Polymeric agents and compositions for inhibiting corrosion

Abstract

The present disclosure relates to methods, compositions, and agents for inhibiting corrosion in various substrates, such as metal substrates. The present disclosure also relates to corrosion inhibitors comprising organometallic polymers such as metal-organic frameworks (MOFs), including compositions and methods comprising MOFs for inhibiting corrosion in metal substrates.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] The present application claims priority from the content of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to methods, compositions, and agents for inhibiting corrosion in various substrates, such as metal substrates. The present disclosure also relates to corrosion inhibitors comprising organometallic polymers such as metal-organic frameworks (MOFs), including compositions and methods comprising MOFs for inhibiting corrosion in metal substrates. Background Art

[0004] Protecting substrates such as metal substrates from atmospheric corrosion presents a difficult challenge and is of great economic significance. The numerous metal substrates that require protection from corrosion typically include aluminum alloys, ferrous metals, zinc metals, and alloys used in protective coatings used in the aerospace industry.

[0005] It is well known that pigment-grade corrosion inhibitors for use in organic primers require anionic species with inhibitor activity that have limited but effective solubility in water. For these reasons, chromate-based corrosion inhibitors have been preferred in two corrosion control technologies applied to aluminum protection against atmospheric corrosion, such as those provided in conversion coatings and high-performance organic primers. For decades, hexavalent chromate ions have been demonstrated to be excellent corrosion inhibitors for many metal and alloy systems. However, the toxicity and carcinogenicity of chromate ions have been known for some time, and extensive research has been conducted over the past 30 years to find environmentally acceptable alternatives.

[0006] It is generally known that the number of inorganic corrosion inhibitor species that can be used as chromate substitutes is actually limited to a few anionic species, including molybdates, phosphates, borates, silicates and cyanamides, if toxicity, efficiency and price are taken into account. As a result, all commercial non-chromate corrosion inhibitor pigments are molybdates, phosphates, borates, silicates or cyanamides, or combinations of these compounds. Compared to chromates, the inherent limitations of their corrosion protection mechanisms make anionic species less effective inhibitors for corrosion in general and atmospheric corrosion of aluminum in particular. There is a need for alternative inhibitors of atmospheric corrosion that may be more effective non-toxic alternatives to hexavalent chromates.

[0007] In contrast, a large number of organic corrosion inhibitors have recently become known and are used in various corrosion control technologies. When used in conversion coating technology and in organic coatings, the excessive solubility in water and / or volatility of most known organic inhibitors are limiting factors.

[0008] Considerable progress has been made in identifying alternative corrosion inhibitors, and salts of transition metals and rare earth metals offer possible alternatives for many applications, including deoxidation and pickling solutions, etchants, anodizing and conversion coatings, primer paints, and sealants. For example, cerium chloride was discovered in the early 1980s (Hinton et al.) to be an excellent inhibitor for aluminum alloys. Alkali metal salts of carboxylic acids, such as cinnamate, have also been found to effectively inhibit corrosion of mild steel.

[0009] Combinations of rare earth metal ions with effective organic inhibitors have also been found to suppress both anode and cathode reactions (i.e., mixed inhibitors). For example, Behrouzvaziri et al. (2008) and Blin et al. (2007) have utilized electrochemical studies to show that lanthanum hydroxycinnamate provides corrosion inhibition in chloride solutions. For aluminum alloys, Ho et al. (2006) and Markley et al. (2007) have shown that diphenyl cerium phosphate and dibutyl cerium phosphate are very good corrosion inhibitors for aluminum alloys. For example, US5298148 describes a series of powder coating formulations selected from lanthanum acetate, lanthanum butyrate, lanthanum oxalate, lanthanum nitrate, lanthanum hydroxide, lanthanum oxide, and lanthanum tungstate.

[0010] Organic compounds with aromatic properties, such as carbocyclic and heterocyclic aromatic structures, have also been found to be effective corrosion inhibitors for aluminum and its alloys and can be provided, for example, in the form of metal salts or metal complexes. For example, WO 2004 / 085551 relates to corrosion inhibiting coatings comprising rare earth-based organic compounds and / or combinations of rare earth metals and organic compounds for use in coatings including epoxy primers, for the corrosion protection of metals. Most known alternative chromate-based corrosion inhibitors suffer from various problems, including limited corrosion inhibition activity or incompatibility with various coating combinations.

[0011] There is a need to identify alternative corrosion inhibitors for protecting substrates, for example in metal substrates such as metal alloys, which are chromate-free corrosion inhibitors suitable for use in protective compositions. Summary of the Invention

[0012] Research was conducted to identify improved coating compositions and chromate-free corrosion inhibitors for protecting various substrates, such as metal substrates, from corrosion. During this research, it was identified that typical corrosion inhibiting agents, such as organic heterocyclic compounds, can problematically react with other components of the composition, for example, with resins used in paint compositions. In light of these identified problems, further research was conducted and surprisingly, various organometallic polymers were identified as being effective as corrosion inhibitors while offering the advantage of compatibility with a wide range of components in the composition.

[0013] In a first aspect, a method of protecting a substrate from corrosion is provided, comprising applying a protective composition comprising a corrosion inhibitor to a surface of the substrate, wherein the corrosion inhibitor comprises a metal organic framework material (MOF).

[0014] The substrate can be a metal substrate. It should be appreciated that the metal substrate can comprise any substrate material whose surface is at least partially metallic. The metal substrate can include any metal that needs to be protected from corrosion. The metal substrate can be a copper-rich alloy, for example, a copper-rich aluminum alloy.

[0015] MOFs can include metal ions or metal clusters, each coordinated to one or more organic ligands to form a one-dimensional, two-dimensional, or three-dimensional network. MOFs can be selected to have a porous three-dimensional network.

[0016] The one or more organic ligands of the MOF can be selected from optionally substituted aryl, heteroaryl, or heterocyclic compounds. The one or more organic ligands can be selected from optionally substituted aryl, heteroaryl, or heterocyclic compounds comprising at least two heteroatoms selected from N, O, and S. The one or more organic ligands can be selected from optionally substituted aryl, heteroaryl, or heterocyclic compounds comprising at least one exocyclic sulfur group. The exocyclic sulfur group can be selected from thiols and thioketones. The organic ligands can be selected from optionally substituted, optionally fused, 5- or 6-membered mono- or bicyclic aryl, heteroaryl, or heterocyclic compounds comprising at least one exocyclic sulfur group selected from thiols and thioketones. The at least one exocyclic sulfur group can be a thiol.

[0017] The optionally substituted aryl, heteroaryl or heterocyclic compound may be unsubstituted or substituted with alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl, formyl, alkanoyl, cycloalkanoyl, aroyl, heteroaroyl, carboxyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, heteroaryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, heterocyclylaminocarbonyl, heteroarylaminocarbonyl, cyano, alkoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, alkanoate, Cycloalkanoate, aromatic ester, heterocyclic ester, heteroaromatic ester, alkylcarbonylamino, cycloalkylcarbonylamino, arylcarbonylamino, heterocyclylcarbonylamino, heteroarylcarbonylamino, nitro, alkylthio, cycloalkylthio, arylthio, heterocyclylthio, heteroarylthio, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, heterocyclylsulfonyl, heteroarylsulfonyl, hydroxyl, halo, haloalkyl, haloaryl, haloheterocyclyl, haloheteroaryl, haloalkoxy, haloalkylsulfonyl, silylalkyl, alkenylsilylalkyl, alkynylsilylalkyl, amino, thiol, and thionyl. The optionally substituted aryl, heteroaryl, or heterocyclic compound may be unsubstituted or substituted with the following groups: halo, alkyl, formyl, amino, thiol, and thione. The optionally substituted aryl, heteroaryl, or heterocyclic compound may be unsubstituted or substituted with the following groups: amino, thiol, and thione.

[0018] In an embodiment, a method of protecting a substrate from corrosion comprises applying a protective composition comprising a corrosion inhibitor to a surface of the substrate, wherein the corrosion inhibitor comprises a metal organic framework material (MOF), wherein the MOF comprises metal ions or metal clusters, each coordinated to one or more organic ligands to form at least one-dimensional, two-dimensional, or three-dimensional network, and wherein the one or more organic ligands are selected from optionally substituted aryl, heteroaryl, or heterocyclic compounds, wherein each of the aryl, heteroaryl, or heterocyclic compounds comprises at least one exocyclic sulfur group.

[0019] In an embodiment, the one or more organic ligands are selected from compounds of Formula 1:

[0020]

[0021] in:

[0022] A is a 5- or 6-membered aryl, heteroaryl or heterocyclic ring, optionally substituted with one or more substituents and optionally fused to one or more aryl or heteroaryl rings, wherein the dashed line represents one or more optional double bonds;

[0023] X 1 Selected from N, NR 1 , O, S, CR 2 and CR 3 R 4 ;

[0024] X 2 Selected from N, NR 5 , O, S, CR 6 and CR 7 R 8 ;

[0025] X 3 Selected from N, NR 9 , CR 10 and CR 11 R 12 ;

[0026] R 1 、R 5 and R 9 Each is independently selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0027] R 2 、R 3 、R 4 、R 6 、R 7 、R 8 、R 10 、R 11 and R 12 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted.

[0028] In an embodiment, X 1 Selected from N, NR 1 , O and S. In an embodiment, X 1 It may be selected from N, NH and S.

[0029] In an embodiment, X 3 Selected from N and CR 10 In an embodiment, R 10 is selected from thiols and thioketones. In an embodiment, X 3 It's C-SH.

[0030] In an embodiment, X 1 Selected from N, NR 1 , O and S; and X 3 Selected from N and CR10 In an embodiment, X 1 is selected from N, NH and S. In an embodiment, R 10 is selected from thiols and thioketones. In an embodiment, X 3 It's C-SH.

[0031] The metal ion or metal cluster of MOF can include one or more metal ions selected from rare earth, alkaline earth and transition metal.Metal can be selected from Zn, La, Pr, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Co, Y, Ca, Sr, Ba, Sc, Zr and its combination.Metal ion can be selected from Zn, Pr and Ce.In coordination framework materials, the metal ion or metal cluster of MOF generally include single type of metal ion.In coordination framework materials, metal ion or metal cluster can include mixed metal system, for example, metal ion or metal cluster can contain two or more different metals.

[0032] The MOF can be formed into solid particles suitable for dispersion in the composition. The average diameter of the MOF particles can be in the range of 20 nm to 50 μm, 40 nm to 30 μm, 60 nm to 10 μm, 80 nm to 5 μm, or 100 nm to 1 μm. The average diameter of the MOF particles can be in the range of 100 nm to 1 μm. The MOF can be selected to have a substantially white coloration.

[0033] In a second aspect, a corrosion inhibiting agent for protecting a substrate from corrosion is provided, wherein the corrosion inhibiting agent is a metal organic framework material (MOF).

[0034] In a third aspect, there is provided the use of a metal organic framework material (MOF) as a corrosion inhibitor for protecting a substrate from corrosion.

