Improved working time to open walk time ratio by adding phenolic catalysts to polyaspartic flooring formulations

Abstract

The present invention provides a polyaspartic acid composition comprising the reaction product of a polyamine and a Michael addition acceptor reacted in the presence of a catalyst, the catalyst comprising a phenolic compound, provided that the phenolic compound is not a phenol substituted with tert-butyl groups at both ortho positions to the oxygen. Suitable phenolic compounds include phenol, phenolic aldehydes, alkylphenols, benzene glycols, cashew nut oil, and combinations thereof. Coatings, adhesives, sealants, composites, castings, and films comprising polyurea compositions can be prepared by reacting a polyisocyanate with the polyaspartic acid composition of the present invention. In particular, floor coatings prepared with the polyaspartic acid composition of the present invention have an extended working time and a short open walk-on time compared to existing floor coatings.

Description

Field of the Invention

[0001] The present invention relates generally to floor coatings and, more particularly, to polyaspartic floor coatings having an extended work time and a short walk-on time. Background of the Invention

[0003] One of the problems in the art is that floor contractors expect polyaspartic floor coatings to have a long working time and as short an open walk time as possible. Commercially available formulations typically provide a working time of 10 to 15 minutes and an open walk time of three and a half to eight hours. Speeding up the reaction results in a decrease in both working time and open walk time. Slowing down the reaction increases both working time and open walk time.

[0004] Therefore, in order to reduce or eliminate the problem, there is a need in the art to provide polyaspartic coating formulations that provide increased working time compared to commercially available formulations, while not significantly increasing open walk-through time. SUMMARY OF THE INVENTION

[0006] Thus, the present invention reduces or eliminates the problems inherent in the art by providing polyaspartic acid formulations catalyzed by phenolic compounds that provide increased operating time compared to commercially available formulations. The formulations of the present invention do not significantly increase open walk time.

[0007] These and other advantages and benefits of the present invention will become apparent from the following detailed description of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The present invention will now be described for purposes of illustration and not limitation with reference to the accompanying drawings, in which:

[0009] Figure 1 The viscosity increase over time for formulations containing various levels of Catalyst A (methanol) is shown;

[0010] Figure 2 Shown is the temperature rise over time for formulations containing various levels of Catalyst A (methanol);

[0011] Figure 3 The viscosity increase over time for formulations containing various alkanol compounds as catalysts is shown;

[0012] Figure 4 The temperature rise over time for formulations containing various alkanol compounds as catalysts is shown;

[0013] Figure 5 is a graph of the viscosity increase over time for formulations containing various amounts of Catalyst A (methanol); and

[0014] Figure 6 is a comparison of the open walk time vs. operating time for formulations using various phenolic compounds as catalysts. DETAILED DESCRIPTION OF THE INVENTION

[0016] The invention will now be described for purposes of illustration and not limitation.Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, etc. in the specification are to be understood as being modified in all instances by the term "about".

[0017] Any numerical range described in this specification is intended to include all subranges of the same numerical precision contained within the range. For example, the range of "1.0 to 10.0" is intended to include all subranges between the stated minimum value of 1.0 and the stated maximum value of 10.0 (and including the stated values), that is, all subranges with a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, for example, 2.4 to 7.6. Any maximum numerical limit described in this specification is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein.

[0018] Accordingly, applicant reserves the right to amend the present specification, including the claims, to expressly recite any sub-ranges contained within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification, such that amendment to expressly recite any such sub-ranges will comply with the requirements of 35 USC § 112(a) and 35 USC § 132(a). The various embodiments disclosed and described in this specification may include, consist of, or consist essentially of the features and characteristics as variously described herein.

[0019] Unless otherwise stated, any patent, publication or other public material identified herein is incorporated by reference in its entirety into this specification, but only to the extent that the incorporated material does not conflict with existing definitions, statements or other public materials explicitly set forth in this specification. Therefore, and to the extent necessary, the explicit disclosure set forth in this specification supersedes any conflicting material incorporated by reference herein. Any material or portion thereof that is said to be incorporated by reference into this specification, but conflicts with existing definitions, statements or other public materials set forth herein, is incorporated only to the extent that no conflict occurs between the incorporated material and the existing public materials. Applicants reserve the right to amend this specification to explicitly state any subject matter or portion thereof incorporated herein by reference.

