WO2016149148A1 - Composition anticorrosion sans solvant et ses procédés d'utilisation - Google Patents

Composition anticorrosion sans solvant et ses procédés d'utilisation Download PDF

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Publication number
WO2016149148A1
WO2016149148A1 PCT/US2016/022225 US2016022225W WO2016149148A1 WO 2016149148 A1 WO2016149148 A1 WO 2016149148A1 US 2016022225 W US2016022225 W US 2016022225W WO 2016149148 A1 WO2016149148 A1 WO 2016149148A1
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Prior art keywords
curable composition
corrosion
curable
microcapsules
resin
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PCT/US2016/022225
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English (en)
Inventor
Ying Lin
Mary M. CARUSO DAILEY
John C. Hulteen
Ryan B. Prince
Jonathan M. Lise
Yongshang Lu
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3M Innovative Properties Company
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Publication of WO2016149148A1 publication Critical patent/WO2016149148A1/fr

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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Definitions

  • the present disclosure broadly relates to compositions for inhibiting corrosion of metals and methods of using the same.
  • metal corrosion There are many situations and applications where metal structures become subject to oxidative corrosion and ultimately fail to fulfill their intended purpose. Examples of failure by metal corrosion include deterioration of heat exchanger elements, corrosion of pipeline distribution systems, and especially the gradual disintegration of steel used for reinforcing concrete structures such as bridge decks and frames which support a wide range of modern buildings.
  • Newly constructed metal structures typically have a protective treatment against corrosion. As the structures age, protection diminishes and corrosion processes occur. A deterrent to such processes would delay the onset of corrosion, especially if the deterrent exerted its effect later in the lifetime of the reinforced structures. Treatments to delay the onset of corrosion, as disclosed in subsequent prior art references, include application of corrosion inhibitors or protective coatings directly to the metal surface or release of protective agents into a matrix material.
  • U.S. Pat. No. 6,075,072 (Guilbert et al.) describes a corrosion protective coating composition, applied over a metal surface, which contains frangible microcapsules which rupture and release fluid upon impact or other stress likely to damage the coating.
  • the fluid, from the microcapsules, contains a film forming component to cover the damaged area of the coating and a corrosion inhibitor for the metal surface.
  • Corrosion protection coatings are commonly applied to manufactured goods (e.g., pipes) under factory conditions. As a result, those techniques requiring specialized equipment (e.g., for powder coating and fusion bonding) and/or ventilation (e.g., for solvent-based coatings) may be readily used.
  • the application methods described above are less desirable if practiced outside the controlled environment of a factory. For example, a pipe that has an anti-corrosion protective coating, if cut during installation or repair in the field, will have bare metal exposed at the site of the cut that needs to be protected.
  • Specialized equipment for powder coating is typically not particularly portable, and solvent-based coatings typically present environmental and/or regulatory issues due to the presence of solvent vapor.
  • solventless liquid anti-corrosion compositions according to the present disclosure can be applied to metal surfaces under field conditions without either of the above concerns.
  • the present disclosure provides a curable composition comprising:
  • microcapsules comprising a polymeric shell enclosing a fill material including at least one of a corrosion inhibitor and a liquid vehicle, wherein the curable composition is liquid, and wherein the curable composition is essentially free of organic solvent other than the liquid vehicle.
  • the present disclosure provides a method of protecting a metal surface comprising, applying a curable composition to the metal surface and curing the curable composition, wherein the curable composition comprises:
  • microcapsules comprising a polymeric shell enclosing a fill material including at least one of a corrosion inhibitor and a liquid vehicle, wherein the curable composition is liquid, and wherein the curable composition is essentially free of organic solvent other than the liquid vehicle.
  • the present disclosure provides an article comprising:
  • a corrosion-resistant protective layer disposed on at least a portion of the metal surface, wherein the corrosion-resistant protective layer comprises a cured reaction product of a curable composition comprising:
  • microcapsules comprising a polymeric shell enclosing a fill material including at least one of a corrosion inhibitor and a liquid vehicle, wherein the curable composition is liquid, and wherein the curable composition is essentially free of organic solvent other than the liquid vehicle.
  • curable means permanently hardenable by a chemical crosslinking reaction (e.g., by action of a curative and/or thermal and/or radiation energy);
  • essentially free of means containing less than 2 percent by weight of, preferably less than 1 percent by weight of, more preferably less than 0.1 percent any weight of, more preferably less than 0.01 percent by weight of, and even more preferably free of;
  • liquid means freely flowable by the force of gravity
  • microcapsule refers to a capsule have a size of 500 microns or less, preferably 500 microns or less, more preferably 200 microns or less, and even more preferably 150 microns or less;
  • organic solvent refers to an organic liquid that is not otherwise reactive with components of the curable composition under ordinary use conditions, and is present solely for the purpose of dissolving or suspending at least one component of the curable composition and/or viscosity control;
  • urethane encompasses curable resins containing isocyanate groups whether cured by reaction with a polyol to form a polyurethane or a polyamine to form a polyurea, or some combination thereof;
  • thermosetting means curable by application of energy (e.g., heat, infrared radiation, or actinic radiation).
