BLOCKED BIO-BASED CARBOXYLIC ACIDS AND THEIR USE IN THERMOSETTING MATERIALS

Abstract

This invention relates to bio-based polyfunctional carboxylic acids reacted with vinyl ether compounds to form liquid vinyl-blocked bio-based polyfunctional carboxylic acids. These liquid vinyl-blocked bio-based polyfunctional carboxylic acids can be mixed with a polyfunctional vegetable oil-based epoxy resin to form a homogeneous curable coating composition. Upon curing at elevated temperature, thermoset coatings are formed which have excellent hardness, solvent resistance, adhesion, and flexibility. The invention also relates to the use of a curable coating composition comprising at least one polyfunctional vegetable oil-based epoxy resin and at least one vinyl-blocked bio-based polyfunctional carboxylic acid, which may be coated onto a substrate and cured thermally. Methods of making the vinyl-blocked bio-based polyfunctional carboxylic acids and curable coating compositions and substrates containing the same are also disclosed.

Claims

1. A curable coating composition comprising: a) at least one vinyl-blocked bio-based polyfunctional carboxylic acid compound comprising the reaction product of: i) at least one bio-based polyfunctional carboxylic acid; and ii) at least one vinyl ether compound; b) at least one polyfunctional vegetable oil-based epoxy resin; c) at least one catalyst; d) optionally, at least one solvent, at least one other additive, or mixture thereof; and e) optionally, at least one pigment.

2. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one bio-based polyfunctional carboxylic acid is selected from dicarboxylic acids, tricarboxylic acids, or mixtures thereof.

3. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one bio-based polyfunctional carboxylic acid is saturated or ethylenically unsaturated.

4. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one bio-based polyfunctional carboxylic acid is optionally substituted.

5. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one bio-based polyfunctional carboxylic acid is aromatic or non-aromatic.

6. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one bio-based polyfunctional carboxylic acid is selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, citric acid, furan dicarboxylic acid, and tartaric acid.

7. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one vinyl ether compound is linear, branched, or cyclic.

8. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid said at least one vinyl ether compound is selected from ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and isobutyl vinyl ether.

9. The curable coating composition of claim 1, wherein for the vinyl-blocked bio-based polyfunctional carboxylic acid the molar ratio of vinyl groups in said at least one vinyl ether compound and carboxylic groups in said at least one bio-based polyfunctional carboxylic acid range from 1.0:1.0 to 10:1.

10. The curable coating composition of claim 1, wherein said vinyl-blocked bio-based polyfunctional carboxylic acid is selected from one of the following: ##STR00052## ##STR00053##

11. The curable coating composition of claim 1, wherein said at least one polyfunctional vegetable oil-based epoxy resin is prepared by the epoxidation of at least one vegetable oil fatty acid ester of a polyol having more than four hydroxyl groups per molecule.

12. The curable coating composition of claim 11, wherein said at least one vegetable oil fatty acid ester of a polyol is prepared by the reaction of at least one polyol with four or more hydroxyl groups per molecule with a mixture of fatty acids or esters of fatty acids with a low molecular weight alcohol.

13. The curable coating composition of claim 12, wherein said polyol with four or more hydroxyl groups per molecule is selected from pentaerythritol, di-trimethylolpropane, di-pentaerythritol, tri-pentaerythritol, sucrose, glucose, mannose, fructose, galactose, and raffinose.

14. The curable coating composition of claim 13, wherein said fatty acids are selected from ethylenically unsaturated fatty acids, saturated fatty acids, or mixtures thereof.

15. The curable coating composition of claim 14, wherein said at least one vegetable oil fatty acid ester of a polyol having more than four hydroxyl groups per molecule is sucrose soyate.

16. The curable coating composition of claim 1, wherein said at least one polyfunctional vegetable oil-based epoxy resin is an epoxidized vegetable oil, vegetable oil-based epoxy resin, or mixture thereof.

17. An object coated with the curable coating composition of claim 1.

18. A method of making a vinyl-blocked bio-based polyfunctional carboxylic acid, comprising the step of reacting at least one bio-based polyfunctional carboxylic acid with at least one vinyl ether compound, at least one optional catalyst, and at least one optional solvent.

19. A method of making a curable coating composition of claim 1, comprising the step of mixing at least one vinyl-blocked bio-based polyfunctional carboxylic acid compound with at least one polyfunctional vegetable oil-based epoxy resin.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0027] FIG. 1 depicts an exemplary epoxidation of a sucrose fatty acid ester.

[0028] FIG. 2 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and azeleic acid (AzA) blocked by different vinyl ether compounds.

