Vanadium complexes with nitrogen and oxygen donor atoms

Abstract

The present invention relates generally to metal complexes of vanadium, iron, manganese or copper with ligands containing at least one nitrogen and at least one oxygen donor atom, such as asymmetric amino acids and Schiff base ligands.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] none Technical Field

[0003] The invention described herein generally relates to metal complexes having ligands containing at least one nitrogen and at least one oxygen donor atom, such as amino acids and phenolic Schiff bases, the combination demonstrating improvement in at least one physical property selected from improved coating hardness, reduced coating peeling, and reduced drying time. Background Art

[0004] Primary paint driers, typically metal carboxylates such as cobalt neodecanoate, are used to catalyze the oxidative drying (curing) of alkyd resins. Typically, these driers are complexes based on transition metals. Cobalt driers are the most commonly used drying catalysts because they result in a highly crosslinked hard film. Highly crosslinked hard films are desirable because they have higher scratch resistance, chemical resistance, and corrosion resistance. However, several environmental studies have indicated the potential reclassification of cobalt-based alkyd driers. Oxy Coat ("BOC") is a primary drier for alkyd resins. BOC has been found to exhibit faster cure and less yellowing of alkyd films at much lower concentrations than cobalt. However, BOC has been found to lack hard film formation when compared to some cobalt driers.

[0005] Therefore, non-cobalt based driers are needed as an alternative.The lack of hardness has limited the use of BOC as a cobalt replacement in more demanding applications such as direct metal painting or decorative coatings to provide scratch resistance, improved corrosion resistance and rapid paint build-up capability.

[0006] Vanadyl sulfonate-based driers generally provide higher hardness in the coating compared to BOC. However, the cure rate is generally slower than BOC, and the desired hardness of the coating is often achieved after an undesirably long time. In addition, these driers exhibit inferior coatings after water immersion, an important test in some areas of general industrial coatings, compared to BOC and cobalt-based driers.

[0007] Various vanadium complexes have been used as primary driers in the aerobic curing of alkyd resins. Vanadyl acetylacetonate (VO(acac)2) is known as a drier but is not generally considered to have excellent properties. Recently, Vinklárek and The group has developed several driers, such as vanadium carboxylates, acetylacetonate derivatives, and dithiocarbamates, and has primarily tested them in solvent-borne alkyd resins. Compared to cobalt-based driers, they generally perform well at lower cobalt loadings than are typically found in cobalt-based driers, and also at higher loadings than are typically found in BOC.

[0008] Several patents describe vanadium-based driers for curing alkyd resins. For example, one mentions the use of photoinitiators in conjunction with vanadium driers (see WO 2007 / 017032 A1); one describes the use of various driers, including vanadium, to cure a specific hybrid alkyd acrylate resin (see US 2010 / 0160551 A1); one specifically uses α-hydroxycarboxylates of various metals, including vanadium, as driers (see WO 2016 / 154205 A1); and one describes a combination of cerium carboxylates and vanadium carboxylates (see CN 108165083 A). Several patents also describe the use of vanadium-based driers in conjunction with added peroxides as oxidants for curing resins, including one from Akzo Nobel using a polymer-bound driers (see US 9751994 B2) and one from Sherwin Williams using various metal-based driers (see US 2010 / 0160551 A1). Two Borchers patents describe vanadium phosphates and vanadyl dicarboxylates, acetylacetonates, and related ligands (see EP 0870811 A2; and US 6063841 A).

[0009] The use of vanadium complexes with organic ligands has been described in various fields of chemistry. Tables I, II and III illustrate the general and specific structures of ligands used in vanadium complexes for other applications. An important feature in the context of the present invention is that chelating ligands (hereinafter abbreviated as L) with at least one oxygen donor atom and one nitrogen donor atom are sometimes used. O,N Ligand), and wherein the chelating ligand having at least two oxygen donor atoms and one nitrogen donor atom is abbreviated as L ONO Ligands (see Table I) are shown with an arc-shaped bond between the N and O atoms, illustrating the bridging groups discussed herein, with the intervening N and O atoms coordinately bonded to the metal atom.

[0010] Table I

[0011]

[0012] As used in this patent application, the ligand used in the vanadium drier, wherein the ligand has two bridging nitrogen atoms and two oxygen atoms, has a general structure defined herein as L O,N,N,O , while ligands with two to four nitrogen atoms are defined herein as LN,N , L N,N,N and L N,N,N,N , and the ligand with only one oxygen atom is defined herein as (L O ). Examples of these ligands are shown in Table II below.

[0013] Table II

[0014]

[0015] WO2003 / 029371A1 mentions a mixture or a plurality of primary driers based on metals (including vanadium) and L with solubilizing groups. O,N,N.O or specific symmetrical Schiff base ligands of the salen type. The general structures of the Salen ligands are shown in Table III, including one of the ligands specified in the patent (the so-called Jacobsen ligand XJ).

[0016] Table III

[0017]

[0018] Patents EP 0304149 B1 and US 5154764A use vanadium salts as driers or additives, which can be used with L N,N and L O A combination of "chelating agents" of this type is described, specifically mentioning 1,10-phenanthroline, 2,2'-bipyridine, and tri-n-octylphosphine oxide (XC) (Table III). EP 1696010 B1 also mentions the possibility of adding bipyridine to vanadium compounds for curing alkyd resins. WO 2001 / 046294 A1, in the same context, mentions the possibility of adding 1,10-phenanthroline and 2,2'-bipyridine.

[0019] Patent WO2015 / 082553A1 also mentions the use of iron-based driers to cure alkyd resins, including the addition of vanadium carboxylate and L N,N and L N,N,N Ligands such as 2,2'-bipyridine, phenanthroline, 1,4,7-triazacyclononane (XD) or various simple amines and porphyrin (L N,N,N,N WO 2021 / 009079 A1 generally mentions nitrogen-donating ligands in the context of alkyd resin curing involving vanadium-based driers. The ligands are not described in further detail, other than mentioning that the ligands contain only nitrogen as the donor atom. Similarly, pure nitrogen-donating ligands are mentioned in WO 2014 / 122432 A1, WO 2014 / 122433 A1, and WO 2014 / 122434 A1 as potential additives for alkyd resin curing involving metal carboxylates containing vanadium.

[0020] In addition to the use of vanadium complexes in the aerobic curing of alkyd resins (or the curing of composite materials in the presence of added peroxides), vanadium complexes with organic ligands have also been described in very different fields. These include, for example, basic spectroscopic research, oxidation reactions of small molecules such as alcohols and sulfides, and use as biologically active compounds.

[0021] Specific L O,N The ligand is 8-hydroxyquinoline with a phenolic OH and an imine-like nitrogen atom (8HQ, see Table IV), which has been used as a ligand for vanadium complexes in many cases but has not been shown to be used for alkyd resin curing (drying). Similarly, the unsymmetrical type L derived from salicylaldehyde O,N Schiff base ligands have a phenolic OH group near the imine. These ligands are sometimes also called "half-salen" ligands and are shown in Table IV as structure HS. One class of those half-salen ligands is L O,N,O type, derived from an amino acid as the amine component, as shown in the structure HS-AA in Table IV.

[0022] Table IV

[0023]

[0024] Schiff base ligands such as HS-His (see Table V) are prepared from the corresponding amino acids and salicylaldehyde and have been described in the literature, but not for alkyd curing (drying) purposes. Vanadium complexes bearing Schiff base ligands synthesized from amino acids (including, for example, the ligand HS-His) can be synthesized in a one-pot process from vanadyl sulfate, the corresponding amino acid, and salicylaldehyde. The same synthesis is also described for complexes with the ligand HS-Trp.

[0025] Table V

[0026]

[0027] HS-His:2-((2-Hydroxybenzylidene)amino)-3-(1H-imidazol-4-yl)propanoic acid

[0028] HS-Trp:2-((2-Hydroxybenzylidene)amino)-3-(1H-indol-3-yl)propanoic acid

[0029] HS-Ser:3-Hydroxy-2-((2-hydroxybenzylidene)amino)propionic acid

[0030] HS-Met:2-((2-Hydroxybenzylidene)amino)-4-(methylthio)butanoic acid

[0031]

[0032] HS-Asp:2-((2-Hydroxybenzylidene)amino)succinic acid

[0033] HS-Glu:2-((2-Hydroxybenzylidene)amino)glutaric acid

[0034] HS-Gly:2-((2-Hydroxybenzylidene)amino)acetic acid

[0035] HS-Lys:6-amino-2-((2-hydroxybenzylidene)amino)hexanoic acid

[0036]

[0037] HS-Tyr:2-((2-hydroxybenzylidene)amino)-3-(4-hydroxyphenyl)propanoic acid

[0038] HS-Phe:2-((2-Hydroxybenzylidene)amino)-3-phenylpropionic acid

[0039] HS-Asn:4-amino-2-((2-hydroxybenzylidene)amino)-4-oxobutanoic acid

[0040] HS-Cys:2-((2-Hydroxybenzylidene)amino)-3-mercaptopropionic acid

[0041]

[0042] HS-Cystine: 3-((2-Carboxy-2-((2-hydroxybenzylidene)amino)ethyl)disulfanyl)-2-((2-hydroxybenzylidene)amino)propanoic acid

[0043] HS-Arg:5-Guandino-2-((2-hydroxybenzylidene)amino)pentanoic acid

[0044] HS-Leu:2-((2-Hydroxybenzylidene)amino)-4-methylpentanoic acid

[0045]

[0046] HS-Pro:1-(2-Hydroxybenzylidene)pyrrolidin-1-ium-2-carboxylate

[0047] mHS-His:2-((1-(2-hydroxyphenyl)ethylidene)amino)-3-(1H-imidazol-4-yl)propanoic acid

[0048] The synthesis and characterization of HS-Gly, HS-Ala, HS-Val, HS-Leu, HS-Ile, HS-Met, HS-Phe, HS-Thr, HS-Asp and HS-His are described in "Preparation and Characterization of New Oxovanadium(IV)Schiff Base Complexes derived from Amino Acids and Aromatic o-Hydroxyaldehydes" by Pessoa, Cavano, Correcia, Duarte, Gillard, Henriques, Higes, Madeira and Tomaz, Inorganica Chimica Acta 293 (1999) 1-11.

[0049] Without being bound by any one theory of operation or mode of application, it is believed that ImP-type ligands will be able to perform the functions of the above-mentioned ligands, as shown in Table VI.

[0050] Table VI

[0051] Summary of the Invention

[0052] This invention relates to a new class of paint driers primarily for waterborne alkyd resins, although they can also be used to improve drying time in solventborne coatings. It addresses the anticipated reclassification of cobalt-based driers, as the new driers are based on metallic vanadium and contain no cobalt. It also addresses the low hardness of BOC, as it provides significantly harder coatings in essentially all resin formulations tested to date. It addresses the slow cure rate of vanadyl sulfonate driers, as the present invention cures at a faster rate. It also addresses the problem of low adhesion, significantly improving adhesion compared to vanadyl sulfonate driers.

[0053] In a first embodiment of the present invention, a method of improving at least one physical property of an oxidatively curable alkyd resin coating is described, said physical property being selected from improved resin hardness, reduced resin foaming, and reduced resin drying time, said method comprising the following steps in any order:

[0054] A metal source of vanadium, iron, manganese or copper is combined with at least one asymmetric ligand, provided that:

[0055] (a) When the asymmetric ligand is L O,N or L O,N,O When the asymmetric ligand comprises at least one of a terminal carboxylic acid group or a phenolic hydroxyl group and at least one of a primary amine or a Schiff base or a pyridinic nitrogen group; and wherein

[0056] (b) When the asymmetric ligand is L containing at least one terminal carboxylic acid O,N,O When the asymmetric ligand comprises at least one phenolic hydroxyl functional group in addition to the at least one terminal carboxylic acid group;

[0057] The improvement is compared to an oxidatively curable alkyd resin coating that does not contain a metal source and at least one asymmetric ligand but instead contains a conventional metal source and ligand.

