Catalyst composition and coating composition comprising the same

Abstract

The catalyst composition comprises a bismuth catalyst, a zinc catalyst, and a phosphorus-containing additive. The phosphorus-containing additive can be selected from the group consisting of (i) orthophosphoric acid, (ii) alkylphosphonic acid, (iii) a phosphate ester formally derived from phosphoric acid and at least one alkoxylated alcohol; (iv) a salt of a phosphate ester formally derived from phosphoric acid and at least one alkoxylated alcohol; and (v) mixtures thereof. The coating composition comprises a polyol, an isocyanate compound, and the above-described catalyst composition.

Description

Technical Field

[0001] This application and the subject matter described herein relate to compositions for catalyzing reactions between polyols and isocyanate compounds, and two-component coating compositions (e.g., 2K polyurethane coatings) comprising such catalyst compositions. Background Technology

[0002] Two-component coating compositions (“2K coatings”) are used in a variety of applications due to their durability, chemical resistance, rapid curing time, excellent adhesion, and flexibility in meeting specific application requirements. For example, polyurethane-based 2K coatings (“2K polyurethane coatings” or “2K poly coatings”) are used as protective coatings in a variety of applications. These 2K polyurethane coating compositions are made from a first component containing a polyol (e.g., a resin containing two or more hydroxyl groups) and a second component containing an isocyanate compound containing at least two isocyanate groups. While the polyol and isocyanate will react when the two components are mixed, 2K polyurethane coating compositions typically contain a catalyst to accelerate this reaction and speed up the curing of the coating. However, catalyzing the reaction between the polyol and isocyanate increases the difficulty of handling the coating composition. For example, catalytic reactions can shorten the pot life of the coating composition.

[0003] The pot life measures how quickly the viscosity of a coating composition increases. It is typically defined as the time required for the viscosity of a coating composition to double from its initial value. A short pot life means that once the two components are combined, the coating composition must be applied quickly to the target substrate, otherwise it becomes unusable due to the increased viscosity. Alternatively, a short pot life means that the applicator must mix small batches of the coating composition, which can be used before the reaction proceeds to the point where the composition becomes inoperable. Given these conflicting needs, the ideal catalyst system strikes a balance between a reasonably long pot life and a short reaction time after coating application.

[0004] Tin-based catalysts are frequently used in 2K polyurethane coating compositions. These catalysts can be formulated to provide a balance between curing time and pot life, enabling 2K polyurethane coating compositions to be used in a variety of applications. However, due to known toxicity issues, the use of tin-based catalysts is under increasing scrutiny from regulatory agencies and industry. Therefore, coating formulators are seeking alternative catalyst systems that offer similar (if not better) performance to known tin-based catalysts.

[0005] Therefore, there remains a need for catalyst systems that do not contain toxic tin-based catalysts but provide a balance between curing time and pot life in two-component coating compositions (e.g., 2K polyurethane coating compositions). The catalyst compositions and coating compositions described herein are designed to meet this need. Summary of the Invention

[0006] In a first embodiment, the present invention provides a catalyst composition comprising (a) a bismuth catalyst comprising a bismuth salt of a first alkyl carboxylic acid; (b) a zinc catalyst comprising a zinc salt of a second alkyl carboxylic acid; and (c) a phosphorus-containing additive. The phosphorus-containing additive may be selected from the group consisting of (i) orthophosphoric acid, (ii) alkylphosphonic acid, (iii) phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; (iv) salts of phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; and (v) mixtures thereof.

[0007] The catalyst composition described herein is considered highly suitable for catalyzing two-component coating compositions, such as 2K polyurethane coating compositions. When used in such coating compositions, the catalyst composition exhibits balanced activity, thereby providing the desired pot life to facilitate coating application to the target substrate and producing a coating that cures to its desired hardness within the desired timeframe.

[0008] Therefore, in a second embodiment, the present invention provides a coating composition comprising the above-described catalyst composition. Specifically, the coating composition comprises (a) a polyol; (b) an isocyanate compound; and (c) a catalyst composition as described herein. Detailed Implementation

[0009] In a first embodiment, the present invention provides a catalyst composition comprising (a) a bismuth catalyst, (b) a zinc catalyst and (c) a phosphorus-containing additive.

[0010] The bismuth catalyst in the catalyst composition can be any suitable bismuth catalyst. In a preferred embodiment, the bismuth catalyst comprises a bismuth salt of a primary carboxylic acid. The bismuth salt can contain bismuth in any suitable oxidation state, such as +1 (i.e., Bi(I)), +2 (i.e., Bi(II)), +3 (i.e., Bi(III)), and +5 (i.e., Bi(V)) oxidation states. In a preferred embodiment, the bismuth catalyst comprises a bismuth(III) salt.

[0011] As described above, the bismuth catalyst comprises a bismuth salt of a first carboxylic acid. The first carboxylic acid can be any suitable carboxylic acid. Suitable first carboxylic acids include aliphatic carboxylic acids, such as C4-C... 28 Aliphatic carboxylic acids. In a preferred embodiment, the first carboxylic acid is C4-C. 12 Alkyl carboxylic acids. Suitable C4-C 12 Alkyl carboxylic acids include straight-chain C4-C6 compounds. 12 Alkyl carboxylic acids and branched C4-C 12 Alkyl carboxylic acids. In a preferred embodiment, the first carboxylic acid is a branched alkyl carboxylic acid, more preferably containing branched C3-C... 11 Branched C4-C of alkyl groups12 Alkyl carboxylic acids. In a preferred embodiment, the first carboxylic acid is neodecanoic acid. Therefore, the bismuth catalyst preferably comprises a bismuth salt of neodecanoic acid. More preferably, the bismuth catalyst comprises bismuth(III) neodecanoate.

[0012] The zinc catalyst in the catalyst composition can be any suitable zinc catalyst. In a preferred embodiment, the zinc catalyst comprises a zinc salt of a second carboxylic acid. The zinc salt can contain zinc in any suitable oxidation state, such as +1 (i.e., Zn(I)) and +2 (i.e., Zn(II)) oxidation states. In a preferred embodiment, the zinc catalyst comprises a zinc(II) salt.

[0013] The zinc catalyst contains a zinc salt of a second carboxylic acid. The second carboxylic acid can be any suitable carboxylic acid and can be the same as or different from the first carboxylic acid in the bismuth catalyst. Suitable second carboxylic acids include aliphatic carboxylic acids, such as C4-C... 28 Aliphatic carboxylic acids. In a preferred embodiment, the second carboxylic acid is C4-C. 12 Alkyl carboxylic acids. Suitable C4-C 12 Alkyl carboxylic acids include straight-chain C4-C6 compounds. 12 Alkyl carboxylic acids and branched C4-C 12 Alkyl carboxylic acid. In a preferred embodiment, the second carboxylic acid is a branched alkyl carboxylic acid, more preferably containing branched C3-C... 11 Branched C4-C of alkyl groups 12 Alkyl carboxylic acids. In a preferred embodiment, the second carboxylic acid is neodecanoic acid. Therefore, the zinc catalyst preferably comprises a zinc salt of neodecanoic acid. More preferably, the zinc catalyst comprises zinc neodecanoate(II), such as the substance commonly referred to as "neodecanonical acid, zinc salt, basic" and with CAS number 84418-68-8.

[0014] The catalyst composition may contain any suitable amounts of bismuth catalyst and zinc catalyst. Preferably, the bismuth catalyst and zinc catalyst are present in the catalyst composition in amounts providing a bismuth to zinc ratio (by mass of each metal) of about 0.9:1 or greater. In another embodiment, the bismuth to zinc ratio is preferably about 1:1 or greater, more preferably about 1.05:1 or greater. While the catalyst composition may contain more bismuth by mass than zinc, it is preferable that the catalyst composition does not contain too much excess bismuth. Thus, in another preferred embodiment, the bismuth catalyst and zinc catalyst are present in the catalyst composition in amounts providing a bismuth to zinc ratio (by mass) of about 1.2:1 or less. In other embodiments, the bismuth to zinc ratio is preferably about 1.15:1 or less. Therefore, in a series of preferred embodiments, the bismuth catalyst and the zinc catalyst are preferably present in the catalyst composition in an amount (by mass) providing a bismuth to zinc ratio of about 0.9:1 to about 1.2:1 (e.g., about 0.9:1 to about 1.15:1), more preferably about 1:1 to about 1.2:1 (e.g., about 1:1 to about 1.15:1) or about 1.05:1 to about 1.15:1.

