Crosslinkable coating system and coatings prepared therefrom

Abstract

A crosslinkable coating system, a method for coating an article with the crosslinkable coating system, and an article coated with the crosslinkable coating system are provided. The coating system includes an amide and an aldehyde containing two or more carbon atoms. The coating system may include a solvent. The coating system may be free or substantially free of formaldehyde and isocyanate. The coating system may include a reaction product of an amide and an aldehyde containing two or more carbon atoms. The coating system may be in powder form.

Description

[Technical Field]

[0001] The present disclosure relates generally to crosslinkable coating systems. The present disclosure further relates to methods of coating articles with crosslinkable coating systems and to articles coated therewith.

[0002] In some embodiments, the coating system includes an amide component including a primary amide, an aldehyde including two or more carbon atoms, and a solvent. The amide component may be present in a molar ratio of 0.5 to 2.5 moles per mole of aldehyde.

[0003] The amide component may be represented by the following formula (I):

[0004] [ka] In the formula, R 1 is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, urea, or amide group.

[0005] The amide component may include a diamide, triamide, or polyamide.

[0006] The aldehyde may be represented by the following formula (II) or (IIB):

[0007] [ka] In the formula, R 2 is a carbon-containing group optionally further substituted with two or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group, and optionally the aldehyde is in a protected form, including an acetal or hydrate. 3 and R 4 are independently carbon-containing groups optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably each R 3 and R 4 is independently an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, alkylamine, or urea group. 3 and R 4 may independently be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 3 and R 4 may independently contain any suitable number of carbon atoms. In some embodiments, each R 3 and R 4 may independently be an oligomer or a polymer. In a preferred embodiment, R 3 and R 4 are independently a carbon-containing group having 1 to 4 carbon atoms. In some preferred embodiments, R on the acetal of formula (IIA) 3 and R 4 The group is R 3 =R 4 In some embodiments, R 3 and R 4 can be linked to form a cyclic acetal.

[0008] The aldehyde may comprise a monoaldehyde. The aldehyde may comprise a dialdehyde or a polyaldehyde. The aldehyde may be an oligomer.

[0009] The amide component and the aldehyde form a reaction product represented by formula (III):

[0010] [ka] In the formula, R 1 is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, urea, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or amide group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group, and optionally the aldehyde is in a protected form, including an acetal or hydrate.

[0011] The coating system may be free or substantially free of formaldehyde.The coating system may be free or substantially free of isocyanates.

[0012] The coating system may be curable at temperatures between 50°C and 150°C, between 75°C and 150°C, between 90°C and 150°C, or between 90°C and 125°C.

[0013] According to one embodiment, the coating system comprises the reaction product of an amide component and an aldehyde containing two or more carbon atoms.

[0014] The reaction product may be a crosslinked product of formula (IV), formula (V), or formula (VI) below.

[0015] [ka] In the formula, R 1 is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0016] The coating system may be in powder form. The coating system may include an organic solvent, water, or both.

[0017] The coating system may be free or substantially free of formaldehyde and structural units derived from formaldehyde. The coating system may be free or substantially free of isocyanates and structural units derived from isocyanates. The present disclosure further provides articles coated with the coating system. [Brief explanation of the drawings]

[0018] [Figure 1]1 is an NMR spectrum of the sample prepared in Example 3, according to one embodiment. [Figure 2] 1 is an NMR spectrum of the sample prepared in Example 4, according to one embodiment. [Figure 3] 1 is an NMR spectrum of the sample prepared in Example 6, according to one embodiment. [Figure 4] 1 is an NMR spectrum of the intermediate product produced in Example 7, according to one embodiment. [Figure 5] 1 is an NMR spectrum of the final sample prepared in Example 9, according to one embodiment. [Figure 6] 1 is an NMR spectrum of the sample produced in Example 12, according to one embodiment.

[0019] definition All scientific and technical terms used herein have meanings commonly used in the art unless otherwise specified. The definitions provided herein are intended to facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure.

[0020] Unless otherwise indicated, the terms "polymer" and "polymeric material" include, but are not limited to, organic homopolymers, copolymers such as block, graft, random and alternating copolymers, terpolymers, and the like, as well as blends and modifications thereof. Furthermore, unless otherwise limited, the term "polymer" is intended to include all possible geometric configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.

[0021] The term "aromatic ring" is used in this disclosure to refer to a conjugated ring system of an organic compound. The aromatic ring may contain only carbon atoms or may contain one or more heteroatoms such as oxygen, nitrogen, or sulfur.

[0022] The term "alkylation" is used in this disclosure to describe a compound that reacts to replace a hydrogen atom or negative charge on a compound with an alkyl group such that the alkyl group becomes covalently attached to the compound.

[0023] The term "alkyl" is used in this disclosure to describe a monovalent group that is a radical of an alkane and includes straight-chain, branched, cyclic, and bicyclic alkyl groups, and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups typically contain 1 to 30 carbon atoms. In some embodiments, alkyl groups contain 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0024] The term "crosslinker" refers to a molecule that can form covalent bonds between separate polymers or between two different regions of the same polymer.

[0025] The term "group" is intended to represent both a specific moiety and a broader class of substituted and unsubstituted structures that include the moiety. Thus, when the term "group" is used to describe a chemical substituent, the described chemical includes the unsubstituted group (e.g., the moiety) and groups having, for example, O, N, Si, or S atoms in the chain (such as alkoxy groups), as well as carbonyl groups or other conventional substitutions. When the term "moiety" is used to describe a chemical compound or substituent, only unsubstituted chemicals are intended to be included. For example, the phrase "alkyl group" is intended to include not only pure open-chain saturated hydrocarbon alkyl substituents such as methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, etc., but also alkyl substituents bearing additional substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, "alkyl group" includes ether groups, haloalkyl, nitroalkyl, carboxyalkyl, hydroxyalkyl, sulfoalkyl, etc. On the other hand, the phrase "alkyl moiety" is limited to include only pure open chain saturated hydrocarbon alkyl substituents, such as, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.

[0026] As used herein, the term "substantially" has the same meaning as "significantly" and can be understood to modify the term that follows it by at least about 90%, at least about 95%, or at least about 98%. The term "substantially free" of a particular compound means that the compositions of the present invention contain less than 1,000 parts per million (ppm) of the recited compound. The term "essentially free" of a particular compound means that the compositions of the present invention contain less than 100 parts per million (ppm) of the recited compound. The term "completely free" of a particular compound means that the compositions of the present invention contain less than 20 parts per billion (ppb) of the recited compound. In the context of the foregoing phrases, the compositions of the present invention contain less than the recited amount of the compound, regardless of whether the compound itself is present in unreacted form or whether it has reacted with one or more other materials.