[0058] In a second embodiment of the first embodiment, the process will have at least one asymmetric ligand comprising Formula XXV or Formula XXVI or Formula XXVII or Formula XXVIII:

[0059] Wherein formula XXV is:

[0060]

[0061] in

[0062] R 1 and R 2 Independently selected from H, C 1-4 straight-chain and branched-chain alkyl groups;

[0063] Y is selected from the following group:

[0064] (a) Straight-chain and branched, substituted and unsubstituted C 1-10 Alkyl, wherein substituents include amine, carbonyl and mercapto,

[0065] (b) linear and branched, substituted and unsubstituted C 6-20 Aryl, wherein the substituent contains heteroatoms and further contains N and O, and wherein the C 6-20 The aryl group optionally also contains C 5-6 and C 5-5 and C 6-6 Fused ring,

[0066] (c) Straight and branched C 7-40 Alkylaryl, which further contains inserted heteroatoms selected from nitrogen, oxygen and sulfur atoms, which are embedded in the main chain or at the end of the chain, and wherein the C 7-40 The alkylaryl group optionally further comprises C 5-6 and C 5-5 and C 6-6 fused ring;

[0067] (d) linear and branched, substituted and unsubstituted C 7-40 Arylalkyl, which also contains heteroatoms, and further contains nitrogen, oxygen and sulfur atoms embedded in the main chain or at the end of the chain, and wherein the C 7-40The arylalkyl group optionally further comprises C 5-6 and C 5-5 and C 6-6 fused ring;

[0068] s is an integer value from 0 to 1 (inclusive);

[0069] t is an integer value from 0 to 1 (inclusive);

[0070] And wherein formula XXVI is:

[0071]

[0072] in

[0073] R 3 and R 4 is selected from the groups previously defined for Y in formula XXV;

[0074] x is an integer value from 0 to 3;

[0075] y is an integer value from 0 to 3;

[0076] And wherein the formula XXVII is:

[0077]

[0078] in

[0079] R 3 and x is as defined above for Y in formula XXVI;

[0080] R 5 and R 7 is selected from the groups defined above for Y in formula XXV;

[0081] And wherein Formula XXVIII is:

[0082]

[0083] in

[0084] R 3 and x is as previously defined for Y of Formula XXVI; and

[0085] R 6 and R 8 is selected from the groups defined above for Y in formula XXV.

[0086] In a third embodiment of the second embodiment, the asymmetric ligand is selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, phenylalanine, proline, pyroglutamic acid, serine, threonine, tryptophan, tyrosine and valine.

[0087] In a fourth embodiment of the second embodiment, the asymmetric ligand is selected from amino acid adducts of salen ligands, i.e.

[0088] 2-((2-hydroxybenzylidene)amino)-3-(1H-imidazol-4-yl)propanoic acid,

[0089] 2-((2-Hydroxybenzylidene)amino)-3-(1H-indol-3-yl)propanoic acid,

[0090] 3-Hydroxy-2-((2-hydroxybenzylidene)amino)propionic acid,

[0091] 2-((2-Hydroxybenzylidene)amino)-4-(methylthio)butanoic acid,

[0092] 2-((2-Hydroxybenzylidene)amino)succinic acid,

[0093] 2-((2-Hydroxybenzylidene)amino)glutaric acid,

[0094] 2-((2-hydroxybenzylidene)amino)acetic acid,

[0095] 6-amino-2-((2-hydroxybenzylidene)amino)hexanoic acid,

[0096] 2-((2-hydroxybenzylidene)amino)-3-(4-hydroxyphenyl)propanoic acid,

[0097] 2-((2-Hydroxybenzylidene)amino)-3-phenylpropionic acid,

[0098] 4-amino-2-((2-hydroxybenzylidene)amino)-4-oxobutanoic acid,

[0099] 2-((2-Hydroxybenzylidene)amino)-3-mercaptopropionic acid,

[0100] 3-((2-carboxy-2-((2-hydroxybenzylidene)amino)ethyl)disulfanyl)-2-((2-hydroxybenzylidene)amino)propanoic acid,

[0101] 5-guanidino-2-((2-hydroxybenzylidene)amino)pentanoic acid,

[0102] 2-((2-Hydroxybenzylidene)amino)-4-methylpentanoic acid,

[0103] 1-(2-hydroxybenzylidene)pyrrolidin-1-ium-2-carboxylate, and

[0104] 2-((1-(2-Hydroxyphenyl)ethylidene)amino)-3-(1H-imidazol-4-yl)propanoic acid.

[0105] In a fifth embodiment of the first embodiment, the method includes a step wherein the MORS ("metals on resin solids") value is from 0.001 to 1.0, inclusive.

[0106] In a sixth embodiment of the first embodiment, the method includes a step wherein the ligand is added in any combination of: preformed with the metal, added to the resin before or after the metal, or added as a prepackaged system.

[0107] In a seventh embodiment of the first embodiment, the method includes a step wherein the asymmetric ligand is an amino acid selected from the group consisting of tryptophan, serine, arginine, methionine, leucine, proline, glycine, glutamine, lysine, tyrosine, phenylalanine, asparagine, cysteine, cystine and aspartic acid, alanine, isoleucine, threonine, valine and selenocysteine.

[0108] In an eighth embodiment of the first embodiment, the method includes a step wherein the ligand is a C1-C6 alkyl substituted asymmetric amino acid.

[0109] In a ninth embodiment of the first embodiment, the method includes a step wherein the ligand is a 2'-hydroxyacetophenone derivative.

[0110] In a tenth embodiment of the first embodiment, the method includes adding BOC, i.e., iron (1+), chloro[9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-chloride (1:1) with said asymmetric ligand.

[0111] In an eleventh embodiment of the seventh embodiment, the method includes the step of adding at least two ligands or a blend thereof.

[0112] In a twelfth embodiment of the first embodiment, the method comprises adding at least one additive selected from the group consisting of anti-skinning agents, UV stabilizers, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, antifouling agents, bactericides, fungicides, algaecides, insecticides, extenders, plasticizers, antifreeze agents, waxes, thickeners, inorganic or organic transparent or non-transparent pigments, cosolvents, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, extenders, waxes, thickeners, thixotropic agents, antioxidants and anti-skinning agents.

[0113] In a thirteenth embodiment of the first embodiment, the metal source and the at least one asymmetric ligand are used in an alkyd paint or an oxidatively curable ink.

[0114] In a fourteenth embodiment of the first embodiment, the metal source and the at least one asymmetric ligand are used in a composite material.

[0115] In a fifteenth embodiment, the metal source and at least one asymmetric ligand are aqueous or solvent-borne.

[0116] These and other objects of the present invention will become apparent when considering the detailed description, drawings / tables and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0117] The blistering device is used to evaluate the degree of blistering that may occur when a paint applied to a metal surface is subjected to conditions that will cause blistering, the formation of blister being relative to some system weakness.

[0118] In the test, a metal panel is painted and sealed at the edges with tape. The bottom half of the panel is immersed in water for 24 hours. The panel is removed and observed for any blisters. Blisters / defects are compared with a reference drier (in this case, vanadium drier, V-TS), which is numbered 2. Coatings with more blisters / defects are assigned the number 3, while coatings with fewer blisters / defects are assigned the number 1.

[0119] The adhesion test utilizes tape firmly applied to a cross-hatched test area, which is then quickly removed by pulling the tape away from the test area to reveal the amount of coating lifted by the test tape. The cross-hatched area is then visually compared to ASTM standards D3002 and D#359, as shown in the following example. Figures 4 to 12 shown.

[0120] Figure 1 is a graph illustrating a foaming level of 2;

[0121] Figure 2 is a graph illustrating a foaming level of 3;

[0122] Figure 3 is a graph illustrating a foaming level of 1;

[0123] Figure 4 A 5B grade is shown, where the cut edge is completely smooth and no square areas within the grid are peeling;

[0124] Figure 5 A 4B rating is shown, where small chip flaking occurs at the intersection of the cuts, affecting no more than 5% of the cross-cut area;

[0125] Figure 6-7 A Class 3B rating is shown where the coating has flaked along cut edges and / or intersections, with significantly greater than 5% but not greater than 15% of the cross-sectional area affected;

[0126] Figure 8-9 A 2B rating is shown where the coating has partially or completely peeled off in strips along the edges of the cut and / or partially or completely peeled off in flaks on different portions of the square, with significantly more than 15% but not significantly more than 35% of the cross-sectional area affected;

[0127] Figure 10-11 shows a Class 1B rating, where the coating has extensive stripping along the edges of the cuts, and / or some squares have partially or completely peeled off, with significantly greater than 35% but not significantly greater than 65% of the cross-sectional area affected; and

[0128] Figure 12 A 0B grade is shown, which is a degree of peeling that exceeds the 1B grade judgment range. DETAILED DESCRIPTION

[0129] The best mode for carrying out the invention will now be described in order to illustrate the best mode known to the applicant at the time of filing the invention. The examples and drawings are illustrative only and are not meant to limit the invention as defined by the scope and spirit of the claims.

[0130] Unless the context clearly indicates otherwise, "and" indicates a parallel relationship; "or" indicates an alternative relationship; when a sentence is expressed in an alternative relationship and followed by "or both" or "a combination of them", it covers both parallel and alternative relationships.

[0131] As used in this application, unless otherwise indicated, the term "about" refers to within 10% of the stated value.

[0132] The present invention has broad application in connection with a variety of solvent- and water-based coating compositions, as such terms are broadly construed herein. Examples of coating compositions include clear or pigmented varnishes, prime coats, filler pastes, glazes, emulsions, and floor coverings, such as linoleum floor coverings. Embodiments of the present invention relate to solvent- and water-based paints and inks, particularly paints, such as high-spec paints for domestic use and paints for general industrial applications.

[0133] Therefore, the term "oxidatively curable coating composition" as used herein is intended to include various colored (e.g., pigments or inks) and colorless materials, including oils and adhesives, which typically form crosslinks and other bond forms through an oxidation reaction process to form a continuous coating. Generally, such coating compositions can be characterized by the presence of a generally (poly) unsaturated resin that reacts to form a solid film on a substrate, the resin initially being present in the oxidatively curable solvent-based coating composition in the form of a liquid dissolved in an organic solvent or a solid dispersed in a continuous liquid phase. The reaction that forms the desired coating upon curing is caused by a polymerization reaction initiated by oxidation. Examples of oxidatively curable coating compositions include those based on alkyd resins, acrylate resins, polyurethane resins, polybutadiene resins, and epoxy ester resins. Typically, the curable (e.g., alkyd resin) portion of the curable composition accounts for about 1 to about 90 weight percent of the total weight of the oxidatively curable solvent-based coating composition, for example, about 20 wt% to about 70 wt% of the total weight of the oxidatively curable solvent-based coating composition.

[0134] Alkyd resins are particularly important members of the class of oxidatively curable coating compositions and are a well-studied class of resins to which the present invention may be applied. Hereinafter, embodiments of the present invention are described with reference to the use of alkyd resins (also referred to as alkyd-based resins or alkyd-based binders). While these represent particularly important embodiments of the present invention, the invention is not limited thereto. For the sake of clarity: the present invention is applicable to a wide range of oxidatively curable coating compositions, typically those containing at least 1 or 2 wt% of unsaturated compounds (e.g., containing unsaturated (non-aromatic) carbon-carbon double or triple bonds).

[0135] As used herein, the terms "alkyd binder" or "alkyd resin" are used interchangeably. Suitable autoxidisable alkyd resins for use in the present invention are generally the esterification reaction products of a polyol with a polyacid (or its anhydride) and an unsaturated fatty acid (or its glyceride), such as those derived from linseed oil, tung oil, tall oil and other drying or semi-drying oils. Alkyd resins are well known in the art and do not require further description herein. Their properties are primarily determined by the nature and proportions of the alcohol and acid used and the degree of condensation. Suitable alkyd resins include long oil, medium oil and short oil alkyd resins. As used herein, long oil alkyd resins have an oil content greater than 55%; medium oil alkyd resins have an oil content of 40% to 55%; and short oil alkyd resins have an oil content of less than 40%, preferably less than 30%. The composition of the long oil, medium oil and short oil alkyds may be modified in order to improve the properties of the resins. For example, polyurethane-modified alkyd resins, silicone-modified alkyd resins, styrene-modified alkyd resins, acrylic-modified alkyd resins (e.g., (meth)acrylic-modified alkyd resins), vinylated alkyd resins, polyamide-modified alkyd resins, and epoxy-modified alkyd resins, or mixtures thereof, are also suitable alkyd resins for use in the compositions of the present invention.

