AU660030B2

AU660030B2 - Marine compositions bearing preferentially concentrated domains of non-tin, organo or inorganic anti-fouling agents

Info

Publication number: AU660030B2
Application number: AU19235/92A
Authority: AU
Inventors: Richard J. Dick; Vincent D. Mcginniss
Original assignee: Battelle Memorial Institute Inc
Current assignee: Battelle Memorial Institute Inc
Priority date: 1991-05-17
Filing date: 1992-05-14
Publication date: 1995-06-08
Anticipated expiration: 2012-05-14
Also published as: WO1992020747A1; CA2107207A1; AU1923592A; JPH06507661A; EP0584204A1

Description

MARINE COMPOSITIONS BEARING

PREFERENTIALLY CONCENTRATED DOMAINS OF

NON-TIN, ORGANO ANTI-FOULING AGENTS

Background of the Invention

The present invention relates to anti-fouling marine coatings and mor particularly to novel low toxicity anti-fouling agents therefor. One of the earliest need for performance-oriented coatings was in the marine environment. Early formulation were designed around known toxins, such as copper and mercury compounds Nineteenth Century marine coatings typically used creosote and natural drying oi formulations bearing the toxins. For ship bottoms, presently, anti-fouling compound based on copper and tin commonly are incorporated into somewhat water- sensitiv binders to afford gradual break-down of the film to permit a sustained release of th "poison". This required self-erosion property necessitates frequent repainting of shi bottoms, depending upon location and severity of exposure conditions.

Today's anti-fouling coatings use two general leaching mechanisms, dependin on the type of resin matrix selected, soluble or insoluble. The insoluble-matrix typ leaves a resinous skeleton intact as the toxicant particles are removed by dissolving int solution in seawater. This also is called the contact type because it depends upon th toxicant migrating to the surface and entering solution by making contact with seawate Since the resins are somewhat water-permeable, the toxic particles may diffuse throug the semi-permeable coating, and as one particle dissolves, another is exposed t 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-foulin topcoats. As a general rule, the insoluble-matrix type of paint does not contain a extended pigment, and the geometry of the dry film requires high toxicant loadings (52 to 74% by volume) to ensure the G12O particles will be in continuous contact with eac other. Below the level of cubic packing (52%), the resin will encase the CU2O particle and prevent solution; above the level of hexagonal packing (74%), the coating will b too resin-poor to maintain film integrity. These figures may vary somewhat in actua practice, and it is common to adjust the leaching rate and the effective range of toxican loading (e.g. by the addition of rosin or other natural resins). In common practice, bot natural resins and extender pigments are frequently used. When high levels of rosin ar used and high errosion might be expected, tougheners such as ester gum, ethy cellulose, and modified rubbers are added. (Paint Handbook, G.E. Weismantel McGraw-Hill, New York, New York, pp 14-43 and 14-44; and R.J. Dick, Marin Paints, Chapter 14). With respect to the toxins presently used in marine anti-fouling paints, rec U.S. federal legislation has severely restricted the use of organo-tin anti-fouling age Toxicity concerns appear to be a prime motivation behind this recent legislation. Pr proposals include, for example, Japanese Patents 56156202 and 52117425 report use of a combination of a napthoquinone and a thiuram disulphide in order to obtain a fouling activity, while Japanese Patent 63243067 proposes the use of diphenylamin Despite these proposals, there still is a substantial need in the anti-fouling arena for ne 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 compositi of a thermoplastic or thermosetting binder, solvent, non-tin, organb anti-fouling age and optionally conventional additives, e.g. leaching agents, opacifying pigments, e The anti-fouling agents are found in preferentially-concentrated domains (hereinaft often referred to as "PCD" or "PCDs") in the cured compositions. The PCDs can termed non-homogeneous, phase-separated, or incompatible in the system. The art te used in describing the PCDs of anti-fouling agents is not limitative of the invention the disclosure herein will demonstate. Preferably, PCDs are created by forming oligomeric adduct of the anti-fouling agent which adduct is formed into PCDs upon t curing of the composition. Additional techniques for forming PCDs of anti-fouli agent will be revealed herein.

The present invention also is addressed to the use of new, low toxicity an fouling agents which comprise pesticide or herbicide compounds having a χ value between about 0.01 and 3, a Z value for vinyl or aromatic compounds of between abo 0.01 and 0.08, and an LD50 value of greater than 200 mg/kg against rats or mice. Su pesticide or algicide compounds broadly can be selected from heterocyclic compound aromatic compounds substituted with heteroatom substituents, various ami compounds, carbocyclic vinyl ether ketones, certain phospho compounds, certai polychlorinated carbocyclic and acyclic compounds, certain chlorinated carbocycl carboxylates, antimony tartrate, boric acid, and cupric oleate. Exemplary aromat compounds include diaromatic compounds linked with a sigma bond or with a carbon heteroatom linkage, fused aromatic rings, and mono-aromatic compounds.

Advantages of the present invention include the ability to formulate marine an fouling compositions which contain low toxicity anti-fouling agents. Another advantag is the ability to formulate marine anti-fouling coating compositions wherein the lo toxicity anti-fouling agents display improved effectiveness by virtue of being formed i PCDs. These and other advantages will be readily apparent to those skilled in the 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 epo resin composition of Example 16 containing an organo toxicant freely-dispersed therei Fig. 2 is an SEM at 10,000 X of a cured epoxy resin composition of Example containing the same organo toxicant free-dispersed therein and a domain-formi polysulfide polymer, Fig. 3 is a pictorial representation of the SEM results of Fig. 2, where A is t discontinuous polysulfide/chlorine compound environment and B is the continuo polysulfide chlorine compound environment;

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

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

Fig. 6 is an Energy Dispersion Spectroscopy analysis for the sulfur content the organo toxicant polymer domains of Fig. 4; Figs. 7 and 8 are SEMs at 500 X and 2,500 X, respectively, showing t domain structures formed in a continuous PVC binder by the domain creating acry 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 Fig. 10 is an Energy Dispersion Spectroscopy analysis at 1,500 X for t 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 t oxygen content of the sample of Figs.7-9;

Fig. 13 is an optical micrograph at 200 X showing the domain structures form 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 a 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 their human toxicity characteristics, the art truly needs to enable anti-fouling agen which exhibit low human toxicity characteristics. Once such agents are identified, th must be compatible with remaining formulation ingredients in marine coatings and oth marine compositions. Also, these low toxicity anti-fouling agents must display effica characteristics making them practical. Use of the non-tin, organo anti-fouling agents in marine composition will provide a modicum of protection to the substrate to which t composition is applied, yet enhanced, long-term protection is desired. Unexpectedly, was discovered that enhanced activity for extended periods of time could be achieved controlling the physical form in which the anti-fouling agents were presented in t cured marine compositions. Phase separation was the term initially used to define suc physical form. Later, the term "preferentially-concentrated domains" was adopted due the variety of techniques developed for achieving the desired physical form of the an fouling agents. Thus, islands, pools, or domains where the anti-fouling agen concentrate are created in the cured composition. Such domains typically will be the si of from about 0.3 μ to 500 μ (micrometers).

