US3575123A - Marine structure coated with an acrylic insoluble water-swellable polymer - Google Patents

Marine structure coated with an acrylic insoluble water-swellable polymer Download PDF

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US3575123A
US3575123A US838269A US3575123DA US3575123A US 3575123 A US3575123 A US 3575123A US 838269 A US838269 A US 838269A US 3575123D A US3575123D A US 3575123DA US 3575123 A US3575123 A US 3575123A
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polymer
marine structure
methacrylate
coating
acrylate
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Thomas H Shepherd
Francis E Gould
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National Patent Development Corp
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National Patent Development Corp
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    • 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
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T70/00—Maritime or waterways transport
    • Y02T70/10—Measures concerning design or construction of watercraft hulls
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/907—Resistant against plant or animal attack

Definitions

  • the present invention relates to the use of water-insoluble hydrophilic acrylic resins.
  • Another object is to develop novel antifoulant compositions.
  • a further object is to provide watercraft and underwater static structures with an improved antifoulant coating.
  • marine coating is used in the present application and claims to cover both coatings for watercraft and underwater static structures.
  • watercraft includes movable boats of all kinds, including but not limited to sailboats, yachts, inboard and outboard motor boats, rowboats, motor launches, canoes, kayaks, water skis, surfboards, ocean liners, tugboats, tankers and other cargo ships, submarines both of the atomic and conventional varieties, aircraft carriers, destroyers, etc.
  • Underwater static structures include but are not limited to wharves, piers, permanently moored watercraft, pilings, bridge substructures, etc.
  • the underwater surface can be made of wood, metal, plastic, fiberglass, concrete or other material.
  • the antifoulant compositions are useful as marine coatings to render the structure (moving or static) resistant to fouling by marine organisms such as barnacles, algae, slime, acornshells (Balanidae), goose mussels (Lepadoids), tube-worms, sea moss, oysters, brozoans, tunicates, etc.
  • hydrophilic acrylic resins be water insoluble since otherwise they cannot be permanently applied to the underwater surface.
  • the hydrophilic acrylic resin should be capable of absorbing at least 20 percent of its weight of water and preferably does not absorb more than about 120 percent of its weight of water. It has been found that linear polymers which are usually alcohol soluble are preferable although cross-linked polymers can also be used providing they are applied while still in a workable condition. These coatings effectively reduce the drag or resistance developed on moving the coated surface through water.
  • the coating absorbs a substantial percentage of water and the waterswollen coating exhibits a low contact angle with the water.
  • the swollen coatings are soft, (particularly if a linear polymer is employed) and the softness can provide a hydrodynamic damping effect and reduce turbulence of the flow.
  • the hydrophilic monomer employed is a hydroxy lower alkyl acrylate or methacrylate or hydroxy lower alkoxy lower alkyl acrylate or methacrylate, e.g. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, 2- hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, dipropylene glycol monomethacrylate and dipropylene glycol monoacrylate.
  • the most preferred monomers are the hydroxyalkyl acrylates and methacrylates, particularly 2- hydroxyethyl methacrylate.
  • polymers of acrylamide, methacrylamide, N-alkyl substituted acrylamide and methacrylamide such as N-propylacrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-propyl methacrylamide, N-butyl acrylamide, N-methyl acrylamide and N-methyl methacrylamide, diacetone acrylamide, N-(2- hydroxyethyl) acrylamide and N-(2-hydroxyethyl) methacrylamide.
  • copolymers of these monomers with each other or with other copolymerizable monomers.
  • the hydrophilic monomer gives a product which is water soluble, e.g. polyacrylamide
  • the copolymerizable monomer can be used in an amount of 0.05 to 50 percent.
  • comonomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, propyl acrylate, butyl acrylate, sec.
  • lower alkoxyethyl acrylates and methacrylates e.g. methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate and ethoxyethyl methacrylate,
  • triethylene glycol acrylate triethylene glycol methacrylate, glycerol monoacrylate and glycerol monomethacrylate.
  • unsaturated amines p-aminostyrene, o-aminostyrene, 2-amino- 4-vinyltoluene, alkylamino alkyl acrylates and methacrylates, e.gi diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl acrylate, t-butylaminoethyl methacrylate, piperidinoethyl acrylate, piperidinoethyl methacrylate, morpholinoethyl acrylate, morpholinoethyl methacrylate, 2-vinylpyridine, 3- vinyl pyridine, 4-vinyl pyridine, 2-ethyl-5-vinylpyridine, dimethylamino propyl acrylate, di
  • amino compounds are alkylaminoethyl acrylates and methacrylates, most preferably t-butyl aminoethyl methacrylate.
  • linear polymers including both homoand copolymers
  • cross-linked hydrophilic copolymers are frequently advantageously employed when antifouling agents are included in the composition to insure more permanent adherence to the underwater structure.