[0020] References throughout this specification to "various non-limiting embodiments," "certain embodiments," etc. mean that particular features or characteristics may be included in the embodiments. Therefore, the use of phrases "in various non-limiting embodiments," "certain embodiments," etc. in this specification does not necessarily refer to a common embodiment, and may refer to different embodiments. In addition, particular features or characteristics may be combined in one or more embodiments in any suitable manner. Therefore, particular features or characteristics illustrated or described in conjunction with various or certain embodiments may be combined in whole or in part with features or characteristics of one or more other embodiments without limitation. Such modifications and variations are intended to be included within the scope of this specification.

[0021] Unless otherwise indicated, the grammatical articles "a", "an", and "the" as used herein are intended to include "at least one" or "one or more", even if "at least one" or "one or more" is explicitly used in some cases. Therefore, these articles are used in this specification to refer to one or more than one or more than one (i.e., "at least one") of the grammatical objects of the article. As an example and not limitation, "a component" means one or more components, and therefore, more than one component may be expected and may be employed or used in the implementation of the described embodiments. In addition, the use of a singular noun includes the plural, and the use of a plural noun includes the singular, unless the context of the usage requires otherwise.

[0022] In a first aspect, the present invention relates to a polyaspartic acid composition comprising the reaction product of a polyamine and a Michael addition acceptor reacted in the presence of a catalyst, wherein the catalyst comprises a phenolic compound, provided that the phenolic compound is not a phenol substituted at both ortho positions of the oxygen with tert-butyl groups.

[0023] In a second aspect, the present invention is directed to a polyurea composition comprising the reaction product of a polyisocyanate and the polyaspartic acid-based composition of the present invention.

[0024] In a third aspect, the present invention relates to a method for preparing a polyaspartic acid composition, which comprises reacting a polyamine with a Michael addition acceptor in the presence of a catalyst, wherein the catalyst comprises a phenolic compound, provided that the phenolic compound is not a phenol substituted at both ortho positions of the oxygen with tert-butyl groups.

[0025] In a fourth aspect, the present invention is directed to one of a coating composition, an adhesive composition, a sealant composition, a composite composition, a casting composition and a film composition, comprising the polyurea composition of the present invention.

[0026] The term "polymer" as used herein includes prepolymers, oligomers, and both homopolymers and copolymers; the prefix "poly" in this context means two or more. Unless otherwise indicated, the term "molecular weight" as used herein when used to refer to a polymer refers to the number average molecular weight.

[0027] 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.

[0028] The term "adhesive" or "adhesive composition" refers to any substance that can adhere or bond two items together. Implicit in the definition of "adhesive composition" or "adhesive formulation" is the concept that the composition or formulation is a combination or mixture of more than one species, component or compound, which can include adhesive monomers, oligomers and polymers as well as other materials.

[0029] "Sealant" or "sealant composition" refers to a composition that can be applied to one or more surfaces to form a protective barrier, for example to prevent the ingress and egress of solid, liquid or gaseous materials, or alternatively to allow selective permeation of gases and liquids through the barrier. In particular, it can provide a seal between surfaces.

[0030] "Casting" or "casting composition" refers to a mixture of liquid chemical components which is typically poured into a mold containing a cavity of the desired shape and then allowed to solidify.

[0031] "Composite" or "composite composition" refers to a material prepared from one or more polymers that contains at least one other type of material (e.g., fiber) that retains its identity while providing the composite with desirable properties. A composite has properties that are different from those of the individual polymers / materials that make it up.

[0032] "Cured", "cured composition" or "cured compound" refers to components and mixtures obtained from reactive curable original compound(s) or mixture(s) thereof, which have undergone chemical and / or physical changes such that the original compound(s) or mixture(s) are transformed into a solid, substantially non-flowing material. Typical curing processes may involve cross-linking.

[0033] The term "curable" means that the original compound(s) or composition material(s) 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(s) or composition material(s) are not cured.

