Liquid curable mediums and siccatives based on vanadium compounds and polymer ligand materials

Abstract

The invention pertains generally to coatings containing a binder curable by an autoxidation mechanism and at least one siccative including a vanadium compound and polymer ligand bearing sulfonate or sulfonic acid moieties, the siccative itself, and various methods, kits, and uses related thereto.

Description

Liquid Curable Mediums and Siccatives based on Vanadium Compounds and Polymer Ligand MaterialsTechnical Field

[0001] The invention described herein pertains generally to the formulation of autoxidizing formulations in combination with siccatives suitable for these formulations, the siccatives themselves, and kits, methods, and uses pertaining thereto.Background of the Invention

[0002] Air-drying binders, including polyester resins modified by plant oils known as alkyd resins, are widely used in the paint-producing industry due to their low price, high content of biologically renewable sources and relatively easy biodegradability (Hofland, A., Prog. Org. Coat., 73, 274-282 (2012)). Synthetic resins modified by drying and semidrying plant oils are cured by the action of air oxygen. A chemical process, known as autoxidation, is responsible for transformation of a liquid coating layer to a cured, solid coating film. As autoxidation proceeds sluggishly at ambient conditions, it is commonly accelerated by the action of special catalysts known as primary driers or siccatives. These compounds enable faster decomposition of hydroperoxides that are kinetically stable intermediates generated in the first step of the autoxidation curing process. Use of such catalysts results in considerable acceleration of subsequent reactions in a propagation step of autoxidation, which produces radicals and determines the final structure of cured resins. Crosslinking of airdrying paints and coatings proceeds through addition of radicals on double bond systems and radical recombination in a termination step (Soucek, M. D. et. al; Prog. Org. Coat., 73, 435-454 (2012)).

[0003] Cobalt carboxylates soluble in organic solvents, such as cobalt 2-ethylhexanoate, cobalt neodecanoate and cobalt naphthenate, are currently widely used in the paint-producing industry as primary driers due to high catalytic activity in solventborne and high-solid, air-drying binders (Honzicek, J.; Ind. Eng. Chem. Res. 58, 12485-12505 (2019)). However, application of the cobalt compounds has been legislatively restricted due to potential health and ecological issues (Leyssens, L. et al., Toxicology 387, 43-56 (2017); Simpson, N. et al; Catalysts, 9, 825 (2019)).

[0004] Ongoing toxicological investigation has led to reclassification of such cobalt driers to carcinogens and may ultimately lead to prohibition of their use in paints. Replacements of toxic cobalt that can be used in both waterborne and solventborne coatings as well as curable composite materials are beneficial. Further, enabling water-based alkyd use is of critical importance in reducing volatile organic compounds for the environment. The replacement of both organic solvents and toxic catalysts is of critical importance as the chemical industry looks for more sustainable and environmentally friendly alternatives to existing technologies.

[0005] For adequate incorporation into coating compositions, siccatives should further exhibit high stability toward air-oxygen. They should also exhibit good compatibility to dissolve in a variety of organic solvents and water.

[0006] Such circumstances have led to research in the fields of iron and manganese-based catalysts capable of replacing cobalt-based driers (e.g., WO 2008 / 003652 A1 ; Simpson, N. et al, Catalysts, 9, 825 (2019); Matuskova, E. et al, Materials, 13, 642 (2020).

[0007] Vanadium-based compounds, soluble in organic solvents, are another alternative for cobalt carboxylates reported in research and patent literature. Conventional such compounds include oxidovanadium-based compounds bearing carboxylates (e.g., EP 0 304 149 B1 ; US 6063841 A; Preininger, O. et al., J. Coat. Technol. Res. 13, 479-487 (2016)); acetylacetonates (e.g., US 6063841 ; A, Preininger, O. et al., Prog. Org. Coat. 88, 191-198 (2015); Preininger, O. et al., Inorg. Chim. Acta 462, 16-22 (2017); Charamzova, I. et al., Inorg. Chim. Acta 492, 243-248 (2019)); ketiminates (e.g., US 6063841 A); organophosphates (e.g., US 6063841 A); and dithiocarbamates (e.g., CZ 307597 B6; Charamzova, I. et al., J. Coat. Technol. Res. 2020, 17, 1113-1122.). Some of these compounds were found to be suitable as secondary driers improving visual and mechanical properties of final paint films into which the compounds are incorporated (e.g., WO 2015 / 082553 A1 , WO 2017 / 085154 A1 , WO 2010 / 106033 A1). It is noteworthy, however, that none of the reported vanadium-based driers provide commercial application, owing to low solubility, high production costs or low stability upon storage. Other conventional vanadium-based catalysts include oxidovanadium compounds bearing anions of sulfonic acids as counterions. Such sulfonic acid counterions in conventional systems are molecular in nature, contemplating only small molecule anions of sulfonic acid counterions. Such conventional systems can provide inadequate loading of vanadium metal (therefore requiring costly, additional material to show adequate catalytic effect) and can, in some instances, cause defects in the appearance of coatings to which they are added, for example in the uniformity of the coating finish or in a tendency to yellow following coating cure.

[0008] It is acknowledged in the art that vanadium catalysts can cause unacceptable yellowing in coatings following coating cure. WO 2017 / 085154A1 at 3:1 - 8. It is further believed in the art that the tendency to yellow is due to the formation of aldehydes from unsaturated alkyd chains and subsequent combination of the aldehydes with ambient amines, where the formation of aldehydes is a result of the peroxide oxidation of unsaturated alkyd chains that is catalyzed by vanadium catalysts and other metal driers. Ad Hofland, The Drying of Alkyd Paints, UL SOLUTIONS PROSPECTOR KNOWLEDGE CENTER (NOV. 11 , 2016), https: / / www.ulprospector.com / knowledge / 5512 / pc-the-drying-of- alkyd-paints / . Thus, increasing catalytic activity can increase the reactions that cause coating yellowing. At the same time, improvements in cured coating hardness (to a point) and dry time are positively correlated with catalytic activity. Therefore, the art predicts a tradeoff between yellowing on the one hand and hardness and dry time on the other with respect to modifications of vanadium catalysts that affect catalytic activity. Indeed, WO 2017 / 085154A1 regards the yellowing caused by vanadium catalysts as a characteristic inherent to the vanadium material and seeks to solve this problem by using smaller concentrations of molecular vanadium catalyst (i.e., removing thevanadium) and supplementing with iron-based driers to achieve reduced yellowing while balancing “initial and final hardness” of a coating, acknowledging the perceived trade-off between yellowing and hardness for alkyd coating formulations including vanadium catalysts. WO 2017 / 085154A1 at 3:16 - 4:2.

[0009] Additional, non-cobalt, vanadium-based catalysts providing improved or maintained hardness, cure time, and appearance (uniformity of coating finish and lessened tendency to yellow following coating cure) in cured solventborne or waterborne coatings over conventional systems would be advantageous. Alternative, non-cobalt, vanadium-based accelerants for curable composite materials would also be advantageous. The present invention addresses this.Summary of the Invention

[0010] The present invention is directed to siccatives including at least one polymer ligand material in combination with at least one vanadium compound as well as formulations including said siccatives.

[0011] One aspect of the invention is a siccative for an autoxidizing coating formulation, wherein the siccative includes a vanadium compound and a polymer ligand including at least one structural unit derived from an ethylenically unsaturated monomer including a sulfonic acid or sulfonate moiety capable of coordinating a vanadium atom, and, optionally, a solvent. In further aspects of the invention, the at least one ethylenically unsaturated monomer bearing a sulfonic acid or sulfonate moiety is of Formula I:Formula II:or Formula III:where each of Ri, R2, and R3 are independently hydrogen or a C1 to C3 alkyl group; where each R4 is a methoxy group; where z is 0 or 1 ; where each Rs is of Formula IIA:wherein the nitrogen is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; or of Formula I IB:wherein the oxygen is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; such that any ethylenically unsaturated monomer of Formula II is either a sulfonate or sulfonic acid acrylate monomer or a sulfonate or sulfonic acid acrylamide monomer; where each Re is independently a C1 to C9 alkyl group; where y is 0 or 1 ; where each R? is independently a C1 to C9 alkyl group; and where each Q is SO3H or SOr X, where X is a cation of a salt.

[0012] Another aspect of the invention involves a coating composition comprising the above siccative, a binder curable by autoxidation mechanism, and, optionally, other components, including additives for coatings such as solvents, antioxidants (sometimes referred to as antiskinning agents), additional siccatives, auxiliary or secondary driers, colorants (including inks and colored pigments),fillers, plasticizers, viscosity modifiers, crosslinkers, UV light absorbers, stabilizers, antistatic agents, flame retardants, lubricants, emulsifiers (in particular where an oxidatively curable coating composition or formulation of the invention is aqueous-based), anti-foaming agents, viscosity modifiers, antifouling agents, biocides (e.g. bactericides, fungicides, algaecides and insecticides), anticorrosion agents, antireflective agents, anti-freezing agents, waxes and thickeners.

[0013] In yet further embodiments of the invention, the invention pertains to methods of forming the above coating compositions, methods of coating an article with the above coating compositions, the use of the above siccatives and components therein for coatings containing a binder curable by autoxidation mechanism, and kits for forming the above coating compositions.

[0014] This Summary is not intended to be limiting. The vanadium compound and polymer ligand siccative composition, coating composition containing the same, methods of forming a coating composition, methods of forming a coated article, and uses and kits for forming coating compositions of the present disclosure may be combined with one or more optional aspects as further disclosed herein.

[0015] These and other objects of this invention will be evident when viewed in light of the detailed description and appended claims.Detailed Description of the Invention

[0016] The present disclosure broadly relates to siccatives for use in autoxidizing compositions like coatings or composites. In particular, the disclosure relates to such siccatives that include vanadium- based materials in association with polymeric ligand material. Such vanadium-based materials, as they pertain to the disclosure herein, are hereinafter referred to as “vanadium compounds.” In one aspect of the invention, the vanadium compound of the inventive siccative is an oxidovanadium species. Such polymeric ligand material, as it pertains to the disclosure herein, is hereinafter referred to as “polymer ligand” and includes at least one structural unit bearing a sulfonic acid or sulfonate moiety capable of coordinating a vanadium atom. Such siccatives can yield coatings having improved or maintained hardness, improved or maintained dry or cure times, and improved or maintained appearance, such as with respect to uniformity of cured coating finish or coating yellowing, in comparison to conventional coating compositions. Such siccatives, in composite formulations, as accelerants, can aid effective curing to permit reduction or avoidance of toxic cobalt accelerators without sacrificing the ability to cure.

[0017] The present disclosure further relates to coating compositions containing the inventive siccatives including vanadium compound and polymer ligand. Such coating compositions further include a binder curable by autoxidation mechanism, such as an alkyd binder or resin, and may optionally include other materials.

[0018] The present disclosure further relates to formulations for composite materials, wherein the formulations include siccatives including the vanadium compound and polymer ligand materials as an accelerant, a polymeric binder material such as, for example, an unsaturated polyester, a vinyl ester, or an acrylic ester, an initiator material, such as a peroxide initiator, and optionally, other materials.

[0019] The present disclosure further relates to methods of forming such coatings or composites, coated articles employing such coatings or composite materials employing such formulations, and kits and uses relating thereto.GLOSSARY OF TERMS

[0020] Terms such as “a,” “an,” and “the” are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terms “a,” “an,” and “the” are used interchangeably with the term “at least one.” The phrases “at least one of’ and “comprises at least one of’ followed by a list refers to any one of the items in the list and any combination of two or more items in the list.

[0021] The term “about” is used here in conjunction with numeric values to include normal variations in measurements as expected by persons skilled in the art and is understood have the same meaning as “approximately” and to cover a typical margin of error, such as ± 5 % of the stated value.

[0022] The term “aliphatic group” is used here to refer to a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.

[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 (linear), branched, cyclic, and bicyclic alkyl groups, and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise indicated, the alkyl groups typically contain from 1 to 30 carbon atoms. In some embodiments, the 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, etc.

[0024] The term “aromatic ring” is used in this disclosure to refer to a conjugated ring system of an organic compound. Aromatic rings may include carbon atoms only, or may include one or more heteroatoms, such as oxygen, nitrogen, or sulfur.

