US20150232691A1 - Blocked bio-based carboxylic acids and their use in thermosetting materials - Google Patents

Blocked bio-based carboxylic acids and their use in thermosetting materials Download PDF

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US20150232691A1
US20150232691A1 US14/428,047 US201314428047A US2015232691A1 US 20150232691 A1 US20150232691 A1 US 20150232691A1 US 201314428047 A US201314428047 A US 201314428047A US 2015232691 A1 US2015232691 A1 US 2015232691A1
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acid
bio
vinyl
polyfunctional carboxylic
carboxylic acid
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Dean C. Webster
Erin Pavlacky
Curtiss Kovash, JR.
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North Dakota State University Research Foundation
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/08—Epoxidised polymerised polyenes
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/40—Succinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/42—Glutaric acid esters
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/44—Adipic acid esters
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/46—Pimelic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/48—Azelaic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/50—Sebacic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
    • C07C69/704—Citric acid esters
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical

Definitions

  • This invention relates to bio-based polyfunctional carboxylic acids reacted with vinyl ether compounds to form liquid vinyl-blocked bio-based polyfunctional carboxylic acids.
  • These liquid vinyl-blocked bio-based polyfunctional carboxylic acids can be mixed with polyfunctional vegetable oil-based epoxy resins to form a homogeneous mixture. Upon curing the homogeneous mixtures at elevated temperature, thermoset coatings are formed which have excellent hardness, solvent resistance, adhesion, and flexibility.
  • the invention also relates to the use of a curable coating composition comprising polyfunctional vegetable oil-based epoxy resins and vinyl-blocked bio-based polyfunctional carboxylic acids, which may be coated onto a substrate and cured.
  • the substrate can be any common substrate such as paper, polyester films such as polyethylene and polypropylene, metals such as aluminum and steel, glass, urethane elastomers, primed (painted) substrates, and the like.
  • Vegetable oil based materials have been used a long time in paints and varnishes and in alkyd resins.
  • Vegetable oils are derived from the seeds of various plants and are chemically triglycerides of fatty acids. That is, vegetable oils consist of three moles of fatty acids esterified with one mole of glycerol. As shown below in Formula I, fatty acids are linear carboxylic acids having 4 to 28 carbons and may be saturated or ethylenically unsaturated.
  • Naturally-occurring vegetable oils are by definition mixtures of compounds, as are the fatty acids comprising them. They are usually either defined by their source (soybean, linseed, etc.) or by their fatty acid composition.
  • a primary variable that differentiates one vegetable oil from another is the number of double bonds in the fatty acid; however, additional functional groups can be present such as hydroxyl groups in castor oil and epoxide groups in vernonia oil. Table 1 below identifies the typical fatty acid composition for some commonly occurring vegetable oils.
  • Sucrose ⁇ -D-fructofuranosyl- ⁇ -D-glucopyranoside
  • SEFA sucrose esters of fatty acids
  • SEFOSE sucrose esters can be used as binders and reactive diluents for air-drying high solids coatings.
  • Formula II displays the possible molecular structure of a sucrose ester with full substitution.
  • Procter and Gamble has reported a process to prepare highly substituted vegetable oil esters of sucrose using transesterification of sucrose with the methyl esters of sucrose (U.S. Pat. No. 6,995,232).
  • An epoxide group is a three-membered, cyclic ether containing two carbon atoms and one oxygen atom.
  • An epoxide can also be called an oxirane.
  • an epoxy group has the structure shown in formula III in which R and R′ are organic moieties representing the remainder of the compound.
  • Epoxy resins are materials consisting of one or more epoxide groups. Due to the strained nature of the oxirane ring, epoxide groups are highly reactive and can be reacted with nucleophiles such as amines, alcohols, carboxylic acids. Thus, epoxy resins having two or more epoxy groups can be reacted with compounds having multiple nucleophilic groups to form highly crosslinked thermoset polymers. Oxiranes can also be homopolymerized. Epoxy resins having two or more epoxy groups can be homopolymerized to form highly crosslinked networks. Crosslinked epoxy resins are used in a large number of applications including coatings, adhesives, and composites, among others. The most commonly used epoxy resins are those made from reacting bisphenol-A with epichlorohydrin to yield difunctional epoxy resins.