[0027] As used herein, the term "substantially not" has the same meaning as "not significantly" and can be understood to have the opposite meaning of "substantially," i.e., modifying the term that follows it by 25% or less, 10% or less, 5% or less, or 2% or less.

[0028] The term "about" is used herein in conjunction with numerical values ​​to include normal variations in measurement as would be expected by one of ordinary skill in the art, and is understood to have the same meaning as "approximately," encompassing a typical range of error, such as ±5% of the stated value.

[0029] Terms such as "a," "an," and "the" are not intended to refer to a singular entity only, but include a general class of which a particular example may be used for illustration.

[0030] The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "including at least one of," followed by a list, refer to any one of the items in the list, and any combination of two or more items in the list.

[0031] As used herein, the term "or" is generally used in its ordinary sense, including "and / or," unless the context clearly dictates otherwise. The term "and / or" refers to one or all of the listed elements or a combination of any two or more of the listed elements.

[0032] The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.; or 10 or less includes 10, 9.4, 7.6, 5, 4.3, 2.9, 1.62, 0.3, etc.). When a range of values ​​is stated "up to" or "at least" a particular value, then all values ​​are included within that range.

[0033] As used herein, the terms "have," "having," "include," "including," "comprise," "comprising," and the like are used in their open-ended sense and generally mean "including, but not limited to." "Consisting essentially of," "consisting of," and the like will be understood to be encompassed by "comprising," and the like. As used herein, "consisting essentially of," with respect to a composition, product, method, and the like, means that the components of the composition, product, method, and the like are limited to the recited components and any other components that do not materially affect the basic and novel characteristics of the composition, product, method, and the like.

[0034] The terms "preferred" and "preferably" refer to embodiments that may offer certain benefits, under particular circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention, including the claims.

[0035] Any directions referred to herein, such as "up," "down," "left," "right," "upper," "lower," and other directions and orientations, are provided herein for clarity when referring to the figures and are not intended to limit the actual device or system or the use of the device or system. The devices or systems described herein may be used in several directions and orientations. DETAILED DESCRIPTION OF THE INVENTION

[0036] The present disclosure relates generally to crosslinkable coating systems. The present disclosure further relates to methods of coating articles with crosslinkable coating systems and to articles coated therewith.

[0037] A wide variety of coatings have been used to coat surfaces of articles, structures, packaging, and the like. For example, protective and / or decorative coatings may be applied to wood, wood products, metals, polymers, packaging materials, and the like. With respect to coatings in general, it is desirable to use coating systems that are free of isocyanates and formaldehyde. Additionally, there is a need to find alternative crosslinking chemistries and methodologies to systems that contain isocyanates or formaldehyde. In particular, there is a need to find alternative crosslinking chemistries and methodologies for two-component coating systems that typically contain isocyanates, and one-component coating systems that typically contain formaldehyde.

[0038] The coating system of the present disclosure can be used for many purposes and to coat a variety of materials. The coating system is suitable for use as a coating for wood, wood products, metals, polymers, packaging materials, and the like. The coating system can be used, for example, to coat structural features, architectural elements, articles, containers, packaging, and the like. All such items may be collectively referred to herein as "articles." The present disclosure provides methods of coating articles with the coating composition, and articles coated with the coating composition.

[0039] According to one embodiment, the crosslinkable coating system is based on two reactive compounds, an amide component and an aldehyde, optionally a catalyst, and optionally an amine. The amide and aldehyde can react to form a 2-hydroxy-alkylamide. This product can further react with another amide to form a bisamide. The reaction can be characterized as follows:

[0040] [ka]

[0041] The amide may be a diamide or polyamide. When a diamide is reacted with a dialdehyde, the reaction product can be further reacted to form oligomers and polymers. The aldehyde may optionally be in a protected form, such as an acetal or hydrate. In one embodiment, the crosslinkable coating system comprises the reaction product of an amide and an aldehyde. In one embodiment, the crosslinkable coating system comprises the reaction product of a primary amide and an aldehyde. In one embodiment, the crosslinkable coating system comprises the reaction product of a diamide and an aldehyde. In one embodiment, the crosslinkable coating system comprises the reaction product of a diamide and a dialdehyde. In one embodiment, the crosslinkable coating system comprises the oligomeric or polymeric reaction product of a diamide and a dialdehyde. The crosslinkable coating system may also comprise the reaction product of one or more different unsubstituted or substituted amides with one or more different aldehydes.

[0042] The combination of an amide and an aldehyde provides a crosslinkable coating composition that is free or substantially free of formaldehyde, isocyanates, or both. According to one embodiment, the crosslinkable coating composition is free or substantially free of both formaldehyde and isocyanates. Many prior art one-component compositions contain formaldehyde. The crosslinkable coating composition of the present disclosure can be a one-component composition that is free or substantially free of formaldehyde. Many prior art two-component compositions contain isocyanates. The crosslinkable coating composition of the present disclosure can be a two-component composition that is free or substantially free of isocyanates.

[0043] The coating composition can be used to prepare polymeric coatings that are free or substantially free of formaldehyde and structural units derived from formaldehyde. The coating composition can be used to prepare polymeric coatings that are free or substantially free of isocyanates and structural units derived from isocyanates. The coating composition can be used to prepare polymeric coatings that are free or substantially free of formaldehyde and structural units derived from formaldehyde, and free or substantially free of isocyanates and structural units derived from isocyanates.

[0044] In some embodiments, the coating composition of the present disclosure may be a one-component system or a two-component system. In other words, the coating composition may be a one-part system or a two-part system. A coating composition that is a one-part system refers to a coating system in which the components are premixed, i.e., the reagents are provided as a premixed mixture. Such a premixed mixture does not need to be mixed immediately before applying the coating to an article or surface to be coated with the coating system. In embodiments in which the coating composition is a one-part system, the reactivity of the reagents (unsubstituted or substituted amide, aldehyde, and optional catalyst) can be selected so that the reaction does not occur too early (e.g., before application of the coating composition). For example, the amide and / or aldehyde can be selected to have higher or lower reactivity. Furthermore, at least some of the functional groups of the reagents can be protected using protecting groups (e.g., by forming an acetal group or a hydrate on the aldehyde) that prevent reaction from occurring until the protecting group is removed.

[0045] A coating composition that is a two-part coating system refers to a coating system composition that is not in a premixed form. It refers to a coating system that is comprised of two mixtures of the coating system reagents. The reagents in the two mixtures are substantially non-reactive until the two mixtures (or "two parts") are combined together. Combining the two "parts" of a two-part coating system allows the reagents to react to form a coating.

[0046] amide According to one embodiment, the crosslinkable coating system comprises the reaction product of an amide and an aldehyde. The amide may preferably be a primary amide.

[0047] According to one embodiment, the amide is represented by the following formula (I):

[0048] [ka] In the formula, R1 is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 R is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group. 1 R may be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 1 may contain any suitable number of carbon atoms. In some embodiments, R 1 may be an oligomer or a polymer.