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

Conventional non-tin, organo anti-fouling agents may be used in the presen invention for forming PCDs thereof. The preferred non-tin anti-fouling agents useful i the present invention, however, broadly are selected from compounds which hav exhibited terrestrial biologic activity, e.g. known herbicides and pesticides. For presen purposes., herbicides are to be interpreted broadly as including not only compound which selectively and/or broadly kill various plant life, but also include various plan growth regulators, algicides, and the like. Pesticides, for present purposes, also shoul be broadly interpreted as compounds which are selectively and/or broadly toxic t harmful plant infestations, such as acaricides. These compounds, however, mu exhibit low toxicity to humans. For present purposes, "low toxicity to humans" i determined when the LD50 value is greater than 200 mg/kg against rats or mice.

Within the broad spectrum of biologically active compounds described abov these compounds also must possess a χ factor of between about 0.01 and 3, and a value for vinyl or aromatic compounds of between 0.01 and 0.08. The χ factor is base upon the McGinniss predictive relationship as defined in Organic Coatings in Piasti Chemistry,. Vols. 39 and 46, pp 529-534 and 214-223, respectively (1978 and 198 respectively). The McGinniss predictive relationship defines the χ factor as a weig fraction of heteroatoms contained in the monomer or in the monomer repeat unit of a oligomer or polymer. The McGinniss predictive relationship defines the Z parameter a the weight fraction of π electrons contained in the monomer or in the monomer repe unit of an oligomer or polymer (e.g. π electron density of aromatic or viny compounds). Biologically-active compounds (as defined herein) that possess a χ facto and Z parameter within the ranges defined herein, and possess the requisite LD50 valu will be compounds which display anti-fouling characteristics in marine coatings.

Though such compounds will exhibit anti-fouling characteristics, not all may b totally acceptable for all applications such as, for example, some high performanc marine coatings requirements, e.g. submarine exterior coatings. Nevertheless, th compounds will possess anti-fouling characteristics and low toxicity to humans whic 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, factor, and Z parameter requirements possessed by the disclosed organo anti-foulin agents/reactants of the present invention and are offered as illustrative of the precepts o the present invention. TAB g l

4-allyl-2-methoxyphenol (Eugenol)

LD50 value of 2,000 mg/kg (rats) χ factor (O) of 0.195 Z parameter of 0.05

2. diphenylacetonitrile

C≡ N

LD50 value of 3,500 mg/kg (rats) χ factor (nitrogen) of 0.072 Z parameter of 0.062 3. 2,3-dichloro- 1 ,4-napthoquinone

LD50 value of 1,500 mg/kg (rats) χ factor (Cl) of 0.313 χ factor (O) of 0.141 Z parameter of 0.035

cetylpyridinium chloride

LD50 value of 200 mg/kg (rats) χ factor (N) of 0.04 χ factor (Cl) of 0.10 Z parameter of 0.172 diphenylamine

Low mammalian toxicity χ factor (N) of 0.083 Z parameter of 0.071

6. boric acid

B-(OH)3

LD50 of 3,000 mg/kg (rats) χ factor (O) of 0.777 χ factor (B) of 0.175

7. 2-chloro-N,N-diallylacetamide

0 II _/CH₂CH = CH₂

CICHgCN

^CH₂CH = CH₂

LD50 value of 700 mg/kg (rats) χ factor (Cl) of 0.205 χ factor (O) of 0.092 χ factor (N) of 0.081 Z parameter of 0.023 8. cetyltrimethylammonium bromide

LD50 value of 500 mg/kg (rats) χ factor (N) of 0.038 χ factor (Br) of 0.22

9. 2-isopropylarrύno-4^hloro-6-ethylamino triazine

LD50 value of 1,869 mg/kg (rats) χ factor (N) of 0.325 χ factor (Cl) of 0.244 Z parameter of 0.041

10. dimethoxythiophosphate derivative of diphenyl sulfide

LD50 value of 2,030 mg/kg (rats) χ factor (O) of 0.21 χ factor (S) of 0.21 χ factor (P) of 0.13 Z parameter of 0.013

11. ethyl 4-chloro-alpha(4-chlorophenyl) alpha-hydroxy benzene acetate

OH

o=c

I 0-CH(CH-_j)₂

LD50 value of 5,000 mg/kg (rats) χ factor (O) of 0.18 χ factor (C) of 0.27 Z parameter of 0.022 12. methyl, diethylamino, dimethoxythiophosphate derivative of pyrimidine

LD50 value of 2,000 mg/kg (rats) .10 χ factor (O) of 0.16 χ factor (N) of 0.14 χ factor (S) of 0.105 χ factor (P) of 0.102 Z parameter of 0.007 lδ

13. ethoxylated nonylphenol

0C₂H₄(0C₂H₄)₇0H

LD50 value of 4,000 25 χ factor (O) of 0.25

Z parameter of 0.0105

14. unsymmetrical hydrazine derivative of succinic acid

LD50 value of 8,400 χ factor (O) of 0.30 χ factor (N) of 0.175

15. allyl, methylhydroxy substituted cyclopententone ester o dimethylpropenyl cyclopropane carboxylic acid

LD50 value of 1,000 χ factor (O) of 0.11 Z parameter of 0.021

16. 2,5-dichloro,3-amino benzoic acid

LD50 value of 5,620 χ factor (O) of 0.155 χ factor (N) of 0.068 χ factor (Cl) of 0.345 Z parameter of 0.015

17. cinnamic acid

o

χ factor (O) of 0.216 Z parameter of 0.054

18. 2,-6-dichloro, 4-rtitroaniline

10 LD50 value of 5,000 χ factor (O) of 0.155 χ factor (N) of 0.135 χ factor (Cl) of 0.343 Z parameter of 0.029

15

19. dichloro, isopropenyl anilide

25 χ factor (O) of 0.070 χ factor (N) of 0.061 χ factor (α) of 0.309 Z parameter of 0.035 20. dodecylguanidine monoacetate