[0029] FIG. 3 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and succinic acid (SuA) blocked by different vinyl ether compounds.

[0030] FIG. 4 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and citric acid (CiA) blocked by different vinyl ether compounds and furan dicarboxylic acid (FDCA) blocked by isobutyl vinyl ether (IBVE).

[0031] FIG. 5 depicts the thermogravimetric analysis of cured coatings made using epoxidized sucrose soyate and ethyl vinyl ether (EVE) blocked acids (succinic (SuA), adipic (AdA), glutaric (GIA), pimelic (PiA), subaric (SbA), azeleic (AzA), and sebacic (SeA)).

DESCRIPTION OF THE INVENTION

Terminology and Definitions

[0032] Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, catalyst compositions, resin compositions, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

[0033] As used in the specification and the appended claims, the singular forms a, an, and the include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a vinyl ether compound includes a single vinyl ether compound as well as a combination or mixture of two or more vinyl ether compounds, reference to a carboxylic acid encompasses a single carboxylic acid as well as two or more carboxylic acids, and the like.

[0034] As used in the specification and the appended claims, the terms for example, for instance, such as, or including are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

[0035] In this specification and the claims that follow, optional or optionally means 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. For example, the phrase optionally substituted means that a non-hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Vinyl-Blocked Bio-Based Polyfunctional Carboxylic Acids

[0036] The invention relates to vinyl-blocked bio-based polyfunctional carboxylic acids comprising the reaction product of at least one bio-based polyfunctional carboxylic acid and at least one vinyl ether compound. The vinyl-blocked bio-based polyfunctional carboxylic acids are liquid at room temperature.

[0037] As used herein, a bio-based polyfunctional carboxylic acid means a bio-based acid comprising at least two carboxylic acid groups. For example, the bio-based polyfunctional carboxylic acid may be selected from dicarboxylic acids, tricarboxylic acids, or mixtures thereof. The dicarboxylic acids and tricarboxylic acids may be saturated or ethylenically unsaturated, optionally substituted by one or more substituents, and aromatic or non-aromatic. Unsaturation and/or substitution may occur in one or more positions anywhere on the alkyl chains of the dicarboxylic acids and tricarboxylic acids.

[0038] For example, the bio-based polyfunctional carboxylic acid may be a saturated dicarboxylic acid having the following general structure: HOOC(CH.sub.2).sub.nCOOH. In one embodiment, n may be an integer ranging from 0 to 22, preferably 2 to 16, more preferably 6 to 10. For example, the saturated dicarboxylic acid includes, but is not limited to, oxalic acid (n=0), malonic acid (n=1), succinic acid (n=2), glutaric acid (n=3), adipic acid (n=4), pimelic acid (n=5), suberic acid (n=6), azelaic acid (n=7), sebacic acid (n=8), undecanedioic acid (n=9), dodecanedioic acid (n=10), tridecanedioic acid (n=11), tetradecanedioic acid (n=12), pentadecanedioic acid (n=13), hexadecanedioic acid (n=14), heptadecanedioic acid (n=15), octadecanedioic acid (n=16), nonadecanedioic acid (n=17), icosanedioic acid (n=18), henicosanedioic acid (n=19), docosanedioic acid (n=20), tricosanedioic acid (n=21), and tetracosanedioic acid (n=22).

[0039] In another embodiment, the saturated dicarboxylic acid may be substituted by, for example, hydroxyl groups, as in tartaric acid, for example.

[0040] In another embodiment, the bio-based polyfunctional carboxylic acid may be an ethylenically unsaturated dicarboxylic acid selected from, for example, maleic acid, fumaric acid, glutanoic acid, traumatic acid, and muconic acid.

[0041] In one embodiment, the bio-based polyfunctional carboxylic acid may be selected from saturated and ethylenically unsaturated tricarboxylic acids, including, not limited to, citric acid, isocitric acid, homoisocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, 3-carboxy-cis,cis-muconic acid, and homoaconitic acid.

[0042] In a further embodiment, the bio-based polyfunctional carboxylic acid may be selected from aromatic and non-aromatic dicarboxylic acids and tricarboxylic acids, including, but not limited to, (ortho-) phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, and 2,5-furandicarboxylic acid (FDCA).