[0035] In a fourth aspect, a corrosion inhibiting composition for application to a substrate is provided, comprising at least one corrosion inhibitor selected from metal organic framework materials (MOFs).

[0036] The corrosion inhibiting composition may include a film-forming organic polymer. The composition may be a coating composition. The coating composition may be a powder coating composition, such as a powder coating composition suitable for use in various steel powder coatings. The coating composition may include one or more resins, such as epoxy resins. The coating composition may be a paint composition, such as an epoxy resin-based paint composition. The coating composition may be a spray composition. It will be appreciated that the composition may include one or more additives, such as pigments, fillers, and extenders. The MOF may be selected to have a light or substantially white color. The composition may be substantially free of pigment additives. For example, the composition may include less than 1%, less than 0.1%, less than 0.01%, less than 0.001%, and less than 0.0001% of any pigment additive.

[0037] In a fifth aspect, a method of preparing a corrosion inhibiting composition for application to a substrate is provided, comprising forming the composition by mixing a film-forming organic polymer and at least one corrosion inhibitor selected from metal organic frameworks (MOFs).

[0038] In a sixth aspect, a coated substrate is provided, comprising a substrate coated with a corrosion inhibiting composition comprising a metal organic framework (MOF). The coated substrate may include one or more layers of a coating applied to the substrate before and / or after application of the corrosion inhibiting composition. The corrosion inhibiting composition may be applied as a direct coating to the surface of the substrate. The corrosion inhibiting composition may comprise a film-forming organic polymer. The substrate may be a metal alloy. The coated substrate may be an aerospace part.

[0039] It should be appreciated that any one or more of the embodiments described above for the first aspect may also be employed as embodiments of the other aspects described above. For example, the second, third, fourth, fifth, or sixth aspects may relate to a MOF comprising metal ions or metal clusters, each of which is coordinated to one or more organic ligands to form at least one, two, or three-dimensional network, and wherein the one or more organic ligands are selected from optionally substituted aryl, heteroaryl, or heterocyclic compounds, wherein each of the aryl, heteroaryl, or heterocyclic compounds comprises at least one exocyclic sulfur group. DETAILED DESCRIPTION

[0040] This disclosure describes the following various non-limiting embodiments related to research conducted to identify alternative chromate-free corrosion inhibitors.It has surprisingly been discovered that metal organic frameworks (MOFs) are useful as corrosion inhibiting agents and can be advantageously employed in film-forming compositions.

[0041] General terms

[0042] As used herein, the term "substrate" refers to any structure that may need protection from corrosion and that can be cleaned and / or protected and / or modified to provide unique properties. The substrate may include any other material having at least a portion of its surface that is metallic or susceptible to corrosion. The substrate may be a metal substrate.

[0043] As used herein, the term "metal substrate" refers to a structure having a surface that is at least partially metallic and that can be cleaned and / or protected and / or modified to provide unique properties. A "metal substrate" is not limited to any particular type of metal surface, and with respect to the application of corrosion inhibiting coatings, such metal substrates typically include copper-rich alloys, for example, copper-rich aluminum alloys.

[0044] As used herein, the term "protective composition" refers to any composition suitable for providing some form of corrosion protection to a substrate. For example, the protective composition may include a powder coating composition for protecting steel from corrosion or a film-forming organic polymer-based composition for protecting aluminum alloys from corrosion.

[0045] As used herein, when used without limitation, the term "extender" or "extender pigment" refers to a class of pigments that are typically incorporated into paint formulations to provide bulk to the resulting coating after the paint cures, but which may be added for other reasons, such as to reduce cost. Extenders may additionally or alternatively be active components in making the overall system more corrosion resistant. Extenders that add bulk are often referred to as "fillers" or "extenders / fillers."

[0046] As used herein, the term "coating" refers to a polymeric material (organic or inorganic) that can be applied to a substrate as a liquid (e.g., paint) or solid (e.g., powder) to form a polymeric film. Such polymeric materials include, but are not limited to, powder coatings, paints, sealants, conductive polymers, sol-gels (e.g., manufactured by Boeing Co., having offices in Chicago, 111.), and other similar polymeric materials. TM ), silicates, silicones, zirconates, carbonates, etc. "Coatings" consist of a complex mixture of binders, solvents, pigments, and additives. Many coatings contain one or more substances from each of the four categories. Coating properties—such as gloss and color—are related to the film surface, i.e., as a two-dimensional entity. However, the overall properties of a coating are related to its three-dimensional structure. Phase continuity is a volumetric concept, and coating performance depends on the integrity of the binder phase.

[0047] As used herein, the term "film-forming organic polymer" or "film-forming polymeric material" refers to any polymeric material that can be used to make a coating, including monomers, comonomers, resins, or polymers. Polymeric materials may also be referred to as "binders" and may be organic or inorganic. Organic polymeric materials generally have a carbon backbone and inorganic polymeric materials generally have an organosilicon backbone. Organic binders are made from organic monomers and oligomers, from which they generally derive their name. Examples of these may be acrylic, epoxy, urethane, melamine, etc. Binders include epoxy-based resin binders, such as water-reducible epoxy polyamide systems (for organic polymeric materials) or non-epoxy-based resin binders, such as urethanes, ureas, acrylates, alkyds, melamines, polyesters, vinyls, vinyl esters, silicones, siloxanes, silicates, sulfides, silicate polymers, epoxy novolacs, epoxy phenolic resins, drying oils, hydrocarbon polymers, etc.

[0048] As used herein, the term "weight percent (wt %)" when used without limitation generally refers to the weight percent of a particular solid ingredient, such as pigments, extenders, etc., compared to all solid components present - excluding polymeric resins, pigments, extenders, etc. For example, if the only solid component present in the coating is the corrosion inhibiting carbon pigment, then the corrosion inhibiting carbon pigment is considered to have a wt % of 100.

[0049] Throughout this specification, the word "comprise" or variations such as "comprises" or "comprising" will be understood to mean the inclusion of the stated elements, integers, or steps, or groups of elements, integers, or steps, but not the exclusion of any other elements, integers, or steps, or groups of elements, integers, or steps. The various embodiments disclosed and described in this specification may comprise, consist of, or consist essentially of the various described features and characteristics herein. The words "comprise, consist of, or consisting essentially of" encompass those embodiments that consist of or consist essentially of the various described features and characteristics.

[0050] Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the present disclosure and is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present disclosure as it existed before the priority date of each claim of this application.

[0051] Chemical terms

[0052] It should be understood that an aromatic group means a cyclic group having 4m+2π electrons, where m is an integer equal to or greater than 1. As used herein, "aromatic" and "aryl" are used interchangeably to refer to aromatic groups, regardless of the valence of the aromatic group. Thus, aryl refers to monovalent aromatic groups, divalent aromatic groups, and higher polyvalent aromatic groups.

[0053] The term "bound" refers to a ring, moiety or group that is bound to at least one other ring, moiety or group via a single covalent bond.

[0054] The term "fused" refers to one or more rings that share at least two common ring atoms with one or more other rings.

[0055] A heteroaromatic group is an aromatic group or ring that contains one or more heteroatoms, such as N, O, S, Se, Si, or P. As used herein, "heteroaromatic" and "heteroaryl" are used interchangeably, and heteroaryl refers to monovalent aromatic groups, divalent aromatic groups, and higher polyvalent aromatic groups that contain one or more heteroatoms.

[0056] The term "optionally substituted" means that the functional group is substituted or unsubstituted at any available position. It should be understood that "unsubstituted" refers to a hydrogen radical. Substitution may be with one or more functional groups selected from the group consisting of, for example, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl, formyl, alkanoyl, cycloalkanoyl, aroyl, heteroaroyl, carboxyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, heteroaryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, heterocyclylaminocarbonyl, heteroarylaminocarbonyl, cyano, alkoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, alkanoate, cycloalkanoate, Aromatic acid ester, heterocyclic acid ester, heteroaromatic acid ester, alkylcarbonylamino, cycloalkylcarbonylamino, arylcarbonylamino, heterocyclylcarbonylamino, heteroarylcarbonylamino, nitro, alkylthio, cycloalkylthio, arylthio, heterocyclylthio, heteroarylthio, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, heterocyclylsulfonyl, heteroarylsulfonyl, hydroxyl, halo, haloalkyl, haloaryl, halogen heterocyclyl, halogen heteroaryl, haloalkoxy, haloalkylsulfonyl, silylalkyl, alkenylsilylalkyl, alkynylsilylalkyl, amino, thiol and thionyl. In an embodiment, optional substitution can be selected from one or more functional groups: halo, alkyl, formyl, amino, thiol and thioketone. Optional substitution can include the salt of functional group, for example carboxylate. In another embodiment, optional substitution can be selected from one or more functional groups of amino, thiol and thioketone. It should be appreciated that other groups not specifically described can also be used.

[0057] "Alkyl," whether used alone or in compound words such as alkoxy, alkylthio, alkylamino, dialkylamino, or haloalkyl, means a straight or branched chain hydrocarbon radical ranging in size from one to about 10 carbon atoms or more. Thus, alkyl moieties include moieties ranging in size, for example, from one to about 6 carbon atoms or more, such as methyl, ethyl, n-propyl, isopropyl, and / or butyl, pentyl, hexyl, and higher isomers, including those straight or branched chain hydrocarbon radicals ranging in size from about 6 to about 10 carbon atoms or more, unless specifically limited to smaller radicals.

[0058] "Alkenyl," whether used alone or in compound words such as alkenyloxy or haloalkenyl, means a straight or branched chain hydrocarbon containing at least one carbon-carbon double bond, including moieties ranging in size, for example, from two to about 6 carbon atoms or more, such as methylene, ethylene, 1-propenyl, 2-propenyl, and / or butenyl, pentenyl, hexenyl, and higher isomers, including those ranging in size from about 6 to about 10 carbon atoms or more, unless specifically limited to a smaller group.

[0059] "Alkynyl," whether used alone or in compound words such as alkynyloxy, means a straight or branched chain hydrocarbon containing at least one carbon-carbon triple bond, comprising moieties ranging in size from two to about 6 carbon atoms or more, such as ethynyl, 1-propynyl, 2-propynyl, and / or butynyl, pentynyl, hexynyl, and higher isomers, including those ranging in size from about 6 to about 10 carbon atoms or more, unless specifically limited to a smaller group.

[0060] "Cycloalkyl" refers to mono- or polycarbocyclic ring systems of varying sizes, e.g., from about 3 to about 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl. The term cycloalkoxy refers to the same groups attached through an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. The term cycloalkylthio refers to the same groups attached through a sulfur atom, such as cyclopentylthio and cyclohexylthio.

[0061] "Cycloalkenyl" refers to a non-aromatic mono- or polycyclic carbocyclic ring system of about 3 to about 10 carbon atoms containing at least one carbon-carbon double bond, such as cyclopentenyl, cyclohexenyl, or cycloheptenyl. The term "cycloalkenyloxy" refers to the same groups attached through an oxygen atom, such as cyclopentenyloxy and cyclohexenyloxy. The term "cycloalkenylthio" refers to the same groups attached through a sulfur atom, such as cyclopentenylthio and cyclohexenylthio.

