Extended operating time polyaspartic floor coating formulations

Abstract

A polyaspartic acid composition comprising the reaction product of a polyamine, a Michael addition acceptor, and a polyisocyanate wherein the reaction with the polyisocyanate is carried out in the presence of a zirconium metal catalyst. The composition of the present invention can be used in floor coatings providing increased operating times for large coating areas while maintaining relatively short open walk times, coating hardness, and appearance.

Description

Field of the Invention

[0001] The present invention relates generally to floor coatings, and more particularly to polyaspartic floor coatings having extended worktime while maintaining fast walk on time, hardness and appearance. Background of the Invention

[0003] When applying floor coatings, especially coatings used to cover large areas, flooring contractors desire a long working time, i.e., a coating that can be applied over a long period of time before gelling, setting, and curing. This enables the contractor to apply the coating thoroughly and evenly to an area and to apply the desired coating thickness. Another, somewhat contradictory goal is to have the coating cure and harden in a relatively short time so that people can walk on the floor coating without leaving footprints that would indicate that the coating was not fully cured and then leave an uneven appearance where people walked. However, when the cure time is slowed to have a long working time, the open walk time will generally be longer as well. Conversely, when a coating is formulated to cure faster to have a desirably short open walk time, the working time will generally be shorter as well.

[0004] In addition, the coating has other properties that make it desirable, including coating strength or hardness, adhesion, abrasion resistance, UV resistance, and appearance of the coating. Thus, there is a need in the art for a polyaspartic coating formulation that will provide increased working time for such large coating area applications while maintaining other desirable properties, such as relatively short open walk-through time, coating hardness, and appearance. Summary of the invention

[0005] In a first aspect, a polyaspartic acid-based composition comprises the reaction product of a polyamine, a Michael addition acceptor, and a polyisocyanate, wherein the reaction with the polyisocyanate is carried out in the presence of a zirconium metal catalyst.

[0006] The polyamine may be selected from ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluenediamine, 2,4′- and / or 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 2,4,4′-triamino-5-methyldicyclohexylmethane and amine-terminated polyether polyols.

[0007] The Michael addition acceptor may be selected from the group consisting of dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, acrylates, and combinations thereof.

[0008] The polyisocyanate may be selected from ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, bis-(4-isocyanatocyclohexyl)methane (H 12 MDI), cyclohexane 1,4-diisocyanate, bis-(4-isocyanato-3-methyl-cyclohexyl)methane, pentane diisocyanate-bio-based, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate, any isomers thereof, and any combination thereof.

[0009] The zirconium metal catalyst may contain an alkoxy or aryloxy component.

[0010] In another embodiment, the zirconium metal catalyst conforms to the formula: (RO-) n Zr-(-OX R'Y) 4-n , wherein RO- is a hydrolyzable group or substrate reactive group having a surface hydroxyl group or a proton; X is an adhesive functional group such as a phosphate, a pyrophosphate, a sulfonyl or a carboxyl group; R' is a thermoplastic functional group such as an aliphatic and non-polar isopropyl, butyl, octyl, isostearyl, cycloalkyl and weakly polar dodecylbenzyl, or an aromatic benzyl, cumylphenyl; Y is one or more thermosetting functional groups such as an acryloyl, a methacryloyl, a mercapto and an amino group; and n is an integer between 0 and 4.

[0011] In various embodiments, the zirconium metal catalyst comprises a phosphite or sulfite component.

[0012] In yet another embodiment, the zirconium metal catalyst is selected from zirconium IV2,2 (bis-2-propenol methyl) butanol, trineodecanol-O; zirconium IV2.2 (bis-2-propenol methyl) butanol, tri(dodecyl) benzenesulfonate-O; zirconium IV2,2 (bis-2-propenol methyl) butanol, tri(dioctyl) phosphate-O; zirconium IV2,2 (bis-2-propenol methyl) butanol, tri-2-methyl-2-propenol-O; zirconium IV2,2 (bis-2-propenol methyl) butanol, tri(dioctyl) pyrophosphate-O; zirconium IV2,2 (bis-2-propenol methyl) butanol, tri-2-propenol-O; zirconium IV2,2 (bis-2-propenol methyl) butanol, tri(2 -ethylenediamino)ethyl atom-O; the adduct of zirconium IV tetra(2,2-bispropenylatomethyl)butanolate and 2 moles of ditridecyl hydrogen phosphite; zirconium IV bis-2,2(bis-2-propenylatomethyl)butanolate, bis(p-aminobenzoate-O); zirconium IV bis-2,2(bis-2-propenylatomethyl)butanolate, bis(3-mercapto)propanoate-O; zirconium IV 1,1(bis-2-propenylatomethyl)butanolate, tris(2-amino)phenyl atom; zirconium IV 2-ethyl, 2-propenylatomethyl-1,3-propanediol, cyclodi-2,2-(bis-2-propenylatomethyl)butanolate pyrophosphate-O,O; zirconium IV bis-2-ethylhexanolate, cyclo(di-2-ethylhexyl)pyrophosphate; zirconium tetra-n-propoxide; and mixtures thereof.

[0013] In yet another embodiment, the zirconium metal catalyst is selected from zirconium IV 2,2 (bis-2-propenolatomethyl) butanolate, tri-2-methyl-2-propenolato-O; an adduct of zirconium IV tetra(2,2-bispropenolatomethyl) butanolate and 2 moles of ditridecyl hydrogen phosphite; zirconium tetra-n-propoxide; and mixtures thereof.

[0014] The coating may include the polyaspartic acid composition, which may then be applied to a substrate, which may be a floor. The substrate may be metal, plastic, wood, cement, concrete or glass.

[0015] These and other advantages and benefits of the present invention will become apparent from the following detailed description of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will now be described for purposes of illustration and not limitation.