  • FIG. 1 is a schematic side view of an exemplary article 100 according to the present disclosure.
  • Curable compositions according to the present disclosure comprise a curable resin.
  • Suitable curable resins include aminoplast resins, urethane resins (e.g., 1-part and 2-part urethane resins), epoxy resins (e.g., 1-part and 2-part epoxy resins), acrylic resins, acrylated isocyanurate resins, cyanate resins, urea-formaldehyde resins, isocyanurate resins, and combinations thereof, for example.
  • Epoxy resins and polyurethane resins are preferred.
  • the curable resin may be a one-part curable resin that is activated by heat, and/or infrared radiation, and/or actinic radiation (e.g., visible or ultraviolet light).
  • the curable resin may be a multi-part (e.g., a two-part) curable resin that is activated by mixing two or more components together and optionally heating the resultant mixture.
  • suitable two-part curable resins include two-part epoxy resins such as those having a polyepoxide in a part A and a curative for the polyepoxide (e.g., a polyamine, a polythiol, or a catalyst) in a Part B, and include two-part urethane resins such as those having a polyisocyanate in a part A and a curative for the polyisocyanate (e.g., a polyamine, a polyol, and/or a catalyst).
  • any curative will be present in at least an amount effective to cause curing of the curable composition (i.e., an effective amount), while the effective amount will typically vary with the specific formulation chosen; e.g., as is known in the art.
  • the curative e.g., polyamine, polyol, or polythiol
  • the curative may be present in a stoichiometric ratio of curative to curable resin in a range of from 0.8 to 1.35; for example, in a range of from 0.85 to 1.20, or in a range of from 0.90 to 0.95, although stoichiometric ratios outside these ranges may also be used.
  • Curable resins useful in practice of the present disclosure may comprise at least one curable epoxy resin.
  • the epoxy resins may be monomeric, dimeric, oligomeric or polymeric epoxy materials containing at least one epoxy functional group per molecule.
  • Such resins may be aromatic or aliphatic, cyclic or acyclic, monofunctional or poly functional.
  • the backbone of the resin may be of any type, and substituent groups thereon can be any group not having a nucleophilic group or electrophilic group (such as an active hydrogen atom) which is reactive with an oxirane ring.
  • substituent groups include halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups, amide groups, nitrile groups, and phosphate groups.
  • the molecular weights of the epoxy resins may range from about 100 g/mol for monomeric or oligomeric resins to 50,000 g/mol or more for polymeric resins.
  • Suitable epoxy resins are typically a liquid at room temperature.
  • soluble solid epoxy resins may also be used as long as the overall curable composition is liquid; for example, at room temperature or the use temperature.
  • Epoxy resins may be used alone or in combination.
  • Types of epoxy resins that can be used include, for example, the reaction product of bisphenol A and epichlorohydrin, the reaction product of phenol and formaldehyde (novolac resins and/or resole resins) and epichlorohydrin, peracid epoxies, glycidyl esters, glycidyl ethers, the reaction product of epichlorohydrin and p-aminophenol, the reaction product of
  • Epoxy resins may be glycidyl ethers. Suitable glycidyl ether epoxy resins include, for example, glycidyl ethers of bisphenol A and F, aliphatic diols, and cycloaliphatic diols. In some embodiments, curable epoxy resins have a molecular weight in the range of from about 170 g/mol to about 10,000 g/mol. In other embodiments, curable epoxy resins have a molecular weight in the range of from about 200 g/mol to about 3,000 g/mol.
  • Useful glycidyl ether epoxy resins include linear polymeric epoxides having terminal epoxy groups (e.g., a diglycidyl ether of polyoxyalkylene glycol) and aromatic glycidyl ethers (e.g., those prepared by reacting a dihydric phenol with an excess of epichlorohydrin).
  • linear polymeric epoxides having terminal epoxy groups e.g., a diglycidyl ether of polyoxyalkylene glycol
  • aromatic glycidyl ethers e.g., those prepared by reacting a dihydric phenol with an excess of epichlorohydrin.
  • Examples of useful dihydric phenols include resorcinol, catechol, hydroquinone, and the polynuclear phenols including ⁇ , ⁇ '-dihydroxydibenzyl, p,p'-di(hydroxyphenyl) sulfone, ⁇ , ⁇ '- dihydroxybenzophenone, 2,2'-dihydroxyphenyl sulfone, 2,2-dihydroxy-l, l-dinaphthylmethane, and the 2,2'-, 2,3-', 2,4'-, 3,3'-, 3,4'-, and 4,4'-isomers of di(hydroxyphenyl)methane,
  • Suitable commercially available aromatic and aliphatic epoxides include di(glycidyl ether) of bisphenol A (e.g., EPON 828, EPON 872, EPON 1001, EPON 1310 and EPONEX 1510 available from Hexion Specialty Chemicals GmbH in Rosbach, Germany), DER-331, DER-332, and DER-334 (available from Dow Chemical Co.
