Paints containing driers based on vanadium compounds with sulfonic acid anions as counterions

Abstract

This invention generally relates to paints containing a binder curable by an auto-oxidation mechanism and at least one drying agent comprising a vanadium sulfonate compound of formula (VII), wherein R 1 and R 2 Independently selected from hydrogen, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C6-C 10 Aryl and benzyl; and aryl and benzyl can optionally be independently selected from C1-C. 20 Alkyl and hydroxy (C1-C2) alkyl groups are substituted with up to three substituents.

Description

[0001] Cross-references to related applications

[0002] The invention described herein is a continuation-in-part of Czech patent application PV 2020-366, filed on June 24, 2020, entitled " hmoty obsahujícísikativy na bázi The translation of "vanadus kompenzujícími anionty sulfonovych kyselin" is "paint containing a drier based on a vanadium compound with sulfonic acid anions as counterions," and this is fully incorporated by reference. Technical Field

[0003] The inventions described herein generally relate to formulations of air-drying paints and primary drying agents suitable for these formulations. Background Technology

[0004] Air-drying binders, including polyester resins modified with vegetable oils and known as alkyd resins, are widely used in the paint manufacturing industry due to their low cost, high biorenewable resource content, and relatively easy biodegradability (Hofland, A., Prog. Org. Coat., 73, 274-282 (2012)). Synthetic resins modified with drying and semi-drying vegetable oils are cured in the presence of oxygen in the air. A chemical process known as auto-oxidation is responsible for transforming the liquid paint layer into a robust and durable coating. Because auto-oxidation occurs slowly under ambient conditions, it is typically accelerated by the action of special catalysts known as primary driers. These compounds enable the more rapid decomposition of hydroperoxides, kinetically stable intermediates of auto-oxidation generated in the first step of the curing process. This leads to a significant acceleration of subsequent reactions that generate free radicals in the extended steps of auto-oxidation, which determine the final structure of the cured resin. Crosslinking of air-drying paints is achieved by adding free radicals to the double bond system and by free radical recombination in the termination step (Soucek, MD et al.; Prog. Org. Coat., 73, 435-454 (2012)).

[0005] Cobalt carboxylates soluble in organic solvents, such as cobalt 2-ethylhexanoate, cobalt neodecanoate, and cobalt naphthenate, are widely used as primary drying agents in the paint manufacturing industry due to their high catalytic activity in solvent-based and high-solids air-drying binders. J.; Ind. Eng. Chem. Res. 58, 12485-12505 (2019)). However, due to health and ecological concerns, the use of cobalt compounds should be restricted 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 carboxylate is under in-depth review by the European Chemicals Agency and has been preliminarily classified as a suspected reproductive toxin.

[0006] Ongoing toxicological investigations could lead to its reclassification as a carcinogen and a ban on its use in commercially available paints. This situation has accelerated research into iron- and manganese-based catalysts that could 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 an alternative to cobalt carboxylate reported in research and patent literature. These include compounds containing carboxylates (EP 0304149B1, US 6063841 A, Preininger, O. et al.; J. Coat. Technol. Res. 13, 479-487 (2016)), acetylacetone (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. Acta 492, 243-248 (2019)), ketoimines (US6063841A), organophosphates (US 6063841 A), and dithiocarbamates (CZ). Vanadium oxide compounds (307597B6, Charamzová, I. et al.; J. Coat. Technol. Res. 2020, 17, 1113-1122.) were found. Some of these compounds were found suitable as secondary driers to improve the visual and mechanical properties of the final paint film (WO 2015 / 082553 A1, WO 2017 / 085154 A1, WO 2010 / 106033 A1). Notably, none of the reported vanadium-based driers have achieved commercial application due to low solubility, high production costs, or low storage stability. This invention proposes an alternative to toxic cobalt, which can be used in water-based and solvent-based paints. The realization of the use of water-based alkyd resins is crucial for reducing volatile organic compounds in the environment. Alternatives to organic solvents and toxic catalysts are essential as the chemical industry seeks more sustainable and environmentally friendly alternatives to existing technologies.

[0007] This invention relates to vanadium-based driers (see M. Petranikova, AHTkaczyk, 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 performance obtained from readily available raw materials through a simple one-step route. The driers of this invention should further exhibit high stability to air oxygen. Their solubility should be readily modulated by a given substitution mode of the sulfonate anion, thereby allowing other driers to dissolve in a variety of organic solvents and water. They should be suitable for different types of air-drying paints. Summary of the Invention

[0008] This invention relates to vanadium-based drying agents.

[0009] One aspect of the present invention relates to the formulation of a paint preparation comprising: a binder capable of curing via an auto-oxidation mechanism; and at least one drier comprising a vanadium compound of formula (VII).

[0010]

[0011] Where R 1 and R 2 Independently selected from hydrogen, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C6-C 10 Aryl and benzyl; and aryl and benzyl can optionally be independently selected from C1-C2. 20 Alkyl and hydroxy (C1-C2) alkyl groups are substituted with up to three substituents.

[0012] In another aspect of the invention, the adhesive that can be cured by an auto-oxidation mechanism is selected from alkyd resins, epoxy ester resins, and resins modified by vegetable oils or fatty acids.

[0013] In another aspect of the invention, the formulation comprises one or more vanadium sulfonate compounds of formula (VII) having a total concentration of at least 0.001% to 0.1% by weight in the dry matter content of the paint, more preferably at least 0.003% to 0.1% by weight in the dry matter content of the paint, and most preferably at least 0.006% to 0.06% by weight in the dry matter content of the paint.

[0014] In paint formulations, C1-C 12 The alkyl halide is C1-C12 Fluoroalkyl groups.

[0015] In one aspect of the invention, the paint formulation contains water, while in another aspect of the invention, the paint formulation is non-aqueous.

[0016] The paint formulation also contains ligands selected from the following: Bispidon, N4py type, TACN type, Cyclam and cross-bridged ligands, as well as Trispicen type ligands.

[0017] Paint formulations also contain metal ligand complexes, such as the chloride (1:1) of chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid-kN3,kN7]-ferric(1+) as shown below.

[0018]

[0019] Paint formulations may optionally contain pigments and optionally contain oxalic acid.

[0020] Alkyd resins used in paint formulations can be solvent-based or water-based, and their end use is typically in paint formulations.

[0021] The present invention includes the use of formula (VII), wherein the compound of formula (VII) is dissolved in dimethyl sulfoxide or an alcohol or a mixture thereof before being incorporated into a paint.

[0022] The present invention also includes the use of vanadium sulfonate compounds of formula (VII) in dimethyl sulfoxide, alcohols, or mixtures thereof as driers for paints containing curable binders.

[0023]

[0024] Among them, R 1 and R 2 Independently selected from hydrogen, C1-C 12 Alkyl, C1-C8 fluoroalkyl, C6-C 10 Aryl, benzyl; wherein, C6-C 10 The aryl and benzyl groups can optionally be independently selected from C1-C2. 20 Alkyl and hydroxyl (C1- C2 The alkyl group is substituted with one to at most three substituents.

[0025] These and other objects of the present invention will become apparent when viewed in light of the specific embodiments. Detailed Implementation

[0026] To illustrate the best mode known at the time the applicant filed this invention, the best mode for carrying out the invention will now be described. The embodiments and drawings are merely illustrative and are not intended to limit the invention as measured by the scope and spirit of the claims.

[0027] Unless the context clearly indicates otherwise: "and" indicates combination; "or" indicates choice; when an item is expressed as a choice, followed by "or both" or "the combination thereof," it indicates both combination and choice.

[0028] As used in this application, the term "approximately" means within 10% of the stated value, unless otherwise stated.

[0029] This invention has broad applicability in relation to a variety of solvent-based and water-based coating compositions, and the term should be interpreted broadly herein. Examples of coating compositions include clear or colored varnishes, primers, filler pastes, glazes, emulsions, and floor coverings, such as linoleum floor coverings. Embodiments of the invention relate to solvent-based and water-based paints and inks, particularly paints, such as high-specification paints for household use and paints for general industrial applications.

[0030] The term "oxidatively curable coating composition" as used herein is therefore intended to encompass a variety of colored (e.g., by pigments or inks) and colorless materials comprising oils and binders, which form a continuous coating through an oxidative reaction process that typically forms crosslinks and other bond forms. Generally, such coating compositions are characterized by the presence of a typical (poly)unsaturated resin that reacts to form a solid film on a substrate, the resin initially present in the oxidatively curable solvent-based coating composition in a liquid form dissolved in an organic solvent or in a solid form dispersed in a continuous liquid phase. The reaction that forms the desired coating upon curing is caused by an oxidation-initiated polymerization reaction. Examples of oxidatively curable coating compositions include resins based on alkyd resins, acrylates, polyurethanes, polybutadiene, and epoxy esters. Typically, the curable (e.g., alkyd resin) portion of the curable composition comprises from about 1% to about 90% by weight of the total weight of the oxidatively curable solvent-based coating composition, for example, from about 20% to about 70% by weight of the total weight of the oxidatively curable solvent-based coating composition.

[0031] Alkyd resins are a particularly important class of oxidatively curable coating compositions and are a well-studied class of resins to which this invention can be applied. Hereinafter, embodiments of the invention are described with reference to the use of alkyd resins, also known as alkyd-based resins or alkyd (based) binders. While these represent particularly important embodiments of the invention, the invention is not limited thereto. It should be understood that the invention is applicable to a wide range of oxidatively curable coating compositions, typically containing at least 1% or 2% by weight of unsaturated compounds (e.g., those containing unsaturated (non-aromatic) carbon-carbon double or triple bonds).

[0032] As used herein, the terms "alkyd resin binder" or "alkyd resin" are used interchangeably. Auto-oxidizable alkyd resins suitable for use in this invention are generally products of the esterification reaction of polyols with polyacids (or their anhydrides) and unsaturated fatty acids (or their glycerides) derived from linseed oil, tung oil, tall oil, and other drying or semi-drying oils. Alkyd resins are well known in the art and do not require further description herein. Properties are determined primarily by the nature and ratio of the alcohol and acid used, and the degree of condensation. Suitable alkyd resins include long-oil and medium-oil alkyd resins, such as those derived from 45% to 70% by weight of fatty acids. The composition of long-oil and medium-oil alkyd resins can be modified to improve resin properties. For example, polyurethane-modified alkyd resins, silicone-modified alkyd resins, styrene-modified alkyd resins, acrylic-modified alkyd resins (e.g., (meth)acrylic acid-modified alkyd resins), vinyl-modified 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 this invention.