[0015] As mentioned above, the catalyst composition also contains phosphorus-containing additives. While not wishing to be bound by any particular theory, it is believed that the phosphorus-containing additives modulate the activity of the catalyst in the catalyst composition through some unknown mechanism, thereby extending the pot life of the coating composition compared to coating compositions containing the same catalyst but without phosphorus-containing additives. The effect of phosphorus-containing additives on the pot life of the coating composition is thought to be influenced by the specific catalyst or catalyst combination present in the coating composition. In fact, it has been surprisingly found that including both bismuth and zinc catalysts in the coating composition mitigates the effect of phosphorus-containing additives on the pot life, enabling the production of coating compositions with extended pot lifespans that can be customized to specific application needs.

[0016] Phosphorus-containing additives are preferably selected from the group consisting of (i) orthophosphoric acid, (ii) alkylphosphonic acid, (iii) phosphate esters, (iv) salts of phosphate esters, and (v) mixtures of any two or more of the above. Suitable alkylphosphonic acids include, but are not limited to, those containing straight-chain or branched C1-C1 chains. 28 Alkyl groups, more preferably straight-chain or branched C1-C 15 Alkyl phosphonic acids. In a preferred embodiment, the alkyl phosphonic acid comprises a straight-chain C1-C1 chain. 15 Alkyl groups, such as n-butyl or dodecyl. Therefore, in a preferred embodiment, the phosphorus-containing additive is selected from n-butylphosphonic acid, dodecylphosphonic acid, and mixtures thereof.

[0017] Phosphorus-containing additives suitable for additive compositions also include phosphate esters and salts of phosphate esters. Suitable phosphate esters are monoesters, diesters, or tripesters formally derived from phosphoric acid (e.g., orthophosphoric acid) and at least one alcohol. As used herein, the term "formally derived" adopts the same meaning as the definition of "ester" in the IUPAC Chemical Terminology Compendium, 2nd Edition ("Gold Book"), edited by AD McNaught and A. Wilkinson, Blackwell Scientific Publications, Oxford (1997). Therefore, phosphate esters do not need to be prepared by the direct reaction of phosphoric acid with an alcohol.

[0018] Phosphate esters can be derived in any form from suitable phosphoric acid, but orthophosphoric acid is particularly preferred. Alcohols suitable for phosphate esters include those having straight-chain or branched alkyl groups, such as straight-chain or branched C1-C... 35 Alcohols. Preferably, the alcohols are straight-chain or branched C6-C. 35 Alcohols, especially branched C6-C... 35 Alcohols (e.g., C6-C) 15 Alcohol). In a preferred embodiment, the alcohol that formally derives the phosphate ester is isotredecanol. Alcohols can be alkoxylated, for example, by reacting the alcohol with a suitable epoxide (e.g., ethylene oxide, propylene oxide, butane oxide, or mixtures thereof). Thus, in a preferred embodiment, the phosphorus-containing additive is selected from those formally derived from phosphoric acid (preferably orthophosphoric acid) and at least one alkoxylated C6-C... 35 Phosphate esters of alcohols. In a more preferred embodiment, the phosphorus-containing additive is selected from phosphate esters formally derived from orthophosphoric acid and at least one alkoxylated isotridecyl alcohol, more preferably ethoxylated isotridecyl alcohol.

[0019] As described above, suitable phosphorus-containing additives include salts of phosphate esters, such as any of the aforementioned phosphate ester salts. Such salts can be prepared by reacting one of the hydroxyl groups of a phosphate monoester or diester with a suitable base such as an alkali metal hydroxide, an alkaline earth metal hydroxide, a hydroxide of an ammonium compound, or an amine compound (e.g., a tertiary amine). In a preferred embodiment, the catalyst composition comprises a salt of a phosphate ester, more preferably an amine salt of a phosphate ester. Thus, in a preferred embodiment, the catalyst composition comprises a form derived from phosphoric acid (preferably orthophosphoric acid) and at least one C6-C... 35 The amine salt of a phosphate ester of an alcohol (preferably isotredecanol) (e.g., a quaternary ammonium salt derived from an amine such as a tertiary amine). In yet another preferred embodiment, the catalyst composition comprises, in form, derived from phosphoric acid (preferably orthophosphoric acid) and at least one alkoxylated C6-C... 35The amine salt (e.g., a quaternary ammonium salt derived from an amine, such as a tertiary amine) of a phosphate ester of an alcohol (preferably an alkoxylated isotredecanol). More preferably, the catalyst composition comprises, in the form of phosphoric acid (preferably orthophosphoric acid) and at least one alkoxylated C6-C... 35 The catalyst composition comprises an N,N-dimethylcyclohexylammonium salt of a phosphate ester of an alcohol (preferably alkoxylated isotrigine alcohol). In another preferred embodiment, the catalyst composition preferably comprises an N,N-dimethylcyclohexylammonium salt of a phosphate ester formally derived from orthophosphoric acid and at least one ethoxylated isotrigine alcohol.

[0020] In a preferred embodiment, the phosphorus-containing additive is a phosphate ester compound conforming to the structure of formula (I): (I) .

[0021] In the structure of equation (I), R 1 It is the formula — (R) 2 —O) a —R 3 The group, wherein a is selected from positive integers from 0 and 1 to 100, each R 2 It is an independently chosen alkyl diene, and R 3 Selected from alkyl groups. X 1 and X 2 Independently selected from hydroxyl, -(R 11 —O) b —R 12 and O - (i.e., negatively charged oxygen atoms covalently bonded to phosphorus atoms resulting from the deprotonation of hydroxyl groups on phosphate), where each b is independently selected from zero and positive integers from 1 to 100, and each R 11 It is an independently selected alkyl diene, and each R 12 It is an independently selected alkyl group . A is selected from inorganic cations and organic cations. d represents the charge on the phosphate ester, if X... 1 and X 2 If none of them are 0, then it is 0. If X 1 or X 2 One of them is —O - If X, then it is -1, or if X 1 and X 2 All are -O - If d is zero, then variable e is 1; if d is -1 or -2, then variable e is a positive integer. Variable f is a positive integer equal to the valence of cation A. If d is zero, then variable g is zero; if d is -1 or -2, then variable g is a positive integer. Furthermore, the values ​​of variables d, e, f, and g are the closest values ​​to zero that satisfy the equation (de) + (fg) = 0. In a preferred embodiment, each R...2 and R 11 Independently selected from C2-C4 alkyldiyl groups, such as ethane-1,2-diyl, 1-methylethane-1,2-diyl, 2-methylethane-1,2-diyl, 1-ethylethane-1,2-diyl, and 2-ethylethane-1,2-diyl. In another preferred embodiment, each R 3 and R 12 Independently selected from C1-C 35 Alkyl, more preferably C6-C 35 Alkyl (e.g., C6-C) 15 Alkyl group). Preferably, the values ​​of a and b are independently selected from positive integers from 0 and 1 to 20 (e.g., 1 to 15 or 1 to 10), more preferably a and b are each positive integer values. In a preferred embodiment, A is selected from alkali metal cations, alkaline earth metal cations, group 12 element cations (e.g., zinc cations), group 13 element cations (e.g., aluminum cations or hydroxyaluminum cations), and quaternary ammonium cations (e.g., N,N-dimethylcyclohexylammonium cations).

[0022] Therefore, in a series of preferred embodiments, the phosphorus-containing additive comprises a compound of formula (I), wherein: (i)R 1 For the formula — (R) 2 —O) a —R 3 The group, wherein a is selected from positive integers from 0 and 1 to 20, preferably from 0 and 1 to 10, more preferably from 1 to 20, and even more preferably from 1 to 10; (ii) Each R 2 It is an independently selected C2-C4 alkyldiyl, more preferably an alkyldiyl independently selected from ethyl-1,2-diyl, 1-methylethyl-1,2-diyl, 2-methylethyl-1,2-diyl, 1-ethylethyl-1,2-diyl, and 2-ethylethyl-1,2-diyl; and (iii) Each R 3 Independently selected from C1-C 35 Alkyl, more preferably C6-C 35 Alkyl, or even more preferably C6-C 15 Alkyl (e.g., 11-methyldodecyl-1-yl).