  • the cross-linking agent is present in an amount of 0.1 to 2.5 percent, most preferably not over 2.0 percent, although from 0.05 to percent, or even percent, of cross-linking agents can be used.
  • cross-linking agents include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-butylene dimethacrylate, l,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, divinyl benzene, divinyl toluene, diallyl tartrate, allyl pyruvate, allyl maleate, divinyl tartrate, triallyl malamine, N,N-methylene bis-acrylamide, glycerine trimethacrylate, diallyl maleate, divinyl ether, diallyl monoethylene glycol citrate, ethylene glycol vinyl allyl citrate, allyl vinyl maleate, diallyl itaconate, ethylene glycol diester of itac
  • polyallyl sucrose e.g. pentaallyl sucrose, sucrose diacrylate, glucose dimethacrylate, pentaerythritol tetraacrylate, sorbitol dimethacrylate, diallyl aconitate, divinyl citraconate, diallyl fumarate.
  • ethylenically unsaturated acids or salts thereof such as acrylic acid, cinnamic acid, carotonic acid, methacrylic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, mesaconic acid and citraconic acid.
  • partial esters such as mono 2-hydroxypropyl itaconate, mono 2-hydroxyethyl itaconate, mono Z-hydroxyethyl citraconate, mono 2- hydroxypropyl aconitate, mono 2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, monomethyl itaconate, monoethyl itaconate, mono Methyl Cellosolve ester of itaconic acid (Methyl Cellosolve is the monomethyl ether of diethylene glycol), Mono Methyl Cellosolve ester of maleic acid.
  • partial esters such as mono 2-hydroxypropyl itaconate, mono 2-hydroxyethyl itaconate, mono Z-hydroxyethyl citraconate, mono 2- hydroxypropyl aconitate, mono 2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, monomethyl itaconate, monoethyl itaconate, mono Methyl Cellosolve ester of itaconic
  • the polymers can be prepared as casting syrups, e.g. as prepared in applicants parent application, as aqueous dispersions, by aqueous suspension polymerization or as solutions in organic solvents such as ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, formamide, dimethyl sulfoxide or other appropriate solvent.
  • organic solvents such as ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, formamide, dimethyl sulfoxide or other appropriate solvent.
  • Polymerization can be carried out at 20 to 150 C., frequently 35 or 40 C. to 90 C. and can be completed after applying as a marine coating.
  • the polymerization can be carried out employing a free radical catalyst in the range of 0.05 to 1 percent of the polymerizable monomers.
  • Typical catalysts include I -butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2, 4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide; cumene hydroperoxide and dicumyl peroxide.
  • Irradiation e.g. by ultraviolet light or gamma rays, also can be employed to catalyze the polymerization.
  • Example A was repeated using xylene in place of the silicone oil and employing 300 grams of 2-hydroxyethyl methacrylate and the quantity of isopropyl percarbonate increased to 0.99 gram. An 85 percent yield of polymer beads was obtained.
  • EXAMPLE C The procedure of example A was repeated replacing the 2- hydroxyethyl methacrylate by 100 grams of 2-hydroxypropyl methacrylate to produce a thermoplastic solvent soluble hydrophilic finely divided bead polymer.
  • EXAMPLE D Eight hundred grams of ethylene glycol monomethyl ether, I grams of Z-hydroxyethyl methacrylate, 20 grams of acrylic acid and 2 grams of t-butyl peroctoate were charged into a flask. The solution was heated and stirred under a carbon dioxide atmosphere for 6 hours. The product of this example while thermoplastic and solvent soluble has the capability of curing to cross-linked solvent insoluble polymer by further heating, particularly if additional catalyst is added.
  • EXAMPLE E A casting syrup was made from 100 parts of 2-hydroxyethyl acrylate, 0.2 parts of ethylene glycol dimethacrylate and 0.4 parts t-butyl peroctoate.
  • EXAMPLE F Ten kilograms of 2-hydroxyethyl methacrylate, 150 grams of ethylene glycol dimethacrylate and 4.0 grams of t-butyl peroctoate were heated with stirring for 50 minutes at 95 C. to yield a syrup having a viscosity of 420 centipoises at 30 C. To this syrup was added 20 grams of ethylene glycol dimethacrylate and 20 grams of t-butyl peroctoate and the syrup stirred until a homogeneous solution was obtained.
  • EXAMPLE G Seventy-five liters of ethanol, 1 kilogram of butylaminoethyl methacrylate, 1.5 kilograms of N-isopropyl acrylamide and 22.5 kilograms of hydroxyethyl methacrylate (containing 0.3 percent of ethylene glycol dimethacrylate) together with 100 grams of t-butyl peroctoate were charged into a vessel and the solution heated at C. for 7 hours to effect polymerization to a percent conversion level.
  • hydrophilic polymers of the invention can be incorporated with the hydrophilic polymers of the invention to provide coatings to prevent fouling by marine organisms any of the conventional inorganic or organic antifoulants including cuprous oxide, copper powder, mercuric oxide, cuprous oxide-mercuric oxide (e.g.
