Patent Description:
Bisphenol-A (BPA) is a cross-linker for synthetic resins used as coatings, and began to replace resins based on natural oils (oleoresins) in the mid-<NUM>. BPA-based coatings have high corrosion resistance compared to oleoresins and are widely used, e.g., in food packaging. In the United States, over <NUM> billion beer, beverage, and food cans are coated with half a million metric tons of BPA-containing epoxy resins each year, and the global market is more than twice that large. Although there are currently no U. Food and Drug Administration (FDA) or other U. regulatory restrictions on the use of BPA-based resins in most food containers, BPA-related health hazards have been recognized by regulators, policymakers, and consumers. Controversy over health implications has caused concern over the use of BPA in food packaging. BPA is banned from use in applications such as infant feeding plastic bottles, and California recently listed BPA as a hazardous material.

There is much interest in cost-effective and functional replacements for BPA-based epoxy resins in can coatings that may contact food. Desirable characteristics for alternative coatings are numerous and challenging, including coating integrity (adhesion, strength, flexibility, pH/corrosion resistance, and the like) under sterilization, handling, and storage, no effect on food taste, compliance with FDA guidelines on direct food contact use, cost-effective, compatible with established manufacturing processes, and the like.

Many attempts to develop a viable solution have been made. Natural oils may be functionalized with hydroxyl or carboxyl groups and may be converted to polyesters and polyurethanes for use in coatings, inks, adhesives, foams, and the like. However, oleoresins often exhibit poor corrosion resistance. For example, it is believed that acidic tomato juice readily damages oleoresin coatings. Chemistries such as vinylation, acrylation, polyesterifcation, polyolefinination, and use of a variety of cross-linkers have been explored, but have not been successful because of failure in one or more desirable characteristics, such as flexibility, adhesion, application method, cure speed, corrosion resistance, or hydrolysis under low pH.

Some epoxy-based resin alternatives have been investigated using alternative cross-linkers, such as diglycidyl ethers of n-alkyl diphenolates, isosorbide, and bisguaiacol. However, these alternatives are costly and have been reported to suffer from problems such as estrogen receptor activity, epichlorohydrin toxicity, and poor hydrolytic stability. <CIT> discloses a curable composition for electrical applications, the curable composition comprising a compound having at least two alpha, beta-unsaturated groups and an equivalent weight of less than <NUM>/mol, a catalyst capable of initiating a Michael reaction and a Michael donor having an equivalent weight of less than <NUM>/mol, and a package for using this composition in electical splices. <NPL>, is directed to acetoacetylated polymers and resins capable of undergoing a variety of crosslinking reactions. <NPL> is directed to reactions of various nucleophiles with tert-butyl acetoacetate. <CIT> discloses a process whereby selected polyols are reacted with a tertiary-butyl acetoacetate at a temperate of <NUM>. <CIT> discloses a process, which a reaction of a polyetherpolyol with diketene (<NUM>-methyleneoxetan-<NUM>-one). In <CIT> is directed to a one-part curable composition comprising: at least one Michael donor; at least one Michael acceptor; and one or more encapsulated catalysts, the one or more encapsulated catalysts prepared in capsules having an average particle size of from <NUM> to <NUM> to a portion up to all of the one-part curable adhesive composition. Further, <CIT> also discloses articles prepared from the one-part composition selected from an adhesive, a sealant, a coating, an elastomer and a foam and a method for preparing the one-part curable composition as well as a method for bonding at least two or more substrates using the one-part curable composition.

The present application appreciates that developing corrosion resistant resins, e.g., for replacing BPA-cross-linked resins in can coatings, may be a challenging endeavor.

The present invention provides a method for preparing a AAG composition according to claim <NUM> and the preferred aspects are set out in the dependent claims.

The present invention provides a method for preparing a polyol-AAG composition according to claim <NUM> and the preferred aspects are set out in the dependent claims.

The present invention provides a poly(AAG)-composition according to claim <NUM> and the preferred aspects are set out in the dependent claims.

The accompanying figures, which are incorporated in and constitute a part of the specification, illustrate example methods and compositions and are used merely to illustrate example aspects.

As used herein, the term "AAG" means an acetoacetyl group. For example, triglyceride-methyl-AAG and polyol-methyl-AAG may refer to, respectively:
<CHM>.

As used herein, a "β-ketoacid" means a group including a carboxylic acid separated from a carbonyl by one intervening carbon atom, e.g., -C(=O)CH<NUM>CO<NUM>H. Likewise, as used herein, a "β-ketoester" means a group including a carboxylic acid ester separated from a carbonyl by one intervening carbon atom, e.g., -C(=O)CH<NUM>CO<NUM>R.

As used herein, an epoxidized triglyceride means a triester of glycerol, CH(CH<NUM>OH)<NUM>, with at least one epoxide group in or on at least one fatty acid side-chain.

In various aspects, a method for preparing a AAG composition is provided. The method includes providing a poly-functional compound including two or more functional groups. Each functional group independently being hydroxy, amino, or alkenyl. The method includes reacting the poly-functional compound under conditions effective to form the AAG composition by one or more of the following. For example, the method may include reacting the poly-functional compound under conditions effective to form the AAG composition by contacting the poly-functional compound with a ketene compound, wherein the poly-functional compound includes at least one hydroxy group. The method may include reacting the poly-functional compound under conditions effective to form the AAG composition by contacting the poly-functional compound with a β-ketoester, wherein the poly-functional compound includes at least one hydroxy or amino group. The method may include reacting the poly-functional compound under conditions effective to form the AAG composition by contacting the poly-functional compound with a peroxo reagent and one or more of: a β- ketoimide, a β-ketoester, and a β-ketoacid, wherein the poly-functional compound includes at least one alkenyl group. The method may include reacting the poly-functional compound under conditions effective to form the AAG composition by contacting the poly-functional compound with a mercaptoalkanol in the presence of an initiator effective to form a mercaptoalkanol-substituted compound. The poly-functional compound may include at least one alkenyl group. The method may include further reacting the mercaptoalkanol-substituted compound with one or more of: the β-ketoester and the β-ketoacid effective to form the AAG composition.

In some aspects, the poly-functional compound may be a natural oil derived from any organism, for example, plants, mammals, reptiles, fish, mollusks, crustaceans, fungi, algae, diatoms, and the like. In some aspects, the poly-functional compound excludes triglycerides derived from oil of one or more of: legume seeds, non-legume seeds, and terrestrial animal fat. In some aspects, the poly-functional compound may exclude triglyceride-derived oils from any source.

In several aspects, the method may be conducted substantially in the absence of solvent.

The method may include contacting the poly-functional compound with the β- ketoester to form a reaction mixture. The poly-functional compound may include one or more of: the hydroxyl group; and the amino group. The method may include allowing the poly- functional compound and the β-ketoester to react substantially in the absence of solvent effective to form the AAG composition.

For example, the polyfunctional compound may be a polyol and the corresponding AAG composition may be a polyol-AAG composition. The polyfunctional compound may be a polyamine and the corresponding AAG composition may be a polyamine-AAG composition. The polyfunctional compound may be a polyol-polyamine and the corresponding AAG composition may be a polyol-polyamine-AAG composition.