[0136] Preferably, the at least one autoxidisable alkyd binder is selected from short oil, medium oil or long oil unmodified alkyd resins, silicone modified alkyd resins, polyurethane modified alkyd resins or combinations thereof. Most preferably, the alkyd binder is a long oil (unmodified) alkyd resin, silicone modified alkyd resin, polyurethane modified alkyd resin or combinations thereof.

[0137] The amount of alkyd binder in the composition of the present invention may generally be about 20 wt.% to 98 wt.%, such as about 30 wt.% to about 90 wt.%, preferably about 35 wt.% to 70 wt.%, based on the total weight of the composition.

[0138] As used herein, the term "drier" (also synonymously referred to as "drier" when in solution) refers to an organometallic compound that is soluble in organic solvents and adhesives as well as aqueous solvents. They are added to unsaturated oils and adhesives in order to significantly reduce their drying time, i.e., the conversion of their films into a solid phase. Driers are available in solid or solution form. Suitable solvents are organic solvents and adhesives or aqueous solvents. Unless otherwise specified, the drier is present in an amount expressed as a weight percentage of the metal based on the weight of the adhesive solids (or resin).

[0139] As used herein, the term "drier composition" refers to a mixture of the presently claimed driers. The drier composition according to the present invention may contain several drier compounds and result in improved coating hardness, reduced coating peeling and reduced drying time.

[0140] Where weight percentages (wt.% or % w / w) are mentioned herein, unless the context clearly indicates otherwise, this means the weight percentage relative to the solid resin resulting from curing (i.e., the components of the oxidatively curable solvent-based coating composition used to provide the coating upon curing). Thus, for oxidatively curable alkyd coating compositions, the weight percentages herein are based on the total weight of the components of the composition that are incorporated into the alkyd coating once cured. For example, the composition resulting from carrying out the process according to the first aspect of the invention or the process according to the second aspect of the invention typically comprises from about 0.0001 to about 1% w / w, e.g., from about 0.0005 to about 0.5% w / w, of water, or from about 0.01 to about 1% w / w, e.g., from about 0.05 to about 0.5% w / w, of water, based on the components of the composition that results from the coating upon curing.

[0141] Oxidative curing type solvent-based composition refers herein to a composition based on an organic (i.e., non-aqueous) solvent or an inorganic solvent (e.g., water-based) consistent with the nomenclature used in the art. With regard to organic solvents, a non-limiting exemplary list of suitable solvents includes aliphatic (including alicyclic and branched) hydrocarbons, such as hexane, heptane, octane, cyclohexane, cycloheptane, and isoparaffins; aromatic hydrocarbons, such as toluene and xylene; ketones, such as methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as isopropyl alcohol, n-butanol, and n-propyl alcohol; glycol monoethers, such as the monoethers of ethylene glycol and diethylene glycol; monoether glycol acetates, such as 2-ethoxyethyl acetate; and mixtures thereof. Including isomeric variants. Therefore, the term hexane includes a mixture of hexanes. According to an embodiment of the present invention, the solvent is a hydrocarbon-based (i.e., hydrocarbon) solvent, such as an aliphatic hydrocarbon-based solvent, such as a solvent comprising a mixture of hydrocarbons. Examples include paint spirit and solvents available under the tradenames Shellsol from Shell Chemicals and Solvesso and Exxsol from Exxon.

[0142] The composition of the present invention comprises a transition metal drier which is a complex of a transition metal ion and a ligand as defined herein, and optionally with an additional counterion complexed with water or solvent molecules.

[0143] The transition metal ion used in the present invention is vanadium. The valence of the metal can be from +2 to +5. Embodiments of the present invention may include mixtures of transition metal ions. Where a vanadium-containing drier is provided, this is typically a V(II), (III), (IV) or (V) compound, and where an iron-containing drier is provided, this is typically an Fe(II) or Fe(III) compound. When a manganese drier is provided, it is typically an Mn(II), (III) or (IV) compound.

[0144] To enhance the activity of the transition metal ion, so-called promoting compounds, such as carboxylic acids or pentadentate amines, are also included. As the language implies, carboxylic acid or polydentate amine promoter ligands are compounds that are capable of coordinating with transition metal ions through more than one donor site within the ligand and are used to accelerate the drying (curing process) of the oxidatively curable coating composition after application.

[0145] According to some embodiments of the present invention, the polydentate amine accelerator ligand is a di-, tri-, tetra-, penta-, or hexa-dentate ligand coordinated by nitrogen and / or oxygen donor atoms. In specific embodiments of the present invention, the ligand is a di-, tri-, tetra-, penta-, or hexa-dentate nitrogen donor ligand, particularly a tri-, tetra-, penta-, or hexa-dentate nitrogen donor ligand. However, the present invention is not limited thereto. Examples of various polydentate accelerator ligands are discussed below.

[0146] After preparation, the solution of the metal drier can be contacted with, for example added to, the coating composition at a concentration of 0.001 to 1% MORS ("metal on resin solids").

[0147] The resulting composition comprising the metal drier is typically a solution, ie, a single homogeneous phase, or an emulsion or dispersion, eg, comprising discrete regions of an aqueous solution comprising the transition metal drier.

[0148] As used in this application, the term "binder solution (alkyd resin)" refers to one of the following: SYNAQUA 4804 (waterborne short oil alkyd resin, Arkema); SYNAQUA 2070 (waterborne medium oil alkyd resin, Arkema); Beckosol AQ101 (waterborne long oil alkyd resin, Polyont Composites USA Inc.); Worlée Kyd S 351 (solventborne medium oil alkyd resin, Worlée); and TOD 3AK0211Y (water-reducible alkyd resin, TOD, China) and other binder solutions having similar properties to those described above. In a more general sense, "alkyd resin" refers to a synthetic resin made by a condensation reaction (releasing water) between a polyol (glycerol, etc.) and a dibasic acid (or phthalic anhydride). It is the non-volatile portion of the paint vehicle. After drying, it binds the pigment particles to the paint film as a whole.

[0149] As used herein, the term ("V-TS") is vanadyl p-toluenesulfonate, as shown below in formula (I).

[0150]

[0151] As used herein, BOC is iron (1+), chloro[9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1), as shown in the following formula (III).

[0152]

[0153] As used in this application, the term "secondary driers", synonymously "auxiliary driers" means Calcium-Hydrochem (based on calcium neodecanoate in organic solvents, Borchers; and Octa Soligen Zirconium 10 aqua (zirconium 2-ethylhexanoate in an organic solvent, Borchers) and other secondary driers with similar properties to those described above. In addition, one or more auxiliary driers may be added to the fully formulated oxidatively curable coating composition. Such auxiliary driers may be optional additional components within the formulations of the present invention, but are generally not present in the formulations of the present invention. Such auxiliary driers include fatty acid soaps of zirconium, bismuth, barium, cerium, calcium, lithium, strontium, and zinc. Typically, the fatty acid soaps are optionally substituted octoates, hexanoates, and naphthenates. Without being bound by theory, auxiliary driers (sometimes called through-drying agents) are generally understood to reduce the adsorption effect of the primary driers on solid particles typically present in oxidatively curable coating compositions. Other non-metallic auxiliary driers may also be present if desired. As is known in the art, the concentration of auxiliary driers in oxidatively curable coating compositions (or formulations of the present invention) is generally from about 0.01 wt.% to 2.5 wt.%.

[0154] The coating composition may also contain one or more additives conventionally present in curable coating compositions, such as, but not limited to, UV stabilizers, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, antifouling agents, bactericides, fungicides, algaecides, insecticides, extenders, plasticizers, antifreeze agents, waxes, and thickeners.

[0155] In certain embodiments, the coating composition of the present invention includes at least one colorant. The colorant component of the coating composition can include one or more inorganic or organic, transparent or non-transparent pigments. Non-limiting examples of such pigments are titanium dioxide, iron oxide, mixed metal oxides, bismuth vanadate, chromium oxide green, ultramarine, carbon black, lamp black, monoazo and diazo pigments, anthraquinone, isoindolinone, isoindolinone, quinophthalone, phthalocyanine blue and phthalocyanine green, dioxazine, quinacridone and diketo-pyrrolopyrrole; and extender pigments, including ground and crystalline silica, barium sulfate, magnesium silicate, calcium silicate, mica, mica iron oxide, calcium carbonate, zinc oxide, aluminum hydroxide, aluminum silicate and aluminum silicate, gypsum, feldspar, talc, kaolin, etc. The amount of the pigment used to form the coating composition is understood to vary according to the composition application and can be zero when a transparent composition is desired.

[0156] The composition according to the invention can be used as a clear varnish or can comprise a pigment. Examples of pigments suitable for use are metal oxides, such as titanium dioxide or iron oxide, or other inorganic or organic pigments.

[0157] The coating composition may also contain one or more additives, such as UV stabilizers, cosolvents, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, extenders, plasticizers, antifreeze agents, waxes, thickeners, thixotropic agents, etc. In addition, the coating composition according to the present invention may optionally contain various antioxidants and anti-skinning agents known in the art of formulating coating compositions, such as: phenol derivatives, such as pyrogallol, 2,6-di-tert-butylhydroxytoluene, hydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate- 1076 (available from Ciba SC), bis(2-mercapto-ethyl)-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) sulfide- 1035 (available from Ciba SC), monomethyl ether of hydroquinone, propenylphenol, 4-acetoxystyrene, isoeugenol, lauryl gallate; thioethers such as phenothiazine, dodecyl sulfide, didodecyl thiodipropionate; phosphines such as trimethylphosphine, tri-n-octylphosphine, triphenylphosphine; phosphites such as trimethylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, ethyl-bis(2,4-di-tert-butyl-6-methylphenyl)phosphite- 38 (available from Ciba SC), tris(2,4-di-tert-butylphenyl)phosphite- 168 (available from Ciba SC), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite- 626 (available from General Electric); phosphonites such as tetrakis(2,4-di-tert-butylphenyl)(1,1-biphenyl)-4,4'-diylbisphosphonite- P-EPQ (available from Ciba SC); dicarbonyl compounds, such as 2,4-pentanedione, dibenzoylmethane, 2,4-hexanedione, 1,3-cyclohexanedione, oxopropionic acid, diethyl 2-methyl-3-oxosuccinate, oxaloacetic acid; oximes, such as butanone oxime, butyraldehyde oxime, cyclohexanone oxime; hydroxyacetone, diethylhydroxylamine, 3,5-dimethylpyrazole, ascorbic acid, hindered amine light stabilizers (HALS), such as 123 and 292 (available from Ciba SC), 2,3-butenediol, dibenzoyloxybutene, zinc dibenzylthiocarbamate, vitamin E, vitamin E acetate, hypophosphorous acid, 2-butylbenzofuran, 3,4-dihydro-2-ethoxy-2H-pyran, dodecyl mercaptan, dicyclopentadiene.

[0158] According to the curable coating composition of various aspects of the present invention can be used as decorative coating, for example, be applied to wood substrates, for example door or window frame, or be used for other base materials, for example those made of synthetic materials (for example plastics, comprise elastomeric materials), concrete, leather, textiles, glass, pottery or metal. According to the curable coating composition of various aspects of the present invention can be used as industrial coating, for example, be applied on the metal substrate, for example, be used for automotive parts, bridges, equipment or be used for coil coating. Then the composition applied so can be solidified. The present invention also provides composition when solidifying.

[0159] The present invention therefore also provides a method comprising applying a composition to a substrate. The composition so applied may then be cured.

[0160] The coating composition of the present invention can be applied to a substrate using any known method. Non-limiting examples of such application methods include coating (e.g., with a paint pad or scraper, or by brushing or roller coating), spraying (e.g., air-entrained spraying, airless spraying, thermal spraying, and electrostatic spraying), flow coating (e.g., dip coating, curtain coating, roller coating, and reverse roller coating), and electrophoretic deposition. (See generally R. Lambourne, Editor, Paint and Surface Coating: Theory and Practice, Eilis Horwood, 1987, p. 39, etc.).

[0161] The coating composition of the present invention can be applied and fully cured under ambient temperature conditions of about -10°C to 50°C. Curing of the polymer composition according to the present invention can generally be carried out very quickly and can generally be carried out at temperatures of -10°C to +50°C, in particular 0°C to 40°C, more particularly 3°C to 25°C. However, the composition of the present invention can be cured by additional heating.