[0023] In the preferred embodiments of each of the foregoing: (iv) X 1 Yes - O - ; (v) A is a quaternary ammonium cation, more preferably an N,N-dimethylcyclohexylammonium cation; (vi) X 2 Yes—(R) 11—O) b —R 12 , where b is selected from 0 and positive integers from 1 to 20, preferably from 0 and positive integers from 1 to 10, more preferably from positive integers from 1 to 20, and even more preferably from positive integers from 1 to 10; (vii) Each R 11 It is an independently selected C2-C4 alkyldiyl, more preferably an alkyldiyl independently selected from ethyl-1,2-diyl, 1-methylethyl-1,2-diyl, 2-methylethyl-1,2-diyl, 1-ethylethyl-1,2-diyl, and 2-ethylethyl-1,2-diyl; and (viii) Each R 12 Independently selected from C1-C 35 Alkyl, more preferably C6-C 35 Alkyl, or even more preferably C6-C 15 Alkyl (e.g., 11-methyldodecyl-1-yl).

[0024] In another preferred embodiment of each of the foregoing: (ix) X 1 and X 2 Each is -O - ; (x) A is a quaternary ammonium cation, more preferably an N,N-dimethylcyclohexylammonium cation.

[0025] The catalyst composition may contain a mixture of two or more of the phosphorus-containing additives described above. For example, the catalyst composition may contain a mixture of orthophosphoric acid and alkylphosphonic acid. Alternatively, the catalyst composition may contain a mixture of at least one phosphate ester and at least one phosphate ester salt (e.g., an amine salt of a phosphate ester). Furthermore, when the phosphorus-containing additive contains a phosphate ester as described above, the phosphorus-containing additive may contain a mixture of monoesters, diesters, and triesters of phosphate, as well as salts of such monoesters, diesters, and triesters. Preferably, the catalyst composition contains a mixture of a phosphate ester as described above and a salt of such a phosphate ester, and more preferably a quaternary ammonium salt of such a phosphate ester.

[0026] The catalyst composition may contain any suitable amount of phosphorus-containing additives. To provide the desired increased pot life of the coating composition, the catalyst composition preferably contains about 25 wt.% or more of phosphorus-containing additives based on the total mass of bismuth, zinc, and phosphorus-containing additives present in the catalyst composition. In other preferred embodiments, the catalyst composition preferably contains about 30 wt.% or more (more preferably about 35 wt.% or more) of phosphorus-containing additives based on the total mass of bismuth, zinc, and phosphorus-containing additives present in the catalyst composition. To avoid potentially detrimental effects on the curing (drying time) and / or hardness of coatings made from the catalyst-containing coating composition, the catalyst composition preferably contains about 80 wt.% or less of phosphorus-containing additives based on the total mass of bismuth, zinc, and phosphorus-containing additives present in the catalyst composition. In other preferred embodiments, the catalyst composition preferably contains about 75 wt.% or less (more preferably about 70 wt.% or less) of phosphorus-containing additives based on the total mass of bismuth, zinc, and phosphorus-containing additives present in the catalyst composition. Therefore, in a series of preferred embodiments, based on the total mass of bismuth, zinc and phosphorus-containing additives present in the catalyst composition, the catalyst composition contains about 25 wt.% to about 80 wt.% (e.g., about 25 wt.% to about 75 wt.% or about 25 wt.% to about 70 wt.%), more preferably about 30 wt.% to about 80 wt.% (e.g., about 30 wt.% to about 75 wt.% or about 30 wt.% to about 70 wt.%), or about 35 wt.% to about 80 wt.% (e.g., about 35 wt.% to about 75 wt.% or about 35 wt.% to about 70 wt.%) of phosphorus-containing additives.

[0027] In addition to the bismuth catalyst, zinc catalyst, and phosphorus-containing additives mentioned above, the catalyst composition may also contain other components. For example, the catalyst composition may contain a suitable solvent or liquid medium in which the components are dispersed. Suitable solvents include, but are not limited to, higher alkanes that are liquid at ambient temperature, such as C42-4 ... 10 -C 15 Alkanes.

[0028] According to specific embodiments, the catalyst compositions described herein consist essentially of the aforementioned bismuth catalyst, zinc catalyst, and phosphorus-containing additive. As used herein, the phrase "consistently of..." describes a catalyst composition containing the listed components and optionally additional components, provided that the inclusion of such additional components does not substantially alter or affect the fundamental properties of the catalyst composition. Given that one objective of the catalyst composition is to catalyze the reaction between polyols and isocyanate compounds while maintaining the desired potency of the catalytic mixture, it should be understood that components that would shorten the potency of the catalytic mixture to a level lower than that achieved when using only the combination of bismuth and zinc catalysts are excluded from catalyst compositions consisting essentially of bismuth catalyst, zinc catalyst, and phosphorus-containing additive. Furthermore, given that another objective of the catalyst composition is to reduce the amount of tin-based catalyst used to catalyze the reaction between polyols and isocyanate compounds, it should be understood that components that would introduce a significant amount of tin (e.g., the amount of tin compounds typically used to catalyze this reaction) are excluded from catalyst compositions consisting essentially of bismuth catalyst, zinc catalyst, and phosphorus-containing additive. In contrast, it should be understood that the presence of other inert materials (e.g., solvents, surfactants, etc.) that do not substantially affect the fundamental properties of the catalyst composition is permissible, and catalyst compositions containing such materials fall within the range of catalyst compositions that are essentially composed of bismuth catalysts, zinc catalysts, and phosphorus-containing additives.

[0029] As described above, the catalyst composition is considered highly suitable for catalyzing reactions occurring in two-component coating compositions, more specifically, two-component polyurethane coating compositions. Therefore, in a second embodiment, the present invention provides a coating composition comprising (a) a polyol, (b) an isocyanate compound, and (c) any of the above-described catalyst compositions.

[0030] As used herein, the term polyol refers to compounds and polymers containing two or more hydroxyl groups. Coating compositions may contain any suitable polyol. Suitable polyols include, but are not limited to, polyester polyols, polyether polyols, polycarbonate polyols, polycarbonate-polyester polyols, polyacrylic acid polyols (i.e., acrylic polymers containing two or more hydroxyl groups), polyurethane polyols, polycaprolactone polyols, polyolefin polyols, and mixtures of any two or more of the foregoing. In a preferred embodiment, the polyol is an acrylic polymer containing two or more hydroxyl groups (e.g., hydroxyl-functionalized acrylic polymers).

[0031] Hydroxyl-functional acrylic polymers suitable for coating compositions can be prepared using free radical polymerization techniques known in the art. These acrylic polymers are typically prepared by addition polymerization of one or more monomers. At least one of the monomers will contain a reactive hydroxyl group, or may subsequently react to generate a reactive hydroxyl group. Representative hydroxyl-functional monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 4-hydroxypentyl acrylate, 2-hydroxyethyl ethyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxyethyl chloroacrylate, diethylene glycol methacrylate, tetraethylene glycol acrylate, and p-vinylbenzyl alcohol. Typically, the hydroxyl-functional monomers are copolymerized with one or more monomers having olefinic unsaturation, such as: (i) Esters of acrylic acid, methacrylic acid, crotonic acid, thiocyanate or other unsaturated acids, such as: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, pentyl acrylate, 3,5,5-trimethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, dimethylaminoethyl methacrylate, isobornyl methacrylate, ethyl thiocyanate, methyl crotonic acid and ethyl crotonic acid; (ii) Vinyl compounds, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl m-chlorobenzoate, vinyl p-methoxybenzoate, vinyl α-chloroacetate, vinyltoluene, and vinyl chloride; (iii) Styrene-based materials, such as styrene, α-methylstyrene, α-ethylstyrene, α-bromostyrene and 2,6-dichlorostyrene; (iv) Allyl compounds, such as allyl chloride, allyl acetate, allyl benzoate, and allyl methacrylate; or (v) Other copolymerizable unsaturated monomers such as ethylene acrylonitrile, methacrylonitrile, dimethyl maleate, isopropyl acetate, isopropyl isobutyrate, acrylamide, methacrylamide, dienes such as 1,3-butadiene, and halogenated materials such as 2-(N-ethylperfluorooctene sulfonamide) ethyl (meth)acrylate.

