. factor (O) of 0.073 .chi. factor (N) of 0.190 .chi. factor (Cl) of 0.161 Z parameter of 0.03634. N,N-diallyl-2-chloroacetamide ##STR33## LD50 value of 750 .chi. factor (O) of 0.092 .chi. factor (N) of 0.081 .chi. factor (Cl) of 0.205 Z parameter of 0.02335. aminoacetic acid derivative of methylphosphonate ##STR34## LD50 value of 4,300 .chi. factor (O) of 0.473 .chi. factor (N) of 0.083 .chi. factor (P) of 0.18336. 3,5-dinitro,4-N,N-dipropylamino benzene sulfonamide ##STR35## LD50 value of 10,000 .chi. factor (O) of 0.277 .chi. factor (N) of 0.162 .chi. factor (S) of 0.092 Z parameter of 0.01737. 2-chloro-2-propenyl diethylcarbamodithioate ##STR36## LD50 value of 850 .chi. factor (N) of 0.064 .chi. factor (S) of 0.294 .chi. factor (Cl) of 0.163 Z parameter of 0.0092______________________________________

As the data will demonstrate, the foregoing biologically-active compounds display efficacy as anti-fouling agents. Their diminished toxicity to humans is a decided benefit compared to conventional organo-fin anti-fouling agents.