[0018] As used herein, the term "polymer" includes prepolymers, oligomers, and homopolymers and copolymers; the prefix "poly" in this context means two or more. As used herein, unless otherwise indicated, when used to refer to a polymer, the term "molecular weight" refers to the number average molecular weight.

[0019] As used herein, the term "coating composition" refers to a mixture of chemical components that will cure and form a coating when applied to a substrate.

[0020] "Cured," "cured composition," or "cured compound" refers to components and mixtures obtained from reactive curable starting compounds or mixtures thereof that have undergone chemical and / or physical changes that convert them into solid, substantially non-flowing materials. Typical curing processes may involve cross-linking.

[0021] The term "curable" means that the original compound or composition material can be converted into a solid, substantially non-flowing material by chemical reaction, cross-linking, radiation cross-linking, etc. Thus, the compositions of the present invention are curable, but unless otherwise specified, the original compound or composition material is not cured.

[0022] As used herein, the term "curing time" refers to the time to reach Stage D (Method B) as defined in ASTM D5895-03 (2008) - Standard Test Methods for Evaluating Drying or Curing During Film Formation of Organic Coatings Using Mechanical Recorder.

[0023] As used herein, the term "polyamine" refers to a compound comprising at least two free primary and / or secondary amine groups. Polyamines include polymers comprising at least two pendant and / or terminal amine groups.

[0024] As used herein, the term "polyisocyanate" refers to a compound containing at least two unreacted isocyanate groups. Polyisocyanates include diisocyanates and diisocyanate reaction products, including, for example, biuret, isocyanurate, uretdione, carbamate, urea, iminooxadiazinedione, oxadiazinedione, carbodiimide, acylurea, allophanate groups and any combination thereof.

[0025] The coating compositions described herein may include two-component coating compositions. As used herein, the term "two-component" refers to a coating or coating composition comprising at least two components, which must be stored in separate containers due to their mutual reactivity. For example, two-component polyaspartic acid coating systems and compositions may include a hardener / crosslinker component comprising a polyisocyanate compound and a separate adhesive component comprising a polyaspartic acid compound. These two separate components are usually mixed shortly before application. When the two separate components are mixed and applied to a substrate as a film, the mutually reactive compounds in the two components react to crosslink and form a cured coating film.

[0026] The polyisocyanates that can be used for the present invention can include any organic polyisocyanates with aliphatic, alicyclic, aromatic aliphatic and / or aromatic free isocyanate groups, which are liquid at room temperature or dispersed in a solvent or solvent mixture at room temperature. In various non-limiting embodiments, the polyisocyanates can have a viscosity of 10-15,000 mPa s at 23 ° C, 10-5,000 mPa s at 23 ° C, or 50-1,000 mPa s at 23 ° C. In certain embodiments, the polyisocyanates can include polyisocyanates or polyisocyanate mixtures with only aliphatic and / or alicyclic isocyanate groups, which have an (average) NCO functionality of 2.0-5.0 and a viscosity of 10-5,000 mPa s at 23 ° C, 50-1,000 mPa s at 23 ° C, or 100-1,000 mPa s at 23 ° C.

[0027] In various embodiments, the polyisocyanate may include a polyisocyanate or polyisocyanate mixture based on one or more aliphatic or alicyclic diisocyanates, such as ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate (HDI); 2,2,4-trimethyl-1,6-hexamethylene diisocyanate; 1,12-dodecamethylene diisocyanate; 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI); bis-(4-isocyanatocyclohexyl)methane (HDI); 12MDI); cyclohexane 1,4-diisocyanate; bis-(4-isocyanato-3-methyl-cyclohexyl)methane; PDI (pentane diisocyanate-bio-based) any isomer thereof; or any combination thereof. In various embodiments, the polyisocyanate component may include a polyisocyanate or polyisocyanate mixture based on one or more aromatic diisocyanates, such as phenylene diisocyanate; toluene diisocyanate (TDI); diphenylmethane diisocyanate (MDI); any isomer thereof; or any combination thereof. In various embodiments, the polyisocyanate component may include a triisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane or TIN); isomers thereof; or derivatives thereof.

[0028] Additional polyisocyanates (including various diisocyanates) that may also be included in the polyurea compositions of the present invention may include those described in US Pat. Nos. 5,075,370; 5,304,400; 5,252,696; 5,750,613; and 7,205,356. Combinations of any of the foregoing polyisocyanates may also be used.

[0029] The indicated diisocyanates and triisocyanates can be used as such or as derivatized polyisocyanates containing biuret, isocyanurate, uretdione, carbamate, urea, iminooxadiazinedione, oxadiazinedione, carbodiimide, acylurea and / or allophanate groups. In various non-limiting embodiments, the polyurea includes a derivatized polyisocyanate containing biuret, isocyanurate, uretdione, carbamate, iminooxadiazinedione, oxadiazinedione, carbodiimide, acylurea and / or allophanate groups. In various embodiments, the polyisocyanate component includes IPDI, HDI, H 12 One or more of the above structural groups prepared from MDI and / or cyclohexane 1,4-diisocyanate.

[0030] The polyisocyanates may be hydrophilically modified to be water dispersible. The hydrophilically modified water dispersible polyisocyanates may be obtained, for example, by covalent modification with an internal emulsifier containing anionic groups, cationic groups or nonionic groups.

[0031] Polyether urethane type water-dispersible polyisocyanates can be formed by, for example, a reaction between a polyisocyanate and a monopolyoxyalkylene polyether alcohol less than a stoichiometric amount. The preparation of such hydrophilically modified polyisocyanates is described in, for example, U.S. Patent No. 5,252,696. Polyether allophanate type water-dispersible polyisocyanates can be formed by, for example, a reaction between a polyoxyalkylene polyether alcohol and two polyisocyanate molecules under allophanation conditions. The preparation of such hydrophilically modified polyisocyanates is described in, for example, U.S. Patent No. 6,426,414. The polyoxyalkylene polyether alcohol for preparing polyether type hydrophilically modified water-dispersible polyisocyanates can include, for example, polyethylene oxide residues and / or polypropylene oxide residues.

