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Title:
POLYASPARTIC COATING COMPOSITIONS
Document Type and Number:
WIPO Patent Application WO/2014/151307
Kind Code:
A1
Abstract:
Two-component coating systems and compositions are disclosed. The coating compositions form crosslinked polyurea coatings and have relatively long pot life and set-to-touch time and a relatively short hard dry time. The coating compositions include a polyisocyanate, a polyaspartic ester, and a poiyetheraspartic ester.

Inventors:
SQUILLER, Edward, P. (722 Augusta Drive, Bridgeville, PA, 15017, US)
WAYT, Terrell, D. (1304 5th Street, Moundsville, WV, 26041, US)
FORSYTH, John (9515 Springfield Drive, Allison Park, PA, 15101, US)
BEST, Kurt, E. (1641 Norman Drive, Sewickley, PA, 15143, US)
OLSON, Ahren (5926 Victor Circle, Aliquippa, PA, 15001, US)
EKIN, Abdullah (111 Swaoger Street, Coraopolis, PA, 15108, US)
Application Number:
US2014/025420
Publication Date:
September 25, 2014
Filing Date:
March 13, 2014
Export Citation:
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Assignee:
BAYER MATERIALSCIENCE LLC (100 Bayer Road, Pittsburgh, PA, 15205-9741, US)
SQUILLER, Edward, P. (722 Augusta Drive, Bridgeville, PA, 15017, US)
WAYT, Terrell, D. (1304 5th Street, Moundsville, WV, 26041, US)
FORSYTH, John (9515 Springfield Drive, Allison Park, PA, 15101, US)
BEST, Kurt, E. (1641 Norman Drive, Sewickley, PA, 15143, US)
OLSON, Ahren (5926 Victor Circle, Aliquippa, PA, 15001, US)
EKIN, Abdullah (111 Swaoger Street, Coraopolis, PA, 15108, US)
International Classes:
C08G18/48; C08G18/00; C08G18/72; C08G69/02; C08L71/02
Domestic Patent References:
WO2011126562A22011-10-13
WO2013026804A22013-02-28
Foreign References:
US20040110917A12004-06-10
Other References:
ANGELOFF ET AL.: "Two-component aliphatic polyurea coatings for high productivity applications.", JOURNAL OF PROTECTIVE COATINGS & LININGS (USA), vol. 19, no. 8, 2002, pages 42 - 47, XP055279520
See also references of EP 2970556A4
Attorney, Agent or Firm:
BROWN, N., Denise et al. (Bayer Materialscience LLC, 100 Bayer RoadPittsburgh, PA, 15205-9741, US)
Download PDF:
Claims:
WHAT IS CLAIMED IS:

1. A two-component coating system comprising:

(A) a first component comprising a polyisocyanate; and

(B) a second component comprising:

(B1 ) polyaspartic ester; and

(B2) a polyetheraspartic ester,

wherein (A), (B1 ) and (B2), and their respective amounts, are selected so as to provide a two-component coating system that, when (A) and (B) are mixed:

(i) forms a coating composition having a solids content of at least 70% by weight, based on the total weight of the mixture,

(is) has a pot life of at least 25 minutes; and

(iii) after application of the mixture to a substrate, the mixture has a set-to- touch time of at least 40 minutes and a hard dry time of no more than 130 minutes.

2. The two-component coating system of claim 1 , wherein the coating composition has a solids content of at least 80 percent by weight and a pot life of at least 30 minutes.

3. The two-component coating system of claim 1 , wherein (B1 ) comprises a polyaspartic ester corresponding to formula:

wherein: n is an integer of 2 to 4; X represents an aliphatic residue; and R1 and R2 represent organic groups that are inert to isocyanate groups under reaction conditions and that may be the same or different organic groups. The two-component coating system of claim 3, wherein (B1 ) comprises (i) a polyaspartic ester having the structure of formula (IV):

; and polyaspartic ester having the structure of formula

.

5. The two-component coating system of claim 4, wherein the relative weight ratio the polyaspartic ester of formula (IV) to the polyaspartic ester of formula (V) is 1 :2 to

2:1.

6. The two-component coating system of claim 5, wherein the relative weight ratio the polyaspartic ester of formula (IV) to the polyaspartic ester of formula (V) is 1 :1.2 to 1.2:1.

7. The two-component coating system of claim 4, wherein:

(i) the polyaspartic ester of formula (IV) is present in component (B) in an amount of 1 to 40 percent by weight, based on the total weight of reactants in component (B); and

(ii) the polyaspartic ester of formula (V) is present in component (B) in an amount of 30 to 50 percent by weight, based on the total weight of reactants in

component (B).