NH 0

II II n - Ci^δNH - C- NH - CH₃C - OH

LD50 value of 1,000 χ factor (O) of 0.111 10 χ factor (N) of 0.146

21. trichlorophenyl acetic acid

20

LD50 value of 1,780 χ factor (O) of 0.134 χ factor (Cl) of 0.445 Z parameter of 0.025

25

22. diphenyl ether, chlorophenyl derivative of the isobutyric acid ester hydroxyacetonitrile

LD50 value of 451 (toxic to fish) χ factor (O) of 0.114 χ factor (N) of 0.033 χ factor (Cl) of 0.085 Z parameter of 0.043

23. trihydroxybenzoic acid

χ factor (O) of 0.471 Z parameter of 0.035 24. 3-indolacetic acid

0

χ factor (O) of 0.198

10 χ factor (N) of 0.086 Z parameter of 0.037

25. 3,5-dichloro-N-(3,3-dimethylpropyne)benzamide

15

LD50 value (dermal) of 8,350 χ factor (O) of 0.063 χ factor (N) of 0.055

25 χ factor (Cl) of 0.278 Z parameter of 0.039 26. dimethylphosphoramide ammonium salt

0 0 II CH₃CH₂-0- P- C-NH₂

0NH₄

LD50 value (dermal) of 2,400 10 χ factor (O) of 0.276 χ factor (N) of 0.165 . χ factor (P) of 0.182

15 27. napthalene acetamide

LD50 value of 1,000 χ factor (O) of 0.086 25 χ factor (N) of 0.076

Z parameter of 0.065 28. dimethylethylphenoxy-cyclohexyl-2-propynyl sulfite

LD50 value of 2,200

10 χ factor (O) of 0.146 χ factor (S) of 0.098 Z parameter of 0.034

15 29. o-phenylphenol

LD50 value of 2,700 χ factor (O) of 0.094

25 Z parameter of 0.071

30. phthalic acid

10 χ factor (O) of 0.386 Z parameter of 0.036

31. chlorophenyl-isopropyl, propynyl carbamate

15

χ factor (O) of 0.064 χ factor (N) of 0.112 χ factor (Cl) of 0.142

25 Z parameter of 0.040

32. N-phenyl,N-butynyl chloroacetamide

LD50 value of 1,177

10 χ factor (O) of 0.072 χ factor (N) of 0.063 χ factor (Cl) of 0.160 Z parameter of 0.045

15

33. amino, chloro, phenyl derivative of aza^'cyclohexamine

LD50 value of 3,030

25 χ factor (O) of 0.073 χ factor (N) of 0.190 χ factor (Cl) of 0.161 Z parameter of 0.036 34. N^f-diallyl-2-chloroacetamide

LD50 value of 750 χ factor (O) of 0.092 χ factor (N) of 0.081 χ factor (Cl) of 0.205 Z parameter of 0.023

35. aminoacetic acid derivative of methylphosphonate

0 0

II II

H0-C- CH₂-NH-CH₂- P-0H

OH

LD50 value of 4,300 χ factor (O) of 0.473 χ factor (N) of 0.083 χ factor (P) of 0.183 36. 3,5-dinitro,4-N,N-dipropylamino benzene sulfonamide

LD50 value of 10,000 χ factor (O) of 0.277 χ factor (N) of 0.162 ^" χ factor (S) of 0.092

Z parameter of 0.017

37. 2-chloro-2-propenyl diethylcarbamodithioate

LD50 value of 850 χ factor (N) of 0.064 χ factor (S) of 0.294 χ factor (Cl) of 0.163

Z parameter of 0.0092

As the data will demonstrate, the foregoing biologically active compound display efficacy as anti-fouling agents. Their diminished toxicity to humans is a decide benefit compared to conventional organo-tin anti-fouling agents. Broadly, the low toxicity anti-fouling agents of the present invention can described as biologically active terrestrial compounds (e.g. pesticides and herbicide that are heterocyclic, aromatic with heteroatomic substituents, amino compounds, an carbocyclic ketone vinyl ethers. The aromatic compounds can be further identified mono-aromatic, fused aromatic ring compounds, and diaromatic compounds linked wit a sigma bond or with a carbon or divalent heteroatomic substituent. In addition to th ring compounds, hetero-substituted aliphatic compounds that are biologically active an possess the requisite χ value and Z parameter also may find use as anti-fouling agents i accordance with the precepts of the present invention. Additionally, compounds whic do not quite fit any of the foregoing definitions also should be recognized as include within the scope of the anti-fouling agents of the present invention. These include bori acid which has been demonstrated to be quite active as an anti-fouling agent, as the dat will testify. Additional compounds include, for example, antimony tartrate and cupri oleate. Illustrative of additional low toxicity antifouling agents/reactants of the prese 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-(aUyloxy) phenyl methylcarbamate

2-(allylthio)-2-thiazoline „ l,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-l,4-napthoquinone

3-amino-5-nitro-o-toluamide

3-amino- 1 ,2,4-triazole ammonium sulfamate antimony potassium tartrate 2-^Moro- -ethylarnmo-6-isopropylamino-S-triazine

4-chloro-m-chlorocarbanilate

6-chloropiperonyl chrysanthemumate N-butyl-N-ethyl-α,α,α-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-methoxylpropylaιrdno)-6-methylthio-S-triazine bis (pentachloro-2,4-cyclopentadien- 1-yl) boric acid

N-(4-bromo-3-chlo^ophenyl)-N'-methoxy-N^, -methyl urea

5-(bromomethyl)-l,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-eu ylamino-6methylmercapto-S-triazine

4-tert-butyl-2-chlorophenylmethyl methylphosphoramidite o-(4-tert-butyl-2-chlorophenyl)o-methylphosphoramidothionate 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-methylthio-4-cyclohexene- 1 ,2-docarboximide

1-napththyl n-methylcarbamate S-[[(p-chloropheπyl) 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 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-cUoro-N'-(3,4-dicUorophenyl) N,N-dimethylformamidine

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

1 ,4-dicMoro-2,5-dimethoxybenzene l-(chloro-2-norbornyl)-3,3-dimethylurea S-(p-chloro-α-phenylbenzyl) O,O-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-phenyIphenol 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