[0025] As used in this application, “aryl” can be, for example, phenyl (CBHS) or naphthyl (C10H7) . Substituted aryls can involve, for example, p-tolyl (CH3C6H4), 1 ,4-dimethylphenyl ((CHS^CBHS), 2,4,6- trimethylphenyl ((CHsbCeFL), 4-ethylphenyl (C2H5C6H4) , 4-isopropylphenyl (C3H7C6H4) , 4- undecylphenyl (C11 H23C6H4) , 4-dodecylphenyl (C12H25C6H4) , 4-tridecylphenyl (C13H27C6H4) , 4- hexadecylphenyl (C16H33C6H4) , 4-octadecylphenyl (C18H37C6H4) , 4-methoxyphenyl ((OCHSICBFL).

[0026] The term “crosslinker” refers to a molecule capable of forming a covalent linkage between separate polymers or between two different regions of the same polymer.

[0027] The term “ethylenically unsaturated” with reference to a monomer or chemical group herein refers to a substance having an ethylene linkage capable of forming a link within a polymer material. Exemplary ethylenically unsaturated monomers include esters of acrylic acid (or “acrylatemonomers”), vinyl monomers, vinyl acetate monomers, styrene monomers, and other monomers suitable for use in coating and composite materials.

[0028] The term “group” is intended to be a recitation of both the particular moiety, as well as a recitation of the broader class of substituted and unsubstituted structures that includes the moiety. Thus, when the term “group” is used to describe a chemical substituent, the described chemical material includes the unsubstituted group (e.g., the moiety) and that group with O, N, Si, or S atoms, for example, in the chain (as in an alkoxy group) as well as carbonyl groups or other conventional substitution. Where the term “moiety” is used to describe a chemical compound or substituent, only an unsubstituted chemical material is 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, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group” includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls, hydroxy alkyls, sulfoalkyls, etc. On the other hand, the phrase “alkyl moiety” is limited to the inclusion of only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.

[0029] The term “heteroatom” is used herein to refer to an atom other than carbon or hydrogen. Examples of heteroatoms include N, P, S, O, and the like.

[0030] Unless context dictates otherwise, molecular weight, as used herein, refers to weight average molecular weight (“Mw”), measured by gel permeation chromatography using polystyrene standards. According to particular embodiments, Mws are measured according to standard methods such as ISO 13885-1.

[0031] As used herein, the term “polymer” (or associated references to materials as “polymeric”) refers to molecules including organic components and composed of repeating units (polymerized monomers). A polymer, as referred to herein, has a weight average molecular weight of at least 1000. That is, the term “polymer,” as used herein, may include some oligomers by some definitions of the term “oligomer.” Unless otherwise indicated, the terms “polymer” and “polymeric material” include, but are not limited to, organic homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.

[0032] As used here, the term “or” is generally employed in its usual sense including “and / or” unless the content clearly dictates otherwise. The term “and / or” means one or all of the listed elements or a combination of any two or more of the listed elements.

[0033] The term “structural unit” or “residue” as used herein with reference to a polymer or polymeric material refers to a group that may be derived from a monomer to form at least part of a polymer orpolymeric material. In some embodiments, structural units or residues are formed from monomers that are ethylenically unsaturated.

[0034] By a “well-defined complex” is meant herein (as the term is used customarily in the art) a complex that has been isolated such that it is susceptible to characterization (i.e., definition) and analysis (e.g., to determine its structure and degree of purity). In contrast, a complex that is “not-well- defined” is one that is prepared without isolation from the medium (e.g., reaction medium) in which it is prepared. Well-defined complexes often consist of a single active component, whereas complexes that are not well-defined often, but not necessarily, comprise more than one active component. For example, a mixture of mononuclear and dinuclear species may exist or a mixture of different ancillary ligands may be present.

[0035] The recitations of numerical ranges by endpoints include 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.). Where a range of values is “up to” or “at least” or “at most” a particular value, that value is included within the range.

[0036] The words “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain 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 disclosure, including the claims.

[0037] As used in this application, the formulation of vanadyl acetylacetonate is as shown below:SICCATIVE COMPOSITIONS

[0038] As used herein, the term “siccatives” (which are also referred to synonymously as “driers” when in the context of paints and coatings or “accelerants” when part of a composite material formulation) refers to combinations of organic and metallic compounds that are soluble in solvents and binders. Siccatives are added to unsaturated oils, coating binders, or other coating compositions in order to appreciably reduce their drying times, i.e., the transition of liquid or gel coating films to the solid phase (e.g., by curing). Siccatives are available either as solids or in solution. Suitable solvents are water, organic solvents, binders, and mixtures thereof.

[0039] In the context of coatings, the inventors have found that the present selection of siccative materials in a coating composition improves or maintains the drying (or curing) speed of the coating composition, improves or maintains cured coating hardness, and improves or maintains qualities ofresultant coating appearance (e.g., reduction in the tendency to yellow), relative to conventional siccatives.

[0040] The inventive siccatives include at least one vanadium compound. The valency of the vanadium in the vanadium compound may range from +2 to +5. The vanadium in the vanadium compound is usually provided as a V(l I), (III), (IV) or (V) vanadium. In some embodiments, such compounds may include at least one oxidovanadium functional group, such as at least one oxidovanadium(IV) (also known as vanadyl) functional group. In some embodiments, the vanadium compound is a solvated oxidovanadium(IV) functional group or associated salts. In some embodiments, the vanadium compound is oxidovanadium(IV) pentahydrate (or other hydrate, or a mixture of hydrates) or associated salts.

[0041] Embodiments of the invention further include mixtures of vanadium compounds with additional transition metal ions, selected from the group consisting of iron, manganese, and mixtures thereof. Where iron metal ions are provided, this is usually from an Fe(ll) or Fe(lll) compound. Where manganese metal ions are provided, this is usually from a Mn (II), (III) or (IV) compound.

[0042] The inventive siccative further includes polymer ligand. The polymer ligand, as it is referred to throughout this disclosure, includes at least one structural unit derived from an ethylenically unsaturated monomer including a sulfonic acid or sulfonate moiety capable of coordinating a vanadium atom. By “capable of coordinating a vanadium atom,” as used throughout this specification, it is meant that the sulfonate moiety or the sulfonic acid moiety, when deprotonated, are capable of forming a coordinate linkage with a vanadium atom. In preferred embodiments, the at least one ethylenically unsaturated monomer is of Formula I:Formula II:or Formula III:where each of Ri, R2, and R3 are independently hydrogen or a C1 to C3 alkyl group; where each R4 is a methoxy group; where z can be 0 or 1 ; where each R5 is of Formula HA:wherein the nitrogen of Formula HA is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; or Formula IIB:wherein the oxygen of Formula IIB is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q;such that any ethylenically unsaturated monomer of Formula II is either a sulfonate or sulfonic acid acrylate structural unit or a sulfonate or sulfonic acid acrylamide structural unit; where each Re is independently a C1 to C9 alkyl group; where y can be 0 or 1 ; where each R? is independently a C1 to C9 alkyl group; and where each Q is a sulfonic acid moiety, SO3H, or a salt consisting of a sulfonate moiety in combination with an appropriate counterion, SO3 X, where X is the cation counterion of the salt.

[0043] When Q is SO3 X, the cation of the salt, X, may be any suitable salt counterion for the abovedescribed sulfonate moiety. Exemplary such counterions include Na+and K+counterions.

[0044] Exemplary such monomers include 4-styrene sulfonic acid or salts thereof, an anethol sulfonic acid or salts thereof, 2-acrylamido-2-methylpropane sulfonic acid or salts thereof, allyl sulfonic acid or salts thereof, vinyl sulfonic acid or salts thereof, and mixtures thereof.

[0045] In some embodiments, the polymer ligand may optionally include at least one structural unit derived from comonomers, which are ethylenically unsaturated monomers that do not include sulfonic acid or sulfonate moieties. Exemplary such comonomers include esters of (meth)acrylic acids and itaconic acids, styrene monomers, vinyl monomers, and mixtures thereof. In some embodiments of the invention, carboxylic acid-functional monomers (e.g., maleic acid acrylate monomers, or other acrylic monomers having a carboxylic acid or carboxylate functional group in their pendant chain) are excluded from such comonomers.

[0046] In some embodiments, the monomers used to form the polymer ligands contain less than about 20 wt. % carboxylic acid-functional comonomers, in further embodiments, less than about 10 wt. % carboxylic acid-functional comonomers, in further embodiments, less than about 5 wt. % carboxylic acid-functional comonomers, in further embodiments, less than about 1 wt. % carboxylic acid-functional comonomers, and in still further embodiments, the monomers used to form the polymer ligands are essentially or substantially absent carboxylic acid-functional comonomers (they comprise less than 0.01 wt. %), where wt. % here refers to the weight of carboxylic acid-functional comonomers relative to the weight of all monomers used to form the polymer ligand, expressed as a percent.

[0047] In some embodiments, the monomers used to form the polymer ligand are composed entirely of monomers of Formulas I, II, or III. In further embodiments, the monomers used to form the polymer ligand are composed entirely of monomers of Formula I. In further embodiments, the monomers used to form the polymer ligand are composed entirely of monomers of Formula II. In further embodiments, the monomers used to form the polymer ligand are composed entirely of monomers of Formula III. In further embodiments, the monomers used to form the polymer ligand are composed entirely of monomers of Formulas I and III.

[0048] In further embodiments, monomers of Formulas I, II, or III, make up at least about 20 wt. % of all monomers used to form the polymer ligand, in further embodiments at least about 30 wt. %, in still further embodiments at least about 40 wt. %, and in yet still further embodiments at least about 80 wt. %. In further embodiments, monomers of Formulas I, II, or III, make up at most about 95 wt. % of all monomers used to form the polymer ligand, in further embodiments at most about 90 wt. %, in still further embodiments at most about 85 wt. %, and in yet still further embodiments at most about 82.5 wt. %. In each case, the balance of monomers used to form the polymer ligand, if there is any balance, is made up of comonomers, as defined above.

[0049] In further embodiments, monomers of Formulas I and III, make up at least about 20 wt. % of all monomers used to form the polymer ligand, in further embodiments at least about 30 wt. %, in still further embodiments at least about 40 wt. %, and in yet still further embodiments at least about 80 wt. %. In further embodiments, monomers of Formulas I and III, make up at most about 95 wt. % of all monomers used to form the polymer ligand, in further embodiments at most about 90 wt. %, in still further embodiments at most about 85 wt. %, and in yet still further embodiments at most about 82.5 wt. %. In each case, the balance of monomers used to form the polymer ligand, if there is any balance, is made up of comonomers, as defined above.

[0050] In preferred embodiments, the polymer ligand of the siccative has a Mw of at least 1 ,000, in further embodiments, at least about 1 ,500, in further embodiments, at least about 4,000, in further embodiments, at least about 8,000, in further embodiments, at least about 15,000, in still further embodiments, at least about 25,000, and in yet still further embodiments, at least about 30,000. In preferred embodiments, the polymer ligand of the siccative has a Mw of at most about 70,000, in further embodiments, at most about 65,000, in further embodiments, at most about 60,000, in further embodiments, at most about 55,000, in further embodiments, at most about 50,000, in still further embodiments, at most about 40,000, and in yet still further embodiments, at most about 35,000.

[0051] The polymer ligand may be formed by any suitable means for polymerizing the abovedescribed monomers as recognized by one having ordinary skill in the art. For example, the polymer ligand may be formed by radical polymerization (e.g., by standard bulk, solution, suspension, or emulsion polymerizations) or a reversible-deactivation radical polymerization, such as reversible addition chain transfer (“RAFT”) polymerization, atom transfer radical polymerization (“ATRP”), or nitroxide-mediated radical polymerization, or by other suitable means. A skilled person will be able to select the appropriate reaction conditions and any additional components for each means of polymerizing the above-described monomers based on knowledge of the polymerization technique and the specific monomers employed and with the target molecular weight ranges in mind.