8. The two-component coating system of claim 1 , wherein (B2) corresponds to formula (VI):

wherein: n is an integer of 2 to 4; m is independently an integer of 1 to 5; Z represents an aliphatic residue; R1 and R2 represent organic groups that are inert to isocyanate groups under reaction conditions and that may be the same or different organic groups; and R3 independently represents a Ci-Ce alkyl residue.

9. The two-component coating system of claim 8, wherein (B2) has the formula:

wherein x, y, and z are independently an integer of 1 to 5 and x+y+z is an integer of 3 to

15.

10. The two-component coating system of claim 9, wherein the polyetheraspartic ester is present in component (B) in an amount of 10 to 50 percent by weight, based on the total weight of reactants in component (B).

11. The two-component coating system of claim 10, wherein the polyetheraspartic ester is present in component (B) in an amount of 15 to 30 percent by weight, based on the total weight of reactants in component (B).

12. The two-component coating system of claim 1 , wherein (B) further comprises (B3) an aliphatic imine.

13. A two-component coating system comprising:

(A) a first component comprising a polyisocyanate; and

(B) a second component comprising:

(B1 a) polyaspartic ester having the formula (IV):

(B1b) a polyaspartic ester having the formula (V):

nd

of 3 to 15, wherein (A), (B1 a), (B1 b) and (B2), and their respective amounts, are selected so as to provide a two-component coating system that, when (A) and (B) are mixed:

(i) forms a coating composition having a solids content of at least 70% by weight, based on the total weight of the mixture,

(ii) has a pot life of at least 25 minutes; and

(iii) after application of the mixture to a substrate, the mixture has a set-to- touch time of at least 40 minutes and a hard dry time of no more than 130 minutes.

14. The two-component coating system of claim 13, wherein the coating composition has a solids content of at least 80 percent by weight and a pot life of at least 30 minutes.

15. The two-component coating system of claim 13, wherein the relative weight ratio the polyaspartic ester of formula (IV) to the polyaspartic ester of formula (V) is 1 :2 to

2:1

16. The two-component coating system of claim 15, wherein the relative weight ratio the polyaspartic ester of formula (IV) to the polyaspartic ester of formula (V) is 1 :1.2 to 1.2:1.

17. The two-component coating system of claim 13, wherein:

(i) the polyaspartic ester of formula (IV) is present in component (B) in an amount of 1 to 40 percent by weight, based on the total weight of reactants in component (B); and

(ii) the polyaspartic ester of formula (V) is present in component (B) in an amount of 30 to 50 percent by weight, based on the total weight of reactants in component (B).

18. The two-component coating system of claim 17, wherein the polyetheraspartic ester is present in component (B) in an amount of 10 to 50 percent by weight, based on the total weight of reactants in component (B).

19. The two-component coating system of claim 18, wherein the polyetheraspartic ester is present in component (B) in an amount of 15 to 30 percent by weight, based on the total weight of reactants in component (B).

20. A two-component coating system comprising:

(A) a first component comprising a polyisocyanate; and

(B) a second component comprising:

(B1 ) 0.1 to 40 percent by weight, based on the total weight of reactants in (B), of a polyaspartic ester having the formula (IV):

(IV);

(B2) 30 to 50 percent by weight, based the total weight of reactants in (B), of a polyaspartic ester having the formula (V):

and

(B3) 10 to 50 percent by weight, based on the total weight of reactants in (B), of a polyetheraspartic ester having the formula:

Description:
POLYASPARTIC COATING COMPOSITIONS

[0001] This specification relates to coating systems and

compositions comprising polyaspartic esters. This specification also relates to improving the curing properties of coating compositions comprising polyaspartic esters.

BACKGROUND OF THE INVENTION

[0002] Two-component coating systems and compositions based on poiyurethanes and/or polyureas are widely used in industry because of the many advantageous properties exhibited by these coating chemistries. Two-component coating systems generally comprise a liquid binder component and a liquid hardner/crosslinker component. The liquid binder component may comprise an isocyanate-reactive component such as a polyol and/or a polyamine, and the liquid crosslinker component may comprise a polyisocyanate component. The addition reaction of the polyisocyanate component with the isocyanate-reactive component, produces highly crosslinked polyurea and/or polyurethane networks that form coating films when applied to substrates.

[0003] The reaction of polyisocyanates with polyamines results in highly crosslinked polyurea coatings that exhibit excellent mechanical and chemical resistance properties (e.g., abrasion, solvent, and weathering resistance). However, primary polyamines and polyisocyanates generally react together very rapidly to produce polyureas. Often, therefore, typical pot lives or gel times of two-component polyurea coating compositions are only between several seconds and a few minutes. Thus, polyurea coatings often cannot be applied manually, but must be applied using specialized spray equipment that accurately meters and mixes the binder and crosslinker components immediately before spray application.

[0004] Thus, it would be desirable to provide two-component polyurea coating compositions that exhibit relatively high solids level (for environmental and cost reasons, for example), good workability, which is a combination of a pot life of significantly more than a few minutes, a relatively long set-to-touch time and a relatively short hard dry time. It would also be desirable if certain of these coatings are weatherable.

SUMMARY OF THE INVENTION

[0005] In some respects, the invention is directed to two-component coating systems comprising: (A) a first component comprising a

polyisocyanate; and (B) a second component comprising (B1) a

polyaspartic ester and (B2) a poiyetheraspartic ester. The two-component coating system, when (A) and (B) are mixed, (i) forms a coating

composition having a solids content of at least 70% by weight, based on the total weight of the mixture, (ii) has a pot life of at least 25 minutes, and (iii) after application of the mixture to a substrate, the mixture has a set-to- touch time of at least 40 minutes and a hard dry time of no more than 130 minutes.

[0006] In other respects, the present invention is directed to two- component coating systems that comprise: (A) a first component comprising a polyisocyanate; and (B) a second component comprising: (B1a) a polyaspartic ester having the formula:

; (B1 b) a polyaspartic ester having the formula:

in which x, y, and z are independently an integer of 1 to 5 and x+y+z is an integer of 3 to 15. The two-component coating system, when (A) and (B) are mixed, (i) forms a coating composition having a solids content of at least 70% by weight, based on the total weight of the mixture, (ii) has a pot life of at least 25 minutes; and (iii) after application of the mixture to a substrate, the mixture has a set-to-touch time of at least 40 minutes and a hard dry time of no more than 130 minutes.

[0007] In still other respects, the present invention is directed to two-component coating systems that comprise: (A) a first component comprising a polyisocyanate; and (B) a second component comprising: (B1 a) 0.1 to 40 percent by weight, based on the total weight of reactants in (B), of a polyaspartic ester having the formula:

; (B1 b) 30 to 50 percent by weight, based on the total weigf of reactants in (B), of a polyaspartic ester having the formula:

; and (B2) 10 to 50 percent by weight, based on the total weight of

in which x, y, and z are independently an integer of 1 to 5 and x+y+z is an integer of 3 to 15. [0008] It is understood that the invention disclosed and described in this specification is not limited to the embodiments summarized in this Summary. The reader will appreciate the foregoing details, as well as others, upon considering the following detailed description of various non- limiting and non-exhaustive embodiments according to this specification.

DETAILED DESCRSPTIQM

[0009] Various embodiments are described and illustrated in this specification to provide an overall understanding of the structure, function, properties, and use of the disclosed coating compositions and applied coatings. It is understood that the various embodiments described and illustrated in this specification are non-limiting and non-exhaustive. Thus, the invention is not limited by the description of the various non-limiting and non-exhaustive embodiments disclosed in this specification. The features and characteristics described in connection with various embodiments may be combined with the features and characteristics of other embodiments. Such modifications and variations are intended to be included within the scope of this specification. As such, the claims may be amended to recite any features or characteristics expressly or inherently described in, or otherwise expressly or inherently supported by, this specification. Further, Applicant(s) reserve the right to amend the claims to affirmatively disclaim features or characteristics that may be present in the prior art. Therefore, any such amendments comply with the requirements of 35 U.S.C. § 1 12, first paragraph, and 35 U.S.C. § 132(a). The various embodiments disclosed and described in this specification can comprise, consist of, or consist essentially of the features and characteristics as variously described herein.

[0010] Any patent, publication, or other disclosure material identified herein is incorporated by reference into this specification in its entirety unless otherwise indicated, but only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material expressly set forth in this specification. As such, and to the extent necessary, the express disclosure as 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 which conflicts with existing definitions, statements, or other disclosure material set forth herein, is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material. Applicant reserves the right to amend this specification to expressly recite any subject matter, or portion thereof, incorporated by reference herein.

[0011] In this specification, other than where otherwise indicated, all numerical parameters are to be understood as being prefaced and modified in all instances by the term "about", in which the numerical parameters possess the inherent variability characteristic of the underlying

measurement techniques used to determine the numerical value of the parameter. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter described in the present description should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0012] Also, any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of "1.0 to 10.0" is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include ail higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification such that amending to expressly recite any such subranges would comply with the requirements of 35 U.S.C. § 1 12, first paragraph, and 35 U.S.C. § 132(a).

[0013] The grammatical articles "one", "a", "an", and "the", as used in this specification, are intended to include "at least one" or "one or more", unless otherwise indicated. Thus, the articles are used in this specification to refer to one or more than one (i.e., to "at least one") of the grammatical objects of the article. By way of example, "a component" means one or more components, and thus, possibly, more than one component is contemplated and may be employed or used in an implementation of the described embodiments. Further, 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.

[0014] A problem with prior two-component polyurea coating systems and compositions is that the combined liquid coating compositions can rapidly gel and cure, which severely limits pot life. Aliphatic primary poiyamines, for example, generally react too rapidly with polyisocyanates to be formulated into a two-component coating system of acceptable

commercial value. However, efforts to decrease the crossiinking rate of the polyisocyanates and poiyamines that form polyurea coatings, thereby increasing the pot life of the mixed coating composition, also tend to simultaneously increase the cure time of a coating film applied to a substrate. The present inventors unexpectedly discovered that certain mixtures comprising one or more polyaspartic esters and one or more polyetheraspartic esters can be crosslinked with polyisocyanates while . simultaneously exhibiting a relatively long pot life, a relatively long set-to- touch time, and a relatively short cure time.

[0015] Polyaspartic esters are sterically hindered secondary poiyamines that react slower with polyisocyanates than primary poiyamines. The controlled reactivity of polyaspartic esters is believed to be due to the sterically hindered environment of the secondary amine groups, which are located in a beta position relative to an ester carbonyl, and due to potential hydrogen bonding between the secondary amine groups and the ester carbonyl. Polyaspartic esters may be prepared by the Michael addition reaction of polyamines with dialkyl maleate. Like polyaspartic esters, polyetheraspartic esters are sterically hindered secondary polyamines. Polyetheraspartic esters may be prepared by the Michael addition reaction of polyetheramines with dialkyl maleate.

[0016] The present inventors unexpectedly discovered that the addition of a polyetheraspartic ester to a binder component of certain two- component polyurea coating systems (the binder component also comprising a polyaspartic ester) can, in some cases, provide coating compositions that have a relatively high solids content and simultaneously exhibit a relatively long pot life and, when deposited upon a substrate, can exhibit a relatively long set-to-touch time and a relatively short cure time. In particular, in embodiments of the present invention, the coating composition has a solids (i.e., non-volatile) content of at least 70 percent by weight, such as at least 80 percent by weight, or, in some cases, at least 90 percent by weight, or at least 99 percent by weight, based on the total weight of the mixture, (ii) has a pot life of at least 25 minutes, at least 30 minutes, at least 45 minutes, or, in some cases, at least 60 minutes; and (iii) after application of the mixture to a substrate, the mixture has a set-to-touch time of at least 40 minutes, such as at least 45 minutes, or at least 50 minutes, and/or a hard dry time of no more than 130 minutes, such as no more than 120 minutes, or no more than 110 minutes.

[0017] 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 has a viscosity of 2500 cps at 25°C when measured according to ASTM Standard D 7395-07 using a Brookfield R/S Rheometer with a C50-1 spindle. As used herein, "set-to-touch" and "hard dry" refer to the Gardner Circular Drytimes measured according to ASTM D 5895-03 (2008) at 24°C and 50% relative humidity of a 6 mils (dry film thickness) coating deposited on a glass substrates after an acetone wipe.

[0018] As used herein, the term "set-to-touch" refers to the time to achieve Stage A (Test 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, which is incorporated by reference into this specification. As used herein, the term "hard dry" refers to the condition of a liquid coating composition in which a film formed from the coating composition achieves Stage C as defined in ASTM D5895-03 (2008). As used herein, the terms "cure" and "curing" refer to the progression of a liquid coating composition from the liquid state to a cured state. A Stage D drying condition as defined in ASTM D 5895-03 is equivalent to a "dry-through" condition.

[0019] The coating systems and compositions described herein may comprise two-component coating systems and compositions. As used herein, the term "two-component" refers to a coating system or coating composition comprising at least two components that must be stored in separate containers because of their mutual reactivity. For instance, two- component polyurea coating systems and compositions may comprise a hardener/crosslinker component comprising an isocyanate-functional compound, and a separate binder component comprising an amino- functional compound. The two separate components are generally not mixed until shortly before application because of the limited pot life of the mixture. 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.

[0020] As used herein, the term "coating system" refers to a set of chemical components that may be mixed to form an active coating composition that may be applied and cured to form a coating film. As used herein, the term "coating composition" refers to a mixture of chemical components that will cure and form a coating when applied. Accordingly, a coating composition may be formed from a coating system by mixing the chemical components comprising the coating system. Furthermore, when a list of constituents is provided in this specification that are individually suitable for forming the components of the coating system or coating composition described herein, it should be understood that various combinations of two or more of those constituents, combined in a manner that would be known to those of ordinary skill in the art, may be employed and is contemplated.