2-(2,4-dihydroxyphenyl)-l-cyclohexene-l-carboxylic acid-β-lactone -0-diethylphosphorothioate

2-κ;hloro-4-dimet ylamino-6-met ylpyrimidine

3-(2-cyclopenten-l-yl)-2-methyl-4-oxo-2-cyclopenten-l-yl chrysanthemunate α-cyclohexyl-α-phenyl-3-pyridyl-methanol, hydrochloride

N'-cyclo-octyl-N,N-dimethylurea 3\4^,-dichlorocyclopropanecarboxanilide

2,4-dichlorophenoxyacetic acid

2,4-d,α-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-memyl-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) O,O-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-(dichlorofluoromethylthio)-N'N' -dimethyl-n-phenyl sulf amide

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'-dichlbro-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 α-(Diethoxyphosphinothioylthio) gamma-butyrolactone

O,O-diethyl s-carboethoxymethyl phosphorothioate O,O-diethyl O-naphthyla ido phosphorothioate

0,0-diethyl 0-3,5,6-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,Cκ-imethyl-S-2-(acetyIamino)-ethyldithiophosphate

N-dimethylamino succinamic acid l,l-dimethyl-3-[3-(n-tert-butyl-carbamoyloxy)phenyl]urea

O,O-dimethyl s-carboethoxymethyl phosphorothioate

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

0,0-dimethyl-o-p-cyanophenyl phosphorothioate o,o-dimemyl-s-[5-ethoxy-l,3,4-thiadiazol-2(3H)-onyl-(3)-methyl] phosphorodithioate N,N-dimethyl-N'-(2-methyl-4*<hlorophenyl)-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-(l-methyl-n-heptyl)-4,6-dinitrophenyl crotonate

N^-dimethyl-2,2-diphenylacetamide diphenylacetonitrile diphenylamine 2,6-dinitro-N,N-di-n-propyl-p-toluidine

Di-n-propyl-2,5-pyridine-dicarboxylate l,r-ethylene-2,2'-dipyridinium dibromide

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

3-(3,4-dichlorphenyl)-l,l-dimethyl-urea n-dodecyl thiocyanate n-dodecylguanidine acetate

Ethyl N^-dipropylthiolcarbamate

2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate ethoxymethylbis (p-chlorophenyl) carbinol l,2-κ-ihydro-6-ethoxy-2,2,4-trimethylquinone ethyl-N,N-diisobutyl thiolcarbamate ethylenebis (dithiocarbamato) zinc

3-phenyl-l,l-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- 1 -yl chrysanthemunate 2-heptadecyl-2-imidazoline

7-cMoro-4,6-dimethoxycoumaran-3-one-2-spiro- -(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)-ώbenzofuran-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-methyluracil isopropyl-4,4'-diboromobenzilate isopropyl 4,4'-dichlorobenzilate isopropyl mercaptophenyl-acetate, O,O-dimethyl phosphorodithioate

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

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

S-[l,2-bis(ethoxy-carbonyl)ethyl] O,O-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-diamino-s-triazine-2-yl)methyl] 0,0-dimethyl phosphorodithioate

2-isopropylamino- (3-methoxypropylamino)-6-methylthio-s-triazine l,l,l-trichloro-2,2-bis(p-methoxyphenyl) ethane

2-memoxy-4-isopropylammo-6-diethylammo-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'-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 l,2-*dmyάtopyrioazine-3,6-dione

3,3'-ethyIenebis-(tetrahydro-4,6-dimethyl-2H-l,3,5-thiadiazone-2-thione) S-eutylhexahydro-lH-azepine-l--carbothioate 3-(p-chlorphenyl)-l,l-dimethylurea 3-φ-chlorophenyl)-l,l-dimethylureatrichloroacetate disodium ethylene bisdithiocarbamate l^-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,l-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-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-

2-propyltoluene piperonyl cyclonene polychlorobenzoϊc acid, dimethylamine salt 2,4-bis-(isopropylamino)-6-methoxy-s-triazine 2-methyl-mercapto- ,6-bis(isopropylamino)-s-triazine 2-chloro-n-isopropylacetanilide 3 ',4'-dichloropropionalide 2-cUoro-4,6-bis(isopropyl-amino)-s-triazine di-n-propyl-3-methyl-6,7-methylenedioxy-l,2,3,4-tetra-hydronaphthalene-

1,2-dicarboxylate 5-amino-4-chloro-2-phenyl-3(2H) pyridazinone pyrethrin l 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

1 -(2-methyl-cyclohexyl)-3-phenylurea l-(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)-l,l-dichloroethane ethylene- 1,2-bis (tWocarbamoyldimethylthio-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-methanonaphthalene- 5,8-dione

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

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) cyclopropa carboxylate

O,0,0',0'-tetramethyl O,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

O,O-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-tricWoro-n-φentacUoro-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-κjUoro-4-(di-emylarnino)-6-(emylaπιmo)-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 accomplished by a variety techniques, depending upon the available functionality of t anti-fouling agent. For example, ethylenic unsaturation in the anti-fouling agent can copolymerized with acrylate or other ethylenically unsaturated monomers in conventio fashion. See, for example, Acrylic Monomer, product literature, Dow Badisc Company, Form No. A-GB-101; Preparation, Properties and Uses of Acrylic Polyme product liturature, Rohm and Haas Company, Form CM-19 B/eh; and U.S. Pat. 4,566,962, the disclosures of which are expressly incorporated herein by referen Anti-fouling agents with reactive hydroxyl or other active hydrogen functionality (e.g NH, -NH2, -SH, or the like) can be reacted with a polyisocyanate for forming an an fouling agent adduct. See, for example, Macromolecular Synthesis, C.G. Overberg Editor, Vol. 1, pp 69-74, John Wiley & Sons, Inc., New York, New York (1963), t disclosure of which is expressly incorporated herein by reference. Additional reactio will be readily apparant to those skilled in such art, as stated above, depending upon t reactive functionality in the anti-fouling agent

Additional techniques for forming PCDs include, for example, complexi (association or other mechanism) of the anti-fouling agent with another ingredient in t formulation, e.g., pigment, polymer or oligomer additive, or the like. Anoth technique involves the anti-fouling agent being relatively more miscible in discontinuous phase (or particles), than in the continuous phase of the coating. Agai PCDs would be formed. Regardless or the technique, so long as PCDs of the an fouling agent are formed in the fianl product, improved long-term anti-fouling activi will be expressed by the anti-fouling agents. The formulation of the marine compositions containing the anti-fouling agents the present invention is practiced in conventional fashion as those skilled in the a appreciate utilizing conventional film-forming binders appropriate for mari environments. Marine compositions broadly for present purposes include, for examp coatings, elastomers, sealants, caulks, grouts, concretes, and like polymeric structu appropriate for the marine environment The form of the marine composition can be a coating, as rigid or elastomeric (including foamaceous) objects, as a sealant or a three-dimensional configured structure such as villous trailing fingers in the exterior marine vessels. Conventional additives, organic solvents (including reactive solvents diluents), and the like are incorporated into the formulation. The proportion of a fouling agent generally is between about 1 and 20 weight percent by weight of t formulation.

