CA1160387A - Antifoulant compositions of organotin containing polymers - Google Patents
Antifoulant compositions of organotin containing polymersInfo
- Publication number
- CA1160387A CA1160387A CA000372228A CA372228A CA1160387A CA 1160387 A CA1160387 A CA 1160387A CA 000372228 A CA000372228 A CA 000372228A CA 372228 A CA372228 A CA 372228A CA 1160387 A CA1160387 A CA 1160387A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000002519 antifouling agent Substances 0.000 title abstract description 13
- 239000008199 coating composition Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000000049 pigment Substances 0.000 claims description 11
- -1 phenylvinyl radicals Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 239000003701 inert diluent Substances 0.000 claims description 4
- 150000005840 aryl radicals Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 28
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 16
- 239000003973 paint Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000003628 erosive effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 1
- 102000001324 CD59 Antigens Human genes 0.000 description 1
- 108010055167 CD59 Antigens Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000905957 Channa melasoma Species 0.000 description 1
- 241001269524 Dura Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- WCMMILVIRZAPLE-UHFFFAOYSA-M cyhexatin Chemical compound C1CCCCC1[Sn](C1CCCCC1)(O)C1CCCCC1 WCMMILVIRZAPLE-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 description 1
- DNENLKYRLFOCFN-UHFFFAOYSA-M tricyclopentyl(fluoro)stannane Chemical compound C1CCCC1[Sn](C1CCCC1)(F)C1CCCC1 DNENLKYRLFOCFN-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
KGW (CASE 1310)DC
ANTIFOULANT COMPOSITION AND METHOD
Abstract of the Disclosure - The durability of coatings formed from antifouling compositions containing a biologically active organotin-containing polymer as the film-forming component is improved by the presence of at least one biologically inactive organotin-containing polymer in an amount of from 0.01 to 10% based on the weight of the initial coating composition.
-i-
ANTIFOULANT COMPOSITION AND METHOD
Abstract of the Disclosure - The durability of coatings formed from antifouling compositions containing a biologically active organotin-containing polymer as the film-forming component is improved by the presence of at least one biologically inactive organotin-containing polymer in an amount of from 0.01 to 10% based on the weight of the initial coating composition.
-i-
Description
~L1L6C~3~7 P~iTIFOULANT COMPOSITION AND METHOD
This invention xelates to novel bi.ologically active polymeric materials. More specifically~ it relates to novel n~arine antifoulant compositions containing mixtures of organotin polymers as the film-forming component, wherein S at least one of the said organotin polyrners is biologicalLy active.
Organotin polymers, such as those described in U. S. Patents 3,167,473, 4,064,338, and 4,121,034 are known to be effective film-forming antifoulant agents which can serve as the binder component of a marine antifoulant paint.
Such paints are typically comprised of binder; pigments such as red iron oxide, titanium dioxide, and zinc oxide; thickeners such as bentonite and fumed silica; extenders such as talc;
and inert diluents typified by mineral spirits, naphtha, xy~ene, methyl isobutylketone, etc~
Typical film-forming organotin--containing polymers useful as biologically active binders in marine antifoulant compositions are disclosed in U. S. Patents 3,167,473, 4,064,338, and 4,121,034. Coatings resulting from the drying of such compositions exhibit weak structural integrity, particularly under dynamic flow conditions such as exposure to moving sea water, due to the inability of the relatively soft organotin polymer to bind the solid additives into a tightly cohesive matrix. Consequently, the useful life of such coatings when exposed to dynamic flow conditions is relatively short due to weakness of the binder-piyment interaction that results in excessive erosion of the coating.
~ ~3t37 It is the object of this invention to provide a novel rnethod for improving the dynamic cohesive strength of marine antifoulant coatings based on biologically active, film-forming . organotin polymers through the addition of another film-forming S organotin polymer which is not necessarily biologically activeO
It has now been found that the dynamic cohesive . strength of a marine antifoulant coating is improved or modified .
: resulting in a predictable and extended performance lifetime under dynamic conditions by utilizing a film-forming system based on a combination of organotin-containing polymers whereby at least one of said organotin polymers contains less than 15 mole % of triorganotin compound and the other contains more than 25 mole % of the triorganotin compound.