[0052] In some embodiments, the polymer ligand exhibits a free acid value of at least about 50 mg KOH / g polymer ligand, in further embodiments at least about 70 mg KOH / g polymer ligand, in further embodiments at least about 80 mg KOH / g polymer ligand, in still further embodiments at least about 100 mg KOH / g polymer ligand, and in yet still further embodiments at least about 125 mg KOH / g polymer ligand. In some embodiments, the polymer ligand exhibits a free acid value of at most about 325 mg KOH / g polymer ligand, in further embodiments at most about 310 mg KOH / g polymer ligand,in further embodiments at most about 300 mg KOH / g polymer ligand, in still further embodiments at most about 290 mg KOH / g polymer ligand, and in yet still further embodiments at most about 275 mg KOH / g polymer ligand. Unless otherwise indicated, free acid value of a polymer as reported herein is determined titrimetrically according to ISO 2114-2000 and, with respect to a polymer ligand, represents the free acid value of the polymer ligand following polymerization and acid treatment and in the absence of vanadium compound and other complexing agents capable of altering the observed free acid value.

[0053] Without being bound by theory, it is believed that the sulfonate or sulfonic acid moieties of the polymer ligand material coordinate with the vanadium compound to form a complex. Said complex is believed to provide catalytic action in a coating formulation.

[0054] In some embodiments, the siccative includes sufficient sulfonate or sulfonic acid moiety from polymer ligand and sufficient vanadium compound so as to provide a ratio of at least about 1 .5:1 moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium, in further embodiments at least about 1 .8:1 , in further embodiments at least about 1 .9:1 , in further embodiments at least about 2.0:1 , in still further embodiments at least about 2.2:1 , and in still further embodiments, at least about 2.5:1. In some embodiments, the siccative includes at most about 10:1 moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium, in further embodiments at most about 8:1 , in further embodiments at most about 5:1 , in further embodiments at most about 4:1 , in still further embodiments at most about 3:1 , and in still further embodiments, at most about 2.7:1 . In each instance and throughout this disclosure, the ratio of moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium is calculated as the ratio of: the moles of sulfonate moiety in the siccative (average number of sulfonic acid or sulfonate moieties per molecule polymer ligand times the moles of polymer ligand molecules in the siccative) to the moles of vanadium atom from vanadium compound in the siccative. For instance, a siccative containing 0.015 moles of a polymer ligand, each polymer ligand having an average number of sulfonate or sulfonic acid moieties of 340, and 2.474 moles of vanadium atoms from vanadium compound would have a ratio of 2.06:1 moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium (((0.015 moles polymer ligand)*(340 sulfonate or sulfonic acid moieties per polymer ligand molecule)) / (2.474 moles vanadium atoms from vanadium compound) = 2.06).

[0055] Without being bound by theory, it is believed that each vanadium atom in the siccative is coordinated by the sulfonate moieties of the polymer ligand and thus each may be coordinated by one or multiple sulfonate moieties of the polymer ligand in accordance with the charge of the vanadium compound in a relevant complex. In some embodiments, the siccative includes sufficient sulfonate moiety from polymer ligand relative to vanadium atoms in the siccative to enable complex formation so that the ratio of sulfonate moiety from polymer ligand to vanadium atom in the siccative is approximately equivalent to the charge of the vanadium compound. For example oxidovanadium(IV) pentahydrate has a charge of plus two and thus may require two sulfonate moieties from polymer ligand to stabilize in a complex and thus dissolve in solution as well as provide improved catalytic activity. A stoichiometric excess of sulfonate or sulfonic acid moiety from polymer ligand to vanadiumatom from vanadium compound in the siccative (e.g., greater than 2:1 in the case of oxidovanadium(IV) pentahydrate) may, in some cases, further be beneficial to improve regeneration of catalytically active species during curing, which can lead to improved curing performance despite using a lower quantity vanadium compound. An excess of vanadium metal atoms may be beneficial to allow some adsorption on solid particles without losing too much siccative activity. The skilled person will be able to take into account these considerations when practicing the invention.

[0056] Generally, vanadium metal content in a siccative can be calculated knowing the mass of the various components therein. The mass of the vanadium metal can be determined from a siccative sample using Microwave Plasma Atomic Emission Spectroscopy (“MP-AES”). For a given vanadium metal content in the siccative, and a polymer ligand of a particular molecular weight, Mw, having a particular monomer content of a particular monomer type, each element selected from or within the ranges and materials provided elsewhere in this application, a skilled person can calculate the amount of polymer ligand that will provide the aforementioned molar ratios of sulfonate or sulfonic acid moiety from polymer ligand to vanadium atom from vanadium compound.

[0057] In some embodiments, the siccative further includes an additional ligand, such as a polydentate amine (e.g., TRISPICEN-type, CYCLAM and Cross-Bridged-type, TMTACN-type, TACN- type, N4py-type, Bispidon-type), a carboxylate, or a 1 ,3 diketone, as described in PCT patent application publication number WO2023117421 A1 , which is incorporated by reference herein in its entirety.

[0058] In some embodiments, the siccative is provided in a solid form, for example, a powder.

[0059] In some embodiments, the siccative further includes a solvent and the vanadium compound and polymer ligand may be dissolved, dispersed, or otherwise mixed in the solvent. Depending on the application, in some embodiments, the contents of the siccatives contemplated herein can be dissolved in water and that mixture can subsequently be dissolved in a further solvent if desired, such as dimethyl sulfoxide (DMSO), glycols such as propylene glycol, ethylene glycol, a C2-C9 glycol, or their mixture.

[0060] In some embodiments, the siccatives contemplated herein further optionally include so-called secondary or auxiliary driers (defined further, below) or colorants.

[0061] In some embodiments, the inventive siccatives include at least approximately 5 wt. % solvent, in further embodiments at least approximately 20 wt. % solvent, in further embodiments at least approximately 30 wt. % solvent, in still further embodiments at least approximately 40 wt. % solvent, and in yet still further embodiments at least approximately 44 wt. % solvent. In some embodiments, the inventive siccative includes at most approximately 99 wt. % solvent, in further embodiments at most approximately 90 wt. % solvent, in further embodiments at most approximately 60 wt. % solvent, in still further embodiments at most approximately 50 wt. % solvent, and in yet still further embodiments at most approximately 46 wt. % solvent.

[0062] In some embodiments, the invention comprises a kit that may consist of two formulations, wherein each formulation includes one of a vanadium compound or a polymer ligand. Theformulations of said kits are physically separated from each other, for instance in separate cartridges, sachets, or the like.

[0063] In each of the kits of the invention, one or more of the two formulations may comprise additional components (e.g., an optional, secondary drier). The components of such kits are generally combined with one another, whereby to provide a siccative composition that may be used as described further in this disclosure.

[0064] In some exemplary embodiments the siccative comprises a complex of vanadium compound and polymer ligand, wherein the complex is formed via combination of a polymer ligand and either the vanadium compound itself or a vanadium compound pre-cursor under heat, acidic, and / or reflux conditions in a process for forming the complex. For example, the following Reaction Schemes 1 , 2, and 3 demonstrate exemplary embodiments of said process utilizing exemplary and / or representative materials.

[0065] Reaction Scheme 1 .

[0067] Reaction Scheme 3.

[0068] In each of Reaction Schemes 1-3, the reaction products include a representation of two polymer ligand molecules (subscript 2) complexing the vanadium compound. A person having ordinary skill in the art will understand that this notation is imperfect and does not imply that two polymer molecules would be needed to coordinate each vanadium pentahydrate in the Reaction Scheme products, but rather that two sulfonate acid moieties (each having a single negative charge and coming from two separate polymer ligand molecules or the same polymer ligand molecule) coordinate the shown vanadium pentahydrate and balance its +2 charge. Further, the end-groups of each example polymer ligand is shown as a methyl group, but in practice may vary depending on the means of synthesis of the particular polymer. In each of Reaction Schemes 1 and 2, hydrobromic acid is used to provide the acidic condition, while Reaction Scheme 3 is conducted in an aqueous environment. Each mixture is heated to 110 °C. A person of ordinary skill, with the benefit of this disclosure, will be able to select heat and acid conditions as necessary for any particular starting materials to form an appropriate complex. Further, and for sake of clarity, a person having ordinary skill in the art will understand that other means of polymer ligand and vanadium compound complex formation are possible. Without being bound by theory, it is believed that complexation of vanadium compound and polymer ligand will also happen at ambient conditions, but at a slower rate. In Reaction Schemes 1-3, vanadium pentoxide is provided as a vanadium compound precursor and forms an oxidovanadium(IV) pentahydrate vanadium compound in the reactions. Note, while oxidovanadium(IV) pentahydrate is shown in the figures, one of ordinary skill will understand this to be only one exemplary hydrated state of a vanadium compound provided for illustrative purposes, where oxidovanadium(IV) (aq.), indicating a distribution of oxidovanadium(IV)-based compounds having various hydrated states may provide a more accurate description of the oxidovanadium(IV)-based compounds in the products of exemplary Reaction Schemes 1-3.

[0069] According to particular embodiments, the siccative composition described herein consists essentially of the polymer ligand and vanadium compound described above. As used herein, the phrases “consists essentially of” and “consisting essentially of” describe siccative compositions that contain the enumerated components and, optionally, additional components, provided the inclusion of such additional components does not materially alter or affect the essential characteristics of the siccative composition. Given that aims of the siccative composition include but are not limited to catalyzing the autoxidation reaction of binders curable by autoxidation mechanism while maintaining or improving hardness, dry time, and appearance characteristics in cured coating compositions containing the binder, it will be understood that additional components that decrease hardness, lengthen dry time, and mar appearance of the cured coatings containing the binder relative to outcomes obtained for mixtures including the same binders and conventional driers (such as molecular vanadium catalysts) are excluded from siccative compositions that consist essentially of the polymer ligand and vanadium compound. Further, given that another aim of the siccative composition is to reduce or eliminate the amount of cobalt-based catalyst(s) used to catalyze the curing reaction of autoxidizing binders, it will be understood that the inclusion of components contributing appreciable amounts of cobalt (e.g., amounts of cobalt compounds that would customarily be used to catalyze the reaction for curing a coating) is excluded from siccative compositions that consist essentially of thepolymer ligand and vanadium compound siccative. By way of contrast, it will be understood that the presence of other inert materials (e.g., solvents, surfactants, etc.) that do not materially affect the essential characteristics of the siccative composition is permitted, and siccative compositions containing such materials are within the scope of a siccative composition consisting essentially of the polymer ligand and vanadium compound.

[0070] In some embodiments, the invention is the use of a sulfonic acid or sulfonate moiety-bearing polymer ligand and a vanadium compound as a siccative.COATINGS

[0071] The invention has broad utility in relation to a wide variety of solvent and water-based coating compositions, which term is to be interpreted broadly herein. Examples of coating compositions include clear or colored varnishes, primary coats, filling pastes, glazes, emulsions and floor coverings, e.g. linoleum floor coverings. Embodiments of the invention relate to solvent and water-based paints and inks, particularly paints such as high-specification paints intended for domestic use and paints intended for general industrial applications.

[0072] Use of the term “oxidatively curable coating compositions” herein is thus intended to embrace a wide variety of colored (e.g. by way of pigment or ink) and non-colored materials, including clear coats, oils, and binders, which form a continuous coating through the course of oxidative reactions, typically to form cross-linkages and other bond formations. Generically, such coating compositions may be characterized by the presence of typically (poly) unsaturated resins that react to form a solid film on a substrate, the resins being initially present in the oxidatively curable coating compositions either as liquids, dissolved in an organic solvent or as solids dispersed in a continuous liquid phase. Reaction to form the desired coating upon curing arises from polymerization reactions initiated by oxidation. Examples of binders or resins curable by autoxidation mechanism include alkyd-, acrylate-, urethane-, polybutadiene- and epoxy ester-based resins.

[0073] Alkyd resins are a particularly important member of the class of binders or resins curable by autoxidation mechanisms and are a well-studied class of resin to which the present invention may be applied. Hereinafter, embodiments of the invention are described with reference to the use of alkyd resins, also referred to as alkyd-based resins or alkyd(-based) binders. Whilst these represent particularly significant embodiments of the invention, the invention is not to be so limited. To be clear: the invention is applicable to a wide range of oxidatively curable coating compositions, typically those comprising at least 1 or 2% by weight of an unsaturated compound (e.g., comprising unsaturated (non-aromatic) double or triple carbon-carbon bonds).

