Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1668—Vinyl-type polymers

Definitions

• Fouling of surfaces exposed to an aquatic environment is a serious problem.
• surfaces of ships such as the hull, offshore marine structures such as oil rigs, sea water conduit systems for seaside plants, buoys, heat-exchangers, cooling towers, de-salination equipment, filtration membranes, docks, and the like may all experience some degree of fouling when continually exposed to water.
• fouling can inhibit vessel performance and capabilities.
• fouling may substantially increase fuel consumption and may necessitate extensive and more frequent maintenance, all of which raise the overall costs of operation.
• Fouling may also reduce ship speed, maneuverability, and range, which impede performance.
• attachment of regionally specific aquatic organisms on ships that traverse the world can lead to the unwanted invasion and infestation of these organisms to non-indigenous harbors. In some instances, this can have severe adverse effects on local aquatic ecosystems.
• biocidal coatings have been linked to environmental problems (e.g., tin based biocidal coatings, etc.). For example, while moored in harbors, paint chips and leaching have led to sediment accumulations of toxins resulting in harm or destruction of non-targeted sea life (e.g., oysters). Accordingly, the development of an effective alternative to these biocidal coatings would be desirable.
• anti-fouling materials refer to products, agents, or compositions which may provide biocidal and/or fouling release properties when used alone or in combination with other materials or substances.
• the anti-fouling materials described herein may include one or more of a number of suitable copolymers (e.g., block copolymers, graft copolymers, etc.) which provide biocidal and/or fouling release characteristics. Examples of suitable polymeric materials which can be used to form biocidal coatings are depicted in Figures 1-2, 4, 7, and 10-16 herein.
• the copolymer includes one or more rubbery polymer sequences having a carbon and/or silicone backbone combined with one or more polymer sequences which include one or more biocidal groups.
• the copolymer may also include one or more polymer sequences which enhance the texture or fouling release properties of the copolymer and/or the final product which incorporates the copolymer. It may also be desirable to include functional groups which are capable of serving as sites for cross-linking reactions in the copolymer.
• the copolymers may have a molecular weight from 5,000 to 100,000, or, desirably, 10,000 to 75,000, or, suitably, 10,000 to 50,000. Quite commonly, the copolymers include two or more blocks wherein each block contains about 10 to 100 subunits.
• an anti-fouling material comprises the following copolymer:
• m may be an integer from 0 to 100, 0 to 65, 10 to 75, or more desirably 20 to 50; n maybe an integer from 0 to 100, 0 to 65, 10 to 75, or more desirably 20 to 50; at least one of m and n ⁇ 0;
• In is an initiator group;
• EC is an end cap group;
• x maybe an integer from 1 to 200, 10 to 150, 25 to 100, or more desirably 35 to 75;
• ' p may be an integer from 0 to 75, 0 to 50, 10 to 50, 10 to 25, or more desirably 20 to 50;
• R 1 may be a hydrogen, methyl group, or other alkyl group (e.g., lower alkyl group);
• R and R may be independently a cross-linking group, - C 10 alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, phenyl
• m may be an integer from 0 to 100, 0 to 65, or more desirably 0 to 50; n may be an integer from 1 to 100, 0 to 65, or more desirably 20 to 50; x may be an integer from 1 to 200, 1 to 150, or more desirably 1 to 100; y may be an integer from 1 to 100, 10-75, or more desirably 20 to 50;
• In is an initiator group;
• EC is an end cap group;
• R 1 is a hydrogen or lower alkyl group (e.g., a methyl group);
• R 2 is a cross-linking group, C ⁇ - C 10 alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, or phenyl;
• L 1 is a linking group;
• R 3 is a biocidal group that is toxic to organisms that cause fouling in an aquatic environment or a group that can be cle
• m may be an integer from 0 to 100, 10 to 75, or more desirably 20 to
• y may be an integer from 1 to 100, 10 to 75, or more desirably 20 to 50; x maybe an integer from 1 to 200, 10 to 150, 25 to 100, or more desirably 35 to 75;
• In may be an initiator group;
• R 1 may be a hydrogen or methyl group;
• R may be a cross-linking group, C ⁇ - C 10 alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, or phenyl;
• L 1 may be a linking group;
• R 4 may be a biocidal group that is toxic to organisms that cause fouling in an aquatic environment or a group that can be cleaved to provide a biocidal group;
• R x is an H or Me;
• EC may be an end cap group.