~ :
:
Summar~ of the Inventlon Thls invention provides an improved composition or ~ protectin~ marine surfaces against the gxowth of fouling organisms, : said composition consisting essentially of:
(a) 1 to 30% by weight of the total composition : of a biologically active film-forming polymer derived in part from a first triorganotin compound exhibiting the formula R35nOOCR7 whereln i5 selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, ~5 and Rl is a polymerizable group selected from the group consisting of vinyl, ~-~methylvinyl, and phenylvinyl radicals, 9 1 6(13~17 wherein repeating units der:ived from said compound constitute from 25-80 mole % of the total repeatlng units pre~ent in said polymer, the remaining 20-75 mole % of sald repeating . units being derived from at least one ethylenically unsaturated compound that is : copolymerizable with said first triorganotin compound, . (b) 1 to 50~O by weight of the total composition of at least one metalliferous pigment, and (c) 30 to 80~o by weight o~ the total composition of an~ inert diluent, ~ .
the improvement which consists of the presence in said composition of from ~
:: : : 0.01 to 10% by weight of the total composition of a :
biologically inactive film forming polymer derived in part from a second triorganotin compound exhibiting the formula R2SnOOCR3, wherein : R2 i~ selected from the same group as R and R3 iS selected from the same group as R' and the repeating units derived from said triorganotin . compound constitute ~rom l to 15 mole % of the total : 25 repeating units present, the remaining 85-99 mole O
of said repeating units keing derived from at least one ethylenically unsaturated compound that is copolymerlzable with said second triorganotin compound.
~60387 Through the selection o the ratios of the polymers compxising the film-forminy component of the paint system, predicta~le and extended performance lietimes xelative to prior art compositions under dynamic condi~ions can be achieved.
The novel feature of the composition of this invent-on resides in ~he presence in said composition of a polymer derived from a monom~r mixture containing a relatively small amount of biologically active triorganotin compound, the remaining monomers being those which are known to yield tough, dura~le films when in polymer form. The concentration of triorganotin species in the final polymer is insufficient to yield significant biological activity as specified in U. S. Patents 4,064,338 and 4,121,034.
The auxiliary organotin polymeric binder, when incorporated at usefu~ concentrations r must be compatible with the biologically active organotin polymer and the solvent system utilized in the coating composition~ It must provide sufficient cohesiveness to the coating (without adversely affecting the antifoulant properties of the coating), to extend the performance lifetime of said coatings.
~he auxiliary organotin polymeric binders are film-formers in their own right, yielding tough, glassy coatings.
When used as the auxiliary binder, as the minor component of the binder system, the dynamic cohesive stxength of the coatlng formed from the antifoulant paint is improved, allowing extended performance lifetime without sacrificing antifoulant properties~
3~7 The concentration of the organotin polymer auxiliary binder to be incorporated into the biologically active organotin polymer containing anti-foulant paint will depend on the upper concentration limit of compatibility and on the effecti~e concentration for op~imizing dynamic cohesive strength while maintaining antifouling performance. The effective concentration will vary depending on the pigment type(s) utilized in the coating compositions.
In the foregoing formulae, R and R2 represent those hydrocarbon radicals normally associated with biologically active triorganotin compounds.
For example, R and R may be an aLkyl radical containing from 1 to 8 carbon atoms, a cycloaliphatic radical such as cyclopentyl or cyclohexyl, or a phenyl radical. It is ~mderstood that R and R may be inertly substituted, e.g. may be æ a nonreactive substituent such as alkyl, cycloaIkyl, æyl, araIkyl, aIkaryl, aIkenyl, ether, halogen ester, etc.
me composition of the biologically active organotin polymer con-sists of at least one of the R3SnOOCRl co~pounds and at least one copolymer-izable compound selected from the groups which are described in the pertinent sections of U. S. Patents 3,167,473, 4,064,338, and 4,121,034. The concentra-tion of the ~ SnOOCRl co~lpound is from 25 to 80 mole % of the total monomers present m said polymer. me polymer can be prepared by either polymeriza-tion of the desired mono~er mixture or by reacting a prefoxmed organic poly-mer containing a reactive carboxylic acid with a suitable triorganotin com-pound.
~ 3~7 The composition of the auxiliary organotin polymeric binder consists of at least one of the R2SnOOCR3 compounds and at least one copolymerizable compound selected from the groups which are described in the pertinent sections of U. S.
Patents 3,167,473, 4,064,338, and 4,121,034~ The concentration of the R2SnOOCR3 compound is <15 ~ole ~ of the total monomers present in said polymerD The polymer can be prepared by either polymeri~ation of the desired monomer mixture or by reacting a preformed organic polymer containing a reactive carboxylic acid with a suitable triorganotin compound.
