US 3795741 A
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ELF, Liv 424 288 lPLfiYHNG CERTAIN ORGANOTIN COOUNDS Pasquale haul Minieri, Woodside, N.Y., assignor to 'Henneco Chemicals, line, lslo Drawing. Confinuation-in part of application Sea. No. 3,233, lien. 15, 1970, which is a continuation-impart of application See. No. 708,782, Feb. 28, 1968, both now ailsendeared is application Man a, 1972, Sen. l loo int. (Ella A0111 9/ i4 @lalms asses on macros n;
Marine antifoulant compositions comprise an organic water-resistant film-forming vehicle and an organotin compound that has the structural formula wherein each R represents an alkyl group having from 4 to 8 carbon atoms or a phenyl group; one of the X substituents represents phenyl or menthyl; the other X sub This is a continuation-in-part of my copending patent application Serial Number. 3,233, which was filed on Jan. 15,1970 which has been abandoned, and which is a com tinuation-in-part of my patent application Ser. No. 708; 7-82, which was filed on Feb. 28, 1968 and which has been abandoned This invention relates to marine antifoulant compositions and to their use in the protection of ship and boat bottoms, wharves, doclts,-pilings, and the like from attack: by marine organisms that have a deteriorative effect on such objects. More particularly, it relates to marine anti ioulant compositions that contain as their active ingredient certain toxic organotin compounds and to the use of these compositions in the control of marine organisms, fungi, and bacteria.
In the past metal salts and metal oxides, such as copper naphthcnate, copper acrylate, zinc naphthenate, mercury oxides, and the like, have been used in marine anti" foulant paints and other antifouling compositions. These materials have not been entirely satisfactory in this ap= plication because they are not sufiiciently active against the undesirable marine organisms, because they cause electrolytiocorrosion of the substrate, because they are toxic to fish and other desirable marine life, or because they are'cxpensive to use.
in accordance with this invention, it has been found that certain organotin compounds have unusual and valuable activity as marine antifouling agents. These compounds, which are highly effective in preventing marine fouling of p a variety of surfaces, have a long-lasting antifouling effect ea ing 5R r r o y are; atl' ltifiei t V F.?3 Q) l I A Jails Patented Mar. 5, save 3 795 741 and are tgxic to a wide variety of undesirable marine ort sani m ut as used they have negligible toxicit to dcsir- MAlilitsllF ANOUL C0 OSITIONSS EMI= able marine life and to human beings. y
' These organotin compounds have the structure formula trl-n-butyl(2-phenyl-4-chlorophenoxy)tin; 'tri-n-butyl(2,4-dichloro-d-phenylphenoily)tin; tri-n-buty1( 2,4-dinitro-6-phenylphenoxy) tin; tri-n-butyl 4-methylphenoxy tin;
tri-n-butyl (2-methyl-4-menthylphenoxy tin;
trioctyl(2,4-dichloro-6-phenylphenoxy )tin; triphenyl(2-phenyl-4-chlorophenoxy)tin; triphenyl(2,4-dichloro-6-phenylphenoxy)tin; triphenyl 2,4-dinitro-d-phenylphenoxy)tin triphenyl(4-menthylphenoxy)tin; tgiphenyl(Z-methyl-4-menthylphenoxy )tin; triphenyl(2-bromo-6-menthylphenoxy)tin;
and the like. One of these organotin compounds or a mixture of two or more of them may be used in the marine antifouling compositions of this invention.
The organotin compounds may be prepared by any suitable and convenient procedure. For egxa mple, they may be prepared by the reaction of a substituted phenol with triphenyl tin hydroxide or a trialkyl tinhydroxide in a hy drocarbon or ketone solvent or by the reaction of an alkali metal salt of a substituted phenol with triphenyl tin chloride or a trialkyl tin chloride in a suitable solvent. The preparation and properties of these compounds are described in detail in [1.5. Pat. No. 3,524,869.
The organotin compounds are usually applied to the surface that is to be protected against attack by fouling organisms as compositions that comprise: an organic waterresistant film-forming vehicle and an amount of the 'active material that will accomplish the desired protec tive result. In most cases from about 1 pound to 10 pounds and preferably 0.5 pound to 3 pounds, of the organotin compound is used per gallon of the composition. In addi= tion the compositions may contain pigments, fillers, sol
vents, stabilizers, auxiliary antifouling agents, and other additives in the amounts ordinarily employed for these purposes.
