WO2020180979A1 - Composition époxydique thermodurcissable pour revêtement en poudre - Google Patents

Composition époxydique thermodurcissable pour revêtement en poudre Download PDF

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Publication number
WO2020180979A1
WO2020180979A1 PCT/US2020/020972 US2020020972W WO2020180979A1 WO 2020180979 A1 WO2020180979 A1 WO 2020180979A1 US 2020020972 W US2020020972 W US 2020020972W WO 2020180979 A1 WO2020180979 A1 WO 2020180979A1
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Prior art keywords
powder coating
coating composition
thermosetting epoxy
curing
epoxy resin
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PCT/US2020/020972
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English (en)
Inventor
Nikhil K. E. Verghese
Mukesh Agrawal
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Sabic Global Technologies B.V.
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Publication of WO2020180979A1 publication Critical patent/WO2020180979A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/03—Powdery paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0272—After-treatment with ovens

Definitions

  • VOC volatile organic compounds
  • steel is used for broad purposes in the engineering industry. Steel, as most of the metals employed in service life, is subject to deterioration either by corrosion at room temperature or by oxidation at high temperature. To prevent oxidation, chemical reaction, and erosion of steel at high temperatures, protective coatings are often applied. Powder coating provides a reliable barrier coating for substrates such as aluminum, steel, and other metal alloys. It also provides UV protection, abrasion resistance, and corrosion resistance.
  • Thermosetting epoxy resins exhibit excellent properties of toughness, corrosion resistance, and chemical resistance, as well as low cost. The properties make these resins ideal as coating materials in a variety of applications such as automotive coatings, building materials, and household electronic appliances.
  • the epoxy resins have applicability as environmentally friendly powder coatings because they contain no organic solvents.
  • powder coating formulations including conventional epoxy resins often lack high temperature stability, for example at temperatures higher than 160°C.
  • thermosetting epoxy powder coating compositions that can provide powder coatings with high temperature stability, good mechanical properties, and improved chemical stability.
  • a powder coated substrate comprises a substrate; and a thermosetting epoxy powder coating composition, wherein the thermosetting epoxy powder coating composition is powder coated on the substrate, wherein the thermosetting epoxy powder coating composition comprises: 100 parts by weight of an epoxy resin composition; 30 to 200 parts by weight of an aromatic dianhydride curing agent; optionally a curing catalyst; and optionally an additional curing promoter, wherein an anhydride to epoxy stoichiometric ratio (A/E) is 0.1 : 1 to 1.6: 1, preferably 0.5: 1 to 1.3: 1, more preferably 0.6: 1 to 1.2: 1, as determined by molar ratio of total anhydride functionalities to total epoxy functionalities in the thermosetting epoxy powder coating composition, wherein the amounts are based on the total parts by weight of the epoxy resin composition and the aromatic dianhydride curing agent, and wherein the aromatic dianhydride curing agent is of formula (1)
  • thermosetting epoxy powder coating composition after curing has a glass transition temperature of 120 to 320°C, preferably 160 to 320°C, more preferably 180 to 320°C, even more preferably 200 to 320°C, still more preferably 250 to 320°C, as determined by dynamic mechanical analysis, and wherein the thermosetting epoxy powder coating composition after curing has an impact resistance of greater than 2 Newton meters, preferably greater than 3 Newton meters, more preferably greater than 4 Newton meters, when measured according to ASTM D2794.
  • thermosetting epoxy powder coating composition to at least one surface of the substrate; preferably wherein the applying comprises electrostatically applying the thermosetting epoxy powder coating composition in particulate form.
  • thermosetting epoxy powder coating composition for forming a powder coating on a substrate.
  • the thermosetting epoxy powder coating composition includes an epoxy resin composition, an aromatic dianhydride curing agent, optionally an additional curing promoter, and optionally a curing catalyst.
  • an aromatic dianhydride for example bisphenol-A dianhydride (BPA-DA)
  • BPA-DA bisphenol-A dianhydride
  • the thermosetting epoxy powder coating composition including the aromatic dianhydride as an epoxy curing agent can provide a cured thermoset product, for example as a powder coating on a substrate, having good high heat resistance properties, such as a glass transition temperature of 230°C or greater.
  • thermosetting epoxy powder coating composition including an epoxy resin composition, an aromatic dianhydride curing agent, optionally an additional curing promoter, and optionally a curing catalyst.
  • the thermosetting epoxy powder coating composition after curing has a glass transition temperature (T G ) of greater than or equal to 120°C.
  • T G glass transition temperature
  • the thermosetting epoxy powder coating composition after powder coating a substrate and curing has an impact resistance of greater than 2 Newton meters (N m) when measured according to ASTM D2794.
  • the aromatic dianhydride curing agent is soluble in the epoxy resin composition.
  • the thermosetting epoxy powder coating composition is substantially free of monoanhydride.
  • the stoichiometric ratio between the aromatic dianhydride curing agent and the epoxy resin composition is 0.1 : 1 to 2.0: 1 or 0.1 : 1 to 1.6: 1, preferably 0.4: 1 to 1.2: 1 or 0.5: 1 to 1.3: 1, more preferably 0.6: 1 to 1.2: 1 or 0.6: 1 to 1 : 1.
  • the stoichiometric ratio is the molar ratio of total anhydride functionalities to the total epoxy functionalities in the thermosetting epoxy powder coating composition.
  • the stoichiometric ratio is also referred to herein as the anhydride to epoxy (A/E) ratio.
  • the thermosetting epoxy powder coating composition includes 100 parts by weight of the epoxy resin composition, based on the total parts by weight of the epoxy resin composition, the aromatic dianhydride curing agent, and optionally the additional curing promoter.
  • the epoxy resin composition can include one or more epoxy resins, such as bisphenol A epoxy resin, a triglycidyl-substituted epoxy resin, a tetraglycidyl-substituted epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, a cycloaliphatic diglycidyl ester epoxy resin, a cycloaliphatic epoxy resin comprising a ring epoxy group, an epoxy resin containing a spiro-ring, a hydantoin epoxy resin, or a combination thereof.
  • the epoxy resin is bisphenol-A diglycidyl ether (BPA-DGE).
  • the epoxy resin composition may include one or more“high heat” epoxy compounds of formulas (I) to (IX):
  • R 1 and R 2 at each occurrence are each independently an epoxide-containing functional group;
  • R a and R b at each occurrence are each independently halogen, Ci-12 alkyl, C2-12 alkenyl, C3-8 cycloalkyl, or Ci-12 alkoxy;
  • p and q at each occurrence are each independently 0 to 4;
  • R 13 at each occurrence is independently a halogen or a Ci- 6 alkyl group;
  • c at each occurrence is independently 0 to 4;
  • R 14 at each occurrence is independently a Ci - 6 alkyl, phenyl, or phenyl substituted with up to five halogens or Ci- 6 alkyl groups;
  • R g at each occurrence is independently Ci-12 alkyl or halogen, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloalkyl group; and
  • t is 0 to 10.
  • the epoxy resin composition does not include a compound of formulas (I) to (IX). That is, the epoxy resin composition, and by extension the thermosetting epoxy powder coating composition, is free of the high heat epoxy compounds of formulas (I) to (IX).
  • the epoxy resin composition does not include a compound of formulas (I) to (IX).