• n may be an integer from 1 to 100, 10 to 75, or more desirably 20 to
• x maybe an integer from 1 to 200, 10 to 150, 25 to 100, or more desirably 35 to 75; p may be an integer from 0 to 75, 10 to 50, or more desirably 20 to 50;
• In may be an initiator group;
• R 1 may be a hydrogen or methyl group;
• L 1 may be a linking group;
• R 2 may be a biocidal group that is toxic to organisms that cause fouling in an aquatic environment or a group that can be cleaved to provide a biocidal group;
• R may be a fouling release group, an alkyl group, or other texturizing group;
• R x is an H or Me; and
• EC may be an end cap group.
• a biocidal composition may comprise a block copolymer having a formula:
• n may be an integer from 1 to 100, 10 to 75, or more desirably 20 to
• x maybe an integer from 1 to 200, 10 to 150, 25 to 100, or more desirably 35 to 75; p may be an integer from 0 to 75, 10 to 50, or more desirably 20 to 50;
• In may be an initiator group;
• L 1 may be a linking group;
• R and R may be independently a cross-linking group, Ci - C 10 alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, or phenyl;
• R may be a biocidal group that is toxic to organisms that cause fouling in an aquatic environment or a group that can be cleaved to provide a biocidal group;
• R 4 maybe a fouling release group, an alkyl group, or other texturizing group;
• R x is an H or Me; and
• EC may be an end cap group.
• a biocidal composition may comprise a structure having the formula:
• m may be integer between 1 to 15 or more desirably 4 to 10; n may be an integer between 2 to 50, 5 to 25, or more desirably 10 to 16; p may be an integer between 0 to 10 or more desirably 2 to 4; x may be an integer between 5 to 25 or more desirably 10 to 15; y may be an integer between 0 to 20 or more desirably 3 to 11; and q may be an integer between 2 to 15, 2 to 10, or more desirably 2 to 5.
• cross-linking group refers to a substituent which includes a functional group capable of reacting with another chemical moiety to cross link the polymer.
• initiator group (“In”) refers to a substituent added to a terminus of the copolymer as a result of a reaction employed to initiate polymerization.
• end cap group (“EC”) refers to a substituent added to a terminus of the copolymer as a result of a reaction which terminates polymerization.
• the initiator group (“In) and/or end cap group may include functional groups which alter or influence the physical/chemical properties and character of the copolymer.
• the initiator and end cap groups are chosen such that they do not have any significant effect on the overall physical characteristics of the copolymer (e.g., result in the introduction of a hydrogen atom, lower alkyl group or trimethyl silyl group).
• Figure 1 is a schematic depiction of one embodiment of a block copolymer suitable for use as an anti-fouling material or to form an anti-fouling coating.
• Figure 2 is a schematic depiction of one embodiment of a graft copolymer suitable for use as an anti-fouling material or to form an anti-fouling coating.
• Figure 3 provides a schematic depiction of a number of oligomers that may be joined to form various embodiments of copolymers which may be used as anti- fouling materials.
• Figure 4 shows one embodiment of a synthetic strategy for making Polyvinylmethyl siloxane-b-Polydimethyl siloxane-b-Polybiocide (where "biocide” is poly-(TRlCL-MAE).
• Figure 5 shows NMR results for TRICL-MAE (5a); PVMS-b-PDMS (5b); and polymeric material prepared as shown in Figure 4 (5c).
• Figure 6 shows the gel permeation chromatography (GPC) results for the polymeric material prepared as shown in Figure 4.
• Figure 7 shows another embodiment of a synthetic strategy for making Polyisoprene-b-Polybiocide.
• Figure 8 shows NMR results for the composition prepared as shown in Figure 7.
• Figure 9 shows the GPC results for the composition prepared as shown in Figure 7.