Broadly, the low toxicity anti-fouling agents of the present invention can 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 X value and Z parameter also may find use as anti-fouling agents in accordance with the precepts of the 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 antifouling 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-1-one ester of 2,2-dimethyl-3-(2methylpropenyl cyclopropanecarboxylic acid) 4-allyl-2-methoxyphenol o-(allyloxy) phenyl methylcarbamate 2-(allylthio)-2-thiazoline 1,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-2-norbornene 4-ethylamino-6-isopropylamino-2-methylthio-1,3,5-triazine 2-amino-3-chloro-1,4-napthoquinone 3-amino-5-nitro-o-toluamide 3-amino-1,2,4-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-.alpha.,.alpha.,.alpha.-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-1-yl) boric acid N-(4-bromo-3-chlorophenyl)-N'-methoxy-N'-methyl urea 5-(bromomethyl)-1,2,3,4,7,7-hexachloro-2-norbornene S-(O,O-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 O,O-dimethyl-2,2,2-trichloro-1-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 methylphosphoramidite o-(4-tert-butyl-2-chlorophenyl)o-methyl phosphoramidothionate butyl 3,4-dihydro-2,2-dimethyl-4-oxo-1,2h-pyran-6-carboxylate n-butyl-9-hydroxyfluorene-(9)-carboxylate 2-(p-tert-butylphenoxy) cyclohexyl 2-propynyl sulfite 1-butyn-3-yl m-chlorophenyl-carbamate N-trichloro-methylthio-4-cyclohexene-1,2-docarboximide 1-napththyl n-methylcarbamate S-[[(p-chlorophenyl) thiol]methyl]O,O-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 1-(3-chlorallyl)-3,5,7-triaza-1-azoniaadamantane chloride ethyl 4,4'-dichlorobenzylate 5-chloro-2-benzothiazolethiol zinc salt p-chlorobenzyl p-fluorophenyl sulfide 1-chloro-N'-(3,4-dichlorophenyl) N,N-dimethylformamidine 4-chloro-3,5-dimethyl phenoxy-ethanol 1,4-dichloro-2,5-dimethoxybenzene 1-(chloroo2-norbomyl)-3,3-dimethylurea S-(p-chloro-.alpha.-phenylbenzyl) O,O-diethyl phosphorodithioate p-chlorophenyl ester of benzene-sulfonic acid N-3-chlorophenyl-1-(isopropyl-carbamoyl-1)-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-1-(2,4,5-trichloro-phenyl) vinyl dimethyl phosphate N'-(4-chlorophenoxy) phenyl N,N-dimethylurea Isopropyl N-(3-chlorophenyl) carbamate Copper (cuprio) oleate Copper 8-quinolinolate 2-(2,4-dihydroxyphenyl)-1-cyclohexene-1-carboxylic acid-lactone O,O-diethylphosphorothioate 2-chloro-4-dimethylamino-6-methylpyrimidine 3-(2-cyclopenten-1-yl)-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemunate .alpha.-cyclohexyl-phenyl-3-pyridyl-methanol, hydrochloride N'-cyclo-octyl-N,N-dimethylurea 3',4'-dichlorocyclopropanecarboxanilide 2,4-dichlorophenoxyacetic acid 2,4-d,.alpha.-chlorocrotyl ester 3,5-dimethyl-1,3,5,2H-tetrahydrothiadiazine-2-thione, tetra-hydro-3,5-dimethyl-2H-1,3,5-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 1,3-diaza-2,4-cyclopentadiene N,N-di-n-butyl-p-chlorobenzene-sulfonamide 3,6-dichloro-o-anisic acid 0-(2-chloro-4-nitrophenyl) O,O-dimethyl phosphorothioate 2,6-dichlorobenzonitrile 2,3-dichloro-1,4-naphthoquinone 1,3-bis(1-hydroxy-2,2,2-trichloroethyl) urea 3,4-dichlorobenzyl methylcarbamate (80%) mixture with 2,3-dichlorobenzyl methylcarbamate (20%) 1,1-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 1-(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 .alpha.(Diethoxyphosphinothioylthio) gamma-butyrolactone O,O-diethyl s-carboethoxymethyl phosphorothioate O,O-diethyl O-naphthylamido phosphorothioate O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate 2,2'-dihydroxy-3,5,3',5',4"-pentachlorotriphenylmethane 2"-sodium sulfonate O,O-diisopropyl s-diethyldithiocarbamoyl phosphorodithioate 2,4-dimethylbenzyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropanecarboxylate O,O-dimethyl-S-2-(acetylamino)-ethyl dithiophosphate N-dimethylamino succinamic acid 1,1-dimethyl-3-[3-(n-tert-butyl-carbamoyloxy)phenyl]urea O,O-dimethyl s-carboethoxymethyl phosphorothioate O,O-dimethyl O-(3-chloro-4-nitrophenyl) phosphorothioate O,O-dimethyl-o-p-cyanophenyl phosphorothioate o,o-dimethyl-s-[5-ethoxy-1,3,4-thiadiazol-2(3H)-onyl-(3)-methyl]phosphorodithioate N,N-dimethyl-N'-(2-methyl-4-chlorophenyl)-formamidine hydrochloride O,O-dimethyl o-(4-nitro-m-tolyl) phosphorothioate o,s-dimethyl tetrachloro thiotere-phthalate 4'-dimethyltriazenoacetanilide dinitrocyclohexylphenol 2,4'-dinitro-4-trifluoromethyl diphenylether 2-(1-methylon-heptyl)-4,6-dinitrophenyl crotonate N,N-dimethyl-2,2-diphenylacetamide diphenylacetonitrile diphenylamine 2,6-dinitro-N,N-di-n-propyl-p-toluidine Di-n-propyl-2,5-pyridine-dicarboxylate 1,1'-ethylene-2,2'-dipyridinium dibromide 2,3-dicyano-1,4-dithia-anthraquinone 3-(3,4-dichlorphenyl)-1, 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 1,2-dihydro-6-ethoxy-2,2,4-trimethylquinone ethyl-N,N-diisobutyl thiolcarbamate ethylenebis (dithiocarbamato) zinc 3-phenyl-1,1-dimethylurea trichloroacetate ferric dimethyl-dithiocarbamate O,O-dimethyl S-(N-formyl-N-methylcarbamoyl-methyl)phosphorodithioate 2-formyl-4-chlorophenoxyacetic acid 3-furfuryl-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemunate 2-heptadecyl-2-imidazoline 7-chloro-4,6-dimethoxycoumaran-3-one-2-spiro-1'-(2'-methoxy-6'-methylcyclohex-2'-en-4'-one) 1,1,1,3,3,3,-hexachloro-2-propanone 1,5a,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 isobomyl thiocyanoacetate isobutyl triphenylmethylamine 5-bromo-3-isopropyl-6-methyluracil isopropyl-4,4'-diboromobenzilate isopropyl 4,4'-dichlorobenzilate isopropyl mercaptophenyl-acetate, O,O-dimethyl phosphorodithioate 3-cyclohexyl-6,7-dihydro-1H-cyclopentapyrimidine-2,4(3H,5H)-dione 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea S-[1,2-bis(ethoxy-carbonyl)ethyl]O,O-dimethyl phosphorodithioate manganese ethylenebisdithiocarbamate 4-chloro-2-methylphenoxyacetic acid 2,6-(4-chloro-2-methylphenoxy) propionic acid sec-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate s-[(4,6-diamino-s-triazine-2-yl)methyl]O,O-dimethyl phosphorodithioate 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthio-s-triazine 1,1,1-trichloro-2,2-bis(p-methoxyphenyl) ethane 2-methoxy-4-isopropylamino-6-diethylamino-s-triazine S-(N-methoxymethylcarbamoylmethyl) dimethyl phosphorothiolothiononate alpha-methylbenzyl 3-(dimethoxy-phosphinyloxy)-cis-crotonate m-(1-methyl butyl) phenyl methyl-carbamate methyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate 3,3'-methylenebis (4-hydroxycoumarin) 2,2'-methylenebis (3,4,6-trichlorophenol) -methyl-2-oxo-1,3-dithio(4,5-b)quinoxaline O,O-dimethyl S-(2,5-dichlorophenyl-thio)-methyl phosphorodithioate (2-methylpiperidino)propyl-3,4-dichlorobenzoate 6-(methylsulfonyl)-2,6-dinitro-n,n-dipropylaniline methyl-2,3,5,6-tetrachloro-n-methoxy-n-methylterephthalamate O-methyl O-(2,4,5-trichloro-phenyl) amidophosphorothiomate 3-(p-bromophenyl)-1-methyl-1-methoxyurea 1,2-dihydropyridazine-3,6-dione 3,3'-ethylenebis-(tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazone-2-thione) S-ethyl hexahydro-1H-azepine-1-carbothioate 3-(p-chlorphenyl)-1,1-dimethylurea 3-(p-chlorophenyl)-1,1-dimethylurea trichloroacetate disodium ethylene bisdithiocarbamate 1,2-dibromo-2,2-dichloroethyl dimethyl phosphate beta-naphthoxyacetic acid 3-(3,4-dichlorophenyl)-1-methyl-1-n-butylurea 3-(hexahydro-4,7-methanoindan-5-yl)-1,1-dimethylurea N-1-naphthyl-phthalamic acid p-chlorophenyl p-phenyl 4-chlorobenzenesulfonate s-propylbutyl-ethylthiocarbamate phenothiazine ethyl mercapto-phenylacetate O,O-dimethyl-phosphorodithioate n-phenyl-1-(ethylcarbamoyl-1) ethylcarbamate (d isomer) phosphoric acid, 2-chloro-1-(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 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-1,2,3,4-tetra-hydronaphthalene-1,2dicarboxylate 5-amino-4-chloro-2-phenyl-3(2H) pyridazinone pyrethrin I 8-quinolinol dimethyl 2,4,5-trichlorophenyl phosphorothionate salicylanilide 1-(3,4-methylene-dioxyphenoxy)-3,6,9-trioxoundecane sodium 2-(2,4-dichlorophenoxy)ethyl sulfate 1-(2-methyl-cyclohexyl)-3-phenylurea 1-(2,4,5-trichlorophenoxy) propionic acid N'-chlor-2-methyl-p-valerotoluidide 1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene methyl 3,4-dichlorocarbanilate 2,4,5-trichlorophenoxyacetic acid trichlorobenzyl chloride 2,2-bis(p-chlorophenyl)-1,1-dichloroethane ethylene-1,2-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-1,2,3,4,4a,8a-hexahydro-1,4-methanonaphthalene 5,8-dione N-(1,1,2,2-tetrachloro-ethyl-sulfenyl)-cis-.alpha.-4-cyclohexene-1,2-dicarboximide 2,4,5,6-tetrachloroiso-phthalonitrile 1,2,4,5-tetrachloro-3-nitrobenzene p-chlorophenyl 2,4,5-trichlorophenyl sulfone 5,6,7,8-tetrahydro-1-naphthyl methylcarbamate 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropanecarboxylate O,O,O',O'-tetramethyl O,O'-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 O,O-dimethyl (1-hydroxy-2,2,2-trichloroethyl)phosphonate 2,3,6-trichlorobenzoic acid trichlorobenoic acid, dimethylamine salt 4,5,7-trichlorobenzthiadiazole-2,1,3 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-1,3,5-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-dinitro-o-toluamide.

