CN118647679A

CN118647679A - Coating containing a drier based on vanadium compounds with various acid anions

Info

Publication number: CN118647679A
Application number: CN202280090209.4A
Authority: CN
Inventors: N·J·辛普森; M·克鲁斯曼; J·霍尔斯特德; S·布兰德
Original assignee: Boehringer Ingelheim Pharma GmbH and Co KG
Current assignee: Boehringer Ingelheim Pharma GmbH and Co KG
Priority date: 2021-12-22
Filing date: 2022-12-07
Publication date: 2024-09-13

Abstract

The present invention relates generally to a coating comprising: a binder curable by an autoxidation mechanism and at least one drier containing a sulfonate compound of vanadium of formula (VII) in combination with at least one mineral acid and optionally at least one organic acid,Wherein R ¹ and R ² are independently selected from the group consisting of: hydrogen, C ₁-C₁₂ alkyl, C ₁-C₁₂ haloalkyl, C ₆-C₁₀ aryl, benzyl; and wherein aryl and benzyl may be optionally substituted with up to three substituents independently selected from the group consisting of C ₁-C₂₀ alkyl and hydroxy (C ₁-C₂) alkyl.

Description

Coating containing a drier based on vanadium compounds with various acid anions

Technical Field

The invention described herein relates generally to formulations of air-drying coatings and combinations of main siccatives and mineral acids suitable for use in these formulations.

Background

Air-drying adhesives, including polyester resins modified with vegetable oils, known as alkyd resins, are widely used in the paint production industry (Hofland, a., prog. Org. Coat.,73,274-282 (2012)) due to their low cost, high content of biorenewable resources and relatively easy biodegradability. The synthetic resin modified by the dried and semi-dried vegetable oil is cured under the influence of air oxygen. A chemical process called autoxidation is responsible for converting a liquid paint layer into a solid durable coating. Since autoxidation proceeds slowly under ambient conditions, it is generally accelerated by the action of a special catalyst called a main drier (PRIMARY DRIER). These compounds enable faster decomposition of hydroperoxides, which are kinetically stable intermediates for the autoxidation that occurs in the first step of the curing process. It leads to a significant acceleration of the subsequent reactions in the propagation step of the autoxidation, generating free radicals that determine the final structure of the cured resin. Crosslinking of the air-drying coating is carried out by free radical addition on the double bond system and free radical recombination in the termination step (Soucek, m.d. et al; prog.org. coat.,73,435-454 (2012)).

Cobalt carboxylates soluble in organic solvents, such as cobalt 2-ethylhexanoate, cobalt neodecanoate and cobalt naphthenate, are currently widely used as main driers in the paint industry due to their high catalytic activity in solvent-type high solids air drying bindersJ.; ind. Eng. Chem. Res.58,12485-12505 (2019)). However, due to health and ecological concerns, the use of cobalt compounds should be limited by legislation in the near future (Leyssens, l.et al.; toxicology 387,43-56 (2017); simpson, n.et al.; catalysts,9,825 (2019)). Currently, cobalt carboxylates are under deep examination by the European chemical administration (European CHEMICALS AGENCY) and are initially classified as suspected reproductive poisons.

Ongoing toxicological investigation may lead to its reclassification as a carcinogen and prohibit its use in commercial coatings. This situation has accelerated research in the area of iron and manganese based catalysts that can replace cobalt based driers (WO 2008/003652 A1;Simpson,N.et al;Catalysts,9,825 (2019),E.et al; materials,13,642 (2020)). Vanadium-based compounds soluble in organic solvents are another alternative to cobalt carboxylates reported in research and patent literature. These include vanadium oxide compounds with carboxylates (EP 0304 149 B1,US 6063841 A,Preininger,O.et al;J.Coat.Technol.Res.13,479-487 (2016)), acetylacetonate (US 6063841 A,Preininger,O.et al;Prog.Org.Coat.88,191-198(2015),Preininger,O.et al;Inorg.Chim.Acta 462,16-22(2017),Charamzová,I.et al;Inorg.Chim.Acta492,243-248(2019))、 ketimine (US 6063841A), organophosphates (US 6063841A) and dithiocarbamates (CZ 307597B6, charamzov, I.et al; J.coat. Technology. Res.2020,17, 1113-1122.). Some of these compounds were found to be suitable as secondary driers improving the visual and mechanical properties of the final paint film (WO 2015/082553 A1,WO 2017/085154A1, WO 2010/106033 A1). Notably, none of the reported vanadium-based driers has been commercially used due to low solubility, high production costs, or low stability upon storage. The present invention brings about a substitute for toxic cobalt, which can be used for both aqueous and solvent-based coatings. Enabling the use of water-based alkyd resins is critical to the reduction of volatile organic compounds in the environment. As the chemical industry seeks more sustainable and environmentally friendly alternatives to the prior art, the replacement of organic solvents and toxic catalysts is of paramount importance.

The present invention relates to vanadium-based siccatives (see M.Petranikova,A.H.Tkaczyk,A.Bartl,A.Amato,V.Lapkovskis and C.Tunsu,"Vanadium sustainability in the context of innovative recycling and sourcing development",Waste Management 113(2020)521,544), which have improved properties obtainable from readily available raw materials by a simple one-step route: the siccatives of the invention should also exhibit high stability to air oxygen their solubility should be easily changed by the substitution pattern of a given sulfonate anion, allowing the dissolution of other siccatives in combination with at least one mineral acid selected from phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, boric acid, hydrobromic acid, perchloric acid and hydroiodic acid and combinations and blends thereof with other mineral acids and combinations with other organic acids.

Czech patent application No. PV 2020-366 filed on 6/24/2020, entitled "N t ě rove hmoty obsahuj i SIKATIVY NA b ariVanadu skompenzuj i.i mi anionty sulfonovych kyselin ", translated into" coating containing a drier based on a vanadium compound with a sulfonic acid anion as counter ion ", describes the use of a vanadium compound of a sulfonic acid anion.

Disclosure of Invention

The present invention relates to a combination of a vanadium-based drier and at least one mineral acid and a blend of a vanadium-based drier and at least one organic acid.

One aspect of the invention relates to formulating a coating formulation comprising: a binder curable by an autoxidation mechanism; and at least one drier comprising a vanadium compound of formula (VII) in combination with at least one mineral acid:

Wherein R ¹ and R ² are independently selected from the group consisting of: hydrogen, C ₁-C₁₂ alkyl, C ₁-C₁₂ haloalkyl, C ₆-C₁₀ aryl, benzyl; and wherein aryl and benzyl may be optionally substituted with up to three substituents independently selected from the group consisting of C ₁-C₂₀ alkyl and hydroxy (C ₁-C₂) alkyl.

In another aspect of the invention, the adhesive curable by an autoxidation mechanism is selected from the group consisting of: alkyd resins, epoxy ester resins and resins modified with vegetable oils or fatty acids.

In another aspect of the invention, the formulation comprises one or more sulfonate compounds of vanadium of formula (VII) in a total concentration of at least 0.001wt.% to 0.3wt.%, more preferably at least 0.003 to 0.3wt.%, most preferably at least 0.006 to 0.06wt.%, based on the dry matter content of the coating.

In a further aspect of the invention, depending on the application, the siccatives based on formula (VII) may be dissolved in water or polar organic solvents, such as dimethyl sulfoxide (DMSO), acetic acid, alcohols, esters, ethers, solvents with more than one alcohol, ester and ether functional group, and mixtures thereof.

In the coating formulation, the C ₁-C₁₂ haloalkyl is C ₁-C₁₂ fluoroalkyl.

In one aspect of the invention, the coating formulation comprises water, while in another aspect of the invention, the coating formulation is non-aqueous.

The coating formulation further comprises a ligand selected from the group consisting of: bispidon, N4py, TACN, cyclam and bridged ligands (cross-bridged ligand) and TRISPICEN ligands.

The coating formulation also includes a metal-ligand complex, such as iron (1+), chloro [ dimethyl 9, 9-dihydroxy-3-methyl-2, 4-bis (2-pyridinyl-kN) -7- [ (2-pyridinyl-kN) methyl ] -3, 7-diazabicyclo [3.3.1] nonane-1, 4-dicarboxylate-kN 3, kN7] -, chloride (1:1):

The coating formulation may optionally comprise a pigment, and optionally a combination of an organic acid, such as oxalic acid, and an inorganic acid.

The alkyd resin of the coating formulation may be a solvent-borne or aqueous resin, and the end use application is typically a formulation for a coating.

The invention includes the use of formula (VII) wherein the compound of formula (VII) is dissolved in dimethyl sulfoxide, an ester, an ether, a solvent having more than one alcohol, ester, ether functionality, or an alcohol or water, or mixtures thereof, prior to incorporation into a coating.

The invention also includes the use of a vanadium sulfonate compound of formula (VII) in dimethyl sulfoxide, an ester, an ether, a solvent or an alcohol having more than one alcohol, ester, ether function or mixtures thereof as a drier for coatings containing curable binders,

Wherein R ¹ and R ² are independently selected from the group consisting of: hydrogen, C ₁-C₁₂ alkyl, C ₁-C₈ fluoroalkyl, C ₆-C₁₀ aryl, benzyl; wherein C ₆-C₁₀ aryl and benzyl may be optionally substituted with one to three substituents independently selected from C ₁-C₂₀ alkyl and hydroxy (C ₁-C₂) alkyl.

These and other objects of the present invention will be apparent from the detailed description and appended claims.

Detailed Description

The best mode for carrying out the invention will now be described to illustrate the best mode known to the applicant at the time of filing the present invention. The examples and figures are illustrative only and are not meant to limit the invention, which is measured by the scope and spirit of the claims.

Unless the context clearly indicates otherwise: the term "and" means the conjunctive term; "or" word means an anti-sense conjunctive; when an item is indicated by a disjunctive followed by "or both" or "a combination thereof," both conjunctions and disjunctive are intended.

As used in this disclosure, the term "about" is within 10% of the stated value unless otherwise indicated.

The present invention has broad application to a variety of solvent and water-based coating compositions, which term should be interpreted broadly herein. Examples of coating compositions include clear or colored varnishes, primers, caulks, glazes, emulsions and floor coverings, such as linoleum floor coverings. Embodiments of the present invention relate to solvent and water-based coatings and inks, particularly coatings, such as high specification coatings for household use and coatings for general industrial applications.

Thus, the term "oxidatively curable coating composition" as used herein is intended to include a wide variety of colored (e.g., by pigments or inks) and colorless materials, including oils and binders, which form a continuous coating through an oxidation reaction process, typically forming crosslinks and other bonding forms. In general, such coating compositions may be characterized by the general presence of (poly) unsaturated resins that react to form a solid film on the substrate, the resins initially being present in the oxidatively curable solvent-based coating composition in the form of a liquid dissolved in an organic solvent or in the form of a solid dispersed in a continuous liquid phase. The reaction to form the desired coating upon curing results from an oxidation-initiated polymerization reaction. Examples of oxidatively curable coating compositions include alkyd-based resins, acrylate-based resins, polyurethane-based resins, polybutadiene-based resins, and epoxy ester-based resins. Typically, the curable portion (e.g., alkyd) of the curable composition will constitute from about 1 to about 90 wt.% of the total weight of the oxidatively curable solvent-based coating composition, such as from about 20wt.% to about 70wt.% of the total weight of the oxidatively curable solvent-based coating composition.

Alkyd resins are a particularly important member of the class of oxidatively curable coating compositions and are a well-studied class of resins to which the present invention can be applied. Hereinafter, embodiments of the present invention are described with respect to the use of alkyd resins (also referred to as alkyd-based resins or alkyd (base) binders). While these represent particularly important embodiments of the present invention, the present invention is not limited thereto. Clearly, it is: the present invention is applicable to a variety of oxidatively curable coating compositions, typically those comprising at least 1 or 2 weight percent unsaturated compounds (e.g., comprising unsaturated (non-aromatic) carbon-carbon double or triple bonds).

As used herein, the terms "alkyd binder" or "alkyd resin" are used interchangeably. Suitable autoxidisable alkyd resins for use in the present invention are typically the esterification reaction products of a polyol with a polybasic acid (or anhydride thereof) and an unsaturated fatty acid (or glyceride thereof), for example derived from linseed oil, tung oil, tall oil and from other drying or semi-drying oils. Alkyd resins are well known in the art and need not be further described herein. These properties are determined mainly by the nature and proportion of the alcohols and acids used and the degree of condensation. Suitable alkyds include long and medium oil alkyds, e.g., derived from 45 to 70wt.% fatty acids. To improve the properties of the resin, the composition of long and medium oil alkyd resins may be modified. 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 invention.