• Figure 10 shows an illustration of a synthetic strategy for making Polymethylhydrosiloxane-co-polydimethylsiloxane-g-Poly-(TRlCL-MAE).
• Figures 11 shows an illustration of Polyisoprene-b-PDMS-b-Poly-(TRiCL- MAE)-co-polymethoxyethyl methacrylate which may be used as an anti-fouling material according to another embodiment.
• Figure 12 shows an illustration of Polyisoprene-b-PDMS-b-Poly-(TRlCL- MAE) which may be used as an anti-fouling material according to another embodiment.
• Figure 13 shows an illustration of Polyisoprene-b-PDMS-b-Poly Zinc acrylate-co-polymethoxyethyl methacrylate which may be used as an anti-fouling material according to another embodiment.
• Figure 14 shows an illustration of Polyisoprene-b-Poly-(TRlCL-MAE)-co- poiymethacrylate siloxane which may be used as an anti-fouling material according to another embodiment.
• Figure 15 shows an illustration of Polybutadiene-b-Poly-(TRlCL-MAE)-co- polymethacrylate siloxane which may be used as an anti-fouling material according to another embodiment.
• Figure 16 shows an illustration of Polybutadiene-b-PDMS-b-Poly-(TwcL- MAE) which may be used as an anti-fouling material according to another embodiment.
• the anti-fouling materials described herein comprise a copolymer which includes a number of block sequences which provide the copolymer with biocidal and/or fouling release activity.
• the various embodiments of anti-fouling materials may be used independently (e.g., as a single coating layer) or in combination with other materials (e.g., paint pigment, etc.) to decrease the amount of fouling experienced by structures and other surfaces exposed to an aquatic environment (e.g., marine environments, freshwater environments, etc.).
• the composition of a coating material which includes the anti-fouling material may also include other compounds such as curing agents, crosslink initiators, etc.
• microphase separation of the copolymer may be used to provide increased biocidal activity at the surface of the copolymer due to increased positioning of the biocidal groups at the surface.
• the degree of microphase separation may be controlled by controlling the amount of the various block polymer sequences in the overall polymer.
• Figures 1-3 show various embodiments of copolymers that may be used as anti-fouling materials.
• the copolymer may comprise a number of block polymer sequences which may include a biocidal group (e.g., Triclosan, quaternary ammonium, pyridinium, etc.), a fouling release group (e.g., hydrophilic groups such as polyether groups, hydrophobic groups such as perfluroalkyl groups, liquid crystalline groups such as deuterobenzene groups, self-organizing groups, etc.), and the like.
• a biocidal group e.g., Triclosan, quaternary ammonium, pyridinium, etc.
• a fouling release group e.g., hydrophilic groups such as polyether groups, hydrophobic groups such as perfluroalkyl groups, liquid crystalline groups such as deuterobenzene groups, self-organizing groups, etc.
• the copolymer may include a polymer sequence which provides fouling release characteristics (e.g., sequence A or sequence C) in combination with a polymer sequence which provides biocidal characteristics.
• any of the polymer sequences used in the copolymer may also include one or more crosslinking groups (e.g., epoxy, olefin, amine, acid, aldehyde, ester, etc.).
• crosslinking groups e.g., epoxy, olefin, amine, acid, aldehyde, ester, etc.
• sequence A is a rubbery block which includes a silicone or carbon backbone.
• Sequence A may be any suitable linear or branched carbon polymer sequence or a polysiloxane.
• sequence A may be made using isoprene, butadiene, or silicone monomers.
• sequence A does not include any biocide or textural functional groups.
• Sequence A often contributes to the toughness of the anti-fouling materials (e.g., sequence A may provide additional strength or toughness versus a polysiloxane polymer).
• sequence A may include biocidal and/or textural functional groups and may not provide fouling release properties to the resulting copolymer.
• Sequence B from Figure 1 generally includes a carbon polymer backbone and one or more biocidal functional groups.
• Sequence C typically includes a carbon polymer backbone and one or more textural functional groups (e.g., methoxyethyl methacrylate, etc.) that may be used to enhance the anti-fouling/fouling release characteristics of the copolymer.