Any of the organic water-resistant film-forming vehicles that arecommonly used in marine coatings may be used in the marine antifoulant compositions of this invention. These include, for example, polyvinyl chloride; vinyl chloride copolymers with vinyl acetate, vinyl propionate, vinyl butyrate, styrene, methyl methacrylate, and dimethyl maleate that contain about percent to percent of vinyl chloride; polyvinyl acetals; polyesters; alkyl resins; chlorinated rubber; phenol-formaldehyde resins; urea-formaldehyde resins; polyurethane; acrylic ester resins and.
a... r stanza-i methacrylic ester resins; epoxy resins; oleoresinous var= nishes; and the like. Especially satisfactory results have been obtained using the following organic water-resistant film-forming vehicles:
(a) Ethyl acrylate-methyl methacrylate copolymers hav ing viscosities in the range of about 250 to 335 centipoises at 30 0.;
(b) Mixtures containing 50 percent to 90 percent by weight of rosin and percent to 50 percent by weight of a vinyl chloride vinyl acetate copolymer containing 70 percent to 95 percent of vinyl chloride;
(0) Linseed oil-modified glyceryl phthalate alkyd resins;
(d) Polyvinyl butyral;
(e) Epoxy resins prepared by the condensation of epichlorhydrin and bisphenols; and
(f) Styrene-butadiene polymers containing percent to 70 percent of styrene.
Polymers having molecular weights in the range of about 400 to 1,000,000 can be used as the film-forming vehicle in the compositions of this invention. For each of the afore mentioned types of polymers, the preferred molecular weight range is that at which its solubility, viscosity, tensile strength, flexibility, and other properties are most satisfactory for use in surface-coating compositions The molecular weights of alkyd resins, polyesters, oleoresinous varnishes, and epoxy resins are preferably between about 400 and 5,000. For vinyl halide homopolymers and copolymers, styrene homopolymers and copolymers, acrylic and methacrylic ester resins, polyurethane, phenol-formaldehyde resins, and urea-formaldehyde resins, the pre ferred molecular weights are between about 20,000 and 250,000.
The organotin compounds may be incorporated into the marine antifoulant compositions by any suitable procedure. For example, a solution of the organotin compound in toluene or xylene may be added to the vehicle, or the compound per se may be added to the vehisis and other ingredients of the composition.
In another embodiment of the invention, the organotin compound is dissolved in an organic solvent that is prcferably a hydrocarbon or ketone, such as toluene, xylene, v
acetone, methyl isobutyl ke'tone, or petroleum spirits, and the resulting composition is used to impregnate textiles, rope, wood, leather, paper, and the like. Materials treated in this way are resistant to attack by marine organisms, fungi, and bacteria, particularly in outdoor uses where the surfaces are exposed to a significant degree to water.
This invention is further illustrated by the examples that follow.
EXAMPLE I Triphenyl(2,4-dichloro-fi-phenylphenoxy)tin was tested against a number of marine organisms by the procedure described by Miller in Industrial and Engineering Chemistry Product Research and Development, 3 (3), 226- 230 (1964), In this test porous carbon plates impregnated with the test compound are immersed vertically in the sea from a pier. Test specimens are removed periodic ally and the types of organisms attached to the test sur-= faces are noted. For comparative purposes, plates impregnated with tin oxide, a commercial anti-fouling agent, were included in the tests The data obtained are summarized in Table I.
From the data in Table I, it will be seen that some of the test plates treated with triphenyl(2,4-dichloro-6= phenyl-phenoxy)tin were not completely covered by fouling organisms after 18 months exposure in the sea, Whereas all of those treated with the commercial anti= it'ouling agent, tributyl tin oxide, had failed after 2. months immersion.