The following examples show how the present invention has been practiced should not be construed as limiting. In this application, all percentages and proportio are by weight and all units are in the metric system, unless otherwise expres 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 thr neck reaction flask fitted with a mechanical stirrer, thermometer, and reflux conden was charged with a polysulfide polymer (200 g of LP-3 polysulfide polymer, Thioko 1,2-dicyano, tetrachlorobenzene (100 g of Nopocide brand, Diamond Shamroc potassium hydroxide (80 g), and dimethyl sulfoxide (100 ml). The reaction mixture heated for three hours to a temperature of 105° C, cooled to room temperature, wash and subjected to vacuum for removal of solvent. The resulting polymeric struct 45701-1 can be represented conventionally as follows:

EXAMPLE 2 .

An anti-fouling agent-modified adduct was synthesized in accordance with t following reaction scheme. Toluene (100 ml) was added to a roundbottomed fla followed by the addition of hydroxyethyl methacrylate (14 ml) and toluene diisocyan (17 ml). This mixture was stirred for one hour at room temperature followed by addition of triethylamine catalyst (three drops). After two hours, 3,4-dichloroanal (16 ml) was added to the solution which then was heated to 50° C and held for 10 ho The resulting solid product was filtered through number 40 filter paper and washed additional alliquots of toluene and hexane. Infrared analysis showed the expec urethane-amide structures consistent with the desired reaction product 45701-3 whic illustrated conventionally below.

EXAMPLE 3 A pressure reactor fitted with a pressure gauge was loaded with 3-(3, dichlorophenyl)- 1,1 -dimethyl urea (45 g) and propylene oxide (150 ml). The react was sealed and heated to 80° C (a pressure reading of 50 psi) and held for 20 hou The sample removed from the reactor was analyzed by IR and showed broadening of t NH bands and the presence of hydroxyl functionality and some polyether functionali (1100 cm'l). Preparation of this material is similar to that preparation described in Polymer Science, vol. 15, 427-446 (1955). Reaction production 45701-4 can represented conventionally below. It will be observed that the reaction product contai a hydroxyl group which could be reacted with isocyanate or other functionality for incorporation into a curable resin.

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

EXAMPLE 5 Addition of a 10% solution of CuCl2 in ethanol to a 10% solution of hydroxyquinoline formed a dark brown complex immediately. This complex 45701 was washed with hexane and dried without further purification. The structure of t complex can be represented conventionally as follows:

EXAMPLE 6 The procedure of Example 2 was repeated using 2,5-dichloroanaline instead ,4-dichloroanaline. Reaction product 45701-7 is illustrated below:

NHC-0~CH₂CH₂-0— C-C = CH₂

II II I

0 0 CH₃ EXAMPLE 7 1,5-napthalene diisocyanate (25 g) was reacted with l,3-diaza-2, cyclopentadiene (14 g) using the urethane reaction procedure as set forth in Example The resulting reaction product 45701-8 is represented conventionally below:

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

EXAMPLE 9

Two different modified polymeric structures were prepared. Polymeric structur 45701-10 was prepared by adding DER 331 resin (11 g) to 2-mercaptobenzothiazole (1 g) dissolved in toluene solvent (35 ml). This reaction mixture was heated to 90" C three hours until a clear solution was obtained. The second polymeric structu identified as 45701-11 was prepared by the same reaction procedure utilizing morpholi in place of 2-mercaptobenzothiazole. Both structures can be represented conventional below:

EXAMPLE 10 In order to demonstrate the affect which PCDs of organo anti-fouling displa anti-fouling formulations (Control Paint) were compounded as follows:

TABLE 1

Test panels were 15.24 cm x 30.48 cm (6 in x 12 in) in dimension and we constructed of a white plastic top surface and a black plastic bottom surface. The te panels were coated on both sides with the two formulations above-tabulated at a fil thickness of about 5 mils dry. The test panels then were exposed horizontally with t white surface upward and the black surface downward in the ocean at Daytona Beac Florida, U.S.A. A control panel consisted of 12 wt-% triphenyl tin hydroxide dispers in a resinous vinyl binder (80 wt-parts of a vinyl chloride polymer, VAGH bran Union Carbide Corporation, New York, New York) reduced in methyl ethyl keto solvent to 50% solids content The following results were recorded.

TABLE 2

Rating After Exposure"

Sample 4 Months 462 Days

Control Paint- No Ann-Fouling Additive 0 0

Control Paint- Nopocide Freely Added at 20 wt-% 0

Control Paint- Polymeric Additive 45701-1 at 20 wt-%

* 10 is perfect protection

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

EXAMPLE 11 The Control Paint of Example 10 was formulated with additional polymeric a as-is anti-fouling additives and evaluated as in Example 10, with the following resul being recorded: TABLE?

Sample Rating After Exposure* (Additive at 20 wt-%^{^}1 4 Months 462 Davs

Control Paint- No Anti-Fouling Additive 0 0

Control Paint- 3,4-Dichloroaniline 0 0

Control Paint- 2,5-Dichloro aniline 0

Control Paint-

2,6-Dichloro-

4-Nitroaniline 0 0

Control Paint- 3,4-Dichloroaniline Polymer of Example 2 5-6 5-6

Control Paint- 2,5-Dichloroaniline Polymer of Example 8 1-2

Control Paint- 2,6-Dichloroaniline- 4-Nitroaniline Polymer like that of Example 6 7-9

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 gample Rating After Exposure" (Additive at 20 wt-%) 4 Months

Control Paint- No Anti-Fouling Additive

Control Paint- Hexachloro-5-Norborene- 2,3-Dicarboxylic Anhydride 0

Control Paint- Hexachloro-5-Norborene- 2,3-Dicarboxylic Anhydride Polymer of Example 4 3-4

Control Paint- Phenothiazine 0

Control Paint- Phenothiazine Polymer of of Example 8 0-1

Control Paint-

50/50 Weight Mixture of 2-Mercapto- benzothiazole and Morpholine 0

Control Paint-

50/50 Weight Mixture of 2-Mercaρto- benzothiazole and Morpholine Polymer that of Example 11

Again, the efficacy of the PCD anti-fouling agents is established.