Preferably, the at least one autoxidisable alkyd binder is selected from medium 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, silicone modified alkyd, polyurethane modified alkyd or combinations thereof.

The alkyd binder may generally be present in the compositions of the invention in an amount of from about 20wt.% to 98wt.%, for example from about 30wt.% to about 90wt.%, preferably from about 35wt.% to 70wt.%, based on the total weight of the composition.

As used herein, the term "drier" (which is also synonymously referred to as "drier (siccative)", when in solution) refers to an organometallic compound that is soluble in organic solvents and binders. They are added to unsaturated oils and binders to significantly reduce their drying time, i.e. their film to solid phase transition. The drier may be provided in solid or solution form. Suitable solvents are organic solvents and binders. The amount of drier present is expressed as a weight percentage of metal based on the weight of the binder solids (or resin), unless otherwise indicated.

As used herein, the term "drier composition" refers to a mixture of the drier claimed in the present invention. The drier composition according to the present invention may comprise several drier compounds. The inventors have found that the choice of drier in the coating composition of the present invention increases the drying speed of the coating composition.

When referring to weight percentages (wt.% or% w/w) herein, unless the context clearly dictates otherwise, this refers to the weight percentages relative to the solid resin resulting from curing (i.e., the components of the oxidatively curable coating composition that are used to provide the coating upon curing). Thus, for an oxidatively curable alkyd coating composition, the total weight of the components of the composition that become (i.e., are incorporated into) the alkyd coating (i.e., once cured) is based on the weight percentages herein. For example, the compositions resulting from practicing the methods of the first aspect of the invention or the second aspect of the invention typically comprise 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 from the coating upon curing.

Consistent with the terminology used in the art, oxidatively curable solvent-based compositions herein refer to compositions based on organic (i.e., non-aqueous) solvents. Examples of suitable solvents include aliphatic (including cycloaliphatic 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 isopropanol, n-butanol and n-propanol; ethylene glycol monoethers, such as monoethers of ethylene glycol and diethylene glycol; shan Miyi glycol acetates, such as 2-ethoxyethyl acetate; and mixtures thereof. Including isomeric variants. Thus, the term hexane includes mixtures of hexane. According to an embodiment of the invention, the solvent is a hydrocarbon-based (i.e. hydrocarbon) solvent, such as an aliphatic hydrocarbon-based solvent, e.g. a solvent comprising a mixture of hydrocarbons. Examples include petroleum spirits and solvents from SHELL CHEMICALS under the trademark Shellsol, and Solvesso and Exxsol from Exxon.

The composition of the present invention comprises a transition metal drier which is a complex of a transition metal ion and a sulfonic acid counterion. Each of these will now be described.

The transition metal ion used in the present invention is vanadium. The valence of the metal may be +2 to +5. An embodiment of the invention is a mixture of transition metal ions. In the case of vanadium containing driers this is usually a V (II), (III), (IV) or (V) compound, and in the case of iron containing driers this is usually an Fe (II) or Fe (III) compound. In the case of manganese drying agents, this is generally a Mn (II), (III) or (IV) compound.

In order to enhance the activity of the transition metal ions, so-called promoting compounds, such as carboxylic acids or pentadentate amines, are also included. As the language suggests, the carboxylic acid or multidentate amine promoter ligand is a compound that is capable of coordinating to transition metal ions through more than one donor site in the ligand and is used to accelerate the drying (curing process) of the post-application oxidatively curable coating composition.

According to some embodiments of the invention, the multidentate amine promoter ligand is a di-, tri-, tetra-, penta-, or hexadentate ligand coordinated through nitrogen and/or oxygen donor atoms. In a specific embodiment of the invention, the ligand is a di-, tri-, tetra-, penta-or hexadentate nitrogen donor ligand, in particular a tri-, tetra-, penta-or hexadentate nitrogen donor ligand. However, the present invention is not limited thereto. Examples of various multidentate promoter ligands are discussed below.

The metal driers as described herein, e.g., as preformed complexes of transition metal ions and multidentate promoting ligands, are typically dissolved in water at a concentration of from about 0.001 to about 10wt.%, e.g., from about 0.01 to about 5wt.%, or from about 0.001 to about 1wt.%, based on the weight of the water. Increasing the concentration of the metal drier in the aqueous solution allows for relatively small volumes of the aqueous solution containing the metal drier to be added to the coating composition. This may be desirable to those skilled in the art. The actual amount of metal drier depends on the number of metal atoms present in the metal drier molecule and its total molecular weight, as well as the desired degree of incorporation. For example, if the desired complex has a molecular weight of 560 and contains one iron ion (MW 56), and the level of iron is mentioned to be 0.1%, the amount of compound dissolved in water is 1% (w/w) or 10 g/kg water. If the complex is not preformed, but is formed in situ, the metal salt will also typically be dissolved in water at a concentration of about 0.001 to about 1wt.% based on the ratio of metal ions to water. An appropriate amount of a multidentate promoting ligand may then be added to form the desired complex.

After preparation, the solution of metal drier may then be contacted with, e.g., added to, the coating composition.

The resulting composition comprising the metal drier and typically 0.0001-1% water, based on the weight of the oxidatively curable resin, will typically be a solution, i.e. a single homogeneous phase. However, it may also be an emulsion or dispersion, for example comprising discrete areas of an aqueous solution containing a transition metal drier.

The term "binder solution (alkyd resin)" as used in the present application refers to one of the following: SYNAQUA 4804 (aqueous short oil alkyd, archema); SYNAQUA 2070 (aqueous medium oil alkyd resin, arkema); beckosol AQ101 (aqueous long oil alkyd, polyont Composites USA inc.); worle ekyd S351 (solvent medium oil alkyd, worle); and TOD 3AK0211Y (Water-dilutable alkyd resin, TOD, china) and other binder solutions having similar characteristics to those described above. In a more general sense, "alkyd resin" refers to a synthetic resin made by the condensation reaction (liberation of water) between a polyol (glycerol, etc.) and a dibasic acid (or phthalic anhydride). Which is the non-volatile portion of the paint carrier. After drying, it binds the pigment particles together with the paint film as a whole.

The term "catalyst" as used in the present application means: borchi Oxy-Coat 1101 (BOC 1101, in water, borchers); borchi Oxy-Coat (BOC, in propylene glycol, borchers); borchers Deca Cobalt 7a (cobalt neodecanoate drier, borchers in organic solvents); borchers Deca Cobalt 10 (cobalt neodecanoate drier, borchers in hydrocarbon solvents); cur-Rx (2-ethylhexanoic acid vanadium drier, borchers); vanadyl acetylacetonate (VO (acac) ₂) (99%, CAS:14024-18-1, acros); V-TS (vanadium-based drier, 9.4% V); V-DS (vanadium-based drier, 5.5% V) and other catalysts having similar characteristics to the catalysts described above.

The term "ligand" as used herein preferably refers to TMTACN-N, N, N-trimethyl-1, 4, 7-triazacyclononane and other ligands having similar characteristics as described above and below.

Other suitable "ligands" include the following:

BISPIDON

the Bispidon class is typically in the form of iron transition metal catalysts. The bispidon ligand preferably has the formula:

wherein:

Each R is independently selected from the group consisting of: hydrogen, F, cl, br, hydroxy, C _1-4 -alkyl O-, -NH-CO-H, -NH-CO-C _1-4 alkyl, -NH ₂、-NH-C_1-4 alkyl, and C _1-4 alkyl;

R1 and R2 are independently selected from the group consisting of: c _1-24 alkyl, C _6-10 aryl, and groups containing one or two heteroatoms (e.g., N, O or S) capable of coordinating to a transition metal;

R3 and R4 are independently selected from the group consisting of: hydrogen, C _1-8 alkyl, C _1-8 alkyl-O-C _1-8 alkyl, C _1-8 alkyl-O-C _6-10 aryl, C _6-10 aryl, C _1-8 hydroxyalkyl, and- (CH ₂)_n C (O) OR5, wherein R5 is independently selected from hydrogen and C _1-4 alkyl;

n is 0 to 4

X is selected from the group consisting of: c=o, - [ C (R6) ₂]_y -, wherein y is 0 to 3; each R6 is independently selected from the group consisting of: hydrogen, hydroxy, C _1-4 alkoxy, and C _1-4 alkyl.

Typically r3=r4 and is selected from-C (O) -O-CH ₃、-C(O)-O-CH₂CH₃、-C(O)-O-CH₂C₆H₅ and CH ₂ OH. Typically, the heteroatom capable of coordinating to the transition metal is provided by pyridin-2-ylmethyl optionally substituted with C _1-4 alkyl or aliphatic amines optionally substituted with C _1-8 alkyl. Typically X is c=o or C (OH) ₂.

Typical groups for R1 and R2 are-CH ₃、-C₂H₅、-C₃H₇, -benzyl 、-C₄H₉、-C₆H₁₃、-C₈H₁₇、-C₁₂H₂₅、-C₁₈H₃₇ and pyridin-2-yl. An example of a class of bispidon is that in which at least one of R1 or R2 is pyridin-2-ylmethyl or benzyl or optionally alkyl-substituted amino-ethyl, such as pyridin-2-ylmethyl or N, N-dimethylamino-ethyl.

Two examples of Bispidon are dimethyl 2, 4-bis- (2-pyridinyl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate (N2 py3 o-C1) and dimethyl 2, 4-bis- (2-pyridinyl) -3-methyl-7- (N, N-dimethyl-amino-ethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate and the corresponding iron complexes. FeN2py3o-C1 may be prepared as described in WO 02/48301. Other examples of bispidon are those compounds which do not have a methyl group in the 3-position, but rather have a longer alkyl chain (e.g. a C ₄-C₁₈ alkyl or a C ₆-C₁₈ alkyl chain), such as isobutyl, (n-hexyl) C ₆, (n-octyl) C ₈, (n-dodecyl) C ₁₂, (n-tetradecyl) C ₁₄, (n-octadecyl) C ₁₈; these can be prepared in a similar manner.

N4py type

The N4 py-type ligand is typically in the form of an iron transition metal catalyst. The N4 py-type ligand is typically of formula (II):

wherein:

Each of R1 and R2 independently represents-R4-R5;

R3 represents hydrogen, C _1-8 alkyl, aryl selected from the group consisting of homoaromatics having a molecular weight below 300, or C _7-40 arylalkyl, or-R4-R5,

Each R4 independently represents a single bond or a linear or branched C _1-8 alkyl-substituted-C _2-6 -alkylene, C _2-6 alkenylene, C _2-6 oxyalkylene, C _2-6 aminoalkylene, C _2-6 alkenylether, C _2-6 carboxylate or C _2-6 carboxamide, and

Each R5 independently represents an optionally N-alkyl substituted aminoalkyl or an optionally alkyl substituted heteroaryl selected from the group consisting of: a pyridyl group; pyrimidinyl; pyrazinyl; triazolyl; a pyridazinyl group; 1,3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; an oxazolidinyl group; a pyrrole group; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl can be attached to the compound through any atom in the ring of the heteroaryl of choice.

According to some embodiments, R1 or R2 represents pyridin-2-yl; or R2 or R1 represents 2-amino-ethyl, 2- (N-methyl or ethyl) amino-ethyl or 2- (N, N-dimethyl or diethyl) amino-ethyl. R5, if substituted, generally represents 3-methylpyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl.

Examples of N4Py ligands include N4Py itself (i.e., N-bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine, which is described in WO 95/34628); and MeN4py (i.e. N, N-bis (pyridin-2-yl-methyl) -1, 1-bis (pyridin-2-yl) -1-aminoethane) and BzN py (N, N-bis (pyridin-2-yl-methyl) -1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane), which are described in EP 0909809.