[0033] Preferably, at least one auto-oxidizable alkyd resin binder is selected from unmodified medium-oil or long-oil alkyd resins, silicone-modified alkyd resins, polyurethane-modified alkyd resins, or combinations thereof. Most preferably, the alkyd resin binder is a long-oil (unmodified) alkyd resin, a silicone-modified alkyd resin, a polyurethane-modified alkyd resin, or a combination thereof.

[0034] The amount of alkyd resin binder in the compositions of the present invention can typically range from about 20% by weight to 98% by weight based on the total weight of the composition, for example from about 30% by weight to about 90% by weight, preferably from about 35% by weight to 70% by weight.

[0035] As used herein, the term "drier" (also synonymously "desiccant" when in solution) refers to organometallic compounds soluble in organic solvents and binders. They are added to unsaturated oils and binders to significantly reduce their drying time, i.e., the transition of their films to the solid phase. Driers are available in solid or solution form. Suitable solvents are organic solvents and binders. Unless otherwise stated, the amount of drier present is expressed as a weight percentage of the metal based on the weight of the binder solids (or resin).

[0036] As used herein, the term "drier composition" refers to a mixture of driers as claimed in this invention. Drier compositions according to the invention may include a variety of drier compounds. The inventors have found that the selection of driers in coating compositions improves the drying speed of the coating compositions.

[0037] When weight percentages (% by weight or % by weight) are mentioned herein, unless the context explicitly indicates otherwise, it means the weight percentage of the component used to provide a coating upon curing in a solvent-based coating composition that relates to the solid resin obtained upon curing, i.e., an oxidatively curable resin. Therefore, for an oxidatively curable alkyd resin coating composition, the total weight of the compositional components that become (i.e., incorporate into) (i.e., after curing) the alkyd resin coating is the weight on which the weight percentages herein are based. For example, compositions obtained by performing the method according to the first aspect of the invention or the method according to the second aspect of the invention typically contain water based on about 0.0001% by weight to about 1% by weight, for example, about 0.0005% by weight to about 0.5% by weight, or about 0.01% by weight to about 1% by weight, for example, about 0.05% by weight to about 0.5% by weight, of the compositional components upon coating curing.

[0038] Consistent with the nomenclature used in the art, the term "oxidatively curable solvent-based composition" herein refers to a composition based on an organic (i.e., non-aqueous) solvent. Examples of suitable solvents include aliphatic (including alicyclic and branched) hydrocarbons, such as hexane, heptane, octane, cyclohexane, cycloheptane, and isoalkanes; aromatic hydrocarbons, such as toluene, xylene, etc.; 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; monoether ethylene glycol acetates, such as 2-ethoxyethyl acetate; and mixtures thereof. Isomers are included. Thus, the term hexane includes mixtures of hexane. According to embodiments of the invention, the solvent is a hydrocarbon-based (i.e., hydrocarbon) solvent, such as an aliphatic hydrocarbon-based solvent, such as a solvent comprising a mixture of hydrocarbons. Examples include petroleum solvent oils and solvents available under the trademarks Shellsol of Shell Chemicals, and Solvesso and Exxsol of Exxon.

[0039] The compositions of the present invention comprise transition metal driers, which are complexes of transition metal ions and sulfonic acid counterions. Each of these will now be described.

[0040] The transition metal ion used in this invention is vanadium. The valence of the metal can range from +2 to +5. Embodiments of this invention are mixtures of transition metal ions. When a vanadium-containing drying agent is provided, it is typically a V(II), (III), (IV), or (V) compound; when an iron-containing drying agent is provided, it is typically a Fe(II) or Fe(III) compound; when a manganese-containing drying agent is provided, it is typically a Mn(II), (III), or (IV) compound.

[0041] To enhance the activity of transition metal ions, so-called accelerator compounds, such as carboxylic acids or pentadentate amines, are also included. As the description implies, carboxylic acid or pentadentate amine accelerator ligands are compounds capable of coordinating with transition metal ions through more than one donor site within the ligand, and are used to promote the drying (curing process) of oxidatively curable coating compositions after application.

[0042] According to some embodiments of the invention, the polydentate amine accelerator ligand is a bidentate, tridentate, tetradentate, pentadentate, or hexadentate ligand coordinated to a nitrogen and / or oxygen donor atom. In a particular embodiment of the invention, the ligand is a bidentate, tridentate, tetradentate, pentadentate, or hexadentate nitrogen donor ligand, particularly a tridentate, tetradentate, pentadentate, or hexadentate nitrogen donor ligand. However, the invention is not limited thereto. Examples of various polydentate accelerator ligands are discussed below.

[0043] Metal driers as described herein, for example in the form of pre-formed complexes of transition metal ions and multidentate accelerator ligands, are typically dissolved in water at a concentration of about 0.001 wt% to about 10 wt%, for example, about 0.01 wt% to about 5 wt%, or about 0.001 wt% to about 1 wt%. Increasing the concentration of the metal drier in the aqueous solution allows for the addition of a relatively smaller volume of the metal drier-containing aqueous solution to the coating composition. This is likely desirable to those skilled in the art. The actual amount of metal drier used 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 mentions an iron level of 0.1%, then the amount of compound dissolved in water is 1% (wt / wt) or 10 g / kg water. If the complex is not pre-formed but formed in situ, then the metal salt will also typically be dissolved in water at a concentration of about 0.001 wt% to about 1 wt% based on the ratio of metal ions to water. Then, an appropriate amount of multidentate promoter ligand can be added to form the desired complex.

[0044] After preparation, the solution of the metal drier can then be brought into contact with the coating composition, for example, by adding it to the coating composition.

[0045] The resulting composition, comprising a metal drier and typically about 0.0001% to 1% water based on the weight of the oxidizable curable coating, is usually a solution, i.e., a single homogeneous phase. However, it can also be, for example, an emulsion or dispersion comprising a discontinuous region containing an aqueous solution of a transition metal drier.

[0046] As used in this application, the term "binder solution (alkyd resin)" refers to one of the following: SYNAQUA 4804 (waterborne short-oil alkyd resin, Arkema); SYNAQUA 2070 (waterborne medium-oil alkyd resin, Arkema); Beckosol AQ101 (waterborne long-oil alkyd resin, Polyont Composites USA Inc.); Worlée Kyd S 351 (solvent-based medium-oil alkyd resin, Worlée); and TOD 3AK0211Y (water-dilutable alkyd resin, TOD, China), as well as other binder solutions having similar characteristics to the above. In a more general sense, "alkyd resin" refers to a synthetic resin made by a condensation reaction (releasing water) between a polyol (glycerol, etc.) and a diacid (or phthalic anhydride). It is the non-volatile component of the paint carrier. After drying, it bonds pigment particles to the paint film as a whole.

[0047] As used in this application, the term "catalyst" refers to: Borchi Oxy-Coat 1101 (BOC 1101, in water, Borchers); Borchi Oxy-Coat (BOC, in propylene glycol, Borchers); Borchers Deca Cobalt 7aqua (cobalt neodecanoate drier, in organic solvents, Borchers); Borchers Deca Cobalt 10 (cobalt neodecanoate drier, in hydrocarbon solvents, Borchers); Cur-Rx (vanadium 2-ethylhexanoate drier, Borchers); vanadium acetylacetonate oxyacetate (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 those described above.

[0048] As used in this application, the term "ligand" preferably refers to TMTACN-N,N,N-trimethyl-1,4,7-triazacyclononane and other ligands having similar characteristics to those shown above and below.

[0049]

[0050] Other applicable "ligands" include the following:

[0051] BISPIDON

[0052] Bispidons are typically in the form of iron transition metal catalysts. Bispidon ligands preferably have the following formula:

[0053]

[0054] in:

[0055] Each R is independently selected from hydrogen, F, Cl, Br, hydroxyl, C 1-4 -alkylO-, -NH-CO-H, -NH-CO-C 1-4 Alkyl, -NH2, -NH-C 1-4 Alkyl and C 1-4 alkyl;

[0056] R1 and R2 are independently selected from C 1-24 Alkyl, C 6-10 Aryl groups and groups containing one or two heteroatoms (e.g., N, O, or S) capable of coordinating with transition metals;

[0057] R3 and R4 are independently selected from hydrogen, C 1-8 Alkyl, C 1-8 Alkyl-OC 1-8 Alkyl, C 1-8 Alkyl-OC 6-10 Aryl, C 6-10 Aryl, C 1-8 Hydroxyalkyl and -(CH2) n C(O)OR5, where R5 is independently selected from hydrogen and C. 1-4 alkyl,

[0058] n is between 0 and 4

[0059] X is selected from C=O, -[C(R6)2] y -, where y is between 0 and 3; and

[0060] Each R6 is independently selected from hydrogen, hydroxyl, C 1-4 Alkoxy and C 1-4 alkyl.

[0061] Typically, R3 = R4 and is selected from -C(O)-O-CH3, -C(O)-O-CH2CH3, -C(O)-O-CH2C6H5, and CH2OH. The heteroatoms capable of coordinating with transition metals are usually selected by C... 1-4 Alkyl-substituted pyridin-2-ylmethyl or optionally C1-8 Alkyl-substituted aliphatic amines are provided. Typically, X is C=O or C(OH)2.

[0062] Typical groups for -R1 and -R2 are -CH3, -C2H5, -C3H7, benzyl, -C4H9, and -C6H. 13 -C8H 17 -C 12 H 25 and -C 18 H 37 And -pyridin-2-yl. An example of a class of bispidons is one 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.

[0063] Two examples of bispidons are 2,4-di-(2-pyridinyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonyl-9-one-1,5-dicarboxylic acid dimethyl ester (N2py3o-C1) and 2,4-di-(2-pyridinyl)-3-methyl-7-(N,N-dimethyl-amino-ethyl)-3,7-diaza-bicyclo[3.3.1]nonyl-9-one-1,5-dicarboxylic acid dimethyl ester and their corresponding iron complexes. FeN2py3o-C1 can be prepared as described in WO 02 / 48301. Other examples of bispidons are those that do not have a methyl group at the 3-position, but instead have a longer alkyl chain (e.g., C4-C). 18 Alkyl or C6-C 18 Alkyl chains, such as isobutyl, (n-hexyl)C6, (n-octyl)C8, (n-dodecyl)C6, etc. 12 (n-Tetradecyl)C 14 (n-octadecyl)C 18 Bispidon; these can be prepared in a similar manner.