Among the metalliferous pigments that can b~ included are inert compounds such as iron oxide, zinc oxide, titanium dioxide and talc, and biologically active compounds such as cuprous oxide, copper thiocyanate, tributyltin fluoride, tricyclopentyltin fluoride, tricyclohexyltin hydroxide, triphenyltin fluoride, and triphenyltin hydroxide.
The following examples illustrate the present method and the improved coating compositions obtained thereby.
Preparation of the _uxiliar~ binder.
A 2-liter capacity polymerization reactor equipped with a N2 inlet, H2O cooled condens~r, thermometer, ar.d stirrer is charged with 37.5g tributyltin methacrylate, 137.8g butyl methacrylate, 5U0 ml "Hi Flash Naphtha~", and 0.036g benzoyl peroxide. The contents of the flask are heated at 80C for 8 hours to obtain greater than 95~ conversion of monomers to polymer.
'I 16~)3i~'~
The polymer solution prepared in Example 1 was added at 5, 10, and 25% solids volume concentr~tion to a 50% by weight solution of a biologically active organotin polymer prepared as described in Example 1 of U. S. Paten~ No. 4,064,338. All solutions were miscible and none exhibited phase separation after 6 months at room temperature (77F).
Dry films prepared from the mixtures of the two polymer solutions as described in Example 2 were clear and transparent and remained so when examined 6 months after preparation. These results demonstrate excellent compatibility between the bIologicalIy active organotin polymer and the auxiliary organotin film-forming pol~mer.
EXA~IPLE 4 The antifouling properties of the auxiliary binder prepared as described in Example 1 was compared to that of the biologically acti~e organotin polymer. Fiberglass discs with a 2.5 inch radius were coated with clear films of the two polymers. The test discs toqether with untreated discs were immersed below tide level in the ocean at Biscayne Bay, Florida.
After 5 weeks o immersionr the untreated discs and the disc coated with the auxiliary binder coating were completely fouled whereas the disc coated with the biologically active organotin polymer was completely free of fouling organisms showing that the organotin polymeric auxiliary binder is not an eEfective antiEoulant agent.
-~Q3~7 EX~MPLh 5 Fiberglass ~anels (8 inches by 12 inches) were coated with the polymer mixtures from Example 2 which contain the auxiliary binder at 5 and 10g solids volume concentra-tion. The test panels together wit:h untreated panels were immersed beiow tide level in the ocean at Biscayne Bay, Florid~.
After 12 months of immersion, the coated panels ; were free of fouliny organisms whereas the untreated panels were completely fouled, demonstrating that the auxiiiary binder does not adversely affect antifouling performance of the biologically active organotln polymer.
EXA~IPLE 6 Antifouling paints suitabLe for test purposes were prepared according to known commercial practices.
Table I shows the coating compositions of test panels ~
treated with an'ifouling paints containing the biologically active organotin film-forming polymer but without the auxiliary organotin polymeric binder. Constituent concentrations are in volume percent, as 100~ solid.
TABLE I
. . . ~
A B C D E F G H
Biologically Active Organotin Polymer 75 60 60 60 45 45 ~5 Iron Oxide25 12.5 0 40 20 0 55 27.50 ZnO 0 12.525 0 20 40 0 27.550 . . _ _ _ _ _ Pigment Volume Concentration (PVC) Paint E was modified so as to contain varying ~mounts of the auxiliary organotin polymeric ~inder as shown in Table II.
~ 3~ ~
3 d~
E-l E-2 E-3 E-4 Bioiogicaliy Active Organotin Polymer Auxiliary Grganotin Polymeric Binder (Ex. l, as 100% so~id~
The paint~ were adjusted to a solids content of 25% by weight, by the addition of xylene. Test panels were trea~ed wi~h the test paints to give dry coating thickness of 300~.
The resistance to erosion in moving sea w~ter of the test coatings described in Exarnple 6 were tested using apparatus specifically designed to measure the rate of eroslon of coatings under dynamic conditions as described by de la Court et al in J. Oil Col~ Chera.
AssocO, 56, 388 (1973). The results are summarized in Figures l and 2.
Figure l shows the rate of erosion in moving sea water of coatings A-I described in Example 6 (without auxiliary binder). Increasing pigment volume concentration and zinc oxide cause an increase in erosion rate. The rLlinimum erosion rate obtainable, 0 7~day, demonstrates that a 300~ coating will completely wear of in 430 days~
Figure 2 shows the influence on erosion of the auxiliary binder in coatings E-1 - E-4, described in Example 6, when added as an auxiliary bi.nder to coating composltion E of Example 6. At a concentration of 5P6 by volume of the binder system, erosion rate in moving sea water is reduced to 0.2~/day, giving a 30011 coating a lifetime of 1500 days, a 300~ .increase over the coating of Example 2 which erodes at 0.7~1/day.