  • organotin compounds including triphenyltin chloride, triphenyltin bromide, tri p-cresyltin chloride, triethyltin chloride, tributyltin chloride, phenyl diethyltin fluoride, tri (p-chlorophenyltin) chloride, tri (mchlorophenyltin) chloride, dibutyl ethyltin bromide, dibutyloctyltin bromide, tricyclohexyltin chloride, triethyltin stearate, tributyltin stearate, triethyltin fluoride, tributyltin fluoride, diphenyl ethyltin, chloride, diphenyl ethyltin fluoride, triphenytin hydroxide, triphenyltin thiocyanate, triphenyltin
  • SA-546 1, 3- trichloro-4,6-dinitrobenzene
  • the quantity of antifouling agent required in the coating as would be expected varies with the particular agent used and the severity of fouling tendency encountered in the particular service to which the coated vessel or static structure is to be used. in general, the amount of antifouling agent employed will range from 2 to 50 percent of the resin, although as little as 0.1 percent of antifoulant can be used based on the resin.
  • pigments and fillers such as titanium dioxide, red lead, bone black, red iron oxide, talc, aluminum silicate, fullers earth, pumice, zinc oxide, calcium carbonate, etc.
  • the coatings of the present invention can be applied to the surfaces to be subjected to underwater conditions from solution in organic solvents or from aqueous dispersions.
  • Suitable solvents include lower aliphatic alcohols such as methanol, ethanol, propanol and isopropanol or mixtures of these solvents with higher boiling alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diacetone alcohol, n-butanol, sec. butanol, isobutanol and mixtures of these solvents with water.
  • the coatings of the present invention generally exhibit adequate adhesion to marine surfaces protected by corrosion resistant finishes such as epoxy or vinyl-based paints, to previously applied antifouling finishes and to polyesterfiberglass laminates.
  • corrosion resistant finishes such as epoxy or vinyl-based paints
  • Typical of such finishes are those shown in Sparmann U.S. Pat. No. 2,970,923, Scott U.S. Pat. No. 3,214,279 and Robins U.S. Pat. No. 3,236,793.
  • the thickness of the coating applied will vary with the particular formulation employed and the method of application. it can be from 0.1 mil to 250 mils or more in thickness. Usually it will be between 0.3 mil, and mils.
  • the coatings can be applied to the marine surface, e.g. boat bottom or hull or wharf piling by any conventional procedure such as brushing, dipping, spraying, roller coating etc.
  • Coating applied at boat yards, marinas or similar locations will normally be placed in water soon after drying. These coatings if made from linear, alcohol soluble polymers will remain alcohol soluble. However, as pointed out supra it is also possible to provide cured or cross-linked coatings which exhibit improved mechanical durability. There can be used the peroxide catalysts referred to supra alone or as part of a two-component catalyst system which is mixed into the coating solution immediately prior to application. Alternatively, the coating can be cured by incorporating a free radical initiator and heating the coated surface after drying.
  • Two-component catalyst systems for effecting cure at ambient conditions include peroxides of the type referred to supra together with such amine accelerators as N,N-dimethylaminoethyl acetate, N,N-dimethyl aniline, N,N- dimethyl aminoethanol, N,N-dimethyl toluidine.
  • the accelerator can he used in an amount of 0.05 to 1 part per part of peroxide, e. g. a mixture of 89 percent benzoyl peroxide and l 1 percent dimethylaniline can be employed.
  • FIG. 1 shows a boat having a coating according to the invention
  • FIG. 2 is a sectional view along the line 2-2 of FIG. 1.
  • the boat 2 in water 4 has a coating 6 of hydroxyethyl methacrylate polymer below the water line 8. If desired, the entire boat can be coated with the polymer. The thickness of the coating 6 is greatly exaggerated for illustrative purposes.
  • EXAMPLE 1 2-hydroxyethyl methacrylate (50 parts) and Ti0 (30 parts) are ground in a pebble mill to a fine powder (Hegeman 7-8). Additional 2-hydroxyethyl methacrylate (50 parts) is added along with ethylene glycol dimethyacrylate (0.2 part), cobalt naphthenate a conventional metallic paint dryer or catalyst (0.1 part) and t-butyl peroctoate (0.4 part). The resulting viscous syrup is painted onto a wooden boat hull and cured at 20 to 35 C. The resulting protective marine coating is characterized by its ability to discourage bamacle and algae growth and corrosion on prolonged underwater exposure. Additionally, it reduces the drag on moving the coated hull through water.
  • EXAMPLE 2 The procedure of example 1 is repeated with the modification that the coating syrup is cast onto a steel hull and cured at 100 C. in the absence of cobalt naphthenate. The drag on moving the coated hull through water was reduced compared to an uncoated hull.
  • EXAMPLE 3 The procedure of example 1 is repeated employing an isomeric mixture of hydroxy isopropyl methacrylate isomer is place of the hydroxyethyl methacrylate.