TACN type

TACN-Nx is preferably in the form of an iron transition metal catalyst. These ligands are based on 1,4, 7-Triazacyclononane (TACN) structures but have one or more pendant nitrogen groups for complexation with transition metals to provide tetradentate, pentadentate or hexadentate ligands. According to some embodiments of the TACN-Nx type ligand, the TACN scaffold has two pendant nitrogen-containing groups (TACN-N ₂) complexed with a transition metal. The TACN-Nx ligand is generally of formula (III):

Wherein the method comprises the steps of

Each R20 is independently selected from: c _1-8 -alkyl; c _3-8 cycloalkyl; a heterocycloalkyl selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, 1,4, 7-triazacyclononyl, 1,4,8, 11-tetraazacyclotetradecyl, 1,4,7,10, 13-pentazapentadecyl, 1, 4-diaza-7-thia-cyclononyl, 1, 4-diaza-7-oxa-cyclononyl, 1,4,7, 10-tetraazacyclododecyl, 1, 4-dioxanyl (dioxanyl), 1,4, 7-trithia-cyclononyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be attached to the compound through any atom in the ring of the selected heterocycloalkyl; heteroaryl groups selected from the group consisting of: pyridyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3, 5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl group may be attached to the compound through any atom in the heteroaryl ring selected; aryl selected from the group consisting of homoaromatic compounds having a molecular weight below 300; or C _7-40 aralkyl optionally substituted with substituents selected from the group consisting of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylate, sulfonate, amine, alkylamine and N ⁺(R21)₃,

R21 is selected from the group consisting of hydrogen, C _1-8 alkyl, C _2-6 alkenyl, C _7-40 aralkyl, aralkenyl, C _1-8 oxyalkyl, C _2-6 oxyalkenyl, C _1-8 aminoalkyl, C _2-6 aminoalkenyl, C _1-8 alkyl ether, C _2-6 alkenyl ether, and-CY ₂ -R22,

Y is independently selected from H, CH ₃、C₂H₅、C₃H₇, and

R22 is independently selected from C _1-8 alkyl-substituted heteroaryl selected from the group consisting of: a pyridyl group; pyrimidinyl; pyrazinyl; triazolyl; a pyridazinyl group; 1,3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; an oxazolidinyl group; a pyrrole group; carbazolyl; indolyl; and isoindolyl, wherein said heteroaryl can be attached to said compound through any atom in the ring of the heteroaryl of choice; and

Wherein at least one R20 is-CY ₂ -R22.

R22 is typically selected from optionally alkyl-substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, quinolin-2-yl. R22 is typically pyridin-2-yl or quinolin-2-yl.

CYCLAM and bridged ligands

The cyclam and bridging ligand are preferably in the form of manganese transition metal catalysts. The cyclam ligand is typically of formula (IV):

wherein:

Q is independently selected from

P is 4;

R is independently selected from: hydrogen, C _1-6 alkyl, CH ₂CH₂ OH, pyridin-2-ylmethyl, and CH ₂ COOH, or N where one of R is connected to the other Q through an ethylene bridge; and

R1, R2, R3, R4, R5 and R6 are independently selected from: H. c _1-4 alkyl and C _1-4 alkyl hydroxy.

Examples of non-bridged ligands are 1,4,8, 11-tetraazacyclotetradecane (cyclam), 1,4,8, 11-tetramethyl-1, 4,8, 11-tetraazacyclotetradecane (Me 4 cyclam), 1,4,7, 10-tetraazacyclododecane (cyclan), 1,4,7, 10-tetramethyl-1, 4,7, 10-tetraazacyclododecane (Me 4 cyclan) and 1,4,7, 10-tetrakis (pyridin-2-ylmethyl) -1,4,7, 10-tetraazacyclododecane (Py 4 cyclan). For Py4cyclen, iron complexes are preferred.

Preferred bridging ligands are of formula (V):

Wherein the method comprises the steps of

R1 is independently selected from H, C _1-20 alkyl, C _7-40 alkylaryl, C _2-6 alkenyl, or C _2-6 alkynyl.

All nitrogen atoms in the macrocyclic polycyclic ring may coordinate to the transition metal. In formula (VI), each R1 may be the same. Where each R ¹ is Me, this provides the ligand 5, 12-dimethyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane (L), a complex [ Mn (L) Cl ₂ ] of which can be synthesized according to WO 98/39098. Where each r1=benzyl, this is the ligand 5, 12-dibenzyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane (L '), the complex [ Mn (L') Cl ₂ ] of which can be synthesized as described in WO 98/39098. Other suitable bridging ligands are described in WO 98/39098.

TRISPICEN type of lamp

Trispecen is preferably in the form of an iron transition metal catalyst. the trispecen-type ligand is preferably of formula (VI):

R17R17N-X-NR17R17 (VI)，

wherein:

x is selected from-CH ₂CH₂-、-CH₂CH₂CH₂-、-CH₂C(OH)HCH₂ -;

Each R17 independently represents a group selected from: c _1-8 alkyl; c _3-8 cycloalkyl; a heterocycloalkyl selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, 1,4, 7-triazacyclononyl, 1,4,8, 11-tetraazacyclotetradecyl, 1,4,7,10, 13-pentazapentadecyl, 1, 4-diaza-7-thia-cyclononyl, 1, 4-diaza-7-oxa-cyclononyl, 1,4,7, 10-tetraazacyclododecyl, 1, 4-dioxanyl, 1,4, 7-trithia-cyclononyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be attached to the compound through any atom in the ring of the heterocycloalkyl of choice; heteroaryl groups selected from the group consisting of: pyridyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3, 5-triazinyl; quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl can be attached to the compound through any atom in the ring of the heteroaryl of choice; aryl selected from homoaromatic homopolymers having a molecular weight below 300; and C _7-40 aralkyl optionally substituted with a substituent selected from the group consisting of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylate, sulfonate, amine, alkylamine, and N ⁺(R19)₃, wherein

R19 is selected from the group consisting of hydrogen, C _1-8 alkyl, C _2-6 alkenyl, C _7-40 aralkyl, C _7-40 aralkenyl, C _1-8 oxyalkyl, C _2-6 oxyalkenyl, C _1-8 aminoalkyl, C _2-6 aminoalkenyl, C _1-8 alkyl ether, C _2-6 alkenyl ether, and-CY ₂ -R18, wherein each Y is independently selected from H, CH ₃、C₂H₅、C₃H₇, R18 is independently selected from optionally substituted heteroaryl selected from the group consisting of: a pyridyl group; pyrimidinyl; pyrazinyl; triazolyl; a pyridazinyl group; 1,3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; an oxazolidinyl group; a pyrrole group; carbazolyl; indolyl; and isoindolyl, wherein said heteroaryl can be attached to said compound through any atom in the ring of the heteroaryl of choice; and at least two R17 are-CY ₂ -R18.

The heteroatom donor group is preferably pyridinyl optionally substituted with-C ₁-C₄ alkyl, for example 2-pyridinyl.

Other preferred heteroatom donor groups are imidazol-2-yl, 1-methyl-imidazol-2-yl, 4-methyl-imidazol-2-yl, imidazol-4-yl, 2-methyl-imidazol-4-yl, 1-methyl-imidazol-4-yl, benzimidazol-2-yl and 1-methyl-benzimidazol-2-yl. Preferably, three R17 are CY ₂ -R18.

The ligand Tpen (N, N, N ', N' -tetrakis (pyridin-2-yl-methyl) ethylenediamine) is disclosed in WO 97/48787. Other suitable trispecen are described in WO 02/077145 and EP 1001009A.

Preferably, the ligand is selected from the group consisting of 2, 4-bis- (2-pyridinyl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylic acid dimethyl ester, 2, 4-bis- (2-pyridinyl) -3-methyl-7- (N, N-dimethyl-amino-ethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylic acid dimethyl ester, 5, 12-dimethyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane, 5, 12-dibenzyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane, N-bis (pyridin-2-yl-methyl-1, 1-bis (pyridin-2-yl) -1-aminoethane and N, N-bis (pyridin-2-yl-methyl-1, 1-bis (pyridin-2-yl) -phenyl-1-aminoethane.

Other ligands

Other multidentate promoting ligands known to those skilled in the art may also be used, as will be discussed below. Typically, these ligands can be used in preformed transition metal complexes that contain multiple promoting ligands.

First, the multidentate promoting ligand may be a bidentate nitrogen donor ligand, such as 2,2' -bipyridine or 1, 10-phenanthroline, both of which are known in the art for use as multidentate promoting ligands in metal driers. Typically 2,2' -bipyridine or 1, 10-phenanthroline is provided as a ligand in a manganese or iron containing complex. Other bidentate multidentate facilitating ligands include bidentate amine-containing ligands. 2-aminomethylpyridine, ethylenediamine, tetramethyl ethylenediamine, diaminopropane and 1, 2-diaminocyclohexane.

A variety of bi-to hexadentate oxygen-containing donor ligands are also known, including mixed oxygen-containing and nitrogen-containing donor ligands. For example, WO 03/029371A1 describes tetradentate diimines of the formula:

R₁-C(A₁-O)＝N-R₂-N＝C(A₂-O)-R₃

wherein:

Both a ₁ and a ₂ are aromatic residues;

R ₁ and R ₃ are covalently bonded groups, such as hydrogen or organic groups; and

R ₂ is a divalent organic group.

The use of 1, 3-diketones as multidentate promoting ligands is described in both EP 1382648 A1 and WO 00/11090A1 and EP 1382648 also describes the use of complexes comprising 1, 3-diketones (or 1, 3-diimines) and bidentate diamines (including bipyridines and phenanthrolines).

As used in the present application, BOC is iron (1+), chloro [ dimethyl 9, 9-dihydroxy-3-methyl-2, 4-bis (2-pyridinyl-kN) -7- [ (2-pyridinyl-kN) methyl ] -3, 7-diazabicyclo [3.3.1] nonane-1, 4-dicarboxylate-kN 3, kN7] chloride (1:1) as shown below.

As used herein, the term "secondary drier", synonymous "co-drier" refers to Calcium-Hydrochem (based on Calcium neodecanoate in organic solvents, borchers); and Octa Soligen Zirconium aqua (zinc 2-ethylhexanoate in organic solvent, borchers) and other co-driers having similar characteristics to those described above. In addition, one or more co-driers may be added to the fully formulated oxidatively curable coating composition. Such co-siccatives may be optional additional components in the formulations of the present application, but are not typically present in the formulations of the present application. Such auxiliary driers include fatty acid soaps of zirconium, bismuth, barium, cerium, calcium, lithium, strontium and zinc. Typically, fatty acid soaps are optionally substituted octanoates, hexanoates, and naphthenates. Without being bound by theory, a co-drier (sometimes referred to as a dry-out agent) is generally understood to reduce the adsorption of the main drier to solid particles typically present in oxidatively curable coating compositions. Other non-metal based auxiliary driers may also be present if desired. The concentration of the co-drier in the oxidatively curable coating composition (or formulation of the application) is typically from about 0.01wt.% to 2.5wt.%, as is known in the art.

The formulations of the present invention can and will typically be used to prepare fully formulated oxidatively curable coating compositions. As known to those skilled in the art, the term "fully formulated oxidatively curable coating composition" refers to an oxidatively curable formulation comprising, in addition to a binder (oxidatively curable material, which is primarily an oxidatively curable alkyd resin according to the invention), other components, an aqueous or non-aqueous solvent/liquid continuous phase and any metal drier for accelerating the curing process. Such other components are typically included to impart desired properties to the coating composition, such as color or other visual characteristics such as gloss or mattness, physical, chemical and even biological stability (e.g., enhanced biological stability imparted to the coating composition by the use of biocides), or modified texture, plasticity, adhesion and viscosity.

For example, such optional additional components may be selected from solvents, antioxidants (sometimes referred to as antiskinning agents), other siccatives, auxiliary siccatives, colorants (including inks and colored pigments), fillers, plasticizers, viscosity modifiers, UV light absorbers, stabilizers, antistatic agents, flame retardants, lubricants, emulsifiers (especially when the oxidatively curable coating compositions or formulations of the invention are water-based), defoamers, viscosity modifiers, stain repellents, biocides (e.g., bactericides, fungicides, algicides, and insecticides), preservatives, antireflective agents, antifreeze agents, waxes, and thickeners. Typically, the formulation prepared according to an embodiment of the method of the second aspect of the invention will comprise, in addition to the alkyd resin and optionally other binders and chelating agents present in the formulation of the invention, at least one organic solvent selected from the list of solvents described above, a filler and a general antiskinning agent. Those skilled in the art are familiar with the incorporation of these and other components into oxidatively curable coating compositions to optimize the properties of such compositions.

It will be appreciated that some of these optionally present other components have more than one functional property. For example, some fillers may also be used as colorants. The nature and amount of any other components may be determined according to the knowledge of one skilled in the art and will depend on the intended application of the curable coating composition. Examples of other components that may optionally be present are discussed in the following paragraphs, which are intended to be illustrative and not limiting.

As used herein, the term "environmental conditions" refers to temperature and humidity, i.e., laboratory conditions, rather than climate controlled conditions.

The invention provides air-drying paint containing vanadium compounds taking sulfonic acid anions as counter ions and application of the compounds in the air-drying paint. These driers significantly accelerate the drying and hardening of the alkyd resin. They are suitable for solvent-borne, aqueous, high solids coatings and other monomer-modified alkyd coatings. Furthermore, they are useful in inks and composite coatings.