  • Epoxidation of the double bonds in unsaturated vegetable oils results in compounds which incorporate the more reactive epoxy group.
  • Epoxide groups, or oxirane groups, as discussed, can be synthesized by the oxidation of vinyl groups.
  • a number of other processes and catalysts have been developed to also achieve epoxidized oils in good yields.
  • Epoxides generated from the epoxidation of double bonds of ethylenically unsaturated fatty acids are known as internal epoxides—both carbons of the heterocyclic ring are substituted with another carbon.
  • the most commonly used epoxy resins are the bisphenol-A diglycidyl ether resins.
  • the epoxy groups on these resins are of the type known as external epoxides—three of the four substituent groups on the heterocyclic ring are hydrogen atoms.
  • epoxidized oils are as stabilizers and plasticizers for halogen-containing polymers (i.e., poly(vinyl chloride)) (Karmalm et al., Polym. Degrad. Stab. 94:2275 (2009); Fenollar et al., Eur. Polym. J. 45:2674 (2009); and Bueno-Ferrer et al., Polym. Degrad. Stab. 95:2207 (2010)), and reactive toughening agents for rigid thermosetting plastics (e.g., phenolic resins).
  • halogen-containing polymers i.e., poly(vinyl chloride)
  • Epoxidized vegetable oils have found use as plasticizers for polyvinyl chloride (PVC). When crosslinked directly using the epoxy groups, the resulting products are relatively soft due to the aliphatic nature of the vegetable oil backbone. Epoxidized vegetable oils have been further functionalized using acrylation, methacrylation, and hydroxylation.
  • Epoxy resins based on polyfunctional vegetable oil esters of sucrose can be crosslinked into high performance thermosets using cyclic anhydrides. See WO 2011/097484, the disclosure of which is incorporated herein by reference.
  • thermosets While the epoxy resin is 100% bio-based, the system uses petrochemical derived cyclic anhydride crosslinkers, which reduces the overall bio-based content of the thermosets. It is therefore of interest to use crosslinkers which are also bio-based to form thermosets that are 100% bio-based.
  • polyfunctional acids there are a large number of polyfunctional acids available, which are either currently available from bio-derived processes or for which bio-based processes are being derived. Some of these acids are shown in Table 2 below. These polyfunctional acids may be used as crosslinkers for vegetable oil-based epoxy resins, such as, for example, the epoxidized vegetable oil sucrose esters, since the acid groups are reactive with the epoxy groups and the functionality is two or greater.
  • the reversible reaction of carboxylic acids with vinyl ether compounds leads to liquid, low viscosity materials, i.e., the carboxylic acids can be “blocked” via reactions with vinyl ether compounds.
  • the vinyl group can “deblock” from the carboxylic acid group and allow the acid to react with an epoxy group. See Nakane et al., Prog. Org. Coat. 31:113-120 (1997); Yamamoto et al., Prog. Org. Coat. 40:267-273 (2000), the disclosures of which are incorporated herein by reference.
  • the blocking vinyl ether group can also be removed thermally.
  • the invention relates to liquid vinyl-blocked bio-based polyfunctional carboxylic acids formed by the reaction of at least one bio-based polyfunctional carboxylic acid with at least one vinyl ether compound.
  • the invention in another embodiment, relates to a homogeneous mixture of the liquid vinyl-blocked bio-based polyfunctional carboxylic acids of the invention mixed with at least one polyfunctional vegetable oil-based epoxy resin, such as, for example, epoxidized vegetable oil sucrose ester resin.
  • a homogeneous mixture of the liquid vinyl-blocked bio-based polyfunctional carboxylic acids of the invention mixed with at least one polyfunctional vegetable oil-based epoxy resin, such as, for example, epoxidized vegetable oil sucrose ester resin.