[0049] According to one embodiment, the amide is formaldehyde and has the following formula (IA):

[0050] [ka]

[0051] According to one embodiment, the amide is a substituted primary amide in which the carbonyl carbon is substituted. According to one embodiment, the carbonyl carbon is substituted with an alkyl. One example of such an amide is acetamide, which is represented by the following formula (IB-1):

[0052] [ka]

[0053] According to one embodiment, the carbonyl carbon is substituted with a vinyl group. One example of such an amide is methacrylamide, represented by formula (IB-2) below:

[0054] [ka]

[0055] According to one embodiment, the carbonyl carbon is substituted with a phenyl group. An example of such an amide is benzamide, represented by formula (IB-3) below:

[0056] [ka]

[0057] According to one embodiment, the amide is a diamide and has the following formula (IC):

[0058] [ka] In the formula, R 1 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 R is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group. 1 R may be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 1 may contain any suitable number of carbon atoms. In some embodiments, R 1 may be an oligomer or a polymer.

[0059] According to one embodiment, the diamide is malonamide (malonic acid diamide) represented by the following formula (IC-1):

[0060] [ka]

[0061] According to one embodiment, the diamide is a phthalamide represented by the following formula (IC-2):

[0062] [ka]

[0063] In some embodiments, Formula (I) is not or does not include a polyether.

[0064] The amide may be a triamide or polyamide similar to the diamide of formula (IC). The amide may further include a branched amide functionality such as the following structure:

[0065] [ka] wherein m is 2, 3, or 4.

[0066] aldehyde The aldehyde can be a monoaldehyde, dialdehyde, trialdehyde, or polyaldehyde. The aldehyde can be an oligomer or polymer. The aldehyde can optionally be in a protected form, such as an acetal or hydrate, prior to reaction. In some embodiments, the aldehyde is a liquid at room temperature (about 20° C. to 25° C.). The aldehyde can also have low toxicity and an acceptable odor.

[0067] In some embodiments, the aldehyde is a monoaldehyde. Examples of suitable aldehydes include heptanal, octanal, cyclohexanecarboxaldehyde, benzaldehyde, furfural, vanillin, hydroxymethylfurfural ("HMF"), pivalaldehyde, hydroxypivalaldehyde, aliphatic aldehydes obtained by oxidative cleavage of double bonds, and the like. In some cases, the aldehyde may be bio-based, obtained from a non-petroleum source.

[0068] The aldehyde may be represented by the following formula (II):

[0069] [ka] In the formula, R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 R is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group. 2 R may be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 2 may contain any suitable number of carbon atoms. In some embodiments, R 2 may be an oligomer or a polymer.

[0070] In some embodiments, the aldehyde in the crosslinkable coating system of the present disclosure is a polyaldehyde selected from the group consisting of terephthalaldehyde, glutaraldehyde, glyoxal, dimethoxyacetaldehyde, methylglyoxal, cyclohexanedicarbaldehyde, malondialdehyde bis(dimethyl acetal), 5,5′-(oxy-bis(methylene))bis-2-furfural, bis(dimethyl acetal) of imidazolidone, tetra-dimethyl acetal of glycoluril, bis(dimethyl acetal) of polyglycidyl ether, tri(aminoethyl dimethyl acetal) of itaconic acid, tri(aminoethyl dimethyl acetal) of TMPEOTA, and poly(dimethyl acetal) of polycyclocarbonate.

[0071] In some embodiments, the aldehyde is a dialdehyde and is represented by the following formula (IIA):

[0072] [ka] In the formula, R2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 6 R is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group. 2 R may be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 2 may contain any suitable number of carbon atoms. In some embodiments, R 2 may be an oligomer or a polymer.

[0073] In some embodiments, the dialdehyde can be an alicyclic dialdehyde such as cyclohexanedicarboxaldehyde, represented by formula (IIA-1) below:

[0074] [ka]

[0075] In some embodiments, the aldehyde can be represented by the following formula (IIB):

[0076] [ka] In the formula, R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group. 2R may be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 2 may contain any suitable number of carbon atoms. In some embodiments, R 2 may be an oligomer or a polymer. 3 and R 4 are independently carbon-containing groups optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably each R 3 and R 4 is independently an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, alkylamine, or urea group. 3 and R 4 may independently be straight-chained, branched-chained, or cyclic and may contain zero, one, or more double bonds. 3 and R 4 may independently contain any suitable number of carbon atoms. In some embodiments, each R 3 and R 4 may independently be an oligomer or a polymer. In a preferred embodiment, R 3 and R 4 are independently a carbon-containing group having 1 to 4 carbon atoms. In some preferred embodiments, R on the acetal of formula (IIA) 3 and R 4 The group is R 3 =R 4 In some embodiments, R 3 and R 4 can be linked to form a cyclic acetal.

[0077] [ka]

[0078] In some embodiments, the aldehyde is in a protected form as a hydrate, which can be obtained by the reaction of water with the aldehyde and can be represented by the following formula:

[0079] [ka] In the formula, R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group. 2 R may be straight chain, branched chain, or cyclic and may contain zero, one, or more double bonds. 2 may contain any suitable number of carbon atoms. In some embodiments, R 2 may be an oligomer or a polymer.

[0080] In the following, the term aldehyde describes the aldehyde or hydrate or acetal.

[0081] In some embodiments, the aldehyde is a polyaldehyde, such as terephthalaldehyde, glutaraldehyde, glyoxal, dimethoxyacetaldehyde, methylglyoxal, cyclohexanedicarbaldehyde, and malondialdehyde bis(dimethyl acetal), 5,5′-(oxy-bis(methylene))bis-2-furfural, bis(dimethyl acetal) of imidazolidone, tetra-dimethyl acetal of glycoluril, bis(dimethyl acetal) of polyglycidyl ether, tri(aminoethyl dimethyl acetal) of itaconic acid, tri(aminoethyl dimethyl acetal) of TMPEOTA, poly(dimethyl acetal) of polycyclocarbonate.

[0082] In some embodiments, the aldehyde is oligomeric or polymeric. Oligomeric or polymeric aldehydes can contain multiple aldehyde functional groups. For example, the aldehyde can be a dialdehyde obtained by condensation of a hydroxyaldehyde, such as 5,5'-[oxy-bis(methylene)]di(2-furaldehyde). The dialdehyde can be formed by crotonization with an enolizable ketone, such as cyclohexanone. In one example, the dialdehyde is formed from HMF and cyclohexanone. The ketone can be used in an HMF / cyclohexanone ratio greater than 1. The aldehyde can also be a dialdehyde obtained by coupling two hydroxyaldehydes with a dicarbamate.