  • bisphenol A e.g., EPON 828, EPON 872, EPON 1001, EPON 1310 and EPONEX 1510 available from Hexion Specialty Chemicals GmbH in Rosbach, Germany
  • DER-331, DER-332, and DER-334 available from Dow Chemical Co.
  • diglycidyl ether of bisphenol F e.g., EPICLON 830 available from Dainippon Ink and Chemicals, Inc.
  • PEG.sub.1000DGE available from Polysciences, Inc., Warrington, Pennsylvania
  • silicone resins containing diglycidyl epoxy functionality e.g., flame retardant epoxy resins (e.g., DER 580, a brominated bisphenol type epoxy resin available from Dow Chemical Co. in Midland,
  • epoxy resins based on bisphenols are commercially available under the trade designations D.E.N., EP ALLOY, and EPILOX.
  • Suitable urethane resins may include a polyisocyanate and a curative for the
  • polyisocyanate such as, for example, a polyol, a polyamine, and/or a catalyst (e.g., dibutyltin dilaurate or l,4-diazabicyclo[2.2.2]octane (DABCO)) or latent catalyst (e.g., a photoactivated organometallic catalyst as described in U.S. Pat. No. 4,740,577 (DeVoe et al.)).
  • the polyisocyanate may be a blocked version that generates isocyanate groups upon heating, for example.
  • Useful polyisocyanates include, for example, aliphatic polyisocyanates (e.g., 1,3-bis(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-diocyanates
  • hexamethylene diisocyanate or trimethylhexamethylene diisocyanate alicyclic polyisocyanates (e.g., hydrogenated xylylene diisocyanate or isophorone diisocyanate); aromatic polyisocyanates (e.g., tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate); adducts of any of the foregoing polyisocyanates with a polyhydric alcohol (e.g., a diol, low molecular weight hydroxyl group-containing polyester resin, water, etc.); adducts of the foregoing polyisocyanates (e.g., isocyanurates, biurets); and mixtures thereof.
  • a polyhydric alcohol e.g., a diol, low molecular weight hydroxyl group-containing polyester resin, water, etc.
  • adducts of the foregoing polyisocyanates e.g., isocyan
  • Useful commercially available polyisocyanates include, for example, those available under the trade designation ADIPRENE from Chemtura Corporation, Middlebury, Connecticut (e.g., ADIPRENE L 0311, ADIPRENE L 100, ADIPRENE L 167, ADIPRENE L 213,
  • ADIPRENE L 315 ADIPRENE L 680, ADIPRENE LF 1800A, ADIPRENE LF 600D,
  • AIRTHANE and VERSATHANE from Air Products and Chemicals, Allentown, Pennsylvania (e.g., AIRTHANE APC-504, AIRTHANE PST-95A, AIRTHANE PST-85A, AIRTHANE PET- 91A, AIRTHANE PET-75D, VERSATHANE STE- 95A, VERSATHANE STE-P95,
  • polyisocyanates such as, for example, those mentioned above may be blocked with a blocking agent according to various techniques known in the art.
  • blocking agents include ketoximes (e.g., 2-butanone oxime); lactams (e.g., epsilon-caprolactam); malonic esters (e.g., dimethyl malonate and diethyl malonate); pyrazoles (e.g., 3,5- dimethylpyrazole); alcohols including tertiary alcohols (e.g., t-butanol or 2,2-dimethylpentanol), phenols (e.g., alkylated phenols), and mixtures of alcohols as described.
  • Exemplary useful commercially-available blocked polyisocyanates include those marketed by Chemtura
  • ADIPRENE BL 11 ADIPRENE BL 16
  • ADIPRENE BL 31 blocked polyisocyanates marketed by Baxenden Chemicals, Ltd., Accrington,
  • TRIXENE e.g., TRIXENE BL 7641, TRIXENE BL 7642, TRIXENE BL 7772, and TRIXENE BL 7774.
  • Suitable amine curatives include aromatic, alkyl-aromatic, or alkyl polyfunctional amines, preferably primary amines.
  • useful amine curatives include 4,4'- methylenedianiline; polymeric methylene dianilines having a functionality of 2.1 to 4.0 which include those known under the trade designations CURITHANE 103, commercially available from the Dow Chemical Company, and MDA-85 from Bayer Corporation, Pittsburgh,
  • polyol(s) may be added to the curable composition, for example, to modify (e.g., to retard) cure rates as required by the intended use.
  • the curable compositions comprise at least about 20 percent by weight of curable resin, in some embodiments at least about 40 percent by weight of curable resin, and in some embodiments at least about 50 percent by weight of curable resin. In some embodiments of the present disclosure, the curable compositions comprise less than about 90 percent by weight of curable resin, in some embodiments less than about 80 percent by weight of curable resin, and in some embodiments less than about 70 percent by weight of curable resin.
  • the amount of curable resin present in the curable composition ranges of from 10 to 40 percent by weight, preferably from 15 to 30 percent by weight, and more preferably from 20 to 25 percent by weight based on the total weight of the curable composition, although amounts outside of these ranges may also be used. Percent weight is based upon the total weight of the curable composition (i.e., whether it is a one part or two- part composition (Parts A and B combined)).
  • the curable composition includes microcapsules comprising a polymeric shell
  • microcapsules (preferably organic) enclosing at least one of a corrosion inhibitor and a liquid vehicle.
  • the function of the microcapsules is to rupture when mechanical damage to the cured anti-corrosion coating occurs, thereby releasing the corrosion inhibitor at the damage site.
  • the microcapsules each include both the liquid vehicle and the corrosion inhibitor.
  • the liquid vehicle and the corrosion inhibitor may be present in different microcapsules that mix together after rupture of the microcapsules.
  • the contents of the microcapsules When the microcapsules are ruptured, the contents of the microcapsules preferably flow readily into coating defects, such as cracks or voids produced by impact or other damaging forces. This may require control of fluid viscosity less than 100 centipoise, preferably between about 10 centipoise and about 50 centipoise.
  • microcapsules can be manufactured. These varied processes provide different techniques for producing microcapsules, alternative materials for the composition of the microcapsule shell, and various different functional materials within the shell. Some of these various processes are shown in U.S. Pat. Nos. 3,516,846 (Matson); 3,516,941 (Matson); 3,778,383 (Harris); 4,087,376 (Foris et al.); 4,089,802 (Foris et al.); 4, 100,103 (Foris et al.); 4,251,386; 4,493,869 (Sweeney et al.); 4,898,633(Saeki et al.);
  • a wide variety of different materials may be used in making the capsule shells, including gelatin and synthetic polymeric materials.
  • a popular materials for shell formation is the polymerization reaction product between urea and formaldehyde or melamine and formaldehyde, or the polycondensation products of monomeric or low molecular weight polymers of dimethylolurea or methylolated urea with aldehydes.
  • microcapsule forming materials are disclosed, for example, in U.S. Pat. Nos. 3,516,846 (Matson) and 4,087,376 (Foris et al.), and British Patent Specification Nos. 2,006,709 (Mitsubishi Paper Mills Ltd.) and
  • Suitable materials may also include cellulosic materials, copolymers, such as those produced by reaction of isobornyl methacrylate with acrylic acid or methacrylic acid,
  • condensation polymers including nylon, polyurethane, polyurea, and polycarbonate polymers.
  • a preferred capsule wall material of this type is derived from urea, formaldehyde, and melamine monomers. Use of interfacial polymerization techniques, produces continuous-wall, non-porous microcapsules comprising these monomeric species.
  • a polyurethane shell material also formed by interfacial polymerization, provides porous microcapsules which tend to gradually lose their fluid fill material. This type of microcapsule assures controlled corrosion protection until the microcapsule fill material is exhausted.
  • Thermoplastic polymeric materials may be used to generate the microcapsule polymeric shell; for example, as described in U.S. Pat. No. 6,506,494 (Brandys et al.).
  • polysulfone, polyurethanes-urea, poly(ethylene glycol), and aliphatic polyesters have been used as polymeric shells for microcapsules.
  • preparation of a poly(methyl methacrylate) polymeric shell (PMMA) microcapsules using technology adaptable to practice of the present disclosure has been accomplished using a solvent evaporation technique as described by Teeka et al.
  • Preferred materials for the polymeric shell also include copolymers of methyl methacrylate and
  • Materials for forming the capsule walls preferably comprise substances maintaining structural integrity to temperatures of at least 160 °C, although this is not a requirement.
  • Corrosion inhibitors suitable for encapsulation include water insoluble amines such as VERSAMINE
  • benzimidazoles including 1-methylbenzimidazole, 1 -phenyl benzimidazole and 2- phenylbenzimidazole; substituted thiophosphates exemplified by diethylthiophosphate and dioctylthiophosphate; thiourea and substituted structures thereof, represented by allylthiourea, phenylthiourea, and 1,3-diphenylthiourea; benzothiazole, benzotriazole, and alkyl, aryl, aralkyl and other substituted versions thereof.
  • Some preferred corrosion inhibitors include solutions of metal sulfonate salts available as barium-containing NACORR 1151 and zinc-containing NACORR 1551 and NACORR 1552 from King Industries of Norwalk, Conn., and LUBRIZOL 219 phosphate zinc complex available from Lubrizol Inc. of Wickliffe, Ohio.
  • the fill material may also include a marker dye.
  • Marker dyes for use in the disclosure are preferably soluble in phthalate esters and include hydrophobic dyes such as SUDAN YELLOW 146 or SUDAN BLUE, which are anthraquinone type dyes made by BASF of Mount Olive, New Jersey.
  • Suitable liquid vehicles include virtually any liquid material, preferably that is liquid at or near room temperature.
  • the liquid vehicle has a normal boiling point of at least 120 °C, more preferably at least 130 °C, more preferably at least 140 °C, and even more preferably at least 150 °C; however, this is not a requirement.
  • suitable liquid vehicles may include mineral spirits, mineral oils, butyl cellosolve, phthalate esters, vegetable oils (e.g., tung oil, linseed oil, soybean oil), dipentene, amyl acetate, benzothiazole, silicone oils (e.g., D-5 SILICONE OIL available from General Electric Co., Schenectady, New York), xylene, and other hydrophobic liquids boiling at about 150 °C or higher and capable of surviving at about a pH of 2.0.
  • vegetable oils e.g., tung oil, linseed oil, soybean oil
  • dipentene amyl acetate
  • benzothiazole e.g., silicone oils (e.g., D-5 SILICONE OIL available from General Electric Co., Schenectady, New York), xylene, and other hydrophobic liquids boiling at about 150 °C or higher and capable of surviving at about a pH of 2.0.
  • Curable compositions according to the present disclosure can be made by simple mixing of the components by any suitable technique, or in the case of a two part system it may be supplied in a form that requires mixing by the user.
  • curable compositions according to the present disclosure are essentially free of volatile organic solvents (e.g., solvents falling within the definition of volatile organic compounds defined in the U.S. Code of Federal Regulations, 40: Chapter 1, Subchapter C, Part 51, Subpart F, 51.100 as of the filing date of the present application).
  • the curable compositions are essentially free of solvents having a normal boiling point of 100 °C or less, more preferably 150 °C or less, and more preferable 200 °C or less.
  • the curable composition is essentially free of, or even free of, added solvent (i.e., solvent that is intentionally added during formulation of the curable composition as opposed to adventitious solvent that is present as a contaminant in a raw material used to make it.
  • the curable composition is essentially free of water, preferably free of all but adventitious water.
  • the curable composition is preferably liquid at 20 °C and one atmosphere of pressure; however, it may be effectively used even if a solid as long as it can be melted at a temperature lower than its application temperature to the substrate.
  • the curable composition further comprises a filler.
  • exemplary fillers include sodium potassium aluminum silicate, talc, titanium dioxide, magnesium oxide, calcium oxide, silica, clay, organic polymer particulate fillers, glass beads, ceramic
  • Filler may be present in an amount up to about 60 percent by weight, preferably 30 to 60 percent by weight, based on the total weight of the curable composition, although this is not a requirement.
  • Curable and/or cured compositions according to the present disclosure may include other additives or adjuvants which may change the characteristics of coating formulations without detracting from their latent repair and corrosion inhibiting performance.
  • Curable compositions according to the present disclosure can be applied to the metal surface of the substrate to form a corrosion-resistant protective layer; for example, as shown in FIG. 1.
  • article 100 comprises corrosion-resistant protective layer 110 disposed on metal surface 120 of substrate 130.
  • Corrosion-resistant protective layer 110 comprises cured resin 140 and microcapsules 150.
  • Curable compositions can be applied to the metal surface of the substrate and then cured to provide a corrosion-resistant protective layer on the metal surface that enhance corrosion protection.
  • the curable composition may be applied to the substrate by any suitable method such as, for example, spray coating, brush coating, and dip coating.
  • Exemplary substrates have a metal surface, which may be an exterior and/or interior surface, even though the substrate itself may or may not consist of many components, some of which may not be metal and which may form a portion of the surface of the substrate.
  • the substrate is metallic.
  • Exemplary metals for use in the substrate include ferrous metals (e.g., iron and steel) and other oxidizable metals (e.g., copper, silver, aluminum, and tin).
  • the substrate may be in sheet, roll, or wire form, or it may be fabricated into a complex shape such as a vehicle body part, pipe, reinforcing rod, or cabinet part, for example.
  • curable compositions according to the present disclosure is that of a patch that can be applied in the field to repair damaged corrosion resistant coatings and/or as a protective coating over freshly exposed metal; for example, as in the case of a reinforcing rod with a corrosion resistant coating that is cut to length during construction of a road or building, thereby creating a fresh metallic surface at the cut site.
  • the present disclosure provides a curable composition comprising: a curable resin;
  • microcapsules comprising a polymeric shell enclosing a fill material including at least one of a corrosion inhibitor and a liquid vehicle, wherein the curable composition is liquid, and wherein the curable composition is essentially free of organic solvent other than the liquid vehicle.
  • the present disclosure provides a curable composition according to the first embodiment, wherein the curable resin comprises an epoxy resin.
  • the present disclosure provides a curable composition according to the first embodiment, wherein the curable resin comprises a polyurethane resin.
  • the present disclosure provides a curable composition according to any one of the first to third embodiments, wherein the polymeric shell comprises an acrylic polymer.
  • the present disclosure provides a curable composition according to any one of the first to fourth embodiments, wherein the liquid vehicle comprises a a corrosion inhibiting oil.
  • the present disclosure provides a method of protecting a metal surface comprising, applying a curable composition to the metal surface and curing the curable composition, wherein the curable composition comprises:
  • microcapsules comprising a polymeric shell enclosing a fill material including at least one of a corrosion inhibitor and a liquid vehicle, wherein the curable composition is liquid, and wherein the curable composition is essentially free of organic solvent other than the liquid vehicle.
  • the present disclosure provides a method according to the sixth embodiment, wherein the curable resin comprises an epoxy resin.
  • the present disclosure provides a method according to the sixth embodiment, wherein the curable resin comprises a polyurethane resin.
  • the present disclosure provides a method according to any one of the sixth to eighth embodiments, wherein the polymeric shell comprises an acrylic polymer.
  • the present disclosure provides a method according to any one of the sixth to ninth embodiments, wherein the liquid vehicle comprises a corrosion inhibiting oil.
  • the present disclosure provides an article comprising:
  • a corrosion-resistant protective layer disposed on at least a portion of the metal surface, wherein the corrosion-resistant protective layer comprises a cured reaction product of a curable composition comprising:
  • microcapsules comprising a polymeric shell enclosing a fill material including at least one of a corrosion inhibitor and a liquid vehicle, wherein the curable composition is liquid, and wherein the curable composition is essentially free of organic solvent other than the liquid vehicle.
  • the present disclosure provides an article according to the eleventh embodiment, wherein the curable resin comprises an epoxy resin.
  • the present disclosure provides an article according to the eleventh embodiment, wherein the curable resin comprises a polyurethane resin.
  • the present disclosure provides an article according to any one of the eleventh to thirteenth embodiments, wherein the polymeric shell comprises an acrylic polymer.
  • the present disclosure provides an article according to any one of the eleventh to fourteenth embodiments, wherein the liquid vehicle comprises an oil.
  • TMN-100X (90 wt.%) Surfactant from the Dow Chemical, Midland, Michigan.
  • C3031 trifunctional caprolactone polyol terminated by primary hydroxyl groups with a weight average molecular weight of 300 grams/mole available as CAPA 3031 from Perstorp Holding AB
  • Microcapsule size and distribution was analyzed using a Horiba LA-950 Laser Scattering Particle Size Distribution Analyzer from Horiba, Kyoto, Japan according to the manufacturer's directions. Samples were analyzed in triplicate. Thermal gravimetric analysis (TGA) experiments were performed on a TGA2950 thermogravimetric analyzer with a heating rate of 10 °C/min under nitrogen atmosphere. Scanning electron microscopy (SEM) was performed using an XL30 ESEM FEG scanning electron miocroscope from FEI Co., Hillsboro, Oregon.
  • PE1 describes the synthesis of L219-containing PMMA-co-MAA microcapsules.
  • a glass jar was charged with 200 g of acetone and 20 g of PMMA-co-MAA .
  • the mixture was heated (ca. 60 °C) in order to effect dissolution of the polymer. After 30 minutes, the polymer was completely dissolved; and the solution was then allowed to cool down to room temperature. L219 (80 g) was then added, and the mixture was stirred to yield a homogeneous solution.
  • a 5-gallon pail was charged with 9 L of distilled water and agitated at 150 rpm with a Labmaster stirrer equipped with a 2-inch (5-cm) turbine blade.
  • ACCUSPRAY SPRAY GUN MODEL HG09 (3M Company) spray gun (20 psi) into the water. Immediately, a white precipitate began to form. Once all of the solution had been sprayed, the mixture was allowed to stir for another 30 minutes. The microcapsules were then collected by filtration (Buchner), washed with a small amount of water and allowed to air dry overnight (ca. 14 h), whereby 75 grams of discreet non-agglomerated microcapsules were recovered.
  • the size and size distribution of the microcapsules was characterized by laser diffraction (LA-950 laser particle size analyzer, Horiba). A typical mean size of the microcapsules was 50 ⁇ 10 micrometers in diameter.
  • the core-shell structure of the microcapsules was confirmed by analysis of crushed microcapsules, wherein the PMMA-co-MAA shell showed a thickness of 3 micrometers. Weight fractions of L219 and PMMA-co-MAA shell were measured by thermal gravimetric analysis (TGA). TGA results indicated that the capsules had an uptake of 75 wt.% of L219.
  • EXAMPLES 1-2 AND COMPARATIVE EXAMPLE A Microcapsules from PE1 were added to SK328 at various concentrations (as indicated in Table 2) and mixed with a DAC 150 SPEEDMIXER dual asymmetric centrifuge from FlackTek Corp., Landrum, South Carolina (2000 rpm) resulting in a curable epoxy composite resin.
  • CECR1 was coated on cold-rolled steel bars (1/8 inch (0.32 cm) x 1 inch (2.5 cm) x 8 inches
  • CECR1 was coated on grit blasted steel plates (4 inches x 4 inches, (10 cm x 10 cm)), at a thickness of 0.8 mm, on one side with the other side and edges touched up with a paintbrush. Coatings were allowed to stand at room temperature for 7 days. The resulting coated steel plates were impacted at variety of impact energies (70 in-lbf, 80 in-lbf, 90 in-lbf, 100 in-lbf (7.9 J, 9.0 J, 10.1 J, 11.3 J)) with a drop weight tester (model 9310) from Instron Corp., Norwood, Massachusetts. The accelerated corrosion test (above) was repeated on these samples.
  • Microcapsules from PE1 were added to a mixed two-part urethane coating according to the following formulation: 20 g of PE1 microcapsules, 100 g of Part A (50 g of DESW and 50 g of TLV), 100 g of Part B (70 g of C2043, 30 g of C3031, and 0.02 g of DBTDL) (EXAMPLE 7).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition durcissable comprenant : une résine durcissable ; et des microcapsules comprenant une coque polymère qui enferme un matériau de remplissage comprenant au moins l'un parmi un inhibiteur de corrosion et un véhicule liquide, la composition durcissable étant liquide et la composition durcissable étant essentiellement dépourvue de solvant organique autre que le véhicule liquide. La composition durcissable peut être revêtue sur une surface métallique d'un substrat et durcie pour former une couche protectrice résistant à la corrosion.
PCT/US2016/022225 2015-03-17 2016-03-11 Composition anticorrosion sans solvant et ses procédés d'utilisation WO2016149148A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903722A (zh) * 2019-12-02 2020-03-24 湖南太子化工涂料有限公司 一种耐候性环保金属表面油漆及其制备方法
CN115725229A (zh) * 2021-12-06 2023-03-03 烟台大学 自修复的阻燃耐熔滴耐磨耗聚氨酯涂料应用所用材料

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2041319A (en) 1932-10-22 1936-05-19 William D Mcgurn Internal combustion engine
US2048206A (en) 1932-06-08 1936-07-21 Monopower Corp Transmission
GB1156725A (en) 1965-08-02 1969-07-02 Ciba Ltd Process for the Encapsulation of Dispersible Materials
US3505244A (en) * 1965-04-30 1970-04-07 Union Carbide Corp Encapsulated corrosion inhibitor
US3516846A (en) 1969-11-18 1970-06-23 Minnesota Mining & Mfg Microcapsule-containing paper
US3516941A (en) 1966-07-25 1970-06-23 Minnesota Mining & Mfg Microcapsules and process of making
US3778383A (en) 1970-05-26 1973-12-11 Ciba Geigy Ag Process for the encapsulation of substances which are finely distributed in a liquid and capsule compositions produced thereby
US4087376A (en) 1974-07-10 1978-05-02 Ncr Corporation Capsule manufacture
US4100103A (en) 1976-12-30 1978-07-11 Ncr Corporation Capsule manufacture
GB2006709A (en) 1977-09-28 1979-05-10 Mitsubishi Paper Mills Ltd Production of micro-capsules
US4251386A (en) 1977-07-27 1981-02-17 Fuji Photo Film Co., Ltd. Method for preparing microcapsules
GB2062570A (en) 1979-10-02 1981-05-28 Fuji Photo Film Co Ltd Process of producing microcapsules
US4493869A (en) 1983-10-11 1985-01-15 Minnesota Mining And Manufacturing Company Fragrance-releasing microcapsules on a see-through substrate
US4740577A (en) 1987-08-28 1988-04-26 Minnesota Mining And Manufacturing Company Energy polymerizable polyurethane precursors
US4898633A (en) 1985-02-08 1990-02-06 Minnesota Mining And Manufacturing Company Article containing microencapsulated materials
US4976961A (en) 1986-07-18 1990-12-11 Minnesota Mining And Manufacturing Company Encapsulated cosmetic materials and process of making
WO1999046338A1 (fr) * 1998-03-13 1999-09-16 Minnesota Mining And Manufacturing Company Revetement latent utile pour une reparation de surfaces metalliques
US6506494B2 (en) 1999-12-20 2003-01-14 3M Innovative Properties Company Ambient-temperature-stable, one-part curable epoxy adhesive