The vinyl ether compounds may be linear, branched, or cyclic, and optionally substituted. For example, the vinyl ether compounds may have the following general structure:

##STR00016##

[0043] wherein R may be a liner, branched, or cyclic C.sub.1-C.sub.18-alkyl group. For example, linear vinyl ether compounds include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, undecyl vinyl ether, dodecyl vinyl ether, tridecyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinyl ether, heptyl vinyl ether, and octadecyl vinyl ether. Branched vinyl ether compounds include, but are not limited to, isopropyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, and 2-ethyl hexyl vinyl ether. Cyclic vinyl ether compounds include, but are not limited to, cyclohexyl vinyl ether. Substituted vinyl ether compounds include, but are not limited to, hydroxybutyl vinyl ether.

[0044] Structures of exemplary vinyl-blocked bio-based polyfunctional carboxylic acids of the invention and their corresponding starting bio-based polyfunctional carboxylic acids and vinyl ether compounds are shown below in Table 3.

TABLE-US-00003 TABLE 3 Structures of exemplary vinyl-blocked bio-based polyfunctional carboxylic acids Bio-based polyfunctional carboxylic acids/vinyl ether compounds Vinyl-blocked bio-based polyfunctional carboxylic acids [00017] [00018] [00019] [00020] [00021] [00022] [00023] [00024] [00025] [00026] [00027] [00028]

[0045] The vinyl-blocked bio-based polyfunctional carboxylic acids may be synthesized by a variety of methods. In one embodiment, the vinyl-blocked bio-based polyfunctional carboxylic acids are synthesized by reacting the at least one bio-based polyfunctional carboxylic acid with the at least one vinyl ether compound, at least one optional catalyst, and at least one optional solvent. In one embodiment, the molar ratio of vinyl groups in the at least one vinyl ether compound and carboxylic groups in the at least one bio-based polyfunctional carboxylic acid used for the synthesis of the vinyl-blocked bio-based polyfunctional carboxylic acids may range from 1.0:1.0 to 10:1, more preferably 4.0:1 to 6.0:1.0. Preferably, a stoichiometric excess of moles of vinyl ether groups relative to the carboxylic acid groups is used.

[0046] In one embodiment, the optional catalyst may be selected from phosphoric acid, hydrochloric acid, sulfuric acid, and the like. In a further embodiment, the optional catalyst may be present in an amount ranging from about 0.01% to about 5.0% by wt., preferably about 0.5% to about 2.0% by wt., even more preferably about 0.1% to about 1.0% by wt., of the total reaction mixture.

[0047] In one embodiment, the optional solvent may be selected from benzene, toluene, xylene, heptane, hexane, and the like. In a further embodiment, the optional solvent may be present in an amount ranging from about 0.1% to about 50.0% by wt., preferably about 0.5% to about 15.0% by wt., even more preferably about 1.0% to about 2.0% by wt., of the total reaction mixture. Solvents may be used during the synthesis to reduce viscosity and facilitate the synthesis reaction.

[0048] After reacting, the optional catalyst may be removed using a base, such as, for example, potassium hydroxide, in water via liquid-liquid extraction. Excess vinyl ether may be removed using known methods in the art, for example, rotary evaporation.

[0049] In one embodiment, the reaction to make the vinyl-blocked bio-based polyfunctional carboxylic acids of the invention may be carried out at temperatures dependent on the vinyl ether compound used. For example, a reaction temperature of about 30 C. may be used for ethyl vinyl ether, about 70 C. may be used for propyl vinyl ether, and about 80 C. may be used for butyl or isobutyl vinyl ether. In one embodiment, the reaction temperature may range from about 25 C. to about 100 C., more preferably, from about 30 C. to about 90 C., even more preferably, from about 50 C. to about 70 C.

Curable Coating Compositions Comprising Vinyl-Blocked Bio-Based Polyfunctional Acids and Polyfunctional Vegetable Oil-Based Epoxidized Resins

[0050] The invention also relates to curable coating compositions comprising the vinyl-blocked bio-based polyfunctional carboxylic acids described above and polyfunctional vegetable oil-based epoxidized resins.

[0051] The polyfunctional vegetable oil-based epoxy resins include, but are not limited to, epoxidized vegetable oils, vegetable oil-based epoxy resins, and mixtures thereof. Polyfunctional as used herein in the phrase polyfunctional vegetable oil-based epoxy resin means the presence of two or more epoxide groups. Polyfunctional vegetable oil-based epoxy resins that may be used in the invention may be prepared in the manner disclosed in WO 2011/097484, the disclosure of which is incorporated by reference. For example, polyfunctional vegetable oil-based epoxy resins are prepared from the epoxidation of vegetable oil fatty acid esters of polyols having >4 hydroxyl groups/molecule. Polyol esters of fatty acids (PEFA's) containing four or more vegetable oil fatty acid moieties per molecule can be synthesized by the reaction of polyols with 4 or more hydroxyl groups per molecule with either a mixture of fatty acids or esters of fatty acids with a low molecular weight alcohol, as is known in the art. The former method is direct esterification while the latter method is transesterification. A catalyst may be used in the synthesis of these compounds. As shown in FIG. 1 with sucrose, as an exemplary polyol to be used in the invention, esterified with a vegetable oil fatty acid, epoxide groups may then be introduced by oxidation of the vinyl groups in the vegetable oil fatty acid to form epoxidized polyol esters of fatty acids (EPEFA's). The epoxidation may be carried out using reactions known in the art for the oxidation of vinyl groups with in situ epoxidation with peroxyacid being a preferred method.