[0062] The terms "carbocycle" and "carbocyclyl" refer to ring systems of, for example, about 3 to 10 carbon atoms, wherein the ring atoms are all carbon atoms and which may be aromatic, non-aromatic, saturated or unsaturated and may be substituted and / or carry fused rings. Examples of such groups include benzene, cyclopentyl, cyclohexyl or fully or partially hydrogenated phenyl, naphthyl and fluorenyl.

[0063] "Aryl" whether used alone or in compound words such as arylalkyl, aryloxy or arylthio, means: (i) an optionally substituted mono- or polycyclic aromatic carbocyclic moiety of, e.g., about 6 to about 60 carbon atoms, such as phenyl, naphthyl or fluorenyl; or (ii) an optionally substituted partially saturated polycyclic carbocyclic aromatic ring system in which the aryl and cycloalkyl or cycloalkenyl groups are fused together to form a cyclic structure, such as tetrahydronaphthyl, indenyl, indanyl or fluorenyl.

[0064] "Heterocyclyl" or "heterocycle" whether used alone or in compound words such as heterocyclyl, means: (i) an optionally substituted cycloalkyl or cycloalkenyl radical of about 3 to about 60 ring members which may contain one or more heteroatoms such as nitrogen, oxygen or sulfur (examples include pyrrolidinyl, morpholino, thiomorpholino or fully or partially hydrogenated thienyl, furanyl, pyrrolyl, thiazolyl, Azolyl, (i) an optionally substituted, partially saturated polycyclic ring system in which an aryl (or heteroaryl) ring and a heterocyclic group are fused together to form a cyclic structure (examples include chromanyl, dihydrobenzofuranyl, and indolinyl); or (ii) an optionally substituted, fully or partially saturated polycyclic fused ring system having one or more bridges (examples include quinuclidinyl and dihydro-1,4-epoxynaphthyl).

[0065] "Heteroaryl" or "hetaryl" whether used alone or in compound words such as heteroaryloxy, means: (i) an optionally substituted mono- or polycyclic aromatic organic moiety of about 1 to about 10 ring members, wherein one or more ring members is an element(s) other than carbon, e.g., nitrogen, oxygen, sulfur or silicon; the heteroatom(s) interrupting the carbocyclic structure and having a sufficient number of delocalized pi electrons to provide aromatic character, provided that the ring does not contain adjacent oxygen and / or sulfur atoms. Typical 6-membered heteroaryl groups are pyrazinyl, pyridazinyl, pyrazolyl, pyridinyl and pyrimidinyl. All regioisomers are contemplated, e.g., 2-pyridinyl, 3-pyridinyl and 4-pyridinyl. Typical 5-membered heteroaryl rings are furanyl, imidazolyl, Azolyl, iso Azolyl, isothiazolyl, The term "bicyclic" refers to any of the following: oxadiazolyl, pyrrolyl, 1,3,4-thiadiazolyl, thiazolyl, thienyl, triazolyl, and silole. All regioisomers are contemplated, e.g., 2-thienyl and 3-thienyl. Bicyclic groups are typically benzo-fused ring systems derived from the heteroaryl groups named above, e.g., benzofuranyl, benzimidazolyl, benzothiazolyl, indolyl, indolizinyl, isoquinolinyl, quinazolinyl, quinolinyl, and benzothienyl; or (ii) optionally substituted partially saturated polycyclic heteroaryl ring systems in which the heteroaryl and cycloalkyl or cycloalkenyl groups are fused together to form a cyclic structure, such as a tetrahydroquinolinyl or indolizinyl ring.

[0066] "Formyl" means a -CHO moiety.

[0067] "Alkanoyl" means a -C(=O)-alkyl group, wherein the alkyl group is as defined above. In one embodiment, the alkanoyl group ranges in size from about C2 to C 20 An example is acyl.

[0068] "Aroyl" means a -C(=O)-aryl group, wherein the aryl group is as defined above. In one embodiment, the size of the aroyl group ranges from about C7 to C 20 Examples include benzoyl and 1- and 2-naphthoyl.

[0069] "Heterocyclic acyl" means a -C(=O)-heterocyclic group, wherein the heterocyclic group is as defined above. In one embodiment, the heterocyclic acyl group ranges in size from about C4 to C 20 .

[0070] "Heteroaroyl" means a -C(=O)-heteroaryl group, wherein the heteroaryl group is as defined above. In one embodiment, the heteroaroyl group ranges in size from about C6 to C 20 An example is pyridylcarbonyl.

[0071] "Carboxy" means a -CO2H moiety.

[0072] "Oxycarbonyl" refers to a carboxylate group -CO2R.

[0073] "Alkoxycarbonyl" refers to a -CO2-alkyl group, wherein the alkyl group is as defined above. In one embodiment, the size of the alkoxycarbonyl group ranges from about C2 to C 20 Examples include methoxycarbonyl and ethoxycarbonyl.

[0074] "Aryloxycarbonyl" means a -CO2-aryl group in which the aryl group is as defined above. Examples include phenoxycarbonyl and naphthoxycarbonyl.

[0075] "Heterocyclyloxycarbonyl" means a -CO2-heterocyclyl group in which the heterocyclyl group is as defined above.

[0076] "Heteroaryloxycarbonyl" means a -CO-heteroaryl group in which the heteroaryl group is as defined above.

[0077] "Aminocarbonyl" refers to a carboxylic acid amide group -C(=O)NHR or -C(=O)NR2.

[0078] "Alkylaminocarbonyl" means a -C(=O)NHR or -C(=O)NR2 group in which R is an alkyl group as defined above.

[0079] "Arylaminocarbonyl" means a -C(=O)NHR or -C(=O)NR2 group in which R is an aryl group as defined above.

[0080] "Heterocyclylaminocarbonyl" refers to a -C(=O)NHR or -C(=O)NR2 group, where R is a heterocyclic group as defined above. In certain embodiments, NR2 is a heterocyclic ring, which is optionally substituted.

[0081] "Heteroarylaminocarbonyl" refers to a -C(=O)NHR or -C(=O)NR2 group, where R is a heteroaryl group as defined above. In certain embodiments, NR2 is a heteroaryl ring, which is optionally substituted.

[0082] "Cyano" means a -CN moiety.

[0083] "Hydroxyl" means a -OH moiety.

[0084] "Alkoxy" means an -O-alkyl group, wherein the alkyl group is as defined above. Examples include methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, pentoxy, hexoxy and higher isomers.

[0085] "Aryloxy" means an -O-aryl group, wherein the aryl group is as defined above. Examples include, but are not limited to, phenoxy and naphthoxy.

[0086] "Alkenyloxy" means an -O-alkenyl group, wherein the alkenyl group is as defined above. An example is allyloxy.

[0087] "Heterocyclyloxy" means an -O-heterocyclyl group in which the heterocyclyl group is as defined above.

[0088] "Heteroaryloxy" means an -O-heteroaryl group wherein the heteroaryl group is as defined above. An example is pyridyloxy.

[0089] "Alkanoate" means a -OC(=O)-R group, where R is an alkyl group as defined above.

[0090] "Arylate" means a -OC(=O)-R group where R is an aryl group as defined above.

[0091] "Heterocyclic ester" means a -OC(=O)--R group, where R is a heterocyclic group as defined above.

[0092] "Heteroarylate" means a -OC(=O)-R group where R is a heteroaryl group as defined above.

[0093] "Amino" means a -NH2 moiety.

[0094] "Alkylamino" means a -NHR or -NR2 group, wherein R is an alkyl group as defined above. Examples include, but are not limited to, methylamino, ethylamino, n-propylamino, isopropylamino, and the different butylamino, pentylamino, hexylamino, and higher isomers.

[0095] "Arylamino" means a -NHR or -NR2 group in which R is an aryl group as defined above. An example is phenylamino.

[0096] "Heterocyclylamino" means a -NHR or -NR2 group, wherein R is a heterocyclic group as defined above. In certain embodiments, NR2 is a heterocyclic ring, which is optionally substituted.

[0097] "Heteroarylamino" means a -NHR or -NR2 group, wherein R is a heteroaryl group as defined above. In certain embodiments, NR2 is a heteroaryl ring, which is optionally substituted.

[0098] "Carbonylamino" refers to a carboxylic acid amide group -NHC(=O)R, which is attached to the rest of the molecule through a nitrogen atom.

[0099] "Alkylcarbonylamino" means a -NHC(=O)R group where R is an alkyl group as defined above.

[0100] "Arylcarbonylamino" means a -NHC(=O)R group where R is an aryl group as defined above.

[0101] "Heterocyclylcarbonylamino" means a -NHC(=O)R group where R is a heterocyclyl group as defined above.

[0102] "Heteroarylcarbonylamino" means a -NHC(=O)R group where R is a heteroaryl group as defined above.

[0103] "Nitro" means a -NO2 moiety.

[0104] "Alkylthio" means an -S-alkyl group, wherein the alkyl group is as defined above. Examples include, but are not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, and the different butylthio, pentylthio, hexylthio and higher isomers.

[0105] "Arylthio" means an -S-aryl group in which the aryl group is as defined above. Examples include phenylthio and naphthylthio.

[0106] "Heterocyclylthio" means an -S-heterocyclyl group in which the heterocyclyl group is as defined above.

[0107] "Heteroarylthio" means an -S-heteroaryl group in which the heteroaryl group is as defined above.

[0108] "Sulfonyl" means a -SO2R group attached to the rest of the molecule through the sulfur atom.

[0109] "Alkylsulfonyl" means a -SO2-alkyl group in which the alkyl group is as defined above.

[0110] "Arylsulfonyl" means a -SO2-aryl group in which the aryl group is as defined above.

[0111] "Heterocyclylsulfonyl" means a -SO2-heterocyclyl group in which the heterocyclyl group is as defined above.

[0112] "Heteroarylsulfonyl" means a -SO2-heteroaryl group in which the heteroaryl group is as defined above.

[0113] "Aldehyde" means a -C(=O)H group.

[0114] "Alkanal" means an alkyl-(C=O)H group, wherein the alkyl group is as defined above.

[0115] "Alkylsilyl" means an alkyl group attached to the rest of the molecule through a silicon atom, which may be substituted with up to three independently selected alkyl groups, each of which is as defined above.

[0116] "Alkenylsilyl" means an alkenyl group attached to the rest of the molecule through a silicon atom, which may be substituted with up to three independently selected alkenyl groups, each alkenyl group being as defined above.

[0117] "Alkynylsilyl" means an alkynyl group attached to the rest of the molecule through a silicon atom, which may be substituted with up to three independently selected alkynyl groups, each alkenyl group being as defined above.

[0118] The term "halo" or "halogen" refers to fluorine, chlorine, bromine or iodine, whether used alone or in a compound word such as a haloalkyl, haloalkoxy or haloalkylsulfonyl. Further, when used in a compound word such as a haloalkyl, haloalkoxy or haloalkylsulfonyl, the alkyl group may be partially halogenated or completely substituted with a halogen atom, which may be independently identical or different. Examples of haloalkyl include, but are not limited to, -CH2CH2F, -CF2CF3 and -CH2CHFCl. Examples of haloalkoxy include, but are not limited to, -OCHF2, -OCF3, -OCH2CCl3, -OCH2CF3 and -OCH2CH2CF3. Examples of haloalkylsulfonyl include, but are not limited to, -SO2CF3, -SO2CCl3, -SO2CH2CF3 and -SO2CF2CF3.

[0119] The terms "sulfhydryl," "sulfur," "mercapto," or "thiol" refer to any organosulfur group containing a sulfhydryl moiety -SH, including R-SH groups, where R is a moiety containing a carbon atom for covalent bonding to the -SH moiety, for example, an alkylthio group as defined above. In one embodiment, the thiol or thiol group is a sulfhydryl moiety -SH.

[0120] The term "thione" or "thioketone" refers to any organosulfur group containing a -C=S moiety, including an RC=S group, for example, where R is an alky group as defined above. In one embodiment, the thione group is a -C=S moiety.

[0121] Metal-organic framework materials

[0122] Metal organic framework materials (MOFs) have surprisingly been identified as effective corrosion inhibitors for substrates such as metal substrates and can be used in protective coating compositions without problematic reactions with other components in compositions such as epoxy resin-based compositions. Surprisingly, MOFs can be used as corrosion inhibitors in resin-based paint compositions, thereby providing protective coatings for metal substrates such as aluminum alloys. It will be appreciated that various types of MOFs have been previously studied and used for other types of applications, such as hydrogen storage and catalysis, but it will be appreciated that MOFs have never been used or considered suitable as corrosion inhibitors before.

[0123] In an embodiment, the substrate is a metal substrate. It should be appreciated that the metal substrate can comprise any substrate material at least a portion of which is metal on its surface. The metal substrate can include any metal that needs to be protected from corrosion. In one embodiment, the metal substrate comprises a metal or alloy selected from aluminum, such as an aluminum alloy. In one embodiment, the metal substrate is an aluminum alloy, for example, an alloy of aluminum with one or more metals selected from copper, magnesium, manganese, silicon, tin and zinc. The aluminum alloy can be an alloy that includes copper. In one embodiment, the metal substrate can be a copper-rich alloy, such as a copper-rich aluminum alloy. The aluminum alloy can be an aerospace alloy, for example, AA2XXX and AA7XXX types. The aluminum alloy can be an automotive alloy, for example, AA6XXX types. The aluminum alloy can be a marine alloy, for example, AA5XXX types.

[0124] It should also be recognized that MOF is a one-dimensional, two-dimensional or three-dimensional structure provided by an organometallic polymer framework material including multiple metal ions or metal clusters, each of which is coordinated to one or more organic ligands. MOF can provide a porous structure including multiple holes. MOF can be crystalline or amorphous, for example, it should be recognized that one-dimensional, two-dimensional or three-dimensional MOF structure can be amorphous or crystalline. It should be recognized that the metal cluster comprises two or more metal ions partially connected by a metal-metal bond. It should also be recognized that the one-dimensional structure comprises, for example, a linear structure of metal atoms connected by organic ligands. It should be recognized that the two-dimensional structure comprises, for example, a sheet or layered structure with the length and width (such as, area) size of the metal atoms connected by organic ligands. It should also be recognized that the three-dimensional structure comprises, for example, a spherical or cubic structure with the length, width and height (such as, volume) size of the metal atoms connected by organic ligands. One-dimensional, two-dimensional or three-dimensional MOF structures can be at least partially amorphous or at least partially crystalline, for example, a MOF having ordered regions that provide crystallinity and disordered regions that provide amorphous properties. In one embodiment, the MOF provided is a two-dimensional structure and / or a three-dimensional structure. In one embodiment, the MOF is crystalline and can, for example, include a suitable amount of uniformity. In another embodiment, the MOF is amorphous, for example, as described in an article by Bennett et al. entitled "Amorphous Metal-Organic Frameworks" published in the ACS publication Accounts of Chemical Research on April 7, 2014. It should be recognized that crystalline MOFs are porous framework materials comprising an infinite array of metal nodes connected by organic linkers. Amorphous MOFs still retain the basic structural units and connectivity of their crystalline counterparts, but they lack periodic order on an arbitrarily long scale.

[0125] The organic ligands of the MOF are typically selected from heterocyclic compounds, which may be optionally substituted with and optionally fused to one or more substituents or groups. It will be appreciated that in addition to the organic ligands, the metal-organic framework material may also incorporate other ligands with metals or metal clusters, for example, anions such as acetates or halides may provide additional ligands and may, for example, be derived from the metal salts used to form the MOF.

[0126] In another embodiment, the MOF comprises a plurality of metal ions or metal clusters, each coordinated to one or more organic ligands, wherein:

[0127] The metal ions or metal clusters include one or more metals selected from alkaline earth metals, rare earth metals, and transition metals; and

[0128] The organic ligand is selected from optionally substituted, optionally fused aryl, heteroaryl or heterocyclic compounds.

[0129] The one or more organic ligands of the MOF may be selected from optionally substituted aryl, heteroaryl or heterocyclic compounds. In an embodiment, the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds comprising at least two heteroatoms selected from N, O and S. In another embodiment, the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds comprising at least one exocyclic sulfur group. The exocyclic sulfur group may be selected from thiol and thiol groups. In another embodiment, the organic ligand is selected from optionally substituted, optionally fused, 5 or 6-membered mono- or bicyclic aryl, heteroaryl or heterocyclic compounds comprising at least one exocyclic sulfur group, at least one exocyclic sulfur group being selected from thiol and thiol. In another embodiment, at least one exocyclic sulfur group is a thiol.

[0130] A series of different types of MOFs can be suitable as corrosion inhibitors. MOF can also be referred to as porous coordination polymers (PCPs). The title of A Betard and R Fischer in the Chemical Reviews article is "Metal-Organic Framework Thin Films:From Fundamentals to Applications" (2012) and Yaghi et al. Acc.Chem.Res.2001,34,319-330 describes a series of MOFs. For example, suitable MOFs can be selected from those with zeolite-net topology, i.e. zeolite-net metal organic framework materials (ZMOFs). In an embodiment, MOF is a zeolite imidazolate framework material (ZIF). MOF can have isoreticular expansion on the framework. MOFs can utilize single metal ion-based molecular building blocks (MBBs) with coordination including chelation (and mixed ligand chelation (heterochelation)) and bridging from organic heterocyclic ligands, which contain coordination and bridging functions and which together form secondary building units (SBUs). Multiple SBUs together form metal-organic framework materials, which can have three-dimensional porous structures with substantially uniform channels and cages. MOFs are typically formed as hardened particles from reactions involving metal salts, organic ligands, and suitable solvents, as described further below.

[0131] In one embodiment, the metal ligand directed assembly method can be used to form MOFs with rigid secondary building units (SBUs), such as rigid tetrahedral SBUs. The properties of the MOF, such as pore size, can be modified by selecting suitable reagents, for example, various metal salts containing different metal cations and counter anions, different organic heterocyclic ligands, solvents, and structure directing agents (SDAs).

[0132] In another embodiment, a MOF comprises a plurality of molecular building blocks (MBBs), each having a metal cluster that forms a secondary building block (SBU) together with one or more organic ligands, each of which is connected together to form a network. It should be appreciated that the configuration and connection of the SBUs forming a framework are described by a topological structure, which is also referred to as a "net," which is typically assigned a three-letter symbol (e.g., "pcu net"), as provided in the database of the Reticular Chemistry Structure Resource. A MOF can be based on a single metal as a vertex in the framework.

[0133] MOFs can also be formed by seeding with a reagent. For example, silicon and titanium dioxide nanoparticles or microspheres can be used as seeding reagents. Methods for forming MOFs using seeding or crystallization reagents are described in WO2011 / 133999 (PCT / AU2010 / 001056).

[0134] MOFs can also be formed by flow chemistry methods, for example, as described in Rubio-Martinez et al., “Versatile, High Quality and Scalable Continuous Flow Production of Metal-Organic Frameworks,” published online in Scientific Reports on June 25, 2014.

[0135] MOFs can be modified postsynthetically. For example, to incorporate mixed metals or optional guest molecules. MOFs can also be formed and then modified using ligand exchange methods. A method for forming MOFs using ligand exchange is described in a paper by Jiang et al., titled "Postsynthetic ligand exchange for the synthesis of benzotriazole-containing zeolitic imidazolate framework," published online in Chem. Commun. on March 2, 2015.

[0136] The MOF can be formed into solid particles suitable for dispersion in the composition. In an embodiment, the average diameter of the MOF particles is in the range of 20 nm to 50 μm, 40 nm to 30 μm, 60 nm to 10 μm, 80 nm to 5 μm, or 100 nm to 1 μm. In one embodiment, the average diameter of the MOF particles is in the range of 100 nm to 1 μm.

[0137] Metals and metal salts for MOFs

[0138] The metal or metal cluster of MOF generally include one or more metals selected from rare earth and transition metals. In one embodiment, the metal is selected from alkaline earth metals, transition metals and rare earth metals, for example, selected from Zn, La, Pr, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Co, Y, Bi, Cd, Pb, Ag, Sb, Sn, Cu, Fe, Ni, Li, Ca, Sr, Mg, Zr, Nd, Ba, Sc and combinations thereof. In another embodiment, the metal is selected from Zn, Pr and Ce. The metal or metal cluster of MOF generally include a single type of metal in a coordination framework material. In another embodiment, the metal or metal cluster can include a mixed metal system in a coordination framework material, for example, the metal or metal cluster can contain two different metals.

[0139] Some specific examples of metal salts suitable for use in MOFs are nitrates, chlorides, and acetates of the metals described above.

[0140] Organic ligands

[0141] The MOF may comprise an organic ligand selected from optionally substituted aryl, heteroaryl or heterocyclic compounds.

[0142] The organic ligand can be a monovalent or multivalent ligand capable of coordinating or chelating to the metal atom of the MOF. For example, the organic ligand can be a monovalent, divalent, trivalent, tetravalent, pentavalent or hexavalent ligand. In one embodiment, the organic ligand can chelate or coordinate to two separate metal atoms of the MOF and thus provide a bridge or connection between the metal atoms in the metal organic framework material. For the secondary structural unit of the MOF, the ratio of organic ligand: metal atom can be changed, for example, the ratio can be 3:1 (e.g., wherein three separate bidentate organic ligands are coordinated to the metal atom to form a 6-coordinate metal complex as a secondary structural unit). The ratio of organic ligand: metal can be changed, for example, the ratio can be 2:1, 3:1, 4:1, 5:1 or 6:1, depending on the metal atom and organic ligand of the metal complex forming the SBU.

[0143] The one or more organic ligands of the MOF may be selected from optionally substituted aryl, heteroaryl or heterocyclic compounds. In an embodiment, the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds comprising at least two heteroatoms, wherein the at least two heteroatoms are selected from N, O and S. In another embodiment, the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds comprising at least one exocyclic sulfur group. The exocyclic sulfur group may be selected from thiol and thiol groups. In another embodiment, the organic ligand is selected from optionally substituted, optionally fused, 5- or 6-membered mono- or bicyclic aryl, heteroaryl or heterocyclic compounds comprising at least one exocyclic sulfur group, wherein the at least one exocyclic sulfur group is selected from thiol and thiol. In another embodiment, the at least one exocyclic sulfur group is a thiol.

[0144] For example, the organic ligand used in the MOF can be selected from ligands that can alone provide corrosion inhibition properties, such as described in Harvey et al., “The effect of inhibitor structure on the corrosion of AA2024 and AA7075,” Corrosion Science, 53 (2011), pp2184-2190.

[0145] In another embodiment, the one or more organic ligands are selected from compounds of Formula 1:

[0146]

[0147] in

[0148] A is a 5- or 6-membered aryl, heteroaryl or heterocyclic ring, optionally substituted with one or more substituents and optionally fused to one or more aryl or heteroaryl rings, wherein the dashed line represents one or more optional double bonds;

[0149] X 1 Selected from N, NR 1 , O, S, CR 2 and CR 3 R 4 ;

[0150] X 2 Selected from N, NR 5 , O, S, CR 6 and CR 7 R 8 ;

[0151] X 3 Selected from N, NR 9 , CR 10 and CR 11 R 12;

[0152] R 1 、R 5 and R 9 Each is independently selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0153] R 2 、R 3 、R 4 、R 6 、R 7 、R 8 、R 10 、R 11 and R 12 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted.

[0154] In an embodiment, X 1 Selected from N, NR 1 , O and S. In another embodiment, X 1 is selected from N, NH and S. In another embodiment, X 1 It's N.

[0155] In an embodiment, X 3 Selected from N and CR 10 In another embodiment, R 10 In another embodiment, X 3 It's C-SH.

[0156] In an embodiment, X 2 Selected from N, NR 5 , O and S. In another embodiment, R 5 In another embodiment, X 2 is selected from N, S and N-NH2. In another embodiment, X 2 It's N.

[0157] In an embodiment, X 1 Selected from N, NR 1 , O and S; X 2 Selected from N, NR 5 , O and S; and X3 Selected from N and CR 10 In another embodiment, X 1 is selected from N, NH and S. In another embodiment, R 10 In another embodiment, X 3 It's C-SH.

[0158] In another embodiment, X 1 Is N. In another embodiment, X 2 Is N. In another embodiment, X 3 It's C-SH.

[0159] The optionally fused group of ring A may be monocyclic or polycyclic. The optionally fused group of ring A may be an optionally substituted monocyclic or bicyclic aryl ring, heteroaryl ring or heterocycle, for example, wherein the compound of formula 1 is a bicyclic compound. The monocyclic aryl group may be an optionally substituted 6-membered ring, such as benzene. The polycyclic aryl group may be two or more optionally substituted 6-membered rings fused together, such as naphthalene, anthracene, pyrene, tetracene and pentacene. The heteroaryl group may be selected from a 5-membered monocyclic ring, such as thiophene, furan, pyrrole, thiazole, imidazole, 1,3-thiazole, 1,3,4- oxadiazole, 1,3,4-thiadiazole, or a 6-membered ring such as pyridine and triazine, wherein each ring may be optionally substituted.

[0160] The optional substituents of Ring A may be selected from halo, cyano, amino, hydroxy, alkanoic acid, alkanoate, carbamoyl, C1-C 10 Alkoxycarbonyl, C1-C 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkylamino, C3-C 10 Cycloalkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkenyl, C2-C 10 Alkynyl, C3-C 10 Cycloalkynyl, aryl and aryl C1-C 10 Alkyl, heteroaryl and heteroaryl C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 10Cycloalkoxy, and wherein each occurrence of amino, alkanoic acid, alkanoate, alkoxycarbonyl, alkyl, haloalkyl, alkylamino, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, alkoxy and cycloalkoxy can be optionally substituted, for example, further substituted with one or more of halo, hydroxy, amino, nitro, carboxylic acid. In an embodiment, the optional substitution can be one or more functional groups selected from halo, alkyl, formyl, amino, thiol and thioketone. The optional substituent can include a salt of a functional group, such as a carboxylate. In another embodiment, the optional substitution can be one or more functional groups selected from amino, thiol and thioketone.

[0161] In another embodiment, the one or more organic ligands of the MOF may be selected from compounds of Formula 1(a):

[0162]

[0163] in

[0164] A is a 5- or 6-membered aryl, heteroaryl or heterocyclic ring, optionally substituted with one or more substituents and optionally fused to one or more aryl or heteroaryl rings, wherein the dashed line represents one or more optional double bonds;

[0165] Y 1 Selected from S or SH, where Y 1 When S is the dotted line, it represents a double bond, or when Y 1 The dotted line does not exist when it is SH;

[0166] X 1 selected from N, NH, O and S;

[0167] X 2 Selected from N, NR 5 , O, S, CR 6 and CR 7 R 8 ;

[0168] R 5 Selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0169] R 6 、R 7 and R 8 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted.

[0170] In one embodiment, Y 1 In another embodiment, X 1 is selected from N, NH and S. In another embodiment, X 1 is selected from N and S. In another embodiment, X 1 and X 2 Each is independently selected from S, N and NH.

[0171] In another embodiment, X 1 Is N. In another embodiment, X 2 is N. In another embodiment, Y 1 It’s SH.

[0172] Ring A can be aromatic, heteroaromatic, or partially unsaturated. For example, Ring A can contain one or more double bonds between ring atoms. Ring A can also contain one or more optional substituents or optional fused groups. In another embodiment, A is a 5- or 6-membered heteroaryl ring or a heterocyclic ring.

[0173] In another embodiment, the one or more organic ligands of the MOF may be selected from heterocyclic compounds of Formula 1(a)(i):

[0174]

[0175] in

[0176] According to the above described formula 1(a), A, Y are defined as 1 、X 1 and X 2 ;

[0177] A 1 、A 2 and A 3 Each independently selected from C═O, C═S, N, NR 13 、O、S、SO2、CR 14 , CR 15 R 16 ;

[0178] R 13 Selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0179] R14 、R 15 and R 16 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted, and optionally R 13 、R 14 、R 15 and R 16 Two of the Rs are joined together to form an optionally substituted aryl or heteroaryl ring fused to the A ring.

[0180] In an embodiment, A 1 and A 3 It's CR 14 In another embodiment, R 14 In another embodiment, A 1 and A 3 Each is independently selected from C-SH and C-NH2. In another embodiment, A 1 and A 3 In another embodiment, Y 1 In another embodiment, X 1 and X 2 is N, in another embodiment, A 2 It's N.

[0181] Some specific examples of compounds of Formula 1(a)(i) are provided below:

[0182]

[0183] In another embodiment, the one or more organic ligands of the MOF may be selected from compounds of Formula 1(a)(ii):

[0184]

[0185] in

[0186] Ring A is an optionally substituted 5-membered heterocyclic ring, wherein the dashed line represents one or more optional double bonds;

[0187] According to the above described formula 1(a), X is defined as 1 、X 2 and Y 1 ;

[0188] A 1 and A 2 Each independently selected from C═O, C═S, N, NR13 、O、S、SO2、CR 14 and CR 15 R 16 and are optionally taken together to form an optionally substituted aryl ring, heteroaryl ring or heterocycle J fused to the A ring;

[0189] R 13 Selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0190] R 14 、R 15 and R 16 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted, and optionally R 13 、R 14 、R 15 and R 16 Two of the Rs are joined together to form an optionally substituted aryl or heteroaryl ring fused to the A ring.

[0191] Some specific examples of compounds of Formula 1(a)(ii) are provided below:

[0192]

[0193] In another embodiment, the one or more organic ligands of the MOF may be selected from compounds of Formula 1(a)(iii):

[0194]

[0195] in

[0196] Each A and B ring is independently an optionally substituted 5-membered heterocyclic ring, wherein the dashed line represents one or more optional double bonds;

[0197] Each X is independently defined according to Formula 1(a) described above. 1 、X 2 and Y 1 ;

[0198] Each A 1 、A 2 、B 1 and B2 Independently selected from C=O, C=S, N, NR 13 、O、S、SO2、CR 14 and CR 15 R 16 ;

[0199] R 13 Selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0200] R 14 、R 15 and R 16 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 alkynyl, aryl, and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl, or heteroaryl group may be optionally substituted;

[0201] Z is selected from C=O, C=S, N, O, S, SO2, SS, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl; and

[0202] At least one A 1 or A 2 and B 1 or B 2 Selected from NR 13 , CR 14 and CR 15 R 16 , and R 13 、R 14 、R 15 and R 16 At least one of represents a bond to Z.

[0203] Some specific examples of compounds of Formula 1(a)(iii) are provided below:

[0204]

[0205] In another embodiment, the one or more organic ligands of the MOF may be selected from compounds of Formula 1(b):

[0206]

[0207] in

[0208] Ring A is an optionally substituted 5-membered heterocyclic ring, wherein the dashed line represents one or more optional double bonds;

[0209] X is defined according to Formula 1 described above. 1 、X 2 and X 3 ;

[0210] A 1 and A 2 Each independently selected from C═O, C═S, N, NR 13 、O、S、SO2、CR 14 and CR 15 R 16 and are optionally taken together to form an optionally substituted aryl ring, heteroaryl ring or heterocycle J fused to the A ring;

[0211] R 13 Selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted; and

[0212] R 14 、R 15 and R 16 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted, and optionally R 13 、R 14 、R 15 and R 16 Two of the Rs are joined together to form an optionally substituted aryl or heteroaryl ring fused to the A ring.

[0213] It will be appreciated that any of the embodiments described above for Formula 1 may also provide embodiments for any of Formulas 1(a)(i)-(iii) or 1(b).

[0214] Organic ligand compounds can exist as one or more stereoisomers. Various stereoisomers can include enantiomers, diastereomers, and geometric isomers. Those skilled in the art will recognize that one stereoisomer can be more active than other stereoisomers (one or more). In addition, those skilled in the art will know how to separate such stereoisomers. Therefore, the present disclosure includes mixtures of compounds described herein, individual stereoisomers, and optionally active mixtures.

[0215] Some specific examples of aryl, heteroaryl and heterocyclic organic compounds suitable for use as organic ligands for MOFs are shown in Table 1 below:

[0216] Table 1

[0217]

[0218]

[0219]

[0220]

[0221] Methods for preparing MOFs

[0222] A major goal in MOF synthesis is to establish synthesis conditions that lead to defined inorganic building blocks without decomposing the organic linkers. At the same time, the kinetics of crystallization must be suitable to allow nucleation and growth of the desired phase to occur.

[0223] The term conventional synthesis is generally applied to reactions performed by conventional electrical heating without any parallel reactions. Reaction temperature is one of the main parameters for MOF synthesis, and a distinction is normally made between solvothermal and nonsolvothermal temperature ranges, which dictate the type of reaction setup that must be used. Although a well-known definition of a solvothermal reaction has not yet been established, we use Rabenau's definition, which refers to reactions occurring above the boiling point of the solvent at autogenous pressure in a closed vessel. Nonsolvothermal reactions, therefore, occur below or at the boiling point at ambient pressure, simplifying the synthesis requirements. The latter reactions can be further categorized as reactions occurring at room temperature or at elevated temperatures.

[0224] Some outstanding MOFs have even been obtained at room temperature by simply mixing the starting materials; these are, for example, MOF-5, MOF-74, MOF-177, HKUST-1 or ZIF-8. This method is sometimes called direct precipitation reaction and shows that the crystallization of some MOFs must occur on a short time scale. Some of these MOFs, such as ZIF-8, show good thermal and chemical stability. Variations in the reaction temperature have a strong influence on product formation, and generally more compact / dense structures are observed at higher temperatures. In some systems, an increase in the reaction temperature is also necessary to obtain suitable crystallinity and reaction rates, especially if kinetically more inert ions are used. However, the temperature has a strong influence on the morphology of the crystals, and prolonged reaction times can even lead to degradation of the MOF.

[0225] Typically, MOF synthesis occurs in a solvent at temperatures ranging from room temperature to about 250°C. Energy is generally introduced using conventional electrical heating, i.e., from a heat source, oven, or by convection heat transfer. Alternatively, energy can also be introduced by other means, such as by electric potential, electromagnetic radiation, mechanical waves (ultrasound), or mechanically. The energy source is closely related to the duration, pressure, and energy per molecule introduced into the system, and each of these parameters can have a strong influence on the product formed and its morphology.

[0226] Different methods can lead to new compounds that are not otherwise obtainable. Furthermore, alternative routes can lead to compounds with different particle sizes and size distributions, as well as morphologies that can have an impact on the properties of the material.

[0227] WO2010058123 and EP1070538 disclose methods for the hydrothermal preparation of MOFs. Similarly, WO20100076220 discloses a method for obtaining crystalline porous metal organic compounds in liquid phase at elevated temperatures.

[0228] EP1373277 discloses a method for the hydrothermal preparation of zinc terephthalate framework materials with excellent yields. The method involves reacting a mixture of a zinc salt and terephthalic acid. This method requires the presence of a base (triethylamine) and a lactam or lactone solvent. However, even with the shortened reaction time compared to other methods, continuous stirring for at least 3 hours is still required to obtain a small amount of MOF product.

[0229] Additionally, all known preparation methods require the obtained MOF crystals to be separated from the mother liquor and further dried to obtain the final MOF product.

[0230] The synthesis method for obtaining MOFs can utilize solvothermal conditions. This method generally provides for a synthesis that is carried out in the presence of an organic solvent and at high temperatures (up to 130°C or higher) for a considerable period of time (from more than 12 hours to several days). General information on the synthesis of a range of MOF materials has been reported in numerous publications, including Yaghi et al., Nature 402 (1999) 276-279; B. Chen, M. Eddaoudi, Yaghi et al., Science 291 (2001) 1021-1023; Yaghi et al., Science 295 (2002) 469-472; Yaghi et al., Nature 423 (2003) 705-714; Yaghi et al., Science 300 (2003) 1127-1129.

[0231] The synthesis process described in US2003 / 0004364 involves the use of an inorganic zinc salt [Zn(NO3)2·6H2O] as [ZnO] 6+ The core precursor and ditopic carboxylic acid are used as organic linkers dissolved in a solvent. The product is then crystallized by slowly diffusing a dilute base solution into the reaction mixture solution to initiate crystallization or by transferring the solution to a closed container and heating it to a predetermined high temperature (solvothermal method).

[0232] Another method (Huang, L.; Wang, H.; Chen, J.; Wang, Z.; Sun, J.; Zhao, D.; Yan, Y. Microporous Mesoporous Mater. 2003, 58, 105) can involve using [Zn(NO3)2·6H2O], the corresponding dipolar carboxylic acid and amine in an organic solvent and stirring such a mixture at room temperature for several hours. Alternatively, the zinc salt Zn(CH3COO)2·2H2O can be used as [Zn4O] 6+ Precursors of the nucleus. (DJ Tranchemontagne, JR Hunt, OMYaghi, Tetrahedron, 2008, 64, 8553).

[0233] As described above, MOFs can also be formed by seeding with reagents, for example, using silicon and titanium dioxide nanoparticles or microspheres (WO 2011 / 133999, PCT / AU2010 / 001056), by flow chemistry methods (“Versatile, High Quality and Scalable Continuous Flow Production of Metal-Organic Frameworks”, Rubio-Martinez et al., Scientific Reports, published online 25 June 2014), or by post-synthetic modification, for example, using ligand exchange methods (“Postsynthetic ligand exchange for the synthesis of benzotriazole-containing zeolitic imidazolate framework”, Jiang et al., Chem. Commun, published online 2 March 2015).

[0234] Compositions and formulations

[0235] A corrosion inhibiting composition is provided, comprising at least one corrosion inhibitor selected from a metal organic framework (MOF). The MOF can be any one or more of the MOFs described herein. The composition is suitable for use in and application to various substrates, such as metal substrates, and can be provided, for example, as a coating composition. The composition can contain one or more other additives or corrosion inhibiting agents suitable for a particular substrate type.

[0236] An advantage of MOFs is that they can provide corrosion inhibition properties without problematic reactions with components of the composition. For example, MOFs can be used in epoxy resin compositions without problematic reactions with the epoxy resin and retaining corrosion inhibition properties.

[0237] Another advantage of some MOFs is that they can provide particles that are substantially white in color or pigmentation. It should be appreciated that substantially white in color or pigmentation means that the MOF can be white, ivory, cream, bone, beige, and gray. MOFs can therefore be used in coating compositions without the need to apply an additional primer or enamel coating. MOFs can provide both pigmentation and corrosion inhibition properties. MOFs can provide a single coating or layer that allows the composition to be applied. In one embodiment, the MOF has a lighter or substantially white pigmentation. In another embodiment, the organic ligands and / or metals used to prepare the MOF are selected to form a MOF with a lighter or substantially white pigmentation. Examples of MOFs that can be obtained as white colored powders or particles are MOFs that include a metal selected from at least one of lanthanum, yttrium, and zinc. In one embodiment, the organic ligands of the white colored MOF can be selected from optionally substituted benzimidazoles, triadiazoles, and triazoles. More specific examples of the ligand forming the white colored MOF may include 1H-benzimidazole, 2-amino-5-mercapto-1,2,4-thiadiazole, 1,2,4-triazole-3-thiol, and benzotriazole.

[0238] The corrosion inhibiting composition can be a coating composition comprising a film-forming organic polymer. It should be appreciated that a film-forming organic polymer is an organic polymer that is capable of forming a film after application to a metal surface. The coating composition can be a paint composition. The coating composition can include one or more resins, such as epoxy-based resins. The coating composition can be a paint composition, such as an epoxy-based paint composition.

[0239] The coating composition can be a powder coating composition, such as a powder coating composition suitable for powder coating of various metal substrates, including the aluminum alloys described herein or steel.

[0240] The coating composition may be a spray composition.

[0241] The coating composition can be applied to the substrate in a wet or "partially cured" condition where it dries or cures over time, i.e., the solvent evaporates. The coating can dry or cure naturally or by accelerated means, such as ultraviolet light curing systems, to form a film or "cured" paint. The coating can also be applied in a semi-cured or fully cured state, such as an adhesive.

[0242] The composition may include a list of ingredients and / or components and may also include a list of instructions for preparing and mixing the ingredients and / or components together to make the coating composition.

[0243] It should be appreciated that the composition may include one or more additives, such as pigments, fillers, and extenders. Examples of suitable additives with which the corrosion inhibitors described herein may be combined include, for example, binders, solvents, pigments (including soluble or insoluble extenders, fillers, corrosion inhibiting pigments, etc.), solvents, additives (e.g., curing agents, surfactants, dyes, amino acids, etc.), etc. Note that some additives may also be appropriately considered pigments, and vice versa (e.g., matting agents). More specifically, these "additives" include, but are not limited to, glycine, arginine, methionine and amino acid derivatives (such as methionine sulfoxide, methyl sulfoxide and iodide / iodate), gelatin and gelatin derivatives (such as animal glue and fish glue), linear dextrins and cyclodextrins (including α and β cyclodextrins), trifluoromethanesulfonic acid, trifluoromethanesulfonates, acetates, talc, kaolin, organic-based ion exchange resins (such as organic-based cation and anion exchange resins), organic-based ion exchange resins (such as organic-based cation and anion exchange resins), organic-based ion exchange resins that have been pre-exchanged or reacted with salts, oxides and / or mixed oxides of rare earth materials, and metal sulfates (such as sulfates of rare earth materials, magnesium sulfate, calcium sulfate (anhydrous or hydrated form), strontium sulfate, barium sulfate, etc.).

[0244] It will be appreciated that the composition may comprise or consist of any one or more of the components or additives described herein.

[0245] The composition may also contain other additives such as rheology modifiers, fillers, toughening agents, thermal or UV stabilizers, fire retardants, lubricants, surfactants. The additive(s) are typically present in an amount of less than about 10% based on the total weight of the combination of the activation treatment or solvent(s), reagent(s), and additive(s). Examples include:

[0246] (a) Rheology modifiers, such as hydroxypropyl methylcellulose (e.g., Methocell 311, Dow), modified urea (e.g., Byk 411, 410), and polyhydroxycarboxylic acid amides (e.g., Byk 405);

[0247] (b) film-forming agents, such as esters of dicarboxylic acids (e.g., Lusolvan FBH, BASF) and glycol ethers (e.g., Dowanol, Dow);

[0248] (c) wetting agents, such as fluorochemical surfactants (e.g., 3M Fluorad) and polyether-modified polydimethylsiloxanes (e.g., Byk 307, 333);

[0249] (d) surfactants, such as fatty acid derivatives (e.g. Bermadol SPS 2543, Akzo) and quaternary ammonium salts;

[0250] (e) dispersants, such as nonionic surfactants based on primary alcohols (e.g., Merpol 4481, Dupont) and alkylphenol-formaldehyde-disulfide condensates (e.g., Clariants 1494);

[0251] (f) defoaming agents;

[0252] (g) Anticorrosive agents such as phosphates (e.g. ADD APT, Anticor C6), alkylammonium salts of succinic acid (2-benzothiazolylsulfide) (e.g. Irgacor 153CIBA) and triazine dithiol;

[0253] (h) Stabilizers, such as benzimidazole derivatives (e.g. Bayer, Preventol BCM, biocidal film protection);

[0254] (i) leveling agents, such as fluorocarbon-modified polymers (e.g. EFKA 3777);

[0255] (j) Pigments or dyes, such as fluorescent agents (Royale Pigment and chemicals);

[0256] (k) organic and inorganic dyes, such as fluoroscein; and

[0257] (1) Lewis acids such as aluminum chloride, zinc chloride, strontium chloride, calcium chloride and aluminum chloride.

[0258] (m) Suitable flame retardants, which prevent the spread of flame, heat release and / or smoke generation, which may be added alone or optionally include:

[0259] Phosphorus derivatives, such as molecules containing phosphate, polyphosphate, phosphite, phosphazine and phosphine functional groups, for example, melamine phosphate, dimelamine phosphate, melamine polyphosphate, ammonium phosphate, ammonium polyphosphate, pentaerythritol phosphate, melamine phosphite and triphenylphosphine.

[0260] Nitrogen-containing derivatives, such as melamine, melamine cyanurate, melamine phthalate, melamine phthalimide, melam, melem, cyanuramide, melam cyanurate, melem cyanurate, cyanuramide cyanurate, hexamethylenetetramine, imidazole, adenine, guanine, cytosine and thymine.

[0261] Molecules containing borate functional groups, such as ammonium borate and zinc borate.

[0262] • Molecules containing two or more alcohol groups, such as pentaerythritol, polyvinyl alcohol, polyethylene glycol and carbohydrates, for example, glucose, sucrose and starch.

[0263] • Molecules that endothermally release non-flammable decomposition gases, such as metal hydroxides, for example, magnesium hydroxide and aluminum hydroxide.

[0264] Expandable graphite.

[0265] Example

[0266] In order that the present disclosure may be more clearly understood, embodiments of the present disclosure are described in more detail below by reference to the following non-limiting experimental materials, methods, and examples.

[0267] Preparation of MOF

[0268] By M x+ (NO3) x General process for preparing MOFs using 2-mercaptobenzimidazole (MBI–compound 1)

[0269] 7.4 g (49.4 mMol) of MBI was added to 400 ml of a 90:10 MeOH:DMF solution. This was followed by the addition of 200 ml of a 90:10 MeOH:DMF solution (i.e., a 3:1 molar ratio of ligand to metal) containing 16.4 mMol of dissolved metal nitrate. The mixture was stirred at a temperature between 60 and 80°C for one hour. Stirring was stopped and ~1 ml of triethylamine was added as a catalyst for the formation of the coordination polymer. Heating was maintained for 24 hours. After 24 hours, a fine precipitate formed.

[0270] The resulting precipitate was collected by filtration and then washed three times with methanol. FTIR spectra were then collected and if the peak at 1649 cm -1 If the DMF amide peak at 4° is still present, continue washing until the peak disappears. Then obtain the X-ray diffraction pattern and TGA curve of the precipitate.

[0271] Example 1

[0272] Zn(NO3)2.6H2O+MBI was prepared according to the general method described above.

[0273] Example 2

[0274] Ce(NO3)2.6H2O+MBI was prepared according to the general method described above.

[0275] Example 3

[0276] Pr(NO3)3.6H2O+MBI was prepared according to the general method described above.

[0277] Example 4

[0278] La(NO3)3.6H2O+MBI was prepared according to the general method described above.

[0279] Example 5

[0280] Y(NO3)3.6H2O+MBI was prepared according to the general method described above.

[0281] By M x+ General process for preparing MOF from (NO3)2+1,2,4-triazole-3-thiol (TT-compound 4)

[0282] 5 g (49.4 mMol) of TT was added to 400 ml of a 90:10 MeOH:DMF solution. Subsequently, 200 ml of a 90:10 MeOH:DMF solution (i.e., a 3:1 molar ratio of ligand to metal) containing 16.4 mMol of dissolved metal nitrate was added. The mixture was stirred at a temperature between 60 and 80°C for one hour. Stirring was stopped and ~1 ml of triethylamine was added as a catalyst for the formation of the coordination polymer. Heating was maintained for 24 hours. After 24 hours, a fine precipitate formed.

[0283] The resulting precipitate was collected by filtration and then washed three times with methanol. FTIR spectra were then collected and if the peak at 1649 cm -1 If the DMF amide peak at 4° is still present, continue washing until the peak disappears. Obtain the X-ray diffraction pattern and TGA curve of the precipitate.

[0284] Example 6

[0285] Zn(NO3)2.6H2O+TT was prepared according to the general method described above.

[0286] Example 7

[0287] Ce(NO3)2.6H2O+TT was prepared according to the general method described above.

[0288] Example 8

[0289] Pr(NO3)3.6H2O+TT was prepared according to the general method described above.

[0290] Example 9

[0291] La(NO3)3.6H2O+TT was prepared according to the general method described above.

[0292] Example 10

[0293] Y(NO3)3.6H2O+TT was prepared according to the general method described above.

[0294] By M x+ General process for preparing MOF from (NO3)2+2,5-dimercapto-1,3,4-thiadiazole (DMT–compound 5)

[0295] 7.43 g (49.4 mMol) of DMT was added to 400 ml of a 90:10 MeOH:DMF solution. Subsequently, 200 ml of a 90:10 MeOH:DMF solution (i.e., a 3:1 molar ratio of ligand to metal) containing 16.4 mMol of dissolved metal nitrate was added. The mixture was stirred at a temperature between 60 and 80°C for one hour. Stirring was stopped and ~1 ml of triethylamine was added as a catalyst for the formation of the coordination polymer. Heating was maintained for 48 hours. A fine precipitate formed after 24 hours.

[0296] The resulting precipitate was collected by filtration and then washed three times with methanol. FTIR spectra were then collected and if the peak at 1649 cm -1 If the DMF amide peak at 4° is still present, continue washing until the peak disappears. Then obtain the X-ray diffraction pattern and TGA curve of the precipitate.

[0297] Example 11

[0298] Zn(NO3)2.6H2O+DMT was prepared according to the general method described above.

[0299] Example 12

[0300] Ce(NO3)2.6H2O+DMT was prepared according to the general method described above.

[0301] Example 13

[0302] Pr(NO3)3.6H2O+DMT was prepared according to the general method described above.

[0303] Example 14

[0304] La(NO3)3.6H2O+DMT was prepared according to the general method described above.

[0305] Example 15

[0306] Y(NO3)3.6H2O+DMT was prepared according to the general method described above.

[0307] By M x+ (NO3) xGeneral process for preparing MOFs from 2-amino-5-mercapto-1,2,4-triazole (AMT–compound 6)

[0308] 5.7 g (49.4 mMol) of AMT was added to 400 ml of a 90:10 MeOH:DMF solution. Subsequently, 200 ml of a 90:10 MeOH:DMF solution (i.e., a 3:1 molar ratio of ligand to metal) containing 16.4 mMol of dissolved metal nitrate was added. The mixture was stirred at a temperature between 60 and 80°C for one hour. Stirring was stopped and ~1 ml of triethylamine was added as a catalyst for the formation of the coordination polymer. Heating was maintained for 24 hours. After 24 hours, a fine precipitate formed.

[0309] The resulting precipitate was collected by filtration and then washed three times with methanol. FTIR spectra were then collected and if the peak at 1649 cm -1 If the DMF amide peak at 4° is still present, continue washing until the peak disappears. Then obtain the X-ray diffraction pattern and TGA curve of the precipitate.

[0310] Example 16

[0311] Zn(NO3)2.6H2O+AMT was prepared according to the general method described above.

[0312] Example 17

[0313] Ce(NO3)2.6H2O+AMT was prepared according to the general method described above.

[0314] Example 18

[0315] Pr(NO3)3.6H2O+AMT was prepared according to the general method described above.

[0316] Example 19

[0317] La(NO3)3.6H2O+AMT was prepared according to the general method described above.

[0318] Example 20

[0319] Y(NO3)3.6H2O+AMT was prepared according to the general method described above.

[0320] By M x+ (NO3) x General process for preparing MOFs from 2-mercaptopyrimidine (MP–compound 7)

[0321] The general procedures for preparing the compounds are as described above.

[0322] Example 21

[0323] Zn(NO3)3.6H2O+MP was prepared according to the general method described above.

[0324] Example 22

[0325] Pr(NO3)3.6H2O+MP was prepared according to the general method described above.

[0326] By M x+ (NO3) x N y (NO3) y General process for preparing MOFs using 2-mercaptobenzimidazole (MBI–compound 1)

[0327] The general procedures for preparing the compounds are as described above.

[0328] Example 23

[0329] Pr(NO3)3.Ce(NO3)3+MBI was prepared according to the general method described above.

[0330] Example 24

[0331] Pr(NO3)3.La(NO3)3+MBI was prepared according to the general method described above.

[0332] By M x+ (NO3) x N y (NO3) y General process for preparing MOFs using 2-mercaptobenzimidazole (MBI–compound 1)

[0333] The general procedures for preparing the compounds are as described above.

[0334] Example 25

[0335] Zn(NO3)3.Ce(NO3)3+MBI was prepared according to the general method described above.

[0336] Example 26

[0337] Zn(NO3)3.Pr(NO3)3+MBI was prepared according to the general method described above.

[0338] By M x+ (NO3) x N y (NO3) y General process for preparing MOFs from 1,2,4-triazole-3-thiol (TT–compound 4)

[0339] 3.5 g (34.6 mMol) of TT was dissolved in 400 ml of a 90:10 solution of MeOH:DMF. 2.5 g of Pr(NO) (5.71 mMol) and 1.7 g of Zn(NO) (5.71 mMol) were dissolved in separate 100 ml of a 90:10 solution of MeOH:DMF. The metal solutions were then added to the TT solution and the mixture was heated to 60-80°C while stirring for the first hour. Stirring was stopped and 1 ml of TEA was added. Overnight, a very light green precipitate formed on the inner surface of the reaction vessel. The precipitate and sediment were collected by filtration and the solid material was washed with methanol.

[0340] Example 27

[0341] Zn(NO3)3.Ce(NO3)3+TT was prepared according to the general method described above.

[0342] Example 28

[0343] Zn(NO3)3.La(NO3)3+TT was prepared according to the general method described above.

[0344] Example 29

[0345] Zn(NO3)3.Pr(NO3)3+TT was prepared according to the general method described above.

[0346] Example 30

[0347] Zn(NO3)3.Y(NO3)3+TT was prepared according to the general method described above.

[0348] By M x+ (NO3) x N y (NO3) y General process for preparing MOFs from 2,5-dimercapto-1,3,4-thiadiazole (DMT–compound 5)

[0349] The general procedures for preparing the compounds are as described above.

[0350] Example 31

[0351] Zn(NO3)3.Ce(NO3)3+DMT was prepared according to the general method described above.