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 Month 4 Months

Control Paint-

3,5-Dichloro-N-

(3,3-Dimethylproyne) Benzamide orPronamide of Example 10 0 0

Control Paint-

Pronamide Polymerized with

50/50 Methylmethacrylate and

Butyl Acrylate 7 7

Control Paint— d-rr w-Allerthrin of

Example 10 0-1 0

Control Paint- d-Trans-AJleτύ n Polymerized with 50/50 Methylmethacrylate and Butyl Acrylate 7 7

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

EXAMPLE 14 The Control Paint of Example 10 was formulated with additional anti-foulin additives and evaluated with the following results being recorded: TABLE 6

Sample Rating After Exposure* (Additive at 20 wt-%1 1 Month 4 Months

Control Paint-

3- (3,4-Dichlorophenyl)- 1,1- dimethyl urea (See Example 3) 0

Control Paint- Urea of Above Attached to Urethane Prepolymer of 2 Moles of Toluene Diisocyanate and Polypropylene Glycol (200 Molecular Weight)

Control Paint- Reaction Product of 1,5-Naphthalene Diisocyanate and l,3-Diaza-2,4-Cyclopendadiene (See Example 7) 6-7

Control Paint-

Cyclopendadiene above Polymerized with 2 Moles of Naphthalene Diisocyanate and 1 Mole of Ethylene Glvcol 6-7 6-7

The above-tabulated results further confirm the invention.

EXAMPLE 15 Testing of several additional anti-fouling agents in the paint formulatio described in Example 12 was conducted for 6 months and the results compared t several polymerized versions of the same anti-fouling agents, with the following result being recorded: TABLE 7

Anti-Fouling General Rating

Panel # Agent 1 Mo. 4 Mos. 6 Mos. 6 Mos.*

5 13-A1 Eugenol** 0

13-A2 Eugenol** 0

0

0 4-6

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 o the anti-fouling agent

**Eugenol is 99% 4-allyl-2-methoxyphenol. 5

EXAMPLE 16 An epoxy resin system was examined for its ability to be modified so as t preferentially influence the concentration or location of an anti-fouling agent (No ocid N-96 , see Example 1) within its structure. A direct comparison was made between epoxy resin (EPON 828 epoxy resin, diglycidyl ether of bis-phenol A, Shell Chemic Company) and the same epoxy resin containing a domain structuring polymeric materi such as a polysulfide resin (LP-32 polysulfide resin, Thiokol Corporation). Bo systems contained the same anti-fouling agent The compositions formulated are s forth below:

TABLE 8

Sample (g-) Ingredient

Epon 828 9 6 9

LP-32 - 3

Hexachlorophene 1.41 1.29

Polymer of Nopocide N-96 and LP-32 polysulfide (3 parts LP-32 and 1.24 parts Nopocide) — — 1.7

Ancamine AD* HO 3Λ 5.10

*Amine hardner, 485 amine value, Pacific Anchor Corp.

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

Energy Dispersion Spectoscopy (EDS) analysis of the sample surface f chlorine from the hexachlorophene anti-fouling agent showed that there were tw distinct domains or regions where the chlorine could be found. Chlorine was identifie in both the sea-like structures and the small round island structures in the sample (Fi 2). What was unexpected, however, was the discovery that the chorine concentratio and, thus, the concentration of anti-fouling agent, was significantluy higher (48%) in t round island domains and lower (36%) in the sea-like domains of the sample. pictorial representation of these results is displayed in Fig.3.

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

EXAMPLE 17 In this example, an unreacted toxicant was evaluated with respect to its ability preferentially concentrate in domains of another material created within a continuo polymeric binder or carier. For example, certain types of acrylic copolymers dispers in a polyvinyl chloride (PVC) polymer can create discrete domains wherein a toxica molecule can preferentially concentrate. In this case, the toxicant was the 3, dichloroanaline-based acrylate monomer of Example 2 (80 wt-% concentration, sha melting point at 180° C), the continuous phase was VAGH PVC polymer (see Examp 10), and the domain-creating polymer was a mixture of polyhydroxyethylmethacryla (10 wf-% concentration, melting point less than 250° C) and a polymer of a methacryl acid ester of an amino carbamate monomer (10 wt-% concentration, melting point great than 300° C).

Scanning electron micrographs are shown at Figs. 7 and 8 for PVC containi 20 to 30 wt-% of the mixture set forth in Table 11. The domains created by t polymeric and unreacted monomer mixture in the PVC can be distinguished easil Surprisingly, the toxicant monomer molecules are preferentially concentrated with t acrylic ingredients which created the domains in the PVC binder. An oxygen densit map (oxygen is analyzed rather than chlorine because of the chlorine content of th binder) of the film surface (see Figs 9-12) clearly indicates that the only place oxyge resides is in the domains. Interestingly, the oxygen is not distributed in the domain voi or sea-like regions of the PVC. The oxygen maps clearly outline only thos regions/domains or islands where the toxicant molecules reside, and not in the sea continuous phase of the PVC. The light or bright areas in these figures are due to th 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 hexachlorophen toxicant-was replaced by Nopocide N-96. Thus, a blend of domain-forming LP-3 polysulfide resin and the Nopocide is being evaluated with respect to the formation o PCDs of Nopocide. The cured epoxy resin system was subjected to SEM and E 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. is evident that the LP-32 polysulfide polymer created discrete domains. Fig. 14 displa the EDS analysis of chlorine at 200 X, while Fig. 15 is for sulfur. A comparison of t two EDS maps reveals that chlorine and sulfur both are present at the same location the cured epoxy resin system. Chlorine comes from the Nopocide toxicant, while sul comes from the LP-32 polysulfide resin. Again, then, the formation of PCDs of no tin, organo anti-fouling agents is seen to have been achieved. Here, such formation due to the preferential formation of domains by the LP-32 polysulfide polymer with t concomitant preferential concentration of the toxicant with the polysulfide polymer.