US7179480B2 (en) 2002-04-24 2007-02-20 3M Innovative Properties Company Sustained release microcapsules
US7192993B1 (en) 2003-03-04 2007-03-20 The United States Of America As Represented By The Secretary Of The Army Self-healing coating and microcapsules to make same
WO2014149743A1 (fr) * 2013-03-15 2014-09-25 Honda Motor Co., Ltd. Compositions d'inhibition de corrosion
WO2015061522A1 (fr) * 2013-10-23 2015-04-30 Autonomic Materials, Inc. Formulations d'agent d'auto-réparation contenant des inhibiteurs de corrosion liquides

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2048206A (en) 1932-06-08 1936-07-21 Monopower Corp Transmission
US2041319A (en) 1932-10-22 1936-05-19 William D Mcgurn Internal combustion engine
US3505244A (en) * 1965-04-30 1970-04-07 Union Carbide Corp Encapsulated corrosion inhibitor
GB1156725A (en) 1965-08-02 1969-07-02 Ciba Ltd Process for the Encapsulation of Dispersible Materials
US3516941A (en) 1966-07-25 1970-06-23 Minnesota Mining & Mfg Microcapsules and process of making
US3516846A (en) 1969-11-18 1970-06-23 Minnesota Mining & Mfg Microcapsule-containing paper
US3778383A (en) 1970-05-26 1973-12-11 Ciba Geigy Ag Process for the encapsulation of substances which are finely distributed in a liquid and capsule compositions produced thereby
US4087376A (en) 1974-07-10 1978-05-02 Ncr Corporation Capsule manufacture
US4089802A (en) 1974-07-10 1978-05-16 Ncr Corporation Capsule manufacture
US4100103A (en) 1976-12-30 1978-07-11 Ncr Corporation Capsule manufacture
US4251386A (en) 1977-07-27 1981-02-17 Fuji Photo Film Co., Ltd. Method for preparing microcapsules
GB2006709A (en) 1977-09-28 1979-05-10 Mitsubishi Paper Mills Ltd Production of micro-capsules
GB2062570A (en) 1979-10-02 1981-05-28 Fuji Photo Film Co Ltd Process of producing microcapsules
US4493869A (en) 1983-10-11 1985-01-15 Minnesota Mining And Manufacturing Company Fragrance-releasing microcapsules on a see-through substrate
US4898633A (en) 1985-02-08 1990-02-06 Minnesota Mining And Manufacturing Company Article containing microencapsulated materials
US4976961A (en) 1986-07-18 1990-12-11 Minnesota Mining And Manufacturing Company Encapsulated cosmetic materials and process of making
US4740577A (en) 1987-08-28 1988-04-26 Minnesota Mining And Manufacturing Company Energy polymerizable polyurethane precursors
WO1999046338A1 (fr) * 1998-03-13 1999-09-16 Minnesota Mining And Manufacturing Company Revetement latent utile pour une reparation de surfaces metalliques
US6075072A (en) 1998-03-13 2000-06-13 3M Innovative Properties Company Latent coating for metal surface repair
US6506494B2 (en) 1999-12-20 2003-01-14 3M Innovative Properties Company Ambient-temperature-stable, one-part curable epoxy adhesive
US7179480B2 (en) 2002-04-24 2007-02-20 3M Innovative Properties Company Sustained release microcapsules
US7192993B1 (en) 2003-03-04 2007-03-20 The United States Of America As Represented By The Secretary Of The Army Self-healing coating and microcapsules to make same
US20080152815A1 (en) * 2003-03-04 2008-06-26 Stephenson Larry D Self-healing coating and microcapsules to make same
WO2014149743A1 (fr) * 2013-03-15 2014-09-25 Honda Motor Co., Ltd. Compositions d'inhibition de corrosion
WO2015061522A1 (fr) * 2013-10-23 2015-04-30 Autonomic Materials, Inc. Formulations d'agent d'auto-réparation contenant des inhibiteurs de corrosion liquides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PAN ET AL.: "Structure and Mechanical Properties of Consumer-Friendly PMMA Microcapsules", INDUSTRIAL AND ENGINEERING CHEMISTRY RESEARCH, vol. 52, 2013, pages 11253 - 11265
TEEKA ET AL.: "Preparation of Poly (methyl methacrylate) Microcapsule with Encapsulated Jasmine Oil", ENERGY PROCEDIA, vol. 56, 2014, pages 181 - 186

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903722A (zh) * 2019-12-02 2020-03-24 湖南太子化工涂料有限公司 一种耐候性环保金属表面油漆及其制备方法
CN115725229A (zh) * 2021-12-06 2023-03-03 烟台大学 自修复的阻燃耐熔滴耐磨耗聚氨酯涂料应用所用材料
CN115725229B (zh) * 2021-12-06 2023-05-23 烟台大学 自修复的阻燃耐熔滴耐磨耗聚氨酯涂料应用所用材料

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