[0032] Polyisocyanates can also be covalently modified with ionic groups or potential ionic internal emulsifying groups to form hydrophilically modified water-dispersible polyisocyanates. Ionic groups or potential ionic groups can be cationic or anionic. As used herein, the term "ionic group or potential ionic group" refers to a chemical group that is non-ionic under certain conditions and ionic under certain other conditions. For example, in various embodiments, the ionic group or potential ionic group can include a carboxylic acid group; a carboxylate group; a sulfonic acid group; a sulfonate group; a phosphonic acid group; a phosphonate group; or any combination thereof. In this regard, for example, a carboxylic acid group, a sulfonic acid group, and a phosphonic acid group are potential ionic groups, while a carboxylate group, a sulfonate group, and a phosphonate group are ionic groups in the form of a salt (e.g., a sodium salt).

[0033] For example, carboxylate (carboxylic acid) groups, sulfonate (sulfonic acid) groups or phosphonate (phosphonic acid) groups can be covalently introduced into polyisocyanates to form hydrophilically modified water-dispersible polyisocyanates. Ionic groups or potential ionic groups can be introduced by the reaction between the isocyanate groups of polyisocyanates and carboxylic acids, sulfonic acids, phosphonic acids or their salts that are less than the stoichiometric amount of amino-functional or hydroxy-functional. Examples include, but are not limited to, dimethylol propionic acid (DMPA), N-(2-aminoethyl)-2-aminoethanesulfonic acid (AAS); N-(2-aminoethyl)-2-aminopropionic acid; 2-(cyclohexyl-amino)ethanesulfonic acid; 3-(cyclohexyl-amino)-1-propanesulfonic acid (CAPS); 2-aminoethylphosphonic acid; or its salt.

[0034] If free carboxylic acid, sulfonic acid or phosphonic acid is incorporated into the polyisocyanate, the acid can be neutralized with a neutralizing agent, such as a tertiary amine, including but not limited to a trialkyl-substituted tertiary amine. The preparation of hydrophilically modified water-dispersible polyisocyanates is described, for example, in U.S. Pat. No. 6,767,958. Water-dispersible polyisocyanate mixtures based on triisocyanatononane (TIN) are described in International Patent Application Publication No. WO01 / 62819.

[0035] The NCO content of the nonionic hydrophilically modified water-dispersible polyisocyanate may be 5 to 25% by weight of the polyisocyanate molecule. The NCO content of the ionic hydrophilically modified water-dispersible polyisocyanate may be 4 to 26% by weight of the polyisocyanate molecule.

[0036] As known to those skilled in the art, polyaspartic acid esters can be prepared by reacting polyamines with Michael addition acceptors, i.e., electron withdrawing groups such as cyano, keto, or esters (electrophiles) in Michael addition reactions. Examples of suitable Michael addition acceptors include, but are not limited to, acrylates and diesters such as dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

[0037] The polyaspartic acid composition may comprise one or more polyaspartic acid esters corresponding to formula (I):

[0038]

[0039] in

[0040] n is an integer from 2 to 4,

[0041] X represents an aliphatic residue;

[0042] R 1 and R 2 independently of one another represent organic groups which are inert towards isocyanate groups under the reaction conditions; and

[0043] n is at least 2.

[0044] In formula (I), the aliphatic residue X may correspond to a linear or branched alkyl and / or cycloalkyl residue of an n-valent polyamine which reacts with the dialkyl maleate in a Michael addition reaction to give the polyaspartate. For example, the residue X may correspond to an aliphatic residue from an n-valent polyamine, including but not limited to ethylenediamine; 1,2-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; 2,5-diamino-2,5-dimethylhexane; 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane; 1,11-diaminoundecane; 1,12-diaminododecane; 1-amino-3,3,5-trimethyl-5-amino-methylcyclohexane; 2,4'- and / or 4,4'-diaminodicyclohexylmethane; 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane; 2,4,4'-triamino-5-methyldicyclohexylmethane; aliphatic primary amino groups and a number average molecular weight (M n ) is 148 to 6,000 g / mol; any isomers thereof, and any combination thereof.

[0045] In various embodiments, the residue X can be obtained from 1,4-diaminobutane; 1,6-diaminohexane; 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane; 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane; 4,4'-diaminodicyclohexylmethane; 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane; or 1,5-diamine-2-methyl-pentane.

[0046] The polyamines useful in the present invention may include amine-terminated polyether polyols (i.e., polyether polyamines), such as primary amine-terminated and secondary amine-terminated polyether polyols having an average molecular weight greater than 1,500, having a functionality of about 2 to about 6 in various embodiments, about 2 to 3 in certain embodiments, and an amine equivalent weight of about 750 to about 4,000. In some embodiments, a mixture of amine-terminated polyethers may be used. In certain embodiments, the amine-terminated polyethers have an average molecular weight of at least about 2,500. These materials may be prepared by various methods known in the art.

[0047] The amine-terminated polyethers useful in the present invention are, for example, polyethers prepared by adding a suitable initiator to a lower alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof, and then aminating the resulting hydroxyl-terminated polyol. When two or more oxides are used, they may be present as a random mixture or as blocks of one or another polyether. In the amination step, for ease of amination, it is highly desirable that the terminal hydroxyl groups in the polyol are substantially all secondary hydroxyl groups. Typically, the amination step does not completely replace all hydroxyl groups. However, most hydroxyl groups are replaced by amino groups. Therefore, in some embodiments, the amine-terminated polyether has more than 50% active hydrogen in the form of amine hydrogen. If ethylene oxide is used, it is desirable to terminate the hydroxyl-terminated polyol with a small amount of a higher alkylene oxide to ensure that the terminal hydroxyl groups are substantially all secondary hydroxyl groups. The polyol thus prepared is then reductively aminated by known techniques, for example, as described in U.S. Pat. No. 3,654,370.