TABLE I iiriphenyl(2,4-dichloro-B-pehnylphenoxy)tin as a marine antifqulant} Amount compound Fouling on surface l Months in plate immersed Test compound (grams) 1 2 3 4 5 6 7 8 9 1 Triphenyl(2,4- 0.133 0 0 0 0 0 0 0 0 0 diehloro-o- 0.02300 0 0 0000 0 phenylpheuoxy) n. Tributyltinoxidsl 0.097 0 0 0 0 1 0 0 0 0 y 00200020100000 None Completely fouled 2 Tri honyl(2,4 0.133 0 0 5 0 0 0 0 0 0 'chloro-(i- 0.023 0 0 2 0 0 0 0 0 0 phenylphenoxy) v n. Tributyl tin oxide. 0 007 More than 50% fouled; test discontinued 0. 020 More than 50% fouled;
test discontinued 3 Triphenyl(2,4 0.133 0 0 7 0 0 0 0 0 0 dichloro-(i- .023 0 0 5 0 2 0 0 0 0 pihenylphenoxy) n. 4 do 0133000000000 0.02310 0 0 0000 O 5 .-do 0.1330020 0 00000 0.0232020 0 0000 0 6 do 0.133 0 0 l0 0 0 0 0 0 0 0. 023 More than 50% fouled;
test discontinued 0.1330070 0 0005 0 0.1330070 0 0005 0 0.1830075 0 0005 O 1 Percent 0! surfaces covered by organisms: (1) Brsnaeles, (2) Encrust' ing bryozoans, (3) Algae, (4) Bugula, (5) Hydroids, (6) Oysters, (7) Tube worms, (8) Tumcates, (9) Slime forming microorganisms.
EXAMPLE 2 Using the procedure described in Example 1, the effectiveness of a number of organotin derivatives of sub stituted phenols as marine antif oulants was determined. In each case the number of months that the treated carbon plates were immersed in sea water before more than 50 percent of the surfaces of the plates was covere with marine growth was noted. The compounds tested and the results of the test are summarized in Table II.
From the data in Table II it will be seen that each of the compounds of this invention was at least as eifective as a marine antifouling agent as tributyl tin oxide,
. TABLE IE [Evaluation of organotin derivatives of substituted phenols as marine antiioulants] Immersion Amount time compound (months) q in plate beiore 50% Test compound (grams) ioullng 'lripheuyl(2-phenyl-i-ohl0rophenoxy)tin 0. 0118 2 .0377 Triphnnyl(2,4-dinitro-fi'phenylphenoxy)tin. was 2 .054 s Triphenyl(4-menthylnhenoxy) tin 0. 811i 302 0. tiriphenyl(Zonethyl -emonthylphonoxy)tin t. 0 (.0320 2 7s Triburyl(2,4dichlom-6-phenylphenoxy)tin..... 0. 020 3 .189 t 'lributyl(2-methyl-4-meuthylphenoxy)tin 0. 083 2 1 Tributyl tin oxide 0. 028 g 0.097 2 EXAMPLE 3 I To a paint prepared by mixing together the following materials:
Pounds per gallon of paint Titanium dioxide 1.43 Aluminum silicate w en..- 0.45 Magnesium silicate w-.. 0.98
Ethyl acrylate-methyl methacrylate copolymer (vis-- marty 285 op, at 30C.; Gardner l'loldt vis cosity l) 7 MM, 3,85: Ethylene glycol monoethyl ether awesomeness... 2 -5.9 1
was added 1.00 pound per gallon of paint of triphenyl t2,4 dichloro o phenylphenoxy)tin, The resulting composition had a viscosity of 60 Krebs units.
The paint was applied to 8" x fiberglass test panels, The fronts and backs of the panels were utilized to provide duplicate test surfaces. For comparative purposes, panels were also painted with a proprietary yacht bottom paint that contained tri-n-butyl tin oxide as its antifouling agent. The painted panels were immersed in the ocean near Miami, Fla! The condition of the panels after 6 and 7 months immersion is summarized in Table III.
TABLE III [Evaluation of acrylic ester paint containing marine antifoulants] Percent Period Physical Fouling Fouling Antifouling otlmmen Test condition on res1st= agent sion surface oi paint surface ance l Triphenyl(2,4= 6 monthsc.}Front Good"... None 100 dichloro-iy Bac 0 None 100 phenylphenoxy) 7 months.. Front 7 93 tin Bee i 7 93 Tributyltln 6 months Front 8 9 91 oxide Bac B 12 88 7 months Front a 25 75 ac ..d 8 28 72 1 Ratin s are determined by subtracting percent fouling on surface irom 100%.
1 Green algae. Barnacles and green algae.
From the data in Table III it will be seen that the panels containing triphenyl(2,4 dichloro-6 phenyl phenoxyflin as the antifouling agent had undergone less fouling in 7 months immersion in the ocean than those containing tribntyl. tin oxide as the antifouling agent had undergone in 6 months immersion.