According to the invention, the drier is a compound of formula (VII):

Wherein R ¹ and R ² are independently selected from the group consisting of: hydrogen, C ₁-C₁₂ alkyl, C ₁-C₈ fluoroalkyl, C ₆-C₁₀ aryl, benzyl; and wherein aryl and benzyl may be optionally substituted with one to three substituents independently selected from C ₁-C₂₀ alkyl, hydroxy (C ₁-C₂) alkyl.

As used herein, "alkyl" may be straight or branched. Preferably, the alkyl is a C ₁-C₁₂ alkyl, more preferably a C ₁-C₆ alkyl. A non-exhaustive list of examples of suitable alkyl groups are CH₃、C₂H₅、C₃H₇、C₄H₉、C₅H₁₁、C₆H₁₃、C₇H₁₅、C₈H₁₇、C₉H₁₉、C₁₀H₂₁、C₁₁H₂₃ and C ₁₂H₂₅. In some embodiments, the alkyl group may be a C ₁₃-C₂₀ alkyl group. The alkyl groups may be substituted by halogen, in particular fluorine. Fluoroalkyl may preferably be linear fluoroalkyl, non-limiting examples of which include ：CF₃、C₂F₅、C₃F₇、C₄F₉、C₅F₁₁、C₆F₁₃、C₇F₁₅ and C ₈F₁₇.

As used herein, "aryl" may be, for example, phenyl (C ₆H₅) or naphthyl (C ₁₀H₇). Substituted aryl groups may include, for example, p-tolyl (CH ₃C₆H₄), 1, 4-dimethylphenyl ((CH ₃)₂C₆H₃), 2,4, 6-trimethylphenyl ((CH ₃)₃C₆H₂), 4-ethylphenyl (C ₂H₅C₆H₄), 4-isopropylphenyl (C ₃H₇C₆H₄), 4-undecylphenyl (C ₁₁H₂₃C₆H₄), 4-dodecylphenyl (C ₁₂H₂₅C₆H₄), 4-tridecylphenyl (C ₁₃H₂₇C₆H₄), 4-hexadecylphenyl (C ₁₆H₃₃C₆H₄), 4-octadecylphenyl (C ₁₈H₃₇C₆H₄), 4-methoxyphenyl ((OCH ₃)C₆H₄).

As used herein, "benzyl" is a substituent of formula CH ₂C₆H₅.

The subject of the invention is a coating formulation comprising a binder curable by an autoxidation mechanism and at least one drier, an example of which is a vanadium compound of formula I.

As used in the present application, the formula of cobalt 2-ethylhexanoate ("Co-2 EH") is shown below:

As used in the present application, the molecular formula of vanadyl acetylacetonate ("V-acac") is shown below:

as used in the present application, the formula of "V-SO" is as follows:

The binders curable by the autoxidation mechanism may be alkyd resins or variants of alkyd resins such as acrylic modified alkyd resins, epoxy ester resins and resins modified by vegetable oils or fatty acids.

Preferably, the coating contains one or more siccatives of formula I in a total concentration of at least 0.001wt.%, preferably 0.003 to 0.3wt.%, more preferably 0.006 to 0.3wt.%, most preferably 0.01 to 0.06wt.% vanadium based on dry matter of the coating.

For example, the coating is prepared by dissolving the drier of formula I, followed by treating with an air-dried binder and homogenizing the mixture. The catalyst may be added to the coating formulation in any order, or even the vanadium source and the sulfonic acid source may be used as separate components. Preferably, the siccatives are dissolved in a polar organic solvent, such as dimethyl sulfoxide (DMSO), an ester, an ether, a solvent having more than one alcohol, ester, ether functional group (e.g., a solvent such as Texanol (2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (CAS Reg. No. 25265-77-4) and an alcohol or mixture thereof).

By selecting the R ¹ and R ² groups in formula (VII), the siccatives can be dissolved in any organic solvent. It has been found that the preparation of the siccatives of formula (VII) may be unstable in water-based formulations and easily degrade or precipitate when diluted in water. Which makes them unsuitable for many applications. This problem has been solved by using a water miscible solvent mixture (e.g. an alcohol-ester solvent mixture, e.g. combining 2-methyl-1-pentanol and isobutyl acetate) and a carboxylic acid (e.g. acetic acid). It is believed that the acid provides an important function in the stabilization of the catalyst, as it is well known that vanadate oligomerization, which may lead to deactivation of the siccatives, is sensitive to pH and concentration (see J.J.Cruywagen,in Advances in Inorganic Chemistry,Vol.49(Ed.:A.G.Sykes),Academic Press,1999,pp.127-182). solvent mixture improves the long term stability of the complex and its incorporation in the coating.

Depending on the application, the siccatives based on formula (VII) may be dissolved in water or polar organic solvents, such as dimethyl sulfoxide (DMSO), acetic acid, alcohols, esters, ethers and mixtures thereof.

The drier of formula (VII) wherein R ¹ and R ² contain the same or different C ₁₀-C₂₀ alkyl chains (e.g. 4-dodecylphenyl) is found to be a viscous liquid miscible with aromatic hydrocarbon solvents such as toluene and xylene. This makes the handling of the siccatives possible even in industrial applications, since only the solvents commonly used in the paint production industry are required. This is particularly useful when the binder is a solvent-based or high solids resin.

Alternatively, the coating may be prepared by dissolving the drier directly in the air-drying binder. This is particularly useful when the siccatives are compounds of formula (VII) wherein R ¹ and R ² contain the same or different C ₁₀-C₂₀ alkyl chains (e.g. 4-dodecylphenyl).

The invention relates to the use of vanadium compounds of formula (VII) as siccatives for coatings containing binders curable by an autoxidation mechanism.

It has been found that the siccatives of formula (VII) are active at a resin solids concentration of 0.001 to 0.1wt.% metal based on the air-drying paint.

One of the main advantages of the drier of formula (VII) according to the present invention compared to the currently known vanadium-based driers is that it is simply synthesized in one step from readily available and inexpensive starting materials. The compounds of formula I are easily modified by substitution of the substituents R ¹ and R ², which makes it possible to ensure satisfactory solubility in the organic solvents used for coating production. Furthermore, the compounds of formula (VII) can be easily dissolved in readily available and non-toxic solvent water, among other solvents and carboxylic acids, to ensure stability and effectiveness. The siccatives of formula (VII) are generally blue or green.

Another advantage of the drier of formula (VII) is that the stock solution of the drier of formula (VII) can be stored under an air atmosphere without losing catalytic activity. This makes the treatment of the stock solution possible even for industrial applications, since no inert atmosphere and/or no oxygen conditions are required.

A further advantage of this over the currently known vanadium-based driers is the improved stability to atmospheric oxygen and the ability to cure a wider range of alkyd-based coatings. The compounds of formula I exhibit catalytic activity at much lower concentrations than the cobalt-based driers currently in widespread use. Surprisingly, it has been observed that the siccatives of formula (VII) are combined with catalysts based on cobalt and bispidon, such asOxyCoat may provide improved stiffness compared to the other. In addition, it is noted that it is preferable to combine with other catalysts and amine-based ligands to help further increase hardness.

Another advantage is the relative toxicity, and the product of formula (VII) is expected to produce a non-toxic alternative to existing vanadium catalysts such as vanadyl acetylacetonate.

The siccatives of formula (VII) may be prepared by reacting vanadium (V) oxide with a suitable sulfonic acid or mixture of sulfonic acids (R ¹SO₃H、R²SO₃ H, where R ¹ and R ² may be the same or different) in a water-ethanol mixture in a volume ratio of 1:2.

Compounds of the type given in formula (VII) were previously synthesized by several methods. Vanadyl sulfate is reacted with a suitable barium sulfonate salt for preparing vanadyl triflate (Krakowiak;Inorg.Chem.51,9598-9609(2012))and oxidovanadium p-toluenesulfonate(Movius,W.G.Et al;J.Am.Chem.Soc.92,2677-2683,(1970)).

Another literature method utilizes solvolysis of vanadyl acetylacetonate with p-toluenesulfonic acid (Holmes, S.M. et al; inorg. Synthh. 33,91-103, (2002)). Anhydrous vanadyl mesylate may be prepared by reacting vanadyl chloride (V) with methanesulfonic acid in chlorobenzene, or by direct solvolysis of vanadyl chloride (IV) with methanesulfonic acid (Kumar, S.et al; indian J.chem.23A,200-203, (1984)). The process presented in the present invention uses vanadium (V) oxide (CAS: 1314-62-1) as the vanadium source, which is quite advantageous from an economic point of view when compared to the aforementioned raw materials. Ammonium metavanadate may be used as another economical source of vanadium for the preparation of compounds.

The invention also includes the compound vanadyl p-dodecylbenzenesulfonate, corresponding to formula (VII), wherein R ¹ and R ² are dodecylphenyl. The compounds represent novel compounds prepared within the framework of the present invention.

Embodiments of the invention

Alkyd resin CHS-alkyds 471X 60 (oil=47%, acid number 6mg KOH/g), S471, CHS-alkyds TI870 (oil=87%, acid number 8mg KOH/g), TI870, obtained from Spolchemie a.s. Alkyd resinsSPS15-60D (oil level=50%, acid value 10mg KOH/g, silicone content=30%), SPS15, obtained from Safic-Alcans.r.o.。

Vanadium (V) oxide, methanesulfonic acid, p-toluenesulfonic acid monohydrate, vanadyl sulfate hydrate (V-SO), 2-methyl-1-pentanol and dimethyl sulfoxide (DMSO) were obtained from Acros-Organics. Cobalt 2-ethylhexanoate (Co-2 EH) was obtained from Sigma-Aldrich. Acetic acid was obtained from Riedel-de-Haen. Isobutyl acetate was obtained from ALFA AESAR.

Borchi Oxy-Coat 1101 (BOC 1101 in water), borchi Oxy-Coat (BOC in propylene glycol), borchers Deca Cobalt Aqua (in an organic solvent mixture), borchers Deca Cobalt 10 (in a hydrocarbon solvent) and N, N-trimethyl-1, 4, 7-triazacyclononane (TMTACN) were obtained from Borchers.

Binder solutions SYNAQUA 4804 (aqueous short oil alkyd) and SYNAQUA 2070 (aqueous medium oil alkyd) were obtained from archema; beckosol AQ101 (aqueous long oil alkyd) was obtained from Polyont Composites USA inc., world eKyd S351 (solvent medium oil alkyd) was obtained from world, TOD 3AK0211Y (water dilutable alkyd) was obtained from China TOD.

EXAMPLE 1 Synthesis of vanadyl mesylate ("V-MS")

A suspension of vanadium (V) oxide (5.6 g) in a mixture of ethanol (30 mL) and distilled water (15 mL) was treated with methanesulfonic acid (16 mL) and heated at 110℃for 3 hours. The solution was dark blue, filtered and the volatiles evaporated. The product was washed with diethyl ether and dried in vacuo to give a blue solid. Yield: 15.9g. Elemental analysis (C ₂H₁₆O₁₂S₂ V): calculated: c,6.92; h,4.64; s,18.47. The discovery is as follows: c,6.78; h,4.81; s,18.11.EPR (H2O): aiso |=116.4X10-4T; giso= 1.966.

EXAMPLE 2 Synthesis of vanadyl triflate V-FS

A suspension of vanadium (V) oxide (5.6 g) in a mixture of ethanol (30 mL) and distilled water (15 mL) was treated with trifluoromethanesulfonic acid (22 mL) and heated at 110℃for 6 hours. The solution was blue-green, filtered and the volatiles evaporated. The product was washed with diethyl ether and dried in vacuo to give a blue-green solid. Yield: 21.8g. Elemental analysis (C ₂H₁₀F₆O₁₂S₂ V): calculated: c,5.28; h,2.21; s,14.09. The discovery is as follows: c,5.37; h,1.99; s,14.22.Epr (H ₂O):|A_iso|＝116.4×10^-4T;g_iso = 1.966.

EXAMPLE 3 Synthesis of vanadyl benzenesulfonate V-BS

A suspension of vanadium (V) oxide (5.6 g) in a mixture of ethanol (30 mL) and distilled water (15 mL) was treated with benzenesulfonic acid (39 g) and heated at 110℃for 3 hours. The solution was dark blue, filtered and the volatiles evaporated. The product was washed with diethyl ether and dried in vacuo to give a blue solid. Yield: 27.5g. Elemental analysis (C ₁₂H₂₀O₁₂S₂ V): calculated: c,30.58; h,4.28; s,13.61. The discovery is as follows: c,30.72; h,4.39; s,13.80.Epr (H ₂O):|A_iso|＝116.4×10^-4T;g_iso = 1.966.