[0032] Hydroxyl-functionalized acrylic polymers are readily prepared via conventional free radical addition polymerization techniques. Typically, polymerization is initiated by conventional initiators known in the art to generate free radicals, such as azobis(isobutyronitrile), cumene hydroperoxide, or tert-butyl perbenzoate. Generally, the monomer is heated in the presence of the initiator at temperatures from about 35°C to about 200°C, particularly 75°C to 150°C, to achieve polymerization. If desired, the molecular weight of the polymer can be controlled by monomer selection, reaction temperature and time, and / or by the use of chain transfer agents known in the art.

[0033] The isocyanate compound used in the coating composition can be any isocyanate compound, with isocyanate compounds containing two or more isocyanate groups being particularly preferred. Suitable isocyanate compounds include, but are not limited to, aromatic, alicyclic, and aliphatic polyisocyanates, such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,2,4-phenyltriisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenyl isocyanate. 1,6-Hexamethylene diisocyanate (HDI), isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,6-diisocyanate-2,2,4-trimethylhexane, trimethylhexamethylene diisocyanate, pentane-1,4-diisocyanate, isocyanate-methylcyclohexyl isocyanate, 1,6,11-undecane triisocyanate, para-tetramethylxylene diisocyanate, meta-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,10-dedecylene diisocyanate, m-xylene diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, and mixtures thereof.

[0034] Polyols and isocyanate compounds may be present in the coating composition in any suitable amount. Typically, the total mass of the polyols and isocyanates is from about 25 wt.% to about 90 wt.% of the total mass of the coating composition (e.g., from about 30 wt.% to about 90 wt.%, from about 35 wt.% to about 90 wt.%, from about 40 wt.% to about 90 wt.%, or from about 40 wt.% to about 85 wt.%). Polyols and isocyanate compounds may be present in any suitable relative amount. Typically, polyols and isocyanate compounds are present in the coating composition in an amount that provides about 0.3 to about 2 equivalents of isocyanate groups for each hydroxyl group from the polyol. Polyols and isocyanate compounds are preferably present in the coating composition in an amount that provides about 0.7 to about 1.3 equivalents (more preferably about 0.9 to about 1.3 equivalents, about 1 to about 1.3 equivalents, about 1 to about 1.2 equivalents, or about 1 to about 1.1 equivalents) of isocyanate groups for each hydroxyl group from the polyol.

[0035] As described above, the coating composition comprises any of the catalyst compositions described above. The coating composition may contain any suitable amount of the catalyst composition. The optimal amount of the catalyst composition will depend on several factors, such as the amount of polyol and isocyanate in the coating composition, the ratio of the total number of hydroxyl groups to the total number of isocyanate groups in the coating composition, the concentration of the catalyst and phosphorus-containing additives in the catalyst composition, and the desired pot life of the coating composition once the two components are mixed. Preferably, based on the total weight of the polyol and isocyanate compounds in the coating composition, the coating composition contains about 0.01 wt.% or more (more preferably about 0.05 wt.% or more) of the catalyst composition. Based on the total weight of the polyol and isocyanate compounds in the coating composition, the coating composition preferably contains about 0.5 wt.% or less (more preferably about 0.2 wt.% or less) of the catalyst composition. Therefore, in a series of preferred embodiments, based on the total weight of the polyol and isocyanate compounds in the coating composition, the coating composition preferably contains about 0.01 wt.% to about 0.5 wt.% (e.g., about 0.01 wt.% to about 0.2 wt.%) or about 0.05 wt.% to about 0.5 wt.% (e.g., about 0.05 wt.% to about 0.2 wt.%) of a catalyst composition.

[0036] The amount of catalyst composition added to the coating composition can also be expressed as the amount of one or more catalyst composition components in the coating composition. For example, in a preferred embodiment, the catalyst composition is present in the coating composition in an amount providing about 0.007 wt.% to about 0.01 wt.% (more preferably about 0.008 wt.% to about 0.009 wt.%) of bismuth, based on the total weight of the polyol and isocyanate compounds in the coating composition. In another preferred embodiment, the catalyst composition is present in the coating composition in an amount providing about 0.006 wt.% to about 0.01 wt.% (more preferably about 0.007 wt.% to about 0.009 wt.% or about 0.007 to about 0.008 wt.%) of zinc, based on the total weight of the polyol and isocyanate compounds in the coating composition. In yet another preferred embodiment, the catalyst composition is present in the coating composition in an amount providing about 0.005 wt.% to about 0.04 wt.% (more preferably about 0.006 wt.% to about 0.035 wt.%, about 0.007 wt.% to about 0.035 wt.%, or about 0.008 wt.% to about 0.035 wt.%) of phosphorus-containing additives, based entirely on the total weight of the polyols and isocyanates in the coating composition. Thus, in a particularly preferred embodiment, the catalyst composition is present in the coating composition in an amount providing (i) about 0.007 wt.% to about 0.01 wt.% of bismuth, (ii) about 0.006 wt.% to about 0.01 wt.% of zinc, and (iii) about 0.005 wt.% to about 0.04 wt.% of phosphorus-containing additives, all based on the total weight of the polyols and isocyanates in the coating composition. In another preferred embodiment, the catalyst composition is present in the coating composition in amounts providing (i) about 0.008 wt.% to about 0.009 wt.% bismuth, (ii) about 0.007 wt.% to about 0.009 wt.% zinc, and (iii) about 0.006 wt.% to about 0.035 wt.% phosphorus-containing additives, all based on the total weight of the polyols and isocyanate compounds in the coating composition. In yet another particularly preferred embodiment, the catalyst composition is present in the coating composition in amounts providing (i) about 0.008 wt.% to about 0.009 wt.% bismuth, (ii) about 0.007 wt.% to about 0.008 wt.% zinc, and (iii) about 0.007 wt.% to about 0.035 wt.% phosphorus-containing additives, all based on the total weight of the polyols and isocyanate compounds in the coating composition.In another preferred embodiment, the catalyst composition is present in the coating composition in amounts providing (i) about 0.008 wt.% to about 0.009 wt.% bismuth, (ii) about 0.007 wt.% to about 0.008 wt.% zinc, and (iii) about 0.008 wt.% to about 0.035 wt.% phosphorus-containing additives, all based on the total weight of the polyols and isocyanates in the coating composition. In any of the above embodiments, when the phosphorus-containing additive is orthophosphoric acid, the orthophosphoric acid is preferably present in an amount of about 0.007 wt.% to about 0.012 wt.% based on the total weight of the polyols and isocyanates in the coating composition. When the phosphorus-containing additive in any of the above embodiments is an alkylphosphonic acid, the alkylphosphonic acid is preferably present in an amount of about 0.015 wt.% to about 0.035 wt.% (more preferably about 0.02 wt.% to about 0.032 wt.%) based on the total weight of the polyols and isocyanates in the coating composition. In any of the above embodiments, when the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, the phosphate ester or salt of a phosphate ester is preferably present in an amount of about 0.009 wt.% to about 0.02 wt.% (more preferably about 0.01 wt.% to about 0.015 wt.%), based on the total weight of the polyol and isocyanate compound in the coating composition.