[0083] In some embodiments, the aldehyde is an acrylic (co)polymer that can be obtained by free radical polymerization of a monomer mixture containing an aldehyde-functional monomer. Such an aldehyde-functional monomer can be obtained in various ways. For example, such an aldehyde-functional monomer can be based on acrolein, acrolein diethyl acetal, N-methacrylamidoacetaldehyde dimethyl acetal, 5-(hydroxymethyl)furfural methacrylate (HMF) methacrylate, or 4-methacryloyloxy-3-methoxybenzaldehyde (vanillin methacrylate). Or, the reaction product of aminoacetaldehyde dimethyl acetal (or (methylamino)acetaldehyde dimethyl acetal) with glycidyl ether methacrylate (GMA), glycerol carbonate methacrylate (GCMA), 4-(chloromethyl)styrene (CMS), or 3-acryloyloxy-2-hydroxypropyl methacrylate. Note that R=H or CH3

[0084] [ka] Or it may be based on the reaction product of pivalaldehyde with methacrylic anhydride or 4-(chloromethyl)styrene.

[0085] [ka]

[0086] In some embodiments, the aldehyde may be a polyester resin obtained by esterification or transesterification of a monomer mixture containing an aldehyde-functional monomer. Such aldehyde-functional monomers can be obtained in various ways. For example, such aldehyde-functional monomers can be based on itaconic acid reacted with aminoacetaldehyde dimethyl acetal or (methylamino)acetaldehyde dimethyl acetal via aza-Michael addition.

[0087] [ka]

[0088] Coatings According to one embodiment, the coating system of the present disclosure includes an amide according to formula (I) above (e.g., formulas (IA)-(IC)) and an aldehyde according to formula (II) above (e.g., formulas (IIA)-(IIB)). In some embodiments, the coating system of the present disclosure may also include a solvent. In some embodiments, the amide and aldehyde may be present in a molar ratio of 0.5-2.5 moles, 0.5-2.0 moles, 1.0-2.0 moles, or 1.5-2.5 moles of amide per mole of aldehyde. According to one embodiment, the coating system is crosslinkable.

[0089] According to one embodiment, the crosslinkable coating system is provided as a one-part or two-part composition. The crosslinkable coating system may be a dry powder composition or a solvent-based composition. A dry powder composition is a composition in which each component is in powder form. Dry powder components can be blended together and applied in powder form. Components of a solvent-based system can be either liquid or powder and mixed in a solvent and applied in liquid form.

[0090] In embodiments where the composition is solvent-based, the coating composition comprises at least 1 wt%, at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt%, or at least 40 wt% of the combined amide and aldehyde, based on the total resin solids in the coating composition. The coating composition can comprise no more than 60 wt%, no more than 50 wt%, no more than 40 wt%, no more than 30 wt%, no more than 20 wt%, or no more than 10 wt% of the combined amide and aldehyde, based on the total resin solids in the coating composition.

[0091] Solvent-based compositions can include water or organic solvents, or combinations thereof. Exemplary solvents include ketones, acetates, aromatics, alcohols, ethers, and combinations thereof (including aqueous mixtures).

[0092] The coating composition can also optionally be rheologically modified for different coating applications. For example, the coating composition can be diluted with an additional amount of solvent to reduce the total solids content in the coating composition. Alternatively, a portion of the solvent can be removed (e.g., evaporated) to increase the total solids content in the coating composition. The final total solids content in the coating composition can vary depending on the particular coating application used, the particular coating application, the desired coating thickness, etc.

[0093] In some embodiments, the coating composition has a total solids weight of greater than about 5%, more preferably greater than about 10%, and even more preferably greater than about 15%, based on the total weight of the coating composition. In liquid embodiments, the coating composition also preferably has a total solids weight of less than about 80%, more preferably less than about 60%, and even more preferably less than about 50%, based on the total weight of the coating composition. The solvent (e.g., aqueous or organic solvent) may comprise the remainder of the weight of the coating composition.

[0094] In one embodiment, the coating composition is a powder coating composition. The powder coating composition may include a base powder formed at least in part from the polymer of the present disclosure. The coating composition may include one or more optional ingredients within the particles of the base powder and / or within separate particles. Such optional ingredients may include, for example, crosslinkers, cure accelerators, color pigments, fillers, flow additives, and the like.

[0095] The coating composition may optionally include one or more additional resins in addition to the reaction product of an amide and an aldehyde, for example, to modify the properties of the resulting coating.

[0096] The coating composition may optionally contain one or more additives. When used, the additives preferably improve and preferably do not adversely affect the coating composition or the cured coating formed therefrom. For example, additives may be included in the coating composition to improve the aesthetics of the composition, to facilitate the manufacture, processing, handling, and application of the composition, or to further improve certain functional properties of the coating composition or the cured coating obtained therefrom. Such optional additives include, for example, catalysts, dyes, pigments, toners, extenders, fillers, lubricants, corrosion inhibitors, flow control agents, thixotropic agents, dispersants, antioxidants, adhesion promoters, light stabilizers, co-resins, and mixtures thereof. Each optional additive is preferably included in an amount sufficient to fulfill its intended purpose, but not in an amount that adversely affects the coating composition or the cured coating obtained therefrom.

[0097] In some embodiments, the coating composition includes one or more catalysts. In some embodiments, the coating composition includes an acid catalyst. Suitable acid catalysts are acids with a pKa of less than 7 or less than 6. Acid functional groups on the polymer can also act as catalysts.

[0098] Examples of acid catalysts include Lewis acids (e.g., boron trifluoride etherate) and protic acids (i.e., Bronsted acids). In some embodiments, the acid catalyst is an inorganic protic acid, such as phosphoric acid or sulfuric acid, or an organic protic acid, such as a carboxylic acid, a phosphonic acid, or a sulfonic acid. Exemplary carboxylic acids suitable for use as the acid catalyst include acetic acid, trifluoroacetic acid, and propionic acid. An exemplary phosphonic acid is methylphosphonic acid. Exemplary sulfonic acids include methanesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, para-toluenesulfonic acid (PTSA), and dodecylbenzenesulfonic acid (DBSA). Examples of suitable Lewis acid catalysts are aluminum trichloride (AlCl), benzyltriethylammonium chloride (TEBAC), Cu(OSCF), (CH)BrSBr, FeCl (e.g., FeCl6H0), HBF, BF0(CHCH), TiCl, SnCl, CrCl, NiCl, ZnBr, and Pd(OC(O)CH). The acid catalyst may be unsupported (without a solid support) or supported, for example, covalently bound to a solid support.

[0099] Another useful optional additive is a lubricant (e.g., wax), which facilitates the manufacture of metal closures and other engineered coated articles by imparting lubricity to the coated metal substrate. Preferred lubricants include, for example, carnauba wax and polyethylene-type lubricants. When used, the lubricant is preferably present in the coating composition in an amount of at least about 0.1 wt. %, preferably no more than about 2 wt. %, and even more preferably no more than about 1 wt. %, based on the total weight of solids in the coating composition.