[0162] Coating composition of the present invention can be used as single layer coating, the finish paint, the base paint in the double-layer system, or one or more layers of the multilayer system that comprises clear topcoat coating composition, colorant layer and base paint coating composition, or as primer layer.Typical opaque system can comprise: 1 layer or 2 layers of primer and 1 layer or 2 layers of topcoat (3 layers altogether).Another opaque system can comprise: 1 layer of primer, 1 layer of middle coating and 1 layer of topcoat.The example of transparent system can comprise 1 layer of impregnation primer and 3 layers of topcoat or 3 layers of topcoat that are used for maintenance work.

[0163] The present invention uses L O,N Type, more specifically L O,N,O The present invention relates to vanadium complexes with specific ligands of the ImP type (see Table VI). More specifically, the present invention relates to ligands of the ImP type, wherein the first O-group is a phenolic OH group and the N-group is an imine or aromatic pyridinic nitrogen (see Table VI). The ImP type can be further divided into three types: phenolimines with a fused pyridine ring as the imine component (e.g., 8-hydroxyquinoline, 8HQ and its derivatives, see Table VI), phenolic Schiff bases of the HS type, and a special case of the latter, the HS-AA type, wherein the Schiff base is derived from an α-amino acid as the amine component (see Table VI). Specific examples of ligand types HS and HS-AA are shown in Table VII.

[0164] Specifically excluded are those with L O,N,N,O Vanadium complexes of type ligands, including salen ligands and salen ligand derivatives XJ (Table III). Therefore, the present invention covers L O,N and L O,N,O Structural ligands, especially 8HQ, HS and HS-AA type ligands, but not L O,N,N,O Type ligands (see Table VII).

[0165] Table VII

[0166]

[0167] Specific examples of HS-AA types are shown in the previously provided Table V and the specific examples of HS types shown in the left two entries of Table VIII. Specific non-limiting examples of ImP types are shown in Table VI.

[0168] Table VIII

[0169]

[0170] The present invention uses L O,N Type, more specifically L O,N,O The present invention relates to vanadium complexes of specific ligands of the ImP type (see Table VI presented previously). More specifically, the present invention relates to ligands of the ImP type, wherein the first O-group is a phenolic OH group and the N-group is an imine or aromatic pyridinic nitrogen group (see Table VI). The ImP type can be further divided into three types: phenolimines with a fused pyridine ring as the imine component (e.g., 8-hydroxyquinoline, 8HQ and its derivatives, see Table VI), phenolic Schiff bases of the HS type, and a special case of the latter, the HS-AA type, wherein the Schiff base is derived from an α-amino acid as the amine component (see Table VI). Specific examples of ligand types HS and HS-AA are shown in Table VII presented previously.

[0171] Table IX shows various amino acids that can be used in combination with vanadium according to the present invention, comprising an asymmetric ligand: alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, phenylalanine, proline, pyroglutamic acid, serine, threonine, tryptophan, tyrosine, and valine.

[0172] Table IX

[0173]

[0174]

[0175]

[0176] When viewed more generally, the structure of at least one asymmetric ligand will have the following prerequisites:

[0177] (a) When the asymmetric ligand is L O,N or L O,N,O When the asymmetric ligand comprises at least one terminal carboxylic acid group; or

[0178] (b) When the asymmetric ligand is L O,N or L O,N,O When the asymmetric ligand comprises at least one amine group; and wherein

[0179] (c) When the asymmetric ligand is L O,N,O When the asymmetric ligand comprises at least one hydroxyl group in addition to the at least one terminal carboxylic acid group; or

[0180] (d) When the asymmetric ligand is L O,N,OWhen the asymmetric ligand comprises at least one imine or pyridine type nitrogen donor group and at least one oxygen donor group, the oxygen donor group may be a phenol or carboxylic acid oxygen atom;

[0181] The improvement is compared to an oxidatively curable alkyd coating having a metal source and not having at least one asymmetric ligand, but rather including a conventional metal source and ligand.

[0182] More generally, at least one asymmetric ligand comprises Formula XXV or Formula XXVI or Formula XXVII or Formula XXVIII:

[0183] Wherein formula XXV is:

[0184]

[0185] in

[0186] R 1 and R 2 Independently selected from H, C 1-4 straight-chain and branched-chain alkyl groups;

[0187] Y is selected from the following group:

[0188] (a) Straight-chain and branched, substituted and unsubstituted C 1-10 Alkyl, wherein substituents include amine, carbonyl and mercapto,

[0189] (b) linear and branched, substituted and unsubstituted C 6-20 Aryl, wherein the substituent contains heteroatoms, and further contains N, and optionally contains C 5-6 and C 5-5 and C 6-6 Fused ring,

[0190] (c) Straight chain and branched chain C 7-40 Alkylaryl groups further comprising inserted heteroatoms selected from nitrogen and sulfur atoms, embedded within the main chain or at the chain terminals;

[0191] (d) linear and branched, substituted and unsubstituted C 7-40 Arylalkyl groups, which also contain heteroatoms and further contain nitrogen and sulfur atoms embedded within the main chain or at the chain termini;

[0192] s is an integer value from 0 to 1 (inclusive);

[0193] t is an integer value from 0 to 1 (inclusive);

[0194] And wherein formula XXVI is:

[0195]

[0196] in

[0197] R 3 and R 4 is selected from the groups previously defined for Y;

[0198] x is an integer value from 0 to 3;

[0199] y is an integer value from 0 to 3;

[0200] And wherein the formula XXVII is:

[0201]

[0202] in

[0203] R 3 and x is as defined above for Formula XXVI;

[0204] R 5 and R 7 is selected from the groups previously defined for Y;

[0205] And wherein Formula XXVIII is:

[0206]

[0207] in

[0208] R 3 and x is as defined in Formula XXVI;

[0209] R 6 and R 8 is selected from the groups defined previously for Y.

[0210] As used herein, unless otherwise specified, the term "alkyl" refers to a linear and branched saturated acyclic hydrocarbon monovalent group; the alkyl group may also optionally contain one or more suitable substituents independently selected from amino, halogen, hydroxy, mercapto, haloalkyl, alkoxy, etc. Specific non-limiting examples of linear or branched alkyl groups are C 1-20 Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and stearyl. It should be understood that the alkyl groups may be interrupted by oxygen, sulfur, or nitrogen.

[0211] As used herein, unless otherwise indicated, the term "alkenyl" refers to a linear and branched unsaturated acyclic hydrocarbon monovalent group; the alkenyl group may also optionally contain one or more suitable substituents independently selected from amino, halogen, hydroxyl, mercapto, haloalkyl, alkoxy, and the like. Specific non-limiting examples of linear or branched alkenyl groups are those having 2 to 30 carbon atoms, wherein the position of the double bond may vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl. It is again recognized that alkenyl groups may be interrupted by oxygen, sulfur, or nitrogen.

[0212] As used herein, unless otherwise specified, the term "alicyclic" refers to a monocyclic or polycyclic saturated hydrocarbon monovalent group having 3 to 10 carbon atoms, or a C1-C2-C10 monocyclic or polycyclic saturated hydrocarbon monovalent group having 7 to 10 carbon atoms. 7-10 Polycyclic saturated hydrocarbon monovalent groups. Specific non-limiting examples of alicyclic alkyl or cyclic alkyl groups that may have substituents are cycloalkyl groups having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl, and alkylcycloalkyl groups having 6 to 11 carbon atoms, wherein the position of the alkyl group may vary, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylcycloheptyl, and diethylcycloheptyl. It will be appreciated that alicyclic groups may be intercalated with oxygen, sulfur, or nitrogen.

[0213] As used herein, unless otherwise indicated, the terms "aromatic" and "aryl" refer to any monocyclic or polycyclic aromatic monovalent hydrocarbon radical having from 6 to 30 carbon atoms, including fused benzo-C 4-8 Cycloalkyl (the latter being as defined above), all of which are optionally substituted with one or more substituents independently selected from halogen, amino, haloalkyl, hydroxy, mercapto and nitro.

[0214] As used herein, unless otherwise indicated, the term "heterocycle" refers to a monocyclic or polycyclic, saturated or monounsaturated or polyunsaturated monovalent hydrocarbon radical having 2 to 15 carbon atoms and containing one or more heteroatoms in one or more rings, each of said rings having 3 to 10 atoms (and optionally further containing one or more heteroatoms attached to one or more carbon atoms of said ring), for example in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or one or more heteroatoms of said ring, each of said heteroatoms being independently selected from nitrogen, oxygen, sulfur, selenium and phosphorus, and also including groups in which the heterocycle is fused to one or more aromatic hydrocarbon rings, for example in the form of a benzo-fused, dibenzo-fused or naphthio-fused heterocyclic group, including all possible isomeric forms thereof, wherein each carbon atom of said heterocycle may be substituted independently by a substituent selected from the group consisting of halogen, nitro, C1-7 Alkyl (as defined above, especially methyl), C 3-7 Alkenyl, trifluoromethyl, C 3-10 Cycloalkyl, aryl, arylalkyl, alkylaryl, hydroxy, mercapto, alkoxy (as defined above, in particular methoxy), aryloxy, arylalkoxy, thioC 1-7 Alkyl, thio C 3-10 Cycloalkyl, thioaryl, arylalkylthio, cyano, carboxylic acid or its ester; depending on the number of unsaturations in each of the rings, heterocyclic groups can be subdivided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; when the heteroatom of the non-aromatic heterocyclic group is nitrogen, the latter can be selected from C 1-7 Alkyl, C 3-10 The substituents of the cycloalkyl, aryl, aralkyl and alkaryl groups (each as defined herein) are substituted.

[0215] As used herein, unless otherwise indicated, the term "alkoxy" refers to a substituent wherein an alkyl group is attached to an oxygen atom via a single bond.

[0216] As used herein, unless otherwise indicated, the term "halo" or "halogen" refers to any atom selected from fluorine, chlorine, bromine and iodine.

[0217] As used herein, unless otherwise indicated, the term "arylalkyl" refers to an aliphatic saturated hydrocarbon monovalent radical to which an aryl group (as defined above) is attached, and wherein the aliphatic or aryl group may be optionally substituted with one or more substituents independently selected from halogen, amino, hydroxy, mercapto, alkyl, haloalkyl, and nitro. Specific examples of arylalkyl groups are those having 7 to 40 carbon atoms, wherein the alkyl group may be linear or branched, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl.

[0218] As used herein, unless otherwise indicated, term " alkylaryl " refers to the aryl (as defined above) to which an aliphatic saturated hydrocarbon monovalent group is connected, and wherein the aliphatic group or aryl can be optionally substituted by one or more substituents independently selected from halogen, amino, hydroxyl, sulfhydryl, alkyl, trifluoromethyl and nitro. The specific non-limiting examples of unsubstituted or alkyl-substituted aryl are aryl with 6 to 18 carbon atoms, such as phenyl, diphenyl and naphthyl, and alkylaryl with 7 to 40 carbon atoms, wherein alkyl can be straight or branched, and can be bonded to any position on the aryl, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, diethylphenyl, dibutylphenyl and dioctylphenyl. Alkylaryl can have a substituent in addition, including functional groups such as alkoxy, hydroxyl, cyano, nitro, halide, carboxylic acid etc.

[0219] As used herein, unless otherwise indicated, the term "acyl" refers to a substituent derived from an acid such as an organic monocarboxylic acid, carbonic acid, carbamic acid (yielding a carbamoyl substituent) or the corresponding thioacid or imidic acid (yielding a ureido substituent), wherein the acid molecule includes an aliphatic, aromatic or heterocyclic group. A more specific "acyl" group within the above definition refers to a carbonyl (oxy) group adjacent to an alkyl, cycloalkyl, aryl, arylalkyl or heterocyclic group, all of which are as defined herein.