[0052] Polyols having at least 4 hydroxyl groups per molecule suitable for the process include, but are not limited to, pentaerythritol, di-trimethylolpropane, di-pentaerythritol, tri-pentaerythritol, sucrose, glucose, mannose, fructose, galactose, raffinose, and the like. Polymeric polyols can also be used including, for example, copolymers of styrene and allyl alcohol, hyperbranched polyols such as polyglycidol and poly(dimethylpropionic acid), and the like. Exemplary polyols are shown below in Scheme 3 with the number of hydroxyl groups indicated by (f). Comparing sucrose to glycerol, there are a number of advantages for the use of a polyol having more than 4 hydroxyl groups/molecule including, but not limited to, a higher number of fatty acids/molecule; a higher number of unsaturations/molecule; when epoxidized, a higher number of oxiranes/molecule; and when crosslinked in a coating, higher crosslink density.

[0053] The degree of esterification may be varied. The polyol may be fully esterified, where substantially all of the hydroxyl groups have been esterified with the fatty acid, or it may be partially esterified, where only a fraction of the available hydroxyl groups have been esterified. It is understood in the art that some residual hydroxyl groups may remain even when full esterification is desired. In some applications, residual hydroxyl groups may provide benefits to the resin. Similarly, the degree of epoxidation may be varied from substantially all to a fraction of the available double bonds. The variation in the degree of esterification and/or epoxidation permits one of ordinary skill to select the amount of reactivity in the resin, both for the epoxidized resins and their derivatives.

##STR00029##

[0054] The hydroxyl groups on the polyols can be either completely reacted or only partially reacted with fatty acid moieties. Any ethylenically unsaturated fatty acid may be used to prepare a polyol ester of fatty acids to be used in the invention, with polyethylenically unsaturated fatty acids, those with more than one double bond in the fatty acid chain, being preferred. The Omega 3, Omega 6, and Omega 9 fatty acids, where the double bonds are interrupted by methylene groups, and the seed and vegetable oils containing them may be used to prepare polyol ester of fatty acids to be used in the invention. Mixtures of fatty acids and of vegetable or seed oils, plant oils, may be used in the invention. The plant oils, as indicated above, contain mixtures of fatty acids with ethylenically unsaturated and saturated fatty acids possibly present depending on the type of oil. Examples of oils which may be used in the invention include, but are not limited to, corn oil, castor oil, soybean oil, safflower oil, sunflower oil, linseed oil, tall oil fatty acid, tung oil, vernonia oil, and mixtures thereof. As discussed above, the polyol fatty acid ester may be prepared by direct esterification of the polyol or by transesterification as is known in the art. The double bonds on the fatty acid moieties may be converted into epoxy groups using known oxidation chemistry yielding polyfunctional epoxy resins (EPEFA's)epoxidized polyol esters of fatty acids. Table 4 lists the double bond functionality of some representative fatty acid esters (=/FA) based upon the number of esterified hydroxyl groups (f).

TABLE-US-00004 TABLE 4 Double Bond Functionality of Fatty Acids in Selected Oils Functionality of = for FA esters having the indicated FA functionality Oil Avg. =/FA f = 3 f = 4 f = 6 f = 8 Soybean 1.54 4.62 6.16 9.24 12.32 Safflower 1.66 4.98 6.64 9.96 13.28 Sunflower 1.39 4.17 5.56 8.34 11.12 Linseed 2.10 6.30 8.40 12.60 16.80 Tall Oil 1.37 4.11 5.48 8.22 10.96 Fatty Acid

[0055] The epoxidation of sucrose esters of ethylenically unsaturated vegetable oil fatty acids results in unique bio-based resins having a high concentration of epoxy groups. As has been seen, functionalities of 8 to 15 epoxide groups per molecule may be achieved, depending on the composition of the fatty acid used and the degree of substitution of the fatty acids on the sucrose moiety. This is substantially higher than what can be achieved through epoxidation of triglycerides which range from about 4 for epoxidized soybean oil up to 6 for epoxidized linseed oil.

[0056] The high epoxide functionality of these resins coupled with the rigidity of a polyol having at least 4 hydroxyl groups per molecule, such as sucrose, has significant implications for the use of these polyols and their derivatives in curable coating compositions of the invention. With the epoxidized polyol esters of fatty acids (EPEFA's), crosslinked materials having an outstanding combination of properties can be achieved.

[0057] Preferably, the polyfunctional vegetable oil-based epoxidized resin is selected from epoxidized sucrose soyate (ESS). As discussed above, fatty acids from soybean oil can be used to form esters with sucrose. Sucrose soyate (SS) has many positive properties that make it an ideal starting point for bio-based coatings, including that it is polyfunctional, has low viscosity (300-400 cP) with 100% solids, is 100% bio-based, and is commercially available. Sucrose, soybean oil, and sucrose soyate have the following structures:

##STR00030##

Sucrose Soyate

[0058] In contrast to SS, epoxidized sucrose soyate (ESS) is more versatile. Many types of coatings can be formed from ESS. Also, ESS has many beneficial properties, including 12 epoxy groups per molecule (epoxy equivalent weight of 270 g eq.sup.1), low viscosity (5,000 cP), 100% bio-based, easily synthesized, and is a clear and colorless resin. ESS can be synthesized in the manner disclosed in Pan et al., Green Chemistry 13:965-975 (2011), the disclosure of which is incorporated herein by reference. See also Scheme 4 below.

##STR00031##

[0059] The curable coating compositions comprising the vinyl-blocked bio-based polyfunctional carboxylic acids and the polyfunctional vegetable oil-based epoxidized resins can be prepared by a variety of methods. In one embodiment, this method comprises combining the vinyl-blocked bio-based polyfunctional carboxylic acids described above with the polyfunctional vegetable oil-based epoxidized resins to make curable coating compositions of the invention. As a non-limiting example, the curable coating compositions can be prepared by combining the vinyl-blocked bio-based polyfunctional carboxylic acids, described above, and the polyfunctional vegetable oil-based epoxidized resins in the presence of at least one optional solvent, such as t-butyl acetate (TBA), methyl n-amyl ketone (MAK), ethyl 3-ethoxyproprionate (EEP), and at least one optional catalyst, such as dibutyltindilaurate (DBTDL).

[0060] In one embodiment, for the synthesis of the curable coating compositions of the invention, a stoichiometric equivalent amount of epoxide and blocked acid groups may be used. In another embodiment, the ratio of epoxy equivalents in the polyfunctional vegetable oil-based epoxidized resin to carboxylic equivalents in the vinyl-blocked bio-based polyfunctional carboxylic acids can be varied in order to vary the crosslink density and the properties of the curable coating composition.

[0061] The invention also relates to the use of a curable coating composition which may be coated onto a substrate and cured. The substrate can be any common substrate such as paper, polyester films such as polyethylene and polypropylene, metals such as aluminum and steel, glass, urethane elastomers, primed (painted) substrates, and the like. The invention also provides methods for coating such substrates by applying the curable coating composition to the substrate. The coating may be applied by methods know in the art such as drawdown, conventional air-atomized spray, airless spray, roller, brush. The curable coating composition of the invention may be cured thermally. Upon curing at elevated temperature, thermoset coating compositions of the invention have excellent hardness, solvent resistance, adhesion, and flexibility. In another embodiment of the invention, the invention relates to an article of manufacture comprising a thermoset coating composition of the invention.

[0062] A curable coating composition according to the invention may comprise a pigment (organic or inorganic) and/or other additives and fillers known in the art. For example a curable coating composition of the invention may further contain coating additives. Such coating additives include, but are not limited to, one or more leveling, rheology, and flow control agents such as silicones, fluorocarbons or cellulosics; extenders; reactive coalescing aids such as those described in U.S. Pat. No. 5,349,026, the disclosure of which is incorporated herein by reference; plasticizers; flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; colorants; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti-flooding and anti-floating agents; biocides, fungicides and mildewcides; corrosion inhibitors; thickening agents; or coalescing agents. Specific examples of such additives can be found in Raw Materials Index, published by the National Paint & Coatings Association, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005. Further examples of such additives may be found in U.S. Pat. No. 5,371,148, incorporated herein by reference.

[0063] Examples of flatting agents include, but are not limited to, synthetic silica, available from the Davison Chemical Division of W. R. Grace & Company as SYLOID; polypropylene, available from Hercules Inc., as HERCOFLAT; synthetic silicate, available from J. M. Huber Corporation, as ZEOLEX.

[0064] Examples of viscosity, suspension, and flow control agents include, but are not limited to, polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkylene amine salts of an unsaturated fatty acid, all available from BYK Chemie U.S.A. as ANTI TERRA. Further examples include, but are not limited to, polysiloxane copolymers, polyacrylate solution, cellulose esters, hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide wax, polyolefin wax, hydroxypropyl methyl cellulose, polyethylene oxide, and the like.

[0065] Solvents may also be added to the curable coating compositions in order to reduce the viscosity. Hydrocarbon, ester, ketone, ether, ether-ester, alcohol, or ether-alcohol type solvents may be used individually or in mixtures. Examples of solvents can include, but are not limited to benzene, toluene, xylene, aromatic 100, aromatic 150, acetone, methylethyl ketone, methyl amyl ketone, butyl acetate, t-butyl acetate, tetrahydrofuran, diethyl ether, ethylethoxy propionate, isopropanol, butanol, butoxyethanol, and so on.

EXAMPLES

Example 1

Synthesis of Blocked-Azelaic Acid Compounds (Table 5)

[0066] In a 50-mL single neck round bottom flask, azelaic acid (5.00 g, 0.0266 mol) was combined with 4 molar equivalents (0.106 mol) of the appropriate vinyl ether compound (7.66 g of ethyl vinyl ether, 9.15 g of propyl vinyl ether, or 10.64 g of butyl or isobutyl vinyl ether). To this mixture, solid phosphoric acid (0.017 g, 0.177 mmol) was added. The mixture was stirred for 5 hours at a temperature dependent on the vinyl ether compound used (30 C. for ethyl vinyl ether, 70 C. for propyl vinyl ether, or 80 C. for butyl or isobutyl vinyl ether). After the reaction mixture cooled to room temperature, it was transferred to a 125-mL separatory funnel, where 40 mL of 0.05 M KOH was added. The funnel was capped and shaken to extract the phosphoric acid. The organic layer was isolated, and rotary evaporation was used to remove the excess vinyl ether. Blocked-azelaic acid compounds were recovered in 84-94% yield. Example .sup.1H NMR data for propyl vinyl ether blocked azelaic acid (CDCl.sub.3, , ppm): 0.81 (triplet, 6H, CH.sub.3), 1.234 (singlet, 6H, O2CCH2-CH2-CH.sub.2CH.sub.2CH.sub.2CH2-CH2-CO2), 1.274 and 1.287 (singlet, 6H, OCH(CH.sub.3)O), 1.49 (multiplet, 8H, O2CCH2-CH.sub.2 and OCH2-CH.sub.2CH3), 2.21 (triplet, 4H, O2CCH.sub.2), 3.49 (quartet, 4H, OCH.sub.2CH2-CH3), 5.82 and 5.83 (quartet, 2H, OCH(CH3)O). A small amount of single blocked molecules is present, as evident by some peak splitting and a small carboxylic acid peak present in the NMR.

Example 2

Synthesis of Blocked-Succinic Acid Compounds (Table 5)

[0067] The procedure used for blocking azelaic acid compounds was used for their succinic acid equivalents, using 5.00 g succinic acid and the properly adjusted amounts of vinyl ether and phosphoric acid. Example .sup.1H NMR data for propyl vinyl ether blocked succinic acid (CDCl.sub.3, , ppm): 0.83 (triplet, 6H, CH.sub.3), 1.30 (multiplet, 4H, OCH(CH.sub.2)O), 1.50 (quartet, 4H, OCH2-CH.sub.2CH3), 2.56 (triplet, 4H, O2CCH.sub.2CH.sub.2CO2), 3.33 (quartet, 4H, OCH.sub.2CH2-CH3), 5.86 and 5.87 (s, 2H, OCH(CH2)-O). The presence of other peaks suggests that the product is 3:1 mixture of two blocked carboxylic acids per molecule to one blocked carboxylic acid per molecule.

Example 3

Synthesis of Blocked-Citric Acid Compounds (Table 5)

[0068] In a 50-mL single neck round bottom flask, citric acid (5.00 g, 0.0260 mol) was combined with 6 molar equivalents (0.156 mol) of the appropriate vinyl ether compound (13.45 g of propyl vinyl ether or 15.64 g of butyl or isobutyl vinyl ether). To this mixture, solid phosphoric acid (0.026 g, 0.260 mmol) was added. The mixture was stirred for 18 hours using the same temperatures used for the block-azelaic acid synthesis. The phosphoric acid was extracted using 40 mL of 0.05 M KOH, and the excess vinyl ether was removed via rotary evaporation. Blocked-citric acid compounds were recovered in 84-94% yield.

Example 4

Synthesis of isobutyl vinyl ether blocked 2,5-furandicarboxylic acid (Table 5)

[0069] In a 50-mL single neck round bottom flask, 2,5-furandicarboxylic acid (FDCA; 5.00 g, 0.0320 mol) was combined with isobutyl vinyl ether (IBVE; 12.83 g, 0.128 mol) and solid phosphoric acid (0.021 g, 0.214 mmol). The mixture was stirred for 18 hours at 80 C. The phosphoric acid was extracted using 40 mL of 0.05 M KOH. The organic layer was filtered using a Buchner funnel, and the excess isobutyl vinyl ether was removed from the filtered liquid via rotary evaporation. This resulted in 6.40 g of IBVE-FDCA (56% yield) being recovered, along with the recovery of 1.76 g of unreacted FDCA (80% of the unreacted starting material).

TABLE-US-00005 TABLE 5 Structure of vinyl ether blocked acids produced Blocked Acid Name Abbreviation Structure Ethyl vinyl ether blocked succinic acid EVE-SuA [00032] Propyl vinyl ether blocked succinic acid PVE-SuA [00033] Butyl vinyl ether blocked succinic acid BVE-SuA [00034] Isobutyl vinyl ether blocked succinic acid IBVE-SuA [00035] Ethyl vinyl ether blocked azelaic acid EVE-AzA [00036] Propyl vinyl ether blocked azelaic acid PVE-AzA [00037] Butyl vinyl ether blocked azelaic acid BVE-AzA [00038] Isobutyl vinyl ether blocked azelaic acid IBVE-AzA [00039] Ethyl vinyl ether blocked citric acid EVE-CiA [00040] Propyl vinyl ether blocked citric acid PVE-CiA [00041] Butyl vinyl ether blocked citric acid BVE-CiA [00042] Isobutyl vinyl ether blocked citric acid IBVE-CiA [00043] Isobutyl vinyl ether blocked 2,5- furandicarboxylic acid IBVE-FDCA [00044]

Example 5

Coating Formulation Method

[0070] Coating formulations were made using a 1:1 mole ratio of epoxide to acid and 5% 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) by total weight. For example, epoxidized sucrose soyate (ESS, 5.00 g, 0.0188 equivalents), ethyl vinyl ether blocked azelaic acid (EVE-AzA, 3.12 g, 0.0188 equivalents), and DBU (0.41 g, 0.0027 equivalents) were combined in a formulation cup. The mixture was hand stirred to obtain a consistent solution.

[0071] Coating Application and Curing.

[0072] A Gardco wet film applicator was used to apply a 4 mil thick layer of each formulation onto Bonderite 1000 treated steel and glass substrates. The substrates were then placed in an oven preheated to 170 C., where they were allowed to cure for 4 hours.

[0073] Measurement of Coating Properties.

[0074] Dried film thickness was measured on the steel panels using a Byko-test 8500 (Table 6). Konig hardness of the films was measured using a Byk Gardner pendulum hardness tester on the steel panels (Table 6). Pencil hardness, crosshatch adhesion, MEK double rubs, and reverse impact were measured for dried films on steel panels (Table 6). Thermogravimetric analysis was performed by removing a sample of each coating from the glass substrate and was analyzed using a TA Instruments Q-Series 500 Thermogravimetric analyzer (Table 7). T.sub.10% is the temperature at 10 percent weight loss. FIGS. 2-4 depict the thermogravimetric analysis of the cured coatings.

TABLE-US-00006 TABLE 6 Dry film properties of ESS and blocked acid thermosets prepared MEK Konig Pencil Crosshatch Double Reverse Blocked Acid Film Thickness Hardness Hardness Adhesion Rubs Impact EVE-Azelaic Acid 20.1 8.0 m 96.3 7.6 3H 5B 400+ >168 in .Math. lb PVE-Azelaic Acid 23.1 5.2 m 49.7 1.5 3H 5B 400+ >168 in .Math. lb BVE-Azelaic Acid 13.2 5.4 m 82.0 4.4 3H 5B 400+ >168 in .Math. lb IBVE-Azelaic Acid 11.2 3.4 m 93.7 4.2 2H 5B 400+ >168 in .Math. lb EVE-Succinic Acid 24.6 11.8 m 24.7 7.5 3B 5B 400+ 160 in .Math. lb PVE-Succinic Acid 28.4 3.6 m 20.3 0.6 2B 5B 400+ >168 in .Math. lb BVE-Succinic Acid 33.7 8.7 m 18.7 2.9 2B 5B 400+ >168 in .Math. lb IBVE-Succinic Acid 25.8 5.1 m 25.0 1.0 2B 5B 400+ >168 in .Math. lb EVE-Citric Acid 104 25 m 56.3 1.5 3H OB 70 8 in .Math. lb PVE-Citric Acid 74.1 50.9 m 18.7 0.6 3B 2B 50 20 in .Math. lb BVE-Citric Acid 49.3 28.4 m 24.0 1.0 <EE 3B 100 40 in .Math. lb IBVE-Citric Acid 38.8 20.5 m 67.7 3.2 HB 0B 100 40 in .Math. lb IBVE-FDCA 52.9 5.3 m 55.7 3.2 H 5B 380 140 in .Math. lb