Claims

CLAIMSWe claim:

1. In a non-tin-containing, curable, marine anti-fouling composition o thermoplastic or thermoset binder, solvent and a non-tin, organo anti-fouling agent improvement wherein said anti-fouling agent forms preferentially-concentrated doma in the cured composition.

2. The composition of claim 1, wherein said anti-fouling agent comprise water-insoluble compound having a χ value of between about 0.01 and 0.5, a parameter for vinyl or aromatic compounds of between about 0.01 and 0.08, and LD50 value of greater than 200 mg/kg against rats or mice.

3. The composition of claim 2 wherein the χ value is established by s agent containing heteroatoms selected from the group consisting of sulfur, oxyg nitrogen, halogen, and mixtures thereof.

4. The composition of claim 1 wherein said anti-fouling agent is select from the group consisting of heterocyclic compounds, aromatic compounds containi heteroatomic substituents, amino compounds, and carbocyclic ketone vinyl ethers.

5. The composition of claim 4 wherein said aromatic compound wi heteroatomic substituents is selected from the group consisting of monoaroma compounds; fused aromatic rings; and di-aromatic compounds linked with a sig bond, a dialkylene group, or a divalent heteroatomic group; and mixtures thereof.

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

4-allyl-2-methoxyphenol diphenylacetonitrile

2,3-dichloro- 1 ,4-napthoquinone cetylpyridinium chloride diphenylamine boric acid 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 dimethylphosphoramide ammonium salt 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-dinitiO,4-N,N-dipropylamino benzene sulfonamide 2-chloro-2-propenyl diethylcarbamodithioate and mixtures thereof.

7. The composition of claim 1 wherein said anti-fouling agent is select 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 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-l,2,4-triazole ammonium sulfamate 5 antimony potassium tartrate

2-cMoro- -ethylamino-6-isopropylam o-S-triazine 4-chloro-m-chlorocarbanilate 6-chloropiperonyl chrysanthemumate N-butyl-N-<thyl-α,α,α-trifluorθ 2-6-dinitro-p-toluidine 10 bis (p-chlorophenyl)-3-pyridine methanol bis (dialkylphosphinothioyl) disulfide bis (4-hydroxyiminomethylpyridinum-l-methyl) ether dichloride 2,4-bis (3-methoxylpropylamino)-6-methylthio-S-triazine bis (pentachloro-2,4-cyclopentadien- 1-yl) 15 boric acid

N-(4-bromo-3-chlorophenyl)-N'-methoxy-N' -methyl urea 5-(bromomethyl)-l,2,3,4,7,7-hexachloro-2-norbornene S-(0,0-diisopropyl phosphoro-dithionate of N-(2-mercaptoethyl) benzenesulfonamide 20 benzamidooxy-acetic acid

3-benzylideneamino-4-phenylthiazoline-2-thione bis (p-chlorophenoxy) methane bis (4-chlorophenyl) disulfide 1,1 -bis (p-chlorophenyl) ethane 25 1,1-bis (p-chlorophenyl)-ethanol o,o-dimethyl-o-2,5-dichloro-4-bromophenylthionophosphate O,O-dimethyl-2,2,2-trichloro-l-n-butyryloxyethylphosphonate N-butylacetanilide

2-tert-butylamino-4-chloro-6-ethyl amino-5-triazine 30 2-tert-butylaminc»-4-ethylan^o-6methylmerrapto-S-πiazine

4-tert-butyl-2-cUorophenylmemyl methylphosphoramidite o-(4-tert-butyl-2-cWorophenyl)o-met ylphosphoramidothionate butyl 3,4-dihydro-2, 2-dimethyl-4-oxo-l,2h-pyran-6-carboxylate n-butyl-9-hydroxyfluorene-(9)-carboxylate 35 2-(p-tert-butylphenoxy) cyclohexyl 2-propynyl sulfite l-butyn-3-yl m-chlorophenyl-carbamate N-trichlorcHmethylthio-4-cyclohexene-l^-docarboximide 1-napththyl n-methylcarbamate

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

2-chloro-N,N-diallyl-acetamide

2-chloroallyl diethyl-dithiocarbamate 5 cetyldimethylethylammonium bromide cetyl pyridinium chloride tetrachloro-p-benzoquinone

2-cMoro-4,6-bis(diethylamino)-s-triazine p-chlorobenzyl p-chlorophenyl sulfide 10 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 15 l-chloro-N'-(3,4-dichlorophenyl) N,N-dimethylformamidine

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

1 ,4-dichloro-2,5-dimethoxybenzene l-(chloro-2-norbornyl)-3,3-dimethylurea

S-(p-chloro-α-phenylbenzyl) O,O-diethyl phosphorodithioate

20 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 sulf one 25 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 30 isopropyl N-(3-chlorophenyl) carbamate copper (cupric) oleate copper 8-quinolinolate

2-(2,4-dihydroxyphenyl)-l-cyclohexene-l-carboxylic acid-β-lactone O-diethylphosphorothioate 35 2-chloro-4-dimethylamino-6-methylpyrimidine

3-(2-cyclopenten-l-yl)-2-methyl-4^oxo-2-cyclopenten-l-yl chrysanthemunate α-cyclohexyl-α-phenyl-3-pyridyl-methanol, hydrochloride N'-cyclo-octyl-N,N-dimethylurea 3 4'HU^ orocyclopropanecarboxanilide 2,4-dichlorophenoxyacetic acid 2,4-d,α-chlorocrotyl ester 3,5κlimethyl-l,3,5,2H-tetrahyorotωadiazine-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-memyl-tMo-4-isopropylamino-6-methylamino-s-triazine S-2,3-dichloroallylN,N-dϋsopropylthiolcarbamate l,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-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-(dichlorofluoromemyltMo)-N'N'- limethyl-n-phenyl sulfamide

4,4'-dichloro-N-rnethylbenzene-sulfoanilide 2,3-dichloro-2-methylpropionic acid sodium salt 2,6-dichloro-4-nitroaniline 2,5-dichloro-3-niux>benzoic acid 5,2'-dicMoro-4'-nitro-salicylanilide ethanolamine salt

2',5'-dichloro-4'-nitrososalicylaniride 2,2'-dihydroxy-5,5^,-dichlorophenylmethane l-(2,4-dicMorophenoxyacetyl)-3,5 limethylpyrazole 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-dichlof ophenyl methanesulfonate 2,4-dichlorophenyl 4-nitrophenyl ether