[0048] In some embodiments of the present invention, a single high molecular weight amine-terminated polyol can be used. In addition, a mixture of high molecular weight amine-terminated polyols can be used, such as a mixture of difunctional and trifunctional materials and / or different molecular weight or different chemical composition materials.

[0049] In addition, high molecular weight amine-terminated polyethers or simply polyetheramines are also included within the scope of the present invention and can be used alone or in combination with the above-mentioned polyols. The term "high molecular weight" is intended to include polyetheramines having a molecular weight of at least about 2000. Particularly preferred are the JEFFAMINE series of polyetheramines available from Texaco Chemical Company; they include JEFFAMINE D-2000, JEFFAMIN D-4000, JEFFAMINE T-3000 and JEFFAMINE T-5000.

[0050] For defining the group R in formula (I) 1 and R 2 The phrase "inert towards isocyanate groups under the reaction conditions" means that these groups do not have Zerevitinov-active hydrogens. Zerevitinov-active hydrogens are defined in Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th edition, Georg Thieme Verlag Stuttgart, 1996. In general, groups having Zerevitinov-active hydrogens are understood in the art to mean hydroxyl (OH), amino (NH x ) and thiol (SH) groups. In various embodiments, R 1 and R 2 Independently of each other, C1 to C 10 Alkyl residues, such as methyl, ethyl or butyl residues.

[0051] In various embodiments, the polyaspartic acid composition comprises one or more compounds corresponding to formula (I), wherein n is an integer from 2 to 6, in some embodiments an integer from 2 to 4, and in some embodiments an integer of 2. In embodiments where n=2, the polyaspartic acid composition may comprise one or more compounds corresponding to formula (II):

[0052]

[0053] The polyaspartic acid composition can be prepared by making the corresponding primary polyamine of the following formula:

[0054]

[0055] Prepared by reaction with a diester of the formula:

[0056]

[0057] The preparation of the polyaspartic acid composition of the present invention from the above-mentioned polyamine and Michael addition acceptor starting materials can be carried out at a temperature ranging from 0°C to 100°C. In certain embodiments, the temperature is not greater than 45°C.

[0058] Catalysts suitable for preparing the polyaspartic acid composition of the present invention include phenolic compounds other than sterically hindered phenols substituted with tert-butyl groups at both ortho positions of oxygen. Such compounds have at least one hydroxyl group attached to a carbon atom of a benzene ring. Examples of phenolic compounds that can be used as catalysts in the present invention include, but are not limited to, phenol, catechol, 1,4-benzenediol, cashew nut oil (anacardic acid (anacardic acid acid), cardol and cardanol), phenolic aldehydes (vanillin, 2-methoxyphenol), resorcinol, tris-2,4,6-(dimethylaminomethyl)phenol, 4-ethylresorcinol, 2,5-dimethylresorcinol, phloroglucinol, 2-nitro-phloroglucinol (2-nitrophloro-glucinol), 5-methoxyresorcinol, orcinol, 2-methylresorcinol, 4-bromoresorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 3,5-dihydroxy-benzaldehyde, 2,4-dihydroxy-benzaldehyde, 3,5-dihydroxy methyl benzoate, methyl 2,4-dihydroxybenzoate, 1,2,4-benzenetriol, pyrogallol, 3,5-dihydroxybenzyl alcohol, 2',6'-dihydroxyacetophenone, 2',4'-dihydroxyacetophenone, 3',5'-dihydroxyacetophenone, 2',4'-dihydroxy-propiophenone, 2',4'-dihydroxy-3'-methylacetophenone, 2,4,5-trihydroxy-benzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 3,5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2-nitroresorcinol, 1,3-dihydroxynaphthalene, hydroquinone, methyl hydroquinone, 2,3-dimethylhydroquinone, 2-methoxyhydroquinone, chlorohydroquinone, 2',5'-dihydroxyacetophenone, 2-isopropyl-1,4-benzenediol, 2,5-dihydroxybenzoic acid, 2,3-dicyanohydroquinone, 1,4-dihydroxynaphthalene, 2',5'-dihydroxypropiophenone, 1-(2,5-dihydroxy-4-methylphenyl)ethanone, tert-butylhydroquinone, methyl 2,5-dihydroxybenzoate, (2,5-dihydroxyphenyl)acetic acid, 2,4,5-trihydroxybenzoic acid, 4,7-dihydroxy-3-methyl-1-dihydroindanone, 2,5-dichlorohydroquinone, tetrafluoro-hydroquinone, ethyl 2,5-dihydroxybenzoate, 2-( 2,5-dihydroxybenzylidene) malononitrile, 2-bromo-1,4-benzenediol, (2,5-dihydroxyphenyl)ethyl acetate, 1-(2,4,5-trihydroxyphenyl)-1-butanone, methyl 2,5-dihydroxy-4-methoxybenzoate, 2,6-dinitro-1,4-benzenediol, 2,4,5-trihydroxyphenylalanine, (2,5-dihydroxyphenyl)-(phenyl)methanone, 2,5-di-tert-butyl-1,4-benzenediol, 2-(6-methylheptyl)-1,4-benzenediol, 2-(1,1,3,3-tetramethylbutyl)-l,4-benzenediol, dimethyl 2,5-dihydroxyterephthalate, 2,4,5-Trichloro-3,6-dihydroxybenzonitrile, 2,5-di-tert-amyl-1,4-benzenediol, 2,5-dibromo-1,4-benzenediol, dimethyl phosphonate 2,4-diethyl-3,6-dihydroxy-phenyl ester, pyrocatechol, 2,3-naphthalene diol, 5-methyl-1,2,3-benzenetriol, 4-methylcatechol, 3-methylcatechol, 3-fluorocatechol, 3-methoxycatechol, 4-chlorocatechol, 4,5-dichlorocatechol, 4-tert-butylcatechol, 3, 4,5,6-tetrachloro-1,2-benzenediol, 3-isopropyl-6-methylcatechol, 3-tert-butyl-6-methylcatechol, 3,4-dihydroxybenzonitrile, 3,5-di-tert-butylcatechol, 3,5-diisopropylcatechol, 3,4-dihydroxybenzaldehyde, 4-(1,1,3,3-tetramethylbutyl)-1,2-benzenediol, 4-(1,2-dihydroxyethyl)-1,2-benzenediol, 1-(3,4-dihydroxyphenyl)ethanone, 3,4-dihydroxy Benzoic acid, 3,4,5-trihydroxybenzamide, 4-nitro-1,2-benzenediol, 4-(2-amino-1-hydroxyethyl)-1,2-benzenediol, 5-methyl-3-(1,1,3,3-tetramethylbutyl)-1,2-benzenediol, (3,4-dihydroxyphenyl)acetic acid, 2-(3,4-dihydroxybenzylidene)malononitrile, 3,5-dinitro-1,2-benzenediol, 3,4-dihydroxybenzoic acid methyl ester, 2-chloro-1-(3,4-dihydroxyphenyl)acetic acid 3,4-dihydroxyphenyl)propanoic acid ethyl ester, 2-phenyl-1-(2,3,4-trihydroxyphenyl)ethanone, phenyl(2,3,4-trihydroxyphenyl)methanone, 3,4,5-trihydroxybenzoic acid isopropyl ester, 3,4-dihydroxy-2-methylphenylalanine, 3-bromo-4,5-dihydroxybenzoic acid, 2-(3,4-dihydroxy-5-methoxybenzylidene)malononitrile, 3-(3,4-dihydroxyphenyl)propanoic acid ethyl ester, 2-phenyl-1-(2,3,4-trihydroxy-phenyl)ethanone and 3,4,5-trihydroxy-N-(2-hydroxyethyl)benzamide.