EXAMPLE 4 Synthesis of vanadyl p-toluenesulfonate ("V-TS")

A suspension of vanadium (V) oxide (56 g) in a mixture of ethanol (300 mL) and distilled water (150 mL) was treated with p-toluenesulfonic acid monohydrate (700 g) and heated at 110℃for 3 hours. The solution was dark blue, filtered and the volatiles evaporated. The product was washed with diethyl ether and dried in vacuo to give a blue solid. Yield: 290 grams. Elemental analysis (C ₁₄H₂₄O₁₂S₂ V): calculated: c,33.67; h,4.84; s,12.84. The discovery is as follows: c,33.48; h,4.96; s,12.51.EPR (H2O): aiso |=116.4X10-4T; giso= 1.966.

EXAMPLE 5 Synthesis of vanadyl p-dodecylbenzenesulfonate V-DS

A suspension of vanadium (V) oxide (5.6 g) in a mixture of ethanol (30 mL) and distilled water (15 mL) was treated with p-dodecylbenzenesulfonic acid (48 g) and heated at 110℃for 6 hours. The solution was dark blue, filtered and the volatiles evaporated. The product was washed with hexane at-20 ℃ and dried under vacuum to give a blue highly viscous liquid miscible with aromatic hydrocarbon solvents (e.g. toluene, xylene). Yield: 44.3g. Elemental analysis (C ₃₆H₆₈O₁₂S₂ V): calculated: c,53.51; h,8.48; s,7.94. The discovery is as follows: c,53.85; h,8.84; s,7.67.Epr (acetone): a _iso|＝117.3×10^-4T;g_is o= 1.966.

EXAMPLE 6 Effect of substituents on solvent-borne alkyd curing

The catalytic activity of vanadyl sulfonate on a medium oil alkyd resin modified with a vegetable drying oil S471 was determined. The effect of substituents was studied in five derivatives. The given siccatives were dissolved in DMSO (100 μl) and treated with alkyd S471 (5 g) and the resulting mixture homogenized for 2 minutes. The formulation was cast onto glass plates (size: 305X 25X 2 mm) by a 76 μm gap frame coater. According toEN ISO 9117-4, touch dry time (T ₁), skin dry time (T ₂), hard dry time (T ₃) and dry-through time (T ₄) were measured on a B.K. drying recorder (BYK). The relative hardness of the formulation cast on a glass plate (size: 200X 100X 4 mm) was measured by a frame coater with a 150 μm gap. According toEN ISO 1522, relative hardness was determined 100 days after application using a pendulum durometer with a Persoz pendulum (Elcometer). The drying time and relative hardness were determined under standard laboratory conditions (t=23 ℃, relative humidity=50±10%). Formulations of V-acac and V-SO were prepared in a similar manner. Co-2EH available from suppliers was used.

The drying times given in table I indicate that vanadyl sulfonates have high catalytic activity at concentrations of 0.01 to 0.06wt.% vanadium on a dry matter basis. At this concentration range, all derivatives studied gave completely dried films within 13.0 hours (T ₄. Ltoreq.13.0 hours). At the optimum level (0.03 wt.%) the siccatives gave films with hard surfaces in 3.4 hours (T ₃.ltoreq.3.4 hours) and completely dried films in 5.3 hours (T ₄.ltoreq.5.3 hours). V-TS at concentrations up to 0.003wt.% remains highly active. At this dose, a completely dry film was observed at 14.1 hours after casting. Notably, the drying activity of V-TS was observed even at very low concentrations. At 0.001wt.%, the tack-free time does not exceed 12.9 hours (T ₂ =12.9 hours). We note that V-TS was chosen for the study of other binders due to the catalytic activity observed at very low concentrations.

The relative hardness of the film cured by vanadyl sulfonate measured 100 days after casting of the formulation varied between 32.6% and 52.8%.

Comparison with the drying time of cobalt-based driers (Co-2 EH) demonstrated that V-MS, V-FS, V-BS, V-TS and V-DS worked at much lower concentrations than the commercial driers. The vanadium-based drier V-acac showed lower activity than all vanadyl sulfonates studied at a concentration of 0.03 wt.%. The structural analogues of the compounds with sulfate anions (V-SO) presented herein are totally inactive.

The drying times given in table I indicate that the sulfonate anion containing vanadium compounds have high catalytic activity at concentrations of 0.006-0.06wt.% vanadium on a dry matter content basis. At this concentration range, both derivatives (V-MS and V-TS) gave a completely dried film within 13.9 hours (T ₄. Ltoreq.13.9 hours). At the optimum dose, the aliphatic group containing derivative (V-MS; 0.03 wt.%) gave a film with a hard surface within 3.4 hours (T ₃ =3.4 hours) and a completely dried film within 4.4 hours (T ₄ =4.4 hours).

At the optimum concentration (0.03 wt.%), a film with a hard surface was obtained within 1.2 hours (T ₃ =1.2 hours) using a drier with an aromatic ring (V-TS), and after 2.4 hours (T ₄ =2.4 hours) a completely dried film was already obtained. Notably, drying activity has been observed at very low concentrations (0.001 wt.%). In this case, the tack-free time does not exceed 12.9 hours (T ₂ =12.9 hours).

The relative hardness of the film measured 100 after casting of the formulation varied between 43.0 and 52.8%. Since catalytic activity was observed at very low concentrations (0.003 wt.%) V-TS was chosen for investigation of other binders. A completely dry film was obtained within 14.1 hours.

Comparison with the drying time of cobalt-based driers (Co-2 EH) demonstrates that V-MS and V-TS function at much lower concentrations than commercial driers. The vanadium-based drier V-acac shows lower activity than VMS and V-TS at a concentration of 0.03 wt.%. Structural analogues of compounds with sulfate anions (V-SO) are totally inactive.

TABLE I

^a The formulation was dry to the touch immediately after casting,

^b Not measured due to low surface dryness or surface defects.

EXAMPLE 7 curing of high solids alkyd resins

The catalytic effect of the high-solids binder was evaluated with a drier V-TS and a high-solids binder TI 870. The siccatives were dissolved in DMSO (100 μl) and treated with the given alkyd resin (5 g). The mixture was diluted with dearomatized white spirit to 90wt.% dry matter and homogenized for 2 minutes. The drying time was measured on a formulation cast on a glass plate through a 76 μm gap frame coater. The formulation was coated on a plate for determining relative hardness using a 90 μm gap frame coater. Formulations Co-2EH, V-acac and V-SO were prepared in a similar manner.

The measured dry times and relative hardness values are given in table II. Formulation V-TS/TI870 exhibits catalytic activity at 0.01-0.1wt.% vanadium on a dry matter basis. For this high solids binder, the optimum concentration of drier was determined to be 0.06wt.%. The relative hardness of the films measured 100 days after casting the formulation varied between 17.1% and 24.9%.

Formulation V-TS/TRI841 exhibited catalytic activity at 0.01 to 0.1wt.% vanadium on a dry matter basis. For this high solids binder, the optimum concentration of drier was determined to be 0.03wt.%. The relative hardness of the films measured 100 days after casting the formulation varied between 15.5% and 21.5%.

Comparison with the drying time of the cobalt-based drier Co-2EH shows that the formulation containing V-TS dries better. In practice, the formulation treated with Co-2EH did not dry completely within 24 hours (T ₄ >24 hours), whereas the formulation of V-TS dried completely within 11.5 hours (T ₄. Ltoreq.11.5 hours). The vanadium compounds V-acac and V-SO were inactive at a concentration of 0.06wt.% in the binders TI870 and TRI 841.

Table II

^a Not measured due to low surface dryness or surface defects

Table III

^a Not measured due to low surface dryness or surface defects.

Example 8-curing of alkyd resins modified with another monomer.

The catalytic effect of the siliconized alkyd binder was evaluated with the drier V-TS and the resin SPS 15. The siccatives were dissolved in DMSO (100 μl), treated with a given alkyd resin (5 g) and homogenized for 2 minutes. The drying time was measured for the formulation cast on a glass plate by a frame coater with a 76 μm gap. The formulation was coated on a plate for determining relative hardness using a 150 μm gap frame coater. Formulations Co-2EH, V-acac and V-SO were prepared in a similar manner.

The measured dry times and relative hardness values are given in table IV. Formulation V-TS/SPS15 showed catalytic activity at 0.003 to 0.06wt.% vanadium on a dry matter basis. For this siliconized binder, the optimum concentration of drier was determined to be 0.03wt.%, which is comparable to the medium oil solvent alkyd binder S471. The relative hardness of the films measured 100 days after casting the formulation varied between 32.8% and 46.2%.

Comparison with the drying time of the cobalt-based drier Co-2EH shows that V-TS is catalytically active at much lower concentrations than the commercial cobalt drier. The vanadium compounds V-acac and V-SO were inactive at a concentration of 0.06 wt.%.

Table IV

^a The formulation was dry to touch immediately after casting

^b Not measured due to low dryness or surface defects

EXAMPLE 9 curing of waterborne alkyd and full-paint formulations

The catalytic effect in aqueous systems was evaluated with a drier V-TS in alkyd resin FP262 and in commercial white paint MLP 9289 based on resin FP 262. V-TS (1 g) was dissolved in distilled water (2 g) to obtain a stock solution, which was used to prepare a formulation. The drying time was measured for the formulation cast on a glass plate by a frame coater with a 76 μm gap. Formulations of V-SO were prepared in a similar manner. The V-acac was pre-dissolved in DMSO prior to use. Co-2EH available from suppliers was used.

The measured drying times for formulations FP262 and MLP 9289 are given in tables V and VI, respectively.

Formulation V-TS/FP262 showed high catalytic activity at 0.03 to 0.06wt.% vanadium on a dry matter content basis. At this dose, the open time (T ₂) varied between 2.0 and 5.6 hours; the dry hardening time (T ₃) varied between 6.0 and 11.7 hours. For aqueous resin FP262, the optimum concentration of the drier was determined to be 0.06wt.%. Under the action of Co-2EH, the curing speed of FP262 is faster, but the uniformity is obviously poorer. This is demonstrated by the increase in T ₃ as the concentration increases.

The alkyd-full coating V-TS/MLP 9289 shows high catalytic activity at 0.03-0.06wt.% vanadium on a dry matter basis of the resin. For MLP 9289, the optimum concentration of the siccative was determined to be 0.06wt.%, which is comparable to binder FP 262. This demonstrates that pigments and other additives have little effect on the catalytic activity of the dryer V-TS.

The vanadium compounds V-acac and V-SO were inactive at a concentration of 0.06 wt.%. Notably, no aqueous system was completely dried within 24 hours in this study.

Table V

Table VI

EXAMPLE 10 stability of vanadyl sulfonate in solution

The stability of the siccatives V-TS and V-DS in solution was evaluated. V-TS (1 g) was dissolved in DMSO (4 g) to give a blue solution and stored in a closed glass vial (10 mL) under an air atmosphere at room temperature. The drying time was determined for solvent borne alkyd S471 formulation cast on glass plates by a 76 μm gap frame coater and compared to freshly prepared V-TS solution. The stability of V-DS was evaluated in a similar manner using a solution prepared from V-DS (1 g) and xylene (1 g). Note that the stock solution showed no visual change upon storage.

The measured drying times are given in table VII. The solution of V-TS in DMSO showed only a slight change in catalytic activity over 30 days of storage, as demonstrated by formulation S471, which had a concentration of 0.01 to 0.03wt.% vanadium on a dry matter content basis. In the study, all formulations of V-TS were completely dried within 5.2 hours (T ₄.ltoreq.5.2 hours). Acceptable reduction in catalytic activity was also observed for the V-DS in xylene solution. Storage for 9 days at a concentration of 0.01 to 0.03wt.% prolonged the curing process of the xylene solution. The dry-out time (T ₄) was about twice the value observed for fresh solution.

Table VII

EXAMPLE 11 stability of coating formulation

The stability of V-TS in the coating formulation was evaluated on alkyd resin S471 treated with an antiskinning agent. A solution of V-TS in DMSO (1:4 weight mixture) was treated with alkyd S471 (25 g) and butanone oxime (30 mg). The formulation was dosed into glass vials (5 mL) and stored at room temperature. The drying time was measured for the formulation cast on a glass plate by a frame coater with a 76 μm gap.