4-dichlorotetrahydrothiophene 1,1 -dioxide

4,4'-dichloro-alpha-trichloromethylbenzhydrol

3 ' ,4'-dichloro-2-methacrylanilide α-(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-diethyldithioca bamoyl phosphorodithioate

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

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

N-dimethylamino sύccinamic acid l,l-dimethyl-3-[3-(n-tert-butyl-carbamoyloxy)phenyl]urea

0,0-dimethyl s-carboethoxymethyl phosphorothioate

0,0-dimethyl 0-(3-chloro-4-nitrophenyl) phosphorothioate

O,O-dimethyl-o-p-cyanophenyl phosphorothioate o,o-dimethyl-s-[5-ethoxy-l,3,4-thiadiazol-2(3H)-onyl-(3)-methyl] phosphorodithioate

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

0,0-dimethyl o-(4-nitro-m-tolyl) phosphorothioate o,s-dimethyl tetrachloro thioterephthalate

4'-dimethyltriazenoacetanilide dinitrocyclohexylphenol

2,4' l tro- -trifluorornethyl diphenylether

2-(l-methyl-n-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 l, -ethylene-2,2'-dipyridinium dibromide

2,3-dicyano- 1 ,4-dithia-anthraquinone 3-(3,4-dichlorphenyl)-l, 1 -dimethyl-urea n-dodecyl thiocyanate n-dodecylguanidine acetate ethyl N ,N-dipropyltMolcarbamate 2-(2,4,5-trichlorophenoxy)ethyl-2^-dichloropropionate ethoxymethylbis (p-chlorophenyl) carbinol l,2-<-ihydro-6-e oxy-2.2,4-trimethylquinone ethyl-N,N-diisobutyl thiolcarbamate ethylenebis (dithiocaibamato) zinc 3-phenyl-l,l-dimethylurea trichloroacetate ferric dimethyl-dithiocarbamate

0,0-dimethyl S-(N-formyl-N-methylcarbamoyl-methyl)phosphorodithioate 2-formyl-4-chlorophenoxyacetic acid

7-chIoro-4,6-dimethoxycoumaraπ-3-one-2-spiro- 1 ' -(2' -methoxy-6 '- methylcyclohex-2'-εn-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 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-dmydro-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-diamino-s-triazine-2-yl)methyl] 0,0-dimethyl phosphorodithioate 2-isopropylamino-4-(3-methoxypropylarnmo)-6-methylt o-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-methylbenzyl 3-(dimethoxy-phosphinyloxy)-cis-crotonate m-(l-methyl butyl) phenyl methyl-carbamate methyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate 5 3,3'-methylenebis (-4-hyά oxycoumarin)

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

6-methyl-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 10 4-(methylsulf onyl)-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 15 3,3'-ethylenebis-(tetrahydro-4,6-dimethyl-2H-l,3,5-thiadiazone-2-thione)

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

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

3-(p-chlorophenyl)- 1 , 1 -dimethylurea trichloroacetate disodium ethylene bisdithiocarbamate 20 l,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)-l,l-dimethylurea

N-1-naphthyl-phthalamic acid 25 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) 30 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 35 piperonyl cyclonene polychlorobenzoic acid, dimethylamine salt

2,4-bis-(isopropylamino)-6-methoxy-s-triazine 2-met yl-mercapto-4,6-bis(isopropylamino)-s-triazine 2-chloro-n-isopropylacetanilide 3',4'-dichloropropionalide 2-chIoro-4,6-bis(isopropyl-amino)-s-triazine di-n-propyl-3-methyl-6,7-methylenedioxy-l,2,3,4-tetra-hydronaphthalene-

1 ,2-dicarboxylate 5-arnino-4-chloro-2-phenyl-3(2H) pyridazinone pyrethrin l 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 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 (tMocarbamoyldimethylthio-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- methanonaphthalene-5,8-dione N-(l,l^,2-tetracUoro-ethyl-sulfenyl cis- -cyclohexene-l,2-dicaι1x)xirnide 2,4,5,6-tetrachloroiso-phthaIonitrile 1 ,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-tetrahydrophthalinϋdomethyl 2,2-dimethyl-3-(2-methylpropenyl) cyclopropanecarboxylate O,O,O',O'-tetramethyl O,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

O,O-dimethyl (l-hydroxy-2,2,2-tricMoroethyl)phosphonate

2,3,6-trichlorobenzoic acid trichlorobenzoic 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-l,3,5-triazine

2-cMoro-4-(di-ethylaπ no)-6-(ethylamino)-s-triazine tert-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate

S -propyldipropylthiocarbamate zinc ethylene bisdithiocarbamate zinc dimethyldithiocarbamate

3 ,5-dinitro-o-toluamide and mixtures thereof.

8. The composition of claim 1 wherein said anti-fouling agent contain reactive functionality for reacting with a monomer, oligomer, or polymer, which produ forms preferentially concentrated domains in the cured composition.

9. The composition of claim 8 wherein said monomer, oligomer, or polymer contains heteroatomic substituents selected from the group consisting o nitrogen, sulfur, or both.

10. The composition of claim 1 which comprises a film-forming coatin composition.

11. The composition of claim 6 wherein said anti-fouling agent contain reactive functionality for reacting with a monomer, oligomer, or polymer, which produ forms preferentially concentrated domains in the cured composition.

12. The composition of claim 7 wherein said anti-fouling agent contain reactive functionality for reacting with a monomer, oligomer, or polymer, which produc forms preferentially concentrated domains in the cured composition.

13. The composition of claim 1 which further comprises a compound whi forms discrete domains in the cured composition which compound domains are the sa domains as said anti-fouling agent preferentially concentrated domains.

14. The composition of claim 1 wherein said domains range in size fro about 0.3 to 500 micrometers.

15. In a method for formulating a non-tm-containing, curable marine an fouling composition of a thermoplastic or thermoset binder, solvent and a non-ti organo anti-fouling agent the improvement which comprises providing said anti-foulin agent in a form that forms preferentially concentrated domains in the cured composition.

16. The method of claim 15 wherein said anti-fouling agent contains reactiv functionality for reacting with a monomer, oligomer, or polymer, which product form preferentially concentrated domains in the cured composition.

17. The method of claim 15 wherein said composition further comprises compound which forms discrete domains in the cured composition which compoun domains are the same domains as said anti-fouling agent preferentially concentrate domains.