  • the invention relates to a curable coating composition
  • a curable coating composition comprising at least one vinyl-blocked bio-based polyfunctional carboxylic acid and at least one polyfunctional vegetable oil-based epoxy resin.
  • the curable coating composition of the invention may be coated onto a substrate and cured using techniques known in the art.
  • the substrate can be any common substrate such as paper, polyester films such as polyethylene and polypropylene, metals such as aluminum and steel, glass, urethane elastomers, primed (painted) substrates, and the like.
  • the curable coating composition of the invention may be cured thermally.
  • the invention in another embodiment, relates to a method of making a curable coating composition of the invention comprising the step of mixing at least one vinyl-blocked bio-based polyfunctional carboxylic acid with at least one polyfunctional vegetable oil-based epoxy resin.
  • the invention relates to thermoset coatings formed from the curable coating compositions of the invention.
  • the invention in another embodiment, relates to an article of manufacture comprising a thermoset coating of the invention and a method of making such article.
  • FIG. 1 depicts an exemplary epoxidation of a sucrose fatty acid ester.
  • FIG. 2 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and azeleic acid (AzA) blocked by different vinyl ether compounds.
  • FIG. 3 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and succinic acid (SuA) blocked by different vinyl ether compounds.
  • FIG. 4 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and citric acid (CiA) blocked by different vinyl ether compounds and furan dicarboxylic acid (FDCA) blocked by isobutyl vinyl ether (IBVE).
  • CiA epoxidized sucrose soyate and citric acid
  • FDCA furan dicarboxylic acid
  • IBVE isobutyl vinyl ether
  • FIG. 5 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and ethyl vinyl ether (EVE) blocked acids (succinic (SuA), adipic (AdA), glutaric (GlA), pimelic (PiA), subaric (SbA), azeleic (AzA), and sebacic (SeA)).
  • EVE ethyl vinyl ether
  • a vinyl ether compound includes a single vinyl ether compound as well as a combination or mixture of two or more vinyl ether compounds
  • a carboxylic acid encompasses a single carboxylic acid as well as two or more carboxylic acids, and the like.
  • the invention relates to vinyl-blocked bio-based polyfunctional carboxylic acids comprising the reaction product of at least one bio-based polyfunctional carboxylic acid and at least one vinyl ether compound.
  • the vinyl-blocked bio-based polyfunctional carboxylic acids are liquid at room temperature.
  • a “bio-based polyfunctional carboxylic acid” means a bio-based acid comprising at least two carboxylic acid groups.
  • the bio-based polyfunctional carboxylic acid may be selected from dicarboxylic acids, tricarboxylic acids, or mixtures thereof.
  • the dicarboxylic acids and tricarboxylic acids may be saturated or ethylenically unsaturated, optionally substituted by one or more substituents, and aromatic or non-aromatic. Unsaturation and/or substitution may occur in one or more positions anywhere on the alkyl chains of the dicarboxylic acids and tricarboxylic acids.
  • the bio-based polyfunctional carboxylic acid may be a saturated dicarboxylic acid having the following general structure: HOOC—(CH 2 ) n —COOH.
  • n may be an integer ranging from 0 to 22, preferably 2 to 16, more preferably 6 to 10.
  • the saturated dicarboxylic acid may be substituted by, for example, hydroxyl groups, as in tartaric acid, for example.
  • the bio-based polyfunctional carboxylic acid may be an ethylenically unsaturated dicarboxylic acid selected from, for example, maleic acid, fumaric acid, glutanoic acid, traumatic acid, and muconic acid.
  • the bio-based polyfunctional carboxylic acid may be selected from saturated and ethylenically unsaturated tricarboxylic acids, including, not limited to, citric acid, isocitric acid, homoisocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, 3-carboxy-cis,cis-muconic acid, and homoaconitic acid.