• block sequence C may include dimethyl siloxane, methylhydro siloxane, vinylmethyl siloxane in any combination (e.g., random or in blocks, etc.) as shown in claim 4.
• a graft copolymer is shown where sequence B and sequence A have been grafted together.
• sequence C may also be grafted onto sequence A and/or B (or may be linked to a terminus of one of these blocks).
• sequence A may be grafted onto sequence B, or sequence B grafted onto sequence C, and so on.
• Figure 3 shows in general terms block sequences which may be combined to form the present copolymer.
• the copolymers may be synthesized using a combination of anionic and controlled radical polymerization.
• the copolymers may be crosslinked.
• the crosslinking functionality is provided on sequence A.
• the crosslinking functionality may be provided on sequences B and/or C.
• the copolymers may be blended (i.e., physically mixed) together.
• any of the crosslinked copolymers may be blended with other crosslinked copolymers.
• the copolymers may be used to form an interpenetrating network.
• the interpenetrating network can be made by polymerizing one or more monomers around the biocidal copolymer(s), or, in some circumstances, individual polymers used to make the copolymer (i.e., the polymers have not been added to the other polymers to form the copolymer), to form a polymer network which tightly holds the copolymers and/or individual polymers.
• the crosslinking functionality may be provided using a functional group on a carbon backbone (e.g., vinyl group, etc.), a hydro functionalized siloxane, etc.
• the crosslinking moiety is propyl glycidyl ether side group.
• the biocidal group may be any of a number of suitable groups.
• the biocidal group is propyl, 2-(2',4'-dichlorophenoxy)-5-chlorophenyl ether.
• the copolymers described herein can suppress biological fouling of surfaces exposed to a watery environment by way of the biocidal activity of the biocidal groups, fouling release activity of the polymer sequences, and/or a synergistic combination of both.
• biocidal used alone or in combination with other terms (e.g., groups, activity, etc.) refers to biocidal activity that is toxic to aquatic organisms that cause fouling.
• biocidal does not require the organisms to actually be killed. Rather, “biocidal” also encompasses situations where the activity is sufficient to prevent the organism from attaching to and fouling a surface.
• the biocidal functionality are provided using organic biocidal blocks.
• biocidal blocks may be desirable because they are generally easier to use from a chemistry standpoint, and, may also present less governmental regulatory problems than some other types of biocidal blocks (e.g., biocidal groups comprising heaving metals, etc.).
• the biocidal blocks may include one or more inorganic biocides such as metals, etc (e.g., metal salts of carboxylates).
• biocidal groups coupled to the copolymer may act to impede or suppress the settlement and/or growth of aquatic organisms that would otherwise foul these surfaces.
• biological entities or “organisms,” etc., refers to aquatic biological entities or organisms that cause or contribute to fouling in an aquatic environment (e.g., marine environment). Growth may be suppressed when a biological entity is contacted with a copolymer having a biocide block so that the rate of settlement and/or growth of biological entities on the coated surface is less than that of an uncoated surface.
• a significant number of the biological entities may be destroyed or, desirably, substantially all or all of the biological entities maybe destroyed.
• the copolymer may also simply prevent the biological entities from depositing on the coated surface without actually destroying them.
• the fouling release activity of the copolymer can act to impede or suppress the adhesion of aquatic organisms to the coated surface and/or facilitate ready release of the organisms from the surface.
• the copolymers described herein may have sufficiently low surface energy and sufficiently low modulus of elasticity so that application of an external shear stress to biological entities adhered to the copolymers may result in partial or complete removal of those entities.
• the external shear stress can be provided by moving water (e.g., pressure washer, etc.) or from physical contact with a brush or sand blaster.
• aquatic organisms that cause fouling and which the disclosed copolymers may be used to prevent fouling are Enteromorpha spores, Hydroides Elegans (tube worms), bacteria, germs, microbes, biofilms, crustaceans, tube worms, cyprid larvae, grasses, clams, oysters, and/or barnacles, etc.
• compositions or formulations including an effective amount of a biocidal copolymer can be applied as an antifouling coating having biocidal and/or fouling release activity.