~1~03t~'7 Test panels treated with coating compositions E-l and ~2, described in Example 6, were immersed below tide level in the ocean at Biscayne Bay, Florida~
After 6 months immersion, both panels were free of fouling organisms. Coating E~l eaqily released pigment when ~inger-rubbed after the immersion period, as evidenced by the red stain from the iron oxide, demonstrating that there is a weak pigment binder interaction in the coating.
Coating E-2 did not release pigment when finger-rubbed after the period of immersion, demonstrating the strengthening effect of the organotin polymeric auxiliary binder.
.
3L~L603a7 E~MPLE 9 as Antifouling paints were prepared/in Example 6 utilizing organo~in and non-organotin polymeric auxiliary binders.
Table III shows the coating compositions of tes-t panels treat-ed with the paints.
TABLE III
J K L ~
Biologically Active Organotin 56.4 54 56.4 54-Polymer Iron Oxide 20 20 20 20 ZnO 20 20 20 20 ~rganotin Auxiliary Binder 3.6 6 (Ex. 1, as 100% Solid) Polymethylmethacrylate (*) ~ ~ 3.6 6 Auxiliary Binder ~*) Manu~actured and sold by Rohn & Haas, under the trade ~m~ Acryloid A-10 The paints were adjusted to a solids content of 30~ by weight, by the addition o~ xylene.
Test panels were treated as described in Example 5 with coating compositions J through M and im~tersed below tlde level in the ocean at Biscayne Bay, Florida. After three months immersion, all panels were ~ree o-f fouling organisms.
The resistance to erosion of Table III test coatings was tested by attaching coated test panels to a disc which was immersed in a model seawater medium, prepared from "Instant Ocean Synthetic Sea Salts" (Aquarium Systems, Inc.), and rotated at a circumferential speed of 10 knots for 50 days at a constant temperature o-f 30 C. Applied coating thickness wa 100 microns.
The results are summarized in Table IV and illustrated graphically in ~igure 3.
'11603~ ~
I T~BLE IV
I
Coating Thickness Loss (Microns) After: .
Coating ~ 50 Days .
: - The results demonstrate that the organotin polymeric aux-iliary binder is more effective than the non-organotin . .
polymeric auxiliary binder in extending the performance of -the biologically active organotin polymer antifoulant coatings.
This invention xelates to novel bi.ologically active polymeric materials. More specifically~ it relates to novel n~arine antifoulant compositions containing mixtures of organotin polymers as the film-forming component, wherein S at least one of the said organotin polyrners is biologicalLy active.
Organotin polymers, such as those described in U. S. Patents 3,167,473, 4,064,338, and 4,121,034 are known to be effective film-forming antifoulant agents which can serve as the binder component of a marine antifoulant paint.
Such paints are typically comprised of binder; pigments such as red iron oxide, titanium dioxide, and zinc oxide; thickeners such as bentonite and fumed silica; extenders such as talc;
and inert diluents typified by mineral spirits, naphtha, xy~ene, methyl isobutylketone, etc~
Typical film-forming organotin--containing polymers useful as biologically active binders in marine antifoulant compositions are disclosed in U. S. Patents 3,167,473, 4,064,338, and 4,121,034. Coatings resulting from the drying of such compositions exhibit weak structural integrity, particularly under dynamic flow conditions such as exposure to moving sea water, due to the inability of the relatively soft organotin polymer to bind the solid additives into a tightly cohesive matrix. Consequently, the useful life of such coatings when exposed to dynamic flow conditions is relatively short due to weakness of the binder-piyment interaction that results in excessive erosion of the coating.
~ ~3t37 It is the object of this invention to provide a novel rnethod for improving the dynamic cohesive strength of marine antifoulant coatings based on biologically active, film-forming . organotin polymers through the addition of another film-forming S organotin polymer which is not necessarily biologically activeO
It has now been found that the dynamic cohesive . strength of a marine antifoulant coating is improved or modified .
: resulting in a predictable and extended performance lifetime under dynamic conditions by utilizing a film-forming system based on a combination of organotin-containing polymers whereby at least one of said organotin polymers contains less than 15 mole % of triorganotin compound and the other contains more than 25 mole % of the triorganotin compound.