[0074] Herein, the term “alkyd binder” or “alkyd resin” are used interchangeably. Suitable autoxidizable alkyd resins for use in the invention, are in general the reaction product of the esterification of polyhydric alcohols with polybasic acids (or their anhydrides) and unsaturated fatty acids (or glycerol esters thereof), for example derived from linseed oil, tung oil, tall oil as well as from other drying or semi-drying oils. Alkyd resins are well-known in the art and need not to be further described herein. The properties are primarily determined by the nature and the ratios of the alcoholsand acids used and by the degree of condensation. Exemplary alkyd resins for coatings include long oil and medium oil alkyd resins e.g., derived from 45 wt.% to 70 wt.% of fatty acids, and short oil alkyd resins. To improve the performance of the resins orto allow the resin to function in a water-based coating formulation or water-reducible coating formulation, the composition of the alkyd may be modified. For example, polyurethane modified alkyds, silicone modified alkyds, styrene modified alkyds, acrylic modified alkyds (e.g. (meth)acrylic modified alkyds), vinylated alkyds, polyamide modified alkyds, and epoxy modified alkyds or mixtures thereof are also suitable alkyd resins to be used in the present compositions.

[0075] In some embodiments, the at least one autoxidizable alkyd binder is selected from a medium or long oil unmodified alkyd, a silicone modified alkyd, a polyurethane modified alkyd or a combination thereof. In some embodiments, the alkyd binder is a short oil alkyd, a medium oil alkyd, a long oil alkyd, a silicone modified alkyd, a polyurethane modified alkyd or a combination thereof. Exemplary alkyd resins include SYNAQUA 4804 (waterborne short oil alkyd, Arkema Coating Resins); SYNAQUA 2070 (waterborne medium oil alkyd, Arkema Coating Resins); Beckosol AQ101 (waterborne long oil alkyd, Polynt Composites USA Inc.); WorleeKyd S 351 (solventborne medium oil alkyd, Worlee); and TOD 3AK0211Y (waterreducible alkyd, Guangdong DIC TOD Resins Co., Inc., China) and other binders having similar characteristics to the named above.

[0076] In some further embodiments, the at least one autoxidizable alkyd binder is part of an interpenetrating network (“IPN”) in which crosslinking of the autoxidizable alkyd binder or a second resin or polymer forms a network in which either the second resin or polymer or the autoxidizable alkyd binder, respectively, is entangled. Exemplary such second resins or polymers include resins having (meth)acrylic, vinyl, vinyl acetate, styrene, acrylamido, or polyurethane residues, or mixtures thereof. Suitable second resins or polymers may or may not include crosslinking capabilities.

[0077] In some embodiments, the amount of alkyd binder in the present coating compositions is at least approximately 10 wt.%, in further embodiments, at least approximately 20 wt. %, in further embodiments, at least approximately 30 wt. %, and in still further embodiments, at least approximately 40 wt. %. In some embodiments, the amount of alkyd binder in the present coating compositions is at most approximately 98 wt.%, in further embodiments, at most approximately 90 wt. %, in further embodiments, at most approximately 85 wt. %, and in still further embodiments, at most approximately 70 wt. %.

[0078] Where percentages by weight are referred to herein with respect to coating compositions (wt. % or % w / w), this means, unless a context clearly dictates to the contrary, percentages by weight with respect to the solid film resultant from curing, i.e., components of the oxidatively curable coating compositions that serve to provide the coating upon curing. With an oxidatively curable alkyd coating composition, therefore, the combined weights of the components of the composition that become, i.e., are incorporated into, the alkyd resin coating, once cured, are those with respect to which weight percentages herein are based. For example, in some embodiments, a coating composition according to the present invention can comprise about 0.0001 to about 1% w / w, e.g., about 0.0005 to about0.5% w / w water, or about 0.01 to about 1 % w / w, e.g. about 0.05 to about 0.5% w / w water, based on the components of the composition that, when cured, form the coating.

[0079] By solvent-based or solventborne coating compositions is meant herein, consistent with the nomenclature used in the art, compositions that are based predominately, in their liquid form, on organic (i.e., non-aqueous) solvents (e.g., less than 50 wt. % of solvents in the relevant coating are water). Examples of suitable solvents include aliphatic (including alicyclic and branched) hydrocarbons, such as hexane, heptane, octane, cyclohexane, cycloheptane and isoparaffins; aromatic hydrocarbons such as toluene and xylene; ketones, e.g. methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as isopropyl alcohol, n-butyl alcohol and n-propyl alcohol; glycol monoethers, such as the monoethers of ethylene glycol and diethylene glycol; monoether glycol acetates, such as 2-ethoxyethyl acetate; as well as mixtures thereof. Isomeric variants are included. Thus, the term hexane embraces mixtures of hexanes. Some embodiments of organic solvents include white spirit and solvents available under the trademarks Shellsol, from Shell Chemicals and Solvesso and Exxsol, from Exxon.

[0080] By water-based or waterborne coating compositions is meant herein, coating compositions that, in their liquid form, include solvents being composed of 50 wt. % or greater of water. Such waterbased coating compositions include but are not limited to water-reducible coatings, water-based emulsion coatings (such as alkyd emulsions, which are alkyd formulations dispersed in water with the addition of anionic and / or nonionic surfactants), mechanically dispersed alkyd coatings, and core-shell alkyd hybrid coatings (such as core-shell alkyd-acrylic hybrid coatings).

[0081] By water-reducible coating compositions is meant herein, consistent with the nomenclature used in the art, certain coatings reliant on alkyd resins that have been modified (for example, by the inclusion of functional carboxylic acid groups) to allow their solubility or dispersion in a water phase. It is contemplated and perfectly consistent with the art and the above definitions that some water- reducible coatings will also be considered water-based or waterborne coatings.

[0082] In some embodiments, the complexed siccative, e.g., as a pre-formed complex of vanadium compound and polymer ligand is dissolved in water at a concentration of about 0.001 to about 10 wt.%, e.g., about 0.01 to about 5 wt.%, or about 0.001 to about 1 wt.%, based on the weight of the complex and water. Increasing the concentration of the siccative in the aqueous solution allows a relatively smaller volume of the siccative-containing aqueous solution to be added to the coating composition. This may be desired by the skilled person.

[0083] The resultant composition, comprising the siccative, and water, will typically be a solution, i.e., a single homogeneous phase. However, it may also be an emulsion or dispersion, e.g., comprising discontinuous regions of aqueous solution comprising the vanadium compound and polymer ligand. If the complex is not preformed but formed in-situ (in the siccative solution), a vanadium compound salt may also be, in some embodiments, dissolved in water at a concentration of about 0.001 to about 1 wt.% based on the vanadium ion to water ratio. An appropriate amount of polymer ligand can then be added to form the desired complex. The polymer ligand may also be added prior to the metal ions.

[0084] In some embodiments, additional solvents such as dimethyl sulfoxide (DMSO), glycols (e.g., propylene glycol or ethylene glycol) may optionally be added to aqueous siccative mixtures.

[0085] In embodiments, after preparation, a solution of the siccative may then be contacted with, e.g., added to, a coating composition.

[0086] In alternative embodiments, depending on reactivity with components of the coating composition, the vanadium compound and the polymer ligand of the siccative may be separately added to a coating composition or binder solution (including at least a binder curable by autoxidation mechanism and a solvent) to allow formation of a complex in situ in the coating composition or binder solution.

[0087] A formulation or composition of the invention can, and generally will, be used in the manufacture of a fully formulated oxidatively curable coating composition. By the term “fully formulated oxidatively curable coating composition” is implied, as is known to those of skill in the art, oxidatively curable formulations that comprise additional components over and above the binder (the autoxidatively curable material, which may be alkyd resin), an aqueous or non-aqueous solvent / liquid continuous phase and the siccative intended to accelerate the curing process. Such additional components are generally included to confer desirable properties upon the coating composition, such as color or other visual characteristics such as glossiness or matte-ness), physical, chemical and even biological stability (enhanced biological stability being conferred upon coating compositions by the use of biocides, for example), or modified texture, plasticity, adhesion and viscosity or rheology.

[0088] For example, such optional additional components may be selected from solvents, antioxidants (sometimes referred to as antiskinning agents), additional siccatives, auxiliary or secondary driers, colorants (including inks and colored pigments), fillers, plasticizers, viscosity modifiers, crosslinkers, UV light absorbers, stabilizers, antistatic agents, flame retardants, lubricants, emulsifiers (in particular where an oxidatively curable coating composition or formulation of the invention is aqueous-based), anti-foaming agents, viscosity modifiers, antifouling agents, biocides (e.g. bactericides, fungicides, algaecides and insecticides), anticorrosion agents, antireflective agents, anti-freezing agents, waxes and thickeners. The skilled person is familiar with the incorporation of these and other components into oxidatively curable coating composition to optimize such compositions’ properties.

[0089] It will be appreciated that some of these optional additional components may possess more than one functional property. For example, some fillers may also function as colorants. The nature of any additional components and the amounts used may be determined in accordance with the knowledge of those of skill in the art and will depend on the application for which the curable coating compositions is intended. Examples of optional additional components are discussed in the following paragraphs, which are intended to be illustrative, not limiting.

[0090] In some embodiments, inventive coating formulations optionally further include “secondary driers”, synonymously “auxiliary driers,” which include, for example, fatty acid soaps of zirconium, bismuth, barium, cerium, calcium, lithium, strontium, and zinc. Typically, fatty acid soaps areoptionally substituted octanoates, hexanoates and naphthenates. Without being bound by theory, auxiliary driers (also referred to as “secondary driers” and “through driers”) are generally understood to diminish the effect of adsorption of the main drier on solid particles often present in an oxidatively curable coating composition. Other non-metal based auxiliary driers may also be present if desired. Concentrations of auxiliary driers within oxidatively curable coating compositions are typically between about 0.01 wt.% and 2.5 wt.% as is known in the art. One having skill in the art will recognize that secondary or auxiliary driers may be added directly to a fully formulated coating composition or binder solution or may be added to a siccative composition prior to addition to a fully formulated coating composition or binder solution. Some exemplary secondary driers include Calcium- Hydrochem (based on Calcium neodecanoate in organic solvents, available from Borchers); and Octa Soligen Zirconium 10 aqua (Zr-2-ethylhexanoate in organic solvents, available from Borchers) and other secondary driers having similar characteristics to the named above.

[0091] In embodiments, the coating composition contains one or more inventive siccatives in overall concentration of at least approximately 0.001 % MORS, in further embodiments, at least approximately 0.003 % MORS, in further embodiments, at least approximately 0.006 % MORS, in further embodiments, at least approximately 0.01 % MORS, and in still further embodiments, at least approximately 0.02 % MORS. In embodiments, the coating composition contains one or more inventive siccatives in overall concentration of at most approximately 2.0 % MORS, in further embodiments, at most approximately 1 .0 % MORS, in further embodiments, at most approximately 0.5 % MORS, in further embodiments, at most approximately 0.2 % MORS, and in still further embodiments, at most approximately 0.1 % MORS. Siccatives are present in coatings in amounts expressed as weight percent of the vanadium metal based on the weight of binder solids (or resin) unless stated otherwise (% MORS). It will be appreciated that this measure may apply either to a fully formulated coating composition or to a binder solution, or some intermediate therebetween, because the measure depends on binder resin solids and metal content only. This measure is also abbreviated MORS, metal on resin solid. MORS is calculated in the following way:with md. mass of the drier (or drier solution if in solution), in g; MCd'. metal content of the drier (or drier solution if in solution) in %; SCf. solid content (of binder) in the formulation, in %; and mf. mass of the formulation, in g.

[0092] The amount of siccative in a coating composition may also be expressed as a weight percent in terms of the vanadium metal content on dry coating weight. Vanadium metal content on dry coating weight is measured with respect to a given coating composition by weighing a substrate, casting a film of the coating on the substrate, allowing the film to cure, further drying the cured film to extract residual moisture, weighing the film and substrate to allow determination of the film weight, and then analyzing the film or siccative, prior to combination with the coating, by X-Ray Photoelectron Spectroscopy (“XPS”) or Scanning Electron Microscopy (“SEM”) with Energy Dispersive X-Ray Analysis (“EDX”) to determine vanadium metal content. Vanadium metal content on dry coatingweight can also be calculated if the vanadium metal mass and coating composition components and their respective amounts are known.