[0034] As used herein, the term "pot life" refers to the period of time from the initial mixture of two or more mutually reactive components of a coating system to the point at which the resulting coating composition exhibits an inoperable viscosity.

[0035] As used herein, the term "cure time" refers to the time required to cure as specified in ASTM D5895-03 (2008) - Standard Test Methods for Evaluating Drying or Curing During Film Formation of Organic Coatings Using Mechanical Recorder The time for Stage D (Method B) as defined in Standard Test Method for Evaluating Drying or Curing of Organic Coatings During Film Formation Using a Mechanical Recorder.

[0036] The term "polyurethane" as used herein refers to a polymeric or oligomeric material comprising carbamate groups, urea groups, or both. Thus, the term "polyurethane" as used herein is synonymous with the terms polyurea, polyurethane / urea, and variants thereof. The term "polyurethane" also refers to a crosslinked polymer network wherein the crosslinking bonds comprise carbamate linkages and / or urea linkages, and / or the constituent polymer chains comprise carbamate linkages and / or urea linkages. Carbodiimide crosslinks known to those skilled in the art are also contemplated in the coatings of the present invention.

[0037] The coating compositions described in this specification 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 that must be stored in separate containers due to their mutual reactivity. For example, two-component polyurea coating systems and compositions may include a hardener / crosslinker component containing an isocyanate functional compound, and a separate binder component containing an amino functional compound. Due to the limited pot life of the mixture, the two separate components are typically not mixed until shortly before application. When the two separate components are mixed and applied as a film on a substrate, the mutually reactive compounds in the two components react to crosslink and form a cured coating film.

[0038] 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.

[0039] As used herein, the term "polyisocyanate" refers to a compound containing at least two unreacted isocyanate groups. Polyisocyanates include diisocyanates and diisocyanate reaction products containing, for example, biuret, isocyanurate, uretdione, carbamate, urea, iminooxadiazinedione, oxadiazinedione, carbodiimide, acylurea, allophanate groups and any combination thereof.

[0040] The polyisocyanates useful in the present invention may include any organic polyisocyanate with aliphatic, alicyclic, araliphatic and / or aromatic bound 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 polyisocyanate may 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 polyisocyanate may include a polyisocyanate or a polyisocyanate mixture having only aliphatic and / or alicyclic bound isocyanate groups, having 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.

[0041] 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-trimethyl-cyclohexane (isophorone diisocyanate or IPDI); bis-(4-isocyanatocyclohexyl)methane (HDI); 12 MDI); 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.

[0042] Additional polyisocyanates (including various diisocyanates) that may also be included in the polyurea compositions of the present invention may include the polyisocyanates 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.

[0043] The indicated diisocyanates and triisocyanates can be used as such or as derivatized polyisocyanates containing biuret, isocyanurate, uretdione, carbamate, urea, iminooxadiazinedione, oxadiazinetrione, carbodiimide, acylurea and / or allophanate groups. In various non-limiting embodiments, the polyurea includes a derivatized polyisocyanate containing biuret, isocyanurate, uretdione, carbamate, iminooxadiazinedione, oxadiazinetrione, carbodiimide, acylurea and / or allophanate groups. In various embodiments, the polyisocyanate component comprises IPDI, HDI, H 12 One or more of the above structural groups prepared from MDI and / or cyclohexane 1,4-diisocyanate.

[0044] The polyisocyanates may be hydrophilically modified to be water dispersible. Hydrophilically modified water dispersible polyisocyanates may be obtained, for example, by covalent modification with internal emulsifiers comprising anionic groups, cationic groups or nonionic groups.

[0045] Polyether urethane type water-dispersible polyisocyanates can be formed, for example, by the reaction between polyisocyanates and monopolyoxyalkylene polyether alcohols less than the 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, for example, by the reaction between polyoxyalkylene polyether alcohols 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 alcohols for preparing polyether type hydrophilically modified water-dispersible polyisocyanates can include, for example, polyethylene oxide residues and / or polypropylene oxide residues.