  • the bio-based polyfunctional carboxylic acid may be selected from aromatic and non-aromatic dicarboxylic acids and tricarboxylic acids, including, but not limited to, (ortho-)phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, and 2,5-furandicarboxylic acid (FDCA).
  • aromatic and non-aromatic dicarboxylic acids and tricarboxylic acids including, but not limited to, (ortho-)phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, and 2,5-furandicarboxylic acid (FDCA).
  • the vinyl ether compounds may be linear, branched, or cyclic, and optionally substituted.
  • the vinyl ether compounds may have the following general structure:
  • linear vinyl ether compounds include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, undecyl vinyl ether, dodecyl vinyl ether, tridecyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinyl ether, heptyl vinyl ether, and octadecyl vinyl ether.
  • Branched vinyl ether compounds include, but are not limited to, isopropyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, and 2-ethyl hexyl vinyl ether.
  • Cyclic vinyl ether compounds include, but are not limited to, cyclohexyl vinyl ether.
  • Substituted vinyl ether compounds include, but are not limited to, hydroxybutyl vinyl ether.
  • the vinyl-blocked bio-based polyfunctional carboxylic acids may be synthesized by a variety of methods.
  • the vinyl-blocked bio-based polyfunctional carboxylic acids are synthesized by reacting the at least one bio-based polyfunctional carboxylic acid with the at least one vinyl ether compound, at least one optional catalyst, and at least one optional solvent.
  • the molar ratio of vinyl groups in the at least one vinyl ether compound and carboxylic groups in the at least one bio-based polyfunctional carboxylic acid used for the synthesis of the vinyl-blocked bio-based polyfunctional carboxylic acids may range from 1.0:1.0 to 10:1, more preferably 4.0:1 to 6.0:1.0.
  • a stoichiometric excess of moles of vinyl ether groups relative to the carboxylic acid groups is used.
  • the optional catalyst may be selected from phosphoric acid, hydrochloric acid, sulfuric acid, and the like. In a further embodiment, the optional catalyst may be present in an amount ranging from about 0.01% to about 5.0% by wt., preferably about 0.5% to about 2.0% by wt., even more preferably about 0.1% to about 1.0% by wt., of the total reaction mixture.
  • the optional solvent may be selected from benzene, toluene, xylene, heptane, hexane, and the like. In a further embodiment, the optional solvent may be present in an amount ranging from about 0.1% to about 50.0% by wt., preferably about 0.5% to about 15.0% by wt., even more preferably about 1.0% to about 2.0% by wt., of the total reaction mixture. Solvents may be used during the synthesis to reduce viscosity and facilitate the synthesis reaction.
  • the optional catalyst may be removed using a base, such as, for example, potassium hydroxide, in water via liquid-liquid extraction. Excess vinyl ether may be removed using known methods in the art, for example, rotary evaporation.
  • the reaction to make the vinyl-blocked bio-based polyfunctional carboxylic acids of the invention may be carried out at temperatures dependent on the vinyl ether compound used.
  • a reaction temperature of about 30° C. may be used for ethyl vinyl ether
  • about 70° C. may be used for propyl vinyl ether
  • about 80° C. may be used for butyl or isobutyl vinyl ether.
  • the reaction temperature may range from about 25° C. to about 100° C., more preferably, from about 30° C. to about 90° C., even more preferably, from about 50° C. to about 70° C.
  • Curable Coating Compositions Comprising Vinyl-Blocked Bio-Based Polyfunctional Acids and Polyfunctional Vegetable Oil-Based Epoxidized Resins
  • the invention also relates to curable coating compositions comprising the vinyl-blocked bio-based polyfunctional carboxylic acids described above and polyfunctional vegetable oil-based epoxidized resins.