Linking of the anti-fouling agent with an oligomer or polymer can be accomplished by a variety techniques, depending upon the available functionality of the anti-fouling agent. For example, ethylenic unsaturation in the anti-fouling agent can be copolymerized with acrylate or other ethylenically-unsaturated monomers in conventional fashion. See, for example, Acrylic Monomer, product literature, Dow Badishce Company, Form No. A-GB-101; Preparation, Properties and Uses of Acrylic Polymers, product literature, Rohm and Haas Company, Form CM-19 B/eh; and U.S. Pat. No. 4,566,962, the disclosures of which are expressly incorporated herein by reference. Anti-fouling agents with reactive hydroxyl or other active hydrogen functionality (e.g., --NH, --NH.sub.2, --SH, or the like) can be reacted with a polyisocyanate for forming an anti-fouling agent adduct. See, for example, Macromolecular Synthesis, C. G. Overberger, Editor, Vol. 1, pp 69-74, John Wiley & Sons, Inc., New York, N.Y. (1963), the disclosure of which is expressly incorporated herein by reference. Additional reactions will be readily apparent to those skilled in such art, as stated above, depending upon the reactive functionality in the anti-fouling agent.

Additional techniques for forming PCDs include, for example, complexing (association or other mechanism) of the anti-fouling agent with another ingredient in the formulation, e.g., pigment, polymer or oligomer additive, or the like. Another technique involves the anti-fouling agent being relatively more miscible in a discontinuous phase (or particles), than in the continuous phase of the coating. Again, PCDs would be formed. Regardless or the technique, so long as PCDs of the anti-fouling agent are formed in the final product, improved long-term anti-fouling activity will be expressed by the anti-fouling agents.

The formulation of the marine compositions 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, for example, coatings, elastomers, sealants, caulks, grouts, concretes, 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, or as a three-dimensional configured structure such as villous trailing fingers in the exterior of marine vessels. 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

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), potassium hydroxide (80 g), and dimethyl sulfoxide (100 ml). The reaction mixture was heated for three hours to a temperature of 105.degree. C., cooled to room temperature, washed, and subjected to vacuum for removal of solvent. The resulting polymeric structure 45701-1 can be represented conventionally as follows: ##STR37##

Example 2

An anti-fouling agent-modified adduct was synthesized in accordance with the following reaction scheme. Toluene (100 ml) was added to a roundbottomed 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.degree. 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 45701-3 which is illustrated conventionally below. ##STR38##

Example 3

A pressure reactor fitted with a pressure gauge was loaded with 3(3,4-dichlorophenyl)-1,1-dimethyl urea (45 g) 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 and showed broadening of the NH bands and the presence of hydroxyl functionality and some polyether functionality (1100 cm-1). Preparation of this material is similar to that preparation described in J. Polymer Science, vol. 15, 427-446 (1955). Reaction production 45701-4 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. ##STR39##

Example 4

To 1,4,5,6,7,7-hexachloro-5-norborene-2,3-dicarboxylic anhydride (37 g) was added hydroxyethyl methacrylate (37 ml). This reaction mixture was heated to 87.degree. C. for three hours to produce reaction product 45701-5 which can be represented conventionally as follows: ##STR40##

Example 5

Addition of a 10% solution of CuCl.sub.2 in ethanol to a 10% solution of 8-hydroxyquinoline formed a dark brown complex immediately. This complex 45701-6 was washed with hexane and dried without further purification. The structure of the complex can be represented conventionally as follows: ##STR41##

Example 6

The procedure of Example 2 was repeated using 2,5-dichloroanaline instead of 3,4-dichloroanaline. Reaction product 45701-7 is illustrated below: ##STR42##

Example 7

1,5-napthalene diisocyanate (25 g) was reacted with 1,3-diaza-2,4cyclopentadiene (14 g) using the urethane reaction procedure as set forth in Example 2. The resulting reaction product 45701-8 is represented conventionally below: ##STR43##

Example 8

To DER 331 epoxy resin (Dow epoxy resin, about 300 molecular weight, epoxide equivalent of 150, 33 g, The Dow Chemical Company, Midland, Mich.) was added 35 ml of toluene and phenothiazine (40 g). This mixture was heated to 90.degree. C. for three hours until a clear solution was obtained. The product was used without any further purification. Reaction product 45701-8 can be illustrated conventionally below: ##STR44##

Example 9

Two different modified polymeric structures were prepared. Polymeric structure 45701-10 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.degree. C. for three hours until a clear solution was obtained. The second polymeric structure identified as 45701-11 was prepared by the same reaction procedure utilizing morpholine in place of 2-mercaptobenzothiazole. Both structures can be represented conventionally below. ##STR45##

Example 10

In order to demonstrate the affect which PCDs of organo anti-fouling display, anti-fouling formulations (Control Paint) were compounded as follows:

TABLE 1______________________________________ Amount (wt-parts)Ingredient #1 #2______________________________________Laroflex MP-45 copolymer of 3 3vinyl chloride and vinyl isobutylether (75/25), BASF WyandotteRosin 10 10Epikote 828 X90 (bis-phenol A 0.1 0.1epoxy resin, CelaneseSpecialty Chemicals)Red Iron oxide 5 5Silica 20 20Nopocide (1,2-dicyano-tetra- 20 --chlorobenzene)Anti-fouling agent 45701-1 -- 20(Example 1)Bentone 34 1 1Xylene 50 50______________________________________

Test panels were 15.24 cm.times.30.48 cm (6 in.times.12 in) in dimension and were constructed of a white plastic top surface and a black plastic bottom surface. The test panels were coated on both sides with the two formulations above-tabulated 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, Fla., U.S.A. A control panel consisted of 12 wt-% triphenyl tin hydroxide dispersed in a resinous vinyl binder (80 wt-parts of a vinyl chloride polymer, VAGH brand, Union Carbide Corporation, New York, N.Y.) reduced in methyl ethyl ketone solvent to 50% solids content. After exposure, the control and test panels were inspected and assigned a numerical rating from 0 to 10 based on the amount of surface area of the panel that was free from fouling, a rating of "10" corresponding to perfect protection. The following results were recorded.

______________________________________ Rating After Exposure *Sample 4 Months 462 Days______________________________________Control Paint- 0 0No Anti-Fouling AdditiveControl Paint- 0 0Nopocide Freely Addedat 20 wt-%Control Paint- 9 7Polymeric Additive45701-1 at 20 wt-%______________________________________ * 10 is perfect protection

That the above-tabulated results demonstrate that the polymeric anti-fouling agent displayed improved panel protection compared to the same agent added neat to the marine paint formulation. As later examples will confirm, the polymeric anti-fouling agent was in the form a PCDs in the cured paint.