[0064] N4py type

[0065] N4py type ligands are typically in the form of iron transition metal catalysts. N4py type ligands generally have formula (II):

[0066]

[0067] in:

[0068] Each R1 and R2 independently represents -R4-R5;

[0069] R3 represents hydrogen, C 1-8-alkyl, aryl selected from aromatic compounds with a molecular weight of less than 300, or C 7-40 Arylalkyl, or -R4-R5,

[0070] Each R4 independently represents a single bond or a straight or branched C bond. 1-8 -alkyl-substituted -C 2-6 -alkylene, C 2-6 - Idemenyl, C 2-6 -alkylene oxide, C 2-6 -aminoalkylene, C 2-6 -Alkenyl ether, C 2-6 -Carboxylic acid ester or C 2-6 -Carboxylic acid amides, and

[0071] Each R5 independently represents an N-alkyl-substituted aminoalkyl group or an alkyl-substituted heteroaryl group, wherein the heteroaryl group is selected from pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, Azolyl, pyrrole, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl group can be attached to the compound via any atom in the ring of the selected heteroaryl group.

[0072] According to some embodiments, R1 or R2 represents pyridin-2-yl; or R2 or R1 represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl, or 2-(N,N-di(m)ethyl)amino-ethyl. If substituted, R5 typically represents 3-methylpyridin-2-yl. R3 preferably represents hydrogen, benzyl, or methyl.

[0073] Examples of N4Py ligands include N4Py itself (i.e., N,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 BzN4py (N,N-bis(pyridin-2-yl-methyl-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane), which is described in EP 0909809.

[0074] TACN type

[0075] TACN-Nx is preferably in the form of an iron transition metal catalyst. These ligands are based on the 1,4,7-triazacyclononane (TACN) structure, but have one or more side-chain nitrogen groups for complexing with the transition metal to provide tetradentate, pentadentate, or hexadentate ligands. According to some embodiments of TACN-Nx type ligands, the TACN skeleton has two nitrogen-containing side-chain groups (TACN-N2) that are complexed with the transition metal. TACN-Nx ligands typically have formula (III):

[0076]

[0077] in,

[0078] Each R20 is independently selected from: C 1-8 -alkyl; C 3-8 -Cycloalkyl; selected from the following heterocycloalkyl groups: pyrrolinyl, pyrrolylyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1,4-piperazinyl, tetrahydrothiopheneyl, tetrahydrofuranyl, 1,4,7-triazacyclononyl, 1,4,8,11-tetraazacyclotetradecyl, 1,4,7,10,13-pentazacyclopentadecanyl, 1,4-diaza-7-thiocyclononyl, 1,4-diaza-7-oxacyclononyl, 1,4,7,10-tetraazacyclododecyl, 1,4-dicyclononyl Alkyl, 1,4,7-trithiacyclononyl, tetrahydropyranyl and Azolyl group, wherein the heterocyclic alkyl group may be attached to the compound via any atom in the ring of the selected heterocyclic alkyl group; selected from the following heteroaryl groups: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, Azolyl, pyrrole, carbazolyl, indole, and isoindole, wherein the heteroaryl group may be attached to the compound via any atom in the ring of the selected heteroaryl group; aryl groups selected from those of the same aromaticity with a molecular weight of less than 300; or optionally selected from hydroxyl, alkoxy, phenoxy, carboxylates, formamides, carboxylic esters, sulfonates / esters, amines, alkylamines, and N-hydroxyl groups. + (R21)3 substituent C 7-40 -Arylalkyl group,

[0079] R21 is selected from hydrogen, C 1-8 -alkyl, C 2-6 -Alkenyl, C 7-40 -Arylalkyl, arylalenyl, C 1-8 -Oxyalkyl, C 2-6 -Oxylenyl, C 1-8 -aminoalkyl, C 2-6 -Aminoolefin, C 1-8-alkyl ethers, C 2-6 -Alkenyl ethers and -CY2-R22,

[0080] Y is independently selected from H, CH3, C2H5, C3H7, and

[0081] R22 is independently selected from C 1-8 -alkyl-substituted heteroaryl groups, wherein the heteroaryl group is selected from: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, Azolyl, pyrrole, carbazoyl, indole, and isoyindole, wherein the heteroaryl group can be attached to the compound via any atom in the ring of the selected heteroaryl group; and

[0082] Among them, at least one of R20 is -CY2-R22.

[0083] R22 is typically selected from pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, or quinoline-2-yl groups that are optionally alkyl-substituted. R22 is usually pyridin-2-yl or quinoline-2-yl.

[0084] CYCLAM and cross-bridged ligands

[0085] Cycloam and cross-bridged ligands are preferably in the form of manganese transition metal catalysts. Cycloam ligands typically have formula (IV):

[0086]

[0087] in:

[0088] Q is selected independently

[0089]

[0090] P is 4;

[0091] R is independently selected from: hydrogen, C 1-6 -alkyl, CH2CH2OH, pyridin-2-ylmethyl and CH2COOH, or one of R is connected to the N of another Q via an ethylene bridge; and

[0092] R1, R2, R3, R4, R5, and R6 are independently selected from: H, C 1-4 -alkyl and C 1-4 -alkylhydroxyl.

[0093] Examples of non-cross-bridged ligands are 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me4cyclam), 1,4,7,10-tetraazacyclododecane (cyclen), 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4cyclen), and 1,4,7,10-tetra(pyridin-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (Py4cyclen). For Py4cyclen, an iron complex is preferred.

[0094] Preferred cross-bridged ligands have the following formula (V):

[0095]

[0096] Among them, R 1 Independently selected from H and C 1-20 Alkyl, C 7-40 -alkylaryl, C 2-6 -Alkenyl or C 2-6 -Alkyne group.

[0097] In macropolycyclic rings, all nitrogen atoms can coordinate with transition metals. In formula (VI), each R 1 They can be the same. In each R 1 In the case of a methyl group, this provides the ligand 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane(L), wherein the complex [Mn(L)Cl2] can be synthesized according to WO98 / 39098. In the case where each R1 is benzyl, this is the ligand 5,12-dibenzyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane(L'), whose complex [Mn(L')Cl2] can be synthesized as described in WO98 / 39098. Other suitable cross-bridged ligands are described in WO98 / 39098.

[0098] TRISPICEN type

[0099] Trispicens are preferably in the form of iron transition metal catalysts. Trispicen-type ligands preferably have formula (VI):

[0100] R17R17N-X-NR17R17(VI),

[0101] in:

[0102] X is selected from -CH2CH2-, -CH2CH2CH2-, and -CH2C(OH)HCH2-.

[0103] Each R17 independently represents a group selected from the following: R17; C 1-8 -alkyl; C 3-8 -Cycloalkyl; selected from the following heterocycloalkyl groups: pyrrolinyl, pyrrolylyl, morpholinyl, piperidinyl, piperazinyl, hexamethyleneimine, 1,4-piperazinyl, tetrahydrothiopheneyl, tetrahydrofuranyl, 1,4,7-triazacyclononyl, 1,4,8,11-tetraazacyclotetradecyl, 1,4,7,10,13-pentazacyclopentadecanyl, 1,4-diaza-7-thiocyclononyl, 1,4-diaza-7-oxacyclononyl, 1,4,7,10-tetraazacyclododecyl, 1,4-dicyclononyl Alkyl, 1,4,7-trithiacyclononyl, tetrahydropyranyl and Azolyl group, wherein the heterocyclic alkyl group may be attached to the compound via any atom in the ring of the selected heterocyclic alkyl group; selected from the following heteroaryl groups: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, Azolyl, pyrrole, carbazolyl, indole, and isoindole, wherein the heteroaryl group may be attached to the compound via any atom in the ring of the selected heteroaryl group; aryl groups selected from homoaromatic compounds with a molecular weight of less than 300; and optionally selected from hydroxyl, alkoxy, phenoxy, carboxylates, formamides, carboxylic esters, sulfonates / esters, amines, alkylamines, and N-hydroxyl groups. + (R19)3 substituent C 7-40 Aryl alkyl groups, wherein

[0104] R19 is selected from: hydrogen, C 1-8 -alkyl, C 2-6 -Alkenyl, C 7-40 -Arylalkyl, C 7-40 -Arylene, C 1-8 -Oxyalkyl, C 2-6 -Oxylenyl, C 1-8 -aminoalkyl, C 2-6 -Aminoolefin, C 1-8 -alkyl ethers, C 2-6 -Alkenyl ether and -CY2-R18, wherein each Y is independently selected from H, CH3, C2H5, C3H7, and R18 is independently selected from optionally substituted heteroaryl groups, wherein the heteroaryl group is selected from pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, Azolyl, pyrrole, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl group may be attached to the compound via any atom in the ring of the selected heteroaryl group; and at least two of R17 are -CY2-R18.

[0105] The heteroatom donor group is preferably a pyridinyl group optionally substituted with a -C1-C4-alkyl group, such as a 2-pyridinyl group.

[0106] Other preferred heteroatom donor groups are imidazole-2-yl, 1-methyl-imidazole-2-yl, 4-methyl-imidazole-2-yl, imidazole-4-yl, 2-methyl-imidazole-4-yl, 1-methyl-imidazole-4-yl, benzimidazole-2-yl, and 1-methyl-benzimidazole-2-yl. Preferably, three of R17 are CY2-R18.

[0107] The ligand Tpen (N,N,N',N'-tetra(pyridin-2-yl-methyl)ethylenediamine) is disclosed in WO 97 / 48787. Other suitable trispicens are described in WO 02 / 077145 and EP 1001009A.

[0108] Preferably, the ligand is selected from 2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonyl-9-one-1,5-dicarboxylic acid dimethyl ester, 2,4-di-(2-pyridyl)-3-methyl-7-(N,N-dimethyl-amino-ethyl)-3,7-diaza-bicyclo[3.3.1]nonyl-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,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)-2-phenyl-1-aminoethane.

[0109] Other ligands

[0110] Other multidentate accelerator ligands known to those skilled in the art may also be used, which are discussed below. Typically, these ligands can be used as pre-formed transition metal complexes containing multidentate accelerator ligands.

[0111] First, the multidentate accelerator ligand can be a bidentate nitrogen donor ligand, such as 2,2'-bipyridine or 1,10-phenanthroline, both of which are known in the art as multidentate accelerator ligands in metal drying agents that promote drying. 2,2'-bipyridine or 1,10-phenanthroline is typically provided as ligands in manganese- or iron-containing complexes. Other bidentate-multidentate accelerator ligands include amine-containing bidentate ligands, 2-aminomethylpyridine, ethylenediamine, tetramethylethylenediamine, diaminopropane, and 1,2-diaminocyclohexane.