• a surface may be treated by applying a suitable amount of a coating that comprises one or more biocidal copolymers as described herein.
• it may be desirable to administer the coating composition in an amount which is effective to suppress the settlement and/or growth of biological entities as well as enable their facile release by the application of an external shear stress.
• the mode of applying the coating may vary.
• the composition may be applied to a surface using a brush or mechanical sprayer.
• the surface may be dipped, submerged, or infused with the coating.
• the present copolymer compositions may include linear and/or branched functionalized copolymers (e.g., branched copolymer generated via graft polymerization).
• the average number of functionalized subunits in the functionalized copolymers can vary.
• linear forms of the functionalized copolymer may include from 20 to about 2,000 subunits and linear forms with 50 to 2000 subunits are quite suitable for coatings applications.
• Cyclic forms of alkoxy polysiloxane compounds typically include from 3 to about 12 siloxane subunits and cyclic forms with 3 to 6 units are quite suitable for use in forming the present copolymers.
• PVMS-b-PDMS-b-Polybio Polyvinylmethyl siloxane-b-Polydimethyl siloxane-b- Polybiocide
• V3 Dry 1,3,5- trivinyl-l,3,5-trimethyl cyclotrisiloxane
• D3 hexamethyl cyclotrisiloxane
• V3 Dry 1,3,5- trivinyl-l,3,5-trimethyl cyclotrisiloxane
• D3 hexamethyl cyclotrisiloxane
• the solvent was decanted and the polymer dried and was end functionalized using allyl isobutyryl bromide in toluene using Karstedt's catalyst (platinum (0)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex).
• Karstedt's catalyst platinum (0)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex.
• the end functionalized Polyvinylmethyl siloxane-b-Polydimethyl siloxane polymer was added to a Schlenk flask in toluene followed by methacrylate functionalized biocide, Triclosan (i.e., the Triclosan methacrylate ester shown in Figure 4; "TRICL-MAE").
• the catalyst, copper bromide and ligand, N,N,N',N',N"-pentamethyl- diethylenetriamine were added to the flask and subjected to three freeze-thaw pump cycles. After the freeze-thaw pump cycles, the temperature was raised to 90° C and the polymerization continued for 48 hours. After polymerization, the polymer was recovered by precipitating into methanol and filtration. The polymer was redissolved in toluene and passed through a neutral alumina column to remove the catalyst, precipitated into methanol, filtered and dried.
• Figure 4 shows the synthetic strategy of Example 1.
• the structure of the copolymer was confirmed by NMR, as shown in Figure 5, and the molecular weight was determined by gel permeation clrromatography (GPC), as shown in Figure 6.
• the ratio of PVMS-b-PDMS to Polybio was about 1:1 to about 1:4.
• Polyisoprene-b-Polybiocide (Pl-b-Polybiocide; where "Biocide” is Poly -( TRICL-MAE)) was synthesized as follows. Dry isoprene was added to a Schlenk tube under nitrogen purge followed by dry cyclohexane. n-BuLi was then added and the reaction continued for 4 hours at ambient conditions. The reaction was terminated by adding bromo isobutyryl bromide and the polymer was precipitated into methanol. The solvent was decanted and the polymer dried.
• the end functionalized polyisoprene was added to a Schlenk flask in toluene followed by methacrylate functionalized biocide, Triclosan (TRICL-MAE).
• the catalyst, copper bromide and ligand, N,N,N',N',N"-pentamethyl-diethylenetriamine were added to the flask and subjected to three freeze-thaw pump cycles. After the freeze-thaw pump cycles, the temperature was raised to 90° C and the polymerization continued for 48 hours. After polymerization, the polymer was recovered by precipitating into methanol and filtration. The polymer was redissolved in toluene and passed through a neutral alumina column to remove the catalyst, precipitated into methanol, filtered and dried.
• Figure 7 shows the synthetic strategy of Example 2.
• the structure of the copolymer was confirmed by NMR, as shown in Figure 8, and the molecular weight was determined by gel permeation chromatography (GPC), as shown in Figure 9.