Example 11

The Control Paint of Example 10 was formulated with additional polymeric and as-is anti-fouling additives and evaluated as in Example 10, with the following results being recorded:

TABLE 3______________________________________Sample Rating After Exposure *(Additive at 20 wt-%) 4 Months 462 Days______________________________________Control Paint 0 0No Anti-Fouling AdditiveControl Paint- 0 03,4-DichloroanilineControl Paint- 0 02,5-DichloroanilineControl Paint- 0 02,6-Dichloro-4-NitroanilineControl Paint- 5-6 5-63,4-Dichloroaniline Polymerof Example 2Control Paint- 1-2 12,5-Dichloroaniline Polymerof Example 8Control Paint- 7-9 72,6-Dichloroaniline-4-Nitroaniline Polymer likethat of Example 6______________________________________

Again, these results demonstrate the unexpected efficacy of PCD organo anti-fouling agents.

Example 12

The Control Paint of Example 10 was formulated with additional anti-fouling additives and evaluated with the following results being recorded:

TABLE 4______________________________________Sample Rating After Exposure *(Additive at 20 wt-%) 4 Months______________________________________Control Paint- 0No Anti-Fouling AdditiveControl Paint- 0Hexachloro-5-Norborene-2,3-Dicarboxylic AnhydrideControl Paint- 3-4Hexachloro-5-Norborene-2,3-Dicarboxylic AnhydridePolymer of Example 4Control Paint- 0PhenothiazineControl Paint- 0-1Phenothiazine Polymer ofExample 8Control Paint- 050/50 Weight Mixture of 2-Mercapto-benzothiazole and MorpholineControl Paint- 150/50 Weight Mixture of 2-Mercapto-benzothiazole and Morpholine Polymerof Example 11______________________________________

Example 13

The Control Paint of Example 10 again was formulated with additional anti-fouling additives and evaluated as above with the following results being recorded:

TABLE 5______________________________________Sample Rating After Exposure *(Additive at 20 wt-%) 1 Months 4 Months______________________________________Control Paint- 0 03,5-Dichloro-N-(3,3-Dimethylproyne) Benzamideor Pronamide of Example 10Control Paint- 7 7Pronamide Polymerized with50/50 Methylmethacrylate andButyl AcrylateControl Paint- 0-1 0d-Trans-Allerthrin ofExample 10Control Paint- 7 7d-Trans-Allerthrin Polymerizedwith 50/50 Methylmethacrylateand Butyl Acrylate______________________________________

Yet again, the efficacy of the PCD polymeric anti-fouling agents is demonstrated.

Example 14

The Control Paint of Example 10 was formulated with additional anti-fouling additives and evaluated with the following results being recorded:

TABLE 6______________________________________Sample Rating After Exposure *(Additive at 20 wt-%) 1 Months 4 Months______________________________________Control Paint- 9 03-(3,4-Dichlorophenyl)-1,1-dimethyl urea(See Example 3)Control Paint- 9 7Urea of Above Attachedto Urethane Prepolymer of2 Moles of Toluene Diisocyanateand Polypropylene Glycol(200 Molecular Weight)Control Paint- 6-7 0Reaction Product of1,5-Naphthalene Diisocyanateand 1,3-Diaza-2,4-Cyclopendadiene(See Example 7)Control Paint- 6-7 6-7Cyclopendadiene above Polymerizedwith 2 Moles of NaphthaleneDiisocyanate and 1 Mole ofEthylene Glycol______________________________________

The above-tabulated results further confirm the invention.

Example 15

Testing of several additional anti-fouling agents in the paint formulation described in Example 12 was conducted for 6 months and the results compared to several polymerized versions of the same anti-fouling agents, with the following results being recorded:

TABLE 7______________________________________Anti-Fouling General RatingPanel # Agent 1 Mo. 4 Mos. 6 Mos. 6 Mos.*______________________________________13-A1 Eugenol** 9 3 0 613-A2 Eugenol** 7 3 0 613-C1 2,3-Dichloro- 7 6 0 5 1,4-Naphtha- quinone13-C2 2,3-Dichloro- 5 3 0 5 1,4-Naphtha- quinone13-E1 Diphenyl- 5 4 0 6 analine13-E2 Diphenyl- 5 3 0 6 analine14-C1 N,N-dially- 5 4 0 4-6 2-chloroacetamide14-C2 N,N-dially- 5 4 0 4-6 2-chloroacetamideControl Uncoated Panel 0 0 0 0______________________________________ *Free-radical polymerized version prepared as reported in Examples 2, 4, or 6; or urethane version prepared as reported in Example 2, depending on the functionality of the antifouling agent. **Eugenol is 99% 4allyl-2-methoxyplhenol.

Example 16

An epoxy resin system was examined for its ability to be modified so as to preferentially influence the concentration or location of an anti-fouling agent (Nopocide N-96, see Example 1) within its structure. A direct comparison was made between an epoxy resin (EPON 828 epoxy resin, diglycidyl ether of bis-phenol A, Shell Chemical Company) and the same epoxy resin containing a domain structuring polymeric material, such as a polysulfide resin (LP-32 polysulfide resin, Thiokol Corporation). Both systems contained the same anti-fouling agent. The compositions formulated are set forth below:

TABLE 8______________________________________ Sample (g)Ingredient 1 2 3______________________________________Epon 828 9 6 9LP-32 -- 3 --Hexachlorophene 1.41 1.29 --Polymer of Nopocide -- -- 1.7N-96 and LP-32 polysulfide(3 parts LP-32 and 1.24parts Nopocide)Ancamine AD* 5.10 3.4 5.10______________________________________ *Amine hardner, 485 amine value, Pacific Anchor Corp.

Sample 1 that contained only the hexachlorophene anti-fouling agent and not the domain creating polymer (LP-32 polysulfide), provided an even chlorine distribution throughout the surface of the sample. Sample 1 also showed no regular domain size structure present as can be seen by reference to FIG. 1. Sample 2, however, exhibited a very unique regular domain size (less than 1.mu.) structure or pattern which was created by the LP-32 polysulfide polymer (see FIG. 2).