[0093] In embodiments, the coating composition contains one or more inventive siccatives in overall concentration of at least approximately 0.0005 wt.%, in further embodiments, at least approximately 0.001 wt. %, in further embodiments, at least approximately 0.003 wt. %, in further embodiments, at least approximately 0.01 wt. %, and in still further embodiments, at least approximately 0.02 wt. %, wherein wt. % is here expressed as vanadium metal content on dry coating weight. In embodiments, the coating composition contains one or more inventive siccatives in overall concentration of at most approximately 2.0 wt.%, in further embodiments, at most approximately 1 .0 wt. %, in further embodiments, at most approximately 0.2 wt. %, in further embodiments, at most approximately 0.1 wt. %, and in still further embodiments, at most approximately 0.08 wt. %, wherein wt. % is here expressed as vanadium metal content on dry coating weight.

[0094] The inventive siccative or its separate components can be added in any order to a coating formulation. In embodiments, the siccative is dissolved in water and that mixture can subsequently be dissolved in a further solvent if desired, such as dimethyl sulfoxide (DMSO), and glycols, such as propylene glycol, ethylene glycol, a C2-C9 glycol, or their mixture, and then combining the solution with other components of a coating. Alternatively, the coating may be prepared by dissolving the siccative in water and then combining the solution with other components of the coating. This is particularly useful when the binder is a waterborne resin. Alternatively, the polymeric ligand may be modified with comonomers or certain monomers of Formulas I, II, or III having a more polar character may be selected to provide better stability in waterborne system.

[0095] Alternatively, a coating may be prepared by first combining the inventive siccative or one or both of its components separately, directly in an alkyd binder resin. Where only one of the components of the inventive siccative are first combined with the alkyd binder resin, the remaining components can be subsequently added to the alkyd binder resin or other components of the coating composition, which are then subsequently combined with the mixture of the alkyd binder resin and the first component of the inventive siccative. Such a means of coating preparation may yield a complex that is not-well-defined.

[0096] In some embodiments, the invention comprises a kit that may consist of two or three formulations, wherein each formulation includes one or more of an autoxidizable binder, a vanadium compound, and a polymer ligand. The formulations of said kits are physically separated from each other, for instance in separate cartridges, sachets, or the like.

[0097] In each of the kits of the invention, one or more of the two (or three) formulations may comprise additional components (for example a formulation comprising autoxidizable binder may also comprise a secondary binder resin, a biocide or other coating additive, etc.). The components of such kits are generally combined with one another, whereby to provide a coating composition, which may cure to provide a cured coating. Furthermore, in each of the kits of the invention, the separation of polymer ligand and vanadium compound components and their combination may yield a complex that is not-well-defined.

[0098] In one embodiment, a method for forming a coated substrate or article is provided whereby a coating composition comprising: the inventive siccative of the present disclosure comprising a polymer ligand and a vanadium compound; a binder curable by autoxidation mechanism; and optional additional components (as described above) is provided. The coating composition is subsequently applied to a substrate or article by conventional methods (e.g., by paint brush or roller) and allowed to cure in the presence of ambient air.

[0099] In some embodiments, a method of contacting is provided whereby components of two or three formulations are contacted with one another, wherein each formulation may include one or more of an autoxidizable binder, a vanadium compound, and a polymer ligand. Each of the autoxidizable binder, a vanadium compound, and a polymer ligand may be the materials as described throughout this disclosure with respect to curable coating materials. There is no particular order in which the method of contacting need be carried out. For example, autoxidizable binder may be contacted with polymer ligand and vanadium compound contacted with that mixture afterwards. Alternatively, vanadium compound may be contacted with autoxidizable binder and that mixture contacted with the polymeric ligand afterwards; or polymer ligand and vanadium compound may be simultaneously contacted with autoxidizable binder.

[0100] The vanadium compound used in the coating compositions, formulations, methods, and kits described herein can be introduced as a solid, a suspension, or as a solution in a variety of solvents in combination with or separate from polymer ligand. In some embodiments, the vanadium compound may be introduced in the form of a salt. In such embodiments, there is no particular limitation as to the source of the vanadium compound in a salt. Often, vanadium compound in salt form is commercially available as a solution, for example in a hydrocarbon or other solution to facilitate dissolution in the curable compositions. However, other solvents may also be used, including alcohols, ketones, and water (or aqueous solutions), especially for chloride, sulfate and acetate salts. The invention contemplates use of a mixture of metal salts although a single salt is typically used.

[0101] The polymer ligand used in the coating compositions, formulations, methods, and kits described herein can be introduced as a solid, a suspension, or as a solution in a variety of solvents in combination with or separate from vanadium compound. In some embodiments, the polymer ligand may be provided in a salt, in which one or more of the sulfonic acid moieties of the polymer ligand are deprotonated. Adding the polymer ligand in a solution or suspension can be advantageous in permitting improved and / or easier mixing with the autoxidizing binder. It may be beneficial to dilute polymer ligand in a suitable solvent or water before adding to the autoxidizing binder if it is wished to introduce a very small amount of polymer ligand, so greater accuracy of dosing can be achieved. Depending on the properties of the polymer ligand and the desired autoxidizing binder-polymer ligand formulation, suitable solvents are polar. Exemplary polar solvents are ethylene glycol, propylene glycol, and the like. The skilled person will be able to easily formulate such solutions, generally using one or more solvents in light of the selected materials and the disclosure herein.

[0102] In some embodiments, the invention is the use of a sulfonic acid (or sulfonate) moiety-bearing polymer ligand and a vanadium compound as described herein as a siccative for coatings containing a binder curable by autoxidation mechanism.

[0103] Unless otherwise specified, all measurements herein are made at 23 ± 1 °C and 50% relative humidity.

[0104] It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.

[0105] It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure is to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is also further understood that any range between the endpoint values within the broad range is also discussed herein.

[0106] Reference throughout this specification to “some approaches” or “an approach” or “one embodiment,” “an embodiment,” “certain embodiments,” or “some embodiments,” etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of such phrases in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

[0107] Certain terminology is used herein for convenience only and is not to be taken as a limitation on the present disclosure.