[0046] Polyisocyanates can also be covalently modified with ionic or potentially ionic internal emulsifying groups to form hydrophilically modified water-dispersible polyisocyanates. Ionic groups or potentially ionic groups can be cationic or anionic. As used herein, the term "ionic group or potentially 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 potentially 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 potentially 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).

[0047] 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.

[0048] If free carboxylic acid, sulfonic acid or phosphonic acid is incorporated into the polyisocyanate, the acid may be neutralized with a neutralizing agent such as a tertiary amine, including but not limited to trialkyl substituted tertiary amines. 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.

[0049] 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.

[0050] 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 (electropophiles) 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.

[0051] The polyaspartic acid composition may comprise one or more polyaspartic acid esters corresponding to formula (I):

[0052]

[0053] in:

[0054] n is an integer from 2 to 4

[0055] X represents an aliphatic residue;

[0056] R 1 and R 2 represent independently of one another organic groups which are inert towards isocyanate groups under the reaction conditions; and

[0057] n is at least 2.

[0058] 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 having a number average molecular weight (M n ) is 148 to 6000 g / mol of polyether polyamine; any isomers thereof, and any combination thereof.

[0059] 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.

[0060] The polyamines useful in the present invention may include amine-terminated polyether polyols (i.e., polyether polyamines), such as primary 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 about 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.

[0061] The amine-terminated polyethers that can be used in the present invention are, for example, polyethers prepared by adding low-order alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, to a suitable initiator, and then aminating the resulting hydroxyl-terminated polyols. When two or more oxides are used, they can exist as random mixtures or as blocks of one or another polyether. In the amination step, in order to facilitate amination, it is highly desirable that the terminal hydroxyl groups in the polyols are substantially all secondary hydroxyl groups. Typically, the amination step will not completely replace all hydroxyl groups. However, most hydroxyl groups are replaced by amine groups. Therefore, in some embodiments, the amine-terminated polyethers have more than 50% active hydrogen in the form of amine hydrogen. If ethylene oxide is used, it is desirable to terminate the hydroxyl-terminated polyols with a small amount of higher alkylene oxides to ensure that the terminal hydroxyl groups are substantially all secondary hydroxyl groups. The polyols thus prepared are then reductively aminized by known techniques, for example, as described in U.S. Patent No. 3,654,370.

[0062] In some embodiments of the present invention, a single high molecular weight amine-terminated polyol may be used. In addition, mixtures of high molecular weight amine-terminated polyols may be used, such as mixtures of difunctional and trifunctional materials and / or materials of different molecular weights or different chemical compositions.

[0063] 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 2,000. Particularly preferred are the JEFFAMINE series of polyetheramines available from Texaco Chemical Company; they include JEFFAMINE D-2000, JEFFAMINE D-4000, JEFFAMINE T-3000 and JEFFAMINE T-5000.

[0064] 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, a group having a Zerevitinov-active hydrogen is understood in the art to mean a hydroxyl group (OH), an amino group (NH x ) and thiol (SH) groups. In various embodiments, R 1 and R2 Independently of each other, C1 to C 10 Alkyl residues, such as methyl, ethyl or butyl residues.

[0065] 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 2. In embodiments where n=2, the polyaspartic acid composition may comprise one or more compounds corresponding to formula (II):

[0066]

[0067] The polyaspartic acid composition can be prepared by making the corresponding primary polyamine of the following formula:

[0068]

[0069] Prepared by reaction with a diester of the formula:

[0070] .

[0071] 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.

[0072] Catalysts suitable for preparing the polyaspartic acid compositions of the present invention include phenolic compounds other than sterically hindered phenols substituted with tert-butyl groups at both ortho positions of the 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] Although the invention is described and exemplified in the context of polyurea coating compositions in this specification, the invention is not intended to be so limited. The principles of the invention are equally applicable to polyurethanes, polyureas, polyurethane / urea coatings, adhesives, sealants, composites, castings and films. Example

[0077] 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.

[0078] 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.