  • the epoxide equivalent weight (EEW) of the epoxy resin composition is generally from 100 to 20,000 grams per equivalent (g/eq), preferably from 100 to 5,000 g/eq, more preferably from 100 to 1,000 pg/eq.
  • EW epoxide equivalent weight
  • the terms“epoxide equivalent weight” refers to the number average molecular weight of the epoxide moiety divided by the average number of epoxide groups present in the molecule.
  • the thermosetting epoxy powder coating composition includes 30 to 200 parts by weight of the aromatic dianhydride curing agent, based on the total parts by weight of the epoxy resin composition, the aromatic dianhydride curing agent, and optionally the additional curing promoter.
  • the thermosetting epoxy powder coating composition can include 50 to 150 parts by weight, preferably 60 to 140 parts by weight, more preferably 80 to 120 parts by weight of the aromatic dianhydride curing agent, based on the total parts by weight of the epoxy resin composition, the aromatic dianhydride curing agent, and optionally the additional curing promoter.
  • the aromatic dianhydride curing agent can be of the formula (1)
  • T is -0-, -S-, -SO2-, -SO-, -CyFEy- wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or -O-Z-O- wherein Z is an aromatic C6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Ci- 8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof.
  • the R 1 is a monovalent Ci-13 organic group.
  • T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O- or the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions.
  • T is not -O-, -SO2-, or -SO-.
  • Exemplary groups Z include groups of formula (2)
  • R a and R b are each independently the same or different, and are a halogen atom or a monovalent Ci- 6 alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and X a is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group.
  • the bridging group X a can be a single bond, -O-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a C1-18 organic bridging group.
  • the C1-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the Ci-18 organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C1-18 organic bridging group.
  • a specific example of a group Z is a divalent group of the formula (3a) or (3b)
  • Q is 2,2-isopropylidene.
  • T is -0-Z-0-, preferably wherein Z is derived from bisphenol A (i.e., Z is
  • aromatic dianhydrides include 3,3-bis[4-(3,4- dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4- dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3- dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl
  • the aromatic dianhydride curing agent can be soluble in the epoxy resin composition.
  • the term“soluble in the epoxy resin composition” means that there is a temperature range where a combination of the aromatic dianhydride curing agent and the epoxy resin composition can be combined to form a homogeneous phase.
  • “forming a homogeneous phase” means creating a state where there is no visible separation between the components.
  • the homogeneous phase can be formed in a certain temperature range without regard to any separation that may occur outside of that temperature range, for example, at room temperature.
  • a combination of the aromatic dianhydride curing agent and the epoxy resin composition can be stirred, heated, or heated under stirring to form a
  • the aromatic dianhydride curing agent can be soluble in the epoxy resin composition at a temperature from 50 to 200°C.
  • the aromatic dianhydride curing agent can be soluble in the epoxy resin composition from 80 to 200°C, more preferably from 100 to 190°C, even more preferably from 120 to 180°C.
  • the aromatic dianhydride curing agent can be soluble in the epoxy resin composition without the inclusion of any additives or solvents to improve the solubility of the dianhydride.
  • the thermosetting epoxy powder coating composition is substantially free of solvent or solvents.
  • the thermosetting epoxy powder coating composition is free of solvent.
  • the term“substantially free of solvent” means that the thermosetting epoxy powder coating composition contains less than 500 parts per million (ppm) by weight of solvent.
  • thermosetting epoxy powder coating composition can have greater than 0 to 450 ppm by weight, preferably greater than 0 to 300 ppm by weight, more preferably greater than 0 to 200 ppm by weight, even more preferably greater than 0 to 100 ppm by weight of solvent, based on the total weight of the thermosetting epoxy powder coating composition.
  • thermosetting epoxy powder coating composition optionally includes an effective amount of curing catalyst.
  • the thermosetting epoxy powder coating composition can include 0.1 to 5 weight percent (wt%) of a curing catalyst, based on the total weight of the composition.
  • the thermosetting epoxy powder coating composition can include 0.4 to 4 wt%, preferably 0.6 to 3 wt%, more preferably 0.7 to 2 wt% of the curing catalyst, based on the total weight of the composition.
  • the curing catalyst can be a heterocyclic curing catalyst.
  • Heterocyclic compounds include benzotriazoles; triazines; piperazines such as aminoethylpiperazine, N-(3- aminopropyl)piperazine, or the like; imidazoles such as 1-methylimidazole, 2-methylimidazole, 3-methyl imidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n- propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n- butylimidazole, 1-isobutylimidazole, 2-isobutylimid
  • thermosetting epoxy powder coating composition can further include an additional curing promoter.
  • additional curing promoter encompasses compounds whose roles in curing epoxy resins are variously described as those of a hardener, a hardening accelerator, a curing accelerator, a curing catalyst, and a curing co catalyst, among others.
  • additional curing promoters can include, for example, amines, dicyandiamide, polyamides, amidoamines, Mannich bases, anhydrides,
  • polymercaptans polymercaptans, isocyanates, cyanate esters, and combinations thereof.
  • the additional curing promoter comprises an amine.
  • the amine can be a polyamine, a tertiary amine, an amidine, and combinations thereof.
  • suitable polyamines include amine hardeners such as isophoronediamine, triethylenetetraamine, diethylenetriamine, aminoethylpiperazine, 1,2- and l,3 diaminopropane,
  • the curing promoter comprises a hardener selected from the group consisting of
  • Examples of amine compounds further include tertiary amine hardening accelerators such as triethylamine, tributylamine, dimethylaniline, diethylaniline,
  • benzyldimethylamine a-methylbenzyldimethylamine, N,N-dimethylaminoethanol, N,N- dimethylaminocresol, tri(N,N-dimethylaminomethyl)phenol, and combinations thereof.
  • the additional curing promoter can comprise other amine compounds.
  • other amine compounds include hardeners such as ketimines, which are the reaction products of ketones and primary aliphatic amines; polyether amines, which are the reaction products of polyols derived from ethylene oxide or propylene oxide with amines; amine-terminated polyamides, prepared by the reaction of dimerized and trimerized vegetable oil fatty acids with polyamines; amidoamines, imidazolines, and combinations thereof, for example the reaction product of diethylene triamine and tail-oil fatty acid.
  • hardeners such as ketimines, which are the reaction products of ketones and primary aliphatic amines
  • polyether amines which are the reaction products of polyols derived from ethylene oxide or propylene oxide with amines
  • amine-terminated polyamides prepared by the reaction of dimerized and trimerized vegetable oil fatty acids with polyamines
  • amidoamines, imidazolines, and combinations thereof for example the
  • the additional curing promoter can comprise an anhydride hardener.
  • anhydrides include maleic anhydride (MA), phthalic anhydride (PA), hexahydro-o-phthalic anhydride (HEP A), tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride (MTHPA), methylhexahydrophthalic anhydride (MHHPA), nadic methyl anhydride (methyl himic anhydride, MHA), benzophenonetetracarboxylic dianhydride (BTDA), tetrachlorophthalic anhydride (TCP A), pyromellitic dianhydride (PMDA), trimellitic anhydride (TMA), or a combination thereof.