[0112] Various bidentate to hexadentate ligands with oxygen donors are also known, including ligands with mixed oxygen and nitrogen donors. For example, WO 03 / 029371A1 describes a tetradentate diimine of the following formula:

[0113] R1-C(A1-O)=N-R2-N=C(A2-O)-R3

[0114] in:

[0115] A1 and A2 are both aromatic groups;

[0116] R1 and R3 are covalently bonded groups, such as hydrogen or organic groups; and

[0117] R2 is a divalent organic free radical.

[0118] Both EP 1382648 A1 and WO 00 / 11090A1 describe the use of 1,3-dione as a multidentate promoter ligand. EP 1382648 also describes the use of complexes comprising 1,3-dione (or 1,3-diimide) and bidentate diamines, including bipyridine and phenanthrene.

[0119] As used in this application, BOC is the chloride (1:1) of chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid-kN3,kN7]-ferric(1+).

[0120]

[0121] As used herein, the term "secondary drier" and the synonym "auxiliary drier" refer to Calcium-Hydrochem (based on calcium neodecanoate in an organic solvent, Borchers), Octa Soligen Zirconium 10aqua (based on zirconium 2-ethylhexanoate in an organic solvent, Borchers), and other secondary driers having similar properties to those described above. Furthermore, one or more auxiliary driers may be added to a fully formulated oxidatively curable coating composition. Such auxiliary driers may be optional additional components in the formulations of this invention, but are not typically present in them. Such auxiliary driers include fatty acid soaps of zirconium, bismuth, barium, cerium, calcium, lithium, strontium, and zinc. Typically, the fatty acid soaps are optionally substituted octanoates, hexanoates, and naphthenates. Without being bound by theory, auxiliary driers (sometimes referred to as penetrating driers) are generally understood to reduce the adsorption of solid particles typically present in the oxidatively curable coating composition by the primary drier. Other non-metallic auxiliary driers may also be present if desired. As is known in the art, the concentration of the auxiliary drying agent in an oxidatively curable coating composition (or the formulation of the present invention) is typically from about 0.01% by weight to 2.5% by weight.

[0122] The formulations of the present invention can and generally will be used to manufacture fully formulated oxidatively curable coating compositions. The term "fully formulated oxidatively curable coating composition" implies, as is known to those skilled in the art, an oxidatively curable formulation containing additional components in addition to a binder (an oxidatively curable material, primarily an oxidatively curable alkyd resin according to the present invention), an aqueous or non-aqueous solvent / liquid continuous phase, and any metallic driers intended to accelerate the curing process. Such additional components are generally included to impart desired properties to the coating composition, such as color or other visual characteristics such as gloss or matte, physical, chemical, or even biological stability (e.g., imparting enhanced biological stability to the coating composition through the use of antimicrobial agents), or altered texture, plasticity, adhesion, and viscosity.

[0123] For example, such optional additional components may be selected from: solvents, antioxidants (sometimes called anti-skinning agents), additional drying agents, accelerators, colorants (including inks and colored pigments), fillers, plasticizers, viscosity modifiers, ultraviolet absorbers, stabilizers, antistatic agents, flame retardants, lubricants, emulsifiers (especially when the oxidizable curable coating composition or formulation of the present invention is water-based), defoamers, viscosity modifiers, antifouling agents, antimicrobial agents (e.g., bactericides, fungicides, algaecides, and insecticides), preservatives, antireflective agents, antifreeze agents, waxes, and thickeners. Typically, formulations prepared according to embodiments of the method of the second aspect of the present invention, in addition to the alkyd resins and optionally other binders and chelating agents present in the formulations of the present invention, also contain at least one organic solvent selected from the above-listed solvents, fillers, and general anti-skinning agents. Those skilled in the art are familiar with incorporating these and other components into oxidizable curable coating compositions to optimize the properties of such compositions.

[0124] It should be understood that some of these optional additional components have more than one functional property. For example, some fillers can also be used as colorants. The properties and amounts of any additional component can be determined based on the knowledge of those skilled in the art and will depend on the intended application of the curable coating composition. Examples of optional additional components are discussed in the following paragraphs, which are intended to be illustrative and not limiting.

[0125] As used in this application, the term "environmental conditions" refers to both temperature and humidity, i.e., laboratory conditions as opposed to climate-controlled conditions.

[0126] This invention provides air-drying paints containing vanadium compounds with sulfonic acid anions as counterions, and the application of these compounds in air-drying paints. These driers significantly accelerate the drying and curing of alkyd resins. They are suitable for solvent-based, water-based, and high-solids paints, as well as alkyd resin paints modified with other monomers. Furthermore, they can also be used in inks and composite coatings.

[0127] The drying agent according to the present invention is a compound of formula (VII):

[0128]

[0129] Where R 1 and R 2 Independently selected from hydrogen, C1-C 12 Alkyl, C1-C8 fluoroalkyl, C6-C 10 Aryl and benzyl; and aryl and benzyl can optionally be independently selected from C1-C2. 20 Alkyl or hydroxyl (C1-C2) alkyl groups are substituted with one to at most three substituents.

[0130] As used in this application, "alkyl" can be straight-chain or branched. Preferably, the alkyl group is C1-C2. 12 Alkyl groups, more preferably C1-C6 alkyl groups. A non-exhaustive list of suitable alkyl examples is CH3, C2H5, C3H7, C4H9, C5H 11 C6H 13 C7H 15 C8H 17 C9H 19 C 10 H 21 C 11 H 23 and C 12 H 25 In some embodiments, the alkyl group may be C10. 13 -C 20 Alkyl group. The alkyl group may be substituted with halogens, particularly fluorine. Fluoroalkyl groups are preferably straight-chain fluoroalkyl groups, and non-limiting examples include: CF3, C2F5, C3F7, C4F9, C5F... 11 C6F 13 C7F 15 and C8F 17 .

[0131] As used in this application, "aryl" can be, for example, phenyl (C6H5) or naphthyl (C6H5). 10 H7). The substituted aryl group may include, for example, p-tolyl (CH3C6H4), 1,4-dimethylphenyl ((CH3)2C6H3), 2,4,6-trimethylphenyl ((CH3)3C6H2), 4-ethylphenyl (C2H5C6H4), 4-isopropylphenyl (C3H7C6H4), 4-undecylphenyl (C 11 H 23 C6H4), 4-dodecylphenyl (C 12 H 25 C6H4), 4-Tetrazylphenyl (C 13 H 27 C6H4), 4-hexadecylphenyl (C 16 H 33 C6H4), 4-Octadecanylphenyl (C 18 H 37 C6H4), 4-methoxyphenyl ((OCH3)C6H4).

[0132] As used in this application, "benzyl" is a substituent of the formula CH2C6H5.

[0133] The subject of this invention is a paint formulation comprising a binder that can be cured by an auto-oxidation mechanism and at least one drying agent, an example of which is a vanadium compound of formula I.

[0134] As used in this application, the structure of cobalt 2-ethylhexanoate (“Co-2EH”) is as follows:

[0135]

[0136] As used in this application, the structure of vanadium acetylacetonate (“V-acac”) is as follows:

[0137]

[0138] As used in this application, the structure of "V-SO" is as follows:

[0139]

[0140] Adhesives that can be cured by an auto-oxidation mechanism can be alkyd resins or variants of alkyd resins, such as acrylic-modified alkyd resins, epoxy ester resins, and resins modified with vegetable oils or fatty acids.

[0141] Preferably, the paint contains one or more driers of Formula I, the total concentration of which is at least 0.001% by weight, preferably 0.003% to 0.1% by weight, more preferably 0.006% to 0.1% by weight, and even more preferably 0.01% to 0.06% by weight of vanadium in the dry matter content of the paint.

[0142] Paints are prepared, for example, by dissolving a drier of type I, followed by treatment with an air-drying binder, and homogenization of the mixture. The catalyst can be added to the paint formulation in any order, or even a vanadium source and a sulfonic acid source can be added as separate components. Preferably, the drier is dissolved in a polar organic solvent such as dimethyl sulfoxide (DMSO) and an alcohol, or a mixture thereof. Alternatively, the paint can be prepared by dissolving the drier in water. This is particularly useful when the binder is a water-based resin.

[0143] By choosing R in equation (VII) 1 and R 2The driers can be dissolved in any organic solvent. It has been found that driers of formula (VII) may be unstable in water-based formulations, tending to degrade or precipitate when diluted in water. This makes them unsuitable for many applications. This problem has been solved by using water-miscible solvent mixtures, such as alcohol-ester solvent mixtures combining 2-methyl-1-pentanol and isobutyl acetate, and carboxylic acids such as acetic acid. Acids are considered to play an important role in stabilizing catalysts, as the oligomerization of vanadates, which can lead to drier deactivation, is known to be sensitive to pH and concentration (ref. J.J. Cruywagen, in Advances in Inorganic Chemistry, Vol. 49 (Ed.: AGSykes), Academic Press, 1999, pp. 127-182). Solvent mixtures improve the long-term stability of the complexes and their incorporation into paints.

[0144] Depending on the application, driers based on formula (VII) can be dissolved in water or polar organic solvents such as dimethyl sulfoxide (DMSO), acetic acid, alcohols, esters, and mixtures thereof.

[0145] A drying agent of formula (VII) has been discovered, wherein R 1 and R 2 Containing the same or different C 10 -C 20 Alkyl chains (e.g., 4-dodecylphenyl) are viscous liquids miscible with aromatic solvents such as toluene and xylene. This makes the drying agent useful even for industrial applications, as only solvents commonly used in the paint manufacturing industry are required. This is particularly useful when the binder is a solvent-based or high-solids resin.

[0146] Alternatively, paint can be prepared by directly dissolving the drier in an air-drying binder. When the drier is a compound of formula (VII), where R... 1 and R 2 Containing the same or different C 10 -C 20 This is particularly useful when it involves alkyl chains (e.g., 4-dodecylphenyl).

[0147] The subject of this invention is the use of vanadium compounds of formula (VII) as drying agents for paints containing binders that can be cured by an auto-oxidation mechanism.

[0148] The drier of formula (VII) was found to be active in air-drying paints with a metal concentration ranging from 0.001% to 0.1% by weight in the dry matter content.

[0149] Compared to currently known vanadium-based drying agents, one of the main advantages of the drying agents according to formula (VII) of the present invention is that they are synthesized in a simple one-step process from readily available and inexpensive raw materials. Compounds of formula I are readily synthesized via substituent R... 1 and R 2 The substitution process modifies the compound, ensuring satisfactory solubility in organic solvents used in paint production. Furthermore, in addition to the added solvent and carboxylic acid, compounds based on formula (VII) are readily soluble in readily available, non-toxic water to ensure stability and efficacy. The driers of formula (VII) are typically blue or green.