[0037] In addition to polyols, isocyanate compounds, and catalyst compositions, coating compositions may also contain other ingredients. Examples of such other ingredients include, but are not limited to, solvents, other polymers or polymer dispersions, surfactants, dispersants, defoamers, biocides (e.g., bactericides, fungicides, algaecides, and insecticides), fillers, plasticizers, viscosity modifiers (e.g., thickeners), leveling agents, antisettling agents, crosslinking agents, antistatic agents, flame retardants, lubricants, emulsifiers, antifouling agents, pH buffers, corrosion inhibitors, desiccants, anti-skinning agents, anti-cracking agents, anti-sagging agents, heat stabilizers, UV absorbers / inhibitors, antioxidants, wetting agents, antireflective agents, antifreeze agents, waxes, colorants (including inks and colored pigments), flattening agents, and other inert pigments (e.g., titanium dioxide, dyes, clays, amorphous and surface-treated silica, calcium carbonate, etc., and combinations thereof), flow agents, and various combinations thereof required for specific applications. In one particular embodiment, the coating composition may contain one or more pigments. Representative opaque pigments include white pigments such as titanium dioxide, zinc oxide, and antimony oxide, as well as organic or inorganic colored pigments such as iron oxide, carbon black, and phthalocyanine blue. The coating composition may also contain additive pigments such as calcium carbonate, clay, silica, and talc. The coating composition may also contain one or more solvents, such as ketone solvents, ester solvents, alcohols, glycol ether solvents, and glycol ether ester solvents. Exemplary non-limiting examples of usable solvents include xylene, n-butyl acetate, tert-butyl acetate, n-butyl propionate, naphtha, ethyl 3-ethoxypropionate, toluene, methyl ethyl ketone (MEK), acetone, methyl propyl ketone (MPK), methyl n-pentyl ketone (MAK), and propylene glycol methyl ether acetate (PMA). The coating composition may also contain one or more surface additives (surfactants), such as silicone-based surface additives, which help reduce the surface tension of the coating composition and promote wetting of the target substrate.

[0038] The coating composition described above can be produced by combining a polyol (or a composition containing a polyol), an isocyanate compound (or a composition containing an isocyanate compound), and a prepared catalyst composition containing a bismuth catalyst, a zinc catalyst, a phosphorus-containing additive, and any optionally present components. Alternatively, the coating composition can be prepared by first combining a polyol (or a composition containing a polyol) with the catalyst composition prepared as described above to produce a polyol composition, and then combining the polyol composition with an isocyanate compound (or a composition containing an isocyanate compound) to produce a coating composition. In yet another alternative, the coating composition can be prepared by first combining an isocyanate compound (or a composition containing an isocyanate compound) with the catalyst composition prepared as described above to produce an isocyanate composition, and then combining the isocyanate composition with a polyol (or a composition containing a polyol) to produce a coating composition. For each of the above alternatives, the bismuth catalyst, the zinc catalyst, and the phosphorus-containing additive can be provided separately (i.e., the bismuth catalyst, the zinc catalyst, and the phosphorus-containing additive are provided separately and combined with the polyol and / or isocyanate instead of the previously prepared catalyst composition containing all components). Alternatively, any two of the bismuth catalyst, zinc catalyst, and phosphorus-containing additive may be provided in a suitable combination (e.g., a composition containing the bismuth catalyst, zinc catalyst, and optionally present components), and then combined with a polyol and / or isocyanate and the remaining third component (e.g., a phosphorus-containing additive or a composition containing a phosphorus-containing additive).

[0039] In some embodiments, the present invention provides a kit comprising two or more formulations, said formulations containing components of the above-described coating composition. The formulations in such kits are physically separated from each other, for example, in separate containers, cartridges, pouches, etc. For example, such a kit may include a first formulation comprising a polyol (or a composition comprising a polyol) and a catalyst composition and a second formulation comprising an isocyanate compound (or a composition comprising an isocyanate compound), wherein each formulation is contained in a separate cartridge or pouch from the other formulation.

[0040] The coating compositions described herein are considered suitable for application to any substrate or article by any method. In one embodiment, a method for forming a coated substrate or article is provided, thereby applying any of the above-described coating composition embodiments to at least a portion of the surface of the substrate or article. The coating composition is applied to the substrate or article by conventional methods and cured, typically in ambient air at ambient temperature or slightly elevated temperatures (e.g., up to 80°C). For example, the coating composition can be applied to the surface of the target substrate or article by spraying, brushing, rolling, wiping, or a combination thereof.

[0041] The invention and its potential embodiments described and included in the foregoing description can be further understood by referring to the specific embodiments set forth below. Therefore, these embodiments are included for illustrative purposes only (e.g., to describe potential preferred embodiments of the invention) and are not intended to limit the foregoing description in any way.

[0042] Implementation Scheme 1. A catalyst composition comprising: (a) Bismuth catalysts comprising a bismuth salt of a first alkyl carboxylic acid; (b) Zinc catalysts containing zinc salts of second alkylcarboxylic acids; and (c) Phosphorus-containing additives selected from the group consisting of: (i) orthophosphoric acid, (ii) alkylphosphonic acid, (iii) phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; (iv) salts of phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; and (v) mixtures thereof. The mass ratio of bismuth to zinc is approximately 0.9:1 to approximately 1.2:1.

[0043] Implementation Scheme 2. A catalyst composition comprising essentially the following: (a) Bismuth catalysts comprising a bismuth salt of a first alkyl carboxylic acid; (b) Zinc catalysts containing zinc salts of second alkylcarboxylic acids; and (c) Phosphorus-containing additives selected from the group consisting of: (i) orthophosphoric acid, (ii) alkylphosphonic acid, (iii) phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; (iv) salts of phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; and (v) mixtures thereof. The mass ratio of bismuth to zinc is approximately 0.9:1 to approximately 1.2:1.

[0044] Implementation Scheme 3. The catalyst composition of Implementation Scheme 1 or Implementation Scheme 2, wherein the first alkyl carboxylic acid is C4-C 12 Alkyl carboxylic acids.

[0045] Implementation Scheme 4. The catalyst composition of Implementation Scheme 3, wherein the first alkyl carboxylic acid comprises a first branched C3-C 11 alkyl.

[0046] Implementation Scheme 5. The catalyst composition of Implementation Scheme 4, wherein the first alkyl carboxylic acid is neodecanoic acid.

[0047] Implementation Scheme 6. A catalyst composition of any one of Implementation Schemes 1-5, wherein the second alkylcarboxylic acid is C4-C 12 Alkyl carboxylic acids.

[0048] Embodiment 7. The catalyst composition of Embodiment 6, wherein the second alkyl carboxylic acid comprises a second branched C3-C 11 alkyl.

[0049] Implementation Scheme 8. The catalyst composition of Implementation Scheme 7, wherein the second alkyl carboxylic acid is neodecanoic acid.

[0050] Implementation Scheme 9. A catalyst composition of any one of Implementation Schemes 1-8, wherein the phosphorus-containing additive is selected from C1-C 15 Alkylphosphonic acid.

[0051] Implementation Scheme 10. The catalyst composition of Implementation Scheme 9, wherein the alkylphosphonic acid comprises a straight-chain C1-C1 chain. 15 alkyl.

[0052] Implementation Scheme 11. The catalyst composition of Implementation Scheme 9, wherein the phosphorus-containing additive is selected from n-butylphosphonic acid, dodecylphosphonic acid and mixtures thereof.

[0053] Implementation Scheme 12. A catalyst composition of any one of Implementation Schemes 1-11, wherein the phosphorus-containing additive is selected from (i) phosphate esters that are formally derived from phosphoric acid and at least one alkoxylated alcohol, (ii) salts of phosphate esters that are formally derived from phosphoric acid and at least one alkoxylated alcohol, and (iii) mixtures of (i) and (ii).

[0054] Implementation Scheme 13. A catalyst composition of any one of Implementation Schemes 1-8 or 12, wherein the phosphorus-containing additive is selected from (i) phosphate esters that are formally derived from phosphoric acid and at least one ethoxylated alcohol, (ii) salts of phosphate esters that are formally derived from phosphoric acid and at least one ethoxylated alcohol, and (iii) mixtures of (i) and (ii).

[0055] Implementation Scheme 14. A catalyst composition of any one of Implementation Schemes 1-8 or 12, wherein the catalyst composition comprises a phosphate ester compound of formula (I): (I) Where R 1 For the formula — (R) 2 —O) a —R 3 The group, wherein a is selected from positive integers from 1 to 20; each R 2 It is an independently selected C2-C4 alkyldiyl; R 3 Selected from C1-C 35 Alkyl; X 1 and X 2 Independently selected from hydroxyl, -(R 11 —O) b —R 12 and -O- Each b is independently selected from positive integers from 1 to 20; each R 11 It is an independently selected C2-C4 alkyldiyl; and each R 12 Independently selected from C1-C 35 Alkyl; A is selected from inorganic cations and organic cations; variable d if X 1 and X 2 Neither of them -O - If X is zero, then it is zero. 1 or X 2 One of them is -O - If X, then it is -1, or if X 1 and X 2 All are -O - If d is 0, then e is 1; if d is -1 or -2, then e is a positive integer; f is a positive integer equal to the valence of cation A; if d is zero, then g is zero, and if d is -1 or -2, then g is a positive integer; and the values ​​of variables d, e, f, and g are the closest values ​​to zero that satisfy the equation (de) + (fg) = 0.