  • MA maleic anhydride
  • PA phthalic anhydride
  • HEP A hexahydro-o-phthalic anhydride
  • THPA tetrahydrophthalic anhydride
  • MTHPA methylte
  • the additional curing promoter can include a liquid
  • Exemplary liquid monoanhydride curing agents include norbomene dicarboxylic anhydrides (e.g., methyl-5-norbornene-2,3-dicarboxylic anhydride, or the like), hexahydrophthalic anhydrides (e.g., 1,2-cyclohexanedicarboxylic anhydride, 4- methylhexahydrophthalic anhydride, 5-methylhexahydrophthalic anhydride, or the like), tetrahydrophthalic anhydrides (e.g., 1,2,3,6-tetrahydrophthalic anhydride, l,2,3,6-tetrahydro-4- methylphthalic anhydride, or the like), phthalic anhydrides (e.g., 3-fluorophthalic anhydride), maleic anhydrides (e.g., 2-methylmaleic anhydride, dimethylmaleic anhydride, or the like), succinic anhydrides (e.g., dodecen
  • liquid monoanhydride refers to a monoanhydride compound that is a liquid at a temperature from 15 to 45°C, preferably 20 to 40°C, more preferably 20 to 30°C, even more preferably 20 to 25°C at atmospheric pressure.
  • the additional curing promoter can comprise a phenol-formaldehyde resin.
  • phenol-formaldehyde resins include, for example, novolac type phenol resins, resole type phenol resins, aralkyl type phenol resins, dicyclopentadiene type phenol resins, terpene modified phenol resins, biphenyl type phenol resins, bisphenol type phenol resins,
  • triphenylmethane type phenol resins or a combination thereof.
  • the additional curing promoter can comprise a Mannich base.
  • Mannich bases are the reaction products of an amine with phenol and formaldehyde, melamine-formaldehyde resins, urea-formaldehyde resins, or a combination thereof.
  • exemplary additional curing promoters include substituted ureas, for example 3 -phenyl- 1,1 -dimethyl urea; the reaction product of phenyl isocyanate with
  • dimethylamine the reaction product of toluene diisocyanate with dimethylamine; quaternary phosphonium salts, such as tetraalkyl- and alklytriphenylphosphonium halide; or a combination thereof.
  • the additional curing promoter can comprise a metal salt, for example a copper (II) or aluminum (III) salt of an aliphatic or aromatic carboxylic acid.
  • exemplary metal salts include the copper (II), tin (II), and aluminum (III) salts of acetate, stearate, gluconate, citrate, benzoate, and like anions, or a combination thereof.
  • the additional curing promoter can comprise a copper (II) or aluminum (III) b-diketonate.
  • Exemplary metal diketonates include the copper (II) and aluminum (III) salts of acetyl acetonate.
  • the additional curing promoter can comprise a boron trifluoride-trialkylamine complex. An illustrative boron
  • trifluoride-trialkylamine complex is boron trifluoride-trimethylamine complex.
  • the additional curing promoter can comprise a latent cationic cure catalyst.
  • Latent cationic cure catalysts are used, for example, in UV-cured epoxy resin compositions.
  • Latent cationic cure catalysts include, for example, diaryliodonium salts, phosphonic acid esters, sulfonic acid esters, carboxylic acid esters, phosphonic ylides, triarylsulfonium salts,
  • the curing promoter can be a latent cationic cure catalyst comprising a diaryliodonium salt having the structure
  • the curing promoter is a latent cationic cure catalyst comprising a diaryliodonium salt having the structure
  • the curing promoter is a latent cationic cure catalyst comprising 4-octyloxyphenyl phenyl iodonium hexafluoroantimonate.
  • the thermosetting epoxy powder coating composition does not include a latent cationic cure catalyst.
  • thermosetting epoxy powder coating composition does not include a dicyandiamide, a polyamide, an amidoamine, a Mannich base, a monoanhydride, a phenol-formaldehyde resin, a carboxylic acid functional polyester, a polysulfide, a
  • polymercaptan an isocyanate, and a cyanate ester.
  • thermosetting epoxy powder coating composition does not include benzophenone tetracarboxylic anhydride, a (Ci- 6 alkyl)styrene-maleic anhydride copolymer, chlorendic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, maleic anhydride, methylbutenyl tetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylnadic anhydride,
  • methyltetrahydrophthalic anhydride nadic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride.
  • the amount of additional curing promoter will depend on the type of curing promoter, as well as the identities and amounts of the other components of the composition.
  • the additional curing promoter can be present in an amount of 10 to 100 parts by weight, preferably 20 to 100 parts by weight, more preferably 20 to 80 parts by weight, based on the total parts by weight of the epoxy resin composition, the aromatic dianhydride curing agent, and the additional curing promoter.
  • thermosetting epoxy powder coating composition is substantially free of monoanhydride curing agent and/or monoanhydride.
  • thermosetting epoxy powder coating composition contains less than 500 ppm by weight of monoanhydride.
  • a“monoanhydride free” thermosetting epoxy powder coating composition can have less than 450 ppm by weight, preferably less than 300 ppm by weight, more preferably less than 200 ppm by weight, even more preferably less than 100 ppm by weight of monoanhydride, based on the total weight of the thermosetting epoxy powder coating composition.
  • thermosetting epoxy powder coating composition can include one or more fillers or reinforcing agents.
  • the fillers and reinforcing agents can be in the form of
  • Exemplary fillers or reinforcing agents include, for example, silicates and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, and natural silica sand; boron powders such as boron-nitride powder, and boron-silicate powders; oxides such as T1O2, aluminum oxide, and magnesium oxide; calcium sulfate (as its anhydride, dihydrate, or trihydrate); calcium carbonates such as chalk, limestone, marble, and synthetic precipitated calcium carbonates; talc, including fibrous, modular, needle shaped, and lamellar talc; wollastonite; surface-treated wollastonite; glass spheres such as hollow and solid glass spheres, silicate spheres, cenospheres, and
  • organic fillers such as polytetrafluoroethylene; reinforcing organic fibrous fillers formed from organic polymers capable of forming fibers such as poly(ether ketone), polyimide,
  • fillers and reinforcing agents can be present in an amount of 5 to 90 wt%, based on the total weight of the thermosetting epoxy powder coating composition. Within this range, the content of fillers and reinforcing agents can be 10 to 80 wt%, specifically 20 to 80 wt%, more specifically 40 to 80 wt%, even more specifically 50 to 80 wt%.
  • the thermosetting epoxy powder coating composition comprises fillers of mica and calcium silicate such as wollastonite.
  • Mica can be given the general chemical formula X 2 Y 4-6 Z 8 0 2 o(OHF) 4 , wherein X is K, Na, or Ca; Y is Al, Mg or Fe; and Z is Si or Al.
  • Calcium silicate is a compound obtained by reacting calcium oxide and silica in different ratios, and can take one of four forms, having the chemical compositions Ca 3 0-Si0 4 , Ca 2 Si0 4 , Ca 3 Si 2 0 7 , or CaSi0 3.
  • the filler or reinforcing agent can include particles having one or more morphologies and physical dimensions. For example, one or more of spherical particles, semi- spherical particles, spheroids, oblates, amorphous particles, hollow spheres, porous materials, rods, whiskers, geometric shapes, tubes, fibers having at least one dimension that is longer than another dimension, or the like.
  • the mean or average dimension distribution can be less than or equal to 75 micrometers (pm), less than or equal to 50 pm, less than or equal to 35 pm, less than or equal to 25 mih, or the dimension can be sub-micrometer.
  • the particles can have a bimodal particle size distribution, a trimodal particle size distribution, or a higher modality particle size distribution. In particular aspects, the particles have a bimodal particle size distribution and substantially all of the particles present are spherical.