[0150] Another advantage of the drier of formula (VII) is that the stock solution of the drier of formula (VII) can be stored in an air atmosphere without loss of catalytic activity. Since no inert atmosphere and / or oxygen-free conditions are required, this makes the handling of the stock solution practical even for industrial applications.

[0151] Compared to currently known vanadium-based driers, its further advantages include improved stability to atmospheric oxygen and a wider range of alkyd resin-based paints curing capabilities. The compound of Formula I exhibits catalytic activity at significantly lower concentrations than currently widely used cobalt-based driers. Surprisingly, it has been observed to react with cobalt-based and bispidon-based catalysts, for example... Compared to OxyCoat, the drier of formula (VII) can provide improved hardness. Furthermore, it is noted that preferred combinations with additional catalysts and amine ligands contribute to further improvements in hardness.

[0152] Another advantage is relative toxicity; the product of formula (VII) is expected to produce a non-toxic alternative to existing vanadium catalysts such as vanadium acetylacetonate.

[0153] The drying agent of formula (VII) can be obtained by reacting vanadium (V) oxide with a suitable sulfonic acid or a mixture of sulfonic acids (R). 1 SO3H, R 2 SO3H, where R 1 and R 2 It can be prepared by reaction in a water-ethanol mixture with a volume ratio of 1:2 (either the same or different).

[0154] Compounds of the type given by formula (VII) have been synthesized by several methods. Vanadium trifluoromethanesulfonate (Krakowiak; Inorg. Chem. 51, 9598-9609 (2012)) and vanadium p-toluenesulfonate (Movius, WG et al.; J. Am. Chem. Soc. 92, 2677-2683, (1970)) were prepared by reacting vanadium sulfate with barium salts of appropriate sulfonic acids.

[0155] Another literature method utilizes the solvent decomposition of vanadium oxyacetylacetonate with p-toluenesulfonic acid (Holmes, SM et al.; Inorg. Synth. 33, 91-103, (2002)). Anhydrous vanadium oxyacetylacetonate can be prepared by the reaction of vanadium(V) chloride with methanesulfonic acid in chlorobenzene, or by the direct solvent decomposition of vanadium(IV) chloride with methanesulfonic acid (Kumar, S. et al.; Indian J. Chem. 23A, 200-203, (1984)). The method presented in this invention uses vanadium(V) oxide (CAS: 1314-62-1) as the vanadium source, which is economically advantageous compared to the aforementioned raw materials. Ammonium metavanadate can be used as another economical vanadium source for the preparation of the compound.

[0156] The present invention also includes the compound vanadium dodecylbenzenesulfonate, which corresponds to formula (VII), wherein R 1 and R 2 It is dodecylphenyl. This compound represents a novel compound prepared within the framework of this invention.

[0157] Embodiments of the Invention

[0158] Alkyd resins CHS-Alkyd S 471X 60 (oil content = 47%, acid value 6 mg KOH / g), S471; CHS-Alkyd TI 870 (oil content = 87%, acid value 8 mg KOH / g), TI870, were obtained from Spolchemie. Alkyd resins SPS15-60D (oil content = 50%, acid value 10mg KOH / g, organosilicon content = 30%), SPS15, from Safic-Alcan sro obtained.

[0159] Vanadium (V) oxide, methanesulfonic acid, p-toluenesulfonic acid monohydrate, vanadium oxysulfate hydrate (V-SO), 2-methyl-1-pentanol, and dimethyl sulfoxide (DMSO) are available from Acros-Organics. Cobalt 2-ethylhexanoate (Co-2EH) is available from Sigma-Aldrich. Acetic acid is available from Riedel-de-Haen. Isobutyl acetate is available from Alfa Aesar.

[0160] BorchiOxy-Coat 1101 (BOC1101, in water), Borchi Oxy-Coat (BOC, in propylene glycol), Borchers Deca Cobalt 7aqua (in an organic solvent mixture), Borchers Deca Cobalt 10 (in a hydrocarbon solvent), and N,N,N-trimethyl-1,4,7-triazacyclononane (TMTACN) were obtained from Borchers.

[0161] The binder solutions SYNAQUA 4804 (waterborne short-oil alkyd resin) and SYNAQUA 2070 (waterborne medium-oil alkyd resin) were obtained from Arkema; ​​Beckosol AQ101 (waterborne long-oil alkyd resin) was obtained from Polyont Composites USA Inc.; WorléeKyd S 351 (solvent-based medium-oil alkyd resin) was obtained from Worlée; and TOD 3AK0211Y (water-dilutable alkyd resin) was obtained from TOD China.

[0162] Example 1 - Synthesis of Vanadyl Mesylate (V-MS)

[0163]

[0164] A suspension of vanadium(V) oxide (5.6 g) mixed with ethanol (30 mL) and distilled water (15 mL) was treated with methanesulfonic acid (16 mL) and heated at 110 °C for 3 hours. When the solution turned deep blue, the solution was filtered and the evaporation was evaporated. The product was washed with diethyl ether and dried under vacuum to give a blue solid. Yield: 15.9 g. Elemental analysis (C2H) 16 O 12 S2V): Calculated values: C, 6.92; H, 4.64; S, 18.47. Measured values: C, 6.78; H, 4.81; S, 18.11. EPR (water): |A iso |=116.4×10 -4 T;g iso =1.966.

[0165] Example 2 - Synthesis of Vanadyl Trifluoromethanesulfonate, V-FS

[0166]

[0167] 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 °C for 6 hours. When the solution turned blue-green, the solution was filtered and the evaporation was evaporated. The product was washed with diethyl ether and dried under vacuum to give a blue-green solid. Yield: 21.8 g. Elemental analysis (C2H) 10 F6O 12 S2V): Calculated values: C, 5.28; H, 2.21; S, 14.09. Measured values: C, 5.37; H, 1.99; S, 14.22. EPR (water): |A iso |=116.4×10 -4 T;g iso =1.966.

[0168] Example 3 Synthesis of vanadium oxybenzenesulfonate, V-BS

[0169]

[0170] 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 °C for 3 hours. When the solution turned deep blue, the solution was filtered and the evaporation was evaporated. The product was washed with diethyl ether and dried under vacuum to give a blue solid. Yield: 27.5 g. Elemental analysis (C 12 H 20 O 12 S2V): Calculated values: C, 30.58; H, 4.28; S, 13.61. Measured values: C, 30.72; H, 4.39; S, 13.80. EPR (water): |A iso |=116.4×10 - 4 T;g iso =1.966.

[0171] Example 4 - Synthesis of vanadium p-toluenesulfonate (“V-TS”)

[0172] A suspension of vanadium(V) oxide (56 g) mixed with ethanol (300 mL) and distilled water (150 mL) was treated with p-toluenesulfonic acid monohydrate (700 g) and heated at 110 °C for 3 hours. When the solution turned deep blue, the solution was filtered and the evaporation was evaporated. The product was washed with diethyl ether and dried under vacuum to give a blue solid. Yield: 290 g. Elemental analysis (C 14 H 24 O 12S2V): Calculated values: C, 33.67; H, 4.84; S, 12.84. Measured values: C, 33.48; H, 4.96; S, 12.51. EPR (water): |A iso |=116.4×10 -4 T;g iso =1.966.

[0173]

[0174] Example 5 - Synthesis of Vanadium dodecylbenzenesulfonate, V-DS

[0175]

[0176] 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 °C for 6 hours. When the solution turned deep blue, the solution was filtered and the evaporation was evaporated. The product was washed with hexane at -20 °C and dried under vacuum to give a blue, highly viscous liquid miscible with aromatic solvents (e.g., toluene, xylene). Yield: 44.3 g. Elemental analysis (C 36 H 68 O 12 S2V): Calculated values: C, 53.51; H, 8.48; S, 7.94. Measured values: C, 53.85; H, 8.84; S, 7.67. EPR (acetone): |A iso |=117.3×10 -4 T;g iso =1.966.

[0177] Example 6 - The effect of substituents on the curing of solvent-based alkyd resins

[0178] The catalytic activity of vanadium sulfonate was determined on a medium-oil content alkyd resin modified with vegetable drying oil S471. The effects of substituents were investigated in five derivatives. A given drying agent was dissolved in DMSO (100 μL) and treated with alkyd resin S471 (5 g), and the resulting mixture was homogenized for 2 min. The formulation was cast onto a glass plate (305 × 25 × 2 mm) through a frame applicator with a 76 μm gap. ENISO 9117-4 specifies the finger-touch time (T1), surface drying time (T2), hard drying time (T3), and complete drying time (T4) on a BYK drying recorder. The relative hardness of the formulation cast onto a glass plate (size: 200 × 100 × 4 mm) through a frame applicator with a 150 μm gap is determined. ENISO 1522, relative hardness was determined 100 days after application using an Elcometer with a Persoz-type pendulum. Drying time and relative hardness were determined under standard laboratory conditions (temperature = 23°C, relative humidity = 50 ± 10%). Formulations of V-acac and V-SO were prepared in a similar manner. Co-2EH was used as is from the supplier.

[0179] The drying times given in Table I demonstrate the high catalytic activity of vanadium sulfonates with vanadium concentrations ranging from 0.01 wt% to 0.06 wt% in dry matter. All the derivatives studied within this concentration range formed a fully dried film within 13.0 hours (T4 ≤ 13.0 hours). At the optimal dosage (0.03 wt%), the drying agent formed a film with a hard surface within 3.4 hours (T3 ≤ 3.4 hours) and a fully dried film within 5.3 hours (T4 ≤ 5.3 hours). V-TS maintained high activity even at concentrations up to 0.003 wt%. At this dosage, a fully dried film was observed 14.1 hours after casting. Notably, drying activity of V-TS was observed even at very low concentrations. At 0.001 wt%, the surface drying time did not exceed 12.9 hours (T2 = 12.9 hours). We note that V-TS was chosen to investigate other binders due to the catalytic activity observed at very low concentrations.

[0180] The relative hardness of the film cured by vanadium oxysulfonate varied from 32.6% to 52.8% after 100 days of formulation casting.

[0181] A comparison of drying time with a cobalt-based drying agent (Co-2EH) demonstrates that V-MS, V-FS, V-BS, V-TS, and V-DS function at much lower concentrations than this commercially available drying agent. The vanadium-based drying agent V-acac, at a concentration of 0.03 wt%, exhibits lower activity than all the vanadium sulfonates studied. The structural analogues of the compounds with sulfate anions (V-SO) shown here are completely inactive.