[0220] As used herein, unless otherwise indicated, the term "heterocycle" refers to a monocyclic or polycyclic, saturated or monounsaturated or polyunsaturated monovalent hydrocarbon radical having 2 to 15 carbon atoms and containing one or more heteroatoms in one or more rings, each of said rings having 3 to 10 atoms (and optionally further containing one or more heteroatoms attached to one or more carbon atoms of said ring), for example in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or one or more heteroatoms of said ring, each said heteroatom being independently selected from nitrogen, oxygen, sulfur, selenium, heterocyclyl, including all possible isomeric forms thereof, wherein each carbon atom of said heterocycle may be substituted independently by a substituent selected from the group consisting of halogen, nitro, C 1-7 Alkyl (as defined above, especially methyl), C 3-7 Alkenyl, trifluoromethyl, C 3-10 Cycloalkyl, hydroxyl, mercapto, C 1-7 Alkoxy (as defined above, in particular methoxy), thio C 1-7 Alkyl, thio C 3-10Cycloalkyl, cyano, carboxylic acid or ester groups, depending on the number of unsaturations in each of the rings, heterocyclic groups can be subdivided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; when the heteroatom of the non-aromatic heterocyclic group is nitrogen, the latter can be selected from C 1-7 Alkyl, C 3-10 The substituents of the cycloalkyl, aryl, arylalkyl and alkylaryl groups (each of which is as defined herein) are substituted.

[0221] As used herein, unless otherwise indicated, the term "alkoxy" refers to a substituent wherein an alkyl group is attached to an oxygen atom via a single bond.

[0222] As used herein, unless otherwise indicated, the term "halo" or "halogen" refers to any atom selected from fluorine, chlorine, bromine and iodine.

[0223] As used herein, unless otherwise indicated, the term "acyl" refers to a substituent derived from an acid such as an organic monocarboxylic acid, carbonic acid, carbamic acid (yielding a carbamoyl substituent) or the corresponding thioacid or imidic acid (yielding a ureido substituent), wherein the acid molecule includes an aliphatic, aromatic or heterocyclic group. A more specific "acyl" group within the above definition refers to a carbonyl (oxy) group adjacent to an alkyl, cycloalkyl, aryl, arylalkyl or heterocyclic group, all of which are as defined herein.

[0224] Vanadium complexes with these ligands can be prepared in various ways: several vanadium sources, including VOSO4, VO(H2O)5(pTsO)2 ("V-TS"), Na3VO4, V2O5, VO(acac)2, and NH4VO3 can be used to react with preformed ligands.

[0225] This can be done before the drier is mixed with the paint, adhesive or formulation (short-term or long-term), or by adding the vanadium source and ligand separately to the paint, adhesive or formulation.

[0226] Vanadium complexes with HS-type and HS-AA-type ligands can also be synthesized in a one-pot process by reacting the reagents required for ligand synthesis in the presence of a suitable vanadium source (including VOSO4, VO(H2O)5(pTsO)2, Na3VO4, VO5, VO(acac)2, and NH4VO3) to obtain a ready-to-use drier solution. This simplifies the procedure because the ligand does not have to be synthesized and isolated prior to reaction with the vanadium source.

[0227] The alkyd binders used were SYNAQUA 4804 (a waterborne short oil alkyd from Arkema), Synaqua 2070 (a waterborne medium oil alkyd from Arkema), TOD 3AK0211Y (a water-reducible alkyd from TOD, China), and Beckosol AQ206 (a waterborne medium oil alkyd from Polyut Composites USA Inc.).

[0228] The drier solutions used were Borchi Oxy-Coat 1101 (BOC1101 in water, Borchers), Borchers Deca Cobalt 7aqua (Deca Co 7a in water-dispersible oil, Borchers; synonymous with cobalt neodecanoate (cobalt(2+); 7,7-dimethyloctanoate)) (see formula IV).

[0229]

[0230] WD016 (8-10% aqueous suspension of cobalt drier from TOD, China) and V-TS (vanadium-based drier, 9.4% V, Prof. Jan University of Pardubice, Czech Republic; typically used as a ~10% stock solution in DMSO or a mixture of high-boiling alcohols and esters). See formula (I).

[0231] The ligands 8-hydroxyquinoline (8HQ), 2-((phenylimino)methyl)phenol (HS-1), 2-salicylideneaminophenol (HS-2), and (S,S)-(+)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (XJ) were purchased from commercial sources and used as received.

[0232] The present invention will now be described by way of a series of tables. The formulations used are as follows:

[0233] Table X: Formulation vSAcc (Synaqua 4804-based clearcoat, waterborne)

[0234] entry Element type quantity 1 Synaqua 4804 resin 95.0 2 Borchi Gel 0435 Rheology modifiers 1.5 3 DBE-5 additive 3.5

[0235] Resin solid content: 30.2%

[0236] Table XI: Formulation 11Ya-cc (clear coating based on TOD 3AK0211Y, waterborne)

[0237]

[0238] Resin solid content: 31.4%

[0239] Table XII: Formulation 11Ya-wp (white paint based on TOD 3AK0211Y, waterborne)

[0240]

[0241] Resin solid content: 22.0%

[0242] method

[0243] The formulation for cast film is prepared by weighing the appropriate amount of siccative (usually a stock solution of defined concentration) into a plastic vial, followed by the adhesive solution or formulation. The amount of siccative is calculated based on the value of dry material specified for each adhesive solution. Mixing is achieved by placing the vial in a high-speed mixer (SpeedMixer DAC150.1 FVZ) and spinning at 2000 rpm for 2 minutes. Typically, a seemingly homogeneous mixture is obtained. Before film casting, it is left at ambient conditions for approximately 24 hours.

[0244] For formulation vSAcc, drying time was measured in hours on a BK Drying Recorder Model 3 (The Mickle laboratory engineering Co Ltd.) to give the time required to reach the following dry states: touch dry (ST, i.e. the soft coating no longer flows freely but begins to tear into a hardened film), touch dry (TF, i.e. no longer tears the film but still leaves a continuous line on the coating), and through dry (DH, i.e. no marks left on the film).

[0245] A 100 μm thick film was cast onto a glass strip (30 × 2.4 cm) using a steel cube applicator. This was then placed on a drying time recorder, a needle placed on the film, and the recorder set to measure 24 hours and started. The starting point where the needle was placed on the film was marked on the glass. The drying time was read from the mark left on the film after 24 hours. Drying times given as "24 h" indicate drying times ≥ 24 h, as times longer than 24 hours cannot be determined.

[0246] Films with a thickness of 100 μm were cast on glass sheets (15 / 9 / cm) for the hardness measurement and films for the drying time recording were cast at the same time. These were evaluated on a pendulum hardness tester after the given drying time. Method: Pendulum hardness was measured on a TQC Sheen Pendulum Hardness Tester SP0500 (oscillation time in seconds, starting from an initial amplitude of 6° until an amplitude of 3° was reached). Softer materials dampen the oscillations of the pendulum faster than harder materials, so softer materials have lower hardness values in seconds than harder materials.

[0247] For formulations 11Ya-cc and 11Ya-wp, the drying time was measured in days by placing a filter paper on the coating on a glass plate and placing a 200 g weight with a defined surface area on the filter paper for 30 seconds. The "through dry" state was reached when the filter paper no longer adhered to the coating after this treatment.

[0248] Coating of all glass panels, recording of drying times, hardness measurements and storage were performed in a climate-controlled room at a temperature of 23° C. and a humidity of approximately 50%.

[0249] Blistering and adhesion were measured after a 24-hour water resistance test. To do this, the steel panels were coated in the same manner as the glass panels and allowed to dry for 24 hours. The edges were then sealed with adhesive tape, and the lower half of the panels were immersed in deionized water for 24 hours. The panels were then removed from the water, dried for one hour, and any blistering was recorded and graded relative to a vanadium reference drier (V-TS) as follows: 2 was assigned to coatings with V-TS, coatings with fewer defects / less blistering were graded 1, and coatings with more defects / more blistering were graded 3. Subsequently, cross-section and adhesion tests were performed on the same steel panels according to ASTM Designation D3359-17.

[0250] The catalyst concentration is given as % metal and refers to the amount of catalyst metal relative to the solids content of the binder used and the formulation, respectively. This is also abbreviated as MORS, Metal Based on Resin Solids. MORS is calculated as follows:

[0251]

[0252] The variables are defined as follows: d : mass of the drying agent or drying agent solution, in g; MC d : Metal content of drier (solution), in %; SC f : solid content (of the adhesive) in the formulation, in %; and m f : The mass of the preparation, in g.

[0253] The specific examples of preparation are as follows:

[0254] Example 1: Synthesis of V*8HQ (V*8HQ A) from VO(acac)2 and 8HQ

[0255] To a vial was added VO(acac)2 (164 mg, 0.62 mmol) and 8-hydroxyquinoline (8HQ, 180 mg, 1.24 mmol, 2.0 equiv), followed by DMSO (5.99 g). The solution was stirred until it became homogeneous, at which point it slowly developed a dark color. It was used without further treatment, and the metal content was 0.50%.

[0256] Example 2: Synthesis of V*8HQ (V*8HQ B) from V-TS and 8HQ before preparation of formulation

[0257] To the container used to prepare the test formulation, a DMSO solution of V-TS (76 mg, 10.0 wt%) and a DMSO solution of 8HQ (82 mg, 5.0 wt%, 2.0 molar equivalents) were added. After mixing the two, the solution turned golden brown. The alkyd resin formulation was then added directly, and all substances were mixed in a high-speed mixer.

[0258] Example 3: Synthesis of V*HS-1 (V*HS-1A) from V-TS and HS-1 before preparation of formulation

[0259] To the container used to prepare the test formulation, a solution of V-TS in a mixture of a higher boiling alcohol and an ester (23 mg, 11.8 wt%) and a solution of HS-1 in a mixture of a higher boiling alcohol and an ester (105 mg, 1.0 wt%, 1.1 molar equivalents) were added. Upon mixing, the solution turned yellow. The alkyd resin formulation was then added directly, and all materials were mixed in a high-speed mixer.

[0260] Example 4: Synthesis of V*HS-2 (V*HS-2A) from VO(acac)2 and HS-2

[0261] To a vial was added VO(acac)2 (99 mg, 0.37 mmol) and 2-(2-hydroxybenzylideneamino)phenol (HS-2, 80 mg, 0.37 mmol, 1.0 equiv), followed by DMSO (1.92 g). The solution was stirred until it became homogeneous, at which point it slowly developed a dark color. It was used without further treatment, and the metal content was 0.90%.

[0262] Example 5: Synthesis of V*HS-2 (V*HS-2B) from Na3VO4 and HS-2

[0263] To a round-bottom flask was added Na3VO4 (72 mg, 0.39 mmol) and 2-(2-hydroxybenzylideneamino)phenol (HS-2, 84 mg, 0.39 mmol, 1.0 eq), followed by DMSO (1.70 g), water (0.39 g), and acetic acid (0.078 g, 1.29 mmol, 3.3 eq). The resulting mixture was stirred until it became homogeneous, at which point it developed a dark color. It was used without further treatment, and the metal content was 0.86%.

[0264] Example 6: Synthesis of V*HS-2 (V*HS-2C) from V-TS and HS-2 before preparation of formulation

[0265] To the container used to prepare the test formulation, a solution of V-TS in a mixture of a higher boiling alcohol and an ester (107 mg, 11.8 wt%) and a solution of HS-2 in a mixture of a higher boiling alcohol and an ester (129 mg, 3.9 wt%, 1.0 molar equivalent) were added. Upon mixing, the solution turned reddish-brown. The alkyd resin formulation was then added directly, and all materials were mixed in a high-speed mixer.

[0266] Example 7: Synthesis of ligand HS-His

[0267] N-[(2-Hydroxyphenyl)methylene]-L-histidine (HS-His) was synthesized according to the procedure published in C. Fattuoni, S. Vascellari, T. Pivetta, Amino Acids 2020, 52, 397-407.

[0268] Example 8: Synthesis of V*HS-His (V*HS-His A) from V-TS and HS-His before preparation of formulation

[0269] To the container used to prepare the test formulation, a DMSO solution of V-TS (77 mg, 10.0 wt%) and a DMSO solution of HS-His (96 mg, 4.0 wt%, 1.0 molar equivalent) were added. After mixing the two, the solution turned golden brown. The alkyd resin formulation was then added directly, and all substances were mixed in a high-speed mixer.