  • the filler or reinforcing agent can be treated with a silane coupling agent.
  • Exemplary silane coupling agents include, but are not limited to, aminosilanes, epoxysilanes, mercaptosilanes, styrylsilanes, or a combination thereof.
  • Exemplary aminosilanes include (4- aminobutyl)-dimethylmethoxysilane, N-(2-aminoethyl-3-aminopropyl)-methyldimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, (3-aminopropyl)-methyldiethoxysilane, (3- aminopropyl)-tri ethoxy silane, (3 -aminopropyl)-trimethoxy silane, 3-(N-aminophenyl)- propyltrimethoxy silane, or the like.
  • Exemplary epoxy silanes include 2 -(3, 4-epoxy cyclohexyl- ethyl)-trimethoxysilane, (3-glycidoxy propyl)- bis(trimethylsiloxy)-methylsilane, (3- glycidoxypropyl)-diisopropylethoxysilane, (3-glycidoxypropyl)-dimethylethoxysilane, (3- glycidoxypropyl)-methyldiethoxysilane, (3-glycidoxypropyl)-methyldiisopropenoxysilane, (3- glycidoxypropyl)-trimethoxysilane, or the like.
  • Exemplary mercaptosilanes include (3- mercaptopropy-methyldimethoxysilane, (3-mercaptopropyl)-trimethoxysilane,
  • styrylsilanes include
  • styrylethyltrimethoxy silane 3 -(N-styrylmethyl-2-aminoethylamino)-propyltrimethoxy silane, or the like.
  • the treatment with the silane coupling agent can increase compatibility of the otherwise hydrophilic filler or reinforcing agent with an at least partially non-polar organic phase matrix.
  • the treatment can leave residual active termination sites on the silica (e.g., silanol) that can reduce stability. Therefore, a subsequent or second treatment of the silica can be performed with a capping or passivating agent.
  • exemplary passivating agents include a silazane, such as hexamethyldisilazane. This two-part treatment can remove substantially all of the active termination sites available on the silica that could reduce stability or shelf life, or undesirably increase viscosity or initiate crosslinking over time.
  • the thermosetting epoxy powder coating composition includes an additive composition.
  • the additive composition can include an antioxidant, a heat stabilizer, a light stabilizer, a ultraviolet light stabilizer, a ultraviolet light-absorbing compound, a near infrared light-absorbing compound, an infrared light-absorbing compound, a plasticizer, a lubricant, a release agent, an antistatic agent, a surfactant, an anti-fog agent, an antimicrobial agent, colorants such as pigments and dyes, a high temperature pigment, a surface effect additive, a radiation stabilizer, a flame retardant, flame retardant synergists such as antimony pentoxide, an anti-drip agent, a corrosion inhibiting agent, a defoaming or degassing agent, diluents, an adhesion promoter, a flow control agent, a stress-relief additive, a coating additive, a polymer different from the thermoset (epoxy resin) polymer, or a combination thereof
  • thermosetting epoxy powder coating composition is substantially free of any polymer other than the thermoset (epoxy resin) polymer.
  • the amount of the optional additives used can range generally from 0 to 99 wt%, preferably 0.001 to 95 wt%, more preferably 0.01 to 10 wt%, and most preferably 0.05 to 5 wt%, based on total weight of the thermosetting epoxy powder coating composition.
  • Exemplary corrosion inhibiting agents include calcium nitrite and/or nitrate, sodium nitrite and/or nitrate, sodium benzoate, certain phosphates, fluoroaluminates,
  • Such corrosion inhibiting agents can be employed in the amount of 0 to 50 wt%, preferably 0.1 to 30 wt%, based on total weight of the thermosetting epoxy powder coating composition.
  • Exemplary pigments include titanium dioxide, zinc oxide, iron oxide, chrome oxide, cobalt sulfide (cobalt black), or alloys thereof; carbon black, phthalocyanine blue, phthalocyanine green, quinacridone red, perylene red, isoindolone yellow, dioxazine violet, scarlet 3B lake, red 188 azo red, azo pigment yellow 83, or the like; other metallic powders, such as metal hydroxides, sulfides, sulfates, or the like; and filler pigments.
  • the thermosetting epoxy powder coating composition preferably comprises a high temperature pigment, for example high temperature resistant cobalt black (such as Cobalt Black Ferro F6331-2, manufactured by Ferro). These can be used in amounts of 0 to 80 wt%, preferably 0.1 to 60 wt%, more preferably 25 to 50 wt%, based on total weight of the thermosetting epoxy powder coating composition.
  • Exemplary flow control agents include organic flow control agents such as polyacrylic esters, non-ionic fluorinated alkylester surfactants, non-ionic alkylaryl polyether alcohols, silicones, or the like; and inorganic flow control agents such as fumed silica or fumed alumina, such as ultrafme aluminum oxide (having an average particle diameter of 0.1 pm or less, preferably 0.005 to 0.05 pm).
  • the flow control agents can be used in amounts of 0.5 to 5 wt%, preferably 0.5 to 3 wt%, based on total weight of the thermosetting epoxy powder coating composition.
  • Exemplary defoaming and degassing agents include benzoin (which may also function as an additional curing catalyst), bisphenol A, phenyl acetyl salicylate, bisphenoxy propanol, and 1,4 cyclohexane dimethanol dibenzoate. These can be used in amounts of 0.5 to 5 wt%, preferably 0.5 to 3 wt%, based on total weight of the thermosetting epoxy powder coating composition.
  • thermosetting epoxy powder coating composition can be manufactured by combining the epoxy resin composition, the aromatic dianhydride curing agent, the curing catalyst, and optionally the additional curing promoter at a temperature of 100 to 200°C, preferably 120 to 190°C, more preferably 130 to 180°C to provide the thermosetting epoxy powder coating composition.
  • thermosetting epoxy powder coating composition and/or reaction mixture contains no solvent or reactive diluent.
  • thermosetting epoxy powder coating composition and/or the reaction mixture further includes a solvent with the proviso that the solvent does not render an otherwise insoluble aromatic dianhydride soluble in the epoxy resin composition.
  • the solvent can be C 3-8 ketones, C 4-8 A/ZV-dialkylamides, C 4-16 dialkyl ethers, Ce-u aromatic hydrocarbons, C 3-6 alkyl alkanoates, C 2-6 alkyl nitriles, C 2-6 dialkyl sulfoxides, or a combination thereof.
  • C 3-8 ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and combinations thereof.
  • Examples of C 4-8 A/ A'-dialkylamides include dimethylformamide, dimethylacetamide, A-m ethyl -2-pyrrol i done, and combinations thereof.
  • C 4-16 dialkyl ethers include tetrahydrofuran, dioxane, and combinations thereof.
  • the C 4-16 dialkyl ether can optionally further include one or more ether oxygen atoms within the alkyl groups and one or more hydroxy substituents on the alkyl groups, for example the C 4-16 dialkyl ether can be ethylene glycol monomethyl ether.
  • the aromatic hydrocarbon solvent can be an ethylenically unsaturated solvent.
  • Examples of C 6-12 aromatic hydrocarbons include benzene, toluene, xylenes, styrene, divinylbenzenes, and combinations thereof.
  • Examples of C3-6 alkyl alkanoates include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and combinations thereof.
  • Examples of C2-6 alkyl cyanides include acetonitrile, propionitrile, butyronitrile, and combinations thereof.
  • Examples of C2-6 dialkyl sulfoxides include dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, and combinations thereof.
  • the solvent comprises acetone, methyl ethyl ketone, /V-methyl-2-pyrrolidone, toluene, or a combination thereof.
  • the solvent can be a halogenated solvent such as methylene chloride, chloroform, 1,1,1-trichloroethane, chlorobenzene, or the like.
  • the thermosetting epoxy powder coating composition can be cured, for example, following powder coating of a substrate.
  • the thermosetting epoxy powder coating composition can, for example, be cured thermally or by using irradiation techniques, including UV irradiation and electron beam irradiation.
  • the temperature selected can be 80 to 300°C, and preferably 120 to 250°C.
  • the heating period can be 1 minute to 10 hours, though such heating period may advantageously be 1 minute to 6 hours, preferably 2 minutes to 4 hours, more preferably 15 minutes to 4 hours.
  • Such curing may be staged to produce a partially cured and often tack-free resin, which then is fully cured by heating for longer periods or temperatures within the aforementioned ranges.
  • the cured product of the thermosetting epoxy powder coating composition after curing has a glass transition temperature (T g ) of 120 to 320°C, preferably 160 to 320°C, more preferably 180 to 320°C, even more preferably 200 to 320°C, still more preferably 250 to 320°C, as determined by dynamic mechanical analysis (DMA).
  • T g glass transition temperature
  • the cured product of the thermosetting epoxy powder coating composition after powder coating a substrate and curing has an impact resistance of greater than 2 N m, preferably greater than 3 N m, more preferably greater than 4 N m, when measured according to ASTM D2794.
  • the cured product of the thermosetting epoxy powder coating composition after powder coating a substrate and curing can have a flex strength of from 65 to 200 megapascals (MPa), preferably from 70 MPa to 160 MPa, more preferably from 75 to 150 MPa, as measured according to ASTM D790.
  • MPa megapascals
  • the cured product of the thermosetting epoxy powder coating composition after powder coating a substrate and curing can have a pencil hardness of 6H to 10H, preferably 7H to 10H, as measured according to ASTM D2794.
  • the cured product of the thermosetting epoxy powder coating composition after powder coating a substrate and curing can have a bending resistance of greater than or equal to 4 mm, preferably greater than or equal to 5 mm, more preferably greater than or equal to 6 mm at 23°C.
  • the cured product of the thermosetting epoxy powder coating composition after powder coating a substrate and curing can have a solvent resistance of greater than or equal 80 double rubs, preferably greater than or equal to 100 double rubs using methyl ethyl ketone.
  • thermosetting epoxy powder coating composition results in“a cured product of the thermosetting epoxy powder coating
  • the powder coated substrate includes the cured product of the thermosetting epoxy powder coating composition (i.e., the cured product is disposed on at least one surface of the substrate).
  • the thermosetting epoxy powder coating composition includes 100 parts by weight of the epoxy resin composition, 60 to 185 parts by weight of the aromatic dianhydride curing agent, a flow modifier, a degassing agent, and titanium dioxide, wherein after powder coating a substrate and curing the thermosetting epoxy powder coating composition can have an impact resistance of greater than 4 N m, as measured according to ASTM D2794; and a pencil hardness of 7H to 10H, as measured according to ASTM D2794.
  • thermosetting epoxy powder coating composition includes bisphenol A epoxy, bisphenol A dianhydride, a flow modifier, a degassing agent, and titanium dioxide, wherein after powder coating a substrate and curing the thermosetting epoxy powder coating composition can have an impact resistance of greater than 4 N m, as measured according to ASTM D2794; and a pencil hardness of 7H to 10H, as measured according to ASTM D2794.
  • the thermosetting epoxy powder coating composition includes 100 parts by weight of the epoxy resin composition, 60 to 185 parts by weight of the aromatic dianhydride curing agent, and a heterocyclic curing promoter, wherein the anhydride to epoxy (A/E) ratio is from 0.4 to 1.2, and wherein after curing the thermosetting epoxy powder coating composition can have a T g of 225 to 270°C, preferably 230 to 265°C.
  • the thermosetting epoxy powder coating composition includes 100 parts by weight of bisphenol A diglycidyl ether, 60 to 185 parts by weight of bisphenol A dianhydride, and 2-ethyl-4-methylimidazole, wherein the anhydride to epoxy (A/E) ratio is from 0.4 to 1.2, and wherein after curing the thermosetting epoxy powder coating composition can have a T g of 225 to 270°C, preferably 230 to 265°C.
  • thermosetting epoxy powder coating composition is prepared by combining the epoxy resin composition and the aromatic dianhydride curing agent to form a mixture, as described above.
  • the components of the powder coating composition can be pre-blended or ground in a grinder, and the resulting ground powder mixture exiting from the grinder is then fed into an extruder.
  • the powder mixture can be heated at low temperature and melted into a semi-liquid form. During this process, the components of the molten mixture are thoroughly and uniformly dispersed. Because of the fast operation of the extruder and the relatively low temperature within the extruder, the components of the powder coating composition do not undergo a significant chemical reaction, such as curing.
  • the resulting molten extrudate of the powder coating composition exiting from the extruder can be passed from the extruder onto a flaker which then feeds the flakes into a mill/classifier to obtain a thermosetting epoxy powder coating composition with a desired particle size.
  • the final powder coating product can be packaged in closed containers, using a packaging unit to avoid moisture ingression into the product.
  • thermosetting epoxy powder coating composition can be applied to a substrate by various methods, such as by electrostatic spraying techniques (See e.g., U.S. Pat.
  • thermosetting epoxy powder coating composition can be applied to a substrate by (1) heating the substrate to a suitable curing temperature for the thermosetting epoxy powder coating composition; and (2) applying the thermosetting epoxy powder coating composition by an electrostatic spray or a fluidized bed.
  • thermosetting epoxy powder coating composition can be applied to a cold substrate by (1) applying the thermosetting epoxy powder coating composition to the substrate (e.g. with an electrostatic application method); and (2) heating the thermosetting epoxy powder coating composition and the substrate to a temperature at which the powder flows and cures.
  • powder coated articles can he formed by applying the thermosetting epoxy powder coating composition to a substrate and then curing the curable thermosetting epoxy powder coating composition
  • An exemplary method for making an electrostatically applicable dry powder coating composition comprises the step of blending the epoxy resin composition and the aromatic dianhydride curing agent to form a mixture; passing the mixture through a conventional extruder to obtain a flaked product; and then reducing the mixture into a powder, for example by pulverizing the flaked product.
  • the coating composition can optionally be passed through a sieve to remove particles that are too large or too small.
  • a sieve which eliminates particles of maximum dimension greater than 150 micrometers (pm) can be used, more preferably to provide a D50 particle size of 50 pm or less. The size and amount of the particles depend on the nature of the substrate or article being coated.
  • thermosetting epoxy powder coating composition can be used to coat a variety of substrates.
  • substrates include steel pipes, steel pipelines, rebar, pipe hangers, valves, pumps, gears, manifolds, ladders, mesh, cable and wire rope, I-beams, girders, panels, column coils, anchor plates, strappings, casings, metal parts, or the like.
  • the substrate materials can include, but are not limited to, metals such as steel, cast iron, aluminum, or the like; concrete, cement, thermoset resins, wood, or a combination thereof.
  • thermosetting epoxy powder coating composition can be applied directly to one or more surfaces of the substrate, although for some end-uses a primer can be used.
  • the thermosetting epoxy powder coating composition can be applied to substantially the entire surface of the substrate, or to the entire exterior surface of the substrate. It is preferable that the surface to be coated be first cleaned, such as, for example, by grinding or grit blasting.
  • thermosetting epoxy powder coating composition can be applied either in one pass or in several passes to provide variable thicknesses, after cure, of 0.1 to 2 mm, preferably 0.2 to 1.5 mm, more preferably 0.2 to 1 mm, depending on the desired end-use of the coated article.
  • the articles coated with the thermosetting epoxy powder coating composition can be used for a variety of applications.
  • Exemplary applications include automotive finishes, industrial finishes such as building and construction applications or farm and agricultural applications.
  • building applications include coating aluminum or steel doors and door frames, window frames and sashes, siding, and garage doors.
  • coating compositions can be used for power equipment (tractors, lawn mowers, power tools), as well as for metal implements, tools, sheds, fenceposts, or the like, that are exposed to outdoor weather.
  • a variety of parts for cars, buses, trucks, and train cars can be powder coated for anticorrosion protection.
  • the coatings may also be used on indoor metal objects such as office furniture, filing cabinets, or the like.
  • Other industrial applications include pipelines, such as the internal and/or external surfaces of steel pipes, structural steel used in concrete or in marine environments, storage tanks, valves, oil production tubing and casings, or the like.
  • T g Glass transition temperature
  • Impact resistance for the coatings was measured according to ADTM D2794, which tests for deformation of the coating after impact from a ball or punch at 23°C. Impact resistance is measured using a Gardner Impact Tester and is reported as the impact pressure (in Newton meters, N m) at which deformation is first noted.
  • MEK double rub tests were performed under ambient conditions using a two-pound ballpein hammer as weight.
  • the rounded head of the hammer was wrapped in six-layers of grade 10 cheesecloth and soaked with methyl ethyl ketone. The rounded head of the hammer was then placed on the coating and manually moved back and forth across the coating under its own weight. Each back and forth stroke was counted as 1 double rub.
  • the test was ended and the number of double rubs until substrate exposure was recorded. In cases in which the substrate did not become exposed, the tests were terminated after 100 double rubs. Thus, the actual number of MEK double rubs required to effect exposure of the substrate may be higher than the value of 100 recorded.
  • Hardness was tested using a 1 kg load according to ASTM D3363. Five repeated measurements of the pencil hardness test procedure were performed, with the pencil hardness being the hardness of the pencil used for the test when none of the measurements result in scratches or other disturbances to the appearance. Pencil hardness is reported on the scale of 9B (softest), 8B, 7B, 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H, and 10H (hardest).
  • Table 2 shows the components for high heat resistant epoxy powder coating components of Example 1 and Comparative Example 1. The amount of each component is provided in parts by weight (pbw).
  • Example 1 The mechanical properties for Example 1 and Comparative Example 1 are provided in Table 3.
  • Table 3 shows that BP AD A has improved mechanical properties over PMDA when used as a curing agent for epoxy powder coating formulations.
  • the impact resistance of Example 1 (4.52 N m) was 100% greater than Comparative Example 1 (2.26 N m).
  • the BP ADA powder coating of Example 1 passed the mandrel bend test at 6.35 mm, although the pencil hardness was slightly lower for Example 1.
  • Both Example 1 and Comparative Example 1 passed the chemical resistance test after 100 doubled rubs.
  • Samples were prepared as follows. BPA-DGE was heated at 160°C and BPADA was added thereto. A homogenous and transparent reaction mixture was afforded. The reaction mixture was cooled to 90°C and 2,4-EMI was added while stirring. The resulting mixture was poured into a preheated mold (130°C) and then cured in the mold at 220°C for 60 minutes to provide a rigid and clear casting.
  • Table 4 provides the compositions, anhydride to epoxy (A/E) ratios, and thermal properties of Examples 2 to 6. The amount of each component is provided in parts per hundred resin (phr). Table 4.
  • the BP ADA-based epoxy formulations for powder coatings had high heat resistance as demonstrated by T g of greater than 230°C.
  • the optimum heat resistance was observed at A/E ratio of 0.8, as higher loadings of BP ADA were unexpectedly found to decrease the T g.
  • the data indicate that BP ADA can be used effectively as a curing or co-curing agent to prepare high heat resin formulations for use in applications such as powder coating.
  • a powder coated substrate comprising: a substrate; and a thermosetting epoxy powder coating composition, wherein the thermosetting epoxy powder coating
  • thermosetting epoxy powder coating composition comprises: 100 parts by weight of an epoxy resin composition; 30 to 200 parts by weight of an aromatic dianhydride curing agent; optionally a curing catalyst; and optionally an additional curing promoter, wherein an anhydride to epoxy stoichiometric ratio (A/E) is 0.1 : 1 to 1.6: 1, preferably 0.5: 1 to 1.3: 1, more preferably 0.6: 1 to 1.2: 1, as determined by molar ratio of total anhydride functionalities to total epoxy functionalities in the thermosetting epoxy powder coating composition, wherein the amounts are based on the total parts by weight of the epoxy resin composition, the aromatic dianhydride curing agent, and optionally the additional curing promoter, and wherein the aromatic dianhydride curing agent is of formula (1) as provided herein, wherein the thermosetting epoxy powder coating composition after curing has a glass transition temperature of 120 to 320°C, preferably 160 to 320°C, more preferably 180 to 320°C, even more
  • a powder coated substrate comprising: a substrate; and a
  • thermosetting epoxy powder coating composition wherein the thermosetting epoxy powder coating composition is powder coated on the substrate, wherein the thermosetting epoxy powder coating composition comprises: 100 parts by weight of an epoxy resin composition; 30 to 200 parts by weight of an aromatic dianhydride curing agent; optionally a curing catalyst; and optionally an additional curing promoter, wherein an anhydride to epoxy stoichiometric ratio (A/E) is 0.1 : 1 to 1.6: 1, preferably 0.5: 1 to 1.3: 1, more preferably 0.6: 1 to 1.2: 1, as determined by molar ratio of total anhydride functionalities to total epoxy functionalities in the thermosetting epoxy powder coating composition, wherein the amounts are based on the total parts by weight of the epoxy resin composition, the aromatic dianhydride curing agent, and optionally the additional curing promoter, and wherein the aromatic dianhydride curing agent is of formula (1) as provided herein, wherein the thermosetting epoxy powder coating composition after curing has a glass transition temperature of 120 to 320°C, preferably 160 to 320°
  • the epoxy resin composition comprises an epoxy resin that is a bisphenol A epoxy resin, a triglycidyl-substituted epoxy resin, a tetraglycidyl-substituted epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, a cycloaliphatic diglycidyl ester epoxy resin, a cycloaliphatic epoxy resin comprising a ring epoxy group, an epoxy resin containing a spiro-ring, a hydantoin epoxy resin, or a combination thereof; preferably wherein the epoxy resin composition comprises bisphenol-A diglycidyl ether.
  • Aspect 3 The powder coated substrate of any one or more of the preceding aspects, wherein T is -O- or a group of the formula -O-Z-O- wherein Z is of the formula (2) as provided herein; preferably wherein T is a group of the formula -O-Z-O- wherein Z is a divalent group of formulas (3a) or (3b) as provided herein; more preferably wherein the aromatic dianhydride curing agent comprises bisphenol-A dianhydride.
  • thermosetting epoxy powder coating composition further comprises a curing catalyst, preferably wherein the curing catalyst comprises a substituted or unsubstituted C3-6 heterocycle comprising 1 to 4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur; more preferably wherein the curing catalyst comprises a C3-4 five-membered ring wherein the ring heteroatoms are one or two nitrogen atoms.
  • the curing catalyst comprises a substituted or unsubstituted C3-6 heterocycle comprising 1 to 4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur; more preferably wherein the curing catalyst comprises a C3-4 five-membered ring wherein the ring heteroatoms are one or two nitrogen atoms.
  • thermosetting epoxy powder coating composition further comprises: 0.5 to 5 wt%, preferably 0.5 to 3 wt% of a flow control agent, preferably wherein the flow control agent is a poly(meth)acrylic ester, a non-ionic fluorinated alkylester, non-ionic alkylaryl polyether alcohol, fumed silica, fumed alumina, or a combination thereof, more preferably ultrafme aluminum oxide; and 0.1 to 60 wt%, preferably 25 to 50 wt% of a pigment, preferably wherein the pigment is titanium dioxide, zinc oxide, iron oxide, chrome oxide, carbon black, cobalt sulfide, an alloy thereof, or a combination thereof, more preferably cobalt sulfide, wherein the amounts are based on the total weight of the thermosetting epoxy powder coating
  • thermosetting epoxy powder coating composition further comprises a filler, preferably wherein the filler is fused silica, fumed silica, colloidal silica, aluminum oxide, boron nitride, titanium dioxide, titanium diboride, talc, fly ash, mica, calcium carbonate, calcium silicate, carbon black, zinc oxide, graphite, or a combination thereof; more preferably wherein the filler is mica, calcium silicate, or a combination thereof.
  • the filler is fused silica, fumed silica, colloidal silica, aluminum oxide, boron nitride, titanium dioxide, titanium diboride, talc, fly ash, mica, calcium carbonate, calcium silicate, carbon black, zinc oxide, graphite, or a combination thereof; more preferably wherein the filler is mica, calcium silicate, or a combination thereof.
  • thermosetting epoxy powder coating composition further comprises an additive; preferably wherein the additive is antioxidant, a heat stabilizer, a light stabilizer, a ultraviolet light stabilizer, a ultraviolet light-absorbing compound, a near infrared light absorbing compound, an infrared light-absorbing compound, a plasticizer, a lubricant, a release agent, an antistatic agent, a surfactant, an anti-fog agent, an antimicrobial agent, a pigments, a surface effect additive, a radiation stabilizer, a flame retardant, a flame retardant synergist, an anti-drip agent, a corrosion inhibiting agent, a defoaming agent, a degassing agent, a diluent, an adhesion promoter, a flow control agent, a stress-relief additive, a coating additive, or a combination thereof.
  • the additive is antioxidant, a heat stabilizer, a light stabilizer, a ultraviolet light stabilizer, a ultraviolet light-absorbing compound, a near in
  • thermosetting epoxy powder coating composition comprises 100 parts by weight of an epoxy resin composition; 30 to 200 parts by weight of an aromatic dianhydride curing agent; optionally a curing catalyst; optionally an additional curing promoter; 0.5 to 5 wt% of a flow control agent; and 0.1 to 60 wt% of a pigment, wherein the amounts are based on the total weight of the thermosetting epoxy powder coating composition.
  • thermosetting epoxy powder coating composition is powder coated and cured on the substrate.
  • Aspect 9 The powder coated substrate of any one of the preceding aspects, wherein the substrate is steel, cast iron, aluminum, concrete, cement, a thermoset resin, wood, or a combination thereof; preferably wherein the substrate comprises steel pipe, steel pipeline, rebar, pipe hanger, valve, pump, gear, manifold, ladder, mesh, cable, wire rope, I-beam, girder, panel, column coil, anchor plate, strapping, casing, or metal part.
  • Aspect 10 The powder coated substrate of any one of the preceding aspects, comprising a cured product of the thermosetting epoxy powder coating composition.
  • thermosetting epoxy powder coating composition has at least one of: a pencil hardness of 6H to 10H, preferably 7H to 10H, as measured according to ASTM D2794; a bending resistance of greater than or equal to 4 mm, preferably greater than or equal to 5 mm, more preferably greater than or equal to 6 mm at 23°C; or a solvent resistance of greater than or equal 80 double rubs, preferably greater than or equal to 100 double rubs using methyl ethyl ketone.
  • thermosetting epoxy powder coating composition includes: the epoxy resin composition comprising bisphenol-A diglycidyl ether; the aromatic dianhydride comprising bisphenol A dianhydride, and 2-ethyl-4-methylimidazole.
  • thermosetting epoxy powder coating composition includes: the epoxy resin composition comprising bisphenol-A diglycidyl ether; the aromatic dianhydride comprising bisphenol A dianhydride, and 2-ethyl-4-methylimidazole, wherein the thermosetting epoxy powder coating composition does not comprise a monoanhydride.
  • thermosetting epoxy powder coating composition includes the additional curing promoter; preferably wherein the additional curing promoter is an amine, a dicyandiamide, a polyamide, an amidoamine, a Mannich base, an anhydride, a phenol-formaldehyde resin, a carboxylic acid functional polyester, a polysulfide, a polymercaptan, an isocyanate, a cyanate ester, or a combination thereof; preferably wherein the additional curing promoter is an amine, a dicyandiamide, a polyamide, an amidoamine, a Mannich base, an anhydride, a phenol-formaldehyde resin, a carboxylic acid functional polyester, a polysulfide, a polymercaptan, an isocyanate, a cyanate ester, or a combination thereof; preferably wherein the additional curing promoter is an amine, a dicyandiamide, a polyamide, an amidoamine,
  • benzophenone tetracarboxylic anhydride (Ci- 6 alkyl)styrene-maleic anhydride copolymer, chlorendic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, hexahydro- 4-methylphthalic anhydride, maleic anhydride, methylbutenyl tetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylnadic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, or a combination thereof.
  • a method of manufacturing the powder coated substrate of any one or more of the preceding aspects comprising applying the thermosetting epoxy powder coating composition to at least one surface of the substrate; preferably wherein the applying comprises electrostatically applying the thermosetting epoxy powder coating composition in particulate form.
  • Aspect 13 The method of claim 12, further comprising heating the powder coated substrate at a temperature sufficient to cure the thermosetting epoxy powder coating
  • composition preferably wherein the curing temperature is 120 to 250°C.
  • Aspect 14 The method of claim 12, further comprising preparing the
  • thermosetting epoxy powder coating composition comprising: combining the epoxy resin composition and the aromatic dianhydride curing agent to form a mixture; processing the mixture to obtain a flaked product; and pulverizing the flaked product.
  • Aspect 15 The method of claim 14, wherein the processing comprises melt processing at a temperature less than a curing temperature of the thermosetting epoxy powder coating composition.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • hydrocarbyl refers to a monovalent group containing carbon and hydrogen. Hydrocarbyl can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl, or arylalkyl as defined below.
  • hydrocarbylene refers to a divalent group containing carbon and hydrogen. Hydrocarbylene can be alkylene, cycloalkylene, arylene, alkylarylene, or arylalkylene as defined below.
  • alkyl means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n- pentyl, s-pentyl, and n- and s-hexyl.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )).
  • Cycloalkylene means a divalent cyclic alkylene group, -CiTUn-x, wherein x is the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
  • Aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.
  • Arylene means a divalent aryl group.
  • Alkylaryl means an aryl group substituted with an alkyl group.
  • Arylalkyl means an alkyl group substituted with an aryl group (e.g., benzyl).
  • “Aryloxy” means an aryl group with the indicated number of carbon atoms attached through an oxygen bridge (-0-).
  • Amino means a monovalent radical of the formula— NRR' wherein R and R' are independently hydrogen or a Ci- 30 hydrocarbyl, for example a Ci- 20 alkyl group or a C 6-30 aryl group.
  • “Halogen” or“halogen atom” means a fluorine, chlorine, bromine, or iodine atom.
  • halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present.
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.
  • a heteroatom e.g., 1, 2, or 3 heteroatom(s)
  • each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound.
  • “Substituted” means that the compound, group, or atom is substituted with at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, where each substituent is independently nitro (-NO 2 ), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), Ci- 6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, Ci- 6 haloalkyl, C 1-9 alkoxy, Ci-6 haloalkoxy, C 3 -12 cycloalkyl, C5-1 8 cycloalkenyl, C 6 -12 aryl, C7-1 3 arylalkyl (e.g., benzyl), C 7-12 alkylaryl
  • the indicated number of carbon atoms is the total number of carbon atoms in the compound or group, including those of any substituents.

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Abstract

L'invention concerne un substrat revêtu de poudre comprenant : un substrat ; et une composition de revêtement en poudre époxydique thermodurcissable, la composition de revêtement en poudre époxydique thermodurcissable étant appliquée en poudre sur le substrat, la composition de revêtement en poudre époxydique thermodurcissable comprenant : 100 parties en poids d'une composition de résine époxydique, de 30 à 200 parties en poids d'un agent durcisseur à base de dianhydride aromatique, éventuellement un catalyseur de durcissement, et éventuellement un promoteur de durcissement supplémentaire, un rapport stœchiométrique anhydride sur époxyde (A/E) étant de 0,1:1 à 1,6:1, et l'agent de durcissement à base de dianhydride aromatique répondant à la formule (1) telle que décrite dans la description ; la composition de revêtement en poudre époxydique thermodurcissable après durcissement ayant une température de transition vitreuse située dans la plage allant de 120 à 320 °C, telle que déterminée par DMA, et la composition de revêtement en poudre époxydique thermodurcissable après durcissement ayant une résistance aux chocs supérieure à 2 newtons mètres, lorsqu'elle est mesurée conformément à la norme ASTM D2794.
PCT/US2020/020972 2019-03-04 2020-03-04 Composition époxydique thermodurcissable pour revêtement en poudre WO2020180979A1 (fr)

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Cited By (9)

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CN112143339A (zh) * 2020-09-29 2020-12-29 中国科学院长春应用化学研究所 一种舰载机用环氧树脂涂料及其制备方法
CN112390930A (zh) * 2020-11-04 2021-02-23 黄山新佳精细材料有限公司 耐磨、耐高低温性能优的粉末涂料用环氧树脂及制备方法
CN112592641A (zh) * 2020-12-15 2021-04-02 郑林义 一种软木复合隔温粉末涂层材料及其制备方法、涂层
CN113185893A (zh) * 2021-04-28 2021-07-30 宁波森工钢棒有限公司 耐腐蚀钢棒制备方法以及采用该方法制备的钢棒
US20210261789A1 (en) * 2020-02-26 2021-08-26 Ppg Industries Ohio, Inc. Coating Compositions Containing Lignin and Coatings Formed Therefrom
CN115651491A (zh) * 2022-12-15 2023-01-31 南通欣然粉末涂料有限公司 一种耐腐蚀粉末涂料及生产工艺
CN116515368A (zh) * 2023-05-30 2023-08-01 云南领克新型材料有限公司 一种耐高温易清洁粉末涂料及其制备方法
US11919254B2 (en) 2019-11-12 2024-03-05 Neuvokas Corporation Method of manufacturing a composite material
EP4361227A1 (fr) 2022-10-25 2024-05-01 Pulver Kimya San. ve Tic. A.S. Procédé de production d'une composition de revêtement en poudre durcissable à basse température et composition de revêtement en poudre durcissable à basse température pouvant être obtenue par un tel procédé

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US3542711A (en) * 1967-11-06 1970-11-24 Shell Oil Co Process for preparing polyepoxide/thermoplastic resin fluidized bed coating compositions and resulting products
US3578615A (en) * 1968-04-08 1971-05-11 Shell Oil Co Epoxy resin coatings having improved cathodic disbonding resistance
US3904346A (en) 1971-12-23 1975-09-09 Leslie Earl Shaw Electrostatic powder coating process
DE3610757A1 (de) * 1986-03-29 1987-10-01 Huels Chemische Werke Ag Lagerstabile pulverlacke fuer ueberzuege mit matter oberflaeche
US5178902A (en) 1990-12-21 1993-01-12 Shaw Industries Ltd. High performance composite coating
WO2019035054A1 (fr) * 2017-08-16 2019-02-21 Sabic Global Technologies B.V. Mélanges et articles époxy solides haute température, amorphes, homogènes, et leurs utilisations

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11919254B2 (en) 2019-11-12 2024-03-05 Neuvokas Corporation Method of manufacturing a composite material
US20210261789A1 (en) * 2020-02-26 2021-08-26 Ppg Industries Ohio, Inc. Coating Compositions Containing Lignin and Coatings Formed Therefrom
CN112143339A (zh) * 2020-09-29 2020-12-29 中国科学院长春应用化学研究所 一种舰载机用环氧树脂涂料及其制备方法
CN112390930A (zh) * 2020-11-04 2021-02-23 黄山新佳精细材料有限公司 耐磨、耐高低温性能优的粉末涂料用环氧树脂及制备方法
CN112592641A (zh) * 2020-12-15 2021-04-02 郑林义 一种软木复合隔温粉末涂层材料及其制备方法、涂层
CN113185893A (zh) * 2021-04-28 2021-07-30 宁波森工钢棒有限公司 耐腐蚀钢棒制备方法以及采用该方法制备的钢棒
EP4361227A1 (fr) 2022-10-25 2024-05-01 Pulver Kimya San. ve Tic. A.S. Procédé de production d'une composition de revêtement en poudre durcissable à basse température et composition de revêtement en poudre durcissable à basse température pouvant être obtenue par un tel procédé
WO2024088676A1 (fr) 2022-10-25 2024-05-02 Pulver Kimya San. Ve Tic. A.S. Procédé de production d'une composition de revêtement en poudre durcissable à basse température et composition de revêtement en poudre durcissable à basse température pouvant être obtenue par un tel procédé
CN115651491A (zh) * 2022-12-15 2023-01-31 南通欣然粉末涂料有限公司 一种耐腐蚀粉末涂料及生产工艺
CN115651491B (zh) * 2022-12-15 2023-11-14 北京久顺启航新材料有限公司 一种耐腐蚀粉末涂料及生产工艺
CN116515368A (zh) * 2023-05-30 2023-08-01 云南领克新型材料有限公司 一种耐高温易清洁粉末涂料及其制备方法
CN116515368B (zh) * 2023-05-30 2023-09-29 云南领克新型材料有限公司 一种耐高温易清洁粉末涂料及其制备方法

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