In some aspects, the method may include removing an alcohol byproduct from by one or more of: distillation, reduced pressure, and contact with a molecular sieve. The method may include reacting the poly-functional compound, e.g., with the β-ketoester, under an inert atmosphere. The method may include allowing the poly-functional compound to react, e.g., with the β-ketoester, at a temperature in °C of at least about one or more of: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>, or a range between any two of the preceding values, for example, between about <NUM> and about <NUM>. The method may include allowing the poly-functional compound to react, e.g., with the β-ketoester, for a period of time in hours of at least about one or more of: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>, or a range between any two of the preceding values, for example, between about <NUM> and about <NUM>.

In several aspects, at least a portion of the poly-functional compound may be a polyol derived from a pyrolyzed bio-oil. The pyrolyzed bio-oil is derived from pyrolysis of one or more of: hardwood, softwood, grass, reeds, bagasse, sugarcane, corn stover, and sorghum. At least a portion of the poly-functional compound may be a polyol derived from alkoxylated pyrolyzed bio-oil. At least a portion of the poly-functional compound may include one or more of: a phenol, a cresol, a guaiacol, and a syringol. At least a portion of the poly- functional compound may include one or more of: pyrogallol, catechol, resorcinol, hydroquinone, lignin, and diphenolic acid. In some aspects, at least a portion of the poly- functional may include an unsaturated non-triglyceride oil derived from a marine organism, a mammal, and an insect. The marine organism may include, for example one or more of: algae, water hyacinth, bacteria, and diatoms. The poly-functional compound may include lignin or derivatives thereof. The poly-functional compound may be derived from a petroleum source. For example the poly-functional compound may include a petroleum derived polyol, a petroleum-derived polyamine, a petroleum-derived polyalkene, or a composite or combination thereof. In some aspects, the poly-functional compound may be derived from a natural source, such as a natural oil as described herein, e.g., in all aspects, a natural oil excluding a triglyceride. In several aspects, the poly-functional compound may exclude compounds derived from a petroleum source.

The poly-functional compound may be a polyol and the AAG may be a polyol-AAG. The poly-functional compound may include a C<NUM>-C<NUM> compound substituted with at least one hydroxyl group. At least a portion of the poly-functional compound may be a polyol derived from a hydroxyl-containing fatty acid ester.

In some aspects, at least a portion of the poly-functional compound may be a polyol derived from one or more of: a hydroxyl- containing fatty acid ester.

In various aspects, the ketene compound may include one or more of: <NUM>-methyleneoxetan-<NUM>-one, <NUM>-ethylidene-<NUM>-methyloxetan-<NUM>-one, and <NUM>-benzylidene-<NUM>-phenyloxetane-<NUM>-one. The ketene compound may be derived from one or more of: an α-diazo ketone and an α-halo acyl halide. The ketene compound may be optionally substituted with one or more of: C<NUM>-C<NUM> alkyl and C<NUM>-C<NUM> aryl.

In various aspects, the β-ketoester may be represented by Formula XIV:
<CHM>.

R" may be C<NUM>-C<NUM> alkyl or C<NUM>-C<NUM> aryl. R<NUM> may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl, optionally substituted with -OH or -NH<NUM>. R<NUM> may be H, C<NUM>-C<NUM> alkyl, or C<NUM>-C<NUM> aryl.

In several aspects, the peroxo reagent may include one or more of: hydrogen peroxide, manganese dioxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, and the like.

In some aspects, the β-ketoimide may be represented by Formula VI:
<CHM>.

R<NUM> may be optionally hydroxylated C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl; and R<NUM> may be C<NUM>-C<NUM> alkyl or C<NUM> aryl optionally substituted with one or more of: nitro, carbonyl, haloalkyl, and halogen.

In various aspects, the β-ketoimide may be represented by Formula VII:
<CHM>.

R<NUM> may be optionally hydroxylated C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl; and R<NUM> may be a C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> heteroaryl, or C<NUM> aryl optionally substituted with one or more of: nitro, carbonyl, halogen, and haloalkyl.

In some aspects, the β-ketoimide may be represented by Formula VIII:
<CHM>.

In several aspects, the β-ketoimide may be represented by Formula VIV:
<CHM>.

R<NUM> may be optionally hydroxylated C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl.

In various aspects, the β-ketoacid may be represented by Formula III:
<CHM>.

R<NUM> may be optionally hydroxylated C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl; and R<NUM> may be H, or optionally hydroxylated C<NUM>-C<NUM> alkyl or C<NUM>-C<NUM> aryl.

In some aspects, the β-ketoacid may include one or more of: <NUM>-oxobutanoic acid, <NUM>-oxopentanoic acid, <NUM>-oxohexanoic acid, <NUM>-oxo-<NUM>-phenylpropanoic acid, and the like.

In some examples, the mercaptoalkanol may be, e.g., a C<NUM>-C<NUM> mercaptoalkanol, for example, the mercaptoalkanol may include one or more of: thioglycerol and mercaptoethanol.

In various aspects, a method for preparing a polyol-AAG composition is provided. The method may include contacting the poly-functional compound in the form of an unsaturated polyol with the peroxo reagent and the β-ketoimide to form a reaction mixture. The method may include allowing the unsaturated polyol, the peroxo reagent, and the β-ketoimide to react effective to form the AAG composition as a polyol-AAG composition.

In some aspects, the method may include pre-mixing the peroxo reagent and the β-ketoimide prior to contacting the unsaturated polyol. The method may include pre-mixing the peroxo reagent and the β-ketoimide at a temperature less than about <NUM>. The method may include pre-mixing the unsaturated polyol and the β-ketoimide prior to contacting the peroxo reagent. The method may include allowing the unsaturated polyol, the peroxo reagent, and the β-ketoimide to react at a temperature in °C of at least about one or more of: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>, or a range between any two of the preceding values, for example, between about <NUM> and about <NUM>. The method may include allowing the unsaturated polyol, the peroxo reagent, and the β-ketoimide to react for a period of time in minutes of at least about one or more of: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>,<NUM>, <NUM>, <NUM>, and <NUM>, or a range between any two of the preceding values, for example, between about <NUM> and about <NUM>.

In several aspects, the method may include, after forming the polyol-AAG composition, contacting the reaction mixture with a reducing agent effective to consume at least a portion of remaining peroxo reagent. Suitable reducing reagents may include, for example, sodium sulfite, sodium thiosulfate, and the like. The method may include, after forming the polyol-AAG composition, purifying the polyol-AAG composition by one or more of: contacting the reaction mixture with one of: water, aqueous brine, and aqueous mild acid; separating an aqueous layer from the reaction mixture; contacting the reaction mixture to a chromatography solid phase; and eluting the polyol-AAG composition from the chromatography solid phase to provide the polyol-AAG composition in at least partly purified form.

In various aspects, at least a portion of the unsaturated polyol may be derived from pyrolysis bio-oil. The pyrolysis bio-oil is derived from pyrolysis of one or more of: hardwood, softwood, grass, reeds, bagasse, corn stover, sugarcane, and sorghum.

R<NUM> may be optionally hydroxylated: C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl. R<NUM> may be C<NUM>-C<NUM> alkyl or C<NUM> aryl optionally substituted with one or more of: nitro, carbonyl, haloalkyl, and halogen. The β-ketoimide may be represented by Formula VII:
<CHM>.