[0182] The drying times given in Table I indicate that vanadium compounds containing sulfonate anions exhibit high catalytic activity in the dry matter concentration range of 0.006 wt% to 0.06 wt%. Within this concentration range, both derivatives (V-MS and V-TS) form completely dry films within 13.9 hours (T4 ≤ 13.9 hours). At the optimal dosage, the derivative with aliphatic groups (V-MS; 0.03 wt%) forms a film with a hard surface within 3.4 hours (T3 = 3.4 hours) and a completely dry film within 4.4 hours (T4 = 4.4 hours).

[0183] At the optimal concentration (0.03 wt%), using a drying agent with an aromatic ring (V-TS), a film with a hard surface was obtained in 1.2 hours (T3 = 1.2 hours), and a completely dried film was obtained in 2.4 hours (T4 = 2.4 hours). Notably, drying activity was observed at very low concentrations (0.001 wt%). In this case, the surface drying time did not exceed 12.9 hours (T2 = 12.9 hours).

[0184] The relative hardness of the film, measured 100 days after casting, varied between 43.0% and 52.8%. V-TS was chosen to investigate other binders because catalytic activity was observed at very low concentrations (0.003 wt%). It forms a completely dry film within 14.1 hours.

[0185] A comparison of drying time with cobalt-based drying agents (Co-2EH) demonstrated that V-MS and V-TS functioned at significantly lower concentrations than commercially available drying agents. The vanadium-based drying agent V-acac showed lower activity than V-MS and V-TS at a concentration of 0.03 wt%. The structural analogues of the compounds containing sulfate anions (V-SO) exhibited were completely inactive.

[0186] Table I

[0187]

[0188]

[0189] a The formulation is touch-dry immediately after casting.

[0190] b No measurements were taken due to low surface dryness or surface defects.

[0191] Example 7 Curing of high-solids alkyd resins

[0192] The catalytic effect of the high-solids binder was evaluated using the drier V-TS and the high-solids binder TI870. The drier was dissolved in DMSO (100 μL) and treated with a given amount of alkyd resin (5 g). The mixture was diluted with dearomatic petroleum solvent oil to achieve 90% by weight of dry matter and homogenized for 2 minutes. The drying time of the formulation cast onto a glass plate through a 76 μm gap frame applicator was determined. The formulation was applied to a plate used for measuring relative hardness using a 90 μm gap frame applicator. Formulations Co-2EH, V-acac, and V-SO were prepared in a similar manner.

[0193] The measured drying times and relative hardness values ​​are given in Table II. Formulation V-TS / TI870 exhibited catalytic activity at vanadium concentrations ranging from 0.01 wt% to 0.1 wt% in dry matter. For this high-solids binder, the optimal concentration of the drying agent was determined to be 0.06 wt%. The relative hardness of the film measured after 100 days of casting varied from 17.1% to 24.9%.

[0194] Formulation V-TS / TRI841 exhibited catalytic activity at vanadium concentrations ranging from 0.01 wt% to 0.1 wt% in dry matter. For this high-solids binder, the optimal concentration of the drying agent was determined to be 0.03 wt%. The relative hardness of the film, measured after 100 days of casting, varied from 15.5% to 21.5%.

[0195] A comparison of drying times with the cobalt-based drying agent Co-2EH clearly shows that the formulation containing V-TS dries more completely. In fact, the formulation treated with Co-2EH did not dry completely within 24 hours (T4 > 24 hours), while the formulation with V-TS dried completely within 11.5 hours (T4 ≤ 11.5 hours). In binders TI870 and TRI841, the vanadium compounds V-acac and V-SO were inactive at a concentration of 0.06% by weight.

[0196] Table II

[0197]

[0198]

[0199] a No measurements were taken due to low surface dryness or surface defects.

[0200] Table III

[0201]

[0202] a It was not measured due to low surface dryness or surface defects.

[0203] Example 8 - Curing of alkyd resin modified by another monomer

[0204] The catalytic effect of the silicone alkyd resin binder was evaluated using the drying agent V-TS and the resin SPS15. The drying agent was dissolved in DMSO (100 μL) and treated with a given amount of alkyd resin (5 g) and homogenized for 2 minutes. The drying time of the formulation cast onto a glass plate through a 76 μm gap frame applicator was determined. The formulation was applied to a plate used for determining relative hardness using a 150 μm gap frame applicator. Formulations Co-2EH, V-acac, and V-SO were prepared in a similar manner.

[0205] The measured drying times and relative hardness values ​​are given in Table IV. Formulation V-TS / SPS15 exhibited catalytic activity at vanadium concentrations ranging from 0.003 wt% to 0.06 wt% in dry matter content. For this silanized binder, the optimal drier concentration was determined to be 0.03 wt%, comparable to that of the medium-oil S471 solvent-based alkyd resin binder. The relative hardness of the film measured after 100 days of casting varied from 32.8% to 46.2%.

[0206] A comparison of drying times with cobalt-based desiccants (Co-2EH) clearly shows that V-TS exhibits catalytic activity at much lower concentrations than commercially available desiccants. Vanadium compounds V-acac and V-SO showed no activity at a concentration of 0.06 wt%.

[0207] Table IV

[0208]

[0209]

[0210] a The formulation is touch-dry immediately after casting.

[0211] b No measurements were taken due to low surface dryness or surface defects.

[0212] Example 9 - Curing of waterborne alkyd resins and paint formulations

[0213] The catalytic misuse in aqueous systems was evaluated using V-TS, a drier in alkyd resin FP262 and a commercially available white pigment paint MLP9289 based on FP262. A stock solution (1 g) of V-TS was dissolved in distilled water (2 g) for formulation preparation. The drying time of the formulation cast onto a glass plate through a 76 μm gap frame applicator was determined. Formulations of V-SO were prepared in a similar manner. V-acac was pre-dissolved in DMSO before use. Co-2EH was used as is from the supplier.

[0214] Tables V and VI show the measured drying times for formulations FP262 and MLP 9289, respectively.

[0215] Formulation V-TS / FP262 exhibited high catalytic activity at vanadium concentrations ranging from 0.03 wt% to 0.06 wt% in dry matter. At these concentrations, surface drying time (T2) varied from 2.0 to 5.6 hours, and hard drying time (T3) varied from 6.0 to 11.7 hours. For the waterborne resin FP262, the optimal drier concentration was determined to be 0.06 wt%. Under the action of the cobalt-based drier Co-2EH, FP262 cured faster, but with significantly reduced uniformity. This is evidenced by the increase in T3 with increasing concentration.

[0216] The all-alkyd paint V-TS / MLP 9289 exhibits high catalytic activity in the dry matter of the resin at vanadium concentrations ranging from 0.03 wt% to 0.06 wt%. For MLP 9289, the optimal concentration of the drier was determined to be 0.06 wt%, comparable to that of the binder FP262. This demonstrates that pigments and other additives have minimal impact on the catalytic activity of the drier V-TS.

[0217] The vanadium compounds V-acac and V-SO were inactive at a concentration of 0.06 wt%. Notably, none of the studied aqueous systems were completely dried within 24 hours.

[0218] Table V

[0219]

[0220]

[0221] Table VI

[0222]

[0223] Example 10 Stability of vanadium sulfonate in solution

[0224] The stability of the drying agents V-TS and V-DS in solution was evaluated. V-TS (1 g) was dissolved in DMSO (4 g) to obtain a blue solution, which was stored in sealed glass vials (10 mL) at room temperature under air atmosphere. The drying time of a formulation of solvent-based alkyd resin S471, cast onto a glass plate through a frame applicator with a 76 μm gap, was determined and compared with that of a freshly prepared V-TS solution. The stability of V-DS was evaluated in a similar manner using solutions prepared from V-DS (1 g) and xylene (1 g). Notably, the stock solution showed no visual change after storage.

[0225] The measured drying times are given in Table VII. V-TS solutions in DMSO showed only minor changes in catalytic activity over 30 days of storage, as demonstrated by formulation S471 with vanadium concentrations ranging from 0.01 wt% to 0.03 wt% in dry matter. All V-TS formulations studied were completely dried within 5.2 hours (T4 ≤ 5.2 hours). An acceptable decrease in catalytic activity was also observed for V-DS solutions in xylene. Within the concentration range of 0.01 wt% to 0.03 wt%, storage for 9 days prolonged the curing process of xylene solutions. The complete drying time (T4) was approximately twice that observed for fresh solutions.

[0226] Table VII

[0227]

[0228] Example 11 -Stability of paint formulations

[0229] The stability of V-TS in paint formulations was evaluated on alkyd resin S471 treated with an anti-skinning agent. A solution of V-TS in DMSO (a 1:4 mixture by weight) was treated with alkyd resin S471 (25 g) and methyl ethyl ketone oxime (30 mg). The formulation was dispensed into glass vials (5 mL) and stored at room temperature. The drying time of the formulation cast onto a glass plate through a 76 μm gap frame applicator was determined.

[0230] The measured drying times are given in Table VIII. For V-TS with a metal concentration of 0.03 wt%, a negligible change in catalytic activity after storage was noted, as the stored formulation dried completely within 2.1 hours (T4 = 1.1 to 2.1 hours), while the fresh formulation dried within 1.7 hours (T4 = 1.7 hours). At lower doses (0.01 wt%), a slight decrease in activity was observed over 7 days, with T4 increasing from 7.1 hours to 12.8 hours, as recorded. After this period, the formulation remained stable, as only a negligible change in drying time was observed.

[0231] Table VIII

[0232]

[0233] Example Experimental details from #12 to #18:

[0234] In most cases, V-TS is used in aqueous solution, which must be freshly prepared on the day of use, as it will form a large amount of precipitate after standing for several hours (usually >12-24 hours). V-TS can also dissolve in polar organic solvents without forming a precipitate, but experience with these solutions is limited.

[0235] It was found that adding a base (ethanolamine) to freshly prepared V-TS aqueous solution directly produced a large amount of precipitation. The stable solution obtained after more than two weeks was V-TS (10%) dissolved in a 98:2 water:acetic acid solution.

[0236] Vanadium oxydodecylbenzenesulfonate (“V-DS”) is soluble in most organic solvents, and these solutions appear to be stable. For applications in SB formulations, a solution in xylene is used. For applications in WB formulations, a 70:30 mixture of 2-methyl-1-pentanol and isobutyl acetate is used.