[0100] Another useful optional additive is an organosilicon material, such as a siloxane-based material or a polysilicon-based material. Representative examples of suitable such materials are disclosed in International Patent Application Publication Nos. WO2014 / 089410(A1) and WO2014 / 186285(A1).

[0101] Another useful optional ingredient is a pigment, such as titanium dioxide, which, when used, is present in the coating composition in an amount of about 70% by weight or less, more preferably about 50% by weight or less, and even more preferably about 40% by weight or less, based on the total weight of solids in the coating composition.

[0102] Amides and aldehydes can react to form bisamides.

[0103] Exemplary reactions include the reaction of methacrylamide with octanal;

[0104] [ka]

[0105] Reaction of acetamide with octanal,

[0106] [ka]

[0107] Reaction of benzamide with cyclohexanecarboxaldehyde Examples include:

[0108] [ka]

[0109] The reaction product of the amide and aldehyde may be represented by formula (III):

[0110] [ka] In the formula, R 1 is the same as in formula (I), and R 2 is the same as formula (II).

[0111] If an excess of amide is present, the reaction can proceed further to produce the following formula (IV):

[0112] [ka] In the formula, R 1 is the same as in formula (I), and R 2 is the same as formula (II).

[0113] When an amide is reacted with a dialdehyde, the reaction product may be represented by formula (V).

[0114] [ka] In the formula, R 1 is the same as in formula (I), and R 2 is the same as formula (IIA).

[0115] When a diamide is reacted with a dialdehyde, the reaction may produce an oligomer or polymer represented by formula (VI):

[0116] [ka] In the formula, R 1 is the same as formula (IC), and R 2 is the same as formula (IIA).

[0117] The reaction product (forming the coating composition) can be applied to a surface and cured to induce crosslinking. The resulting coating can be a poly(hydroxy-alkylamide)-functionalized network (when using Formula III or a similar reaction product) or a poly(bisamide)-functionalized network (when using Formula IV or a similar reaction product). According to one embodiment, the coating composition is free or substantially free of isocyanates. According to one embodiment, the coating composition is free or substantially free of formaldehyde. According to one embodiment, the coating composition is free or substantially free of both isocyanates and formaldehyde.

[0118] Curing / crosslinking After being applied to a surface, the coating composition may be cured to cause crosslinking of the composition.

[0119] The coating composition may be cured at temperatures of 150° C. or less, 125° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, 80° C. or less, or 70° C. or less. The coating composition may be cured at temperatures of 50° C. or more, 75° C. or more, 80° C. or more, 90° C. or more, or 100° C. or more. The coating composition may be cured at temperatures ranging from 50° C. to 150° C., from 75° C. to 150° C., from 90° C. to 150° C., or from 90° C. to 125° C. In some embodiments, the coating composition is curable at room temperature.

[0120] In some embodiments, it may be desirable for the coating composition to be non-reactive at low temperatures, such as room temperature. The components of the coating composition may be selected to achieve the desired curing and crosslinking conditions.

[0121] Additives used in the coating composition can also be selected to achieve desired reaction conditions, for example, acid catalysts or polymer chains bearing carboxylic acid functional groups can be used to improve the reactivity of the crosslinking reaction.

[0122] Coating method and coated article The present disclosure provides methods for coating articles with coating compositions, and articles coated with the coating compositions. The coating compositions of the present disclosure can be used for many purposes and to coat a variety of materials. The coating compositions are suitable for use as coatings for wood, wood products, metals, polymers, packaging materials, and the like.

[0123] A coating method according to one embodiment includes applying a coating composition to a surface of an article, the coating composition including an amide according to formula (I) above (e.g., formulas (IA) to (IC)) and an aldehyde according to formula (II) above (e.g., formulas (IIA) to (IIB)).

[0124] In some embodiments, a packaging article has a coating according to an embodiment of the present disclosure disposed on a surface of the packaging article. In one embodiment, the packaging article is a container, such as a food or beverage container, or a portion thereof (e.g., a twist-off closure, a beverage can end, a food can end, etc.), and at least a portion of the interior surface of the container is coated with a coating composition. The coating may include a reaction product of an amide according to Formula (I) above (e.g., Formulas (IA)-(IC)) with an aldehyde according to Formula (II) above (e.g., Formulas (IIA)-(IIB)). The coating may include a network formed from a reaction product of Formula (III) above. The coating may include a network formed from a reaction product of Formula (IV) above. The coating may include a network formed from a reaction product of Formula (V) above. The coating may include a network formed from a reaction product of Formula (VI) above. The coating may be a crosslinked coating resulting from crosslinking the reaction product of Formula (III), Formula (IV), Formula (V), or Formula (VI).

[0125] Illustrative Embodiments Embodiment 1 is amides, Aldehydes containing two or more carbon atoms, and a coating system comprising a solvent.

[0126] Embodiment 2 is the coating system of embodiment 1, wherein the amide is present in a molar ratio of 0.5 to 2.5 moles, 0.5 to 2.0 moles, 1.0 to 2.0 moles, or 1.5 to 2.5 moles of amide per mole of aldehyde.

[0127] Embodiment 3 is a third embodiment of the present invention, wherein the amide is represented by the following formula (I):

[0128] [ka] In the formula, R 1 are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0129] Embodiment 4 is the coating system of any one of embodiments 1-3, wherein the amide comprises acetamide, methacrylamide, benzamide, or a combination thereof.

[0130] Embodiment 5 is the coating system of any one of embodiments 1-4, wherein the amide comprises a diamide, triamide, or polyamide.

[0131] Embodiment 6 is the coating system of any one of embodiments 1-5, wherein the amide comprises malonamide, phthalamide, or a combination thereof.

[0132] Embodiment 7 is a method for preparing a hydroxyl group comprising administering to a subject the method comprising administering to a subject the hydroxyl group ...

[0133] [ka] 7. The coating system of any one of embodiments 1 to 6, wherein m is 2, 3, or 4.

[0134] Embodiment 8 is directed to an aldehyde that may be represented by formula (II) or (IIB):

[0135] [ka] In the formula, R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2

[0023] 8. The coating system of any one of embodiments 1-7, wherein R is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group, and optionally the aldehyde is in a protected form, including an acetal or hydrate. 3 and R 4 are independently carbon-containing groups optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably each R 3 and R 4 is independently an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, alkylamine, or urea group. 3 and R 4 may independently be straight-chained, branched-chained, or cyclic and may contain zero, one, or more double bonds. 3 and R 4 may independently contain any suitable number of carbon atoms. In some embodiments, each R3 and R 4 may independently be an oligomer or a polymer. In a preferred embodiment, R 3 and R 4 are independently a carbon-containing group having 1 to 4 carbon atoms. In some preferred embodiments, R on the acetal of formula (IIA) 3 and R 4 The group is R 3 =R 4 In some embodiments, R 3 and R 4 can be linked to form a cyclic acetal. The aldehyde may include a monoaldehyde. The aldehyde may include a dialdehyde or a polyaldehyde. The aldehyde may be an oligomer.