The drying times measured are given in table VIII, for a V-TS with a metal concentration of 0.03wt.%, a negligible change in catalytic activity was noted on storage, since the stored formulation was completely dried within 2.1 hours (T ₄ =1.1 to 2.1 hours), whereas the fresh formulation was dried within 1.7 hours (T ₄ =1.7 hours). At lower doses (0.01 wt.%) a slight decrease in activity was observed over 7 days, as evidenced by a delay in T ₄ from 7.1 hours to 12.8 hours. After this period of time, the formulation was stable, as only insignificant changes in drying time were observed.

Table VIII

Experimental details of examples 12 to 18:

In most cases, V-TS is used as an aqueous solution, which must be freshly prepared on the day of use, because it forms a large amount of precipitate after standing for several hours (typically >12-24 hours). V-TS can also be dissolved in polar organic solvents without precipitate formation, but the experience obtained with these solutions is limited.

If alkali (ethanolamine) is added, it is found that the freshly prepared V-TS aqueous solution directly gives a large amount of precipitate. However, when V-TS (10%) was dissolved in a 98:2 water: acetic acid solution, a stable solution was produced for more than two weeks.

Vanadyl p-dodecylbenzenesulfonate ("V-DS") can be dissolved in most organic solvents and these solutions appear to be stable. For use in SB formulations, xylene solutions are used. For use in WB formulations, a 70:30 mixture of 2-methyl-1-pentanol and isobutyl acetate was used.

Formulations for cast films are prepared by weighing an appropriate amount of a drier (typically a stock solution of a prescribed concentration) into a plastic vial, and then weighing the binder solution. The amount of drier is calculated with reference to the value of the dry matter specified for each binder solution. Mixing was achieved by placing the vial into a flash mixer (SpeedMixer DAC 150.1 FVZ) and rotating at 2000 revolutions per minute for 2 minutes. Generally, a mixture of uniform appearance is obtained. The film was left at ambient conditions for 24 hours before casting.

The time required to reach the following dry state was measured using a "b.k.drying receivers model 3" (THE MICKLE laboratory engineering Co ltd.). Dry-to-touch (ST, i.e., no longer free to move through the soft coating, but begin to tear the hardened film); surface drying (TF, i.e. no longer tearing the film but leaving a continuous line on the coating); and hard drying (DH, i.e., without leaving any marks on the film).

A100 μm thick film was cast on a glass bar (30X 2.4 cm) by using a steel cube coater. It was then placed on a dry time recorder, a needle was placed on the membrane, the recorder was set to measure and start over 24 hours. The starting point of the needle onto the film is marked on the glass. The drying time was read from the indicia left on the film after 24 hours. The drying time given as "24 hours" means that the drying time is not less than 24 hours, because the time exceeding 24 hours cannot be confirmed.

The coating and drying times of the glass strips were recorded in a climate-controlled chamber at a temperature of 23℃and a humidity of about 45%.

While casting the film to record the drying time, a film 100 μm thick was cast on a glass sheet (15×9 cm) to measure the hardness. After a given drying time, these were evaluated on a pendulum durometer. By usingThe method (oscillation time measured in seconds, starting from an initial amplitude of 6 ° until an amplitude of 3 ° is reached) measures pendulum hardness on a TQC green pendulum durometer SP 0500. Softer materials attenuate the oscillations of the pendulum more rapidly than harder materials, and therefore softer materials have lower hardness values in seconds than harder materials. The coating, storage and hardness measurements of the glass sheets were carried out in a climate controlled chamber at a temperature of 23 ℃ and a humidity of about 45%.

The catalyst concentration is given in metal%, referring to the amount of metal of the catalyst relative to the solids content of the binder and formulation used, respectively. Typically, the catalyst was used in three concentrations, 0.001 metal%, 0.01 metal% and 0.1 metal% for initial testing. According to the general recommendations for these siccatives, the standard concentrations for BOC and Borchers Deca Cobalt a quat are 0.001 and 0.03 metal%, respectively.

Example 12 additional formulations (see tables IX through XI)

Table IX-11Ycc (TOD 3AK0211Y base clear coating, waterborne)

Table X-11Ywp (TOD 3AK0211Y base white paint, water-based)

Entries	Composition of the components	Type(s)	Quantity (g)
				1	TOD 3AK0211 base transparent paint	Resin formulation	70.0
2	Deionized water	Solvent(s)	8.2
				3	Borchi Gen 1252，Borchers	Dispersing agent	0.6
4	Aminopropanol 95%	Amines	0.1
				5	Borchers AF 1171，Borchers	Additive agent	0.1
6	R996 titanium dioxide	Pigment	21.0

Table XI-vSAcc (Synaqua 4804 base clear coating, water-based)

EXAMPLE 13 curing of aqueous resins

This example shows that the aqueous resin (Synaqua 4804 short oil) can be cured. A given drier is dissolved in water (V-TS) or an alcohol-ester mixture (vanadyl p-toluenesulfonate, ("V-TS")) to ensure homogeneity of the aqueous formulation, for example a mixture of 2-methyl-1-pentanol and isobutyl acetate. The commercial driers BOC-1101 and Deca Cobalt 7 aqua were used as references and the optimum dosage levels were as shown in the technical data sheet.

The drying time and hardness measurements were performed as described in the experimental details section above for examples 12 to 18.

Table XII

^b : Adding 0.01 metal% V-TS;

^c : 0.01% metal V-DS was added.

The data show that both V-TS and V-DS can significantly improve drying times compared to BOC and Co. At high concentrations, V-driers can also exceed cobalt-based driers in terms of hardness after short and long curing times. The combination of BOC-1101 and V drier may be advantageous: the two catalysts are compatible, together providing improved drying time and improved hardness.

Example 14 curing of solvent medium oil alkyd resins

The purpose of this example was to find out whether the V-dryer can be used for curing standard solvent-borne alkyd resins (Worle ekyd S). The given siccatives were dissolved in DMSO (V-TS) and a mixture of 2-methyl-1-pentanol and isobutyl acetate (V-DS).

Table XIII

This example shows that in standard medium oil solvent borne alkyd, the V-drier can significantly improve drying time compared to BOC and Co-driers, and the V-drier can improve hardness compared to BOC.

Example 15 curing of other waterborne alkyd resins

The purpose of this example was to find out whether the V-dryer could be used for the curing of other waterborne alkyd resins. Long oil (Beckosol) and medium oil (Synaqua 2070) were used. The drier V-TS is dissolved in water.

Table XIV

The results show that V-TS can be used as a drier for aqueous long-oil and medium-oil alkyd resins.

EXAMPLE 16 curing of full formulation of Water-dilutable alkyd resins

The purpose of this example was to find out whether the V-dryer could be used for curing of full formulations and water-dilutable alkyd resins (formulation 11 Ycc). In this case a clear coat formulation is used.

The given siccatives were dissolved in DMSO (V-TS) and a mixture of 2-methyl-1-pentanol and isobutyl acetate (V-DS).

Table XV

The results show that the V-drier is compatible with all clear coating formulations and water-dilutable alkyd resins. At medium load (1/3 compared to Co), the long-term hardness reached Co-drier levels, exceeding BOC levels. At high load, the hardness after 7 days has exceeded that of BOC and Co, and the hardness after 29 days is more than twice that of Co.

EXAMPLE 17 curing of coloring formulations of Water-dilutable alkyd resins

The purpose of this example was to find out whether the V-dryer could be used for the curing of the coloring preparation of water-dilutable alkyd resins (preparation 11 Ywp).

Table XVI

The results indicate that the V-dryer is compatible with both the full color formulation and the water-reducible alkyd resin. At moderate loading (1/3 compared to Co), some drying loss in the presence of pigment was observed. Under high load, an improved drying time was observed, with hardness after 7 days exceeding that of BOC and equal to that of Co, which has been exceeded after 14 days, twice that reached by Co after 29 days.

EXAMPLE 18 curing of waterborne alkyd full formulation

The purpose of this example was to find out whether V-siccatives can be used for the curing of the waterborne alkyd (vSAcc) full formulation and whether they are compatible with the added ligand and the secondary siccatives, respectively.

The given V drier was dissolved in a mixture of 2-methyl-1-pentanol and isobutyl acetate.

Table XVII

^a : 1.0 Equivalent TMTACN relative to the drier is added;

^b : adding 0.2% metal of Calcium-Hydrochem;

^c : 0.2 metal% Octa Soligen Zirconium a 10aqua was added;

^d : 0.01% metal V-DS was added.

The results show that the V-siccatives are compatible with the clear coat aqueous formulation, the secondary siccatives and the additional ligands. The addition of the secondary drier increases the drying time and the initial hardness. The combination with ligand TMTACN improves drying time, but it increases long term hardness. Under the same load as Co, the V-drier exceeded the hardness achieved with Co after 28 days. The combination of BOC and V-drier achieved the highest hardness, exceeding Co after 14 and 28 days. This suggests that the synergy between the two catalysts provides overall advantages in hardness and drying time.

Example 19-curing was performed using other acids as additives, including oxalic acid, phosphoric acid and hydrochloric acid.

The purpose of this example was to find out whether various acids (including oxalic acid) could improve the V-dryer in the presence of the additive and ligand respectively.

The V drier was dissolved in an aqueous solution of oxalic acid dihydrate (8%) to give a10 wt.% V-TS solution, wherein oxalic acid is 3 molar equivalents relative to vanadium. Oxalic acid was found to stabilize aqueous solutions in a similar manner to acetic acid.

The drying time and hardness measurements were performed as described in the "experimental details of examples 12 to 19" section above. The experiments in Table XVIII were performed with formulation 11Ycc (the experiments with asterisks indicate the relevant formulations) and the experiments in Table XIX were performed with Synaqua 4804short oil.

Table XVIII

Table XIX

The results in Table XVIII show that the hardness is improved in the presence of oxalic acid on one day compared to the experiments without oxalic acid (3 and 4). Instead of acetic acid (5-7), 2% phosphoric acid and hydrochloric acid were also tested, respectively, which indicated that these other two acids also stabilized the aqueous solution of the drier and that phosphoric acid could increase the hardness of the day. The results in table XIX show that while oxalic acid slightly increases the drying time, it increases the one-day hardness of the coating. Although oxalic acid is exemplified above and is a C ₂ dicarboxylic acid, the kind of acid that should increase the hardness of the coating is not limited to only such dicarboxylic acid. In fact, acetic acid (a C ₁ monocarboxylic acid) is also known to be effective. It is reasonable that all of the C ₁-C₁₈ monocarboxylic acids and C ₂-C₁₈ dicarboxylic acids will also effectively increase the hardness of the coating.

It is entirely unexpected that the addition of mineral acids such as phosphoric acid and hydrochloric acid (a class of acids that is quite different from the acids previously tested) resulted in increased hardness compared to monocarboxylic and dicarboxylic acids. In at least one aspect of the invention, the addition of an acid will help prevent decomposition and precipitation of the drier from at least the aqueous solution. While phosphoric acid and hydrochloric acid are two examples of mineral acids, there are other examples. It is believed that the present invention can be applied to, but is not limited to: nitric acid-HNO ₃, sulfuric acid-H ₂SO₄, boric acid-H ₃BO₃, hydrobromic acid-HBr, perchloric acid-HClO ₄, hydroiodic acid-HI, and the like, including combinations thereof.

In a specific application, a combination of at least one organic acid and at least one inorganic acid is used.

Alkyd binders used in this experimental aspect of the invention were SYNAQUA 4804 (waterborne short oil alkyd, arcema) and TOD 3AK0211Y (water-dilutable alkyd, TOD, china). The drier solutions used were Borchi Oxy-Coat 1101 (BOC 1101 in water, borchers) and UPA-FS2 (vanadium-based drier, 9.4% V).

The formulations used are abbreviated herein as "vSAcc" and "11Ya-cc" as follows.

Table XX: formulation vSAcc (Synaqua 4804 base clear coating, aqueous)

Expt.	Composition of the components	Type(s)	Measuring amount
				1	Synaqua 4804	Resin composition	95.0
2	Borchi Gel 0435	Rheology modifier	1.5
				3	DBE-5	Additive agent	3.5

Resin solids content: 30.2%

Table XXI: formulation 11Ya-cc (TOD 3AK0211 base clear coating, waterborne)

Resin solids content: 31.4%

Formulations for cast films are prepared by weighing an appropriate amount of a drier (typically a stock solution of a prescribed concentration) into a plastic vial, and then weighing the binder solution or formulation. The amount of drier is calculated with reference to the value of the dry matter specified for each binder solution. Mixing was achieved by placing the vial into a flash mixer (SpeedMixer DAC 150.1 FVZ) and rotating at 2000 revolutions per minute for 2 minutes. Generally, a mixture of uniform appearance is obtained. The film was left at ambient conditions for about 24 hours before casting. BOC-1101 is used as received.