[0270] Example 9: Synthesis of V*HS-His (V*HS-His B) from V2O5 and HS-His

[0271] To a round-bottom flask was added V2O5 (48 mg, 0.27 mmol) and HS-His (69 mg, 0.27 mmol, 1.0 equiv), followed by DMSO (1.75 g). The solution was stirred in an oil bath at 100°C for 3 hours, then slowly developed a dark color and became homogeneous. It was used without further treatment, and the metal content was 0.72%.

[0272] Example 10: Synthesis of V*HS-His (V*HS-His C) from Na3VO4 and HS-His

[0273] To a round-bottom flask was added Na3VO4 (30 mg, 0.16 mmol) and HS-His (43 mg, 0.16 mmol, 1.0 eq), followed by DMSO (0.60 g), water (0.10 g), and acetic acid (0.03 g, 0.49 mmol, 3.1 eq). The resulting mixture was stirred for 1 hour until it became homogeneous and a dark color formed. It was used without further treatment and had a metal content of 1.01%.

[0274] Example 11: Synthesis of V*HS-His (V*HS-His D) from VO(acac)2 and HS-His

[0275] To a round-bottom flask were added VO(acac)2 (71 mg, 0.027 mmol) and HS-His (70 mg, 0.027 mmol, 1.0 equiv), followed by DMSO (1.79 g). The resulting mixture was stirred and quickly became homogeneous and developed a dark color. It was used without further treatment and had a metal content of 0.71%. Example 12: Synthesis of V*HS-His (V*HS-His E) from V-TS and HS-His in a formulation

[0276] To the container used to prepare the test formulation, a DMSO solution of V-TS (131 mg, 10.0 wt%) and the alkyd resin formulation were added, followed by high-speed mixing. Solid HS-His (12.5 mg, 2.0 eq) was then added to the mixture, followed by high-speed mixing.

[0277] Example 13: Synthesis of V*HS-His (V*HS-His F) from V2O5 in a two-step, one-pot manner

[0278] To a round-bottom flask was added L-histidine (114 mg, 0.73 mmol, 2.3 eq), DMSO (3.13 g), acetic acid (52 mg, 0.86 mmol, 2.7 eq) and salicylaldehyde (88 mg, 0.72 mmol, 2.3 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added VO (57 mg, 0.31 mmol, 1.0 eq). The heterogeneous light yellow mixture was stirred in an oil bath at 60-70° C. overnight until it turned dark brown. It was used without further treatment and had a metal content of 0.93%.

[0279] Example 14: Synthesis of V*HS-His (V*HS-His G) from Na3VO4 in a two-step, one-pot manner

[0280] To a round-bottom flask was added Na3VO4 (300 mg, 0.16 mmol), L-histidine (256 mg, 0.16 mmol, 1.0 eq), DMSO (3.96 g), salicylaldehyde (219 mg, 0.18 mmol, 1.1 eq), water (1.04 g) and acetic acid (302 mg, 0.50 mmol, 3.1 eq). The dark mixture was stirred at ambient temperature until it became homogeneous. It was used without further treatment and had a metal content of 1.37%.

[0281] Example 15: Synthesis of V*2HS-His (V*HS-His G2) from Na3VO4 in a two-step, one-pot manner

[0282] To a round-bottom flask was added Na3VO4 (297 mg, 0.16 mmol), L-histidine (520 mg, 0.33 mmol, 2.1 eq), DMSO (5.0 g), salicylaldehyde (397 mg, 0.33 mmol, 2.0 eq), water (0.94 g) and acetic acid (290 mg, 0.48 mmol, 3.0 eq). The dark mixture was stirred at ambient temperature until it became homogeneous. It was used without further treatment and had a metal content of 1.11%.

[0283] Example 16: Synthesis of V*HS-His (V*HS-His H) from V-TS in a two-step, one-pot manner

[0284] To a round-bottom flask was added NaOAc (193 mg, 1.42 mmol, 2.4 eq), L-histidine (110 mg, 0.71 mmol, 1.2 eq), DMSO (3.37 g) and salicylaldehyde (88 mg, 0.72 mmol, 1.2 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (299 mg, 0.60 mmol, 1.0 eq). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and the metal content was 0.69%.

[0285] Example 17: Synthesis of V*HS-His (V*HS-His I) from VOSO4 in a two-step, one-pot manner

[0286] To a round-bottom flask was added NaOAc (194 mg, 1.42 mmol, 2.4 eq), L-histidine (114 mg, 0.73 mmol, 1.2 eq), DMSO (3.18 g) and salicylaldehyde (87 mg, 0.71 mmol, 1.2 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added VOSO4 pentahydrate (153 mg, 0.60 mmol, 1.0 eq) and water (0.55 g). The mixture was stirred at ambient temperature for three days until it became homogeneous and dark brown. It was used without further treatment and had a metal content of 0.71%.

[0287] Example 18: Synthesis of V*HS-His (V*HS-His I2) from VOSO4 in a two-step, one-pot manner using excess vanadium

[0288] To a round-bottom flask were added NaOAc (93 mg, 0.68 mmol, 1.1 eq), L-histidine (57 mg, 0.37 mmol, 0.6 eq), DMSO (2.27 g) and salicylaldehyde (43 mg, 0.35 mmol, 0.6 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture were added VOSO4 pentahydrate (154 mg, 0.61 mmol, 1.0 eq) and water (0.41 g). The mixture was stirred at ambient temperature for 7 days and then turned into a uniform dark brown color. It was used without further treatment and had a metal content of 1.02%.

[0289] Example 19: Synthesis of V*HS-His (V*HS-His J) from VO(acac)2 by a two-step one-pot method

[0290] To a round-bottom flask was added L-histidine (113 mg, 0.73 mmol, 1.2 eq), DMSO (2.54 g) and salicylaldehyde (85 mg, 0.70 mmol, 1.2 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added VO(acac)2 (160 mg, 0.60 mmol, 1.0 eq). The green-brown mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.06%.

[0291] Example 20: Synthesis of V*HS-AA from V-TS in a two-step, one-pot manner

[0292] Similar to the synthesis of V*HS-His solution from V-TS in a two-step one-pot manner, complexes with HS-AA type ligands were also synthesized using the amino acids cystine, cysteine (Cys), methionine (Met), aspartic acid (Asp), glutamic acid (Glu), tryptophan (Trp), lysine (Lys), tyrosine (Tyr), phenylalanine (Phe), arginine (Arg), leucine (Leu), proline (Pro), asparagine (Asn), glycine (Gly) and serine (Ser).

[0293] Example 21: Synthesis of V*HS-(HW) (V*HS-HW) from VOSO4 in a two-step one-pot manner

[0294] To a round-bottom flask was added NaOAc (184 mg, 1.35 mmol, 2.1 eq), L-histidine (55 mg, 0.35 mmol, 0.6 eq), L-tryptophan (74 mg, 0.36 mmol, 0.6 eq), DMSO (2.27 g) and salicylaldehyde (86 mg, 0.71 mmol, 1.1 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added VOSO4 pentahydrate (160 mg, 0.63 mmol, 1.0 eq) and water (0.42 g). The mixture was stirred at ambient temperature for 7 days until it turned a uniform dark brown color. It was used without further treatment and the metal content was 0.99%.

[0295] Example 22: Synthesis of V*HS-(9aa) (V*HS-9a) from VOSO4 in a two-step, one-pot manner

[0296] To a round-bottom flask were added NaOAc (184 mg, 1.35 mmol, 2.2 equiv), L-histidine (22 mg, 0.14 mmol, 0.2 equiv), L-tryptophan (15 mg, 0.07 mmol, 0.1 equiv), L-methionine (11 mg, 0.07 mmol, 0.1 equiv), L-serine (7 mg, 0.07 mmol, 0.1 equiv), L-glutamic acid (11 mg, 0.07 mmol, 0.1 equiv), and 4-nitropropane (20 mg, 0.1 mmol, 0.1 equiv).

[00145] The reaction mixture was stirred at room temperature for 30 minutes. The mixture was stirred at room temperature for 7 days until it turned a uniform dark brown color. The mixture was used without further treatment and had a metal content of 0.97%.

[0297] Example 23: Synthesis of V*m HS-His (V*mHS-His) from VOSO4 in a two-step, one-pot manner

[0298] To a round-bottom flask was added NaOAc (190 mg, 1.40 mmol, 2.3 eq), L-histidine (113 mg, 0.73 mmol, 1.2 eq), DMSO (2.12 g) and 2'-hydroxyacetophenone (98 mg, 0.72 mmol, 1.2 eq) and stirred at ambient temperature for 30 minutes. To the light yellow mixture was added VOSO4 pentahydrate (153 mg, 0.60 mmol, 1.0 eq) and water (0.40 g). The mixture was stirred at ambient temperature overnight until it became a uniform dark green-brown color. It was used without further treatment and had a metal content of 1.00%.

[0299] Example 24: Synthesis of V*XJ (V*XJ) from V-TS and XJ before preparation of formulation

[0300] To the container used to prepare the test formulation, a DMSO solution of V-TS (127 mg, 10.0 wt%) and an ethyl acetate solution of XJ (225 mg, 5.9 wt%, 1.0 molar equivalent) were added. Upon mixing, the solution turned green. The alkyd resin formulation was then added directly, and all materials were mixed in a high-speed mixer.

[0301] Example 25: Synthesis of V*HS-His (V*HS-His K) using 1.2:0.9 aldehyde:histidine

[0302] To a round-bottom flask was added NaOAc (171 mg, 1.25 mmol, 2.4 eq), L-histidine (68 mg, 0.44 mmol, 0.9 eq), DMSO (1.89 g) and salicylaldehyde (77 mg, 0.63 mmol, 1.2 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (258 mg, 0.52 mmol, 1.0 eq). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.07%.

[0303] Example 26: Synthesis of V*HS-His (V*HS-His L) using 0.8:1.25 aldehyde:histidine

[0304] To a round-bottom flask was added NaOAc (171 mg, 1.25 mmol, 2.5 eq), L-histidine (98 mg, 0.63 mmol, 1.25 eq), DMSO (1.94 g) and salicylaldehyde (51 mg, 0.41 mmol, 0.82 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (252 mg, 0.50 mmol, 1.0 eq). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.05%.

[0305] Example 27: Synthesis of V*HS-His (V*HS-His M) using 2:1 aldehyde:histidine

[0306] To a round-bottom flask was added NaOAc (278 mg, 2.04 mmol, 3.0 equiv), L-histidine (107 mg, 0.69 mmol, 1.0 equiv), propylene glycol (2.27 g) and salicylaldehyde (172 mg, 1.41 mmol, 2.07 equiv) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (340 mg, 0.68 mmol, 1.0 equiv). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.10%.

[0307] Example 28: Synthesis of V*HS-His (V*HS-His N) using 1:2 aldehyde:histidine

[0308] To a round-bottom flask was added NaOAc (276 mg, 2.03 mmol, 2.9 eq), L-histidine (211 mg, 1.36 mmol, 2.0 eq), propylene glycol (2.26 g) and salicylaldehyde (85 mg, 0.69 mmol, 1.0 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (347 mg, 0.70 mmol, 1.0 eq). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.11%.

[0309] Example 29: Synthesis of V*HS-His in Final Formulation (V*HS-His O)

[0310] L-histidine (12.6 mg, 0.08 mmol, 1.2 eq), Synaqua 2070 (10.06 g), salicylaldehyde (18 mg, 0.15 mmol, 2.2 eq) and a 38.2% DMSO solution of V-TS (88 mg, 0.07 mmol, 1.0 eq) were added to a screw-top plastic bottle. The pale yellow formulation was mixed in a high-speed mixer at 2000 rpm for 6 minutes and stored at ambient temperature overnight. It was mixed again for 2 minutes before being used in coating experiments.

[0311] Example 30: Synthesis of V*2Sal (V*2Sal)

[0312] To a round-bottom flask was added NaOAc (184 mg, 1.35 mmol, 2.0 equiv), propylene glycol (2.48 g) and salicylaldehyde (165 mg, 1.35 mmol, 2.0 equiv) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (340 mg, 0.68 mmol, 1.0 equiv). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.10%.

[0313] Example 31: Synthesis of V*Sal (V*Sal)

[0314] To a round-bottom flask was added NaOAc (93 mg, 0.68 mmol, 1.0 eq), propylene glycol (2.67 g) and salicylaldehyde (83 mg, 0.68 mmol, 1.0 eq) and stirred at ambient temperature for 30 minutes. To the yellow mixture was added V-TS (338 mg, 0.68 mmol, 1.0 eq). The dark mixture was stirred at ambient temperature overnight until it became homogeneous. It was used without further treatment and had a metal content of 1.08%.