  • EXAMPLE 4 To a glass-lined reactor was charged 800 lbs. of ethanol, 200 lbs. of hydroxyethyl methacrylate and 0.5 lb. of t-butyl peroctoate. The reactor was flushed with nitrogen and heated to C. over a period of 1 hour. The reactor was stirred at 80 C. for 7 hours, wherein percent conversion of hydroxyethyl methacrylate to polymer was attained.
  • the resulting solution containing 18 percent polymer by weight was used for the formulation of coatings for sailboats and motorboats below the waterline.
  • the boats were made of wood, metal and fiberglass (i.e. polyester impregnated fiberglass).
  • Example 4 was repeated using 20 lbs. of methyl methacrylate and 180 lbs. of hydroxyethyl methacrylate as the monomer charge. A conversion of percent was attained in 7 hours. The resulting solution was used for the formulation of marine coatings in a similar fashion to example 4.
  • Example 4 was repeated using 80 lbs. of methyl methacrylate and lbs. of hydroxyethyl methacrylate as the monomer charge. A conversion of 90 percent was attained in 6 hours. The resulting solution was used for the formulation of marine coatings in a similar fashion to example 4.
  • EXAMPLE 7 A 22-foot polyester fiberglass boat (Aqua Sport) equipped with a IOU-horsepower outboard engine was operated at two different throttle settings between two buoys approximately 1 mile apart. Average times required to travel between buoys going in both directions were determined at each throttle setting. The boat was then removed from the water, the bottom was washed with fresh water and dried. The polymer solution of example 4 was applied with a roller to provide a dry coating thickness of 0.75 to 1.0 mil.
  • the results show a 13 percent reduction in drag resistance at a speed of about knots and a percent reduction at the higher speed.
  • EXAMPLE 8 The apparent viscosity of water at 23 C. was measured using a Brookfield RVT Syncroelectric viscosimeter employing a 01 spindle at 100 rpm. The value obtained was 11.1 centipoises. The spindle was removed, dried, and was coated with the solution prepared in example 4 by dipping and allowing the spindle to drain and dry. The coating thickness was approximately 0.5 mil. The apparent viscosity of water at 23 C. was again measured at 100 rpm. using the coated spindle. A value of 10.7 centipoises was obtained. The peripheral speed of the 01 spindle at 100 rpm. is approximately 0.6 mile per hour. At this speed approximately 4 percent reduction in frictional resistance or drag was obtained.
  • EXAMPLE 9 A 9-foot polyester-fiberglass dinghy was towed behind a motor launch with a rope attached to a spring scale having a capacity of 10 kilograms. The dinghy was towed at 25 knots. An average force of 8 kilograms was noted on the scale. The dinghy was then removed from the water, rinsed with fresh water and dried. The dinghy was then brush coated with the polymer solution of example 4 to provide a 1.5 mil coating, after drying, the dinghy was again towed at 25 knots. An average force of 6.5 kilograms was recorded on the scale. Thus, at 25 knots approximately 18 percent reduction in drag resistance was obtained.
  • EXAMPLE 10 Using a high-shear mixer, 200 grams of triphenyl lead acetate and 50 grams of titanium dioxide were dispersed in 8 kilograms of the polymer solution prepared in example 4. To the dispersion was added 2 kilograms of sec-butyl alcohol. A 01 spindle of a Brookfield viscosimeter was coated with the dispersion by dipping and allowing to dry. An average coating thickness of 0.6 mil was obtained. The apparent viscosity of water was measured as in example 8. A value of 10.5
  • centipoises was obtained.
  • the coating was removed from the spindle and the apparent viscosity" was again determined. A value of l 1.0 centipoises was obtained.
  • the coating composition prepared in example 10 was employed on sailing craft, both of the wood hull type and polyester-fiberglass laminate type to provide a fouling resistant drag-reducing coating.
  • Example 4 was repeated using a monomer charge of 40 lbs. of hydroxypropyl acrylate and 160 lbs. of hydroxyethyl methacrylate. A conversion of 85 percent was achieved after 7 hours. The procedure of example 8 was repeated using this solution. Similar results were obtained. The solution of example 11 was also coated on the bottom of a metal-bottomed motor launch to provide a drag-reducing coating.
  • EXAMPLE 13 To 500 grams of the coating dispersion of example 10 was added 2 grams of ethylene dimethacrylate (ethylene glycol dimethacrylate). 1 gram of benzoyl peroxide and 0.4 gram of N,N-dimethyl aniline. The coating was immediately applied to l a polyester-fiberglass laminated boat hull surface. After drying and standing at 75 F. (about 24 C.) for 2 hours the coating merely swelled but did not dissolve in alcohol. The resulting coating was tougher when water swollen than the coating of example 10. It was also effective as a fouling-resistant dragreducing coating for the boat bottom.