[0021] Two-component coating systems and compositions comprise at least two mutually reactive compounds, which may be referred to as a binder and a hardener/crosslinker. As used herein, the term "binder" refers to the component of a two-component coating system or

composition that comprises an amino-functional resin. As used herein, the terms "hardener" and "crosslinker" are synonymous and refer to the component of a two-component coating system or composition that comprises a polyisocyanate. For example, in a two-component polyurea coating system or composition, the binder may comprise a polyaspartic ester and/or a polyetheraspartic ester, and the hardener/crosslinker may comprise a polyisocyanate. When mixed, a polyamine binder and a polyisocyanate hardener/crosslinker react to form a crosslinked polymer network with urea linkages.

[0022] As used herein, the term "polyisocyanate" refers to

compounds comprising at least two un-reacted isocyanate groups.

Polyisocyanates include diisocyanates and diisocyanate reaction products comprising, for example, biuret, isocyan urate, uretdione, urethane, urea, iminooxadiazine dione, oxadiazine trione, carbodiimide, acyl urea, allophanate groups, and combinations of any thereof. As used herein, the term "polyamine" refers to compounds comprising at least two free primary and/or secondary amine groups. Polyamines include polymers comprising at least two pendant and/or terminal amine groups.

[0023] The polyisocyanate component (A) may include any of the known polyisocyanates of polyurethane chemistry. Examples of suitable lower molecular weight polyisocyanates (e.g., having a molecular weight of 168 to 300 g/mol) include, but are not limited to, 1 ,4-tetra-methylene diisocyanate; methylpentamethylene diisocyanate; 1 ,6-hexamethylene diisocyanate (HDI); 2,2,4-trimethyl-1 ,6-hexamethylene diisocyanate; 1 , 12- dodecamethylene diisocyanate; cyclohexane-1 ,3- and -1 ,4-diisocyanate; 1 -isocyanato-2-isocyanatomethyl cyclopentane; 1 -isocyanato-3- isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI); bis-(4-isocyanato-cyclohexyl)-methane; 1 ,3- and 1 ,4-bis- (isocyanatomethyl)-cyclohexane; bis-(4-isocyanatocyclo-hexyl)-methane; 2,4'-diisocyanato-dicyclohexyl methane; bis-(4-isocyanato-3-methyl- cyclohexyl)-methane; a,(x,a',a'-tetramethyl-1 ,3- and/or -1 ,4-xylylene diisocyanate; 1 -isocyanato-1 -methyl-4(3)-isocyanatomethyl cyclohexane; 2,4- and/or 2,6-hexahydro-toluylene diisocyanate; 1 ,3- and/or 1 ,4- phenylene diisocyanate; 2,4- and/or 2,6-tolune diisocyanate; 2,4- and/or 4,4'-diphenylmethane diisocyanate (MDI); 1 ,5-diisocyanato naphthalene; and combinations of any thereof.

[0024] In various embodiments, polyisocyanate component (A) may comprise an aliphatic diisocyanate, an aliphatic diisocyanate adduct, or an aliphatic diisocyanate prepolymer. Suitable aliphatic diisocyanates include, for example, hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 2,4'- and/or 4,4'-diisocyanato-dicyclohexyl methane; adducts thereof; and prepolymers comprising residues thereof.

[0025] Additional suitable polyisocyanate components include derivatives of the above-mentioned monomeric diisocyanates. Suitable diisocyanate derivatives include, but are not limited to, polyisocyanates containing biuret groups as described, for example, in U.S. Patent Nos. 3, 124,605 and 3,201 ,372, which are incorporated by reference into this specification. Suitable diisocyanate derivatives also include, but are not limited to, polyisocyanates containing isocyanurate groups (symmetric trimers) as described, for example, in U.S. Patent No. 3,001 ,973, which is incorporated by reference into this specification. Suitable diisocyanate derivatives also include, but are not limited to, polyisocyanates containing urethane groups as described, for example, in U.S. Patent Nos. 3,394,164 and 3,644,457, which are incorporated by reference into this specification. Suitable diisocyanate derivatives also include, but are not limited to, polyisocyanates containing carbodiimide groups as described, for example, in U.S. Patent No. 3, 152,162, which is incorporated by reference into this specification. Suitable diisocyanate derivatives also include, but are not limited to, polyisocyanates containing allophanate groups. Suitable

polyisocyanates also include, but are not limited to, polyisocyanates containing uretdione groups.

[0026] In various embodiments, component (A) may comprise an asymmetric diisocyanate trimer (iminooxadiazine dione ring structure) such as, for example, the asymmetric diisocyanate trimers described in U.S. Patent No. 5,717,091 , which is incorporated by reference into this specification. In various embodiments, component (A) may comprise an asymmetric diisocyanate trimer based on hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); or a combination thereof.

[0027] Isocyanate group-containing prepolymers and oligomers based on polyisocyanates may also be used as the polyisocyanate component (A). Polyisocyanate-functional prepolymers and oligomers may have an

isocyanate content ranging from about 0.5% to 30% by weight, and in some embodiments, about 1 % to 20% by weight, and may be prepared by the reaction of starting materials, such as, for example, isocyanate-reactive compounds such as polyols, at an NCO/OH equivalent number ratio of about 1.05:1 to 10:1 , and in some embodiments, about 1.1 :1 to 3:1.

[0028] Examples of other suitable polyisocyanates that may be used as component (A) alone or in combination with each other, and/or in combination with any of the polyisocyanates described above, include the polyisocyanates described in U.S. Patent Nos. 5,126,170; 5,236,741 ; 5,489,704; 5,243,012; 5,736,604; 6,458,293; 6,833,424; 7,169,876; and in U.S. Patent Publication No. 2006/0247371 , which are incorporated by reference into this

specification.

[0029] The polyaspartic ester component (B1 ) may include one or more polyaspartic esters corresponding to formula (I):

Formula (I)

wherein: n is an integer of 2 to 6; X represents an aliphatic residue; and R 1 and R 2 represent organic groups that are inert to isocyanate groups under reaction conditions and that may be the same or different organic groups.

[0030] In formula (I), the aliphatic residue X may correspond to a straight or branched alkyl and/or cycloalkyl residue of an n-valent polyamine that is reacted with a dialkylmaleate in a Michael addition reaction to produce a polyaspartic ester. For example, the residue X may correspond to an aliphatic residue from an n-valent polyamine including, but not limited to, ethylene diamine; 1 ,2-diaminopropane; 1 ,4-diaminobutane; ,6- diaminohexane; 2,5-diamino-2,5-dimethyihexane; 2,2,4- and/or 2,4,4- trimethyl-1 ,6-diaminohexane; 1 ,1 1 -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; polyether polyamines with aliphatically bound primary amino groups and having a number average molecular weight (M n ) of 148 to 6000 g/mol; isomers of any thereof, and combinations of any thereof.

[0031] In various embodiments, the residue X may be obtained from 1 ,4-diaminobutane; ,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.

[0032] The phrase "inert to isocyanate groups under reaction

conditions," which is used to define groups Ri and R2 in formula (I), means that these groups do not have Zerevitinov-active hydrogens. Zerevitinov- active hydrogen is defined in Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10 th ed., Georg Thieme Verlag Stuttgart, 1996, which is

incorporated by reference into this specification. Generally, groups with Zerevitinov-active hydrogen are understood in the art to mean hydroxy I (OH), amino (NH X ), and thiol (SH) groups. In various embodiments, Ri and R2, independently of one another, are Ci to C10 alkyl residues, such as, for example, methyl, ethyl, or butyl residues.

[0033] In various embodiments, polyaspartic ester component (B1) comprises one or more compounds corresponding to formula (I) in which n is an integer from 2 to 6, in some embodiments n is an integer from 2 to 4, and in some embodiments n is 2. In embodiments, where n=2, polyaspartic ester component (B1 ) may comprise one or more compounds corresponding to formula (II):

Formula (II)

[0034] The polyaspartic ester component (B1 ) may be produced by reacting the corresponding primary polyamines of the formula: with maleic or fumaric acid esters of the formula: R OOC C=C COOR 2

H H

[0035] Examples of suitable polyamines include the above- mentioned diamines. Examples of suitable maleic or fumaric acid esters include dimethyl maleate, diethyl maleate, dibutyl maleate, and the corresponding fumarates.

[0036] The production of the polyaspartic ester component (B1 ) from the above-mentioned polyamine and maleic/fumaric acid ester starting materials may take place within a temperature range of 0°C to 100°C. The starting materials may be used in amounts such that there is at least one equivalent, and in some embodiments approximately one equivalent, of olefinic double bonds in the maleic/fumaric acid esters for each equivalent of primary amino groups in the polyamine. Any starting materials used in excess may, if desired, be separated off by distillation following the reaction. The reaction may take place in the presence or absence of suitable solvents, such as methanol, ethanol, propanol, and/or dioxane.