[0079]

[0080] Experiments were conducted to determine whether the reactivity of polyaspartic acid type A could be increased with an alkanol catalyst. Table 1 provides formulations with increasing amounts of catalyst A (methanol). Viscosity and temperature data are presented in Figure 1 and Figure 2 In. If by reference Figure 1 and Figure 2 As can be appreciated, increasing the amount of Catalyst A (methanol) increases the cure rate, which in turn increases the viscosity and the exotherm of the reaction.

[0081] Table I

[0082] Components Ex.IA Ex. IB Ex. IC Ex. ID Ex. IE Ex. IF Polyaspartic acid B 88.05 88.05 88.05 88.05 88.05 88.05 Additive A 8.65 8.65 8.65 8.65 8.65 8.65 Catalyst A 0.0 0.0875 0.175 0.350 1.05 2.10 Isocyanate A 78.29 78.29 78.29 78.29 78.29 78.29

[0083] Additional alkanols were examined for their catalytic effects. Primary alkanols appear to be better catalysts than secondary alkanols, and these are better catalysts than tertiary alkanols. The formulations tested are given in Table II. Viscosity and reaction temperature data are provided in Table II, respectively. Figure 3 and Figure 4 middle.

[0084] Table II

[0085] Components Ex. II-A Ex. II-B Ex. II-C Ex. II-D Polyaspartic acid B 88.05 88.05 88.05 88.05 Additive A 8.65 8.475 8.322 8.245 Catalyst A 0.175 Catalyst D 0.328 Catalyst E 0.4048 Isocyanate A 78.29 78.29 78.29 78.29 OH moles 0.0 0.00547 0.00547 0.00547

[0086] Attempts (Ex. 1-E and Ex. 1-F) were made to catalyze the reaction using very high amounts of Catalyst A (methanol). Figure 5A graph showing the viscosity increase over time for a formulation containing Catalyst A (methanol) is shown. Figure 5 As can be appreciated, at the highest level of Catalyst A (methanol), the rate did not increase as rapidly.

[0087] To determine if the coating reactivity was within acceptable limits, the open time and open walk time were evaluated. The 6000 ppm Catalyst A (methanol) formulation had an open time of 50 minutes and an open walk time of greater than 26 hours. The 12000 ppm Catalyst A (methanol) formulation had an open time of 25 minutes and an open walk time of greater than 19 hours. The formulations with lower indices are presented in Table III.

[0088] Due to the high volatility of Catalyst A (methanol), experiments were attempted using another alkanol, Catalyst B (1-pentanol). Unfortunately, the strong odor of Catalyst B (1-pentanol) prevented its use at higher levels.

[0089] Experiments using stronger types of catalysts are summarized in Table III. Since phenolic compounds have higher pKa, it is expected that they have stronger catalytic effects. Catalyst C (nonylphenol), Catalyst F (resorcinol) and Catalyst G (IRGANOX 1135) were evaluated. Although Catalyst C (nonylphenol) and Catalyst F (resorcinol) were proven to be very active catalysts, Catalyst G (IRGANOX 1135) was proven to be ineffective. Without wishing to be bound by any theory, the inventors speculate that this may be due to the steric hindrance provided by the tertiary butyl group on the ortho position of the oxygen of the phenol.

[0090] In Tables III, IV and V, the "operating time" was evaluated by applying the formulation to a pre-prepared MASONITE board with a roller. A strip of about 12.7 cm (5 inches) wide and 0.203 mm (8 mils) thick was applied. Every five minutes, another 12.7 cm (5 inches) strip overlapping the edges of the two coatings was applied. The end of the operating time was reached when the wet edges were no longer blended together (as observed after curing). Or more simply, when the lap line reflow stopped and appeared as a line in the cured coating, the operating time had been exceeded. Similarly, in Tables III, IV and V, the "open walking time" was evaluated by applying a coating of 0.203 mm (8 mils) to the MASONITE board. An individual of 91 KG (200 pounds) stepped onto the board at intervals. Each step was on a portion of the coating that was not tested. When no marks or indentations were left on the coating after curing, the open walking time was reached.