[0056] Implementation Scheme 15. The catalyst composition of Implementation Scheme 14, wherein each R 2 and R 11 It is ethyl-1,2-dimethyl.

[0057] Implementation Scheme 16. The catalyst composition of Implementation Scheme 14 or Implementation Scheme 15, wherein each A is a quaternary ammonium cation.

[0058] Implementation Scheme 17. The catalyst composition of Implementation Scheme 16, wherein each A is an N,N-dimethylcyclohexylammonium cation.

[0059] Implementation Scheme 18. A catalyst composition of any one of Implementation Schemes 1-8 or 12-17, wherein the phosphorus-containing additive is selected from (i) forms derived from phosphoric acid and at least one alkoxylated C6-C 35 Phosphate esters of alcohols, (ii) formally derived from phosphoric acid and at least one alkoxylated C6-C 35 Salts of phosphate esters of alcohols, and mixtures of (iii) (i) and (ii).

[0060] Implementation Scheme 19. A catalyst composition of any one of Implementation Schemes 1-8 or 12-17, wherein the phosphorus-containing additive is selected from (i) forms derived from phosphoric acid and at least one ethoxylated C6-C 35 Phosphate esters of alcohols, (ii) formally derived from phosphoric acid and at least one ethoxylated C6-C 35 Salts of phosphate esters of alcohols, and mixtures of (iii) (i) and (ii).

[0061] Implementation Scheme 20. A catalyst composition of any one of Implementation Schemes 1-14, wherein the catalyst composition comprises a phosphate ester compound of formula (I). (I) Where R 1 For the formula — (R) 2 —O) a —R 3 The group, wherein a is selected from positive integers from 1 to 20; each R 2 It is an independently selected C2-C4 alkyldiyl; R 3 Selected from C6-C 35 Alkyl; X 1 and X 2 Independently selected from hydroxyl, -(R 11 —O) b —R 12 and -O - Each b is independently selected from positive integers from 1 to 20; each R 11 It is an independently selected C2-C4 alkyldiyl; and each R 12 Independently selected from C6-C 35 Alkyl; A is selected from inorganic cations and organic cations; variable d if X 1 and X 2 Neither of them -O - If X is zero, then it is zero. 1 or X 2 One of them is -O - If X, then it is -1, or if X 1 and X 2 All are -O - If d is 0, then e is 1; if d is -1 or -2, then e is a positive integer; f is a positive integer equal to the valence of cation A; if d is zero, then g is zero, and if d is -1 or -2, then g is a positive integer; and the values ​​of variables d, e, f, and g are the closest values ​​to zero that satisfy the equation (de) + (fg) = 0.

[0062] Implementation Scheme 21. The catalyst composition of Implementation Scheme 20, wherein each R 2 and R 11 It is ethyl-1,2-dimethyl.

[0063] Implementation Scheme 22. The catalyst composition of Implementation Scheme 20 or 21, wherein each A is a quaternary ammonium cation.

[0064] Implementation Scheme 23. The catalyst composition of Implementation Scheme 22, wherein each A is an N,N-dimethylcyclohexylammonium cation.

[0065] Implementation Scheme 24. A catalyst composition of any one of Implementation Schemes 1-8 or 12-23, wherein the phosphorus-containing additive is selected from (i) phosphate esters that are formally derived from phosphoric acid and at least one alkoxylated isotrimethylene alcohol, (ii) salts of phosphate esters that are formally derived from phosphoric acid and at least one alkoxylated isotrimethylene alcohol, and (iii) mixtures of (i) and (ii).

[0066] Implementation Scheme 25. A catalyst composition of any one of Implementation Schemes 1-8 or 12-24, wherein the phosphorus-containing additive is selected from (i) phosphate esters that are formally derived from phosphoric acid and at least one ethoxylated isotrimethylene alcohol, (ii) salts of phosphate esters that are formally derived from phosphoric acid and at least one ethoxylated isotrimethylene alcohol, and (iii) mixtures of (i) and (ii).

[0067] Implementation Scheme 26. A catalyst composition of any one of Implementation Schemes 1-8 or 12-25, wherein the catalyst composition comprises a phosphate ester compound of formula (I). (I) Where R 1 For the formula — (R) 2 —O) a —R 3 The group, wherein a is selected from positive integers from 1 to 20; each R 2 It is an independently selected C2-C4 alkyldiyl; R 3 It is 11-methyldodecyl-1-yl; X 1 and X 2 Independently selected from hydroxyl, -(R 11 —O) b —R 12 and -O - Each b is independently selected from positive integers from 1 to 20; each R 11 It is an independently selected C2-C4 alkyldiyl; and each R 12 It is 11-methyldodecyl-1-yl; A is selected from inorganic cations and organic cations; variable d if X 1 and X 2 Neither of them -O - If X is zero, then it is zero. 1 or X 2 One of them is -O - If X, then it is -1, or if X 1 and X 2 All are -O -If d is 0, then e is 1; if d is -1 or -2, then e is a positive integer; f is a positive integer equal to the valence of cation A; if d is zero, then g is zero, and if d is -1 or -2, then g is a positive integer; and the values ​​of variables d, e, f, and g are the closest values ​​to zero that satisfy the equation (de) + (fg) = 0.

[0068] Implementation Scheme 27. The catalyst composition of Implementation Scheme 26, wherein each R 2 and R 11 It is ethyl-1,2-dimethyl.

[0069] Implementation Scheme 28. The catalyst composition of Implementation Scheme 26 or 27, wherein each A is a quaternary ammonium cation.

[0070] Implementation Scheme 29. The catalyst composition of Implementation Scheme 28, wherein each A is an N,N-dimethylcyclohexylammonium cation.

[0071] Implementation Scheme 30. A catalyst composition of any one of Implementation Schemes 1-29, wherein the mass ratio of bismuth to zinc is from about 1:1 to about 1.2:1.

[0072] Implementation Scheme 31. The catalyst composition of Implementation Scheme 30, wherein the mass ratio of bismuth to zinc is from about 1.05:1 to about 1.15:1.

[0073] Implementation Scheme 32. The catalyst composition according to any one of Implementation Schemes 1-31, wherein the catalyst composition contains about 25 wt.% to about 80 wt.% of phosphorus-containing additives based on the total mass of bismuth, zinc and phosphorus-containing additives present in the catalyst composition.

[0074] Implementation Scheme 33. A coating composition comprising: (a) Polyols; (b) Isocyanate compounds containing two or more isocyanate groups; and (c) The catalyst composition of any one of embodiments 1-32.

[0075] Embodiment 34. The coating composition of Embodiment 33, wherein the polyol is an acrylic polymer containing two or more hydroxyl groups.

[0076] Implementation Scheme 35. A coating composition of Implementation Scheme 33 or Implementation Scheme 34, wherein the coating composition contains about 0.01 wt.% to about 0.2 wt.% of a catalyst composition based on the total weight of the polyol and isocyanate compound in the coating composition.

[0077] Implementation Scheme 36. The coating composition of any one of Implementation Schemes 33-35, wherein the coating composition contains about 0.05 wt.% to about 0.2 wt.% of the catalyst composition based on the total weight of the polyol and isocyanate compound in the coating composition.

[0078] Implementation Scheme 37. The coating composition of any one of Implementation Schemes 33-36, wherein the coating composition contains about 0.005 wt.% to about 0.04 wt.% of the phosphorus-containing additive based on the total weight of the polyol and isocyanate compound in the coating composition.

[0079] Implementation Scheme 38. A coating composition as described in any one of Implementation Schemes 33-37, wherein the coating composition contains about 0.006 wt.% to about 0.035 wt.% of the phosphorus-containing additive based on the total weight of the polyol and isocyanate compound in the coating composition.