[0136] Embodiment 9 is the coating system of embodiment 8, wherein the aldehyde comprises a monoaldehyde.

[0137] Embodiment 10 is the coating system of embodiment 8, wherein the aldehyde comprises a dialdehyde or polyaldehyde.

[0138] Embodiment 11 is the coating system of embodiment 8, wherein the aldehyde comprises cyclohexanedicarboxaldehyde.

[0139] Embodiment 12 is the coating system of embodiment 8, wherein the aldehyde is an oligomer.

[0140] Embodiment 13 is directed to a method for preparing a compound comprising: an amide and an aldehyde forming a reaction product represented by formula (III):

[0141] [ka] In the formula, R 1 is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0142] Embodiment 14 is directed to a method for preparing a compound comprising: an amide and an aldehyde forming a reaction product represented by formula (IV):

[0143] [ka] In the formula, each R 1 are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0144] Embodiment 15 is directed to a method for preparing a compound comprising:

[0145] [ka] In the formula, each R 1 are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0146] Embodiment 16 is directed to a method for preparing a compound comprising: an amide and an aldehyde forming a reaction product represented by formula (VI):

[0147] [ka] In the formula, each R 1 are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0148] Embodiment 17 is the coating system of any one of embodiments 1-16, wherein the coating system is free or substantially free of formaldehyde.

[0149] Embodiment 18 is the coating system of any one of embodiments 1-17, wherein the coating system is free or substantially free of isocyanates.

[0150] Embodiment 19 is the coating system of any one of embodiments 1 to 18, wherein the coating system is curable at a temperature of 50°C to 150°C, 75°C to 150°C, 90°C to 150°C, or 90°C to 125°C.

[0151] Embodiment 20 is the coating system of any one of embodiments 1-19, wherein the coating system comprises at least 1 wt%, at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt%, or at least 40 wt% of the combined amide and aldehyde, based on the total resin solids in the coating system. The coating system may comprise up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 20 wt%, or up to 10 wt% of the combined amide and aldehyde, based on the total resin solids in the coating composition.

[0152] Embodiment 21 is the coating system of any one of embodiments 1-20, wherein the solvent comprises water or an organic solvent, or a combination thereof, and optionally the solvent comprises a ketone, acetate, aromatic, alcohol, ether, or a combination thereof (including aqueous mixtures).

[0153] Embodiment 22 is the coating system of any one of embodiments 1-21, wherein the coating system comprises an acid catalyst, and optionally the acid catalyst has a pKa of less than 7 or less than 6.

[0154] Embodiment 23 is the coating system of embodiment 22, wherein the acid catalyst comprises phosphoric acid, sulfuric acid, acetic acid, trifluoroacetic acid, propionic acid, methylphosphonic acid, methanesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, paratoluenesulfonic acid (PTSA), dodecylbenzenesulfonic acid (DBSA), aluminum trichloride (AlCl), benzyltriethylammonium chloride (TEBAC), Cu(OSCF), (CH)BrSBr, FeCl, HBF, BF0(CHCH), TiCl, SnCl, CrCl, NiCl, ZnBrPd(OC(O)CH), or a combination thereof.

[0155] Embodiment 24 is amides, A coating system comprising a reaction product with an aldehyde containing two or more carbon atoms.

[0156] Embodiment 25 is the coating system of embodiment 24, wherein the reaction product comprises a bisamide.

[0157] Embodiment 26 is a crosslinked product of Formula (IV), Formula (V), or Formula (VI):

[0158] [ka] In the formula, R 1 are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 1 is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R 2 is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R 2 is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

[0159] Embodiment 27 is the coating system of any one of embodiments 24-26, wherein the reaction product comprises the reaction of methacrylamide with octanal.

[0160] [ka]

[0161] Embodiment 28 is the coating system of any one of embodiments 24-26, wherein the reaction product comprises the reaction of acetamide with octanal.

[0162] [ka]

[0163] Embodiment 29 is the coating system of any one of embodiments 24-26, wherein the reaction product comprises the reaction of a benzamide with cyclohexanecarboxaldehyde.

[0164] [ka]

[0165] Embodiment 30 is the coating system of any one of embodiments 24-29, wherein the coating system is in powder form.

[0166] Embodiment 31 is the coating system of any one of embodiments 24-30, wherein the coating system comprises an organic solvent, water, or both, and optionally the solvent comprises a ketone, acetate, aromatic, alcohol, ether, or combinations thereof (including aqueous mixtures).

[0167] Embodiment 32 is the coating system of any one of embodiments 24-31, wherein the coating system is free or substantially free of formaldehyde and structural units derived from formaldehyde.

[0168] Embodiment 33 is the coating system of any one of embodiments 24-32, wherein the coating system is free or substantially free of isocyanates and structural units derived from isocyanates.

[0169] Embodiment 34 is the coating system of any one of embodiments 24-33, wherein the coating system comprises one or more of a crosslinker, a cure accelerator, a filler, a catalyst, a dye, a pigment, a toner, an extender, a lubricant, a corrosion inhibitor, a flow control agent, a thixotropic agent, a dispersant, an antioxidant, an adhesion promoter, a light stabilizer, a co-resin, and combinations thereof.

[0170] Embodiment 35 is an article coated with the coating system of any one of the preceding embodiments. [Example]

[0171] Example 1 Reaction of benzamide with cyclohexanedicarboxaldehyde.

[0172] [ka] 42.40 g (0.35 amide equivalents) of benzamide and 26.25 g (0.35 aldehyde equivalents) of cyclohexanedicarboxaldehyde (PARALOID™ EDGE XL-195, available from Dow Chemical Company, Midland, MI) were placed in a reaction vessel equipped with a thermometer, a mechanical stirrer (100 rpm), and a nitrogen inlet. The reaction mixture was stirred while being heated to 150°C. When the reaction temperature reached 100°C and the mixture was at 100°C, 0.69 g of p-toluenesulfonic acid (PTSA) powder was added to the mixture as a catalyst. Ten minutes after the addition of the catalyst, the resin solidified into a compact at 150°C, and a color change was observed. It was concluded that the benzamide and cyclohexanedicarboxaldehyde had reacted with each other.

[0173] Example 2 Reaction of malonamide with cyclohexanedicarboxaldehyde.