[0091]

[0092] As can be understood by referring to Table III, catalyst C (nonylphenol) seems to be a good choice to increase the reaction rate; however, in some countries, its use may be restricted. Therefore, the catalytic effect of a series of other substituted phenolic compounds was detected, and the results are summarized in Table IV. Although many are suitable catalysts, many of these phenolic compounds have a strong odor. For example, catalyst P (2-methoxyphenol) is a notable catalyst, but has a strong odor. As a result, the inventors narrowed their scrutiny to phenolic compounds existing in nature or those with a pleasant odor. Therefore, catalyst M (vanillin, a phenolic aldehyde) and catalyst O (cashew nut oil, a phenolic lipid) were evaluated. Although catalyst M (vanillin) has a pleasant odor, it produces a yellow film. On the other hand, catalyst O (cashew nut oil) meets these two requirements because it exists naturally and does not have a strong odor.

[0093]

[0094]

[0095] Experiments were conducted to determine if adding a small portion of Polyaspartic Acid C would improve open walk time. The results of these experiments are summarized in Table V. Thick coupons prepared from this formulation showed a slight loss of properties after heating the coupons in an oven at 60°C for several hours. Tensile strength was determined according to ASTM D 412; percent elongation was determined according to ASTM D 412. Shore D hardness was determined using a durometer according to ASTM D 2240.

[0096] Table V

[0097] Components Ex. VA Ex. VB Ex. VC Polyaspartic acid C 2.84 5.52 Polyaspartic acid A 58.84 54.00 52.51 Additive A 4.83 4.83 4.69 Catalyst P 0.38 0.38 1.35 Additive B 0.28 0.28 0.28 Isocyanate A 37.66 37.66 36.62 NCO:OH 1.07 / 1.06 1.07 / 1.06 1.02 Operation time (minutes) 25 25 13 Open walking hours (hours) 8.5 8 6 Hardness, Shore D 72 / 70 74 / 72 73 / 72 Tensile Strength (psi) – Test Block 8033 7783 7430 Elongation (%) - Test Block 5.2 4.7 5.2 Hardness, Shore D, heated 76 / 74 75 / 73 74 / 71 Tensile Strength - (psi) Block - Heated 6020 5925 5388 Elongation (%) Test block - heated 6.65 6.3 14.3

[0098] Figure 6 It is the contrast of the open walking time vs operating time of the formulations using various phenolic compound catalysts to prove which performance is best. The standard formulations (i.e. VI-1 and VI-2) as shown in Table VI are also added to the figure to show the improvement relative to the prior art. Most notably, catalyst P (2-methoxyphenol), catalyst C (nonylphenol), catalyst O (cashew nut oil) and catalyst M (vanillin) obtain better results than standard formulations (VI-1, VI-2).

[0099] Table VI

[0100] Components VI-1 VI-2 Polyaspartic acid A 16.88 28.55 Polyaspartic acid B 22.66 14.28 Polyaspartic acid C 16.94 14.28 Additive A 5.02 4.97 Additive B 1.00 1.00 Isocyanate A 37.50 36.92 NCO:OH 1.07 1.07 Operation time (minutes) 10 15 Open walking hours (hours) 3.5 8

[0101] Various formulations were prepared to evaluate Catalyst O (cashew nut oil) by reducing the isocyanate index, by adding additional polyaspartic acid ester (Polyaspartic acid type C), and by adjusting the Catalyst O (cashew nut oil) content. As is apparent by reference to Table VII, the formulations used in Ex. VII-C, VII-D, and Ex. VII-G appear to be improvements over the control Ex. VII-A.

[0102]

[0103] This specification is written with reference to various non-limiting and non-exhaustive embodiments. However, it will be appreciated by those of ordinary skill in the art that various replacements, modifications or combinations may be made to any disclosed embodiment (or part thereof) within the scope of this specification. Therefore, it is contemplated and understood that this specification supports other embodiments that are not explicitly set forth herein. For example, such embodiments may be obtained by combining, modifying or reorganizing any disclosed steps, components, elements, features, aspects, characteristics, limitations, etc. of the various non-limiting embodiments described in this specification. In this way, the applicant reserves the right to modify the claims during the examination to increase the features variously described in this specification, and such modifications meet the requirements of 35 USC §112(a) and 35 USC §132(a).