[0037] In various embodiments, the polyaspartic ester component (B1 ) may comprise a reaction product of two equivalents of diethyl maleate with one equivalent of 1 ,5-diamine-2-methyl-pentane; 4,4'- diaminodicyclohexylmethane; or 3,3'-dimethyl-4,4'- diaminodicyclohexylmethane. These reaction products may have the molecular structures shown in formulas (lll)-(V), respectively:

Formula (Mi)

Formula (IV)

Formula ..(V)

[0038] In various embodiments, the polyaspartic ester component (B1) may comprise a mixture of any two or more polyaspartic esters, and in some embodiments, a mixture of any two of the polyaspartic esters shown in Formulas (lll)-(V), such as a mixture of the two polyaspartic esters shown in Formulas (IV) and (V). The polyaspartic ester component (B1 ) may also comprise a mixture of the three polyaspartic esters shown in Formulas (III)- (V). For example, in some embodiments, the polyaspartic ester component (B1) comprises a mixture comprising the two polyaspartic esters shown in Formulas (IV) and (V), wherein the relative weight ratio the polyaspartic ester shown in Formula (IV) to the polyaspartic ester shown in Formula (V) in the mixture is 1 :90 to 90:1 , such as 1 :10 to 10:1 , 1 :5 to 5:1 , 1 :2: to 2:1 , 1 :1.5: to 1.5:1 or, in some cases 1 :1.2 to 1.2:1.

[0039] In some embodiments of the present invention, the

polyaspartic ester shown in Formula (IV) is present in component (B) in an amount of 0.1 to 40 percent by weight, such as 1 to 40 percent by weight, based on the total weight of reactants in component (B). In some

embodiments, the polyaspartic ester shown in Formula (V) is present in component (B) in an amount of 30 to 50 percent by weight, such as 35 to 45 percent by weight, based on the total weight of reactants in component (B).

[0040] Examples of other suitable polyaspartic esters that may be used as component (B1) alone or in combination with each other, and/or in combination with any of the polyaspartic esters described above, include the polyaspartic esters described in U.S. Patent Nos. 5, 126, 170; 5,236,741 , 5,489,704; 5,243,012; 5,736,604; 6;458;293; 6,833,424; 7,169,876; and in U.S. Patent Publication No. 2006/0247371 , which are incorporated by reference into this specification. In addition, suitable polyaspartic esters are commercially available from Bayer MaterialScience LLC, Pittsburgh, Pennsylvania, USA, under the tradenames Desmophen® NH 1220,

Desmophen® NH 1420, Desmophen® NH 1520, and Desmophen® NH 1521.

[0041] The polyetheraspartic ester component (B2) may include one or more polyetheraspartic esters corresponding to formula (VI): Formula (VI)

wherein: n is an integer of 2 to 4; m is independently an integer of 1 to 5; Z represents an aliphatic residue; R and R 2 represent organic groups that are inert to isocyanate groups under reaction conditions and that may be the same or different organic groups; and R 3 independently represents a Ci-Cs alkyl residue.

[0042] Polyetheraspartic esters suitable for use in component (B2) may be prepared by reaction of a polyol starter molecule (having a hydroxyl-functionality of 2 to 4) with one or more Ci-Ce epoxides to produce a terminal hydroxy-functional polyether (i.e., a polyether polyol having a hydroxyl-functionality of 2 to 4). The terminal hydroxy I groups may be converted to primary amine groups to produce a terminal amino- functional polyether (i.e., a polyether polyamine having a primary amino- functionality of 2 to 4). The polyether polyamine may be reacted with a dialkylmaleate in a Michael addition reaction to produce a

polyetheraspartic ester (having secondary amino-functionality of 2 to 4 and a primary amino-functionality of 0 to 2, depending on the relative

equivalent ratio of dialkylmaleate to primary amino groups in the Michael addition reaction).

[0043] In formula (VI), the aliphatic residue Z may correspond to a straight or branched alkyl and/or cycioalkyi residue of an n-valent polyol that is alkoxylated with a Ci~Ce epoxide to produce a polyether polyol that is converted to a polyether polyamine (i.e., a polyether comprising at least 2 terminal primary amine groups). For example, the residue Z may

correspond to an aliphatic residue from an n-valent polyol such as ethylene diol; 1 ,2-dihydroxypropane; 1 ,4-dihydroxybutane; 1 ,6-dihydroxyhexane; 2,2,4- and/or 2,4,4-trimethyl-1 ,6-dihydroxyhexane; 1 -hydroxy-3,3,5- trimethyl-5-hydroxymethylcyclohexane; 4,4'-dihydroxydicyclohexylmethane; 3,3'-dimethyS-4,4'-dihydroxydicyclohexylmeihane; 1 ,5-dihydroxy-2-methyl- pentane; 1 ,1 ,1 -tris(hydroxymethyl)propane; and 2,2-bis(hydroxymethyl) ,3- propanediol (pentaerythritol).