~ :
:
Summar~ of the Inventlon Thls invention provides an improved composition or ~ protectin~ marine surfaces against the gxowth of fouling organisms, : said composition consisting essentially of:
(a) 1 to 30% by weight of the total composition : of a biologically active film-forming polymer derived in part from a first triorganotin compound exhibiting the formula R35nOOCR7 whereln i5 selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, ~5 and Rl is a polymerizable group selected from the group consisting of vinyl, ~-~methylvinyl, and phenylvinyl radicals, 9 1 6(13~17 wherein repeating units der:ived from said compound constitute from 25-80 mole % of the total repeatlng units pre~ent in said polymer, the remaining 20-75 mole % of sald repeating . units being derived from at least one ethylenically unsaturated compound that is : copolymerizable with said first triorganotin compound, . (b) 1 to 50~O by weight of the total composition of at least one metalliferous pigment, and (c) 30 to 80~o by weight o~ the total composition of an~ inert diluent, ~ .
the improvement which consists of the presence in said composition of from ~
:: : : 0.01 to 10% by weight of the total composition of a :
biologically inactive film forming polymer derived in part from a second triorganotin compound exhibiting the formula R2SnOOCR3, wherein : R2 i~ selected from the same group as R and R3 iS selected from the same group as R' and the repeating units derived from said triorganotin . compound constitute ~rom l to 15 mole % of the total : 25 repeating units present, the remaining 85-99 mole O
of said repeating units keing derived from at least one ethylenically unsaturated compound that is copolymerlzable with said second triorganotin compound.
~60387 Through the selection o the ratios of the polymers compxising the film-forminy component of the paint system, predicta~le and extended performance lietimes xelative to prior art compositions under dynamic condi~ions can be achieved.
The novel feature of the composition of this invent-on resides in ~he presence in said composition of a polymer derived from a monom~r mixture containing a relatively small amount of biologically active triorganotin compound, the remaining monomers being those which are known to yield tough, dura~le films when in polymer form. The concentration of triorganotin species in the final polymer is insufficient to yield significant biological activity as specified in U. S. Patents 4,064,338 and 4,121,034.
The auxiliary organotin polymeric binder, when incorporated at usefu~ concentrations r must be compatible with the biologically active organotin polymer and the solvent system utilized in the coating composition~ It must provide sufficient cohesiveness to the coating (without adversely affecting the antifoulant properties of the coating), to extend the performance lifetime of said coatings.
~he auxiliary organotin polymeric binders are film-formers in their own right, yielding tough, glassy coatings.
When used as the auxiliary binder, as the minor component of the binder system, the dynamic cohesive stxength of the coatlng formed from the antifoulant paint is improved, allowing extended performance lifetime without sacrificing antifoulant properties~
3~7 The concentration of the organotin polymer auxiliary binder to be incorporated into the biologically active organotin polymer containing anti-foulant paint will depend on the upper concentration limit of compatibility and on the effecti~e concentration for op~imizing dynamic cohesive strength while maintaining antifouling performance. The effective concentration will vary depending on the pigment type(s) utilized in the coating compositions.
In the foregoing formulae, R and R2 represent those hydrocarbon radicals normally associated with biologically active triorganotin compounds.
For example, R and R may be an aLkyl radical containing from 1 to 8 carbon atoms, a cycloaliphatic radical such as cyclopentyl or cyclohexyl, or a phenyl radical. It is ~mderstood that R and R may be inertly substituted, e.g. may be æ a nonreactive substituent such as alkyl, cycloaIkyl, æyl, araIkyl, aIkaryl, aIkenyl, ether, halogen ester, etc.
me composition of the biologically active organotin polymer con-sists of at least one of the R3SnOOCRl co~pounds and at least one copolymer-izable compound selected from the groups which are described in the pertinent sections of U. S. Patents 3,167,473, 4,064,338, and 4,121,034. The concentra-tion of the ~ SnOOCRl co~lpound is from 25 to 80 mole % of the total monomers present m said polymer. me polymer can be prepared by either polymeriza-tion of the desired mono~er mixture or by reacting a prefoxmed organic poly-mer containing a reactive carboxylic acid with a suitable triorganotin com-pound.
~ 3~7 The composition of the auxiliary organotin polymeric binder consists of at least one of the R2SnOOCR3 compounds and at least one copolymerizable compound selected from the groups which are described in the pertinent sections of U. S.