[0059] In various embodiments, phenolic catalysts may be used in coatings, adhesives, sealants, composites, castings, and film formulations in amounts ranging from 1 ppm to 12,000 ppm, in certain embodiments from 10 ppm to 500 ppm, and in selected embodiments from 20 ppm to 200 ppm.

[0060] In addition, metal catalysts may be used. Although the metal component may be based on a variety of metals, including tin, titanium, and zirconium, zirconium has been found to be preferred. In addition, the catalyst may react like a water scavenger and preferably contains one or more components that can help the metal catalyst function like a water scavenger, such as an alkoxy (C 1-4 Alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutyloxy, sec-butoxy, tert-butoxy) and aryloxy (especially C 6-10In another embodiment, the metal catalyst may conform to the formula: (RO-) n Zr-(-OX R'Y) 4-n , wherein RO- is a hydrolyzable group or substrate reactive group having a surface hydroxyl group or a proton; X is an adhesive functional group such as a phosphate, a pyrophosphate, a sulfonyl or a carboxyl group; R' is a thermoplastic functional group such as an aliphatic and non-polar isopropyl, butyl, octyl, isostearyl, cycloalkyl and weakly polar dodecylbenzyl, or an aromatic benzyl, cumylphenyl; Y is one or more thermosetting functional groups such as an acryloyl, a methacryloyl, a mercapto and an amino group; and n is an integer between 0 and 4.

[0061] The components in the catalyst may form alcohols, which may have a negative impact on the hardness or strength of the coating. This will be more obvious in thicker coatings. The alcohol can also act like a catalyst and increase the curing speed of the coating. The metal catalyst may also include other components besides the alkoxy group, such as phosphite or sulfite components. The release of these components or the reaction products of these components with water into the coating may not be as harmful to the coating as the production of alcohol. Although not wishing to be bound by theory, it is believed that these catalyst compounds react with trace amounts of water present in the aspartic acid ester amine resin, or otherwise remove moisture that may be present as moisture in the ambient air and absorbed by the coating during curing, thereby reducing the water available to promote the curing of the coating. As the water is removed from the coating as fast as it is absorbed from the atmosphere or substrate, or the potential water in the resin becomes unavailable, the curing reaction is believed to slow down.

[0062] Catalysts can also promote the reaction of NCO with water and cause the appearance of gases, which will appear as tiny bubbles in the coating, distorting the appearance of the coating. Catalysts with too many of these side reactions are preferably avoided and understood by whether their presence reduces the hardness, strength or appearance of the coating. Catalysts with different compositions and different mechanisms for removing water may be preferred to reduce the impact of such side reactions.

[0063] It is preferred that the added metal catalyst does not negatively affect the stability of the resin during storage. It is preferred that the storage of the catalyst with the aspartic ester amine should not significantly affect the working time or open walk time of the formulation. This is typically tested by storing the resin at elevated temperature (50°C) for 4 weeks in the presence of the catalyst.

[0064] In addition to the catalysts listed in the examples, specific examples of metal catalysts include zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri neodecyl alkanoate-O; zirconium IV 2.2 (bis-2-propenyl methyl) butanol radical, tri (dodecyl) benzene sulfonate radical-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri ((dioctyl) phosphate radical-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri 2-methyl-2-propenyl alkanoate-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri (dioctyl) pyrophosphate radical-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri-2-propenyl alkanoate-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri (dioctyl) pyrophosphate radical-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri-2-propenyl alkanoate-O; zirconium IV 2,2 (bis-2-propenyl methyl) butanol radical, tri (2-ethylenediamino) ethyl radical; zirconium IV tetra (2,2-bis propenyl methyl) butanolate and 2 moles of ditridecyl hydrogen phosphite adduct; zirconium IV bis 2,2 (bis-2-propenyl methyl) butanolate, bis (p-aminobenzoate-O); zirconium IV bis 2,2 (bis-2-propenyl methyl) butanolate, bis (3-mercapto) propionate-O; zirconium IV 1,1 (bis-2-propenyl methyl) butanolate, tri (2-amino) phenyl radical; zirconium IV 2-ethyl, 2-propenyl methyl-1,3-propanediol, cyclodi-2,2-(bis 2-propenyl methyl) butanolate pyrophosphate-O,O; zirconium IV bis 2-ethylhexanolate, cyclo (di-2-ethylhexyl) pyrophosphate and zirconium tetra-n-propoxide. In the above given examples, zirconium IV 2,2(bis-2-propenolatomethyl)butanolate, tris-2-methyl-2-propenolato-O, zirconium IV adduct of tetra(2,2-bispropenolatomethyl)butanolate with 2 moles of ditridecyl hydrogen phosphite and zirconium tetra-n-propoxide, or combinations of these, are preferred metal catalysts.