[0080] Implementation Scheme 39. A coating composition as described in any one of Implementation Schemes 33-38, wherein the coating composition contains about 0.007 wt.% to about 0.035 wt.% of the phosphorus-containing additive based on the total weight of the polyol and isocyanate compound in the coating composition.

[0081] Implementation Scheme 40. The coating composition of any one of Implementation Schemes 33-39, wherein the coating composition contains about 0.008 wt.% to about 0.035 wt.% of the phosphorus-containing additive based on the total weight of the polyol and isocyanate compound in the coating composition.

[0082] Implementation Scheme 41. A coating composition of any one of Implementation Schemes 33-40, wherein the coating composition contains (i) about 0.007 wt.% to about 0.01 wt.% of bismuth, (ii) about 0.006 wt.% to about 0.01 wt.% of zinc, and (iii) about 0.005 wt.% to about 0.04 wt.% of phosphorus-containing additives, all based on the total weight of the polyols and isocyanate compounds in the coating composition.

[0083] Implementation Scheme 42. A coating composition of any one of Implementation Schemes 33-41, wherein the coating composition contains (i) about 0.008 wt.% to about 0.009 wt.% of bismuth, (ii) about 0.007 wt.% to about 0.009 wt.% of zinc, and (iii) about 0.006 wt.% to about 0.035 wt.% of phosphorus-containing additives, all based on the total weight of the polyols and isocyanate compounds in the coating composition.

[0084] Implementation Scheme 43. A coating composition according to any one of Implementation Schemes 33-42, wherein the coating composition contains (i) about 0.008 wt.% to about 0.009 wt.% of bismuth, (ii) about 0.007 wt.% to about 0.008 wt.% of zinc, and (iii) about 0.007 wt.% to about 0.035 wt.% of phosphorus-containing additives, all based on the total weight of the polyols and isocyanate compounds in the coating composition.

[0085] Implementation Scheme 44. A coating composition according to any one of Implementation Schemes 33-43, wherein the coating composition contains (i) about 0.008 wt.% to about 0.009 wt.% of bismuth, (ii) about 0.007 wt.% to about 0.008 wt.% of zinc, and (iii) about 0.008 wt.% to about 0.035 wt.% of phosphorus-containing additives, all based on the total weight of the polyols and isocyanate compounds in the coating composition.

[0086] Implementation Scheme 45. A coating composition of any one of Implementation Schemes 33-43, wherein (i) when the phosphorus-containing additive is orthophosphoric acid, the coating composition contains about 0.007 wt.% to about 0.012 wt.% of orthophosphoric acid, (ii) when the phosphorus-containing additive is alkylphosphonic acid, the coating composition contains about 0.015 wt.% to about 0.035 wt.% of alkylphosphonic acid, and (iii) when the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, the coating composition contains about 0.009 wt.% to about 0.02 wt.% of a phosphate ester or a salt of a phosphate ester, all based on the total weight of the polyol and isocyanate compound in the coating composition.

[0087] Implementation Scheme 46. A coating composition of any one of Implementation Schemes 33-45, wherein (i) when the phosphorus-containing additive is orthophosphoric acid, the coating composition contains about 0.007 wt.% to about 0.012 wt.% of orthophosphoric acid, (ii) when the phosphorus-containing additive is alkylphosphonic acid, the coating composition contains about 0.02 wt.% to about 0.032 wt.% of alkylphosphonic acid, and (iii) when the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, the coating composition contains about 0.009 wt.% to about 0.02 wt.% of a phosphate ester or a salt of a phosphate ester, all based on the total weight of the polyol and isocyanate compound in the coating composition.

[0088] Implementation Scheme 47. A coating composition of any one of Implementation Schemes 33-46, wherein (i) when the phosphorus-containing additive is orthophosphoric acid, the coating composition contains about 0.007 wt.% to about 0.012 wt.% of orthophosphoric acid, (ii) when the phosphorus-containing additive is alkylphosphonic acid, the coating composition contains about 0.015 wt.% to about 0.035 wt.% of alkylphosphonic acid, and (iii) when the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, the coating composition contains about 0.01 wt.% to about 0.015 wt.% of a phosphate ester or a salt of a phosphate ester, all based on the total weight of the polyol and isocyanate compound in the coating composition.

[0089] Implementation Scheme 48. A coating composition of any one of Implementation Schemes 33-47, wherein (i) when the phosphorus-containing additive is orthophosphoric acid, the coating composition contains about 0.007 wt.% to about 0.012 wt.% of orthophosphoric acid, (ii) when the phosphorus-containing additive is alkylphosphonic acid, the coating composition contains about 0.02 wt.% to about 0.032 wt.% of alkylphosphonic acid, and (iii) when the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, the coating composition contains about 0.01 wt.% to about 0.015 wt.% of a phosphate ester or a salt of a phosphate ester, all based on the total weight of the polyol and isocyanate compound in the coating composition.

[0090] Implementation Scheme 49. A coating composition as described in any one of Implementation Schemes 33-48, wherein the phosphorus-containing additive is orthophosphoric acid, and the coating composition contains about 0.007 wt.% to about 0.012 wt.% orthophosphoric acid based on the total weight of the polyol and isocyanate compound in the coating composition.

[0091] Embodiment 50. A coating composition as described in any one of Embodiments 33-49, wherein the phosphorus-containing additive is an alkylphosphonic acid, and the coating composition contains about 0.015 wt.% to about 0.035 wt.% of the alkylphosphonic acid based on the total weight of the polyol and isocyanate compound in the coating composition.

[0092] Implementation Scheme 51. A coating composition as described in any one of Implementation Schemes 33-49, wherein the phosphorus-containing additive is an alkylphosphonic acid, and the coating composition contains about 0.02 wt.% to about 0.032 wt.% of the alkylphosphonic acid based on the total weight of the polyol and isocyanate compound in the coating composition.

[0093] Implementation Scheme 52. A coating composition as described in any one of Implementation Schemes 33-49, wherein the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, and the coating composition contains about 0.009 wt.% to about 0.02 wt.% of the phosphate ester or a salt of a phosphate ester based on the total weight of the polyol and isocyanate compound in the coating composition.

[0094] Implementation Scheme 53. A coating composition as described in any one of Implementation Schemes 33-49, wherein the phosphorus-containing additive is a phosphate ester or a salt of a phosphate ester, and the coating composition contains about 0.01 wt.% to about 0.015 wt.% of the phosphate ester or a salt of a phosphate ester based on the total weight of the polyol and isocyanate compound in the coating composition.

[0095] The following examples further illustrate the above-mentioned topics, but should not be construed as limiting their scope in any way.

[0096] Example 1 This example demonstrates an improvement in the pot life of 2K polyurethane coating compositions achievable using the catalyst composition described herein.

[0097] Several two-component polyurethane coating compositions were produced using a first component (component A) containing a hydroxyl-functional acrylic polymer / resin and a second component (component B) containing an isocyanate compound. Coating compositions for each sample were prepared by first combining the components of component A (as shown in Table 1) and mixing these components for approximately two minutes using a high-speed mixer running at approximately 2,000 rpm. After mixing, the resulting component A was allowed to stand under ambient conditions for approximately 24 hours. Finally, coating compositions for the samples were prepared by combining approximately two parts (by weight) of component A with one part (by weight) of the isocyanate compound (component B). Specifically, component B in all coating compositions was an aliphatic polyisocyanate (Desmodur® N 75 BA from Covestro AG).

[0098] Table 1. Component A of the coating composition formulation used to produce samples 1-1 to 1-18

[0099] In Table 2 below, the bismuth additive used in each coating composition contains a bismuth salt of neodecanoic acid and has a bismuth content of approximately 16% (by mass). The zinc additive used in each coating composition contains a zinc salt of neodecanoic acid and has a zinc content of approximately 15% (by mass). The phosphorus-containing additives (“P-containing additives”) in the coating compositions used for each sample are recorded in Table 2. “DDPA” represents dodecylphosphonic acid, and “NBPA” represents n-butylphosphonic acid. “PAE1” represents a phosphorus-containing additive containing an amine salt of a phosphate ester formally derived from orthophosphoric acid and ethoxylated isotrimethylene alcohol, specifically CAS number 164383-18-0.