Claims

1. A polyaspartic acid composition comprising a reaction product of a polyamine and a Michael addition acceptor reacted in the presence of a catalyst, wherein the catalyst comprises a phenolic compound having at least one hydroxyl group attached to a carbon atom of a benzene ring, provided that the phenolic compound is not a phenol substituted with tert-butyl groups at both ortho positions of the oxygen, wherein the phenolic compound is selected from the group consisting of 2-methoxyphenol, vanillin, nonylphenol, hydroxyvanillin, cashew nut oil, and combinations thereof.

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 any one of claims 1 and 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.

4. A polyurea composition comprising a reaction product of a polyisocyanate and a polyaspartic acid composition according to any one of claims 1 to 3.

5. The polyurea composition according to claim 4, wherein the polyisocyanate is selected from 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-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane ...2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene di 12 MDI), cyclohexane 1,4-diisocyanate, bis-(4-isocyanato-3-methyl-cyclohexyl)methane, PDI (pentane diisocyanate-biobased), phenylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4-isocyanatomethyl-l,8-octane diisocyanate (triisocyanatononane or TIN), any isomers thereof, and any combination thereof.

6. One of an adhesive composition, a sealant composition, a composite composition, a casting composition and a film composition, comprising the polyurea composition according to any one of claims 4 and 5.

7. A coating composition comprising the polyurea composition according to any one of claims 4 and 5.

8. The coating composition according to claim 7, further comprising an additive selected from fillers, pigments, softeners, high boiling point liquids, UV stabilizers, antioxidants, microbicides, algaecides, dehydrating agents, thixotropic agents, wetting agents, flow enhancers, matting agents, anti-slip agents, aerators and extenders.

9. A substrate having applied thereto a coating composition according to any one of claims 7 and 8.

10. The substrate of claim 9, wherein the substrate is selected from the group consisting of metal, plastic, wood, cement, concrete and glass.

11. The substrate of claim 9, wherein the substrate is a floor.

12. A method for preparing a polyaspartic acid composition, comprising reacting a polyamine and a Michael addition acceptor in the presence of a catalyst, wherein the catalyst comprises a phenolic compound having at least one hydroxyl group attached to a carbon atom of a benzene ring, provided that the phenolic compound is not a phenol substituted with tert-butyl groups at both ortho positions to oxygen, wherein the phenolic compound is selected from the group consisting of 2-methoxyphenol, vanillin, nonylphenol, hydroxyvanillin, cashew nut oil, and combinations thereof.

13. The method according to claim 12, 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.

14. The method according to any one of claims 12 and 13, wherein the Michael addition acceptor is selected from the group consisting of dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, acrylates, and combinations thereof.

15. A method for preparing a polyurea composition, comprising reacting a polyisocyanate with a polyaspartic acid-based composition prepared by the method according to any one of claims 12 to 14.

16. The method according to claim 15, wherein the polyisocyanate is selected from 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-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane ...2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2 12 MDI), cyclohexane 1,4-diisocyanate, bis-(4-isocyanato-3-methyl-cyclohexyl)methane, PDI (pentane diisocyanate-biobased), phenylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4-isocyanatomethyl-l,8-octane diisocyanate (triisocyanatononane or TIN), any isomers thereof, and any combination thereof.

17. One of an adhesive composition, a sealant composition, a composite composition, a casting composition and a film composition, comprising the polyurea composition prepared according to any one of claims 15 and 16.

18. A coating composition comprising a polyurea composition prepared according to any one of claims 15 and 16.

19. The coating composition according to claim 18, further comprising an additive selected from fillers, pigments, softeners, high boiling point liquids, UV stabilizers, antioxidants, microbicides, algaecides, dehydrating agents, thixotropic agents, wetting agents, flow enhancers, matting agents, anti-slip agents, aerators and extenders.

20. A substrate having applied thereto a coating composition according to any one of claims 18 and 19.

21. The substrate of claim 20, wherein the substrate is selected from the group consisting of metal, plastic, wood, cement, concrete and glass.

22. The substrate of claim 20, wherein the substrate is a floor.

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