[0065] The metal catalyst preferably comprises 0.0001 to 1 wt % of the coating composition.

[0066] As described herein, the polyaspartic acid composition of the present invention can be combined with a polyisocyanate to prepare a polyurea composition. The polyurea composition of the present invention can be applied to a substrate in the form of a coating composition by conventional methods such as smearing, rolling, pouring or spraying. Suitable substrates include, but are not limited to, metals, plastics, wood, cement, concrete and glass. The substrate to be coated with the polyurea coating composition according to the present invention can optionally be treated with a suitable primer.

[0067] The coatings, adhesives, sealants, composites, castings and films of the present invention may optionally contain additives such as fillers, pigments, softeners, high boiling point liquids, catalysts, UV stabilizers, antioxidants, microbicides, algaecides, dehydrating agents, thixotropic agents, wetting agents, flow enhancers, matting agents, anti-slip agents, aerators and extenders.

[0068] Although the present invention is described and exemplified in the context of polyurea coating compositions in this specification, the present invention is not intended to be so limited. The principles of the present invention are equally applicable to polyurethanes, polyureas, polyurethane / urea coatings, adhesives, sealants, composites, castings and films. Example

[0069] The following non-limiting and non-exhaustive examples are intended to further describe various non-limiting and non-exhaustive embodiments without limiting the scope of the embodiments described in this specification.

[0070] The following materials were used in the preparation of the examples. Unless otherwise indicated, all amounts given in "parts" and "percents" are understood to be by weight.

[0071] Polyaspartic acid type A 100% solids aspartate functional amine, amine value of about 191 mg KOH / g, viscosity @25°C of 1400 mPa·s, commercially available as DESMOPHEN NH 1520 from Covestro LLC, Pittsburgh, Pennsylvania;

[0072] Polyaspartic acid type B 100% solids aspartic acid ester functional amine, amine value of about 201 mgKOH / g, viscosity @25°C of 1450 mPa·s, commercially available as DESMOPHEN NH 1420 from Covestro LLC, Pittsburgh, Pennsylvania;

[0073] Isocyanate A Aliphatic polyisocyanate resin based on hexamethylene diisocyanate, NCO content 23.5±0.5%, viscosity 730±100 mPa·s@23° C., commercially available as DESMODUR N3900 from Covestro LLC, Pittsburgh, Pennsylvania;

[0074] Additive A tert-butyl acetate, commercially available from Aldrich

[0075] Catalyst A Tyzor TnBT, Ti(O-n-butyl)4, commercially available from DorfKetal;

[0076] Catalyst B Ken-react NZ33, zirconium IV 2,2 (bis-2-propenolatomethyl) butanolato, tri-2-methyl-2-propenolato-O, commercially available from Kenrich Petroleum Co.;

[0077] Catalyst C Ken-react KZ 55, an adduct of zirconium IV tetra(2,2-bispropenyloylmethyl)butanolate and 2 mol of ditridecyl hydrogen phosphite, commercially available from Kenrich Petroleum Co.;

[0078] Catalyst D Ken-react Lica 38, titanium IV 2,2 (bis (2-propenyl methyl)) butanolate, tri (dioctyl) pyrophosphate-O, commercially available from Kenrich Petroleum Co.;

[0079] Catalyst E Tyzor TOT, tetrakis(2-ethylhexyl)titanium, commercially available from Dorf Ketal.;

[0080] Catalyst F Ken-react Lica 44, titanium IV 2,2 (bis 2-propenylatomethyl), tris-2-ethylenediamino)ethylato, commercially available from Kenrich Petroleum Co.;

[0081] Catalyst G Tyzor BTP, polymerized butyl titanate, commercially available from DorfKetal;

[0082] Catalyst H Ken-react KRTTS, titanium IV 2-propanolate, triisooctadecanoate-O, commercially available from Kenrich Petroleum Co.;

[0083] Catalyst I Tyzor CLA, a titanate chelated with triethanolamine and acetylacetone, commercially available from DorfKetal;

[0084] Catalyst J Tyzor TPT, titanium tetra-n-propoxide, commercially available from DorfKetal;

[0085] Catalyst K Tyzor NPZ, zirconium tetra-n-propoxide, commercially available from DorfKetal;

[0086] Catalyst L Tyzor IBAY, bis(ethyl 3-oxobutyrate-O1′, O3)bis(2-methyl-1-propanol)titanium, commercially available from DorfKetal;

[0087] Catalyst M Tyzor PITA, ethyl acetoacetate titanium complex, commercially available from DorfKetal;

[0088] Catalyst N Ken-react Lica 38ENP, titanium IV 2,2(bis-2-propenyloylmethyl)butanolate, tri(dioctyl)pyrophosphate-O:ethoxylated nonylphenol 1:1, commercially available from Kenrich Petroleum Co.

[0089] Except for tert-butyl acetate, the remaining materials were used as is, and tert-butyl acetate was dried over an activated molecular sieve. The solvent additive was decanted from the top of the molecular sieve. Coating compositions were prepared in amounts listed in Table 1. The isocyanate component was added before applying the coating. A control composition was prepared that did not contain any metal catalyst. These compositions are referred to herein as control, Example A (prepared with Catalyst A), Example B (prepared with Catalyst B), etc.