  • the polyfunctional vegetable oil-based epoxy resins include, but are not limited to, epoxidized vegetable oils, vegetable oil-based epoxy resins, and mixtures thereof. “Polyfunctional” as used herein in the phrase “polyfunctional vegetable oil-based epoxy resin” means the presence of two or more epoxide groups. Polyfunctional vegetable oil-based epoxy resins that may be used in the invention may be prepared in the manner disclosed in WO 2011/097484, the disclosure of which is incorporated by reference. For example, polyfunctional vegetable oil-based epoxy resins are prepared from the epoxidation of vegetable oil fatty acid esters of polyols having >4 hydroxyl groups/molecule.
  • Polyol esters of fatty acids containing four or more vegetable oil fatty acid moieties per molecule can be synthesized by the reaction of polyols with 4 or more hydroxyl groups per molecule with either a mixture of fatty acids or esters of fatty acids with a low molecular weight alcohol, as is known in the art.
  • the former method is direct esterification while the latter method is transesterification.
  • a catalyst may be used in the synthesis of these compounds. As shown in FIG.
  • sucrose as an exemplary polyol to be used in the invention, esterified with a vegetable oil fatty acid, epoxide groups may then be introduced by oxidation of the vinyl groups in the vegetable oil fatty acid to form epoxidized polyol esters of fatty acids (EPEFA's).
  • EPEFA's epoxidized polyol esters of fatty acids
  • the epoxidation may be carried out using reactions known in the art for the oxidation of vinyl groups with in situ epoxidation with peroxyacid being a preferred method.
  • Polyols having at least 4 hydroxyl groups per molecule suitable for the process include, but are not limited to, pentaerythritol, di-trimethylolpropane, di-pentaerythritol, tri-pentaerythritol, sucrose, glucose, mannose, fructose, galactose, raffinose, and the like.
  • Polymeric polyols can also be used including, for example, copolymers of styrene and allyl alcohol, hyperbranched polyols such as polyglycidol and poly(dimethylpropionic acid), and the like. Exemplary polyols are shown below in Scheme 3 with the number of hydroxyl groups indicated by (f).
  • sucrose to glycerol there are a number of advantages for the use of a polyol having more than 4 hydroxyl groups/molecule including, but not limited to, a higher number of fatty acids/molecule; a higher number of unsaturations/molecule; when epoxidized, a higher number of oxiranes/molecule; and when crosslinked in a coating, higher crosslink density.
  • the degree of esterification may be varied.
  • the polyol may be fully esterified, where substantially all of the hydroxyl groups have been esterified with the fatty acid, or it may be partially esterified, where only a fraction of the available hydroxyl groups have been esterified. It is understood in the art that some residual hydroxyl groups may remain even when full esterification is desired. In some applications, residual hydroxyl groups may provide benefits to the resin.
  • the degree of epoxidation may be varied from substantially all to a fraction of the available double bonds. The variation in the degree of esterification and/or epoxidation permits one of ordinary skill to select the amount of reactivity in the resin, both for the epoxidized resins and their derivatives.
  • the hydroxyl groups on the polyols can be either completely reacted or only partially reacted with fatty acid moieties.
  • Any ethylenically unsaturated fatty acid may be used to prepare a polyol ester of fatty acids to be used in the invention, with polyethylenically unsaturated fatty acids, those with more than one double bond in the fatty acid chain, being preferred.
  • the Omega 3, Omega 6, and Omega 9 fatty acids, where the double bonds are interrupted by methylene groups, and the seed and vegetable oils containing them may be used to prepare polyol ester of fatty acids to be used in the invention. Mixtures of fatty acids and of vegetable or seed oils, plant oils, may be used in the invention.
  • the plant oils contain mixtures of fatty acids with ethylenically unsaturated and saturated fatty acids possibly present depending on the type of oil.
  • oils which may be used in the invention include, but are not limited to, corn oil, castor oil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil, and mixtures thereof.
  • the polyol fatty acid ester may be prepared by direct esterification of the polyol or by transesterification as is known in the art.
  • the double bonds on the fatty acid moieties may be converted into epoxy groups using known oxidation chemistry yielding polyfunctional epoxy resins (EPEFA's)—epoxidized polyol esters of fatty acids.
  • EPEFA's polyfunctional epoxy resins
  • sucrose esters of ethylenically unsaturated vegetable oil fatty acids results in unique bio-based resins having a high concentration of epoxy groups.
  • functionalities of 8 to 15 epoxide groups per molecule may be achieved, depending on the composition of the fatty acid used and the degree of substitution of the fatty acids on the sucrose moiety. This is substantially higher than what can be achieved through epoxidation of triglycerides which range from about 4 for epoxidized soybean oil up to 6 for epoxidized linseed oil.
  • the polyfunctional vegetable oil-based epoxidized resin is selected from epoxidized sucrose soyate (ESS).
  • ESS epoxidized sucrose soyate
  • fatty acids from soybean oil can be used to form esters with sucrose.
  • Sucrose soyate (SS) has many positive properties that make it an ideal starting point for bio-based coatings, including that it is polyfunctional, has low viscosity (300-400 cP) with 100% solids, is 100% bio-based, and is commercially available.
  • Sucrose, soybean oil, and sucrose soyate have the following structures:
  • epoxidized sucrose soyate In contrast to SS, epoxidized sucrose soyate (ESS) is more versatile. Many types of coatings can be formed from ESS. Also, ESS has many beneficial properties, including 12 epoxy groups per molecule (epoxy equivalent weight of 270 g eq ⁇ 1 ), low viscosity (5,000 cP), 100% bio-based, easily synthesized, and is a clear and colorless resin. ESS can be synthesized in the manner disclosed in Pan et al., Green Chemistry 13:965-975 (2011), the disclosure of which is incorporated herein by reference. See also Scheme 4 below.
  • the curable coating compositions comprising the vinyl-blocked bio-based polyfunctional carboxylic acids and the polyfunctional vegetable oil-based epoxidized resins can be prepared by a variety of methods. In one embodiment, this method comprises combining the vinyl-blocked bio-based polyfunctional carboxylic acids described above with the polyfunctional vegetable oil-based epoxidized resins to make curable coating compositions of the invention.
  • the curable coating compositions can be prepared by combining the vinyl-blocked bio-based polyfunctional carboxylic acids, described above, and the polyfunctional vegetable oil-based epoxidized resins in the presence of at least one optional solvent, such as t-butyl acetate (TBA), methyl n-amyl ketone (MAK), ethyl 3-ethoxyproprionate (EEP), and at least one optional catalyst, such as dibutyltindilaurate (DBTDL).
  • TSA t-butyl acetate
  • MAK methyl n-amyl ketone
  • EEP ethyl 3-ethoxyproprionate
  • DBTDL dibutyltindilaurate
  • a stoichiometric equivalent amount of epoxide and blocked acid groups may be used for the synthesis of the curable coating compositions of the invention.
  • the ratio of epoxy equivalents in the polyfunctional vegetable oil-based epoxidized resin to carboxylic equivalents in the vinyl-blocked bio-based polyfunctional carboxylic acids can be varied in order to vary the crosslink density and the properties of the curable coating composition.
  • the invention also relates to the use of a curable coating composition which may be coated onto a substrate and cured.
  • the substrate can be any common substrate such as paper, polyester films such as polyethylene and polypropylene, metals such as aluminum and steel, glass, urethane elastomers, primed (painted) substrates, and the like.
  • the invention also provides methods for coating such substrates by applying the curable coating composition to the substrate.
  • the coating may be applied by methods know in the art such as drawdown, conventional air-atomized spray, airless spray, roller, brush.
  • the curable coating composition of the invention may be cured thermally. Upon curing at elevated temperature, thermoset coating compositions of the invention have excellent hardness, solvent resistance, adhesion, and flexibility.
  • the invention relates to an article of manufacture comprising a thermoset coating composition of the invention.
  • a curable coating composition according to the invention may comprise a pigment (organic or inorganic) and/or other additives and fillers known in the art.
  • a curable coating composition of the invention may further contain coating additives.
  • coating additives include, but are not limited to, one or more leveling, rheology, and flow control agents such as silicones, fluorocarbons or cellulosics; extenders; reactive coalescing aids such as those described in U.S. Pat. No.
  • plasticizers plasticizers; flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; colorants; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti-flooding and anti-floating agents; biocides, fungicides and mildewcides; corrosion inhibitors; thickening agents; or coalescing agents.
  • UV absorbers ultraviolet (UV) absorbers
  • UV light stabilizers tinting pigments
  • colorants defoaming and antifoaming agents
  • defoaming and antifoaming agents anti-settling, anti-sag and bodying agents
  • anti-skinning agents anti-flooding and anti-floating agents
  • biocides, fungicides and mildewcides corrosion inhibitors
  • thickening agents or coalescing agents.
  • flatting agents include, but are not limited to, synthetic silica, available from the Davison Chemical Division of W. R. Grace & Company as SYLOID®; polypropylene, available from Hercules Inc., as HERCOFLAT®; synthetic silicate, available from J. M. Huber Corporation, as ZEOLEX®.
  • viscosity, suspension, and flow control agents examples include, but are not limited to, polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkylene amine salts of an unsaturated fatty acid, all available from BYK Chemie U.S.A. as ANTI TERRA®. Further examples include, but are not limited to, polysiloxane copolymers, polyacrylate solution, cellulose esters, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide wax, polyolefin wax, hydroxypropyl methyl cellulose, polyethylene oxide, and the like.
  • Solvents may also be added to the curable coating compositions in order to reduce the viscosity.
  • Hydrocarbon, ester, ketone, ether, ether-ester, alcohol, or ether-alcohol type solvents may be used individually or in mixtures.
  • solvents can include, but are not limited to benzene, toluene, xylene, aromatic 100, aromatic 150, acetone, methylethyl ketone, methyl amyl ketone, butyl acetate, t-butyl acetate, tetrahydrofuran, diethyl ether, ethylethoxy propionate, isopropanol, butanol, butoxyethanol, and so on.
  • Example 1 H NMR data for propyl vinyl ether blocked azelaic acid (CDCl 3 , ⁇ , ppm): 0.81 (triplet, 6H, CH 3 ), 1.234 (singlet, 6H, O2C—CH2-CH2-CH 2 -CH 2 —CH 2 —CH2-CH2-CO2), 1.274 and 1.287 (singlet, 6H, O—CH(CH 3 )—O), 1.49 (multiplet, 8H, O2C—CH2-CH 2 and O—CH2-CH 2 —CH3), 2.21 (triplet, 4H, O2C—CH 2 ), 3.49 (quartet, 4H, O—CH 2 —CH2-CH3), 5.82 and 5.83 (quartet, 2H, O—CH(CH3)-O).
  • a small amount of single blocked molecules is present, as evident by some peak splitting and a small carboxylic acid peak present in the NMR.
  • Coating formulation method Coating formulations were made using a 1:1 mole ratio of epoxide to acid and 5% 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) by total weight.
  • DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene
  • EVE-AzA ethyl vinyl ether blocked azelaic acid
  • DBU (0.41 g, 0.0027 equivalents
  • a Gardco wet film applicator was used to apply a 4 mil thick layer of each formulation onto Bonderite 1000 treated steel and glass substrates. The substrates were then placed in an oven preheated to 170° C., where they were allowed to cure for 4 hours.
  • EVE-succinic acid EVE-SuA
  • EVE-glutaric acid EVE-GlA
  • EVE-adipic acid EVE-AdA
  • EVE-PiA EVE-pimelic acid
  • EVE-suberic acid EVE-SbA
  • EVE-azelaic acid EVE-AzA
  • EVE-sebacic acid EVE-SeA
  • Azelaic acid, succinic acid, and FDCA have superior solvent resistance, adhesion, and flexibility. Higher hardness of azelaic acid compared to the others suggests a higher crosslinked system is produced. The poor properties of citric acid based coatings suggest a lower inter-ESS crosslinked network is formed.

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