[0237] The formulation for cast film is prepared as follows: A suitable amount of drier, typically a stock solution of a defined concentration, is weighed into a plastic vial, and then the binder solution is added. The amount of drier is calculated by referring to the dry matter values ​​specified for each binder solution. Mixing is achieved by placing the vial into a high-speed mixer (SpeedMixer DAC 150.1FVZ) and rotating at 2000 rpm for two minutes. Typically, a homogeneous mixture is obtained. This mixture is then allowed to stand under ambient conditions for 24 hours before casting.

[0238] The drying time recorder “BKdrying recorders model 3” (The Mickle laboratory engineering Co Ltd.) was used to measure the time required to reach the following drying states: touch dry (ST, i.e., no longer moving freely through the soft coating, but beginning to tear the hardened film), surface dry (TF, i.e., no longer tearing the film but still leaving continuous lines on the coating), and hard dry (DH, i.e., leaving no trace on the film).

[0239] A 100 μm thick film was cast onto a glass strip (30 × 2.4 cm) using a steel cubic applicator. The strip was then placed on a drying time recorder, a needle was positioned on the film, and the recorder was set to measure for more than 24 hours and started. The starting point of the needle placement on the film was marked on the glass. The drying time was read from the mark left on the film after 24 hours. A drying time expressed as "24 hours" indicates a drying time ≥ 24 hours, as times longer than 24 hours could not be measured.

[0240] The coating and drying time of the glass strips were recorded in a climate-controlled room with a temperature of 23°C and a humidity of ca.45%.

[0241] A 100 μm thick film was cast onto a glass plate (15 × 9 cm) to measure hardness while recording the drying time of the cast film. After a given drying time, these were evaluated using a pendulum hardness tester. The method involved measuring the pendulum hardness using a TQC Sheen SP0500 pendulum hardness tester (measured in seconds, starting from an initial amplitude of 6° up to 3°). Softer materials suppressed pendulum oscillations more quickly than harder materials, thus resulting in lower hardness values ​​per second for softer materials. The coating, storage, and hardness measurements of the glass plates were conducted in a climate-controlled chamber at 23°C and ca. 45% humidity.

[0242] Catalyst concentration is given as a percentage of metals, referring to the amount of metal in the catalyst relative to the solid content of the binder and formulation used, respectively. Typically, catalysts are used for initial testing at three concentrations: 0.001%, 0.01%, and 0.1% of metals. For BOC and Borchers Deca Cobalt 7aqua, standard concentrations of 0.001% and 0.03% of metals are used, following general recommendations for these driers.

[0243] Example #12 - Other formulas (see Tables IX to XI)

[0244] Table IX-11Ycc (a water-based transparent coating based on TOD 3AK0211Y)

[0245] entry Element type Quantity (g) 1 TOD 3AK0211Y (72% solids) resin 150.0 2 Dimethylethanolamine amine 3.3 3 Ethylene glycol butyl ether solvent 7.5 4 Deionized water solvent 180.0 5 <![CDATA[20% aqueous solution of NaNO2]]> Anti-flash rust 2.5 6 Borchi Gol 1375, Borchers wetting agent 0.3 7 Borchi Gel 0620(50%),Borchers rheology modifiers 0.6

[0246] Table X-11Ywp (White paint based on TOD 3AK0211Y, water-based)

[0247] entry Element type Quantity (g) 1 Transparent coating based on TOD 3AK0211Y Resin preparations 70.0 2 Deionized water solvent 8.2 3 Borchi Gen 1252, Borchers dispersant 0.6 4 Aminopropanol 95% amine 0.1 5 Borchers AF 1171, Borchers additive 0.1 6 R996 titanium dioxide pigment 21.0

[0248] Table XI-vSAcc (a transparent, water-based coating based on Synaqua 4804)

[0249]

[0250]

[0251] Example #13 - Curing of water-based resins

[0252] This example demonstrates that an aqueous resin (Synaqua 4804 short oil) can be cured. A given drier is dissolved in water (V-TS) or an alcohol-ester mixture (vanadium p-toluenesulfonate (“V-TS”)) to ensure the homogeneity of the aqueous formulation, such as a mixture of 2-methyl-1-pentanol and isobutyl acetate. Commercially available driers BOC-1101 and Deca Cobalt 7aqua are used as references at their optimized dosage levels given in the technical data sheets.

[0253] Drying time and hardness were measured as described in the “Experimental Details of Examples #12 to #18” section above.

[0254] Table XII

[0255]

[0256] b Add 0.01% metal of V-TS;

[0257] c Add 0.01% metal V-DS.

[0258] Data shows that both V-TS and V-DS can significantly improve drying time compared to BOC and cobalt. At high concentrations, V-driers can also outperform cobalt-based dryers in terms of hardness after both short and long curing times. The combination of BOC-1101 and V-driers can be advantageous: the two catalysts are compatible and together improve both drying time and hardness.

[0259] Example #14 - Curing of solvent-based oleoyl alcohol resin

[0260] The purpose of this embodiment is to determine whether V-driers can be used for curing standard solvent-based medium-oil alkyd resin (Worlée Kyd S 351). The given drier is dissolved in DMSO (V-TS) and a mixture of 2-methyl-1-pentanol and isobutyl acetate (V-DS).

[0261] Drying time and hardness were measured as described in the “Experimental Details of Examples #12 to #18” section above.

[0262] Table XIII

[0263]

[0264] This example demonstrates that, in standard oil-solvent alkyds, V-driers can provide significantly improved drying time compared to BOC and cobalt-driers, as well as improved hardness compared to BOC.

[0265] Example 15 - Curing of other water-based alkyds

[0266] The purpose of this embodiment is to determine whether V-drier can be used for curing other water-based alkyds. Long oil (Beckosol 101) and medium oil (Synaqua 2070) were used. The drier V-TS was dissolved in water.

[0267] Drying time and hardness were measured as described in the “Experimental Details of Examples 12 to 18” section above.

[0268] Table XIV

[0269]

[0270] The results show that V-TS can be used as a drying agent for water-based long oils and medium oil alkyds.

[0271] Example #16 Curing of the entire formulation of water-dilutable alkyd

[0272] The purpose of this embodiment is to determine whether V-drier can be used for curing both full-formulation and water-dilutable alkyd (formulation 11Ycc). In this case, a transparent coating formulation is used.

[0273] The given drier is dissolved in DMSO (V-TS) and a mixture of 2-methyl-1-pentanol and isobutyl acetate (V-DS).

[0274] Drying time and hardness were measured as described in the “Experimental Details of Examples 12 to 18” section above.

[0275] Table XV

[0276]

[0277] The results showed that the V-drier was compatible with fully transparent coating formulations and water-dilutable alkyds. Under moderate load (1 / 3 that of cobalt), the long-term hardness reached the level of the cobalt-drier and exceeded that of BOC. Under high load, the hardness after 7 days exceeded that of both BOC and cobalt, and after 29 days it was more than twice that of cobalt.

[0278] Example 17 Curing of pigment formulations with water-dilutable alkyd acids

[0279] The purpose of this embodiment is to determine whether V-drier can be used for curing pigment formulations of water-dilutable alkyd (formulation 11Ywp).

[0280] The given drier is dissolved in DMSO (V-TS) and a mixture of 2-methyl-1-pentanol and isobutyl acetate (V-DS).

[0281] Drying time and hardness were measured as described in the “Experimental Details of Examples 12 to 18” section above.

[0282] Table XVI

[0283]

[0284]

[0285] The results showed that the V-drier was compatible with both full-pigment formulations and water-dilutable alkyds. At medium loads (1 / 3 that of cobalt), some drying loss was observed in the presence of pigment. At high loads, improved drying time was observed, with hardness exceeding that of BOC and becoming comparable to cobalt after 7 days, exceeding cobalt after 14 days, and becoming twice as hard as cobalt after 29 days.

[0286] Example #18 - Curing of the entire formulation of waterborne alkyd

[0287] The purpose of this embodiment is to determine whether V-driers can be used for the curing of whole formulations of aqueous alkyd (vSAcc), and whether they are compatible with the separately added ligands and secondary driers.

[0288] The given V-drier is dissolved in a mixture of 2-methyl-1-pentanol and isobutyl acetate.

[0289] Drying time and hardness were measured as described in the “Experimental Details of Examples 12 to 18” section above.

[0290] Table XVII

[0291]

[0292] a Add 1.0 equivalent of TMTACN relative to the drier;

[0293] b Add 0.2% metal of Calcium-Hydrochem;

[0294] c Add 0.2% metal of Octa Soligen Zirconium 10aqua;

[0295] d Add 0.01% metal V-DS.

[0296] The results showed that the V-drier was compatible with aqueous formulations of transparent coatings containing a secondary drier and additional ligands. The addition of the secondary drier contributed to both drying time and initial hardness. Combination with the ligand TMTACN increased drying time, but it contributed to long-term hardness. Under the same loading as cobalt, the V-drier surpassed the hardness achieved by cobalt after 28 days. The combination of BOC and V-drier achieved the highest hardness, exceeding that of cobalt after 14 and 28 days. This indicates that the synergistic effect between the two catalysts provided an overall advantage in terms of both hardness and drying time.

[0297] Example 19 - Curing with oxalic acid as an additive

[0298] The purpose of this embodiment is to determine whether V-driers can be improved when oxalic acid is present as both an additive and a ligand.

[0299] The V-drier was dissolved in an aqueous solution of oxalic acid dihydrate (8%) to obtain a V-TS solution containing 10% by weight of oxalic acid relative to 3 molar equivalents of vanadium. Oxalic acid was found to stabilize the aqueous solution in a similar manner to acetic acid.

[0300] 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 in Formulation 11Ycc, and the experiments in Table XIX were performed in Synaqua 4804 short oil.

[0301] Table XVIII

[0302]

[0303] Table XIX

[0304]

[0305] The results showed that while oxalic acid slightly increased the drying time, it increased the hardness of the coating. Although oxalic acid, as shown above, is a C2 dicarboxylic acid, the types of acids that improve coating hardness are not limited to this dicarboxylic acid. In fact, acetic acid, a C1 monocarboxylic acid, is also known to be effective. It is reasonable that all C1-C... 18 Monocarboxylic acids and C2-C 18 Dicarboxylic acids are effective in increasing the hardness of coatings.

[0306] To illustrate the best mode known at the time of filing this application, the best mode for carrying out the invention has been described. These embodiments are merely illustrative and are not intended to limit the invention as measured by the scope and value of the claims. The invention has been described with reference to preferred and alternative embodiments. It is obvious that modifications and variations will occur to others upon reading and understanding this specification. All such modifications and variations are intended to be included, provided they fall within the scope of the appended claims or their equivalents.