[0315] As is clear from the above description, ligands, particularly HS and HS-AA type ligands (as shown in Table IV), can be readily synthesized from two components. As shown in many of the above examples, the synthesis illustrates the use of two components (preferably in a 1:1 ratio), wherein the nitrogen and Markush R groups are derived from the amine component and the phenol residue is derived from the aldehyde / ketone residue. However, as shown in Synthesis Examples 25 to 28, good performance can be achieved when the ratio of the amine and aldehyde / ketone components is different from 1:1, for example, when the ratio is 1:2 (Example 28) or 2:1 (Example 29). In its broadest sense, the ratio of the amine or aldehyde / ketone components can be in the range of 0.01:3.0 to 3.0:0.01, respectively.

[0316] In general, the present invention solves the problems outlined previously in the following ways: (1) The new alkyd resin paint driers are based on metallic vanadium and do not contain cobalt; (2) they have improved hardness compared to vanadium driers V-TS, and sometimes even higher hardness than cobalt-based driers; (3) they solve the hardness development problem in V-TS, increasing the hardness development rate and generally also increasing the drying time; and (4) they have significantly improved adhesion after water resistance testing compared to vanadium driers V-TS.

[0317] Specific experimental results illustrating these points are presented below, showing improved hardness, improved drying time, and improved adhesion of coatings compared to coatings prepared without the use of a metal / asymmetric ligand complex.

[0318] Table XIII: Results for Formulation vSAcc

[0319]

[0320] The results in Table XIII show that V*8HQ drier B exhibited the best drying time of all experiments (entry 4), and that both V*8HQ drier A and B gave the highest hardness of all driers after 14 days (entries 4 and 5). Both cases, V*8HQ A and B, also demonstrate that different vanadium sources can be used to prepare these improved driers (here, V-TS and VO(acac)2, respectively).

[0321] Table XIV: Results for Formulation vSAcc

[0322]

[0323] The results in Table XIV show that the drying time is reduced when using the vanadium complexes compared to BOC-1101 and the cobalt drier, and compared to the vanadium drier V-TS. The V*HS-His drier slightly outperforms V*HS-2 (compare entries 6 and 7). With respect to the hardness of the coatings, both vanadium complexes are significantly better than BOC-1101, and several examples also outperform the cobalt drier. The complex V*HS-His again slightly outperforms V*HS-2 (compare entry 6 with entries 11 to 13).

[0324] The results also support that these new vanadium catalysts can be synthesized in different ways with generally equivalent results. The V*HS-2 drier can be synthesized from VO(acac)2, Na3VO4, and V-TS, all of which display essentially identical performance. The V*HS-His drier can be synthesized in a variety of ways from V2O5, VO(acac)2, Na3VO4, and V-TS, by reacting with preformed ligand HS-His and by synthesizing the HS-His and V-complex in a one-pot, two-step fashion. Furthermore, the ligand-to-vanadium ratio can be varied between 2:1 and 1:1 without significantly affecting performance (compare entries 12 and 13).

[0325] Table XV: Results for Formulations vs SAcc

[0326]

[0327] The results in Table XV show that the vanadium complexes with ligands of the type HS-1, HS-2 and HS-His improve the drying time compared to the vanadium drier V-TS (compare entry 3 with entries 5-7). In contrast, the vanadium complexes with ligands XJ (L O,N,N,O The vanadium complexes of the vanadium drier (type) showed very poor drying times (entry 4). Regarding hardness, the results show that in this concentration range, the vanadium drier showed similar values to BOC. However, with the ligand XJ (L O,N,N,O The complex of the α-Hydroxy-1,1-dimethyl-1-propene-1-yl group (type α-Hydroxy-1,1-dimethyl-1-propene-1-yl group) showed very poor hardness (entry 4).

[0328] These results also show that L O,N and L O,N,O The vanadium complex of the novel ligand can also be used effectively at a lower concentration of 0.01% MORS.

[0329] Table XVI: Results for Formulation vSAcc

[0330]

[0331] The results in Table XVI show that driers with ligands of type HS-1, HS-2, and HS-His have good drying times compared to BOC and Co, and most notably, ligand HS-His improves drying time compared to the simple vanadium drier V-TS (compare entries 1-3 with 5-8). In contrast, driers with ligand XJ (L O,N,N,O The vanadium complexes of the cobalt type (type) showed very poor drying times (entry 4). All ligands HS-1, HS-2, HS-His, and 8HQ improved hardness after one day compared to the vanadium drier V-TS (compare entry 3 with entries 5-9), while the latter three ligands also improved hardness after seven and fourteen days. Notably, ligands HS-2 and HS-His also provided higher hardness than the cobalt drier after seven and fourteen days (compare entry 2 with entries 6-8). Again, the ligands XJ (L O,N,N,O The complex of the α-Hydroxy-1,1-dimethyl-1-propene-1-yl group (type α-Hydroxy-1,1-dimethyl-1-propene-1-yl group) showed very poor hardness (entry 4).

[0332] The results in Table XVI also show that vanadium complexes with the ligands of the present invention can also be prepared in paint by adding the ligand to a paint that already contains a vanadium source (entry 8).

[0333] Table XVII: Results for Formulation vSAcc

[0334]

[0335] The results in Table XVII show that all driers based on the ligand HS-His showed significantly improved drying times (entries 4, 5, 11, and 12). This also shows that the driers V*HS-His can be synthesized in different ways, starting from different V sources (V-TS, Na3VO4, and VO(acac)2) and using different synthesis methods (mixing the synthesized ligand and V source in a container before adding the formulation, preparing a stock solution of the driers by thoroughly mixing the synthesized ligand and V source in advance, and synthesizing the driers in a multi-component two-step one-pot process).

[0336] The results in Table XVII also show that all V*HS-AA type driers showed improved hardness development over BOC-1101, the vanadium drier V-TS, and in several cases also outperformed the cobalt driers. Notable cases were V*HS-Trp and V*HS-His, which achieved the same hardness as BOC-1101 after one day (compare entries 1, 6, and 11), and V*HS-His, V*HS-Trp, V*HS-Met, and V*HS-Gly, which exceeded the hardness of the cobalt driers after seven days (compare entries 2, 4, 5, 6, 7, 8, and 10).

[0337] Table XVIII: Results for Formulation vSAcc

[0338]

[0339] The results in Table XVIII show that all V*HS-AA type driers show improved hardness development compared to BOC-1101, the simple vanadium drier V-TS, and in some cases also compared to the cobalt driers. Notable cases are V*HS-Glu, V*HS-Lys, and V*HS-Phe, which show higher or equal hardness than BOC-1101 and the cobalt driers after one day (compare entries 1, 2, 4, 5, and 7), and V*HS-Glu, V*HS-Lys, V*HS-Phe, and V*HS-Asn, which exceed the hardness of the cobalt driers after 21 days (compare entries 2, 4, 5, 7, and 8).

[0340] Table XIX: Results for Formulation vs SAcc

[0341]

[0342] The results in Table XIX show that V*HS-Cystine results in significantly improved drying times compared to the reference driers BOC-1101, Co, and V-TS (compare entries 1, 2, 3, and 5). It also shows that all V*HS-AA type driers show improved hardness development compared to BOC-1101, the simple vanadium drier V-TS, and in several cases, the cobalt driers. Notable cases are V*HS-Cys, V*HS-Arg, and V*HS-Leu, which show higher hardness than BOC, V-TS, and Cobalt after 1 day and 21 days, respectively (compare entries 1, 2, 3, 5, 6, and 7). In addition, V*HS-Pro exceeds the hardness of the three reference driers after 21 days (compare entries 1, 2, 3, and 8).

[0343] Table XX: Results for Formulation vs SAcc

[0344]

[0345] The results in Table XX show that, in particular, the drying agent V*HS-His improves the drying time relative to the conventional vanadium drying agent V-TS (compare entry 3 with entries 4, 7, 8, and 10). Particularly good through-drying times were achieved with the drying agent V*HS-His I2, which has only 0.6 equivalents of ligand and 1.0 equivalents of vanadium (entry 7). This also shows that an excess of vanadium relative to the ligand provides a significantly improved drying agent. In addition, a comparison of V*HS-His I and V*HS-His J shows that the vanadium precursors VOSO4 and VO(acac)2 can be used to synthesize the drying agent V*HS-His (entries 4 and 8). Improved drying times were also achieved with V*m HS-His (entry 9), indicating that the ketone 2'-hydroxyacetophenone can also be used to synthesize improved drying agents instead of salicylaldehyde.

[0346] The hardness results in Table XX also show that all of the new driers of the present invention provide improved results over the conventional vanadium drier, V-TS. Mixtures of ligands can also be used, as is evident from V*HS-HW and V*HS-9a, which provide the highest hardness values in the series after 1, 7, and 14 days (compare entries 3, 5, and 6). Drier V*m HS-His, derived from 2'-hydroxyacetophenone rather than salicylaldehyde, shows less hardness than V-TS after 1 day, but exceeds V-TS after 7 and 14 days (compare entries 3 and 9).

[0347] Furthermore, Table XX shows that the new driers can be successfully combined with other primary and secondary driers. The primary driers, BOC-1101, can be combined with V*HS-His, for example, to provide improved firmness after 1 and 14 days compared to BOC-1101 and V*HS-His alone (compare entries 1, 8, and 11; BOC-1101 was used at the recommended dosage of 0.001% MORS). The addition of the secondary driers, Octa Soligen Zirconium 10 aqua, also provided improved firmness after 1 day (compare entries 8 and 12; the secondary driers were used at the recommended dosage of 0.10% MORS).

[0348] Table XXI: Results for Formulation 11Ya-wp

[0349]

[0350] The results in Table XXI show that driers based on the ligands HS-His and HS-Trp exhibit very good drying times equivalent to the cobalt-based drier WD016 (entries 2, 4, and 5), and generally all driers V*HS-AA exhibit improved drying times compared to BOC-1101 and the reference vanadium drier V-TS (compare entries 1 and 3 with 4-19). The results also show significantly improved hardness development with the V*HS-AA driers. Notable cases are V*HS-His, V*HS-Trp, and V*HS-Met, which exhibit higher or equal hardness to the best reference drier BOC-1101 after one day (compare entries 1, 4, 5, and 7), and V*HS-His, V*HS-Trp, and V*HS-Met, which exhibit higher hardness than all three reference driers after 14 days (compare entries 1-3 with 4, 5, and 7).

[0351] The data in Table XXI show that all V*HS-AA driers exhibited improved adhesion compared to BOC-1101, and some exhibited similar or equal adhesion to the reference driers WD016 and V-TS. Notable cases were V*HS-Phe, V*HS-Cys, and V*HS-Arg (entries 13, 16, and 17).

[0352] Table XXII: Results for solvent-based alkyd resin (Worlée Kyd S351)

[0353]

[0354] The results in Table XXII show that the driers of the present invention can also be successfully used to cure solvent-borne alkyd resins. Compared to the reference drier V-TS, many ligands resulted in slightly worse drying times, with the exception of V*HS-Trp (compare entries 3 and 5). However, some improvement in hardness was observed after 1 day with V*HS-Trp, V*HS-Leu, and V*8HQ (compare entries 3 with 5, 6, and 9) and after 14 days with V*HS-2 (compare entries 3 with 8).

[0355] Table XXIII: Results for Formulation 11Ya-cc

[0356]

[0357] The results in Table XXIII show that the ligand can also be synthesized from different ratios of the two components (in this case, aldehyde and histidine), and the resulting V drier still outperforms the parent drier, V-TS (compare entries 3-5). The drier exhibits excellent drying time and hardness regardless of whether there is a slight excess of either the aldehyde or the amine component.

[0358] Aldehyde preparations only:

[0359] Table XXIV: Results for Formulation 11Ya-wp

[0360]

[0361] The results in Table XXIV demonstrate that the ligand can also be synthesized from different ratios of the two components (in this case, aldehyde and histidine), and the resulting V drier still outperforms the parent drier, V-TS (compare entries 3, 4, and 5). The drier exhibits superior drying time and hardness regardless of whether the aldehyde and amine components are each present in a two-fold excess. If the amine component is present in a two-fold excess relative to the vanadium and aldehyde, the drier exhibits the highest hardness after 1, 7, and 14 days in this formulation (entry 5). The results in this table also demonstrate that these drier solutions are not limited to DMSO as a solvent but can also be prepared in propylene glycol (see Examples 27 and 28).

[0362] It should also be noted that Examples 30 and 31, corresponding to Entries 6 and 7, show that the slurry used to form L can be omitted. ONO Thus, in this particular case, the ratio of the amine or aldehyde / ketone component can be 0-3:1, respectively.

[0363] L ON Ligand:

[0364] Surprisingly, it was found that simplified forms of the above ligands also improve the performance of simple vanadium driers. In particular, we found that α-amino acids can also be used successfully. These natural compounds also belong to the group of asymmetric L ON Although the definition of type ligand is usually not given with the above L ONO The same level of improvement in hardness as with the type ligands was observed, but in some cases we still observed an increase in hardness. In addition, we could observe improved drying times and, most importantly, improved adhesion after soaking the coating in water (water resistance test).

[0365] In general, alkyd resin paint driers based on a combination of vanadium drier V-TS and amino acids solve the problem of better adhesion performance than V-TS after water resistance testing and demonstrate how the performance is improved, also resulting in higher hardness and better drying time compared to vanadium drier V-TS; and combinations of amino acids with other metal precursors such as Fe salts and Mn salts show better drying time, hardness and better adhesion compared to the precursors.

[0366] In the attached Figure 1-12 Specific experimental results illustrating these points are given in , which show reduced blistering and improved adhesion of coatings compared to coatings prepared without the use of V-TS.

[0367] Table XXV: Effect of amino acids on adhesion in formulation Beckosol AQ206-cc

[0368]

[0369] All amino acids listed under Beckosol AQ 206-Clear Coating as materials in the binder were tested in combination with V-TS and are shown in Table XXVI.

[0370] V-TS + Trp showed the best adhesion of all the amino acid ligands tested (entry 2), while the others showed very poor adhesion performance. The overall performance of V-TS with amino acids in the water resistance test / foaming was mediocre, with some showing similar performance (compare entries 1 and 3-6, 11 and 15), and notably, some amino acid combinations showed superior performance to the reference V-TS driers (compare entries 1 and 2, 13, 14, 16 and 17).

[0371] Table XXVI: Effect of amino acids in formulation 11ya-WP on adhesion

[0372]

[0373]

[0374] All amino acids listed under Materials were tested in combination with V-TS, Fe, and Mn in 211Y white pigment as a binder, and only significant results for Fe and Mn are shown in Table XXVI.

[0375] The results in Table XXVI show that compared to the reference V-Ts drier, the amino acid-based driers V-Ts+Trp, V-Ts+Tyr, V-Ts+Phe, V-Ts+Arg, and V-Ts+Leu exhibited the best adhesion (entries 2-6). In particular, V-Ts+Arg exhibited improved drying time—drying in 9 days—compared to the reference V-TS drier, similar hardness at 14 days, and yellowing, but with improved adhesion (entries 1, 5). No blistering was observed in any case.

[0376] The results in Table XXVI (entries 18-24) show the positive impact of amino acids when combined with other metals such as Fe and Mn. Notable cases are Fe+Phe, Fe+Leu, and Fe+Ser, which exhibit better adhesion compared to the reference compounds (entries 18-21). Similarly, Mn+Ser, Mn+Leu, and Mn+Trp all exhibited better hardness over the three days measured, and notably, Mn+Ser exhibited improved adhesion and less yellowing compared to the reference drier, Mn (entries 22, 23).

[0377] Table XXVII: Effect of amino acids on hardness development in formulation vSAcc

[0378]

[0379]

[0380] All amino acids listed under Materials were tested in combination with V-TS, Fe and Mn in Synaqua 4804-clearcoat as binder, and only significant results for Fe and Mn are shown in Table XXVII.

[0381] The results in Table XXVII show that the combination of V-TS and different amino acids improved drying time and hardness compared to the reference drier V-TS, Fe, and Mn. The combinations of V-TS+Ser, V-TS+Csy, V-TS+Leu, and V-TS+Gly showed improved hardness (entries 1-5) over the vanadium drier V-TS. Notably, V-TS+CysD, V-TS+Phe, and V-TS+His improved drying time compared to the reference drier V-TS (entries 1, 9, 11, and 12).

[0382] The versatility of amino acids is evident through increases in hardness when combined with other metals (entries 18-23). Notably, Fe+His showed significant improvements in drying time and hardness measured after 1 day, and also exhibited better hardness after 7 and 14 days (compare entries 18 and 20), with the same results observed for the Mn+His drier (compare entries 22 and 23).

[0383] Table XXVIII: Results for Formulation Synaqua 2070

[0384]

[0385] The results in Table XXVIII show that the drier can also be synthesized directly in the formulation from three components (in this case, an aldehyde, histidine, and a vanadium precursor), and that the resulting formulations exhibit superior performance compared to formulations made with the simple vanadium drier, V-TS, and essentially the same performance as formulations made with the same drier, which was synthesized prior to mixing with the resin (compare entries 1-3). Furthermore, the results also show that good performance is achieved when the drier is synthesized from two organic components without the addition of a base (compare Examples 16 and 29).

[0386] The best mode for carrying out the invention has been described for the purpose of illustrating the best mode known to the applicant at that time. The examples are illustrative only and are not meant to limit the invention, as measured by the scope and advantages of the claims. The invention has been described with reference to preferred and alternative embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding this specification. It is intended to include all such modifications and alterations as long as they come within the scope of the appended claims or their equivalents.

Claims

1. A method for improving at least one physical property of an oxidatively curable alkyd resin coating, said physical property being selected from the group consisting of improved resin hardness, reduced resin yellowing, reduced resin foaming, and reduced resin drying time, said method comprising the following steps in any order: A metal source of vanadium, iron, manganese or copper is combined with at least one asymmetric ligand, provided that: (a) When the asymmetric ligand is L O,N or L O,N,O When the asymmetric ligand comprises at least one of a terminal carboxylic acid group or a phenolic hydroxyl group and at least one of a primary amine or a Schiff base or a pyridinic nitrogen group; and wherein (b) When the asymmetric ligand is L containing at least one terminal carboxylic acid O,N,O In the case of the hydroxy-type, the asymmetric ligand comprises, in addition to the at least one terminal carboxylic acid group, at least one phenolic hydroxyl functional group.

2. The method of claim 1, wherein the at least one asymmetric ligand comprises Formula XXV or Formula XXVI or Formula XXVII or Formula XXVIII: Wherein formula XXV is: in R 1 and R 2 Independently selected from H, C 1-4 straight-chain and branched-chain alkyl groups; Y is selected from the following group: (a) Straight-chain and branched, substituted and unsubstituted C 1-10 Alkyl, wherein substituents include amine, carbonyl and mercapto, (b) linear and branched, substituted and unsubstituted C 6-20 Aryl, wherein the substituent contains heteroatoms and further contains N and O, and wherein the C 6-20 The aryl group optionally also contains C 5-6 and C 5-5 and C 6-6 Fused ring, (c) Straight and branched C 7-40 Alkylaryl, which further contains inserted heteroatoms selected from nitrogen, oxygen and sulfur atoms, which are embedded in the main chain or at the chain terminal, and wherein the C 7-40 The alkylaryl group optionally further comprises C 5-6 and C 5-5 and C 6-6 fused ring; (d) linear and branched, substituted and unsubstituted C 7-40 Arylalkyl, which also contains heteroatoms, and further contains nitrogen, oxygen and sulfur atoms embedded in the main chain or at the chain terminals, and wherein the C 7-40 The arylalkyl group optionally further comprises C 5-6 and C 5-5 and C 6-6 fused ring; s is an integer value from 0 to 1; t is an integer value from 0 to 1; And wherein formula XXVI is: in R 3 and R 4 is selected from the groups defined above for Y in formula XXV; x is an integer value from 0 to 3; y is an integer value from 0 to 3; And wherein the formula XXVII is: in R 3 and x is as previously defined for Y in Formula XXVI; R 5 and R 7 is selected from the groups defined above for Y in formula XXV; And wherein Formula XXVIII is: in R 3 and x is as previously defined for Y in Formula XXVI; and R 6 and R 8 is selected from the groups defined above for Y in formula XXV.

3. The method of claim 2, wherein the asymmetric ligand is selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, phenylalanine, proline, pyroglutamic acid, serine, threonine, tryptophan, tyrosine, and valine.

4. The method of claim 2, wherein the asymmetric ligand is selected from amino acid adducts of salen ligands, namely: 2-((2-hydroxybenzylidene)amino)-3-(1H-imidazol-4-yl)propanoic acid, 2-((2-Hydroxybenzylidene)amino)-3-(1H-indol-3-yl)propanoic acid, 3-Hydroxy-2-((2-hydroxybenzylidene)amino)propionic acid, 2-((2-Hydroxybenzylidene)amino)-4-(methylthio)butanoic acid, 2-((2-Hydroxybenzylidene)amino)succinic acid, 2-((2-Hydroxybenzylidene)amino)glutaric acid, 2-((2-hydroxybenzylidene)amino)acetic acid, 6-amino-2-((2-hydroxybenzylidene)amino)hexanoic acid, 2-((2-hydroxybenzylidene)amino)-3-(4-hydroxyphenyl)propanoic acid, 2-((2-Hydroxybenzylidene)amino)-3-phenylpropionic acid, 4-amino-2-((2-hydroxybenzylidene)amino)-4-oxobutanoic acid, 2-((2-Hydroxybenzylidene)amino)-3-mercaptopropionic acid, 3-((2-carboxy-2-((2-hydroxybenzylidene)amino)ethyl)disulfanyl)-2-((2-hydroxybenzylidene)amino)propanoic acid, 5-guanidino-2-((2-hydroxybenzylidene)amino)pentanoic acid, 2-((2-Hydroxybenzylidene)amino)-4-methylpentanoic acid, 1-(2-hydroxybenzylidene)pyrrolidin-1-ium-2-carboxylate, and 2-((1-(2-Hydroxyphenyl)ethylidene)amino)-3-(1H-imidazol-4-yl)propanoic acid.

5. The method of any one of claims 1 to 4, wherein the vanadium, iron, manganese or copper has a MORS value of 0.001 to 1 wt.%, inclusive.

6. The method of any one of claims 1 to 5, wherein the ligand is added in any combination of: preformed with the metal, added to the resin before or after the metal, or added as a prepackaged system.

7. The method of claim 1, wherein the asymmetric ligand is an amino acid selected from the group consisting of tryptophan, serine, arginine, methionine, leucine, proline, glycine, glutamine, lysine, tyrosine, phenylalanine, asparagine, cysteine, cystine, and aspartic acid, alanine, isoleucine, threonine, valine, and selenocysteine.

8. The method of claim 1, wherein the ligand is a C1-C6 alkyl-substituted asymmetric amino acid.

9. The method according to any one of claims 1 to 8, further comprising: BOC, i.e., iron (1+), chloro[9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1) and the asymmetric amino acid ligand were added.

10. The method of claim 7, wherein the ligand is at least two ligands or a blend thereof.

11. The method of any one of claims 1 to 10, further comprising: Add at least one additive selected from the group consisting of anti-skinning agents, UV stabilizers, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, antifouling agents, bactericides, fungicides, algaecides, insecticides, extenders, plasticizers, antifreeze agents, waxes, thickeners, inorganic or organic transparent or non-transparent pigments, cosolvents, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, extenders, waxes, thickeners, thixotropic agents, antioxidants and anti-skinning agents.

12. The method of any one of claims 1 to 11, wherein the metal source and at least one asymmetric ligand are used in a solvent-based paint or a water-based paint.

13. The method of any one of claims 1 to 12, wherein the metal source and at least one asymmetric ligand are used in an alkyd paint or an oxidatively curable ink.

14. The method of any one of claims 1 to 13, wherein the metal source and at least one asymmetric ligand are used in a composite material.

15. The method of any one of claims 1 to 14, wherein the metal source and at least one asymmetric ligand are aqueous or solvent-borne.

Images