Patents 3,167,473, 4,064,338, and 4,121,034~ The concentration of the R2SnOOCR3 compound is <15 ~ole ~ of the total monomers present in said polymerD The polymer can be prepared by either polymeri~ation of the desired monomer mixture or by reacting a preformed organic polymer containing a reactive carboxylic acid with a suitable triorganotin compound.
Among the metalliferous pigments that can b~ included are inert compounds such as iron oxide, zinc oxide, titanium dioxide and talc, and biologically active compounds such as cuprous oxide, copper thiocyanate, tributyltin fluoride, tricyclopentyltin fluoride, tricyclohexyltin hydroxide, triphenyltin fluoride, and triphenyltin hydroxide.
The following examples illustrate the present method and the improved coating compositions obtained thereby.
Preparation of the _uxiliar~ binder.
A 2-liter capacity polymerization reactor equipped with a N2 inlet, H2O cooled condens~r, thermometer, ar.d stirrer is charged with 37.5g tributyltin methacrylate, 137.8g butyl methacrylate, 5U0 ml "Hi Flash Naphtha~", and 0.036g benzoyl peroxide. The contents of the flask are heated at 80C for 8 hours to obtain greater than 95~ conversion of monomers to polymer.
'I 16~)3i~'~
The polymer solution prepared in Example 1 was added at 5, 10, and 25% solids volume concentr~tion to a 50% by weight solution of a biologically active organotin polymer prepared as described in Example 1 of U. S. Paten~ No. 4,064,338. All solutions were miscible and none exhibited phase separation after 6 months at room temperature (77F).
Dry films prepared from the mixtures of the two polymer solutions as described in Example 2 were clear and transparent and remained so when examined 6 months after preparation. These results demonstrate excellent compatibility between the bIologicalIy active organotin polymer and the auxiliary organotin film-forming pol~mer.
EXA~IPLE 4 The antifouling properties of the auxiliary binder prepared as described in Example 1 was compared to that of the biologically acti~e organotin polymer. Fiberglass discs with a 2.5 inch radius were coated with clear films of the two polymers. The test discs toqether with untreated discs were immersed below tide level in the ocean at Biscayne Bay, Florida.
After 5 weeks o immersionr the untreated discs and the disc coated with the auxiliary binder coating were completely fouled whereas the disc coated with the biologically active organotin polymer was completely free of fouling organisms showing that the organotin polymeric auxiliary binder is not an eEfective antiEoulant agent.
-~Q3~7 EX~MPLh 5 Fiberglass ~anels (8 inches by 12 inches) were coated with the polymer mixtures from Example 2 which contain the auxiliary binder at 5 and 10g solids volume concentra-tion. The test panels together wit:h untreated panels were immersed beiow tide level in the ocean at Biscayne Bay, Florid~.
After 12 months of immersion, the coated panels ; were free of fouliny organisms whereas the untreated panels were completely fouled, demonstrating that the auxiiiary binder does not adversely affect antifouling performance of the biologically active organotln polymer.
EXA~IPLE 6 Antifouling paints suitabLe for test purposes were prepared according to known commercial practices.
Table I shows the coating compositions of test panels ~
treated with an'ifouling paints containing the biologically active organotin film-forming polymer but without the auxiliary organotin polymeric binder. Constituent concentrations are in volume percent, as 100~ solid.
TABLE I
. . . ~
A B C D E F G H
Biologically Active Organotin Polymer 75 60 60 60 45 45 ~5 Iron Oxide25 12.5 0 40 20 0 55 27.50 ZnO 0 12.525 0 20 40 0 27.550 . . _ _ _ _ _ Pigment Volume Concentration (PVC) Paint E was modified so as to contain varying ~mounts of the auxiliary organotin polymeric ~inder as shown in Table II.
~ 3~ ~
3 d~
E-l E-2 E-3 E-4 Bioiogicaliy Active Organotin Polymer Auxiliary Grganotin Polymeric Binder (Ex. l, as 100% so~id~
The paint~ were adjusted to a solids content of 25% by weight, by the addition of xylene. Test panels were trea~ed wi~h the test paints to give dry coating thickness of 300~.
The resistance to erosion in moving sea w~ter of the test coatings described in Exarnple 6 were tested using apparatus specifically designed to measure the rate of eroslon of coatings under dynamic conditions as described by de la Court et al in J. Oil Col~ Chera.
AssocO, 56, 388 (1973). The results are summarized in Figures l and 2.