R<NUM> may be optionally hydroxylated C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl. R<NUM> may be a C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> heteroaryl, or C<NUM> aryl optionally substituted with one or more of: nitro, carbonyl, halogen, and haloalkyl. The β-ketoimide may be represented by Formula VIII:
<CHM>.

The β-ketoimide may be represented by Formula VIV:
<CHM>.

R<NUM> may be optionally hydroxylated: C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl.

In various aspects of the method, the polyol-AAG composition may include: a polyol unit; at least one hydroxyl group bonded to an alkyl chain of the polyol unit; and a β- ketoester group bonded to a carbon atom of the alkyl chain that may be alpha to a carbon atom bearing the hydroxyl group. The polyol-AAG composition may include a hydroxyl value greater than the unsaturated polyol.

In various aspects, a method for preparing a poly(AAG)-composition is provided. The method includes contacting an AAG composition, e.g., any AAG composition described herein, with a cross-linking compound to form a reaction mixture. The method includes allowing the AAG composition and the cross-linking compound to react effective to form the poly(AAG) composition. In some aspects, the AAG composition is any AAG composition described herein. In some aspects, the AAG composition is any AAG composition described herein, provided that the AAG composition is not a triglyceride-AAG composition.

The method includes contacting the AAG composition with the cross-linking compound to form the reaction mixture, the AAG composition being, for example, a AAG-β- ketoester composition. The method includes allowing the AAG composition and the cross- linking compound to react effective to form the AAG composition as, for example, a poly(AAG)-β-ketoester composition.

In some aspects, the AAG composition may be derived from pyrolyzed bio-oil. The pyrolyzed bio-oil is derived from pyrolysis of one or more of: hardwood, softwood, grass, reeds, bagasse, corn stover, sugarcane, and sorghum. The AAG composition may be derived from one or more of: a phenol, a cresol, a guaiacol, and a syringol. The AAG composition may be derived from an alkoxylated pyrolyzed bio-oil. The AAG composition may be derived from a hydroxyl-containing fatty acid ester.

In various aspects, the method may include contacting the AAG composition with the cross-linking compound in the presence of a surfactant. The method may include allowing the AAG composition and the cross-linking compound to react at a temperature in °C of at least about one or more of: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>, or a range between any two of the preceding values, for example, between about <NUM> and about <NUM>. The method may include allowing the AAG composition and the cross-linking compound to react for a period of time in minutes of at least about one or more of: <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>, or a range between any two of the preceding values, for example, between about <NUM> and about <NUM>. The method may include contacting the AAG composition with the cross-linking compound in the presence of one or more of: an inert atmosphere; water; a blowing agent; and a base. The base may include one or more of: magnesium hydroxide, zirconium hydroxide, aluminum hydroxide, and the like.

In some aspects, the method may include applying the reaction mixture to a surface. The method may include heating the reaction mixture and the surface effective to form the poly(AAG)-composition, e.g., the poly(AAG)-β-ketoester composition, as a cross-linked coating on the surface. The method may include contacting the AAG composition and the cross- linking compound to form the reaction mixture at about <NUM> for less than <NUM> minutes. The method may include applying the reaction mixture onto the surface. The method may include heating the reaction mixture and the surface at a temperature of about <NUM> for <NUM> minutes effective to form the poly(AAG)-composition, e.g., the poly(AAG)-β-ketoester composition, as a cross-linked coating on the surface. The surface may be a metal surface. The surface may be an interior surface of a food or beverage container. The surface may include a foil or metal packaging material. The surface may include one or more of: low carbon steel, aluminum, anodized aluminum, silver, and alloys or mixtures thereof. The surface may be one or more of an interior surface or an exterior surface of a medical device. The poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, may form a cross-linked coating on one or more of the interior surface and the exterior surface of the medical device. Further, silver may be included by one or more of: the interior surface, the exterior surface, and the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, forming the cross-linked coating. The silver may be in ionic or oxide form.

In several aspects, the method may include contacting the AAG composition and the cross-linking compound at about <NUM>. The method may include pouring the reaction mixture into a mold, the mold coated in a mold release agent. The cross-linking compound may include one or more of: a diisocyanate, a triisocyanate, and a tetraisocyanate. The cross-linking compound may include a polymer including more than one isocyanate group. The cross-linking compound may include one or more isocyanate cross-linking reagents, e.g.: Luprinate M20, PMDI, Desmodur DA-L, Desmodur DN, Bayhydur <NUM>, VESTANAT® T, VESTANAT® HB, VESTANAT® HT, VESTANAT® B, VESTANAT® DS, and like isocyanate cross-linking reagents.

In various aspects of the method, the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, may include a polyol-polyamido-β-ketoester. The polyol- polyamido-β-ketoester may include: a polyol unit; a β-ketoester group located on an alkyl chain of the polyol unit; and an amide group bonded to a carbon of the alkyl chain that may be alpha to a ketone of the β-ketoester.

In some aspects, the cross-linking compound may include one or more of: a hemiaminal, a hemiaminal ether, a hemiaminal thioether an aromatic hemiaminal, an aromatic hemiaminal ether, an aromatic hemiaminal thioether, a polymer including a hemiaminal, a polymer including a hemiaminal ether, and a polymer including a hemiaminal thioether. The cross-linking agent may include one or more hemiaminal cross-linking reagents (e.g., the CYMEL™ series from Allnex USA, Inc. , Alpharetta, GA), such as CYMEL™ <NUM>, CYMEL® <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM> LF, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>,
CYMEL™ XW <NUM>, CYMEL™ MM-<NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, CYMEL™ <NUM>, and the like. The method may include contacting the AAG composition with the cross-linking compound in the presence of an acid catalyst. The acid catalyst may include one or more of: p-toluene sulfonic acid; methane sulfonic acid; a C<NUM>-C<NUM> carboxylic acid; a C<NUM>-C<NUM> halocarboxylic acid, e.g., trifluoromethane sulfonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and the like; a polymeric sulfonic acid resin; and the like. The method may include contacting the AAG composition with the cross-linking compound in the presence of a Lewis acid catalyst, e.g., boron trifluoride. The method may include removing an alcohol byproduct from the reaction mixture by one or more of: distillation, reduced pressure, and contact with a molecular sieve.

In several aspects of the method, the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, may include a polyol polyamino-β-ketoester. The polyol polyamino-β-ketoester may include: a polyol unit; a β-ketoester group bonded to an alkyl chain of the polyol unit; and an amine group bonded to a carbon beta to a ketone of the β-ketoester.

In many aspects, the crosslinking compound may include a polyamine. For example, the polyamine may include a diamine, triamine, and the like. The polyamine may be aliphatic or cycloaliphatic. The polyamine may be aromatic, aryl, or aralkyl. The polyamine may include a mixture of aliphatic, cycloaliphatic, and aromatic polyamines. For example, the polyamine may include any of the ANACAMINE® series (Air Products, Allentown, Pennsylvania), e.g., ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE® <NUM>. ANACAMINE® <NUM>, ANACAMINE® 1617LV, ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE®<NUM>, ANACAMINE® <NUM>, ANACAMINE®
<NUM>, ANACAMINE® 1922A, ANACAMINE®2014FG, ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE® <NUM>, ANACAMINE® <NUM>, and the like. The polyamine crosslinking agent may crosslink the AAG composition via imine or enamine linkages.

In various aspects, the AAG composition may include a polyol polyeneamine- β-ketoester. The polyol polyeneamine-β-ketoester may include, for example, a polyol unit; a β-ketoester group bonded to an alkyl chain of the polyol unit; and an enamine bonded to a keto-carbon of the β-ketoester and effective to cross-link more than one polyol unit.

The cross-linking compound may include one or more of: a dihydrazine and a dihydrazide. The cross-linking compound may include one or more of: adipic dihyrazide, sebacic dihydrazide, oxalyl dihydrazide, succinic dihydrazide, maleic dihydrazide, malic dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, and the like.

In several aspects of the method, the poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoester composition, may include a polyol polyhydrazone-β-ketoester. The polyol polyhydrazone-β-ketoester may include: a polyol unit; a β-ketoester group bonded to an alkyl chain of the polyol unit; and a hydrazone bonded to a keto-carbon of the β-ketoester and effective to cross-link more than one polyol unit.

In several aspects of the method, the cross-linking compound may include at least two diazonium groups. The diazonium groups may be effective to cross-link two or more AAG compounds of the AAG composition to form azo cross-links. The cross-linking compound may include an aldehyde. The aldehyde may be effective to cross-link the β-ketoesters of two or more AAG compounds of the AAG composition through a methylene cross-link. For example, the aldehyde may be formaldehyde. The cross-linking compound may include at least two α,β-unsaturated carbonyls. The α,β-unsaturated carbonyls may be effective to cross-link two or more polyol-AAG compounds of the AAG composition. The cross-linking compound may be represented by Formula XIV:
<CHM>.

R may be CH<NUM>CH<NUM>, CH<NUM>(CH<NUM>)CH, (CH<NUM>CH<NUM>OCH<NUM>CH<NUM>)n, or (CH<NUM>(CH<NUM>)CHOCH<NUM>(CH<NUM>)CH)n, and n may be an integer from <NUM> to <NUM>.

In various aspects, a poly(AAG)-composition is provided. The poly(AAG)- composition may include a polyfunctional moiety derived from a polyol unit, a polyamine unit, a polyalkene unit, or a combination or composite thereof. The poly(AAG)-composition includes a β-ketoester group bonded to an alkyl chain of the polyfunctional moiety. The poly(AAG)-composition includes one or more of the following. The poly(AAG)- composition may include an amide group bonded to a carbon of the alkyl chain that is alpha to a ketone of the β-ketoester such that the poly(AAG)-composition includes a poly(AAG)amido-β-ketoester composition. The poly(AAG)-composition may include an amine group bonded to a carbon on the alkyl chain that is beta to a ketone of the β-ketoester such that the poly(AAG)- composition comprises a poly(AAG)amino-β-ketoester composition. The poly(AAG)- composition may include a hydrazone group bonded to a keto-carbon of the β-ketoester group such that the poly(AAG)-composition comprises a poly(AAG)hydrazone-β-ketoester composition.

The poly(AAG)-composition may be prepared according to any method of preparing the poly(AAG)-composition described herein. The poly(AAG)-composition may be prepared from any AAG-composition as described herein. For example, the poly(AAG)-composition may be prepared from a AAG-composition derived from the poly-functional compound including two or more functional groups. Each functional group independently being hydroxy, amino, or alkenyl. For example, the poly(AAG)-composition may have structural features corresponding to preparation of the AAG-composition by contacting the poly-functional compound with the ketene compound, wherein the poly-functional compound includes at least one hydroxy group. The poly(AAG)-composition may have structural features corresponding to preparation of the AAG-composition by contacting the poly-functional compound with the β-ketoester, wherein the poly-functional compound includes at least one hydroxy or amino group. The poly(AAG)-composition may have structural features corresponding to preparation of the AAG-composition by contacting the poly-functional compound with a peroxo reagent and one or more of: a β-ketoimide, a β-ketoester, and a β-ketoacid, wherein the poly-functional compound includes at least one alkenyl group. The poly(AAG)-composition may have structural features corresponding to preparation of the AAG-composition by contacting the poly-functional compound with a mercaptoalkanol in the presence of an initiator effective to form a mercaptoalkanol-substituted compound, wherein the poly-functional compound includes at least one alkenyl group; and further reacting the mercaptoalkanol-substituted compound with one or more of: the β-ketoester and the β-ketoacid.

In some aspects, the poly-functional compound may be a natural oil derived from any organism, for example, plants, mammals, reptiles, fish, mollusks, crustaceans, fungi, algae, diatoms, and the like. In all aspects, the poly-functional compound excludes triglycerides derived from oil of one or more of: legume seeds, non-legume seeds, and terrestrial animal fat. In all aspects, the poly-functional compound excludes triglyceride-derived oils from any source. In some aspects, the poly(AAG)-composition may be prepared from a AAG- composition excluding the triglyceride AAG composition.

In some aspects, the poly(AAG) composition, e.g., as a poly(AAG)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, may include: a polyol unit; a β-ketoester group bonded to an alkyl chain of the polyol unit. The poly(AAG)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, may include an amide group bonded to a carbon of the alkyl chain that may be alpha to a ketone of the β-ketoester such that the poly(AAG)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, includes a polyol polyamido-β-ketoester composition. The poly(polyol)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, may include an amine group bonded to a carbon on the alkyl chain that may be beta to a ketone of the β-ketoester such that the poly(AAG)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, includes a polyol polyamino-β-ketoester composition. The poly(AAG)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, may include a hydrazone group bonded to a keto-carbon of the β-ketoester group such that the poly(AAG)-β-ketoester composition, e. g, poly(polyol)-β-ketoester composition, includes a polyol polyhydrazone-β-ketoester composition.

In some aspects, the poly(AAG)-composition, e.g., as the poly(polyol)-β- ketoester composition, may be in the form of one or more of: a cross-linked coating and a cross- linked foam. The poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoester composition, may be in the form of a cross-linked coating on a surface. The poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoester composition, may be in the form of a cross-linked coating on a metal surface. The poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoester composition, may be in the form of a cross-linked coating on an interior surface of a beverage or food container. The surface may include a foil or metal packaging material. The surface may include one or more of: low carbon steel, aluminum, anodized aluminum, silver, and alloys or mixtures thereof. The surface may be one or more of an interior surface or an exterior surface of a medical device. The poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoester composition, may form a cross-linked coating on one or more of the interior surface and the exterior surface of the medical device. Further, silver may be included by one or more of: the interior surface, the exterior surface, and the poly(AAG)-composition, e.g., as the poly(polyol)-β-ketoester composition, forming the cross-linked coating. The silver may be in ionic or oxide form.

In several aspects, the composition may include the polyol unit; the β-ketoester group bonded to an alkyl chain of the polyol unit; and the amide group bonded to the carbon of the alkyl chain alpha to the ketone of the β-ketoester such that the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, includes the polyol
polyamido-β-ketoester composition. The polyol polyamido-β-ketoester composition may include a compound represented by Formula XXV:
<CHM>
or
<CHM>.

R<NUM> may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl, optionally substituted with -OH or -NH<NUM>. R<NUM> may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> alkyl-C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> heteroaryl, or C<NUM>-C<NUM> alkyl-C<NUM>-C<NUM> heteroaryl. R<NUM> may be a polyol derived from one of: a pyrolyzed bio-oil.

In some aspects, the composition may include: the polyol unit; the β-ketoester group bonded to the alkyl chain of the polyol unit; and the amine group bonded to the carbon on the alkyl chain that beta to the ketone of the β-ketoester such that the poly(polyol)-β-ketoester composition includes the polyol polyamino-β-ketoester composition. The polyol polyamino-β-ketoester composition may include a compound represented by Formula XXVIII:
<CHM>.

R<NUM> may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl, optionally substituted with -OH or -NH<NUM>. R<NUM>' may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> alkyl-C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> heteroaryl, or C<NUM>-C<NUM> alkyl-C<NUM>-C<NUM> heteroaryl. R<NUM> may be a polyol derived from one of: a pyrolyzed bio-oil, a modified triglyceride, and a triglyceride from a marine organism. R<NUM>" may be: C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> aryl, CH<NUM>OH, CH<NUM>OCH<NUM>, CH<NUM>SH, CH<NUM>SCH<NUM>,
<CHM>.

In several aspects, the composition may include: the polyol unit; the β-ketoester group bonded to the alkyl chain of the polyol unit; and the hydrazone group bonded to the keto- carbon of the β-ketoester group such that the poly(polyol)-β-ketoester composition includes the polyol polyhydrazone-β-ketoester composition. The polyol polyhydrazone-β-ketoester composition may include a compound represented by Formula XXX:
<CHM>.

R<NUM> may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> aryl, or C<NUM>-C<NUM> heteroaryl, optionally substituted with -OH or -NH<NUM>. R<NUM>‴ may be C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> alkyl-C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> heteroaryl, or C<NUM>-C<NUM> alkyl-C<NUM>-C<NUM> heteroaryl. R<NUM> may be a polyol derived from one of: a pyrolyzed bio-oil, a modified triglyceride, and a triglyceride from a marine organism.

In various aspects, the poly(polyol)-β-ketoester composition may be a product formed by a process according to any method described herein for the poly(polyol)-β-ketoester composition.

An article may include a surface coated with a poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition,. The poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, may include any aspect of the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, described herein, and may be a product formed by a process according to any method described herein for the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition,. The article may be a beverage or food container and the poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, may form a coating on an interior surface of the beverage or food container. The surface may include a foil or metal packaging material. The surface may include one or more of: low carbon steel, aluminum, anodized aluminum, silver, and alloys or mixtures thereof. The surface may be one or more of an interior surface or an exterior surface of a medical device. The poly(AAG)-composition, e.g., as the poly(AAG)-β-ketoester composition, may form a cross-linked coating on one or more of the interior surface and the exterior surface of the medical device. Further, silver may be included by one or more of: the interior surface, the exterior surface, and the poly(AAG)-composition, e.g., as the poly(AAG)-β- ketoester composition, forming the cross-linked coating. The silver may be in ionic or oxide form.

The following examples illustrate the processes and compositions of described herein. The following examples are merely illustrative and should not be construed to limit the scope of the aspects described herein in any way.

Example 1A - Tetraacetoacetoxyethylenediamine (TAAED): A <NUM> <NUM>-neck round bottom flask was charged with ethylene diamine (<NUM>, <NUM> mmol) and t-butyl acetoacetate (<NUM>, <NUM> mmol) and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The solution was brought to <NUM> and stirred under argon. Byproduct t-butanol was collected in the trap. After <NUM>, the temperature was increased to <NUM> and an exotherm to <NUM> was observed. After <NUM>, t-butanol (<NUM>, <NUM> mmol, <NUM>%) was collected and the dark red, molten mixture was allowed to cool to room temperature. The resulting red solid was manually broken to yield an orange-red powder.

Example 1B - Tetraacetoacetoxyethylenediamine (TAAED): A <NUM> <NUM>-neck round bottom flask was charged with ethylene diamine (<NUM>, <NUM> mmol) and excess t-butyl acetoacetate (<NUM>, <NUM> mol) and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The solution was stirred at room temperature under argon for <NUM> and an exotherm to <NUM> was observed. The reaction mixture was heated to <NUM> and the clear solution became yellow. While ramping the temperature to <NUM>, byproduct t-butanol (<NUM>, <NUM> mmol) was collected in the trap. After <NUM> at <NUM>, t-butanol (<NUM>, <NUM> mmol, <NUM>%) was collected in the trap and the solution became dark red in color. The solution was allowed to cool to room temperature and excess starting materials were removed under reduced pressure. The product was analyzed by NMR and IR and was substantially the same as the product obtained in Example 1A.

Example 1C - Hexaacetoacetonoatemelamine (HAAM): A <NUM> flask was charged with melamine (<NUM>), t-butyl acetoacetate (<NUM>), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The solution was stirred and heated at <NUM> for <NUM>. Upon cooling, the solution became a hard, dark red solid. The product was obtained in greater than <NUM>% yield.

Reference Example 2A - Soy-AAG ("Soy-PK"): A <NUM> flask was charged with soy polyol (<NUM>) [Honeybee HB530, MCPU Polymer Engineering, LLC, Richmond, VA] and t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged with argon. The flask was fitted with a Dean- Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated to <NUM> and stirred for <NUM> which resulted in byproduct t-butanol (<NUM>%) collected in the trap. Fourier Transform Infrared (FTIR) spectra of the Soy-AAG product was obtained, as shown in <FIG>. The peak at <NUM>-<NUM> is characteristic of the acetoacetoate functional group. The Soy-AAG product is a solid and may be diluted with methyl ethyl ketone. The physical properties of Soy-AAG is illustrated in tabular form in <FIG>.

Reference Example 2B - Soy-AAG ("Soy-PK"): A <NUM> flask was charged with soy polyol (<NUM>) [Honeybee HB530, MCPU Polymer Engineering, LLC] and t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water- cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated to <NUM> and stirred for <NUM> which resulted in byproduct t-butanol (<NUM>, <NUM> mmol, <NUM>%) collected in the trap. The temperature was increased to <NUM> and the reaction was stirred for an additional <NUM>. Byproduct t-butanol (<NUM>%) was collected. Fourier Transform Infrared (FTIR) spectra of the product was obtained, as shown in <FIG>. The peak at <NUM>-<NUM> is characteristic of the acetoacetoate functional group. The Soy-AAG product is a solid and may be diluted with methyl ethyl ketone. The physical properties of Soy-AAG is illustrated in tabular form in <FIG>.

Example 2C - pentaerythritol-AAG: A <NUM> flask was charged with pentaerythritol (<NUM>, <NUM> mol) and t-butyl acetoacetate (<NUM>, <NUM> mol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated to <NUM> for <NUM>. The product was isolated without any further purification in <NUM>% yield.

Example 2D - sucrose-AAG: A <NUM> flask was charged with sucrose (<NUM>, <NUM> mmol) and t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated at <NUM> for <NUM>. After this time, the reflux ceased and the reaction temperature was increased to <NUM> for an additional <NUM>. Byproduct t-butanol (<NUM>, <NUM> mmol, <NUM>%) was collected.

Example 2E - <NUM>,<NUM>-BD-diAAG: A <NUM> flask was charged with <NUM>,<NUM>-butanediol (<NUM>, <NUM> mmol) and t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated at <NUM> for <NUM>. Byproduct t-butanol (<NUM>, <NUM> mmol, <NUM>%) was collected.

Reference Example 2F - glycerol-triAAG: A flask was charged with glycerol (<NUM>, <NUM> mmol) and t-butyl acetoacetate (<NUM>, <NUM> mol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated to <NUM>. After <NUM> t-butanol (<NUM>, <NUM> mol, <NUM>%) was collected in the trap. The temperature was increased to <NUM> and the reaction was allowed to stir for an additional <NUM>. Byproduct t-butanol (<NUM>, <NUM> mol, <NUM>%) was collected.

Example <NUM> - Arsoy-AAG: A <NUM> flask was charged with jet-milled soy carbohydrate concentrate (<NUM>) (Arsoy, Praeter Industries MKBL4718V <<NUM> micron) and t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated at <NUM> for <NUM>. Byproduct t-butanol (<NUM>%) was collected and a tan paste was obtained.

Example <NUM> - Stearyl-AAG: A <NUM> flask was charged with stearyl alcohol (<NUM>, <NUM> mmol), t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged under argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction mixture was heated at <NUM> for <NUM>. Byproduct t-butanol (<NUM>, <NUM> mmol, <NUM>%) was collected in the trap.

Example 2I - Polyesterpolyether Polyol-AAG: A <NUM> round bottom flask was charged with Boltorn™ P501 (<NUM>) [Perstorp Winning Formulas, Perstorp, Sweden], t-butyl acetoacetate (<NUM>), and purged under argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction mixture was heated at <NUM> for <NUM>. Byproduct t-butanol (<NUM>%) was collected in the trap.

Example 2J - Polyether Polyol-AAG: A <NUM> round bottom flask was charges with JEFFOL® SG360 (<NUM>) [Huntsman, Auburn Hills, Michigan], t-butyl acetoacetate (<NUM>), and purged under argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction mixture was heated at <NUM> for <NUM>. Byproduct t-butanol (<NUM>%) was collected in the trap.

Reference Examples 3A-3C below were performed as follows: The AAG and crosslinker (total <NUM> grams) were weighed in a Flecktec mixing cup along with PTSA (<NUM>-<NUM> wt% in methyl ethyl ketone (MEK)). The contents were mixed at <NUM> rpm for <NUM>. The resulting mixture was coated onto a low carbon steel panel using a <NUM> wet film thickness drawdown bar. The panel was cured at <NUM> for <NUM>.

Reference Example 3A: <NUM>% soy-AAG; <NUM>% CYMEL™ <NUM>, PTSA (<NUM>%). It was
observed from Thermogravimetric Analysis (TGA) that soy-AAG ("Soy-PK") cures faster than its precursor: the non-acetoacetoatylated commercial bio-based polyol [Honeybee HB530, MCPU Polymer Engineering, LLC, Richmond]. The TGA plot of soy-AAG curing with CYMEL™ <NUM> is compared with the bio-based soy polyol curing with CYMEL™ <NUM>, as shown in <FIG>.

The degree of cure, α, can be calculated from the TGA data using the following equation: <MAT> where Δmt,T is the difference in mass at time t and temperature T; Δy is the derivative at the given cure temperature T. The derivative at <NUM> for soy-AAG and polyol-based resin is respectively <NUM> and <NUM>%. Therefore, the degree of cure at <NUM> for soy-AAG is <NUM>%, and the degree of cure for the commercial bio-based polyol is <NUM>%.

Performance data for the soy-AAG cured resin is illustrated in tabular format in <FIG>. The corrosion performance of soy-AAG cured resin was evaluated using Electrochemical Impedance Spectroscopy (EIS). The coating was exposed to <NUM> wt % NaCl and the impedance was measured using a PAR potentiostat/galvanostat and Solartron equipment between the frequency range of <NUM> to <NUM>. The total coating impedance at a frequency of <NUM> was used as a guide to predict the corrosion performance of the coating. The performance for the soy-AAG cured resin coating over a period of <NUM> days is shown in <FIG>. It was evident that the soy-AAG cured resin is on par with the corrosion performance of BPA-based resin and outperforms commercial bio-based BPA-free alternative coatings.

The toxicity of soy-AAG cured resin was assessed using BG1LUC assay, as described in <NPL>. It was found that soy-AAG cured resin has no detectable estrogenic (see <FIG>) or anti-estrogenic activity (see <FIG>).

Reference Example 3B: <NUM>% soy-AAG; <NUM>% CYMEL™ <NUM>; <NUM>% pentaerythritol-AAG;
PTSA (<NUM>%).

Reference Example 3C: <NUM>% soy-AAG; <NUM>% CYMEL™ <NUM>; <NUM>% dipentaerythriol-AAG;
PTSA (<NUM>%).

Reference Example 3D: <NUM>% soy-AAG; <NUM>% PMDI; <NUM>% solids with MEK. The AAG and crosslinker (total <NUM> grams) was weighed in a Flecktec mixing cup along with methyl ethyl ketone. The contents were mixed at <NUM> rpm for <NUM>. The resulting mixture was coated onto a low carbon steel panel using a <NUM> wet film thickness drawdown bar. The panel was cured at <NUM> for <NUM>.

Example 3E - Arsoy-AAG polyamine: A flask was charged with CYMEL™ <NUM> (<NUM>), Arsoy-AAG (<NUM>), p-toluene sulfonic acid (<NUM> %wt). The mixture was diluted with MEK (<NUM> %wt) and stirred until a uniform solution was achieved. The solution was spread onto a low carbon steel coupon (<NUM> film thickness) and heated (cured) at <NUM> for <NUM>. The resulting tackless coating appeared opaque and yellow in color.

Reference Example 3F - Styrenyl-AAG polyamine: A flask was charged with CYMEL™-<NUM> (<NUM>), Styrene-AAG of Example 5A (<NUM>), Soy-AAG of Reference Example 2A/2B (<NUM>) and p-toluene sulfonic acid (<NUM> mol%). The reaction mixture was stirred until a uniform solution was obtained. The reaction mixture was spread onto a low carbon steel coupon (<NUM> thick). The coupon and reaction mixture were heated at <NUM> for <NUM>, resulting in a tackless yellow-brown film.

Reference Example 4A: Soy-AAG (<NUM>), Luprinate M20 (<NUM>), tegostab B4690 (<NUM>), water (<NUM>) and MEK (<NUM>) were rapidly mixed using a spatula at about <NUM> for <NUM>-<NUM>. The resulting mixture was poured into a container coated with a release agent and the foam solids were allowed to expand <NUM>-<NUM> times.

Reference Example 4B: Soy-AAG (<NUM>), Luprinate M20 (<NUM>), tegostab B4690 (<NUM>), water (<NUM>) and MEK (<NUM>) were rapidly mixed at about <NUM> for <NUM>-<NUM>. The resulting mixture was poured into a container coated with release agent and the foam solids were allowed to expand <NUM>-<NUM> times.

Reference Example 4C: Soy-AAG (<NUM>), Luprinate M20 (<NUM>), tegostab B4690 (<NUM>), and water (<NUM>) were rapidly mixed at about <NUM> for <NUM>-<NUM>. The resulting mixture was poured into a container coated with release agent and the foam solids were allowed to expand <NUM>- <NUM> times.

Reference Example 4D: Soy-AAG (<NUM>), Luprinate M20 (<NUM>), tegostab B4690 (<NUM>), water (<NUM>), and Mg(OH)<NUM> (<NUM>) were rapidly mixed at about <NUM> for <NUM>-<NUM>. The resulting mixture was poured into a container coated with release agent and the foam solids were allowed to expand <NUM>-<NUM> times.

Reference Example 4E: Soy-AAG (<NUM>), Luprinate M20 (<NUM>), tegostab B4690 (<NUM>), water (<NUM>), and glycerol-AAG (prepared according to Example <NUM>) (<NUM>) were rapidly mixed at about <NUM> for <NUM>-<NUM>. The resulting mixture was poured into a container coated with release agent and the foam solids were allowed to expand <NUM>-<NUM> times.

Example 5A - Styrene-AAG: A <NUM> flask was charged with <NUM>-(methylacryloyloxy) ethyl acetoacetate (<NUM>, <NUM> mmol), styrene (<NUM>, <NUM> mmol), and AIBN (<NUM>, <NUM> mmol), and purged with argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction was heated to <NUM> and stirred for <NUM>. The reaction mixture was cooled and gave a pale yellow product with low viscosity.

Example 5B - Polyol-diAAG diurethane: Hexamethylene diisocyanate (HDI) was reacted with ethylene glycol to give a hexamethylene diurethane diol. A <NUM> flask was charged with hexamethylene diurethane diol (<NUM>, <NUM> mmol), t-butyl acetoacetate (<NUM>, <NUM> mmol), and purged under argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction mixture was heated to <NUM> for <NUM>. Byproduct t-butanol (><NUM>%) was collected in the trap. The reaction mixture was cooled to give a clear, yellow-orange product.

Example 5C - Polyol-diAAG diurethane: A <NUM> flask was charged with hexamethylene diamine (<NUM>, <NUM> mmol), ethylene carbonate (<NUM>, <NUM> mol), and purged under argon. The flask was fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction mixture was heated to <NUM> for <NUM>. The reaction mixture was cooled to give a crystalline solid.

To a solution of an epoxidized triglyceride, such as epoxidized soybean oil, and choice solvent, may be added acetoacetic acid. The reaction may be promoted by the addition of a mild, non-nucleophilic base. Alternatively, the reaction may be promoted by an acid catalyst.

To a solution of TAAED and choice solvent, may be added an aqueous solution of H<NUM>O<NUM>. The solution may be stirred for a period of time before the addition of a solution of an unsaturated triglyceride in a choice solvent. Alternatively, the TAAED/H<NUM>O<NUM> solution may be added to a flask containing the unsaturated triglyceride solution. It is also conceivable that TAAED, H<NUM>O<NUM>, and the unsaturated triglyceride may be combined at once, though it is presumed that higher yield may be obtainable in a step-wise fashion.

To a solution of TAAED and choice solvent, may be added an aqueous solution of H<NUM>O<NUM>. The solution may be stirred for a period of time before the addition of a solution of an unsaturated fatty acid ester in a choice solvent. Alternatively, the TAAED/H<NUM>O<NUM> solution may be added to a flask containing the unsaturated fatty acid ester. The TAAED, H<NUM>O<NUM>, and the fatty acid ester may be combined at once, though it is presumed that higher yield may be obtainable in a step-wise fashion.

A flask may be charged with alcohols and/or polyols of pyrolized bio-oil, t-butyl acetoacetate, and purged under argon. The flask may be fitted with a Dean-Stark trap, a water-cooled condenser, a thermocouple, and an overhead stirrer. The reaction mixture may be heated to <NUM>-<NUM> for a period of time. The byproduct t-butanol may be collected in the trap and the quantity of t-butanol produced may be indicative of the progression of the reaction.

To the extent that the term "include" or "including" is used in the specification or the claims, it is intended to be inclusive in a manner similar to the interpretation of the term "comprising" when employed as a transitional word in a claim. Furthermore, to the extent that the term "or" is employed (e.g., A or B) it is intended to mean "A or B or both. " When "only A or B but not both" is intended, then the term "only A or B but not both" will be employed. Thus, use of the term "or" herein is the inclusive, and not the exclusive use. As used in the specification and the claims, the singular forms "a," "an," and "the" include the plural. As used herein, the term "approximately" means plus or minus <NUM>% unless otherwise specified.

The terms "optional" and "optionally" mean that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.

In general, "substituted" refers to an organic group as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom. Thus, a substituted group is substituted with one or more substituents, unless otherwise specified. In some aspects, a substituted group is substituted with <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM> substituents. Examples of substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; nitriles (i.e., CN); and the like.

Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups also include rings and ring systems in which a bond to a hydrogen atom is replaced with a bond to a carbon atom. Therefore, substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined below.

Alkyl groups include straight chain and branched chain alkyl groups having from <NUM> to <NUM> carbon atoms, and typically from <NUM> to <NUM> carbons or, in some aspects, from <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM> carbon atoms. Examples of straight chain alkyl groups include groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and <NUM>,<NUM>-dimethylpropyl groups. Representative substituted alkyl groups
may be substituted one or more times with substituents such as those listed above and include, without limitation, haloalkyl (e.g., trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, carboxyalkyl, and the like.

Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups having from <NUM> to <NUM> carbon atoms in the ring(s), or, in some aspects, <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>, <NUM>, or <NUM> carbon atoms. Exemplary monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some aspects, the cycloalkyl group has <NUM> to <NUM> ring members, whereas in other aspects, the number of ring carbon atoms ranges from <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>. Bi- and tricyclic ring systems include both bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclo[<NUM>. <NUM>]hexane, adamantyl, decalinyl, and the like. Substituted cycloalkyl groups may be substituted one or more times with non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, <NUM>,<NUM>-, <NUM>,<NUM>-, <NUM>,<NUM>- <NUM>,<NUM>- or <NUM>,<NUM>-disubstituted cyclohexyl groups, which may be substituted with substituents such as those listed above.

Aryl groups are cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups herein include monocyclic, bicyclic and tricyclic ring systems. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. In some aspects, aryl groups contain <NUM>-<NUM> carbons, and in others from <NUM> to <NUM> or even <NUM>-<NUM> carbon atoms in the ring portions of the groups. In some aspects, the aryl groups are phenyl or naphthyl. Although the phrase "aryl groups" includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like), it does not include aryl groups that have other groups, such as alkyl or halo groups, bonded to one of the ring members. Rather, groups such as tolyl are referred to as substituted aryl groups. Representative substituted aryl groups may be mono-substituted or substituted more than once. For example, monosubstituted aryl groups include, but are not limited to, <NUM>-, <NUM>-, <NUM>-, <NUM>-, or <NUM>-substituted phenyl or naphthyl groups, which may be substituted with substituents such as those listed above.

Aralkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined above. In some aspects, aralkyl groups contain <NUM> to <NUM> carbon atoms, <NUM> to <NUM> carbon atoms, or <NUM> to <NUM> carbon atoms. Substituted aralkyl groups may be substituted at the alkyl, the aryl or both the alkyl and aryl portions of the group. Representative aralkyl groups include but are not limited to benzyl and phenethyl groups and fused (cycloalkylaryl)alkyl groups such as <NUM>-indanylethyl. Representative substituted aralkyl groups may be substituted one or more times with substituents such as those listed above.

Heterocyclic groups include aromatic (also referred to as heteroaryl) and non-aromatic ring compounds containing <NUM> or more ring members of which one or more is a heteroatom such as, but not limited to, N, O, and S. In some aspects, the heterocyclyl group contains <NUM>, <NUM>, <NUM> or <NUM> heteroatoms. In some aspects, heterocyclic groups include mono-, bi- and tricyclic rings having <NUM> to <NUM> ring members, whereas other such groups have <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM> ring members. Heterocyclic groups encompass aromatic, partially unsaturated and saturated ring systems, such as, for example, imidazolyl, imidazolinyl and imidazolidinyl groups. The phrase "heterocyclic group" includes fused ring species including those comprising fused aromatic and non-aromatic groups, such as, for example, benzotriazolyl, <NUM>,<NUM>-dihydrobenzo[<NUM>,<NUM>]dioxinyl, and benzo[<NUM>,<NUM>]dioxolyl. The phrase also includes bridged polycyclic ring systems containing a heteroatom such as, but not limited to, quinuclidyl. However, the phrase does not include heterocyclic groups that have other groups, such as alkyl, oxo or halo groups, bonded to one of the ring members. Rather, these are referred to as "substituted heterocyclic groups. " Heterocyclic groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothiophenyl, tetrahydrofuranyl, dioxolyl, furanyl, thiophenyl, pyrrolyl, pyrrolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, oxadiazolyl, piperidyl, piperazinyl, morpholinyl, thiomorpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl, oxathiane, dioxyl, dithianyl, pyranyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, dihydropyridyl, dihydrodithiinyl, dihydrodithionyl, homopiperazinyl, quinuclidyl, indolyl, indolinyl, isoindolyl,azaindolyl (pyrrolopyridyl), indazolyl, indolizinyl, benzotriazolyl, benzimidazolyl, benzofuranyl, benzothiophenyl, benzthiazolyl, benzoxadiazolyl, benzoxazinyl, benzodithiinyl, benzoxathiinyl, benzothiazinyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzo[<NUM>,<NUM>]dioxolyl, pyrazolopyridyl, imidazopyridyl (azabenzimidazolyl), triazolopyridyl, isoxazolopyridyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, quinolizinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, naphthyridinyl, pteridinyl, thianaphthyl, dihydrobenzothiazinyl, dihydrobenzofuranyl, dihydroindolyl, dihydrobenzodioxinyl, tetrahydroindolyl, tetrahydroindazolyl, tetrahydrobenzimidazolyl, tetrahydrobenzotriazolyl, tetrahydropyrrolopyridyl, tetrahydropyrazolopyridyl, tetrahydroimidazopyridyl, tetrahydrotriazolopyridyl, and tetrahydroquinolinyl groups. Representative substituted heterocyclic groups may be mono-substituted or substituted more than once, such as, but not limited to, pyridyl or morpholinyl groups, which are <NUM>-, <NUM>-, <NUM>-, <NUM>-, or <NUM>-substituted, or disubstituted with various substituents such as those listed above.

Heteroaryl groups are aromatic ring compounds containing <NUM> or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl, imidazopyridinyl (azabenzimidazolyl), pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups include fused ring compounds in which all rings are aromatic such as indolyl groups and include fused ring compounds in which only one of the rings is aromatic, such as <NUM>,<NUM>-dihydro indolyl groups. Although the phrase "heteroaryl groups" includes fused ring compounds, the phrase does not include heteroaryl groups that have other groups bonded to one of the ring members, such as alkyl groups. Rather, heteroaryl groups with such substitution are referred to as "substituted heteroaryl groups. " Representative substituted heteroaryl groups may be substituted one or more times with various substituents such as those listed above.

Heteroaralkyl groups are alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined above. Substituted heteroaralkyl groups may be substituted at the alkyl, the heteroaryl or both the alkyl and heteroaryl portions of the group. Representative substituted heteroaralkyl groups may be substituted one or more times with substituents such as those listed above.

Groups described herein having two or more points of attachment (i.e., divalent, trivalent, or polyvalent) within the compound of the technology are designated by use of the suffix, "ene. " For example, divalent alkyl groups are alkylene groups, divalent aryl groups are arylene groups, divalent heteroaryl groups are heteroarylene groups, and so forth. Substituted groups having a single point of attachment to the compound of the technology are not referred to using the "ene" designation. Thus, for example, chloroethyl is not referred to herein as chloroethylene.

Alkoxy groups are hydroxyl groups (-OH) in which the bond to the hydrogen atom is replaced by a bond to a carbon atom of a substituted or unsubstituted alkyl group as defined above. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, isohexoxy, and the like. Examples of cycloalkoxy groups include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. Representative substituted alkoxy groups may be substituted one or more times with substituents such as those listed above.

The term "amine" (or "amino"), as used herein, refers to NRaRb groups, wherein Ra and Rb are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. In some aspects, the amine is alkylamino, dialkylamino, arylamino, or alkylarylamino. In other aspects, the amine is NH<NUM>, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino. The term "alkylamino" is defined as NRcRd, wherein at least one of Rc and Rd is alkyl and the other is alkyl or hydrogen. The term "arylamino" is defined as NReRf, wherein at least one of Re and Rf is aryl and the other is aryl or hydrogen.

Claim 1:
A method for preparing an acetoacetyl group (AAG) composition comprising:
providing a poly-functional compound comprising two or more functional groups, each functional group independently being hydroxy, amino, or alkenyl, at least a portion of the poly-functional compound being a polyol derived from a pyrolyzed bio-oil or an alkoxylated pyrolyzed bio-oil, provided that the poly-functional compound is not a triglyceride-derived oil; and
reacting the poly-functional compound under conditions effective to form the AAG composition by one or more of:
contacting the poly-functional compound with a ketene compound, wherein the poly-functional compound comprises at least one hydroxy group;
contacting the poly-functional compound with a β-ketoester, wherein the poly-functional compound comprises at least one hydroxy or amino group;
contacting the poly-functional compound with a peroxo reagent and one or more of: a β-ketoimide, a β-ketoester, and a β-ketoacid, wherein the poly-functional compound comprises at least one alkenyl group; and
contacting the poly-functional compound with a mercaptoalkanol in the presence of an initiator effective to form a mercaptoalkanol-substituted compound; the poly-functional compound comprising at least one alkenyl group; and further reacting the mercaptoalkanol-substituted compound with one or more of: the β-ketoester and the β-ketoacid,
wherein the pyrolyzed bio-oil is derived from pyrolysis of one or more of: hardwood, softwood, grass, reeds, bagasse, sugarcane, corn stover, and sorghum.