Engergy Dispersion Spectoscopy (EDS) analysis of the sample surface for chlorine from the hexachlorophene anti-fouling agent showed that there were two distinct domains or regions where the chlorine could be found. Chlorine was identified in both the sea-like structures and the small round island structures in the sample (FIG. 2) What was unexpected, however, was the discovery that the chorine concentration, and, thus, the concentration of anti-fouling agent, was significantly higher (48%) in the round island domains and lower (36%) in the sea-like domains of the sample. A pictorial representation of these results is displayed in FIG. 3.

Similar results were observed for Sample 3. Sample 3 contained larger domain size structures (about 100.mu.), and chlorine from the Nopocide was found only in the areas where the domain or island was located. Areas between the islands did not contain chlorine. A chlorine or sulfur density map of the sample surface follows the outline of the domain structure (see FIGS. 4, 5, and 6).

Example 17

In this example, an unreacted toxicant was evaluated with respect to its ability to preferentially concentrate in domains of another material created within a continuous polymeric binder or carier. For example, certain types of acrylic copolymers dispersed in a polyvinyl chloride (PVC) polymer can create discrete domains wherein a toxicant molecule can preferentially concentrate. In this case, the toxicant was the 3,4-dichloroanaline-based acrylate monomer of Example 2 (80 wt-% concentration, sharp melting point at 180.degree. C.), the continuous phase was VAGH PVC polymer (see Example 10), and the domain-creating polymer was a mixture of polyhydroxyethylmethacrylate (10 wt-% concentration, melting point less than 250.degree. C.), and a polymer of a methacrylic acid ester of an amino carbamate monomer (10 wt-% concentration, melting point greater than 300.degree. C.).

Scanning electron micrographs are shown at FIGS. 7 and 8 for PVC containing 20 to 30 wt-% of the mixture set forth in Table 11. The domains created by the polymeric and unreacted monomer mixture in the PVC can be distinguished easily. Surprisingly, the toxicant monomer molecules are preferentially concentrated with the acrylic ingredients which created the domains in the PVC binder. An oxygen density map (oxygen is analyzed rather than chlorine because of the chlorine content of the binder) of the film surface (see FIGS. 9-12) clearly indicates that the only place oxygen resides is in the domains. Interestingly, the oxygen is not distributed in the domain void or sea-like regions of the PVC. The oxygen maps clearly outline only those regions/domains or islands where the toxicant molecules reside, and not in the sea or continuous phase of the PVC. The light or bright areas in these figures are due to the presence of oxygen and the dark regions are due to the absence of oxygen.

Example 18

Sample 2 of Example 16 was prepared again, except that the hexachlorophene toxicant was replaced by Nopocide N-96. Thus, a blend of domain-forming LP-32 polysulfide resin and the Nopocide is being evaluated with respect to the formation of PCDs of Nopocide. The cured epoxy resin system was subjected to SEM and EDS analysis with the results set forth at FIGS. 13-15.

FIG. 13 is the SEM micrograph of an area of the cured epoxy resin at 200 X. It is evident that the LP-32 polysulfide polymer created discrete domains. FIG. 14 displays the EDS analysis of chlorine at 200 X, while FIG. 15 is for sulfur. A comparison of the two EDS maps reveals that chlorine and sulfur both are present at the same location in the cured epoxy resin system. Chlorine comes from the Nopocide toxicant, while sulfur comes from the LP-32 polysulfide resin. Again, then, the formation of PCDs of non-tin, organo anti-fouling agents is seen to have been achieved. Here, such formation is due to the preferential formation of domains by the LP-32 polysulfide polymer with the concomitant preferential concentration of the toxicant with the polysulfide polymer.

Claims

1. In a non-tin-containing, curable, marine anti-fouling composition consisting of a film of a cured thermoplastic or thermoset binder, and an amount of a non-tin and anti-fouling agent effective for imparting anti-fouling properties to the film of the cured composition when said film is used in a marine environment, the improvement wherein said anti-fouling agent is dispersed in a compound to form a mixture which mixture forms a separate phase of discrete domains of about 0.3 to 500 microns in the film of the cured binder which domains have concentrations of said anti-fouling agent higher than the concentration of said anti-fouling agent in the continuous phase, and wherein said anti-fouling agent consists of a water-insoluble, organo or inorganic compound selected from the group consisting of heterocyclic compounds, aromatic compounds substituted with heteroatom substitutents, amino compounds, carbocyclic vinyl ether ketones, phospho compounds, polychlorinated carbocyclic and acyclic compounds, chlorinated carbocyclic carboxylates, copper (cupric) oleate, alkyl dimethyl benzene, 2,4-d,.alpha.-chlorocrotyl ester, 2,3-dichloro-2-methylpropionic acid sodium salt, diphenylacetrontrile, n-dodecyl thiocyanate, ethyl-N,N-dipropylthiolcarbamate, ethyl-N,N-diisobutyl thiolcarbamate, ethylenebis (dithiocarbamato) zinc, ferric dimethyl-dithiocarbamate, isobornyl thiocyanoacetate, manganese ethylenebisdithiocarbamate, disodium ethylene bisdithiocarbamate, s-propylbutylethylthiocarbamate, piperonyl-bis(2-[2'-n-butoxyethoxy]ethyl)acetal, piperonyl butoxide alpha[2-(2-n-butoxyethoxy)-ethoxy]4,5-methylenedioxy 2-propyltoluene, piperonyl cyclonen, 3',4'-dichloropropionalide, ethylene-1,2-bis (thiocarbamoyldimethylthiocarbamoyldisulfide), 5,6,7,8-tetrahydro-1-naphthyl methylcarbamate, 2-thiocyanoethyl dodecanoate, tetramethylthiuram disulfide, tert-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate, S-propyldipropylthiocarbamate, zinc ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, antimony tartrate, antimony potassium tartrate, boric acid, ammonium sulfamate, and mixtures thereof, and having a X 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 body weight against rats or mice, where X is the weight fraction of heteroatoms contained in the monomer or monomer repeat unit of said anti-fouling agent, Z is the weight fraction of .pi. electrons contained in the monomer or monomer repeat unit of said anti-fouling agent, and LD50 is the lethal oral dose of said anti-fouling agent which is expected to kill 50% of the population of a test group of adult male rats or mice.

2. The composition of claim 1 wherein the X 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 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.