EXAMPLE 4 A paint was prepared by mixing together the following materials: 1
Pounds per gallon Either tributyl(2.4-dichlor06-pl1enylphcnoxy)tin 0r tri huiyl. tin oxides The paint was applied to 8" x 10" fiberglass test panels, and the painted panels were immersed in the ocean near Miami, Florida.
The conditions of the panels after 3 months immersion is summarized in Table IV,
TABLE IV [Evaluation of vinyl copolymer rosin paints containing marine anti= toulants] Percent Physical Fouling Fouling condition on resist- Antiiouling agent of paint surface once Tributyl(2,4-dichloro-6-phenylphenoxy) Goodufls 19 81 n. Tributyl tin oxide .d0. 28 72 Each of the other substituted phenoxy tin compounds disclosed herein can be used in a similar way to impart resistance to attack by marine organisms to materials susceptible to such attack The terms and expressions which have been employed are used as terns of description and not of limitation. There is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof; it is recognized that various modifications are possible within the scope of the invention claimed.
What is claimed is:
1. A marine antifouling composition comprising an organic water-resistant film-forming marine-coating vehicle and an antifouling amount of from about 0.1 pound to 10 pounds per gallon of said composition of an organotin compound having the structural formula wherein each R represents phenyl or an alkyl group having from 4 to 8 carbon atoms; one of the X substituents represents phenyl or menthyl; the other X substituent represents hydrogen haloggg p itpo, or an alkyl group having from 1 to 4 carboii atoms; and Y represents hydrogen, halogen, or nitro.
2. A marine antifouling composition as set forth in claim 1 that contains 0.5 pound to 3 pounds of the organotin compound per gallon of said composition.
3. A marine antifouling composition as set forth in claim I wherein the organotin compound is triphenyl- (2;4-dichloro-6-phenylphenoxy)tin.
4. A marine antifouling composition as set forth in claim 1 wherein the organotin compound is triphenyl- (2,4-dinitro--phenylphenoxy)tin.
5, A marine antifouling composition as set forth in claim 1 wherein the organotin compound is tributyl(2,4-= dichloro-6-phenylphenoxy)tin.
6. A marine antifouling composition as set forth in claim 1 wherein the organotin compound is triphenyl(4 menthyl-phenoxy tin.
'7. A marine antifouling composition as set forth in claim 1 wherein the organotin compound is triphenyl(2= methyl-4-menthylphenoxy)tin,
8, A process for inhibiting the fouling of surfaces ex posed to undesirable marine organisms which comprises applying to said surfaces a biocidal composition compris= ing an organic water-resistant film-forming marine-coating vehicle and an antifouling amount of from about Oil pound to 10 pounds per gallon of said composition of an organotin compound having the structural formula,
wherein each R represents phenyl or an alkyl group hav ing from 4 to 8 carbon atoms; one of the X Substitucnts represents phenyl or menthyl; the other X substituent rep resents hydrogen, halogen, nitro, or an alkyl group having from 1 to 4 carbon atoms; and Y represents hydrogen, halogen, or nitrom 9. The process of claim 8 wherein the biocidal composition contain 0.5 pound to 3 pounds of the organotin compound per gallon of said composition,
10. The process of claim 8 wherein the organotin cornpound is triphenyl (2,4-dich1oro-6-pheny1phenoxy tin.
11. The process of claim 8 wherein the organotin compound is tripheny1( 2,4 dinitro-6-phenylphenoxy)tin.
12. The process of claim 8 wherein the organotin compound is tributyl(2,4-dichl0ro-6-phenylphenoxy)tin.
13. The process of claim 8 wherein the organotin compound is triphenyl(2-methyl-4-menthylphenoxy)tin.
14. The process of claim 8 wherein the organotin com pound is triphenyl(4-menthylphenoxy)tin.
References Cited UNITED STATES PATENTS 3,321,365 5/1962 Menn et al. 424-288 2,970,923 2/1961 Sparmann 106-15 3,524,869 8/1970 Minieri 424-288 ALBERT T. MEYERS, Primary Examiner V. D. TURNER, Assistant Examiner US. Cl. X.R.
106--l5 AF; 117-1385; 260-429.?