[0352] Example 32

[0353] Zn(NO3)3.La(NO3)3+DMT was prepared according to the general method described above.

[0354] Example 33

[0355] Zn(NO3)3.Pr(NO3)3+DMT was prepared according to the general method described above.

[0356] Example 34

[0357] Zn(NO3)3.Y(NO3)3+DMT was prepared according to the general method described above.

[0358] Corrosion testing of MOFs on metal substrates

[0359] General Process for Preparing Coated Metal Substrates

[0360] A two-component epoxy coating was prepared by mixing Epikote 828 (3.0 g) and Aradur 450 hardener (1.8 g) in a "Thinky Mixer" at 2000 rpm for 2 minutes. After a 60-minute "sweating" period, MOF (0.48 g) was added to the epoxy coating along with methyl ethyl ketone (MEK) solvent (0.5 g). Immediately after final mixing, the prepared coating was applied to a metal substrate and heated in a 40°C oven for 12 hours. The coated metal substrate was baked at 80°C for 30 minutes before being used in leaching tests or scribed for neutral salt spray (NSS) testing.

[0361] Example 35

[0362] The TT / epoxy combination was prepared according to the general procedure described above and coated onto ~3 x 5 inch AA2024 aluminum panels.

[0363] Example 36

[0364] The LaTT / epoxy combination was prepared according to the general procedure described above and coated onto ~3 x 5 inch AA2024 aluminum panels.

[0365] Example 37

[0366] The PrTT / epoxy combination was prepared according to the general procedure described above and coated onto ~3 x 5 inch AA2024 aluminum panels.

[0367] Example 38

[0368] The ZnDMT / epoxy combination was prepared according to the general procedure described above and coated onto ~3 x 5 inch AA2024 aluminum panels.

[0369] Example 39

[0370] The Zn(MP) / epoxy combination was prepared according to the general procedure described above and coated onto ~3 x 3 inch AA2024 aluminum panels.

[0371] General Procedure for Leaching Testing

[0372] The MOF / epoxy-coated metal substrate prepared according to the general procedure described above was exposed to 100 ml of 0.1 M NaCl solution contained inside a Perspex reservoir clamped to the surface of the coated metal substrate. At time periods of 1 day, 2 days, 3 days, 7 days, 14 days, 21 days, 28 days, and 35 days, the salt solution was removed and replaced with fresh solution. The removed solution was analyzed for sulfur and metal species by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The experiment was repeated three times and the average results of the three experiments were plotted ( Figure 1 ).

[0373] Example 40

[0374] A Zn(MP) / epoxy-coated aluminum metal substrate was prepared and Zn(MP) was cumulatively leached from the aluminum metal substrate according to Example 39. The amounts of Zn and S were determined by ICP-AES. Figure 1 It was shown that a Zn(MP) / epoxy-coated aluminum metal substrate leached zinc and sulfur into a NaCl solution, providing a corrosion-resistant environment. This provides results that support the advantage that MOFs in coating compositions can be effectively used in protective coating compositions to prevent corrosion of metal substrates without problematic reactions with other components in the composition. This also provides results that support the advantage that MOFs can be used in film-forming compositions.

[0375] General Procedure for Neutral Salt Spray Testing (NSS)

[0376] A MOF / epoxy coated metal substrate prepared according to the general procedure described above was scribed at 80° C. The coated metal substrate was then exposed to 5% salt spray at 35° C. for 12 weeks (2016 hours) according to ASTM B117. The coated metal substrate was removed, rinsed with deionized (DI) water, and photographed at weekly intervals before returning. Figure 2 The results of NSS testing of various MOF / epoxy-coated aluminum-coated substrates obtained are shown.

[0377] Example 41

[0378] A TT / epoxy coated aluminum metal substrate was prepared according to Example 35 and subjected to NSS according to the general procedure described above. Figure 2 a shows that after 12 weeks of exposure, the TT / epoxy coating provided some corrosion inhibition of the aluminum substrate.

[0379] Example 42

[0380] A LaTT / epoxy coated aluminum metal substrate was prepared according to Example 36 and subjected to NSS according to the general procedure described above. Figure 2b shows that after 12 weeks of exposure, the LaTT / epoxy coating provided moderate corrosion inhibition of the aluminum substrate. This provides results that support the advantage that MOFs in coating compositions can be effectively used in protective coating compositions to prevent corrosion of metal substrates without problematically reacting with other components in the composition. This also provides results that support the advantage that MOFs can be used in film-forming compositions.

[0381] Example 43

[0382] A PrTT / epoxy coated aluminum metal substrate was prepared according to Example 37 and subjected to NSS according to the general procedure described above. Figure 2 Figure c shows that after 12 weeks of exposure, the PrTT / epoxy coating provided complete corrosion inhibition of the aluminum substrate. This provides results that support the advantage that MOFs in coating compositions can be effectively used in protective coating compositions to prevent corrosion of metal substrates without problematic reactions with other components in the composition. This also provides results that support the advantage that MOFs can be used in film-forming compositions.

[0383] Example 44

[0384] A ZnDMT / epoxy coated aluminum metal substrate was prepared according to Example 38 and subjected to NSS according to the general procedure described above. Figure 2 d shows that after 12 weeks of exposure, the ZnDMT / epoxy coating provided moderate corrosion inhibition of the aluminum substrate. This provides results that support the advantage that MOFs in coating compositions can be effectively used in protective coating compositions to prevent corrosion of metal substrates without problematically reacting with other components in the composition. This also provides results that support the advantage that MOFs can be used in film-forming compositions.

Claims

1. A method for protecting a substrate from corrosion, comprising applying a protective composition comprising a corrosion inhibitor to a surface of the substrate, wherein the corrosion inhibitor comprises a metal organic framework material (MOF), wherein the MOF comprises metal ions or metal clusters, each of which is coordinated to one or more organic ligands to form at least one-dimensional, two-dimensional or three-dimensional networks, and wherein the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds, wherein each of the aryl, heteroaryl or heterocyclic compounds comprises at least one exocyclic sulfur group. The method according to claim 1 , wherein the substrate is a metal substrate.

3. The method of claim 2, wherein the metal substrate comprises aluminum metal or an alloy.

4. The method according to claim 1, wherein the organic ligand is selected from optionally substituted, optionally fused, 5- or 6-membered mono- or bicyclic aryl, heteroaryl or heterocyclic compounds comprising at least one exocyclic sulfur group selected from thiols and thioketones.

5. The method according to any one of claims 1 to 4, wherein the one or more organic ligands comprising at least one exocyclic sulfur group are selected from compounds of formula 1: in A is a 5- or 6-membered aryl, heteroaryl or heterocyclic ring, optionally substituted with one or more substituents and optionally fused to one or more aryl or heteroaryl rings, wherein the dashed line represents an optional double bond; X 1 Selected from N, NR 1 , O, S, CR 2 and CR 3 R 4 ; X 2 Selected from N, NR 5 , O, S, CR 6 and CR 7 R 8 ; X 3 Selected from N, NR 9 , CR 10 and CR 11 R 12 ; R 1 、R 5 and R 9 Each independently selected from hydrogen, amino, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 alkynyl, aryl, and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl, or heteroaryl group is optionally substituted; and R 2 、R 3 、R 4 、R 6 、R 7 、R 8 、R 10 、R 11 and R 12 Each is independently selected from hydrogen, halide, amino, thiol, thiol, ketone, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, aryl and heteroaryl, wherein each amino, alkyl, alkenyl, alkynyl, aryl or heteroaryl group may be optionally substituted.

6. The method according to claim 5, wherein X 1 is selected from N, NH and S.

7. The method according to claim 5, wherein X 3 Selected from N and CR 10 , and R 10 Selected from thiols and thioketones.

8. The method according to claim 5, wherein X 1 are independently selected from N and S, and X 3 It's C-SH.

9. The method according to claim 5, wherein X 1 It is N, X 2 is N, and X 3 It's C-SH.

10. The method according to claim 1, wherein the metal ions or metal clusters of the MOF are selected from at least one of rare earth metals and transition metals.

11. The method of claim 10, wherein the one or more metals are selected from zinc and rare earth metals of La, Pr, Ce, Co, Y, and any combination thereof.

12. The method according to claim 10, wherein the metal is selected from Zn, Pr and / or Ce.

13. The method of claim 10, wherein the metal is Pr.

14. The method of claim 1, wherein the MOF is in the form of solid particles.

15. The method according to claim 14, wherein the average diameter of the solid particles ranges from 20 nm to 50 μm.

16. The method according to claim 14, wherein the solid particles have an average diameter ranging in size from 100 nm to 1 μm.

17. A corrosion inhibiting composition for application to a substrate, comprising at least one corrosion inhibitor selected from metal organic framework materials (MOFs), wherein the MOF comprises metal ions or metal clusters, each of which is coordinated to one or more organic ligands to form at least one, two or three-dimensional networks, and wherein the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds, wherein each of the aryl, heteroaryl or heterocyclic compounds comprises at least one exocyclic sulfur group, and the ratio of organic ligand:metal is 2:1, 3:1, 4:1, 5:1 or 6:

1.

18. The composition of claim 17, wherein the composition is a coating composition comprising a film-forming organic polymer.

19. The composition of claim 18, wherein the film-forming organic polymer comprises one or more epoxy resins.

20. The composition of claim 17, wherein the composition is a powder coating composition.

21. The composition of claim 17, further comprising one or more additives, said one or more additives comprising one or more pigments, fillers, and extenders.

22. The composition of claim 17, wherein the MOF has a white color.

23. The composition of claim 22, wherein the composition does not contain any additive that is a pigment.

24. A method of preparing a corrosion inhibiting coating composition for application to a substrate, comprising forming the composition by mixing a film-forming organic polymer and at least one corrosion inhibitor selected from metal organic framework materials (MOFs), wherein the MOF comprises metal ions or metal clusters, each of which is coordinated to one or more organic ligands to form at least one-dimensional, two-dimensional or three-dimensional networks, and wherein the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds, wherein each of the aryl, heteroaryl or heterocyclic compounds comprises at least one exocyclic sulfur group.

25. A coated substrate comprising a substrate coated with a corrosion inhibiting composition comprising a metal organic framework material (MOF), wherein the MOF comprises metal ions or metal clusters, each of which is coordinated to one or more organic ligands to form at least one, two or three-dimensional networks, and wherein the one or more organic ligands are selected from optionally substituted aryl, heteroaryl or heterocyclic compounds, wherein each of the aryl, heteroaryl or heterocyclic compounds includes at least one exocyclic sulfur group; and the ratio of organic ligand:metal is 2:1, 3:1, 4:1, 5:1 or 6:

1.

26. The coated substrate of claim 25, wherein the corrosion inhibiting composition is applied as a direct coating to the surface of the substrate.

27. The coated substrate of claim 25, wherein the substrate is a metal alloy and the corrosion inhibiting composition comprises a film-forming organic polymer.

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