• the ratio of PI to Polybiociode was about 1:1 to 1:4, or, desirably, 1:1 to 1:3.
• polymethylhydrosiloxane-co-polydimethylsiloxane-g- polymethacrylate biocide was synthesized as follows. Polymethylhydrosiloxane-co- polydimethylsiloxane (HMS501 from Gelest) and allyl isobutyryl bromide were added to dry toluene in a flask under nitrogen and Karstedt's catalyst was added to this mixture. The temperature was raised to 90° C and the reaction continued for 8 hours. After the reaction, solvent was evaporated and the isobutyryl functionalized HMS 501 was added to a Schlenk tube under nitrogen purge followed by dry THF.
• HMS501 Polymethylhydrosiloxane-co-polydimethylsiloxane-g- polymethacrylate biocide was synthesized as follows. Polymethylhydrosiloxane-co- polydimethylsiloxane (HMS501 from Gelest) and allyl isobutyryl bromide were added
• Figures 11-16 show additional exemplary copolymers that may be used as anti-fouling materials.
• Figure 11 shows Polyisoprene-b-PDMS-b-Polybiocide-co- polymethoxyethyl methacrylate.
• Figure 12 shows Polyisoprene-b-PDMS-b- Polybiocide.
• Figure 13 shows Polyisoprene-b-PDMS-b-Poly zinc acrylate-co- polymethoxyethyl methacrylate. The zinc atom shown in Figure 13 may be coupled to any suitable ligand such as a Cl ion.
• Figure 14 shows Polyisoprene-b- Polymethacrylate siloxane-co-polybiocide.
• Figure 15 shows Polybutadiene-b- Polymethacrylate siloxane-co-polybiocide.
• Figure 16 shows Polybutadiene-b-PDMS- b-Polybiocide.
• block F may be a block of random biocide blocks and textural blocks or may include ordered subblocks of biocide blocks and textural blocks.
• the use of the same base monomer (methacrylate) to polymerize the biocide blocks and textural blocks may provide for this type of arrangement of the blocks.
• Block D may be the rubbery block which provides additional strength and wear resistance to the copolymer.
• Block E may be another textural block which provides desirable foul release characteristics to the copolymer.
• the fouling rating was determined for a number of anti-fouling materials shown in graph 1 below.
• the fouling rating was determined using Designation: D 3623 - 78a (Reapproved 1998), Standard Test Method for Testing Antifouling Panels in Shallow Submergence, American Society for Testing and Materials, as described in the following.
• Each test surface which is free of fouling except for the presence of algal spores and other biological slimes receives a fouling rating of 100.
• the fouling rating is reduced to 95 if only incipient fouling is present. If mature forms of fouling are present, the fouling rating is obtained by subtracting from 95 the sum of the number of individuals present and the percent of the surface area covered by colonial forms.
• Anti-fouling materials A-N referenced in Graph 1, were tested to determine the fouling rating for each material.
• the reference material is a commercially available copper ablative coating.
• Material C is a commercially available anti-fouling coating sold under the tradename Interslick 425 available from International Paints UK.
• Material D is the crosslinked material VI from Table 1 (pgs 67-70) of U.S. Provisional Patent Application No.
• the crosslinked material VI is crosslinked using the cross linking agent shown in the / adjacent column in Table 1 of the '077 patent application.
• Material I is the same as material E except that the Triclosan is coupled to the siloxane backbone using an 11 carbon chain.
• Material L is the same as material E except that it is cross linked with 3-amino-l- (2,4,6,-trichlorophenyl)-2-pyrazolin-5-one.
• Material M is the same as material E except that Triclosan is linked to the polysiloxane using an acrylate rather than the propyl group.
• Material N is a mixture of material M and 10 wt.% free biocide (Triclosan).
• the anti-fouling materials A-N shown in Graph 1, were used to coat a substrate (metal) and placed in seawater (i.e., Indian River lagoon off the coast of Florida) for 80 days.
• seawater i.e., Indian River lagoon off the coast of Florida
• a stated range of 1 to 10 should be considered to include any and all subranges between and inclusive of the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 5.5 to 10).

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