TABLE-US-00007 TABLE 7 Thermal stability of cured coating formulations, as determined by TGA Blocked Acid T.sub.10%, C. EVE-Azelaic Acid 329 PVE-Azelaic Acid 297 BVE-Azelaic Acid 319 IBVE-Azelaic Acid 311 EVE-Succinic Acid 313 PVE-Succinic Acid 311 BVE-Succinic Acid 301 IBVE-Succinic Acid 311 EVE-Citric Acid 312 PVE-Citric Acid 317 BVE-Citric Acid 328 IBVE-Citric Acid 312 IBVE-FDCA 304

Example 6

Synthesis of Additional Ethyl Vinyl Ether-Blocked Bio-Based Polyfunctional Carboxylic Acids, Curable Coatings Containing the Same and Epoxide Sucrose Soyate, and Properties Thereof

[0075] The procedures used to synthesize the vinyl-blocked bio-based polyfunctional carboxylic acid compounds above were used to make the following ethyl vinyl ether (EVE)-blocked bio-based polyfunctional carboxylic acids: EVE-succinic acid (EVE-SuA), EVE-glutaric acid (EVE-GIA), EVE-adipic acid (EVE-AdA), EVE-pimelic acid (EVE-PiA), EVE-suberic acid (EVE-SbA), EVE-azelaic acid (EVE-AzA), and EVE-sebacic acid (EVE-SeA). See Table 8. Coating compositions containing these vinyl-blocked bio-based polyfunctional carboxylic acid compounds and epoxide sucrose soyate (ESS) were made, applied, cured, and properties measured (Table 9) in the same manner as the coating compositions above. FIG. 5 depicts the thermogravimetric analysis of these cured coatings.

TABLE-US-00008 TABLE 8 Structure of ethyl vinyl ether blocked acids produced Blocked Acid Name Abbreviation Structure Ethyl vinyl ether blocked succinic acid EVE-SuA [00045] Ethyl vinyl ether blocked glutaric acid EVE-GIA [00046] Ethyl vinyl ether blocked adipic acid EVE-AdA [00047] Ethyl vinyl ether blocked pimelic acid EVE-PiA [00048] Ethyl vinyl ether blocked suberic acid EVE-SbA [00049] Ethyl vinyl ether blocked azelaic acid EVE-AzA [00050] Ethyl vinyl ether blocked sebacic acid EVE-SeA [00051]

TABLE-US-00009 TABLE 9 Dry film properties of ESS and ethyl vinyl ether blocked acid thermosets prepared MEK Konig Pencil Crosshatch Double Reverse Blocked Acid Film Thickness Hardness Hardness Adhesion Rubs Impact EVE-Succinic Acid 24.6 11.8 m 25 3B 5B 400+ >168 in .Math. lb EVE-Glutaric Acid 20.2 10.9 m 27 2B 5B 400+ >168 in .Math. lb EVE-Adipic Acid 21.9 5.5 m 157 B 5B 400+ >168 in .Math. lb EVE-Pimelic Acid 16.6 1.7 m 160 HB 5B 400+ >168 in .Math. lb EVE-Suberic Acid 29.5 3.1 m 135 H 5B 400+ >168 in .Math. lb EVE-Azelaic Acid 15.3 7.1 m 170 3H 5B 400+ >168 in .Math. lb EVE-Sebacic Acid 25.8 5.7 m 115 HB 5B 400+ >168 in .Math. lb

CONCLUSIONS

[0076] Azelaic acid, succinic acid, and FDCA have superior solvent resistance, adhesion, and flexibility. Higher hardness of azelaic acid compared to the others suggests a higher crosslinked system is produced. The poor properties of citric acid based coatings suggest a lower inter-ESS crosslinked network is formed.