Figure l shows the rate of erosion in moving sea water of coatings A-I described in Example 6 (without auxiliary binder). Increasing pigment volume concentration and zinc oxide cause an increase in erosion rate. The rLlinimum erosion rate obtainable, 0 7~day, demonstrates that a 300~ coating will completely wear of in 430 days~
Figure 2 shows the influence on erosion of the auxiliary binder in coatings E-1 - E-4, described in Example 6, when added as an auxiliary bi.nder to coating composltion E of Example 6. At a concentration of 5P6 by volume of the binder system, erosion rate in moving sea water is reduced to 0.2~/day, giving a 30011 coating a lifetime of 1500 days, a 300~ .increase over the coating of Example 2 which erodes at 0.7~1/day.
~1~03t~'7 Test panels treated with coating compositions E-l and ~2, described in Example 6, were immersed below tide level in the ocean at Biscayne Bay, Florida~
After 6 months immersion, both panels were free of fouling organisms. Coating E~l eaqily released pigment when ~inger-rubbed after the immersion period, as evidenced by the red stain from the iron oxide, demonstrating that there is a weak pigment binder interaction in the coating.
Coating E-2 did not release pigment when finger-rubbed after the period of immersion, demonstrating the strengthening effect of the organotin polymeric auxiliary binder.
.
3L~L603a7 E~MPLE 9 as Antifouling paints were prepared/in Example 6 utilizing organo~in and non-organotin polymeric auxiliary binders.
Table III shows the coating compositions of tes-t panels treat-ed with the paints.
TABLE III
J K L ~
Biologically Active Organotin 56.4 54 56.4 54-Polymer Iron Oxide 20 20 20 20 ZnO 20 20 20 20 ~rganotin Auxiliary Binder 3.6 6 (Ex. 1, as 100% Solid) Polymethylmethacrylate (*) ~ ~ 3.6 6 Auxiliary Binder ~*) Manu~actured and sold by Rohn & Haas, under the trade ~m~ Acryloid A-10 The paints were adjusted to a solids content of 30~ by weight, by the addition o~ xylene.
Test panels were treated as described in Example 5 with coating compositions J through M and im~tersed below tlde level in the ocean at Biscayne Bay, Florida. After three months immersion, all panels were ~ree o-f fouling organisms.
The resistance to erosion of Table III test coatings was tested by attaching coated test panels to a disc which was immersed in a model seawater medium, prepared from "Instant Ocean Synthetic Sea Salts" (Aquarium Systems, Inc.), and rotated at a circumferential speed of 10 knots for 50 days at a constant temperature o-f 30 C. Applied coating thickness wa 100 microns.
The results are summarized in Table IV and illustrated graphically in ~igure 3.
'11603~ ~
I T~BLE IV
I
Coating Thickness Loss (Microns) After: .
Coating ~ 50 Days .
: - The results demonstrate that the organotin polymeric aux-iliary binder is more effective than the non-organotin . .
polymeric auxiliary binder in extending the performance of -the biologically active organotin polymer antifoulant coatings.
Claims (8)
1. In an improved process for protecting marine surfaces against growth of fouling organisms, the said process comprises treating said marine surface with a coating composition containing:
(a) 1 to 30% by weight of the total composition of a biologically active film-forming polymer derived in part from a first triorganotin compound exhibiting the formula R3SnOOCR' wherein R is selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, and R' is a polymerizable group selected from the group consisting of vinyl, .alpha.-methylvinyl, and phenylvinyl radicals, wherein repeating units derived from said compound constitute from 25-80 mole % of the total repeating units present in said polymer, the remaining 20-75 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copolymerizable with said first triorganotin compound, (b) 1 to 50% by weight of the total composition of at least one metalliferous pigment, and (c) 30 to 80% by weight of the total composition of an inert diluent, the improvement which consists of the presence in said composition of from 0.01 to 10% by weight of the total composition: of a biologically inactive film-forming polymer derived in part from a second tri-organotin compound exhibiting the formula R3SnOCCR3, wherein R2 is selected from the same group as R and R3 is selected from the same group as R1 and the repeating units derived from said triorganotin compound con-stitute from 1 to 15 mole % of the total repeating units present, the remaining 85-99 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copoly-merizable with said second triorganotin compound.