  • ethylene dimethacrylate ethylene glycol dimethacrylate
  • benzoyl peroxide 1 gram
  • N,N-dimethyl aniline N,N-dimethyl aniline
  • cuprous oxide pigment a relatively inert material.
  • a large proportion of the cuprous oxide is not effectively used because it is encapsulated in the resin and is unavailable unless the resin itself breaks down.
  • a second disadvantage of cuprous oxide is that it can induce galvanic corrosion. In addition, because of its dark color, it is unsatisfactory as an antifouling ingredient for decorative finishes.
  • hydrophilic water insoluble polymers of the present invention reduces the problem of encapsulation of active antifoulants in impermeable resin systems due to the water-swellable nature of the hydrophilic film.
  • solid organic and organometallic antifoulants do not demonstrate any significant activity unless their concentration in the film exceeds a threshold of about 25 percent by weight of the resin. 1n the systems of the present invention activity at much lower concentrations is noticed indicating that the hydrophilic resin does not impermeably encapsulate the toxicant particles.
  • EXAMPLE 14 This series of experiments was designed as an attempt to determine whether or not one of a variety of toxicants showed any activity against marine organisms when incorporated into unmodified l-lydron-S films. Accordingly, ethanol solutions of l-lydron-S containing concentrations of 232 percent of the active ingredients were applied to panels and immersed at a Miami Beach test facility.
  • example 14 through 16 the formulations containing pigments were prepared on a paint mill. All were applied (with the few exceptions indicated) to 606l-T6 anodized aluminum alloy by doctor-blade coating or brushing.
  • a marine structure which is a watercraft having an adherent coating consisting essentially of either (1) a waterinsoluble hydrophilic acrylic polymer which is swellable to an extent of at least 20 percent in water wherein the coating is sufiicient to reduce the drag of the watercraft when in water or (2) said hydrophilic acrylic polymer having encapsulated therein at least one member of the group consisting of antiifouling agents and pigment.
  • a marine structure having a coating film consisting essentially of a water-insoluble hydrophilic acrylic resin which is swellable to an extent of at least 20 percent in water and containing in the coating film an antifouling agent.
  • a marine structure according to claim 1 wherein the coating polymer is a polymer of a hydrophilic hydroxyalkyl or hydroxyalkoxyalkyl acrylate or methacrylate or acrylamide, alkyl acrylamide, methacrylamide, alkyl methacrylamide or diacetone acrylamide.
  • a marine structure according to claim 3 wherein the coating polymer is a polymer of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
  • a marine structure according to claim 4 wherein the polymer is a copolymer of said acrylate or methacrylate with a minor amount up to 20 percent of a cross-linking agent.
  • a marine structure according to claim 2 wherein the antifouling agent is an organolead compound.
  • a marine structure according to claim 2 wherein the coating polymer is a polymer of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
  • a method of increasing the speed of watercraft comprising moving said watercraft through water while having on the watercraft below the waterline the coating set forth in claim ii.
  • a method according to claim W wherein the coating polymer is a polymer of a hydrophilic hydroxyalkyl or hydroxyalkoxyalltyl acrylate or methacrylate or acrylamide, alkyl acrylamide, methacrylamide, alkyl methacrylamide or diacetone acrylamide.
  • a method according to claim 11 wherein the coating is a homopoiymer of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.
  • a method providing continuous availability of an antifouling agent comprising placing in water a marine structure having the coating composition of claim 2 applied thereto, the swelling of the hydrophilic acrylic resin in water rendering the antifouling agent readily available for its intended purpose.
  • a marine structure according to claim 2 including a pig merit.
  • a marine structure which is a watercraft having an adherent coating film of a water-insoluble hydrophilic acrylic resin which is swellable to an extent of at least 20 percent in water wherein the film is sufficient to reduce the drag of the watercraft when in water,

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US838269A 1966-07-26 1969-07-01 Marine structure coated with an acrylic insoluble water-swellable polymer Expired - Lifetime US3575123A (en)

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US56785666A 1966-07-26 1966-07-26
US65404467A 1967-07-05 1967-07-05
US83826969A 1969-07-01 1969-07-01

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Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3717606A (en) * 1971-04-05 1973-02-20 H Lomasney Solventless coal tar extended antifouling coating
US3822089A (en) * 1968-09-25 1974-07-02 Akademie Ved Contact lens blank or replica made from anhydrous, sparingly cross-linked hydrophilic copolymers
US3912519A (en) * 1973-02-01 1975-10-14 Sumitomo Chemical Co Anti-fouling ship bottom paint
US3973510A (en) * 1974-09-09 1976-08-10 The United States Of America As Represented By The Secretary Of The Navy Submersible object having drag reduction and method
JPS51114432A (en) * 1975-04-02 1976-10-08 Kansai Paint Co Ltd Insoluble matrix type antifouling paint
US3990381A (en) * 1971-01-14 1976-11-09 National Patent Development Corporation Hydrophilic polymer coating for underwater structures
US4073983A (en) * 1975-04-25 1978-02-14 United Chemical Corporation Method and composition for decreasing water resistance to movement
US4111879A (en) * 1976-07-10 1978-09-05 Ihara Chemical Industry Co., Ltd. Composition for inhibiting adhesion of shellfish and algae
US4141755A (en) * 1974-03-26 1979-02-27 National Patent Development Corporation Masonry construction member impregnated with a copolymer of hydroxy alkyl acrylate or methacrylate with long chain alkyl acrylate or methacrylate
US4154818A (en) * 1977-06-09 1979-05-15 Katayama Chemical Works Co., Ltd. Gel product for destroying harmful marine organisms and method of applying the same
US4177302A (en) * 1978-05-30 1979-12-04 Ciba-Geigy Corporation Top coat composition to improve marine antifouling performance
US4212327A (en) * 1978-11-01 1980-07-15 Dayco Corporation Polymeric hose
US4221839A (en) * 1977-03-28 1980-09-09 M&T Chemicals Inc. Method for protecting surfaces against fouling by marine organisms
US4234340A (en) * 1979-05-11 1980-11-18 Pellico Michael A Antifouling marine coating composition containing agar, a plasticizer and a strengthening agent
US4258090A (en) * 1979-01-19 1981-03-24 Institutul De Cergetari In Constructii Si Economia Constructilor Incerc Method for the protection of concrete in sea water
US4283461A (en) * 1979-05-31 1981-08-11 The United States Of America As Represented By The Secretary Of The Navy Piezoelectric polymer antifouling coating
US4389460A (en) * 1977-08-22 1983-06-21 Institut Francais Du Petrole Method of protecting submerged articles against fouling
US4480011A (en) * 1981-07-24 1984-10-30 Institut Francais Du Petrole Anti-corrosion and anti-fouling marine coatings
US4518638A (en) * 1983-01-31 1985-05-21 Rasmussen Oeystein Method for the protection of ships and other objects against fouling
US4596839A (en) * 1981-09-16 1986-06-24 Peters William E Elastomer PTFE composition
US4599368A (en) * 1984-10-31 1986-07-08 Midwest Research Institute Marine anti-fouling coating formulations containing a soluble phase including a organotin polymer in combination with an insoluble phase including a crosslinked organotin polymer
WO1987001309A1 (en) * 1985-08-30 1987-03-12 Peters William E Elastomer ptfe composition, articles, and manufacturing methods
US4695229A (en) * 1984-05-17 1987-09-22 Feuling James J Friction reduction for moving elements in contact with a fluid medium
WO1988003930A1 (en) 1986-11-17 1988-06-02 Keith Kent Self-adhesive, drag reducing polymeric coating
USRE33048E (en) * 1984-10-31 1989-09-05 Midwest Research Institute Marine anti-fouling coating formulations containing a soluble phase including a organotin polymer in combination with an insoluble phase including a crosslinked organotin polymer
US5238749A (en) * 1986-03-27 1993-08-24 Clinitex Corporation Antimicrobial coating process and product
WO1994005437A1 (en) * 1992-09-03 1994-03-17 Isk Biosciences Corporation Control of marine borers by chlorothalonil
US5393819A (en) * 1994-02-25 1995-02-28 Alphaflex Industries Asphalt modifier
US5399598A (en) * 1994-03-03 1995-03-21 Alphaflex Industries Asphalt composition
US5418270A (en) * 1994-04-12 1995-05-23 Alphaflex Industries, Inc. Modified thermoplastic elastomeric compositions
US5488076A (en) * 1973-08-08 1996-01-30 The United States Of America As Represented By The Secretary Of The Navy Water ablative coating for drag reduction applications
US5514023A (en) * 1994-02-23 1996-05-07 Warner; Jon A. Hand launchable hydrodynamic recreational device
US5554214A (en) * 1976-09-03 1996-09-10 The United States Of America As Represented By The Secretary Of The Navy Water ablative coating for vehicle drag reduction
US5571314A (en) * 1973-08-24 1996-11-05 The United States Of America As Represented By The Secretary Of The Navy Formulation and preparation of a gel system for the promotion of rapid solvation in aqueous systems
US5645603A (en) * 1995-07-25 1997-07-08 Peters; William E. Method of enhancing physical properties of non-elastomeric thermoplastic materials and resulting compositions
US6045869A (en) * 1999-01-28 2000-04-04 Gesser; Hyman D. Water-insoluble hydrophilic marine coating and methods
US6372028B1 (en) 1999-10-25 2002-04-16 Hyman D. Gesser Water-insoluble hydrophilic surface coating and methods
US6699091B1 (en) 1999-11-04 2004-03-02 Jon A. Warner Hand-launchable underwater projectile toy
US20050250409A1 (en) * 2004-05-04 2005-11-10 David Silverglate Toy submersible projectile
US20070123139A1 (en) * 2005-05-18 2007-05-31 Warner Jon A Self-propelled hydrodynamic underwater toy
EP2274384A2 (en) * 2008-03-24 2011-01-19 Clemson University Method and compositions for biofouling deterrence
US20140171546A1 (en) * 2012-10-31 2014-06-19 Uschi M. Graham Non-Yellowing easy-to-clean antimicrobial plastic
US9371451B2 (en) 2008-12-04 2016-06-21 Clemson University Research Foundation Deposition of nanocrystalline calcite on surfaces by a tissue and cellular biomineralization

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JPS58120678A (ja) * 1982-01-12 1983-07-18 Mitsubishi Rayon Co Ltd 防汚塗料用組成物
NO152012C (no) * 1983-04-06 1985-07-17 Rasmussen Oeystein Fremgangsmaate til beskyttelse av frittliggende metalliske overflater, saerlig staaloverflater, mot korrosjon
JP5732851B2 (ja) * 2010-04-06 2015-06-10 三菱レイヨン株式会社 防汚塗料組成物、防汚塗膜の製造方法、および防汚塗膜
JP6360909B2 (ja) * 2014-11-18 2018-07-18 中国塗料株式会社 二液型防汚塗料組成物、防汚塗膜、防汚基材および防汚基材の製造方法

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US3154460A (en) * 1960-02-29 1964-10-27 William R Graner Anti-fouling coating
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US3234032A (en) * 1962-07-26 1966-02-08 M & T Chemicals Inc Antifouling marine coating composition
US3266913A (en) * 1962-11-14 1966-08-16 Internat Mineral & Chemical Co Marine antifouling composition and method of treating surfaces
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Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3822089A (en) * 1968-09-25 1974-07-02 Akademie Ved Contact lens blank or replica made from anhydrous, sparingly cross-linked hydrophilic copolymers
US3990381A (en) * 1971-01-14 1976-11-09 National Patent Development Corporation Hydrophilic polymer coating for underwater structures
US3717606A (en) * 1971-04-05 1973-02-20 H Lomasney Solventless coal tar extended antifouling coating
US3912519A (en) * 1973-02-01 1975-10-14 Sumitomo Chemical Co Anti-fouling ship bottom paint
US5488076A (en) * 1973-08-08 1996-01-30 The United States Of America As Represented By The Secretary Of The Navy Water ablative coating for drag reduction applications
US5571314A (en) * 1973-08-24 1996-11-05 The United States Of America As Represented By The Secretary Of The Navy Formulation and preparation of a gel system for the promotion of rapid solvation in aqueous systems
US4141755A (en) * 1974-03-26 1979-02-27 National Patent Development Corporation Masonry construction member impregnated with a copolymer of hydroxy alkyl acrylate or methacrylate with long chain alkyl acrylate or methacrylate
US3973510A (en) * 1974-09-09 1976-08-10 The United States Of America As Represented By The Secretary Of The Navy Submersible object having drag reduction and method
JPS51114432A (en) * 1975-04-02 1976-10-08 Kansai Paint Co Ltd Insoluble matrix type antifouling paint
JPS5321693B2 (xx) * 1975-04-02 1978-07-04
US4073983A (en) * 1975-04-25 1978-02-14 United Chemical Corporation Method and composition for decreasing water resistance to movement
US4111879A (en) * 1976-07-10 1978-09-05 Ihara Chemical Industry Co., Ltd. Composition for inhibiting adhesion of shellfish and algae
US5554214A (en) * 1976-09-03 1996-09-10 The United States Of America As Represented By The Secretary Of The Navy Water ablative coating for vehicle drag reduction
US4221839A (en) * 1977-03-28 1980-09-09 M&T Chemicals Inc. Method for protecting surfaces against fouling by marine organisms
US4154818A (en) * 1977-06-09 1979-05-15 Katayama Chemical Works Co., Ltd. Gel product for destroying harmful marine organisms and method of applying the same
US4389460A (en) * 1977-08-22 1983-06-21 Institut Francais Du Petrole Method of protecting submerged articles against fouling
US4177302A (en) * 1978-05-30 1979-12-04 Ciba-Geigy Corporation Top coat composition to improve marine antifouling performance