4. The composition of claim 1 wherein said anti-fouling agent is selected from the group consisting of:

4-allyl-2-methoxyphenol

2,3-dichloro-1,4-napthoquinone

cetylpyridinium chloride

diphenylamine

2-chloro-N,N-diallylacetamide

cetyltrimethylammonium bromide

2-isopropylamino-4-chloro-6-ethylamino 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 dimethylpropenyl cyclopropane carboxylic acid 2,5-dichloro,3-amino benzoic acid

cinnamic acid

2. -6-dichloro, 4-nitroaniline

dichloro, isopropenyl anilide

dodecylguanidine monoacetate

trichlorophenyl acetic acid

diphenyl ether, chlorophenyl derivative of the isobutyric acid ester of hydroxylacetonitrile

trihydroxybenzoic acid

3-indolacetic acid

3,5-dichloro-N-(3,3-dimethylpropyne)benzamide

napthalene acetamide dimethylethylphenoxy-cyclohexyl-2-propynyl sulfite

o-phenylphenol

phthalic acid

chlorophenyl-isopropyl, propynyl carbamate

N-phenyl,N-butynyl chloroacetamide

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.

5. The composition of claim 1 wherein said anti-fouling agent is selected from the group consisting of:

acrolein phenylhydrazone

ammonium saccharinate

2-allyl-4-hydroxy-3-methyl-2-cyclopenten-1-one ester of 2,2-dimethyl-3-(2-methylpropenyl cyclopropanecarboxylic acid)

4-allyl-2-methoxyphenol o-(allyloxy) phenyl methylcarbamate

2-(allylthio)-2-thiazoline

1,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-2-norbornene

4-ethylamino-6-isopropylamino-2-methylthio-1,3,5-triazine

2-amino-3-chloro-1,4-napthoquinone

3-amino-5-nitro-o-toluamide

3-amino-1,2,4-triazole

2-chloro-4-ethylamino-6-isopropylamino-S-triazine

4-chloro-m-chlorocarbanilate

6-chloropiperonyl chrysanthemumate

N-butyl-N-ethyl-.alpha.,.alpha.,.alpha.-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-1-yl)

N-(4-bromo-3-chlorophenyl)-N'-methoxy-N'-methyl urea

5-(bromomethyl)-1,2,3,4,7,7-hexachloro-2-norbornene

S-(O,O-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 (pochlorophenyl) ethane 1,1-bis (p-chlorphenyl)-ethanol

o,o-dimethyl-o-2,5-dichloro-4-bromophenylthionophosphate

O,O-dimethyl-2,2,2-trichloro-1-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 methylphosphoramidite

o-(4-tert-butyl-2-chlorophenyl)o-methyl phosphoramidothionate

butyl 3,4-dihydro-2,2-dimethyl-4-oxo-1,2h-pyran-6-carboxylate

n-butyl-9-hydroxyfluorene-(9)-carboxylate

2-(p-tert-butylphenoxy) cyclohexyl 2-propynyl sulfite

1-butyn-3-yl m-chlorophenyl-carbamate

N-trichloro-methylthio-4-cyclohexene-1,2-docarboximide

1-napththyl n-methylcarbamate

S-[[(p-chlorophenyl) thiol]methyl]O,O-diethylphosphorodithioate

2-chloro-N,N-diallyl-acetamide

2-chloroallyl diethyl-dithiocarbarnate

cetyldimethylethylammonium bromide

cetylpyridinium 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

1-(3-chlorallyl)-3,5,7-triaza-1-azoniaadamantane chloride

ethyl 4,4'-dichlorobenzylate

5-chloro-2-benzothiazolethiol zinc salt

p-chlorobenzyl p-fluorophenyl sulfide

1-chloro-N'-(3,4-dichlorophenyl) N,N-dimethylformamidine

4-chloro-3,5-dimethyl phenoxy-ethanol

1,4-dichloro-2,5-dimethoxybenzene

1-(chloro-2-norbomyl)-3,3-dimethylurea

S-(p-chloro-.alpha.-phenylbenzyl) O,O-diethyl phosphorodithioate

p-chlorophenyl ester of benzene-sulfonic acid

N-3-chlorophenyl-1-(isopropyl-carbamoyl-1)-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-1-(2,4,5-trichloro-phenyl) vinyl dimethyl phosphate

N'-(4-chlorophenoxy) phenyl N,N-dimethylurea

isopropyl N-(3-chlorophenyl) carbamate

copper 8-quinolinolate

2-(2,4-dihydroxyphenyl)-1-cyclohexene-1-carboxylic acid-lactone O,O-diethylphosphorothioate

2-chloro-4-dimethylamino-6-methylpyrimidine

3-(2-cyclopenten-1-yl)-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemunate

.alpha.-cyclohexyl-.alpha.-phenyl-3-pyridyl-methanol, hydrochloride

N'-cyclo-octyl-N,N-dimethylurea

' . 4'-dichlorocyclopropanecarboxanilide

2,4-dichlorophenoxyacetic acid

3,5-dimethyl-1,3,5,2H-tetrahydrothiadiazine-2-thione, tetra-hydro-3,5-dimethyl-2H-1,3,5-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-diisopropyl thiolcarbamate

1,3-diaza-2,4-cyclopentadiene

N,N-di-n-butyl-p-chlorobenzene-sulfonamide 3,6-dichloro-o-anisic acid

O-(2-chloro-4-nitrophenyl) O,O-dimethyl phosphorothioate

2,6-dichlorobenzonitrile

2,3-dichloro-1, 4-naphthoquinone

1,3-bis(1-hydroxy-2,2,2-trichloroethyl) urea

3,4-dichlorobenzyl methylcarbamate (80%) mixture with 2,3-dichlorobenzyl methylcarbamate (20%)

1,1-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

2,6-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

1-(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

O,O-diethyl s-carboethoxymethyl phosphorothioate

O,O-diethyl O-naphthylamido phosphorothioate

O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate

2,2'-dihydroxy-3,5,3',5',4"-pentachlorotriphenylmethane 2"-sodium sulfonate

O,O-diisopropyl s-diethyldithiocarbamoyl phosphorodithioate

2,4-dimethylbenzyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate

O,O-dimethyl-S-2-(acetylamino)-ethyl dithiophosphate

N-dimethylamino succinamic acid

1,1-dimethyl-3-[3-(n-tert-butyl-carbamoyloxy)phenyl]urea

O,O-dimethyl s-carboethoxymethyl phosphorothioate

O,O-dimethyl O-(3-chloro-4-nitrophenyl) phosphorothioate

O,O-dimethyl-o-p-cyanophenyl phosphorothioate

o,o-dimethyl-s-[5-ethoxy-1,3,4-thiadiazol-2( 3H)-onyl-(3)-methyl]phosphorodithioate

N,N-dimethyl-N'-(2-methyl-4-chlorophenyl)-formamidine hydrochloride

O,O-dimethyl o-(4-nitro-m-tolyl) phosphorothioate

o,s-dimethyl tetrachloro thiotere-phthalate

4'-dimethyltriazenoacetanilide

dinitrocyclohexylphenol

2,4'-dinitro-4-trifluoromethyl diphenylether

2-( 1-methyl-n-heptyl)-4,6-dinitrophenyl crotonate

N,N-dimethyl-2,2-diphenylacetamide

diphenylamine

2,6-dinitro-N,N-di-n-propyl-p-toluidine

di-n-propyl-2,5-pyridine-dicarboxylate

1,1'-ethylene-2,2'-dipyridinium dibromide

2,3-dicyano-1,4-dithia-anthraquinone

3-(3,4-dichlorphenyl)-1, 1-dimethyl-urea

n-dodecylguanidine acetate

2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate

ethoxymethylbis (p-chlorophenyl) carbinol

1. 2-dihydro-6-ethoxy-2,2,4-trimethylquinone

3-phenyl-1,1-dimethylurea trichloroacetate

O,O-dimethyl S-(N-formyl-N-methylcarbamoyl-methyl)phosphorodithioate

2-formyl-4-chlorophenoxyacetic acid

3-furfuryl-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemunate

2-heptadecyl-2-imidazoline

7-chloro-4,6-dimethoxycoumaran-3-one-2-spiro-1'-(2'-methoxy-6'-methylcyclohex-2'-en-4'-one)

1,1,1,3,3,3,-hexachloro-2-propanone

1,5a,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

isobutyl triphenylmethylamine

5-bromo-3-isopropyl-6-methyluracil

isopropyl-4,4'-diboromobenzilate

isopropyl 4,4'-dichlorobenzilate

isorpropyl mercaptophenyl-acetate, O,O-dimethyl phosphorodithioate

3-cyclohexyl-6,7-dihydro-1H-cyclopentapyrimidine-2,4(3H,5H)-dione

3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

S-[1,2-bis(ethoxy-carbonyl)ethyl]O,O-dimethyl phosphorodithioate

4-chloro-2-methylphenoxyacetic acid

2-(4-chloro-2-methylphenoxy) propionic acid

sec-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate

s-[(4,6-diamino-s-triazine-2-yl)methyl]O,O-dimethyl phosphorodithioate

2-isopropylamino-4-(3-methoxypropylamino)-6-methylthio-s-triazine

1,1,1-trichloro-2,2-bis(p-methoxyphenyl) ethane

2-methoxy-4-isopropylamino-6-diethylamino-s-triazine

S-(N-methoxymethylcarbamoylmethyl) dimethyl phosphorothiolothiononate

alpha-methylbenzyl 3-(dimethoxy-phosphinyloxy)-cis-crotonate

m-(1-methyl butyl) phenyl methyl-carbamate

methyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate

3. 3'-methylenebis (4-hydroxycoumarin)

2,2'-methylenebis (3,4,6-trichlorophenol)

6-methyl-2-oxo-1,3-dithio(4,5-b)quinoxaline

O,O-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 O-(2,4,5-trichloro-phenyl) amidophosphorothiomate

3-(p-bromophenyl)-1-methyl-1-methoxyurea

1,2-dihydropyridazine-3,6-dione

3,3'-ethylenebis-(tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazone-2-thione)

S-ethyl hexahydro-1H-azepine-1-carbothioate

3-(p-chlorphenyl)-1,1-dimethylurea

3-(p-chlorophenyl)-1,1-dimethylurea trichloroacetate

1,2-dibromo-2,2-dichloroethyl dimethyl phosphate

beta-naphthoxyacetic acid

3-(3,4-dichlorophenyl)-1-methyl-1-n-butylurea

3-(hexahydro-4,7-methanoindan-5-yl)-1,1-dimethylurea

N-1-naphthyl-phthalamic acid

p-chlorophenyl p-phenyl 4-chlorobenzenesulfonate

phenothiazine

ethyl mercapto-phenylacetate O,O-dimethyl-phosphorodithioate

n-phenyl-1-(ethylcarbamoyl-1) ethylcarbamate (d isomer)

phosphoric acid, 2-chloro-1-(2,4,5-trichlorophenyl)vinyl dimethyl ester

4-amino-3,5,6-trichloropicolinic acid

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

2-chloro-4,6-bis(isopropyl-amino)-s-triazine

di-n-propyl-3-methyl-6,7-methylenedioxy-1,2,3,4-tetra-hydronaphthalene-1,2dicarboxylate

5-amino-4-chloro-2-phenyl-3(2H) pyridazinone

pyrethrin I

8-quinolinol

dimethyl 2,4,5-trichlorophenyl phosphorothionate salicylanilide

1-(3,4-methylene-dioxyphenoxy)-3,6,9-trioxoundecane

sodium 2-(2,4-dichlorophenoxy)ethyl sulfate

1-(2-methyl-cyclohexyl)-3-phenylurea

1-(2,4,5-trichlorophenoxy) propionic acid

N'-chlor-2-methyl-p-valerotoluidide

1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene

methyl 3,4-dichlorocarbanilate

2,4,5-trichlorophenoxyacetic acid

trichlorobenzyl chloride

2,2-bis(p-chlorophenyl)-1,1-dichloroethane

3-tert-butyl-5-chloro-6-methyluracil

2,6-di-tert-butyl-p-tolylmethylcarbamate 2,3,6,7-tetrachloro-4a,8a-epoxy-1,2,3,4,4a,8a-hexahydro-1,4-methanonaphthalene-5,8-dione

N-(1,1,2,2-tetrachloro-ethyl-sulfenyl)-cis-4-cyclohexene-1,2-dicarboximide

2,4,5,6-tetrachloroiso-phthalonitrile

1,2,4,5-tetrachloro-3-nitrobenzene

p-chlorophenyl 2,4,5-trichlorophenyl sulfone

3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropanecarboxylate

O,O,O',O'-tetramethyl O,O'-thiodi-p-phenylene phosphorothioate

1,3,6,8-tetranitrocarbazole

2-(4-thiazolyl) benzimidazole

2,2'-thiobis(4,6-dichlorophenol)

2,3-quinoxaline-dithiol cyclic trithiocarbonate

N-meta-tolyl phthalamic acid

S-2,3,3-trichloroallyl N,N-di-isopropyl-thiolcarbamate

O,O-dimethyl (1-hydroxy-2,2,2-trichloroethyl)phosphonate

2,3,6-trichlorobenzoic acid

trichlorobenoic acid, dimethylamine salt

4. 5,7-trichlorobenzthiadiazole-2,1,3

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-1,3,5-triazine

2-chloro-4-(di-ethylamino)-6-(ethylamino)-s-triazine

3,5-dinitro-o-toluamide

and mixtures thereof.

6. In a non-tin-containing, curable, marine anti-fouling composition consisting of a film of a cured thermoplastic or thermoset binder, and an amount of a non-tin and anti-fouling agent effective for imparting anti-fouling properties to the film of the cured composition when said film is used in a marine environment, the improvement wherein said anti-fouling agent is provided to contain reactive functionality which reactive functionality is used for reacting said anti-fouling agent with a monomer, oligomer, or polymer, to form a product which product forms a separate phase of discrete domains of about 0.3 to 500 microns in the film of the cured binder which domains have concentrations of said anti-fouling agent higher than the concentration of said anti-fouling agent in the continuous phase, and wherein said anti-fouling agent consists of a water-insoluble, organo or inorganic compound selected from the group consisting of heterocyclic compounds, aromatic compounds substituted with heteroatom substituents, amino compounds, carbocyclic vinyl ether ketones, phospho compounds, polychlorinated carbocyclic and acyclic compounds, chlorinated carbocyclic carboxylates, copper (cupric) oleate, alkyl dimethyl benzene, 2,4-d,.alpha.-chlorocrotyl ester, 2,3-dichloro-2-methylpropionic acid sodium salt, diphenylacetronitrile, n-dodecyl thiocyanate, ethyl-N,N-dipropylthiolcarbamate, ethyl-N,N-diisobutyl thiolcarbamate, ethylenebis (dithiocarbamato) zinc, ferric dimethyl-dithiocarbamate, isobornyl thiocyanoacetate, manganese ethylenebisdithiocarbamate, disodium ethylene bisdithiocarbamate, s-propylbutyl-ethylthiocarbamate, piperonyl-bis(2-[2'-n-butoxyethoxy]ethyl) acetal, piperonyl butoxide alpha[2-(2-n-butoxyethoxy)-ethoxy]4,5-methylenedioxy 2-propyltoluene, piperonyl cyclonene, 3',4'-dichloropropionalide, ethylene-1,2-bis (thiocarbamoyldimethylthio-carbamoyldisulfide), 5,6,7,8-tetrahydro-1-naphthyl methylcarbamate, 2-thiocyanoethyl dodecanoate, tetramethylthiuram disulfide, tert-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate, S-propyldipropylthiocarbamate, zinc ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, antimony tartrate, antimony potassium tartrate, boric acid, ammonium sulfamate, and mixtures thereof, and having a X 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 body weight against rats or mice, where X is the weight fraction of heteroatoms contained in the monomer or monomer repeat unit of said anti-fouling agent, Z is the weight fraction of .pi. electrons contained in the monomer or monomer repeat unit of said anti-fouling agent, and LD50 is the lethal oral dose of said anti-fouling agent which is expected to kill 50% of the population of a test group of adult male rats or mice.

7. The composition of claim 6 wherein said monomer, oligomer, or polymer contains heteroatomic substituents and said substituents are selected from the group consisting of nitrogen, sulfur, or both.

8. The composition of claim 1 which consists of a film-forming coating composition.

9. In a non-tin-containing, curable, marine anti-fouling composition consisting of a film of a cured thermoplastic or thermoset binder, and an amount of a non-tin and anti-fouling agent effective for imparting anti-fouling properties to the film of the cured composition when said film is used in a marine environment, the improvement which comprises complexing said anti-fouling agent with a metal ion to form a coordination compound which compound forms a separate phase of discrete domains of about 0.3 to 500 microns in the film of the cured binder which domains have concentrations of said anti-fouling agent higher than the concentration of said anti-fouling agent in the continuous phase, and wherein said anti-fouling agent consists of a water-insoluble, organo or inorganic compound selected from the group consisting of heterocyclic compounds, aromatic compounds substituted with heteroatom substituents, amino compounds, carbocyclic vinyl ether ketones, phospho compounds, polychlorinated carbocyclic and acyclic compounds, chlorinated carbocyclic carboxylates, copper (cupric) oleate, alkyl dimethyl benzene, 2,3-d,.alpha.-chlorocrotyl ester, 2,3-dichloro-2-methylpropionic acid sodium salt, diphenylacetronitrile, n-dodecyl thiocyanate, ethyl-N,N-dipropylthiolcarbamate, ethyl-N,N-diisobutyl thiolcarbamate, ethylenebis (dithiocarbamato) zinc, ferric dimethyl-dithiocarbamate, isobornyl thiocyanoacetate, manganese ethylenebisdithiocarbamate, disodium ethylene bisdithiocarbamate, s-propylbutyl-ethylthiocarbamate, piperonyl-bis(2-[2'-n-butoxyethoxyethyl) acetal, piperonyl butoxide alpha[2-(2-n-butoxyethoxy)-ethoxy]4,5-methylenedioxy 2-propyltoluene, piperonyl cyclonene, 3',4'-dichloropropionalide, ethylene-1,2-bis (thiocarbamoyldimethylthiocarbamoyldisulfide), 5,6,7,8-tetrahydro-1-naphthyl methylcarbamate, 2-thiocyanoethyl dodecanoate, tetramethylthiuram disulfide, tert-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate, S-propyldipropylthiocarbamate, zinc ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, antimony tartrate, antimony potassium tartrate, boric acid, ammonium sulfamate, and mixtures thereof, and having a X 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 body weight against rats or mice, where X is the weight fraction of heteroatoms contained in the monomer or monomer repeat unit of said anti-fouling agent, Z is the weight fraction of .pi. electrons contained in the monomer or monomer repeat unit of said anti-fouling agent, and LD50 is the lethal oral dose of said anti-fouling agent which is expected to kill 50% of the population of a test group of adult male rats or mice.

10. The composition of claim 6 wherein the X value is established by said agent containing heteroatoms selected from the group consisting of sulfur, oxygen, nitrogen, halogen, and mixtures thereof.

11. The composition of claim 6 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.

12. The composition of claim 9 wherein the X value is established by said agent containing heteroatoms selected from the group consisting of sulfur, oxygen, nitrogen, halogen, and mixtures thereof.

13. The composition of claim 9 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.