(a) 1 to 30% by weight of the total composition of a biologically active film-forming polymer derived in part from a first triorganotin compound exhibiting the formula R3SnOOCR' wherein R is selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, and R' is a polymerizable group selected from the group consisting of vinyl, .alpha.-methylvinyl, and phenylvinyl radicals, wherein repeating units derived from said compound constitute from 25-80 mole % of the total repeating units present in said polymer, the remaining 20-75 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copolymerizable with said first triorganotin compound, (b) 1 to 50% by weight of the total composition of at least one metalliferous pigment, and (c) 30 to 80% by weight of the total composition of an inert diluent, the improvement which consists of the presence in said composition of from 0.01 to 10% by weight of the total composition: of a biologically inactive film-forming polymer derived in part from a second tri-organotin compound exhibiting the formula R3SnOCCR3, wherein R2 is selected from the same group as R and R3 is selected from the same group as R1 and the repeating units derived from said triorganotin compound con-stitute from 1 to 15 mole % of the total repeating units present, the remaining 85-99 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copoly-merizable with said second triorganotin compound.
2. The process according to Claim 1 wherein R and R2 are independently selected from the group consisting of alkyl containing from 1 to 8 carbon atoms, cyclopentyl, cyclohexyl, and phenyl radicals.
3. The process of Claim 2 wherein R and R2 are butyl.
4. The process of Claim 1 wherein R1 and R3 are .alpha.-methylvinyl.
5. In an improved coating composition for protecting marine surfaces against growth of fouling organisms said coating composition comprising:
(a) 1 to 30% by weight of the total composition of a biologically active film-forming polymer derived in part from a first triorganotin compound exhibiting the formula R3SnOOCR' wherein R is selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, and R' is a polymerizable group selected from the group consisting of vinyl, .alpha.-methylvinyl, and phenylvinyl radicals, wherein repeating units derived from said compound constitute from 25-80 mole % of the total repeating units present in said polymer, the remaining 20-75 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copolymerizable with said first triorganotin compound, (b) 1 to 50% by weight of the total composition of at least one metalliferous pigment, and (c) 30 to 80% by weight of the total composition of an inert diluent, the improvement which consists of the presence in said composition of from 0.01 to 10% by weight of the total composition of a biologically inactive film-forming polymer derived in part from a second tri-organotin compound exhibiting the formula R?SnOOCR3, wherein R2 is selected from the same group as R and R3 is selected from the same group as R1 and the repeating units derived from said triorganotin compound con-stitute from 1 to 15 mole % of the total repeating units present, the remaining 85-99 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copoly-merizable with said second triorganotin compound.
(a) 1 to 30% by weight of the total composition of a biologically active film-forming polymer derived in part from a first triorganotin compound exhibiting the formula R3SnOOCR' wherein R is selected from the group consisting of alkyl, cycloalkyl, and aryl radicals, and R' is a polymerizable group selected from the group consisting of vinyl, .alpha.-methylvinyl, and phenylvinyl radicals, wherein repeating units derived from said compound constitute from 25-80 mole % of the total repeating units present in said polymer, the remaining 20-75 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copolymerizable with said first triorganotin compound, (b) 1 to 50% by weight of the total composition of at least one metalliferous pigment, and (c) 30 to 80% by weight of the total composition of an inert diluent, the improvement which consists of the presence in said composition of from 0.01 to 10% by weight of the total composition of a biologically inactive film-forming polymer derived in part from a second tri-organotin compound exhibiting the formula R?SnOOCR3, wherein R2 is selected from the same group as R and R3 is selected from the same group as R1 and the repeating units derived from said triorganotin compound con-stitute from 1 to 15 mole % of the total repeating units present, the remaining 85-99 mole % of said repeating units being derived from at least one ethylenically unsaturated compound that is copoly-merizable with said second triorganotin compound.
6. The ccmposition according to Claim 5 wherein R and R2 are independ-ently selected from the group consisting of alkyl containing 1 to 8 carbon atoms, cyclopentyl, cyclohexyl, and phenyl radicals.
7. The composition of Claim 6 wherein R and R2 are butyl.
8. The composition of Claim 5 wherein R1 and R3 are .alpha.-methylvinyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000372228A CA1160387A (en) | 1981-03-03 | 1981-03-03 | Antifoulant compositions of organotin containing polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000372228A CA1160387A (en) | 1981-03-03 | 1981-03-03 | Antifoulant compositions of organotin containing polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160387A true CA1160387A (en) | 1984-01-10 |
Family
ID=4119367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372228A Expired CA1160387A (en) | 1981-03-03 | 1981-03-03 | Antifoulant compositions of organotin containing polymers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1160387A (en) |
-
1981
- 1981-03-03 CA CA000372228A patent/CA1160387A/en not_active Expired
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