Claims

1. A paint formulation, comprising Alkyd adhesives; and At least one drying agent including vanadium compounds of formula (VII), Where R 1 and R 2 Independently selected from C1-C 12 Alkyl, C1-C 12 Haloalkyl, C6-C 10 Aryl and benzyl; wherein aryl and benzyl are optionally independently selected from C1-C2. 20 The alkyl group and the C1-C2 hydroxyalkyl group are substituted with up to three substituents.

2. The paint formulation according to claim 1, wherein, The formulation comprises one or more vanadium sulfonate compounds of formula (VII) at a total concentration of 0.001% to 0.1% by weight in the dry matter content of the paint.

3. The paint formulation according to claim 2, wherein, The formulation comprises one or more vanadium sulfonate compounds of formula (VII) at a total concentration of 0.003% to 0.1% by weight in the dry matter content of the paint.

4. The paint formulation according to claim 3, wherein, The formulation comprises one or more vanadium sulfonate compounds of formula (VII) having a total concentration of 0.006% to 0.06% by weight in the dry matter content of the paint.

5. The paint formulation according to claim 1, wherein, The C1-C 12 The alkyl halide is C1-C 12 Fluoroalkyl groups.

6. The paint formulation according to claim 1, wherein, The formulation also includes water.

7. The paint formulation according to claim 1, wherein, The formulation is non-aqueous.

8. The paint formulation according to claim 1, further comprising ligands selected from the following: Bispidon, N4py type, TACN type, Cyclam and cross-bridged ligands, and Trispicen type ligands.

9. The paint formulation according to claim 8, wherein, The ligand is the bispidon ligand of formula (I). in: Each R is independently selected from hydrogen, F, Cl, Br, hydroxyl, C 1-4 -alkylO-, -NH-CO-H, -NH-CO-C 1-4 Alkyl, -NH2, -NH-C 1-4 Alkyl and C 1-4 alkyl; R1 and R2 are independently selected from C 1-24 Alkyl, C 6-10 Aryl groups and groups containing one or two heteroatoms selected from N, O or S that can coordinate with transition metals; R3 and R4 are independently selected from hydrogen, C 1-8 Alkyl, C 1-8 Alkyl-OC 1-8 Alkyl, C 1-8 Alkyl-OC 6-10 Aryl, C 6-10 Aryl, C 1-8 Hydroxyalkyl and -(CH2) n C(O)OR5, where R5 is independently selected from hydrogen and C. 1-4 alkyl, n is between 0 and 4; X is selected from: C=O, -[C(R6)2] y -, where y is between 0 and 3; and Each R6 is independently selected from hydrogen, hydroxyl, C 1-4 Alkoxy and C 1-4 alkyl; Alternatively, the ligand may be an N4py type ligand of formula (II). in: Each R1 and R2 independently represents -R4-R5; R3 represents hydrogen, C 1-8 -alkyl, or C 7-40 Arylalkyl, or -R4-R5, Each R4 independently represents a single bond or a straight or branched C bond. 1-8 -alkyl-substituted -C 2-6 -alkylene, C 2-6 - Idemenyl, C 2-6 -alkylene oxide, C 2-6 -aminoalkylene, C 2-6 -Alkenyl ether, C 2-6 -Carboxylic acid ester or C 2-6 -Carboxylic acid amides, and Each R5 independently represents an N-alkyl-substituted aminoalkyl group or an alkyl-substituted heteroaryl group, wherein the heteroaryl group is selected from pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, pyrroleyl, carbazoleyl, indolyl, and isoindolyl, wherein the heteroaryl group is optionally linked to the compound via any atom in the ring of the selected heteroaryl group; Alternatively, the ligand may be a TACN-type ligand of formula (III). in: Each R20 is independently selected from: C 1-8 -alkyl; C 3-8 -Cycloalkyl; selected from the following heterocycloalkyl groups: pyrrolinyl, pyrrolylyl, morpholinyl, piperidinyl, hexamethyleneimine, 1,4-piperazinyl, tetrahydrothiopheneyl, tetrahydrofuranyl, 1,4,7-triazacyclononyl, 1,4,8,11-tetraazacyclotetradecyl, 1,4,7,10,13-pentazacyclopentadecanyl, 1,4-diaza-7-thiocyclononyl, 1,4-diaza-7-oxacyclononyl, 1,4,7,10-tetraazacyclododecyl, 1,4-dicyclononyl Alkyl, 1,4,7-trithiacyclononyl, tetrahydropyranyl and Azoxyalkyl group, wherein the heterocyclic alkyl group is optionally linked to the compound via any atom in the ring of the selected heterocyclic alkyl group; a heteroaryl group selected from the following: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, pyrroleyl, carbazoleyl, indoleyl, and isoindoleyl, wherein the heteroaryl group is optionally linked to the compound via any atom in the ring of the selected heteroaryl group; or optionally selected from hydroxyl, alkoxy, phenoxy, carboxylates, formamides, carboxylic esters, sulfonates / esters, amines, and N-hydroxyl groups. + (R21)3 substituent C 7-40 -Arylalkyl group, R21 is selected from hydrogen, C 1-8 -alkyl, C 2-6 -Alkenyl, C 7-40 -Arylalkyl, arylalenyl, C 1-8 -Oxyalkyl, C 2-6 -Oxylenyl, C 1-8 -aminoalkyl, C 2-6 -Aminoolefin, C 1-8 -alkyl ethers, C 2-6 -Alkenyl ethers and -CY2-R22, Y is independently selected from H, CH3, C2H5, C3H7, and R22 is independently selected from C 1-8 -alkyl-substituted heteroaryl groups, said heteroaryl group being selected from: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, pyrrololyl, carbazolel, indoleyl, and isoyindoleyl, wherein said heteroaryl group is optionally linked to the compound via any atom in the ring of the selected heteroaryl group; and Among them, at least one of R20 is -CY2-R22; Alternatively, the ligand may be a cyclam of formula (IV) or a cross-bridged ligand. in: Q is selected independently P is 4; R is independently selected from: hydrogen, C 1-6 -alkyl, CH2CH2OH, pyridin-2-ylmethyl and CH2COOH, or one of R is connected to the N of another Q via an ethylene bridge; and R1, R2, R3, R4, R5, and R6 are independently selected from: H, C 1-4 -alkyl, and C 1-4 -alkylhydroxyl; Alternatively, the ligand may be a cross-bridged ligand of formula (V): in: R 1 Independently selected from H and C 1-20 Alkyl, C 7-40 -alkylaryl, C 2-6 -Alkenyl or C 2-6 -Alynyl group; Alternatively, the ligand may be a trispicen-type ligand of formula (VI): R17R17N-X-NR17R17(VI), in: X is selected from -CH2CH2-, -CH2CH2CH2-, and -CH2C(OH)HCH2-. Each R17 independently represents a group selected from the following: C 1-8 -alkyl; C 3-8 -Cycloalkyl; selected from the following heterocycloalkyl groups: pyrrolinyl, pyrrolylyl, morpholinyl, piperidinyl, hexamethyleneimine, 1,4-piperazinyl, tetrahydrothiopheneyl, tetrahydrofuranyl, 1,4,7-triazacyclononyl, 1,4,8,11-tetraazacyclotetradecyl, 1,4,7,10,13-pentazacyclopentadecanyl, 1,4-diaza-7-thiocyclononyl, 1,4-diaza-7-oxacyclononyl, 1,4,7,10-tetraazacyclododecyl, 1,4-dicyclononyl Alkyl, 1,4,7-trithiacyclononyl, tetrahydropyranyl and Azolane alkyl group, wherein the heterocyclic alkyl group is optionally linked to the compound via any atom in the ring of the selected heterocyclic alkyl group; a heteroaryl group selected from the following: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, pyrroleyl, carbazoleyl, indoleyl, and isoindoleyl, wherein the heteroaryl group is optionally linked to the compound via any atom in the ring of the selected heteroaryl group; and optionally selected from hydroxyl, alkoxy, phenoxy, carboxylates, formamides, carboxylic esters, sulfonates / esters, amines, and N-hydroxyl groups. + (R19)3 substituent C 7-40 alkylaryl, wherein R19 is selected from hydrogen, C 1-8 -alkyl, C 2-6 -Alkenyl, C 7-40 -Arylalkyl, C 7-40 -Arylene, C 1-8 -Oxyalkyl, C 2-6 -Oxylenyl, C 1-8 -aminoalkyl, C 2-6 -Aminoalkenyl, C 1-8 -alkyl ethers, C 2-6 -Alkenyl ether and -CY2-R18, wherein each Y is independently selected from H, CH3, C2H5, C3H7, and R18 is independently selected from optionally substituted heteroaryl groups selected from pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, pyrroleyl, carbazoleyl, indolyl, and isoindolyl, wherein the heteroaryl group is optionally linked to the compound via any atom in the ring of the selected heteroaryl group; and at least two of R19 are -CY2-R18.

10. The paint formulation according to claim 8, wherein, The ligand is N,N,N-trimethyl-1,4,7-triazacyclononane.

11. The paint formulation according to claim 10, further comprising the chloride (1:1) of chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylate-kN3,kN7]-ferric(1+) as shown below.

12. The paint formulation according to claim 1, further comprising pigment.

13. The paint formulation according to claim 1, further comprising: C1-C 18 Monocarboxylic acids are used to make the coating as hard as that without the addition of C1-C. 18 The amount of monocarboxylic acid in paint formulations has increased compared to previous versions; or C2-C 18 Dicarboxylic acid is used to make the coating as hard as that without the addition of C2-C. 18 The amount of dicarboxylic acid in paint formulations has increased compared to previous versions.

14. The paint formulation according to claim 13, wherein, The C2-C 18 The dicarboxylic acid is oxalic acid.

15. The paint formulation according to claim 1, wherein, The alkyd-based binder is a solvent-based or water-based resin.

16. Use of a vanadium sulfonate compound of formula (VII) in dimethyl sulfoxide, alcohol, or mixtures thereof as a drying agent for paints containing alkyd binders. in, R 1 and R 2 Independently selected from C1-C 12 Alkyl, C1-C8 fluoroalkyl, C6-C 10 Aryl, benzyl; among which The C6-C 10 The aryl and benzyl groups are optionally and independently selected from C1-C. 20 Alkyl and C1-C2 hydroxyalkyl groups are substituted with one to at most three substituents.

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