UPA-FS2 is used as an aqueous solution in dilute acid. All dilute acids were prepared in advance to a concentration of 2%, i.e. 98% deionized water and 2% pure acid (acetic acid, phosphoric acid and hydrochloric acid, respectively). In the case of phosphoric acid and hydrochloric acid, a diluted solution was prepared from 85% phosphoric acid and 4N HCl, and appropriate amounts of these acids and water were added to give a solution of these acids at a total concentration of 2% (referring to pure acid). All of these solutions showed no signs of decomposition after 4 months of storage at ambient conditions, in contrast to solutions in deionized water, which formed a relatively large amount of black precipitate within 24 hours after dissolution of the solid drier.

In addition to these three acids, other acids may also be used to stabilize the aqueous solution of the vanadium drier. For example, if the vanadium drier contains 2% of the following acids: sulfuric acid, nitric acid, boric acid, perchloric acid, hydrobromic acid and hydroiodic acid, also obtain a stable aqueous solution of vanadium drier.

In addition, other concentrations of acid also provide stable solutions. A solution of 10% V-dryer V-TS in aqueous solution containing 5% HCl and phosphoric acid, respectively, and in 10% phosphoric acid was prepared. These three solutions did not form any precipitate over a period of four months. Lower amounts of acid may also be used, for example, a solution of 5% v-TS in 1% H ₂SO₄ in water is also stable.

The concentration of V-dryer is not limited to 10%. For example, a 0.5% solution of V-TS in acetic acid (2%) in water is also stable for a period of at least three months.

Combinations of acids may also be used. For example, including 1% each of acetic acid and hydrobromic acid and 1% each of nitric acid and hydroiodic acid, for example, also gives a stable aqueous solution.

These results are also summarized in table XXII.

Table XXII: aqueous V-TS solution

Expt.	Drier	% Drier	Acid 1	% Acid 1	Acid 2	% Acid 2	Stable
								1	V-TS	1.0	-	-	-	-	Whether or not
2	V-TS	30.0	-	-	-	-	Whether or not
								3	V-TS	0.5	AcOH	2％	-	-	Is that
4	V-TS	10	AcOH	2％	-	-	Is that
								5	V-TS	10	Oxalic acid	8％	-	-	Is that
6	V-TS	10	H₃PO₄	2％	-	-	Is that
								7	V-TS	10	H₃PO₄	5％	-	-	Is that
8	V-TS	10	H₃PO₄	10％	-	-	Is that
								9	V-TS	10	HCl	2％	-	-	Is that
10	V-TS	10	HCl	5％	-	-	Is that
								11	V-TS	5	H₂SO₄	1％	-	-	Is that
12	V-TS	10	H₂SO₄	2％	-	-	Is that
								13	V-TS	10	HNO₃	2％	-	-	Is that
14	V-TS	10	H₃BO₃	2％	-	-	Is that
								15	V-TS	10	HBr	2％	-	-	Is that
16	V-TS	10	HI	2％	-	-	Is that
								17	V-TS	10	HClO₄	2％	-	-	Is that
18	V-TS	10	AcOH	1％	HBr	1％	Is that
								19	V-TS	10	HNO₃	1％	HI	1％	Is that

Stable: no-precipitate formed in 24-48 hours; the method comprises the following steps: no precipitation was observed for at least 48 hours, typically 3-4 months.

Only the drying time of the formulation using vSAcc was measured. A "b.k. drying receivers model 3" (THE MICKLE laboratory engineering Co ltd.) dry time recorder was used to measure the time required to reach the following dry state: dry-to-touch (ST, i.e., no longer free to move through the soft coating, but begin to tear the hardened film); surface drying (TF, i.e. no longer tearing the film but leaving a continuous line on the coating); and hard drying (DH, i.e., without leaving any marks on the film).

While casting the film to record the drying time, a film 100 μm thick was cast on a glass plate (15×9 cm) to measure the hardness. After a given drying time, these were evaluated on a pendulum durometer. By usingThe method (oscillation time measured in seconds, starting from an initial amplitude of 6 ° until an amplitude of 3 ° is reached) measures pendulum hardness on a TQC green pendulum durometer SP 0500. Softer materials attenuate the oscillation of the pendulum faster than harder materials, and therefore softer materials have lower hardness values in seconds than harder materials.

All glass sheet coatings, drying time recordings, hardness measurements and storage were performed in a climate controlled chamber at a temperature of 23 ℃ and a humidity of about 47-50%.

The catalyst concentration is given in metal%, referring to the amount of metal of the catalyst relative to the solids content of the binder and formulation used, respectively. This is also abbreviated MORS, the metal on the resin solid. MORS are calculated as follows:

Wherein, m _d: the mass of the drier or the drier solution, g; MC _d: metal content of drier (solution)%; SC _f: solids content (of binder) in the formulation,%; m _f: the quality of the preparation, g.

In the present application, the weight% of metal expressed as dry matter content is defined as explained before and the solids content of the other formulation components is calculated to be included as well. The table provides the method used in the column heading, i.e. whether MORS is used or whether weight percent expressed as dry matter content is used.

In formulation vSAcc, the drying time and hardness were measured (Table XXIII).

Table XXIII: results for formulation vSAcc.

V-TS-PA: phosphoric acid solution of vanadium drier (V-TS), V-TS-AA: acetic acid solution, V-TS-HCl: hydrochloric acid solution. BOC-1101 concentration: 0.001MORS, all V-siccatives: 0.05MORS.

From the data, it can be seen that the drying times of the V-siccatives are better than in the case of BOC, and that they are only slightly affected by the nature of the acid. The optimal drying time is obtained with acetic acid solution. It is also evident from the above data that the development of hardness is also only slightly affected by the nature of the acid. Acetic acid solutions generally produce the hardest coating in this series, next to BOC.

In formulation 11Ya-cc, only hardness was measured (Table XXIV). The drying time is greater than 24 hours.

Table XXIV: results for formulation 11Ya-cc

V-TS-PA: phosphoric acid solution of vanadium drier, V-TS-AA: acetic acid solution, V-TS-HCl: hydrochloric acid solution, V-TS-DMSO: DMSO solution (no acid added). BOC-1101 concentration: 0.001MORS, all V-siccatives: 0.05MORS.

It can be seen from the data that BOC has a higher hardness of 1 day, but after 3 days the coating with V-dryer achieves the same hardness as BOC, whereas after 7 and 14 days they exceed BOC. The development of the hardness of the V-dryer is only slightly affected by the acid properties; the 1 day and 3 day hardness of the phosphoric acid solution of the drier was slightly higher, while the final 14 day hardness of the acetic acid solution of the drier was slightly higher.

The use of various acids in the aqueous solution of the vanadium drier has no adverse effect on the yellowing of the film. Conversely, depending on the formulation, a degree of less yellowing may sometimes be achieved with the choice of acid. The b values for yellowing are included in the table above. For example, in formulation 11Ya-cc, the dilute phosphoric acid solution of the V-drier produced significantly less yellowing than the dilute hydrochloric acid solution of the drier.

The results were significant using a "clear" system, i.e., a pigment-free system, with Table XXVI illustrating the hardness values of the formulations shown in Table XXV.

Table XXV

The data in table XXVS clearly shows a considerable improvement in hardness, which can be very significant for non-pigmented systems. Without being held to any one theory or mode of operation, it is hypothesized that different formulations may benefit from catalysts with different acids. Depending on the formulation, a degree of hardness may sometimes be achieved with the selection of the acid.

Table XXVI

Konig hardness	For 1 day	For 2 days	For 7 days
				Vanadium 2108-A (0.05)	15	17	18
Vanadium 2108-P (0.05)	17	31	64
				Vanadium 2108-A (0.1)	14	15	15
Vanadium 2108-P (0.1)	23	37	68
				Vanadium 2108-A (0.05) +BOC	21	22	21
Vanadium 2108-P (0.05) +BOC	19	31	66
				Vanadium 2108-A (0.1) +BOC	23	23	21
Vanadium 2108-P (0.1) +BOC	21	34	67

In the following further embodiments are disclosed:

In a first embodiment, a coating formulation is described comprising

A binder curable by an autoxidation mechanism; and

At least one drier comprising a vanadium compound of formula (VII)

Wherein R ¹ and R ² are independently selected from the group consisting of: hydrogen, C ₁-C₁₂ alkyl, C ₁-C₁₂ haloalkyl, C ₆-C₁₀ aryl, benzyl; and wherein aryl and benzyl may be optionally substituted with up to three substituents independently selected from the group consisting of C ₁-C₂₀ alkyl and hydroxy (C ₁-C₂) alkyl; and

At least one mineral acid selected from the group consisting of: phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, boric acid, hydrobromic acid, perchloric acid, and hydroiodic acid.

In a second embodiment of the coating formulation of the first embodiment, the binder curable by an autoxidation mechanism is selected from the group consisting of: alkyd resins, epoxy ester resins and vegetable oil or fatty acid modified resins.

In a third embodiment of the coating formulation of the first or second embodiment, the formulation comprises one or more sulfonate compounds of vanadium of formula (VII) in a total concentration of at least 0.001wt.% to 0.3wt.%, preferably at least 0.003wt.% to 0.3wt.%, more preferably 0.006wt.% to 0.6wt.%, based on the dry matter content of the coating.

In a fourth embodiment of the coating formulation of the first, second, or third embodiment, the C ₁-C₁₂ haloalkyl group is a C ₁-C₁₂ fluoroalkyl group.

In a fifth embodiment of the coating formulation of the first, second, third or fourth embodiment, the formulation further comprises water, or wherein the formulation is non-aqueous.

In a sixth embodiment of the coating formulation of the first to fifth embodiments, the ligand is selected from the group consisting of: bispidon, N4py, TACN, cyclam and bridged ligands, and TRISPICEN ligand.

In a seventh embodiment of the coating formulation of the sixth embodiment, the ligand is a bispidon ligand of formula (I):

wherein:

each R is independently selected from the group consisting of: hydrogen, F, cl, br, hydroxy, C _1-4 alkyl O-, -NH-CO-H, -NH-CO-C _1-4 alkyl, -NH ₂、-NH-C_1-4 alkyl, and C _1-4 alkyl;

n 0 to 4;

X is selected from the group consisting of: c=o, - [ C (R6) ₂]_y -, wherein y is 0 to 3; and

Each R6 is independently selected from the group consisting of: hydrogen, hydroxy, C _1-4 alkoxy and C _1-4 alkyl, or wherein the ligand is an N4py ligand of formula (II)

Wherein:

each of R1 and R2 independently represents-R4-R5;

Each R4 independently represents a single bond or a linear or branched C _1-8 alkyl-substituted-C _2-6 alkylene, C _2-6 -alkenylene, C _2-6 -oxyalkylene, C _2-6 -aminoalkylene, C _2-6 -alkenyl ether, C _2-6 carboxylate or C _2-6 carboxamide, and

Each R5 independently represents an optionally N-alkyl substituted aminoalkyl or an optionally alkyl substituted heteroaryl selected from the group consisting of: a pyridyl group; pyrimidinyl; pyrazinyl; triazolyl; a pyridazinyl group; 1,3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; an oxazolidinyl group; a pyrrole group; carbazolyl; indolyl; and isoindolyl, wherein said heteroaryl can be attached to said compound through any atom in the ring of the heteroaryl of choice;

or wherein the ligand is a TACN type ligand of formula (III)

Wherein the method comprises the steps of

Each R20 is independently selected from: c _1-8 alkyl; c _3-8 cycloalkyl; a heterocycloalkyl selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, 1,4, 7-triazacyclononyl, 1,4,8, 11-tetraazacyclotetradecyl, 1,4,7,10, 13-pentazapentadecyl, 1, 4-diaza-7-thia-cyclononyl, 1, 4-diaza-7-oxa-cyclononyl, 1,4,7, 10-tetraazacyclododecyl, 1, 4-dioxanyl, 1,4, 7-trithia-cyclononyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be attached to the compound through any atom in the ring of the heterocycloalkyl of choice; heteroaryl groups selected from the group consisting of: pyridyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3, 5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl group may be attached to the compound through any atom in the ring of the heteroaryl group of choice; aryl selected from homoaromatic compounds having a molecular weight lower than 300; or C _7-40 aralkyl optionally substituted with a substituent selected from the group consisting of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylate, sulfonate, amine, alkylamine, and N ⁺(R21)₃,