US4212327A (en) * 1978-11-01 1980-07-15 Dayco Corporation Polymeric hose
US4258090A (en) * 1979-01-19 1981-03-24 Institutul De Cergetari In Constructii Si Economia Constructilor Incerc Method for the protection of concrete in sea water
US4234340A (en) * 1979-05-11 1980-11-18 Pellico Michael A Antifouling marine coating composition containing agar, a plasticizer and a strengthening agent
US4283461A (en) * 1979-05-31 1981-08-11 The United States Of America As Represented By The Secretary Of The Navy Piezoelectric polymer antifouling coating
US4480011A (en) * 1981-07-24 1984-10-30 Institut Francais Du Petrole Anti-corrosion and anti-fouling marine coatings
US4596839A (en) * 1981-09-16 1986-06-24 Peters William E Elastomer PTFE composition
US4518638A (en) * 1983-01-31 1985-05-21 Rasmussen Oeystein Method for the protection of ships and other objects against fouling
US4695229A (en) * 1984-05-17 1987-09-22 Feuling James J Friction reduction for moving elements in contact with a fluid medium
US4599368A (en) * 1984-10-31 1986-07-08 Midwest Research Institute Marine anti-fouling coating formulations containing a soluble phase including a organotin polymer in combination with an insoluble phase including a crosslinked organotin polymer
USRE33048E (en) * 1984-10-31 1989-09-05 Midwest Research Institute Marine anti-fouling coating formulations containing a soluble phase including a organotin polymer in combination with an insoluble phase including a crosslinked organotin polymer
WO1987001309A1 (en) * 1985-08-30 1987-03-12 Peters William E Elastomer ptfe composition, articles, and manufacturing methods
US5238749A (en) * 1986-03-27 1993-08-24 Clinitex Corporation Antimicrobial coating process and product
WO1988003930A1 (en) 1986-11-17 1988-06-02 Keith Kent Self-adhesive, drag reducing polymeric coating
US5380484A (en) * 1992-09-03 1995-01-10 Isk Biotech Corporation Control of marine borers by chlorothalonil
WO1994005437A1 (en) * 1992-09-03 1994-03-17 Isk Biosciences Corporation Control of marine borers by chlorothalonil
US5514023A (en) * 1994-02-23 1996-05-07 Warner; Jon A. Hand launchable hydrodynamic recreational device
US5393819A (en) * 1994-02-25 1995-02-28 Alphaflex Industries Asphalt modifier
US5399598A (en) * 1994-03-03 1995-03-21 Alphaflex Industries Asphalt composition
US5418270A (en) * 1994-04-12 1995-05-23 Alphaflex Industries, Inc. Modified thermoplastic elastomeric compositions
US5645603A (en) * 1995-07-25 1997-07-08 Peters; William E. Method of enhancing physical properties of non-elastomeric thermoplastic materials and resulting compositions
US6706784B2 (en) 1999-01-28 2004-03-16 Hyman D. Gesser Water-insoluble hydrophilic surface coating and methods
WO2000044835A1 (en) * 1999-01-28 2000-08-03 Gesser Hyman D Water-insoluble hydrophilic marine coating and methods
US20030036595A1 (en) * 1999-01-28 2003-02-20 Gesser Hyman D. Water-insoluble hydrophilic surface coating and methods
US6537609B1 (en) 1999-01-28 2003-03-25 Hyman D. Gesser Water-insoluble hydrophilic marine coating and methods
US6045869A (en) * 1999-01-28 2000-04-04 Gesser; Hyman D. Water-insoluble hydrophilic marine coating and methods
US6372028B1 (en) 1999-10-25 2002-04-16 Hyman D. Gesser Water-insoluble hydrophilic surface coating and methods
US6699091B1 (en) 1999-11-04 2004-03-02 Jon A. Warner Hand-launchable underwater projectile toy
US20040259463A1 (en) * 1999-11-04 2004-12-23 Warner Jon A. Hand-launchable underwater projectile toy
US7052357B2 (en) 2004-05-04 2006-05-30 Big Time Toys, Llc Toy submersible projectile
US20050250409A1 (en) * 2004-05-04 2005-11-10 David Silverglate Toy submersible projectile
US20070123139A1 (en) * 2005-05-18 2007-05-31 Warner Jon A Self-propelled hydrodynamic underwater toy
US8033890B2 (en) 2005-05-18 2011-10-11 Warner Jon A Self-propelled hydrodynamic underwater toy
EP2274384A2 (en) * 2008-03-24 2011-01-19 Clemson University Method and compositions for biofouling deterrence
US20110123477A1 (en) * 2008-03-24 2011-05-26 Mount Andrew S Method and compositions for biofouling deterrence
EP2274384A4 (en) * 2008-03-24 2013-03-06 Univ Clemson METHOD AND COMPOSITIONS FOR PREVENTING ENCRASION OF BIOLOGICAL ORIGIN
US9560848B2 (en) 2008-03-24 2017-02-07 Clemson University Method and compositions for biofouling deterrence
US9371451B2 (en) 2008-12-04 2016-06-21 Clemson University Research Foundation Deposition of nanocrystalline calcite on surfaces by a tissue and cellular biomineralization
US20140171546A1 (en) * 2012-10-31 2014-06-19 Uschi M. Graham Non-Yellowing easy-to-clean antimicrobial plastic
US9765199B2 (en) * 2012-10-31 2017-09-19 Topasol, LLC Non-yellowing easy-to-clean antimicrobial plastic

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GB1303179A (xx) 1973-01-17
NL7004908A (xx) 1971-01-05
GB1303178A (xx) 1973-01-17

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