[0090] Table I

[0091] Components Comparison Example AN Polyaspartic acid A 37.37 37.37 Polyaspartic acid B 20.10 20.10 Additive A 4.41 4.41 catalyst 0.07 Isocyanate A 38.16 38.16

[0092] For glass panels used for appearance testing and pendulum hardness testing Clean and dry with paper towels. Then rinse the panel with acetone or methyl ethyl ketone (MEK) and dry with a clean paper towel. The panels were wiped with a tack cloth and sealed with a standard polyaspartic coating formulation.

[0093] By placing polyaspartic acid, solvent additives and metal catalysts into Flacktek Polyaspartic acid coatings were prepared in a cup. The resin was blended at 2000 rpm in a sieve until homogeneous. The remainder of the mixture was mixed and applied in a constant temperature (25°C) / constant humidity (50% relative humidity) room. The polyaspartic acid blend was added to a glass jar. The polyisocyanate was then added and the mixture was stirred with a glass rod for 30 seconds. The viscosity change over time was measured using a Brookfield viscometer. The substrate was coated using a scraper or a metric 7.62 cm (3 in) wide roller. The goal was to apply a wet coating thickness of 0.203 mm (8 mils).

[0094] The formulation is applied by roller to the prepared Open Time is tested on a 12.7 cm (5 inch) wide plate. A strip approximately 12.7 cm (5 inch) wide is applied. Every five minutes another 12.7 cm (5 inch) strip is applied, overlapping the two coating edges. When the wet edges no longer blend together (as observed after curing), the open time has been reached. Or more succinctly stated, when the lap line backflow (LLFB) stops and appears as a line in the cured coating, the open time has timed out.

[0095] By The open walk-through time is tested by applying 0.203 mm (8 mil) of coating to the board. A person weighing 91 kg (200 lbs) steps on the board at regular intervals. Each step is on an untested portion of the coating. The open walk-through time is achieved when no marks or indentations are left on the coating after curing.

[0096] The handling time and open walk time were conducted in a temperature and humidity controlled room or in a Thermatron in the same room.

[0097] The cured samples were tested according to the ASTM methods listed in Table 2.

[0098] Coatings of 10 mil (0.254 mm) and 20 mil (0.508 mm) were applied to glass panels and then allowed to cure for at least seven days in a constant temperature / humidity chamber before the following physical tests were performed. For appearance, each coat was inspected after curing to see if there were any bubbles within the coating. For hardness testing, samples were poured into 1 / 4 inch aluminum molds, following ASTM D2240, using a Byk-Gardner instrument. In addition, tensile strength was tested according to ASTM D 412. Measurements were made in pounds per square inch (psi) and then converted to megapascals (MPa) as shown in the table below.

[0099] Table II

[0100]

[0101]

[0102] As shown in the above examples, the compositions using zirconium metal catalysts performed best because they improved the operating time while still maintaining a sufficiently low open walk time. In addition, hardness testing showed that they were proven to have no bubbles or very small bubbles in appearance while maintaining high strength and confirmed by tensile strength. In addition, it was found that catalysts containing zirconium metal and phosphite or sulfite in addition to another component were further preferred in achieving high strength and hardness while minimizing bubbles and also obtaining the benefits of longer operating time and relatively short open walk time.

[0103] Various aspects of the subject matter described herein are listed in the following numbered clauses:

[0104] Item 1. A polyaspartic acid composition comprising the reaction product of a polyamine, a Michael addition acceptor, and a polyisocyanate, wherein the reaction with the polyisocyanate is carried out in the presence of a zirconium metal catalyst.

[0105] Item 2. The polyaspartic acid composition of Item 1, wherein the polyamine is selected from ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluenediamine, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,4,4'-triamino-5-methyldicyclohexylmethane and amine-terminated polyether polyols.

[0106] Item 3. The polyaspartic acid composition of Item 1 or 2, wherein the Michael addition acceptor is selected from dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, acrylates, and combinations thereof.

[0107] Clause 4. The polyaspartic acid composition of any one of clauses 1 to 3, wherein the polyisocyanate is selected from ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, bis-(4-isocyanatocyclohexyl)methane (H 12 MDI), cyclohexane 1,4-diisocyanate, bis-(4-isocyanato-3-methyl-cyclohexyl)methane, pentane diisocyanate-bio-based, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate, any isomers thereof, and any combination thereof.

[0108] Item 5. The polyaspartic acid-based composition of any one of Items 1-4, wherein the zirconium metal catalyst comprises an alkoxy or aryloxy component.

[0109] Item 6. The polyaspartic acid composition of any one of Items 1-5, wherein the zirconium metal catalyst conforms to the formula: (RO-) n Zr-(-OX R'Y) 4-n, wherein RO- is a hydrolyzable group or substrate reactive group having a surface hydroxyl group or a proton; X is an adhesive functional group such as a phosphate, a pyrophosphate, a sulfonyl or a carboxyl group; R' is a thermoplastic functional group such as an aliphatic and non-polar isopropyl, butyl, octyl, isostearyl, cycloalkyl and weakly polar dodecylbenzyl, or an aromatic benzyl, cumylphenyl; Y is one or more thermosetting functional groups such as an acryloyl, a methacryloyl, a mercapto and an amino group; and n is an integer between 0 and 4.

[0110] Item 7. The polyaspartic acid-based composition of any one of Items 1-6, wherein the zirconium metal catalyst comprises a phosphite or sulfite component.