Y is independently selected from H, CH ₃、C₂H₅、C₃H₇ and

Wherein at least one R20 is-CY ₂ -R22;

or wherein the ligand is a cyclic or bridged ligand of formula (IV),

Wherein:

Q is independently selected from

P is 4;

R ₁、R₂、R₃、R₄、R₅ and R ₆ are independently selected from: H. c _1-4 alkyl and C _1-4 alkyl hydroxy;

Or wherein the ligand is a bridged ligand of formula (V):

Wherein the method comprises the steps of

R ¹ is independently selected from H, C _1-20 alkyl, C _7-40 alkylaryl, C _2-6 alkenyl, or C _2-6 alkynyl;

or wherein the ligand is a trispecen-type ligand of formula (VI):

R17R17N-X-NR17R17 (VI)，

wherein:

x is selected from-CH ₂CH₂-、-CH₂CH₂CH₂-、-CH₂C(OH)HCH₂ -;

Each R17 independently represents a group selected from: c _1-8 alkyl; c _3-8 cycloalkyl; a heterocycloalkyl selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, 1,4, 7-triazacyclononyl, 1,4,8, 11-tetraazacyclotetradecyl, 1,4,7,10, 13-pentazapentadecyl, 1, 4-diaza-7-thia-cyclononyl, 1, 4-diaza-7-oxa-cyclononyl, 1,4,7, 10-tetraazacyclododecyl, 1, 4-dioxanyl, 1,4, 7-trithia-cyclononyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be attached to the compound through any atom in the ring of the heterocycloalkyl of choice; heteroaryl groups selected from the group consisting of: pyridyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3, 5-triazinyl; quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl can be attached to the compound through any atom in the ring of the heteroaryl of choice; aryl selected from the group consisting of homoaromatic compounds having a molecular weight below 300; and C _7-40 aralkyl optionally substituted with a substituent selected from the group consisting of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylate, sulfonate, amine, alkylamine, and N ⁺(R19)₃, wherein

R19 is selected from the group consisting of hydrogen, C _1-8 alkyl, C _2-6 alkenyl, C _7-40 aralkyl, C _7-40 aralkenyl, C _1-8 oxyalkyl, C _2-6 oxyalkenyl, C _1-8 aminoalkyl, C _2-6 aminoalkenyl, C _1-8 alkyl ether, C _2-6 alkenyl ether, and-CY ₂ -R18, wherein each Y is independently selected from H, CH ₃、C₂H₅、C₃H₇, R18 is independently selected from optionally substituted heteroaryl selected from the group consisting of: a pyridyl group; pyrimidinyl; pyrazinyl; triazolyl; a pyridazinyl group; 1,3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; an oxazolidinyl group; a pyrrole group; carbazolyl; indolyl; and isoindolyl, wherein said heteroaryl can be attached to said compound through any atom in the ring of the heteroaryl of choice; and at least two R17 are-CY ₂ -R18;

preferably, at least one of the ligands is N, N, N-trimethyl-1, 4, 7-triazacyclononane

In an eighth embodiment of the coating formulation of the seventh embodiment, the metal-ligand composition is iron (1+), chloro [ dimethyl 9, 9-dihydroxy-3-methyl-2, 4-bis (2-pyridinyl-kN) -7- [ (2-pyridinyl-kN) methyl ] -3, 7-diazabicyclo [3.3.1] nonane-1, 4-dicarboxylate-kN 3, kN7] -, chloride (1:1):

In a ninth embodiment of the coating formulation of any one of the preceding embodiments, the formulation further comprises a pigment.

In a tenth embodiment of the coating formulation of any of the preceding embodiments, the mineral acid is selected from the group consisting of phosphoric acid and hydrochloric acid.

In an eleventh embodiment of the coating formulation of any of the preceding embodiments, the acid is a blend of at least one inorganic acid and at least one organic acid, and wherein the organic acid is selected from the group consisting of C ₁-C₁₈ monocarboxylic acids or C ₂-C₁₈ dicarboxylic acids, and combinations thereof; the inorganic acid is selected from the group consisting of: phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, boric acid, hydrobromic acid, perchloric acid, and hydroiodic acid, and combinations thereof.

In a twelfth embodiment of the coating formulation of any of the preceding embodiments, the alkyd resin is a solvent-based or aqueous resin.

In a thirteenth embodiment of the coating formulation of the first embodiment, the use of the sulfonate salt formulation of vanadium of formula (VII) is in a coating.

In a fourteenth embodiment of the coating formulation of the first embodiment, the compound of formula (VII) is dissolved in dimethyl sulfoxide, an alcohol, an ester, an ether, a solvent having more than one alcohol, ester, ether functional group, or a mixture thereof prior to incorporation into the coating.

In a fifteenth embodiment of the coating formulation of the first embodiment, the use of a sulfonate compound of vanadium of formula (VII) in dimethylsulfoxide, an alcohol, an ester, an ether, a solvent having more than one alcohol, ester, ether functional group, or mixtures thereof, with at least one mineral acid as a drier for coatings containing curable binders is described

Wherein R ¹ and R ² are independently selected from the group consisting of: hydrogen, C ₁-C₁₂ alkyl, C ₁-C₈ fluoroalkyl, C ₆-C₁₀ aryl, benzyl; wherein the C ₆-C₁₀ aryl and benzyl groups may be optionally substituted with one to three substituents independently selected from C ₁-C₂₀ alkyl and hydroxy (C ₁-C₂) alkyl,

The mineral acid is selected from the group consisting of: phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, boric acid, hydrobromic acid, perchloric acid, and hydroiodic acid, and combinations thereof.

The best mode for carrying out the application has been described in order to explain the best mode known at the time of filing the application. The examples are illustrative only and are not meant to limit the application, which is measured by the scope and value of the claims. The application has been described with reference to preferred and alternative embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the specification. It is intended that the application be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims

1. A coating formulation comprising

A binder curable by an autoxidation mechanism; and

At least one drier comprising a vanadium compound of formula (VII)

2. The coating formulation of claim 1, wherein the binder curable by an autoxidation mechanism is selected from the group consisting of: alkyd resins, epoxy ester resins and resins modified with vegetable oils or fatty acids.

3. The coating formulation according to claim 1 or 2, wherein the formulation comprises one or more sulfonate compounds of vanadium of formula (VII) in a total concentration of at least 0.001wt.% to 0.3wt.%, preferably at least 0.003wt.% to 0.3wt.%, more preferably at least 0.006wt.% to 0.06wt.%, based on the dry matter content of the coating.

4. The coating formulation according to any one of the preceding claims, wherein the C ₁-C₁₂ haloalkyl is C ₁-C₁₂ fluoroalkyl.

5. The coating formulation according to any one of the preceding claims, wherein the formulation further comprises water, or wherein the formulation is non-aqueous.

6. The coating formulation according to any one of the preceding claims, further comprising a ligand selected from the group consisting of: bispidon, N4py, TACN, cyclam and bridged ligands, and TRISPICEN ligand.

7. The coating formulation of claim 6, wherein the ligand is a bispidon ligand of formula (I):

wherein:

n is 0 to 4;

Each R6 is independently selected from the group consisting of: hydrogen, hydroxy, C _1-4 alkoxy, and C _1-4 alkyl;

Or wherein the ligand is an N4 py-type ligand of formula (II):

wherein:

Each of R1 and R2 independently represents-R4-R5;

Each R4 independently represents a single bond or a linear or branched C _1-8 alkyl-substituted-C _2-6 alkylene, C _2-6 -alkenylene, C _2-6 oxyalkylene, C _2-6 aminoalkylene, C _2-6 alkenyl ether, C _2-6 carboxylate or C _2-6 carboxamide, and

Or wherein the ligand is a TACN type ligand of formula (III):

Wherein the method comprises the steps of

Each R20 is independently selected from: c _1-8 alkyl; c _3-8 cycloalkyl; a heterocycloalkyl selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, 1,4, 7-triazacyclononyl, 1,4,8, 11-tetraazacyclotetradecyl, 1,4,7,10, 13-pentazapentadecyl, 1, 4-diaza-7-thia-cyclononyl, 1, 4-diaza-7-oxa-cyclononyl, 1,4,7, 10-tetraazacyclododecyl, 1, 4-dioxanyl, 1,4, 7-trithia-cyclononyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be attached to the compound through any atom in the ring of the heterocycloalkyl of choice; heteroaryl groups selected from the group consisting of: pyridyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3, 5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl group may be attached to the compound through any atom in the ring of the heteroaryl group of choice; aryl selected from the group consisting of homoaromatic compounds having a molecular weight below 300; or C _7-40 aralkyl optionally substituted with a substituent selected from the group consisting of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylate, sulfonate, amine, alkylamine, and N ⁺(R21)₃,

Y is independently selected from H, CH ₃、C₂H₅、C₃H₇, and

Wherein at least one R20 is-CY ₂ -R22;

or wherein the ligand is a cyclic or bridged ligand of formula (IV),

Wherein:

Q is independently selected from

P is 4;

R1, R2, R3, R4, R5 and R6 are independently selected from: H. c _1-4 alkyl and C _1-4 alkyl hydroxy;

Or wherein the ligand is a bridged ligand of formula (V):

Wherein the method comprises the steps of

R ¹ is independently selected from H, C _1-20 alkyl, C _7-40 alkylaryl, C _2-6 alkenyl, or C _2-6 alkynyl; or wherein the ligand is a trispecen-type ligand of formula (VI):

R17R17N-X-NR17R17(VI)

wherein:

x is selected from-CH ₂CH₂-、-CH₂CH₂CH₂-、-CH₂C(OH)HCH₂ -;

Each R17 independently represents a group selected from: c _1-8 alkyl; c _3-8 cycloalkyl; a heterocycloalkyl selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, 1,4, 7-triazacyclononyl, 1,4,8, 11-tetraazacyclotetradecyl, 1,4,7,10, 13-pentazapentadecyl, 1, 4-diaza-7-thia-cyclononyl, 1, 4-diaza-7-oxa-cyclononyl, 1,4,7, 10-tetraazacyclododecyl, 1, 4-dioxanyl, 1,4, 7-trithia-cyclononyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be attached to the compound through any atom in the ring of the heterocycloalkyl of choice; heteroaryl groups selected from the group consisting of: pyridyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3, 5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein said heteroaryl may be attached to said compound through any atom in the ring of the heteroaryl selected; aryl selected from the group consisting of homoaromatic compounds having a molecular weight below 300; and C _7-40 aralkyl optionally substituted with a substituent selected from the group consisting of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylate, sulfonate, amine, alkylamine, and N ⁺(R19)₃, wherein

Preferably, wherein the at least one ligand is N, N, N-trimethyl-1, 4, 7-triazacyclononane

8. The coating formulation of claim 7, further comprising:

Iron (1+), chloro [ dimethyl 9, 9-dihydroxy-3-methyl-2, 4-bis (2-pyridinyl-kN) -7- [ (2-pyridinyl-kN) methyl ] -3, 7-diazabicyclo [3.3.1] nonane-1, 4-dicarboxylate-kN 3, kN7] -, chloride (1:1):

9. The coating formulation according to any one of the preceding claims, further comprising a pigment.

10. The coating formulation according to any one of the preceding claims, wherein the mineral acid is selected from phosphoric acid and hydrochloric acid.

11. The coating formulation according to any one of the preceding claims, wherein the acid is a blend of at least one inorganic acid and at least one organic acid, and wherein the organic acid is selected from the group consisting of C ₁-C₁₈ monocarboxylic acids or C ₂-C₁₈ dicarboxylic acids, and combinations thereof; the inorganic acid is selected from the group consisting of: phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, boric acid, hydrobromic acid, perchloric acid, and hydroiodic acid, and combinations thereof.

12. The coating formulation according to any one of the preceding claims, wherein the alkyd resin is a solvent-borne or aqueous resin.

13. Use of a sulfonate formulation of vanadium of formula (VII) in a coating.

14. Use of a sulfonate compound of vanadium of formula (VII) as defined in claim 1, wherein the compound of formula (VII) is dissolved in dimethyl sulfoxide, an alcohol, an ester, an ether, a solvent having more than one alcohol, ester, ether functional group, or a mixture thereof, prior to incorporation into a coating.

15. Use of a sulfonate compound of vanadium of formula (VII) in dimethylsulfoxide, an alcohol, an ester, an ether, a solvent having more than one alcohol, ester, ether functional group, or a mixture thereof, with at least one mineral acid as a drier for a coating containing a curable binder: