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
  • C09D183/10—Block or graft copolymers containing polysiloxane 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
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1637—Macromolecular compounds

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.
• an anti-fouling material comprises a copolymer having the formula:
• R , R , and R are independently Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl or phenyl;
• R is hydrogen, Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl or phenyl;
• R is Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, phenyl, or a cross linking group;
• R is hydrogen, Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, phenyl, or a cross linking group;
• R 5 R , and R include independently a biocidal group that is toxic to organisms that cause fouling in an aquatic environment; a fouling release group; a texturizing group; or combination thereof.
• the polysiloxane backbone may be a random or block copolymer.
• the polymethacrylate based polymer grafted to the polysiloxane backbone may be a random or block copolymer. Accordingly, the formulas shown herein should be understood to refer to either a block or random copolymer having the specified monomer units in any order.
• an anti-fouling material comprises a random or block copolymer having a formula:
• L and L are linking groups
• R 5 R , and R are independently Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl or phenyl;
• R is hydrogen, Ci- C ⁇ o alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl or phenyl;
• R is Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, phenyl, or a cross linking group;
• R is hydrogen, Ci- Cio alkyl, cyclopentyl, cyclohexyl, benzyl, toluyl, xylyl, phenyl, or a cross linking group;
• R , R , and R include independently a biocidal group that is toxic to organisms that cause fouling in an aquatic environment; a fouling release group; a texturizing group; or combination thereof; and wherein at least one of R , R , and R includes the biocidal group, the fouling release group, or the texturizing group and another one of R , R , and R includes one of the remaining groups from the biocidal group, the fouling release group, or the texturizing group.
• 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.
• a graft copolymer may be prepared that has a polysiloxane copolymer (random or block) attached to a polymethacrylate copolymer (random or block).
• the polymethacrylate copolymer may include biocidal groups, fouling release groups, and/or texturizing groups.
• the polysiloxane copolymer is attached to multiple polymethacrylate copolymers, each of which may have one or more of a texturizing group, foul release group, or biocidal group.
• the texturizing and/or fouling release groups 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 cross linking groups are provided on the polysiloxane copolymer (e.g., H group).
• the cross linking groups may be included as part of the polymethacrylate copolymer.
• the copolymers may have a molecular weight from 5,000 to 50,000, or, desirably, 10,000 to 25,000.
• the polysiloxane copolymer may include two or more blocks where each block contains about 10 to 100 subunits.
• FIG. 1 is a picture of a bacterial assay of a PDMS coating.
• FIG. 2 is a picture of a bacterial assay of a PDMS-co-PMHS-g-PHDFMA coating.
• FIG. 3 is a picture of abacterial assay of a PDMS-co-PMHS-g-PMEMA coating.
• FIG. 4 is a picture of a bacterial assay of a PDMS-co-PMHS -g-PMEMA-b-Biocide coating.
• FIG. 5 is a picture of a bacterial assay of a PDMS-co-PMHS-g-Biocide coating.
• FIG. 6 shows the contact angle of one embodiment of HMS-g-PEG-b-PPF.
• FIG. 7 is a transmission electron microscopy (TEM) image of HMS-g-Biocide.
• FIG. 8 is an atomic force microscopy image of HMS-g-Biocide.
• FIG. 9 is an atomic force microscopy image of PDMS-g-PEG-b-Biocide.
• FIG. 10 is an atomic force microscopy image of HMS-g-PPF-b-PEG.
• the antifouling materials described herein comprise functionalized polysiloxanes and/or salts thereof that exhibit biocidal and/or fouling release activity.
• the various embodiments and descriptions of antifouling materials may be used independently (e.g., as a single coating layer) or in combination with other materials (e.g., paint pigment, etc.) to prevent structures and other surfaces exposed to an aquatic environment (e.g., marine environments, freshwater environments, etc.) from fouling.
• the composition of the coating material includes other compounds such as curing agents, crosslink initiators, and the like.
• Formulas I, II and III show embodiments of a functionalized polysiloxane copolymer, a functionalized polysiloxane block copolymer, and a functionalized polysiloxane homopolymers, respectively.
• the various embodiments of functionalized polysiloxane polymers typically comprise the following the moieties: a crosslinking moiety (e.g., epoxy, olefin, amine, acid, aldehyde, ester, etc.), a biocidal moiety (e.g., Triclosan, quatenary ammonium, pyridinium, polymers and copolymers such as polymethacrylate that include these groups, etc.), a fouling release or textural moiety (e.g., hydrophilic groups such as polyether groups, hydrophobic groups such as perfluroalkyl groups, liquid crystalline groups such as deuterobenzene groups, self-organizing groups, polymers and copolymers
• the functionalized polysiloxanes shown in Formulas I 5 II and III may be combined in a number of ways to provide various embodiments of antifouling materials.
• the functionalized polysiloxanes may be crosslinked (e.g., polysiloxanes of Formulas I crosslinked with other polysiloxanes of Formula I, etc.; polysiloxanes of one of Formulas I, II, or III crosslinked with polysiloxanes of one or both of the remaining polysiloxanes, etc.).
• polysiloxanes of Formulas I, II and III may be blended (i.e., physically mixed) together.
• any of the crosslinked polysiloxanes may be blended with other crosslinked polysiloxanes.
• the polysiloxanes may be combined to provide suitable antifouling materials.
• the functionalized polysiloxanes and/or polymethacrylates in the copolymer may include a pendant crosslinking moiety.
• Suitable examples of such crosslinking moieties include groups having Formula I:
• A is a spacer consisting of alkyl, ether, ester, polyether, phenyl, aryl, heterocyclic, polyaromatic, polypeptide, polysiloxane, polyamide, polysulfone, or polyurethane group.
• E is a terminal functionality consisting of an epoxy, hydroxy, amino, carboxylic, ester, capable of undergoing further reaction when brought into contact with a curing agent.
• the functionalized polysiloxanes and/or polymethacrylates in the copolymer may include a pendant biocidal moiety.
• Suitable examples of such biocidal moieties include groups having Formula II:
• A is a spacer consisting of alkyl, ether, ester, polyether, phenyl, aryl, heterocyclic, polyaromatic, polypeptide, polysiloxane, polyamide, polysulfone, or polyurethane group.
• G is a terminal functionality which is a biocide for aquatic organisms such as in one embodiment, tetracyclines, triclosans, and floxapins, or, in another embodiment, ammonium salts and pyridinium salts.
• the spacer" A" may be selected so that it hydrolyzes and the biocide group "G” is therefore cleavable from the polysiloxane and/or polyrnethacrylate.
• the spacer "A" may be chosen so that it does not undergo hydrolysis and thus the biocide group "G” is not cleavable from the polysiloxane.
• the polysiloxane and/or the polymethacrylate includes both cleavable and non-cleavable biocide groups.
• one compound of polysiloxane includes cleavable biocide groups and is crosslinked to other polysiloxanes, at least one of which includes non-cleavable biocide groups. Suitable examples of biocide groups include triclosan and pyridinium groups, as shown below, respectively:
• the functionalized polysiloxanes and/or polymethacrylates in the copolymer may include a pendant fouling release moiety.
• Suitable examples of such fouling release moieties include groups having Formula III:
• A is a spacer consisting of alkyl, ether, ester, polyether, phenyl, aryl, heterocyclic, polyaromatic, polypeptide, polysiloxane, polyamide, polysulfone, or polyurethane group.
• J is a terminal functionality which affects the physical properties of the polysiloxane to enhance the fouling release action as described herein such as perfluoroalkyl. Suitable examples of "J" groups include:
• the copolymer may be cross linked using any of a number of cross linking agents such as those having two vinyl groups (e.g., divinyl PDMS, divinyl benzene, etc.).
• the contact angle of the copolymer maybe at least 105 degrees, 110 degrees, 115 degrees.
• the present compositions may be used as an antifouling coatings having biocidal activity and/or fouling release activity. These coatings are more or less effective at inhibiting settlement / growth / proliferation of biological entities on the coated surface.
• the functionalized polysiloxane compositions can be used in conjunction with other materials to comprise formulations for use in the antifouling coatings. It is anticipated that the formulation can be used to serve as antifouling coatings in a number of applications.
• the present compositions maybe useful for the coating of ship hulls, heat-exchangers, cooling towers, de-salination equipment, filtration membranes, docks, off-shore oil rigs, and other submerged superstructures as well as any structure or surface subject to fouling in an aquatic environment.
• HMS-82Br 26g was dissolved in 150ml of dry TBDF in a schlenk flask and 8.3ml of methoxy ethyl methacrylate was added to that followed by 0.4 Ig copper (I) bromide and 0.6ml of pentamethyldiethylene triamine.
• the mixture was subjected to three freeze-thaw pump cycle and then allowed to polymerize at 90oC for 72h. After the reaction, the polymerization was stopped by precipitating the mixture in methanol. Copper was removed by passing the polymer through a neutral alumina column. s
• HMS-82Br,20g was dissolved in 150ml of dry THF in a schlenk flask and 6.4 ml of Methoxy ethyl methacrylate was added to that followed by 0.32g copper (I) bromide and 0.46ml of pentamethyldiethylene triamine.
• the mixture was subjected to three jfreeze-thaw pump cycle and then allowed to polymerize at 9O 0 C for 72h. After 72h, 15.7g methacrylatesolutionalized triclosan (biocide) was added to the reaction mixture under nitrogen and the polymerization continued for another 72h. The reaction was stopped by precipitating the mixture in methanol. Copper was removed by passing the polymer through a neutral alumina column.
• HMS-82Br,20g was dissolved in 150ml of dry THF in a schlenk flask and 7.4ml of heptadecafluoro decyl methacrylate was added to that followed by 0.32g copper (T) bromide and 0.46ml of pentamethyldiethylene triamine.
• T copper
• pentamethyldiethylene triamine 0.32g
• copper (T) bromide 0.46ml of pentamethyldiethylene triamine.
• the mixture was subjected to three freeze-thaw pump cycle and then allowed to polymerize at 90oC for 8h. After the reaction, the polymerization was stopped by precipitating the mixture in methanol. Copper was removed by passing the polymer through a neutral alumina column.
• HMS-82Br,20g was dissolved in 150ml of dry THF in a schlenk flask and 7.4ml of heptadecafluoro decyl methacrylate was added to that followed by 0.32g copper (T) bromide and 0.46ml of pentamethyldiethylene triamine.
• T copper
• pentamethyldiethylene triamine pentamethyldiethylene triamine.
• the mixture was subjected to three freeze-thaw pump cycle and then allowed to polymerize at 90oC for 8h. After 8h 5 15.7g of methylmethacrylate triclosan (Biocide) was added to the mixture under nitrogen atmosphere and the reaction was continued for 72 h. Polymerization was stopped by precipitating the mixture in methanol. Copper was removed by passing the polymer through a neutral alumina column.
• HMS-82Br,10g was dissolved in 100ml of dry THF in a schlenk flask and 3.2ml of Methoxy ethyl methacrylate was added to that followed by 0.08g copper (I) bromide and 0.1 ImI of pentamethyldiethylene trimine.
• the mixture was subjected to three freeze-thaw pump cycle and then allowed to polymerize at 90oC for 72h. After 72h, 3.7ml of heptadecafluoro decyl methacrylate was added to the reaction mixture and the reaction was continued for another 24h. After the reaction, the polymerization was stopped by precipitating the mixture in methanol. Copper was removed by passing the polymer through a neutral alumina column.
• HMS-82Br,10g was dissolved in 100ml of dry THF in a schlenk flask and 3.7ml of heptadecafluoro decyl methacrylate was added to that followed by 0.08g copper (I) bromide and 0.1 ImI of pentamethyldiethylene trimine.
• the mixture was subjected to three freeze-thaw pump cycles and then allowed to polymerize at 90 °C for 8h. After 8h, 3.2ml of Methoxy ethyl methacrylate was added to the reaction mixture and the reaction was continued for another 72h. After the reaction, the polymerization was stopped by precipitating the mixture in methanol. Copper was removed by passing the polymer through a neutral alumina column.
• the coatings were prepared by cross linking the polymers by divinyl terminated polydimethyl siloxane using platinum catalyst. These coatings were then tested by growing bacteria (Halomonas pacifica) on the surface of coatings. The results of these assays are shown in FIGS. 1-5.
• FIG. 1 shows the results for a PDMS coating. More specifically, the horizontal rows of dishes in FIG. 1 show the test results for the following coatings.
• the contact angle of the PDMS coating in rows 2 and 3 is 103.
• FIG. 2 shows the results for a PDMS-co-PMHS-g-PHDFMA coating.
• the specific coating applied to the dishes is shown below.
• the contact angle of the PDMS-co- PMHS-g-PHDFMA coating is 120.
• FIG. 3 shows the results for a PDMS-co-PMHS-g-PMEMA coating.
• the specific coating applied to the dishes is shown below.
• the contact angle of the PDMS-co- PMHS-g-PMEMA coating is 107.
• FIG. 4 shows the results for a PDMS-co-PMHS -g-PMEMA-b-Biocide coating. The specific coating applied to the dishes is shown below. The contact angle of the PDMS-co-PMHS -g-PMEMA-b-Biocide coating is 105.
• FIG. 5 shows the results for a PDMS-co-PMHS-g-Biocide coating.
• the specific coating applied to the dishes is shown below.
• the contact angle of the PDMS-co- PMHS-g-Biocide coating is 108.
• FIG. 6 shows the > advancing contact angle, ⁇ a, and the receding contact angle, ⁇ r, for HMS-g-PEG-b- PPF.
• FIGS. 7-10 the morphology of some of the coatings is shown.
• FIG. 7 shows a transmission electron microscopy (TEM) image of HMS-g-Biocide.
• FIG. 8 shows an atomic force microscopy (AFM) image of HMS-g-Biocide.
• FIG. 9 shows an AFM image of PDMS-g-PEG-b-Biocide.
• FIG. 10 shows an AFM image of HMS- g-PPF-b-PEG.
• 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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• 2006
  • 2006-01-04 JP JP2007551287A patent/JP2008527144A/ja active Pending
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