[0174] [ka] 25.53 g (0.5 amide equivalents) of malonamide and 37.50 g (0.5 aldehyde equivalents) of cyclohexanedicarboxaldehyde (PARALOID™ EDGE XL-195) were placed in a reaction vessel equipped with a thermometer, a mechanical stirrer (100 rpm), and a nitrogen inlet. The reaction mixture was heated to 150°C with stirring. When the reaction temperature reached 100°C and the mixture reached 85°C, 0.63 g of p-toluenesulfonic acid (PTSA) powder was added to the mixture as a catalyst. Five minutes after the addition of the catalyst, the resin solidified into a molded body at 150°C, and a color change was observed. It was concluded that the benzamide and cyclohexanedicarboxaldehyde had reacted with each other and polymerized.

[0175] Example 3 Synthesis of dimethyl acetal methacrylamide from MAAH and aminoacetaldehyde dimethyl acetal.

[0176] [ka] 70 g (0.67 mol) of aminoacetaldehyde dimethyl acetal and 300 g of dichloromethane were placed in a 500 mL reaction vessel under constant stirring. 102.64 g (0.67 mol) of methacrylic anhydride (MAAH) was added to the reaction vessel, and the reaction mixture was stirred at 50°C for 10 hours. The reaction mixture was then cooled and placed in a settling ampoule. 100 mL of a basic aqueous solution was added to remove the acrylic acid, followed by a neutral aqueous rinse. The solvent was removed to give the product as a pure viscous liquid in 95% yield. 1 The product was analyzed by H-NMR. 1 The H-NMR spectrum is shown in Figure 1.

[0177] Example 4 Synthesis of polyacetals from polyacrylates and aminoacetaldehyde dimethyl acetals.

[0178] [ka] 10 g (0.021 mol) of di(trimethylolpropane)tetraacrylate, 9 g (0.086 mol) of aminoacetaldehyde dimethyl acetal, and 19 g of DOWANOL™ PM were placed in a 100 mL reaction vessel, and the reaction mixture was stirred at 50° C. for 10 hours. The resulting product was used as is without further purification. The reaction product was obtained in a 50% yield on dry content. 1 The product was analyzed by H-NMR. 1 The H-NMR spectrum is shown in Figure 2.

[0179] Example 5 Synthesis of polyacetals from trimethylolpropane ethoxylate triacrylate and aminoacetaldehyde dimethyl acetal.

[0180] [ka] 45.06 g of aminoacetaldehyde dimethyl acetal was placed in a reaction vessel equipped with a condenser, a stirrer, and a temperature probe. 42.33 g of trimethylolpropane ethoxylate triacrylate was slowly added to the reaction vessel over 10 minutes at room temperature to control the exotherm. The reaction mixture was then stirred at 60° C. for 6 hours.

[0181] Example 6 Synthesis of polyacetals from bisphenol A diglycidyl ether (BADGE) and aminoacetaldehyde dimethyl acetal.

[0182] [ka] 20 g (0.107 mol epoxy) of bisphenol A diglycidyl ether (BADGE), 11.44 g (0.109 mol) of aminoacetaldehyde dimethyl acetal, and 31.4 g of DOWANOL™ PM were placed in a 250 mL reaction vessel, and the reaction mixture was stirred at 50° C. for 10 hours. The resulting reaction mixture was used as is with a dry content of 50%. The crude reaction product was 1The crude reaction product was analyzed by H-NMR. 1 The H-NMR spectrum is shown in Figure 3.

[0183] Example 7 Synthesis of polyacetals from itaconates and aminoacetaldehyde dimethyl acetal.

[0184] [ka] 40 g (0.253 mol) of dimethyl itaconate and 79.8 g (0.253 mol) of aminoacetaldehyde dimethyl acetal were placed in a reaction vessel, and the reaction mixture was heated to 60°C with stirring. Once the temperature reached 60°C, 0.125 g (0.3 wt%) of sodium methoxide was added to the reaction vessel. The reaction vessel was then placed under a vacuum of 120 mmHg for 10 hours. The product was obtained as a pure viscous liquid and was used as is without further purification. The crude reaction product was 1 The H-NMR spectrum is shown in Figure 4.

[0185] Example 8 Synthesis of polyacetals from imidazolidone and glyoxal dimethyl acetal.

[0186] [ka] 5 g (0.058 mol) of 2-imidazolidone and 9 g of DOWANOL™ PM were placed in a 100 mL reaction vessel, and the reaction mixture was stirred at 50° C. until the 2-imidazolidone was completely dissolved. Next, 20 g (0.115 mol) of glyoxal dimethyl acetal and 0.25 g of K-cure (1 wt %) were added to the reaction vessel, and the reaction mixture was kept stirring at 50° C. for 10 hours. The product, with a dry content of 50%, was used as is without further purification.

[0187] Example 9 Synthesis of polyacetals from polycyclocarbonates and aminoacetaldehyde dimethyl acetal.

[0188] [ka] 10 g (0.095 mol) of aminoacetaldehyde dimethyl acetal, 10.4 g (0.0478 mol) of diglycerol dicyclocarbonate, and 20.4 g of DOWANOL™ PM were placed in a 100 mL reaction vessel, and the reaction mixture was stirred at 50° C. for 10 hours. The product, with a dry content of 50%, was used as is without further purification. The crude reaction product was 1 The H-NMR spectrum is shown in Figure 5.

[0189] Example 10 Radical copolymerization of dimethyl acetal methacrylamide (Example 3) in solvent-based acrylic resins 168 g of butyl glycol was placed in a reaction vessel equipped with a condenser, stirrer, and temperature probe and stirred at 115°C under an inert nitrogen atmosphere. A mixture of 48.4 g of dimethyl acetal methacrylamide (from Example 3), 188.1 g of methyl methacrylate, 15.5 g of methacrylic acid, and 7.56 g of TRIGONOX® 21S was added slowly and steadily to the reaction vessel over a period of 2 hours. The reaction mixture was stirred at 115°C for 4 hours, after which 84 g of butyl glycol was added to reach a nonvolatile content of 50%. The resulting acrylic resin had an aldehyde equivalent weight of 901.5 on a solids basis and an acid value of 40.1.

[0190] Example 11 Furanaldehyde was synthesized from 5,5'-[oxybis(methylene)]di-(2-furaldehyde).

[0191] [ka] 10 g (0.079 mol) of hydroxymethylfurfural (HMF) and 100 mL of dichloromethane were placed in a reaction vessel equipped with a condenser, a stirrer, and a temperature probe, and the mixture was stirred under an inert argon atmosphere. A mixture of 0.5 g of trifluoromethanesulfonic acid (triflic acid) and 10 mL of dichloromethane was added dropwise to the reaction vessel at 0 °C, and the temperature was maintained at 0 °C during the addition. After completion of the reaction, the organic phase was washed with 100 mL of water, followed by a second wash with 50 mL of water. The resulting organic phase was dried over anhydrous sodium sulfate. After removing the solids by filtration, the dichloromethane was removed by distillation, and the HMF was removed under vacuum. The resulting product was 1 The product was analyzed by H-NMR, and the spectrum showed that it contained 5% residual HMF.