[0111] Item 8. The polyaspartic acid composition of any one of Items 1 to 7, wherein the zirconium metal catalyst is selected from zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, trineodecanol radical-O; zirconium IV2.2 (bis-2-propenyl methyl) butanol radical, tri(dodecyl) benzenesulfonate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri(dioctyl) phosphate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri-2-methyl-2-propenyl radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri(dioctyl) pyrophosphate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri-2-propenyl radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri-2-propenyl radical-O; Zirconium IV tetra(2,2-bis-propenylatomethyl)butanolato and 2 moles of ditridecyl hydrogen phosphite; Zirconium IV bis-2,2(bis-2-propenylatomethyl)butanolato, bis(p-aminobenzoate-O); Zirconium IV bis-2,2(bis-2-propenylatomethyl)butanolato, bis(3-mercapto)propionate-O; Zirconium IV 1,1(bis-2-propenylatomethyl)butanolato, tris(2-amino)phenylato; Zirconium IV 2-ethyl, 2-propenylatomethyl-1,3-propanediol, cyclodi-2,2-(bis-2-propenylatomethyl)butanolato pyrophosphate-O,O; Zirconium IV bis-2-ethylhexanolato, cyclo(di-2-ethylhexyl)pyrophosphate; Zirconium tetra-n-propoxide; and mixtures thereof.

[0112] Item 9. A polyaspartic acid composition according to any one of Items 1 to 8, wherein the zirconium metal catalyst is selected from zirconium IV 2,2-(bis-2-propenylatomethyl)butanolate, tri-2-methyl-2-propenylato-O; an adduct of zirconium IV tetra(2,2-bis-propenylatomethyl)butanolate and 2 mols of ditridecyl hydrogen phosphite; zirconium tetra-n-propoxide; and mixtures thereof.

[0113] Item 10. A coating comprising the polyaspartic acid-based composition of any one of Items 1-9.

[0114] Item 11. A substrate having applied thereto the coating of Item 10.

[0115] Item 12. The substrate of Item 11, wherein the substrate is selected from the group consisting of metal, plastic, wood, cement, concrete, and glass.

[0116] Clause 13. The substrate of Clause 11 or 12, wherein the substrate is a floor.

Claims

1. A polyaspartic acid composition comprising a reaction product of a polyamine, a Michael addition acceptor and a polyisocyanate, wherein the reaction with the polyisocyanate is carried out in the presence of a zirconium metal catalyst.

2. The polyaspartic acid composition according to claim 1, wherein the polyamine is selected from ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluenediamine, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,4,4'-triamino-5-methyldicyclohexylmethane and amine-terminated polyether polyols.

3. The polyaspartic acid composition according to claim 1, wherein the Michael addition acceptor is selected from dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, acrylates and combinations thereof.

4. The polyaspartic acid composition according to claim 1, wherein the polyisocyanate is selected from ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, bis-(4-isocyanatocyclohexyl)methane (H 12 MDI), cyclohexane 1,4-diisocyanate, bis-(4-isocyanato-3-methyl-cyclohexyl)methane, pentane diisocyanate-bio-based, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate, any isomers thereof, and any combination thereof. The polyaspartic acid composition according to claim 1 , wherein the zirconium metal catalyst comprises an alkoxy or aryloxy component.

6. The polyaspartic acid composition according to claim 1, wherein the zirconium metal catalyst conforms to the formula: (RO-) n Zr-(-OX R'Y) 4-n , wherein RO- is a hydrolyzable group or substrate reactive group having a surface hydroxyl group or a proton; X is an adhesive functional group such as a phosphate, a pyrophosphate, a sulfonyl or a carboxyl group; R' is a thermoplastic functional group such as an aliphatic and non-polar isopropyl, butyl, octyl, isostearyl, cycloalkyl and weakly polar dodecylbenzyl, or an aromatic benzyl, cumylphenyl; Y is one or more thermosetting functional groups such as an acryloyl, a methacryloyl, a mercapto and an amino group; and n is an integer between 0 and 4.

7. The polyaspartic acid composition according to claim 1, wherein the zirconium metal catalyst comprises a phosphite or sulfite component.

8. The polyaspartic acid composition according to claim 1, wherein the zirconium metal catalyst is selected from zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri neodecyl radical-O; zirconium IV2.2 (bis-2-propenyl methyl) butanol radical, tri (dodecyl) benzene sulfonate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri (dioctyl) phosphate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri 2-methyl-2-propenyl radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri (dioctyl) pyrophosphate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri-2-propenyl radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri (dioctyl) pyrophosphate radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri-2-propenyl radical-O; zirconium IV2,2 (bis-2-propenyl methyl) butanol radical, tri )butanolate, tris(2-ethylenediamino)ethylatolate; adduct of zirconium IV tetra(2,2-bispropenylatomethyl)butanolate and 2 moles of ditridecyl hydrogen phosphite; zirconium IV bis-2,2(bis-2-propenylatomethyl)butanolate, bis(p-aminobenzoate-O); zirconium IV bis-2,2(bis-2-propenylatomethyl)butanolate, bis(3-mercapto)propanoate-O; zirconium IV 1,1(bis-2-propenylatomethyl)butanolate, tris(2-amino)phenylato; zirconium IV 2-ethyl, 2-propenylatomethyl-1,3-propanediol, cyclodi-2,2-(bis-2-propenylatomethyl)butanolate pyrophosphate-O,O; zirconium IV bis-2-ethylhexanolate, cyclo(di-2-ethylhexyl)pyrophosphate; zirconium tetra-n-propoxide; and mixtures thereof.

9. The polyaspartic acid composition according to claim 1, wherein the zirconium metal catalyst is selected from zirconium IV 2,2 (bis-2-propenylatomethyl) butanolate, tri-2-methyl-2-propenylato-O; an adduct of zirconium IV tetra(2,2-bis-propenylatomethyl) butanolate and 2 moles of ditridecyl hydrogen phosphite; zirconium tetra-n-propoxide; and mixtures thereof. 10 . A coating comprising the polyaspartic acid composition according to claim 1 .

11. A substrate having applied thereto the coating according to claim 10.

12. The substrate according to claim 11, wherein the substrate is selected from the group consisting of metal, plastic, wood, cement, concrete and glass.

13. The substrate of claim 11, wherein the substrate is a floor.

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