[0100] The amounts of bismuth and / or zinc catalysts in each coating composition are reported in Table 2 as a percentage of metals in the resin solids of the coating composition (%MORS). %MORS is calculated using the following formula: In this formula, m c It is the mass of the catalyst, in grams, MC c It refers to the metal content of the catalyst, expressed as a percentage of the total mass of the catalyst, SC. f This refers to the resin solids content of the coating composition, expressed as a percentage of the total mass of the coating composition, and m f It refers to the mass of the coating composition, in grams.

[0101] The amount of phosphorus-containing additives in each coating composition is reported in Table 2 as a percentage of additives based on resin solids in the coating composition (%WORS). %WORS is calculated using the following formula: In this formula, m a It refers to the mass of phosphorus-containing additives, in grams, SC f This refers to the resin solids content of the coating composition, expressed as a percentage of the total mass of the coating composition, and m f It refers to the mass of the coating composition, in grams.

[0102] The pot life of each coating composition was measured as described herein. AntonPaar MCR-302 rheometer equipped with a geometric conical plate 25-1 was used at 23°C and 1000 s. -1 All viscosities were measured at a shear rate of [missing value]. The initial viscosity of each coating composition was measured immediately after combining components A and B as described above. The viscosity of each coating composition was then measured again at intervals of 15 to 30 minutes until the viscosity doubled from its initial value. The pot life is reported in Table 2 as the time (in minutes) taken for the viscosity of the coating composition to double from its initial value.

[0103] Table 2.

[0104] As can be seen from the data in Table 2, the coating composition containing only a bismuth catalyst (i.e., Sample 1-1) has a pot life of only 30 minutes, which is generally considered too short for practical applications. Adding 0.0087% WORS of orthophosphoric acid (Sample 1-5) extends the pot life to over 360 minutes. The coating composition containing only a zinc catalyst (Sample 1-2) has a pot life of 310 minutes, and adding 0.0087% WORS of orthophosphoric acid (Sample 1-6) again extends the pot life to over 360 minutes. The coating composition containing a combination of bismuth and zinc catalysts (Sample 1-3) exhibits a pot life of 60 minutes. Surprisingly, the use of a combination of bismuth and zinc catalysts in the coating composition was observed to mitigate the effect of phosphorus-containing additives on extending the pot life. This can be seen in the data for Samples 1-7 to 1-12, where the addition of orthophosphoric acid generally produces a less significant increase in pot life compared to those observed in coating compositions using only one catalyst. For example, the addition of 0.0087% WORS of orthophosphoric acid (samples 1-9) yielded a pot life of 90 minutes, which is 30 minutes longer than that of coating compositions containing both catalysts but without any phosphorus-containing additives (samples 1-3). Adding the same amount of orthophosphoric acid to coating compositions containing either a bismuth catalyst or a zinc catalyst alone resulted in a pot life exceeding 360 minutes (see samples 1-5 and 1-6 as described above). In practice, when using both bismuth and zinc catalysts, the pot life of the coating compositions does not exceed 360 minutes until the concentration of orthophosphoric acid reaches 0.0175% WORS (samples 1-12).

[0105] Not wishing to be bound by any particular theory, the inventors believe that a pot life of 60 minutes or longer is preferred for the type of coating composition used in this embodiment, with a more ideal range being 90 to 200 minutes or 90 to 120 minutes. The data in Table 2 show that this pot life range was achieved when both the bismuth catalyst and the zinc catalyst were used in combination with a variety of phosphorus-containing additives as described herein (see, for example, samples 1-9, 1-10, 1-13, 1-14, and 1-15).

[0106] All references cited in this article, including publications, patent applications and patents, are incorporated herein by reference to the same extent that each reference is individually and specifically indicated to be incorporated by reference and fully elaborated in this article.

[0107] In the context of describing the subject matter of this application (particularly in the context of the following claims), the use of the terms “a,” “an,” and “the,” and similar indicators, should be construed as encompassing both singular and plural, unless otherwise stated herein or clearly contradicted by the context. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be construed as open-ended terms (i.e., meaning “including but not limited to”). Unless otherwise stated herein, the description of value ranges herein is intended only as a shorthand method of individually referring to each individual value falling within that range, and each individual value is incorporated into the specification as if it were individually described herein. All methods described herein may be performed in any suitable order unless otherwise stated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., “such as”) provided herein is intended only to better illustrate the subject matter of this application and does not constitute a limitation on the scope of the subject matter, unless otherwise required. The language in the specification should not be construed as indicating that any unclaimed element is essential for practicing the subject matter described herein.

[0108] This document describes preferred embodiments of the subject matter of this application, including the best modes known to the inventors for implementing the claimed subject matter. Variations of those preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to appropriately employ such variations, and the inventors intend to practice the subject matter described herein in ways different from those specifically described herein. Therefore, this disclosure includes all modifications and equivalents of the subject matter recited in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, this disclosure covers any combination of the foregoing elements in all possible variations.

Claims

1. A catalyst composition comprising: (a) A bismuth catalyst comprising a bismuth salt of a first alkyl carboxylic acid; (b) A zinc catalyst comprising a zinc salt of a second alkylcarboxylic acid; and (c) Phosphorus-containing additives selected from the group consisting of: (i) orthophosphoric acid, (ii) alkylphosphonic acid, (iii) phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; (iv) salts of phosphate esters formally derived from phosphoric acid and at least one alkoxylated alcohol; and (v) mixtures thereof. The mass ratio of bismuth to zinc is approximately 0.9:1 to approximately 1.2:

1.

2. The catalyst composition according to claim 1, wherein the first alkylcarboxylic acid is C4-C6. 12 Alkyl carboxylic acids.

3. The catalyst composition according to claim 2, wherein the first alkyl carboxylic acid is neodecanoic acid.

4. The catalyst composition according to any one of claims 1-3, wherein the second alkylcarboxylic acid is C4-C6. 12 Alkyl carboxylic acids.

5. The catalyst composition according to claim 4, wherein the second alkyl carboxylic acid is neodecanoic acid.

6. The catalyst composition according to any one of claims 1-5, wherein the phosphorus-containing additive comprises one or more C1-C14 groups. 15 Alkylphosphonic acid.

7. The catalyst composition according to claim 6, wherein the alkylphosphonic acid comprises a straight-chain C1-C1 group. 15 alkyl.

8. The catalyst composition according to claim 6, wherein the phosphorus-containing additive comprises one or more compounds selected from n-butylphosphonic acid, dodecylphosphonic acid, and mixtures thereof.

9. The catalyst composition according to any one of claims 1-8, wherein the phosphorus-containing additive comprises one or more compounds selected from the group consisting of: (i) compounds formally derived from phosphoric acid and at least one alkoxylated C6-C 35 Phosphate esters of alcohols, (ii) formally derived from phosphoric acid and at least one alkoxylated C6-C 35 Salts of phosphate esters of alcohols, and mixtures of (iii) (i) and (ii).

10. The catalyst composition according to any one of claims 1-9, wherein the mass ratio of bismuth to zinc is about 1:1 to about 1.2:1, preferably about 1.05:1 to about 1.15:

1.

11. The catalyst composition according to any one of claims 1-10, wherein the catalyst composition contains about 25 wt.% to about 80 wt.% of phosphorus-containing additives based on the total mass of bismuth, zinc and phosphorus-containing additives present in the catalyst composition.

12. A coating composition comprising: (a) Polyols; (b) Isocyanate compounds containing two or more isocyanate groups; and (c) The catalyst composition according to any one of claims 1-11.

13. The coating composition according to claim 12, wherein the polyol is an acrylic polymer containing two or more hydroxyl groups.

14. The coating composition according to claim 12 or 13, wherein the coating composition contains about 0.01 wt.% to about 0.2 wt.% of the catalyst composition based on the total weight of the polyol and isocyanate compound in the coating composition.

15. The coating composition according to any one of claims 12-14, wherein the coating composition contains about 0.05 wt.% to about 0.2 wt.% of the catalyst composition based on the total weight of the polyol and isocyanate compound in the coating composition.

Images