[0192] Example 12 Preparation of hydroxymethylfurfural (HMF) methacrylate monomer

[0193] [ka] 100 g (0.793 mol) of hydroxymethylfurfural (HMF), 635.1 g of methyl methacrylate, and 0.7 g (0.0032 mol) of hydroquinone were placed in a reaction vessel equipped with a Dean-Stark receiver. The mixture was stirred at 100°C for 30 minutes to remove traces of water. 11.6 g of zirconium acetylacetonate was added to the reaction vessel, and the reaction mixture was stirred at 100°C for 10 hours. During this time, distillate containing methanol was periodically removed from the Dean-Stark receiver. The reaction mixture was then stirred at 100°C for 10 hours. -2 Methyl methacrylate was removed by distillation under a vacuum of 100 mbar at a temperature of 70°C. The product was redissolved in dichloromethane and washed three times with aqueous potassium bicarbonate. After a final wash with saturated aqueous brine, the organic phase was dried over anhydrous sodium sulfate. After filtration to remove the solids, the solvent was removed for 10 minutes. -2The reaction was distilled under vacuum at 1000 mbar and 70° C. The reaction procedure described gave the product as a viscous brown liquid in a yield of 139 g (90%). 1 H-NMR helped characterize it as HMF methacrylate. 1 H-NMR is shown in Figure 6.

[0194] All references and publications cited herein are expressly incorporated by reference in their entirety into this disclosure, except to the extent they may directly contradict this disclosure. While specific embodiments have been illustrated and described herein, those skilled in the art will understand that various alternative and / or equivalent implementations may be substituted for the specific embodiments illustrated and described without departing from the scope of the present disclosure. It is understood that this disclosure is not intended to be unduly limited by the exemplary embodiments and examples set forth herein, and that such examples and embodiments are presented by way of example only, with the scope of the present disclosure intended to be limited only by the claims set forth herein.

Claims

1. amides, aldehydes containing two or more carbon atoms, and a coating system comprising:

2. 10. The coating system of claim 1, wherein the amide is present in a molar ratio of 0.5 to 2.5 moles per mole of the aldehyde.

3. The amide is represented by the following formula (I): 【Chemistry 1】 In the formula, R １ is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R １ is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

4. The coating system of any one of claims 1 to 3, wherein the amide comprises a diamide, a triamide, or a polyamide.

5. The aldehyde is represented by the following formula (II) or formula (IIB): 【Chemistry 2】 In the formula, R ２ , R ３ , and R ４ are independently carbon-containing groups optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably R ２ , R ３ , and R ４ is independently an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group, and optionally the aldehyde is in a protected form, including an acetal or hydrate.

6. The coating system of any one of claims 1 to 5, wherein the aldehyde comprises a monoaldehyde.

7. The coating system of any one of claims 1 to 6, wherein the aldehyde comprises a dialdehyde or a polyaldehyde.

8. The coating system according to any one of claims 1 to 7, wherein the aldehyde is an oligomer.

9. The amide and the aldehyde form a reaction product represented by formula (III): 【Transformation 3】 In the formula, R １ is H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R １ is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R ２ is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably R ２ is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

10. The amide and the aldehyde form a reaction product represented by formula (IV): 【Chemistry 4】 In the formula, each R １ are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R １ is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R ２ is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably R ２ is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

11. The amide and the aldehyde form a reaction product represented by formula (V): 【Transformation 5】 In the formula, each R １ are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R １ is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R ２ is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably R ２ is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

12. The amide and the aldehyde form a reaction product represented by formula (VI): 【Transformation 6】 In the formula, each R １ are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R １ is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R ２ is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or combinations thereof, and preferably R ２ is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

13. The coating system of any one of claims 1 to 12, wherein the coating system is free or substantially free of formaldehyde.

14. The coating system of any one of claims 1 to 13, wherein the coating system is free or substantially free of isocyanates.

15. 15. The coating system of any one of claims 1 to 14, wherein the coating system is curable at a temperature of from 50°C to 150°C, from 75°C to 150°C, from 90°C to 150°C, or from 90°C to 125°C.

16. amides, and an aldehyde containing two or more carbon atoms.

17. The reaction product is a crosslinked product of formula (IV), (V), or (VI): 【Transformation 7】 In the formula, each R １ are independently H or a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R １ is H or an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group; R ２ is a carbon-containing group optionally further substituted with one or more oxygen, nitrogen, or sulfur atoms, or a combination thereof, and preferably R ２ is an alkyl, aryl, acyl, acrylate, carboxylic acid, urethane, ester, amide, carbonate, alkenyl, alkynyl, alkoxy, alcohol, amine, alkylamine, methacrylate, acrylamide, methacrylamide, vinyl, phenol, ketone, or urea group.

18. 18. The coating system of claim 16 or 17, wherein the coating system is in powder form.

19. The coating system of any one of claims 16 to 18, wherein the coating system comprises an organic solvent, water, or both.

20. 20. The coating system of any one of claims 16 to 19, wherein the coating system is free or substantially free of formaldehyde and structural units derived from formaldehyde.

21. 21. The coating system of any one of claims 16 to 20, wherein the coating system is free or substantially free of isocyanates and structural units derived from isocyanates.

22. The coating system of claim 5 , wherein the coating system is provided as a one-component coating and the aldehyde comprises a blocked aldehyde.

23. 23. The coating system of claim 22, wherein the protected aldehyde comprises an acetal or a hydrate.

24. 10. The coating system of claim 1, wherein the aldehyde is a protected aldehyde including an acetal or a hydrate.

25. 8. The coating system of claim 7, wherein the aldehyde comprises a polyaldehyde selected from the group consisting of terephthalaldehyde, glutaraldehyde, glyoxal, dimethoxyacetaldehyde, methylglyoxal, cyclohexane dicarbaldehyde, malondialdehyde bis(dimethyl acetal), 5,5'-(oxy-bis(methylene))bis-2-furfural, bis(dimethyl acetal) of imidazolidone, tetra-dimethyl acetal of glycoluril, bis(dimethyl acetal) of polyglycidyl ether, tri(aminoethyl dimethyl acetal) of itaconic acid, tri(aminoethyl dimethyl acetal) of TMPEOTA, and poly(dimethyl acetal) of polycyclocarbonate.

26. R on the acetal of formula (IIA) ６ Groups and R ７ 25. The coating system of claim 24, wherein the groups are the same.

27. 25. The coating system of claim 24, wherein the protected aldehyde comprises a cyclic acetal.

28. An article coated with the coating system of any one of claims 1 to 27.

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