[0108] The invention and the potential embodiments thereof described in and embraced by the foregoing description may be further understood by reference to the particular clauses set forth below. As such, these clauses are included for illustrative purposes only (e.g., describing potentially preferred embodiments of the invention) and are not intended to limit the foregoing description in any manner.Clause 1 . A siccative for an autoxidizing formulation, wherein the siccative comprises a vanadium compound and a polymer ligand including at least one structural unit derived from an ethylenically unsaturated monomer bearing a sulfonic acid or sulfonate moiety capable of coordinating with a vanadium atom.Clause 2. A siccative for an autoxidizing formulation, wherein the siccative consists essentially of a vanadium compound and a polymer ligand including at least one structural unit derived from an ethylenically unsaturated monomer bearing a sulfonic acid or sulfonate moiety capable of coordinating with a vanadium atom.Clause 3. The siccative of clauses 1 or 2 wherein the at least one ethylen ically unsaturated monomer bearing a sulfonic acid or sulfonate moiety is of Formula I:Formula II:or Formula III:where each of Ri, R2, and R3 are independently hydrogen or a C1 to C3 alkyl group; where each R4 is a methoxy group; where z is 0 or 1 ; where each R5 is of Formula IIA:wherein the nitrogen is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; or Formula I IB:wherein the oxygen is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; such that any ethylenically unsaturated monomer of Formula II is either a sulfonate or sulfonic acid acrylate monomer or a sulfonate or sulfonic acid acrylamide monomer; where each Re is independently a C1 to C9 alkyl group; where y is 0 or 1 ; where each R? is independently a C1 to C9 alkyl group; and where each Q is SO3H or SCh X, where X is a cation of a salt.Clause 4. The siccative of clause 3, wherein the at least one ethylenically unsaturated monomer of Formulas I, II, or III is selected from the group consisting of 4-styrene sulfonic acid or salts thereof, an anethol sulfonic acid or salts thereof, 2-acrylamido-2-methylpropane sulfonic acid or salts thereof, allyl sulfonic acid or salts thereof, vinyl sulfonic acid or salts thereof, and mixtures thereof.Clause 5. The siccative of any preceding clause, wherein the polymer ligand has a weight average molecular weight of at most about 70,000, at most about 65,000, at most about 60,000, at most about 55,000, at most about 50,000, at most about 40,000, or at most about 35,000.Clause 6. The siccative of any of clauses 3 through 5, wherein the monomers of formulas I, II, and III make up at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, or at least about 80 wt. %. of all monomers used to form the polymer ligand.Clause 7. The siccative of any of clauses 3 through 6, wherein the monomers of formulas I, II, and III make up make up at most about 95 wt. %, at most about 90 wt. %, at most about 85 wt. %, or at most about 82.5 wt. % of all monomers used to form the polymer ligand.Clause 8. The siccative of any of clauses 3 through 7, wherein the monomers of formulas I and III make up at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, or at least about 80 wt. %. of all monomers used to form the polymer ligand.Clause 9. The siccative of any of clauses 3 through 8, wherein the monomers of formulas I and III make up make up at most about 95 wt. %, at most about 90 wt. %, at most about 85 wt. %, or at most about 82.5 wt. % of all monomers used to form the polymer ligand.Clause 10. The siccative of any of clauses 3 through 9, wherein the monomers of formula I make up at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, or at least about 80 wt. %. of all monomers used to form the polymer ligand.Clause 11 . The siccative of any of clauses 3 through 10, wherein the monomers of formula I make up make up at most about 95 wt. %, at most about 90 wt. %, at most about 85 wt. %, or at most about 82.5 wt. % of all monomers used to form the polymer ligand.Clause 12. The siccative of any of clauses 3 through 11 , wherein the monomers of formula II make up at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, or at least about 80 wt. % of all monomers used to form the polymer ligand.Clause 13. The siccative of any of clauses 3 through 12, wherein the monomers of formula II make up make up at most about 95 wt. %, at most about 90 wt. %, at most about 85 wt. %, or at most about 82.5 wt. % of all monomers used to form the polymer ligand.Clause 14. The siccative of the clause any of clauses 3 through 13, wherein the monomers of formula III make up at least about 20 wt. %, at least about 30 wt. %, at least about 40 wt. %, or at least about 80 wt. % of all monomers used to form the polymer ligand.Clause 15. The siccative of any of clauses 3 through 14, wherein the monomers of formula III make up make up at most about 95 wt. %, at most about 90 wt. %, at most about 85 wt. %, or at most about 82.5 wt. % of all monomers used to form the polymer ligand.Clause 16. The siccative of any of clauses 3 through 15, wherein Q is SOs" and X is Na+or K+.Clause 17. The siccative of any preceding clause, wherein the polymer ligand has a weight average molecular weight of at least 1 ,000, at least about 1 ,500, at least about 4,000, at least about 8,000, at least about 15,000, at least about 25,000, or at least about 30,000.Clause 18. The siccative of any of preceding clause, wherein the polymer ligand further comprises structural units derived from comonomers, wherein said comonomers are ethylenically unsaturated monomers that do not include sulfonic acid or sulfonate moieties.Clause 19. The siccative of clause 18, wherein the comonomers are selected from the group consisting of esters of acrylic acid, styrene, vinyl monomers, and mixtures thereof.Clause 20. The siccative of clauses 18 or 19, wherein the monomers used to form the polymer ligands contain less than 20 wt. % carboxylic acid-functional comonomers, less than 10 wt. % carboxylic acid-functional comonomers, less than 5 wt. % carboxylic acid-functional comonomers, less than 1 wt. % carboxylic acid-functional comonomers, or are essentially absent carboxylic acidfunctional comonomers (the monomers used to form the polymer ligands comprise less than 0.01 wt. % of any carboxylic acid-functional monomers), where wt. % here refers to the weight of carboxylicacid-functional comonomers relative to the weight of all monomers used to form the polymer ligand, expressed as a percent.Clause 21 . The siccative of any preceding clause, wherein the polymer ligand is formed via radical polymerization (e.g., standard bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc.) or reversible-deactivation radical polymerization (e.g. reversible addition chain transfer polymerization, atom transfer radical polymerization, nitroxide- mediated radical polymerization, etc.).Clause 22. The siccative of any preceding clause, wherein the valency of the vanadium of the vanadium compound may range from +2 to +5.Clause 23. The siccative of clause 22, wherein the vanadium compound includes a V(ll), (III), (IV) or (V) vanadium atom.Clause 24. The siccative of clause 23, wherein the vanadium compound includes a vanadyl (also known as an oxidovanadium(IV)) functional group.Clause 25. The siccative of clause 24, wherein the vanadium compound is an oxidovanadium(IV) hydrate.Clause 26. The siccative of any preceding clause, further comprising additional transition metal ions, selected from the group consisting of iron, manganese, and mixtures thereof.Clause 27. The siccative of any preceding clause, wherein the siccative includes at least about 1.5:1 , at least about 1.8:1 , at least about 1.9:1 , at least about 2.0:1 , at least about 2.2:1 , or at least about 2.5:1 moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium, where the ratio of moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium is calculated as the ratio of: the moles of sulfonate or sulfonic acid moiety in the siccative (average number of sulfonic acid or sulfonate moieties per polymer ligand molecule times the moles of polymer ligand molecules in the siccative) to the moles of vanadium atom from vanadium compound in the siccative.Clause 28. The siccative of any preceding clause, wherein the siccative includes at most about 10:1 , at most about 8:1 , at most about 5:1 , at most about 4:1 , at most about 3:1 , or at most about 2.7:1 moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium, where the ratio of moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium is calculated as the ratio of: the moles of sulfonate or sulfonic acid moiety in the siccative (average number of sulfonic acid or sulfonate moieties per polymer ligand molecule times the moles of polymer ligand molecules in the siccative) to the moles of vanadium atom from vanadium compound in the siccative.Clause 29. The siccative of any preceding clause, wherein the polymer ligand of the siccative exhibits a free acid value of at least about 50 mg KOH / g polymer ligand, at least about 70 mg KOH / g polymer ligand, at least about 80 mg KOH / g polymer ligand, at least about 100 mg KOH / g polymer ligand, or at least about 125 mg KOH / g polymer ligand, wherein the free acid value is determined titrimetrically according to ISO 2114-2000 with respect to the polymer ligand following acid treatmentand in the absence of vanadium compound and other complexing agents capable of altering the observed free acid value.Clause 30. The siccative of any preceding clause, wherein the polymer ligand of the siccative exhibits a free acid value of at most about 325 mg KOH / g polymer ligand, at most about 310 mg KOH / g polymer ligand, at most about 300 mg KOH / g polymer ligand, at most about 290 mg KOH / g polymer ligand, or at most about 275 mg KOH / g polymer ligand, wherein the free acid value is determined titrimetrically according to ISO 2114-2000 with respect to the polymer ligand following acid treatment and in the absence of vanadium compound and other complexing agents capable of altering the observed free acid value.Clause 31 . The siccative of any preceding clause, wherein the siccative further comprises an additional ligand, such as a polydentate amine (e.g., TRISPICEN-type, CYCLAM and Cross-Bridged- type, TMTACN-type, TACN-type, N4py-type, Bispidon-type), a carboxylate, or a 1 ,3 diketone.Clause 32. The siccative of any preceding clause, wherein the siccative further comprises one or more secondary or auxiliary driers.Clause 33. The siccative of any preceding clause, wherein the siccative further comprises one or more colorants.Clause 34. The siccative of any preceding clause, further including a solvent selected from the group consisting of water or water and C2-C9 glycols or dimethyl sulfoxide, or mixtures thereof.Clause 35. The siccative of any preceding clause, further including a solvent, wherein the siccative includes at least approximately 5 wt. % solvent, at least approximately 20 wt. % solvent, at least approximately 30 wt. % solvent, at least approximately 40 wt. % solvent, or at least approximately 44 wt. % solvent.Clause 36. The siccative of any preceding clause, further including a solvent, wherein the siccative includes at most approximately 99 wt. % solvent, at most approximately 90 wt. % solvent, at most approximately 60 wt. % solvent, at most approximately 50 wt. % solvent, or at most approximately 46 wt. % solvent.Clause 37. The siccative of any of clauses 1 through 33, wherein the siccative is provided in a solid form.Clause 38. The siccative of any of the preceding clauses, wherein the polymer ligand is formed via radical polymerization or RAFT polymerization.Clause 39. A kit comprising a first formulation and a second formulation, wherein the first formulation comprises the vanadium compound of any preceding clause and the second formulation comprises the polymer ligand of any preceding clause, and the first and second formulations of said kit are physically separated from each other (e.g., in separate cartridges, sachets, or the like) such that when the formulations are combined, in any order, the formulations form the siccative of any preceding clause.cialise 40. An oxidatively curable coating composition comprising: a binder curable by autoxidation mechanism; and the siccative of any of clauses 1 through 38.Clause 41 . The coating composition of clause 40, further comprising a solvent and optionally cosolvents.Clause 42. The coating composition of clause 40 or 41 , wherein the binder curable by autoxidation mechanism is selected from the group consisting of an alkyd resin, an epoxy ester resin and a resin modified by plant oils or fatty acids.Clause 43. The coating composition of clause 42, wherein the binder curable by autoxidation mechanism is an alkyd resin.Clause 44. The coating composition of clause 43, wherein the binder curable by autoxidation mechanism is a short oil alkyd, a medium oil alkyd, a long oil alkyd, a waterborne alkyd, a water- reducible alkyd, a silicone modified alkyd, or a polyurethane modified alkyd or a combination thereof.Clause 45. The coating composition of any of clauses 40 through 44, wherein the binder curable by autoxidation mechanism further comprises one or more (meth)acrylic, vinyl, vinyl acetate, styrene, or polyurethane residues, or mixtures thereof.Clause 46. The coating composition of any of clauses 40 through 45, further comprising one or more additional resins, wherein the one or more additional resins comprise (meth)acrylic, vinyl, vinyl acetate, styrene, or polyurethane residues or a combination thereof.Clause 47. The coating composition of clause 46, wherein the binder curable by autoxidation mechanism and the additional resin form an inter-penetrating network.Clause 48. The coating composition of any of clauses 40 through 47, wherein the amount of alkyd binder in the present coating composition is at least approximately 10 wt.%, at least approximately 20 wt. %, at least approximately 30 wt. %, or at least approximately 40 wt. %.Clause 49. The coating composition of any of clauses 40 through 48, wherein the amount of alkyd binder in the present coating composition is at most approximately 98 wt.%, at most approximately 90 wt. %, at most approximately 85 wt. %, or at most approximately 70 wt. %.Clause 50. The coating composition of any of clauses 40 through 49, wherein the coating composition is solventborne or waterborne.Clause 51 . The coating composition of clause 50, wherein the coating composition is water- reducible.Clause 52. The coating composition of any of clauses 40 through 51 , further comprising optional additional components such as solvents, antioxidants or antiskinning agents, additional siccatives, auxiliary or secondary driers, colorants (including inks and colored pigments), fillers, plasticizers, viscosity modifiers, crosslinkers, UV light absorbers, stabilizers, antistatic agents, flame retardants,- solubricants, emulsifiers, anti-foaming agents, viscosity modifiers, antifouling agents, biocides (e.g. bactericides, fungicides, algaecides and insecticides), anticorrosion agents, antireflective agents, antifreezing agents, or waxes and thickeners or combinations thereof.Clause 53. The coating composition of clause 52, wherein the coating composition comprises at least one auxiliary or secondary drier.Clause 54. The coating composition of clause 53, wherein the at least one auxiliary or secondary drier is present in the coating composition in an amount between about 0.01 wt. % and about 2.5 wt. %.Clause 55. The coating composition of clause 54, wherein the at least one auxiliary or secondary drier may be a fatty acid soap of zirconium, bismuth, barium, cerium, calcium, lithium, strontium, or zinc, or a combination thereof.Clause 56. The coating composition of any of clauses 40 through 55, wherein coating composition comprises the siccative in overall concentration of at least approximately 0.001 wt.%, at least approximately 0.003 wt. %, at least approximately 0.006 wt. %, at least approximately 0.01 wt. %, or at least approximately 0.02 wt. %, wherein weight percents indicate the weight percent of vanadium metal as a percentage of the weight of the binder (or resin) solids in the coating composition, which measure is called “metal on resin solids” in the art (MORS).Clause 57. The coating composition of any of clauses 40 through 56, wherein coating composition comprises the siccative in overall concentration of at most approximately 2.0 wt.%, at most approximately 1 .0 wt. %, at most approximately 0.5 wt. %, at most approximately 0.2 wt. %, or at most approximately 0.1 wt. %, wherein weight percents indicate the weight percent of vanadium metal as a percentage of the weight of the binder (or resin) solids in the coating composition, which measure is called “metal on resin solids” in the art (MORS).Clause 58. The coating composition of any of clauses 40 through 57, wherein coating composition comprises the siccative in overall concentration of at least approximately 0.0005 wt.%, at least approximately 0.001 wt. %, at least approximately 0.003 wt. %, at least approximately 0.01 wt. %, or at least approximately 0.02 wt. %, wherein wt. % is expressed as vanadium metal content on dry coating weight.Clause 59. The coating composition of any of clauses 40 through 58, wherein coating composition comprises the siccative in overall concentration of at most approximately 2.0 wt.%, at most approximately 1 .0 wt. %, at most approximately 0.2 wt. %, at most approximately 0.1 wt. %, or at most approximately 0.08 wt. %, wherein wt. % is expressed as vanadium metal content on dry coating weight.Clause 60. The coating composition of clauses 40 through 59, further comprising at least one antiskinning agent present in the coating composition between 0.05 wt. % to 3 wt. % in dry material content antiskinning agent with respect to dry material content of the coating composition.Clause 61 . The coating composition of any of clauses 40 through 60, further comprising at least 5 wt. % in dry material content pigment with respect to dry material content of the coating composition.Clause 62. A method of forming the coating composition of any of clauses 40 through 61 , comprising the steps of: providing: the binder curable by autoxidation mechanism of any of clauses 40 through 61 , and the siccative of any preceding clause; and contacting the binder curable by autoxidation mechanism with the siccative.Clause 63. The method of forming a coating composition of clause 62, wherein the step of contacting the binder curable by autoxidation mechanism with the siccative is accomplished by first contacting the binder curable by autoxidation mechanism with one of the vanadium compound and the polymer ligand of the siccative and then contacting the resulting mixture with the other of the vanadium compound and the polymer ligand of the siccative.Clause 64. The method of forming a coating composition of clause 63, wherein the step of providing further includes providing optional additional components such as antioxidants or antiskinning agents, additional siccatives, auxiliary or secondary driers, colorants (including inks and colored pigments), fillers, plasticizers, viscosity modifiers, crosslinkers, UV light absorbers, stabilizers, antistatic agents, flame retardants, lubricants, emulsifiers, anti-foaming agents, viscosity modifiers, antifouling agents, biocides (e.g. bactericides, fungicides, algaecides and insecticides), anticorrosion agents, antireflective agents, anti-freezing agents, or waxes and thickeners or combinations thereof, and the method further includes the step of contacting the optional additional components with the binder curable by autoxidation mechanism and the siccative.Clause 65. A method of forming a coated article, comprising the steps of casting a film of the coating composition of any of clauses 40 through 61 on the article, and allowing the coating composition to cure.Clause 66. A kit comprising a first formulation and a second formulation, wherein the first formulation comprises the binder curable by autoxidation mechanism of any of clauses 40 through 61 and the second formulation comprises the polymer ligand of any preceding clause and the vanadium compound of any preceding clause, and the first and second formulations of said kit are physically separated from each other (e.g., in separate cartridges, sachets, or the like) such that they may be combined, in any order, to form a coating composition.Clause 67. A kit comprising a first formulation, a second formulation, and a third formulation, wherein the first formulation comprises the binder curable by autoxidation mechanism of any of clauses 40 through 61 , the second formulation comprises the polymer ligand of any of clauses 1 through 65, and the third formulation comprises the vanadium compound of any of clauses 1 through 65, and the first, second, and third formulations of said kit are physically separated from each other(e.g., in separate cartridges, sachets, or the like) such that when the formulations are combined, in any order, they form a coating composition.Clause 68. The kit of any of clauses 66 and 67, wherein the first formulation further comprises optional additional components such as a secondary binder resin, a biocide, or other coating additives.Clause 69. The use of the vanadium compound of any preceding clause and the polymer ligand of any preceding clause as a siccative for coatings containing a binder curable by autoxidation mechanism.EXAMPLES

[0109] Test Methods and Measurements

[0110] Unless otherwise indicated, measurements and results provided below were obtained by subjecting the relevant samples to testing or measurement conducted according to the following conditions and test methods.

[0111] Measurement Conditions

[0112] The coating of all glass plates, recording of dry times, measurement of hardness and yellowing, and storage were performed in a climate-controlled room with a temperature of approximately 23°C and a humidity of approximately 50%.

[0113] Metal Content Measurements and Concentrations

[0114] Siccative and drier concentrations in coatings materials are given in wt. %, referring to the siccative’s metal amount relative to the solid content of the binder in the coating employed. This is also abbreviated MORS, metal on resin solid. MORS is calculated in the following way:

[0115] With mdmass of the drier (or if the drier is in solution, the drier solution), in g; MCd. metal content of the drier (or if the drier is in solution, the drier solution) in %; SCf. solid content (of binder) in the formulation, in %; and mf. mass of the formulation, in g.

[0116] Metal content of the siccative solutions themselves was measured by MP-AES using a Model 4210 MP-AES instrument (available from Agilent Technologies, Inc., Santa Clara, CA) by running each siccative prior to incorporation into any coating or gel coat. Measurements of samples were taken with the assistance of a straight calibration curve developed from a standard vanadium solution. A 1000 ppm vanadium MP-AES calibration solution (Vanadium AA Standard: 1000 pg / mL V in 5% HNO3; Agilent Part No. 5190-8323; available from Agilent Technologies, Inc.) was diluted to 100, 250, and 500 ppm to obtain the calibration curve between 100 ppm and 1000 ppm V. Metal content of driers is given by the manufacturers.

[0117] Coating Dry Time

[0118] A B.K. Drying Recorders model 3 (available from the Mickle Laboratory Engineering Co. Ltd.) dry time recorder was used to measure the time required to reach the three drying states of (i) set-to- touch (ST), which means the paint no longer flows back after the needle has passed through; tack- free (TF) where tearing of the coating is created by the needle, and (iii) dry-hard (DH), where the coating is no longer marked by the needle - further explained in ASTM method D5895-13.

[0119] To measure for waterborne and solventborne coatings, the coated glass plate for each given sample was placed on the dry time recorder, a needle was put on the film, and the recorder was set for measurement over 24 hours. The dry time recorder was then started. The starting point is designated by where the needle was put onto the film— th is was marked on the glass using a marker pen. The three drying phases were identified by the typical flow patterns given at each stage, and the time for completion at each stage was recorded.

[0120] For formulations including water-reducible binders, the dry times in days were measured by placing filter paper on top of each coating sample on the 15x9 cm glass plate in a new, undisturbed location on the plate every 24 hours. For each newly placed filter paper, a weight of 200g with a defined surface area was allowed to sit on the filter paper for 30 seconds. After the 30 seconds, the weight was removed, and the glass plate with filter paper was flipped over. The state of “dry hard” was reached when the filter paper no longer stuck to the coating.

[0011] Konig Pendulum Hardness

[0122] Films of 100 pm thickness were cast on glass sheets (15x9 cm) for measurement of hardness at the same time as when casting films for dry time recording. For each sample, these were evaluated on a pendulum hardness tester after drying times of 24 hours, 7 days and 14 days. Pendulum hardness was measured on a TQC Sheen Pendulum Hardness Tester SP0500 by using the Konig method (measuring the time of oscillations in seconds, starting at an initial amplitude of 6° and until an amplitude of 3° is reached). Softer material dampens the pendulum’s oscillations more quickly than harder material, so softer material has a lower hardness value in seconds than harder material.

[0123] Coating Film Yellowing

[0124] To measure coating film yellowing, a multi-angle spectrophotometer (MA98, X-Rite) was used to take measurements of cured film color after a drying time of 14 days in a dark storage in a climate- controlled room with a temperature of 23°C and a humidity of ca. 50%. The values of yellowing (Ab for transparent coat & b* for white coat) were obtained from background illumination and observer of 45°:as45. Refer to ASTM method E 2539 for further description.

[0125] Preparation of Exemplary Siccatives:

[0126] Siccative 1 :

[0127] In a 250 mL round bottom flask with magnetic stirring bar, 10g poly(sodium-4- styrenesulfonate), (Mw~70 kDa) (CAS 25704-18-1 ; available from Millipore Sigma), 2.25g vanadium pentoxide (CAS 1314-62-1 ; available from Millipore Sigma) and 87.5g distilled water were added and stirred until homogenized. 18g hydrobromic acid (48%) was added to the reaction mixture and heatedto 110°C in an oil bath. The reaction mixture was stirred over 24 hours to obtain a clear blue solution. The mixture volume was reduced using a rotavap to yield an approximate mass of sample of 20g and precipitated in 1 L cold (approximately 2-8 °C) isopropanol. The precipitate was filtered through a P3 fritted filter and washed with excess clean isopropanol. The filtrate was vacuum dried to obtain light green powder. Vanadium metal content was determined by MP-AES to a value of 4.35 wt. % vanadium metal mass on whole complex mass (vanadium compound mass plus polymer ligand mass, excluding solvent mass).

[0128] Siccative 2:

[0129] In a 100 mL round bottom flask with magnetic stirring bar, 5.16g polyanetholsulfonic acid sodium salt (Mw~10 kDa) (CAS 55963-78-5; available from Millipore Sigma), 0.96g vanadium pentoxide (available from Millipore Sigma) and 45.19g distilled water were added and stirred until homogenized. 9.62g hydrobromic acid (48%) was added to the reaction mixture and heated to 110°C in an oil bath. The reaction mixture was stirred over 3 hours to obtain a clear green solution. The mixture volume was reduced using a rotavap to yield an approximate mass of sample of 15g and precipitated in 0.8L cold (approximately 2-8 °C) isopropanol. The precipitate was filtered through a P4 fritted filter and washed with excess clean isopropanol. The filtrate was vacuum dried to obtain light green powder. Vanadium metal content was determined by MP-AES to a value of 3.72 wt. % vanadium metal mass on whole complex mass (vanadium compound mass plus polymer ligand mass, excluding solvent mass).

[0130] Siccative 3:

[0131] In a 50 mL round bottom flask with magnetic stirring bar, 2.5g poly(4-styrenesulfonic acid-co- maleic acid) sodium salt-A (Mw~20 kDa) (CAS 68037-40-1 ; available from Millipore Sigma), 0.64g vanadium pentoxide (available from Millipore Sigma) and 21.88g distilled water were added and stirred until homogenized. 4.66g hydrobromic acid (48%) was added to the reaction mixture and heated to 110°C in an oil bath. The reaction mixture was stirred over 3 hours to obtain a clear green solution. The mixture volume was reduced using a rotavap to yield and approximate sample mass of 10g and precipitated in 0.4L cold (approximately 2-8 °C) isopropanol. The precipitate was filtered through a P4 fritted filter and washed with excess clean isopropanol. The filtrate was vacuum dried to obtain light green powder. Vanadium metal content was determined by MP-AES to a value of 5.75 wt. % vanadium metal mass on whole complex mass (vanadium compound mass plus polymer ligand mass, excluding solvent mass).

[0132] Siccative 4:

[0133] In a 50 mL round bottom flask with magnetic stirring bar, 2.5g poly(4-styrenesulfonic acid-co- maleic acid) sodium salt-B (Mw~20 kDa) (available from Millipore Sigma), 0.60g vanadium pentoxide (available from Millipore Sigma) and 21.88g distilled water were added and stirred until homogenized. 4.66g hydrobromic acid (48%) was added to the reaction mixture and heated to 110°C in an oil bath. The reaction mixture was stirred over 3 hours to obtain a clear green solution. The mixture volume was reduced using a rotavap to yield and approximate sample mass of 10g and precipitated in 0.4Lcold (approximately 2-8 °C) isopropanol. The precipitate was filtered through a P4 fritted filter and washed with excess clean isopropanol. The filtrate was vacuum dried to obtain light green powder. Vanadium content was determined by MP-AES to a value of 4.50 wt. % vanadium metal mass on whole complex mass (vanadium compound mass plus polymer ligand mass, excluding solvent mass).

[0134] Siccative 5:

[0135] Polymerization: In a 500 mL round bottom flask with magnetic stirrer, 30g of sodium 4-vinyl benzene styrene sulfonate (CAS # 2695-37-6; available from Millipore Sigma), 0.69g of RAFT agent (BM 1429, CAS # 870451-09-5; available from Boron Molecular) and 165g of water were added. Upon reagent dissolution, the reaction mixture was heated to 70 °C, stirred at 400 rpm and bubbled with nitrogen gas for 30 minutes. In the meantime, initiator solution was prepared by dissolving 0.15g AAPH (2,2'-Azobis(2-methylpropionamidine) dihydrochloride; CAS # 2997-92-4; available from Millipore Sigma) in 5g water, bubbled with nitrogen gas in an ice bath. The initiator solution was then added into the reaction mixture to begin the polymerization reaction. The polymerization completed after 2 hours. Solid content (after 1 hour at 125 °C): 14.59%. The polymer was passed through a column filled with proton cationic exchanger resin (Amberlite IR 120, available from Millipore Sigma) to acidify the polymer. Solid content (after 1 hour at 125 °C): 11.85%; Mw~9-10 kDa.

[0136] Reaction between Polymer and Vanadium Pentoxide: In a 25 mL round bottom flask, 5g of the above polymer and 0.06g of vanadium pentoxide (available from Millipore Sigma) were added. The reaction mixture was heated to 110 °C while stirred at 300 rpm. The reaction ended after 6.5 hours to obtain a dark blue solution. Solid content (1 hour at 125 °C): 13.52%; vanadium content was determined by calculation to be 4.74 wt. % vanadium metal mass on whole complex mass (vanadium compound mass plus polymer ligand mass, excluding solvent mass).

[0137] Siccative 6:

[0138] Polymerization: In a 500 mL round bottom flask with magnetic stirrer, 20g of 2-acrylamido-2- methylpropane sulfonic acid (CAS # 15214-89-8; available from Millipore Sigma) and 103g of water were added. The reaction mixture was stirred at 400 rpm in an ice bath. RAFT agent solution was prepared by mixing 0.5g RAFT agent (BM 1429; available from Boron Molecular), 0.2g sodium carbonate and 5g water, which were homogenized and then added to the 500 mL round bottom flask. The reaction mixture was bubbled with nitrogen gas for 30 minutes. In the meantime, initiator solution was prepared by dissolving 0.11g AAPH (available from Millipore Sigma) in 5g water, bubbled with nitrogen gas in an ice bath. After 30 minutes, initiator solution was added into the reaction mixture, the ice bath was removed, and reaction mixture was heated to 70 °C to begin the polymerization reaction. The polymerization is completed after 1.5 hours. Solid content (after 1 hour at 125 °C): 15.43%; Mw~10-12 kDa.

[0139] Reaction between Polymer and Vanadium Pentoxide: In a 25 mL round bottom flask, 5g of the above polymer and 0.1g of vanadium pentoxide (available from Millipore Sigma) were added. The reaction mixture was heated to 110 °C while stirred at 300 rpm. The reaction ended after 4.5 hours to obtain a dark blue solution. Solid content (after 1 hour at 125 °C): 17.82%; vanadium content wasdetermined by calculation to be 6.02 wt. % vanadium metal mass on whole complex mass (vanadium compound mass plus polymer ligand mass, excluding solvent mass).

[0140] Each siccative was subsequently tested for performance in alkyd coating formulations as described below.

[0141] Other driers were also used to form coating compositions. These driers included Borchi OXY- Coat 1101 (an aqueous solution of an iron drier, available from Borchers Americas, Inc., Westlake, OH), Borchers® Deca Cobalt 7 aqua (cobalt neodecanoates in water dispersible oil with 6.80-7.20% cobalt metal, available from Borchers Americas, Inc., Westlake, OH), WD 016 (an aqueous suspension of cobalt drier at 8-10% cobalt metal as a percentage of total drier solution weight, including solvent weight, Guangdong DIC TOD Resins Co., Ltd., China), V-TS (a vanadium-based drier complex of oxidovanadium and p-toluenesulfonate, 9.4 wt. % vanadium metal and generally used in a stock solution of ca. 10 % in DMSO or in a mixture of higher-boiling alcohols and esters; courtesy of Prof. Jan Honzicek, University of Pardubice, Czech Republic; wt. % refers here to vanadium metal as a percent of drier complex weight, excluding solvent weight, except where context clearly dictates otherwise).

[0142] The alkyd binders used were SYNAQUA 4804 (waterborne short oil alkyd) and SYNAQUA 2070 (waterborne medium oil alkyd) from Arkema Coating Resins. TOD 3AK0211 Y and TOD 3AK0235Y (water reducible alkyds) from Guangdong DIC TOD Resins Co., Ltd., China.

[0143] BASE COATING FORMULATIONS

[0144] The formulation of paints used were the following, with all amounts expressed in parts out of 100 by mass:

[0145] Table 1 : Base Coating 1 - formulation TOD 3AK0211Y, water-reducible alkyd, clear coatResin solid content with respect to entire base coating composition weight: 31 .50%

[0146] Table 2: Base Coating 2 - formulation TOD 3AK0211Y, water-reducible alkyd, white coatResin solid content with respect to entire base coating composition weight: 22.00%

[0147] Table 3: Base Coating 3 - formulation TOD 3AK0235Y, water-reducible alkyd, clear coatResin solid content with respect to entire base coating composition weight: 32.41%

[0148] Table 4: Base Coating 4 - formulation TOD 3AK0235Y, water-reducible alkyd, white coatResin solid content with respect to entire base coating composition weight: 22.69%

[0149] Table 5: Base Coating 5 - Formulation of Synaqua 4804 short oil, waterborne alkyd, clear coatResin solid content with respect to entire base coating composition weight: 47.62%

[0150] Table 6: Base Coating 6 - Formulation of Synaqua 2070 medium oil, waterborne alkyd, clear coatResin solid content with respect to entire base coating composition weight: 50.48%

[0151] Table 7: Base Coating 7 - formulation TOD 3AK0211Y, water-reducible alkyd, clear coatResin solid content with respect to entire coating composition weight: 31.41%

[0152] COATING PREPARATION

[0153] Each siccative and drier solution was charged to a 25ml plastic cup with screw cap in amounts appropriate to attain the MORS content described below in Tables 8-14 for the corresponding base coatings (as noted in each Table) in light of the amount of binder added. 5 to 6 g of Base Coating is added, the cup is sealed, and then the mixture (for water-reducible coating formulations corresponding to Base Coatings 1 , 2, 3, 4, and 7) is mixed at 3000 rpm for 10 minutes in a high-speed mixer (SpeedMixer DAC 150.1 FVZ). For the waterborne binder samples (corresponding to Base Coatings 5 and 6), the catalyst and binder mixtures were mixed at 2000 rpm for 2 minutes in a high-speed mixer instead of the 3000 RPM mixing step used with the water- reducible binders). The resulting coating and catalyst mixture (for all coating composition types — water-reducible or waterborne) was stored under ambient conditions for 24 hours before coating films were cast onto a glass substrate (i.e., a 30 x 2.4 cm plate for dry time recording measurements and 15 x 9cm plate for Kbnig pendulum hardness measurement and yellowing measurement) using a steel cube applicator. The wet film thickness for all samples is 100 pm. These procedures were followed using the coating formulations identified in each of Tables 1-7 for generating coatings for each siccative (Siccatives 1-6) and each other drier (BOC-1101 , WD 016, and V-TS).

[0154] Each of Siccatives 1-6 and the other driers was tested in each Base Coating as specified below. Results of such testing for dry times, hardness, and yellowing are shown in Tables 8-14, below.

[0155] Table 8: Results in TOD 3AK0211Y Water Reducible Alkyd - Clear Coat (Base Coating 1)

[0156] The results in Table 8 reveal that Siccative 2 (entry 5) shows the best dry-hard dry time, highest hardness and lowest yellowing after 14 days compared to all vanadium-based driers (entries 3-7). For siccatives 1 to 4, the dry times are shorter and the hardnesses are higher than WD 016 (an exemplary cobalt drier), even at a lower MORS. Surprisingly, the yellowing effect was reduced whilst improving the dry time and hardness of the paint by using siccatives 1-4 (compare Ab for coating compositions containing V-TS to that for coating compositions containing Siccatives 1-4). Siccatives 1 through 4) show significantly lower dry time and higher hardness compared to BOC-1101 drier.

[0157] Table 9: Results in TOD 3AK0211Y Water Reducible Alkyd - White Coat (Base Coating 2)

[0158] The results in Table 9 reveal that in TOD 3AK0211 Y white coat, the best dry time was achieved by using WD 016 drier, that was not observed in the clear coat of the same binder (Table 8).The dry times of siccatives 2 and 3 are comparable to WD 016. Particularly, siccative 2 exhibits comparable dry time and yellowing to WD 016 while providing higher hardness.

[0159] Each polymeric siccative again performed better than V-TS, a conventional vanadium-based drier having only a molecular (non-polymeric) carboxylate ligand / soap.

[0160] Table 10: Results in TOD 3AK0235Y Water Reducible Alkyd - Clear Coat (Base Coating 3)

[0161] Table 11 : Results in TOD 3AK0235Y Water Reducible Alkyd - White Coat (Base Coating 4)

[0162] For samples corresponding to Base Coatings 3 and 4 (TOD 3AK0235Y binder, clear & white coats), the dry times of all samples did not provide a useful comparison as the coating formulation samples binders dried very quickly for all coatings (within 1 day dry time for all samples). For samples corresponding to Base Coatings 3 and 4, coatings containing Siccatives 1-4 generally displayed improved or comparable hardness at various times throughout drying relative to other driers. For samples corresponding to Base Coatings 3 and 4, coatings containing Siccatives 1-4 generally displayed reduced or comparable yellowing relative to the conventional vanadium-based drier, V-TS.

[0163] Table 12: Results in Synaqua 4804, Waterborne, Short-Oil Alkyd - Clear Coat (BaseCoating 5)

[0164] For samples corresponding to Base Coating 5 (Synaqua 4804, waterborne, short-oil alkyd clear coat), additional dry times (ST and TF) are shown, as almost all samples (except for Siccative 6) displayed dry-hard dry times beyond 24 hours. For samples corresponding to Base Coating 5, coatings containing Siccatives 1 , 2, and 5 generally displayed comparable dry times at various times throughout drying relative to other driers. Coatings containing Siccative 6 generally displayed improved dry times at various times throughout drying relative to other driers. Coatings containing Siccatives 1 , 2, 5 and 6 generally displayed reduced or comparable yellowing and improved hardness relative to the conventional vanadium-based drier, V-TS.

[0165] Table 13: Results in Synaqua 2070, Waterborne, Medium-Oil Alkyd - Clear Coat (Base Coating 6)

[0166] For samples corresponding to Base Coating 6 (Synaqua 2070, waterborne, medium-oil alkyd clear coat), additional dry times are shown (ST and TF in addition to DH), as almost all samples (except for BOC-1101) displayed dry-hard dry times beyond 24 hours. Coatings containing Siccatives1 , 2, 5 and 6 generally displayed improved (reduced) yellowing and improved or comparable hardness relative to the conventional vanadium-based drier, V-TS.

[0167] Table 14: Results of Catalyst Loading Ladder Study in TOD 3AK0211Y Water Reducible Alkyd - Clear Coat (Base Coating 7)

[0168] For samples in the ladder study (results in Table 14, above), each of the named siccatives or driers was tested in the Base Coating 7 formulation at varying loading levels of siccative / drier (0.01 , 0.05, and 0.1 % MORS).

[0169] Illustrative embodiments have been described, hereinabove. It will be apparent to those skilled in the art that the above compositions and methods may incorporate changes andmodifications without departing from the general scope of this disclosure. It is intended to include all such modifications and alterations within the scope of the present disclosure. Furthermore, to the extent that the term “includes” is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term “comprising” as “comprising” is interpreted when employed as a transitional word in a claim.

[0170] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

What is Claimed is:1 . A siccative composition comprising: a polymer ligand including at least one structural unit derived from an ethylenically unsaturated monomer including a sulfonic acid or sulfonate moiety capable of coordinating a vanadium atom; and a vanadium compound.

2. The siccative of a claim 1 , wherein the at least one ethylenically unsaturated monomer bearing a sulfonic acid or sulfonate moiety is of Formula I:Formula II:or Formula III:where each of R1, R2, and R3 are independently hydrogen or a C1 to C3 alkyl group; where each R4 is a methoxy group; where z is 0 or 1 ; where each R5 is of Formula IIA:wherein the nitrogen is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; or Formula I IB:wherein the oxygen is covalently bonded to the carbonyl carbon of Formula II and Re is covalently bonded to Q; such that any ethylenically unsaturated monomer of Formula II is either a sulfonate or sulfonic acid acrylate monomer or a sulfonate or sulfonic acid acrylamide monomer; where each Re is independently a C1 to C9 alkanediyl group; where y is 0 or 1 ; where each R7 is independently a C1 to C9 alkanediyl group; and where each Q is SO3H or SOs" X, where X is a cation of a salt.

3. The siccative of claim 2, wherein the at least one ethylenically unsaturated monomer of Formulas I, II, or III is selected from the group consisting of 4-styrene sulfonic acid or salts thereof, 2-methoxy-5-[(E)-prop-1-enyl]benzenesulfonic acid or salts thereof, 2-acrylamido-2-methylpropane sulfonic acid or salts thereof, allyl sulfonic acid or salts thereof, vinyl sulfonic acid or salts thereof, and mixtures thereof.

4. The siccative of claims 2 or 3, wherein the monomers of formulas I and III make up from about 20 wt % to 100 wt. % of all monomers used to form the polymer ligand.

5. The polymer ligand of any of claims 2 through 4, wherein Q is SO3 X, wherein X is Na+.

6. The siccative of any preceding claim, further including a solvent selected from the group consisting of water or a mixture of water and C2-C9 glycols, or dimethyl sulfoxide.

7. The siccative of any preceding claim, wherein the polymer ligand has a weight average molecular weight of from 1 ,000 g / mol to about 70,000 g / mol.

8. The siccative of any preceding claim, wherein the polymer ligand further comprises structural units derived from comonomers selected from the group consisting of esters of acrylic acid, styrene, vinyl monomers, and mixtures thereof, wherein said comonomers do not include a sulfonic acid or sulfonate moiety, and wherein said comonomers make up from about 0 wt. % to about 60 wt. % of all monomers used to form the polymer ligand.

9. The siccative of any preceding claim, wherein the vanadium compound includes a vanadyl functional group.

10. The siccative of any preceding claim, wherein the siccative includes vanadium compound and polymer ligand in amounts such that the ratio of moles sulfonate or sulfonic acid moiety from polymer ligand to moles vanadium in the siccative ranges from 1 .5:1 to 10:1 , where the ratio is calculated as the ratio of: the moles of sulfonate moiety in the siccative (average number of sulfonic acid or sulfonate moieties per polymer ligand molecule times the moles of polymer ligand molecules in the siccative) to the moles of vanadium atom from vanadium compound in the siccative.

11. A coating composition comprising: a binder curable by autoxidation mechanism; and the siccative of any preceding claim.

12. The coating composition of claim 11 , wherein the binder curable by autoxidation mechanism is selected from the group consisting of alkyd resin, epoxy ester resin, and resin modified by plant oils or fatty acids.

13. The coating composition of claims 11 or 12, wherein the coating composition comprises siccative in overall concentration of 0.001 wt. % to 0.5 wt. %, preferably 0.005 to 0.3 wt. %, and more preferably 0.01 to 0.2 wt. %, wherein the weight percentages are of the vanadium metal based on the weight of the resin solids.

14. The coating composition of any of claims 11 through 13, wherein the coating composition is water-based.

15. The coating composition of any of claims 11 through 14, further comprising at least about 5 wt. % in dry material content pigment with respect to dry material content of the coating composition.

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