[0044] In some embodiments, each Z in formula (VI) comprises polyetheramine groups that have reacted with the dialkylmaleate in the Michael addition reaction to produce the polyetheraspartic ester, i.e., in these embodiments, the polyetheraspartic ester has a primary amino- functionality of 0. It is also understood that the aliphatic residue Z in formula (VI) may comprise polyetheramine groups that do not react with the dialkylmaleate in the Michael addition reaction to produce the

polyetheraspartic ester. Such polyetheramine groups may have the following formula: wherein Z' corresponds to the straight or branched alkyl and/or cycloalkyl residue of the original polyol starter molecule (e.g., ethyl, propyl, butyl, hexyl, cyclohexyl, dicyclohexylmethyl, 3,3'-dimethyl-dicyclohexylmethyl, 2- methyl-pentyl, 1 ,1 ,1 -tris(methyl)propyl, or 2,2-bis(methyl)-propyl resides).

[0045] In this manner, a polyetheraspartic ester corresponding to formula (VI) may comprise n secondary amino groups, n dialkylmaleate residues, and s primary amino groups, wherein n is an integer of 2 to 4 and s is 0, 1 , or 2. More specifically, if n is 2, then s is 0, 1 , or 2, if n is 3, then s is 0 or 1 , and if n is 4, then s is 0. Such polyetheraspartic esters may correspond to formula (VII): Formula (VI!)

wherein: n is an integer of 2 to 4; s is 0, 1 , or 2; m is independently an integer of 1 to 5; Z represents an alkyl residue; R 1 and R 2 represent organic groups that are inert to isocyanate groups under reaction conditions and that may be the same or different organic groups; and R 3 independently represents a Ci-Ce alkyl residue.

[0046] Such polyetheraspartic esters may be prepared by

employing the polyether polyamine and dialkylmaleate reactants in relative amounts such that there is at least one, in some cases one, olefinic double bond present for each primary amino group. Alternatively, such

polyetheraspartic esters may be prepared by employing an equivalent excess of primary amine groups relative to the equivalents of

dialkylmaleate in the Michael addition reaction used to produce the polyetheraspartic ester from the polyether polyamine and dialkylmaleate reactants.

[0047] The phrase "inert to isocyanate groups under reaction conditions," which is used to define groups Ri and R2 in formulas (VI) and (VII), means that these groups do not have Zerevitinov-active hydrogens. Zerevitinov-active hydrogen is defined in Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10 th ed., Georg Thieme Verlag Stuttgart, 1996, which is incorporated by reference into this specification. Generally, groups with Zerevitinov-active hydrogen are understood in the art to mean hydroxy I (OH), amino (NHx), and thiol (SH) groups. In various

embodiments, Ri and R2, independently of one another, are Ci to C10 alkyl residues, such as, for example, methyl, ethyl, or butyl residues.

[0048] In formulas (VI) and (VII), the Ci-Ce alkyl residue R 3 may correspond to a straight or branched Ci-Ce alkyl residue of one or more Ci-Ce epoxides used to aikoxyiate an n-valent polyol to produce a polyether polyol that is converted to a polyether polyamine that is reacted with dialkylmaleate to produce a polyetheraspartic ester. Suitable Ci-Ce epoxides include, for example, ethylene oxide, propylene oxide, 1 ,2- butylene oxide, 2,3-butylene oxide, 1 ,2-pentylene oxide, 2,3-pentylene oxide, and the like. Accordingly, Ci-Ce a Iky I residues R 3 may be ethyl residues, propyl residues, butyl residues, pentyl residues, hexyl residues, isomers and/or combinations thereof.

[0049] In formulas (VI) and (VII), m is independently 1 to 5, and R 3 independently represents a Ci-Ce alkyl residue. As used in this context, the term "independently" means that the identity of the alkyl residues R 3 in each nth polyether chain may be the same or different. Likewise, the number m of the alkoxy residues in each nth polyether chain may be the same or different.

[0050] Suitable polyether polyamines that may be reacted with dialkylmaleates in Michael addition reactions produce polyetheraspartic esters for component (B2) include the Jeffamine® polyetheramines commercially available from Huntsman Corporation, The Woodlands, Texas, USA.

[0051] By way of example, and without limitation, a

polyetheraspartic ester corresponding to formula (VII) may be based on a tri-functional polyetheramine having repeating oxypropylene units produced by the propoxylation of 1 ,1 ,1 -tris(hydroxymethyl)propane and conversion to the corresponding tri-amine.

[0052] In some of these embodiments, the resulting polyether polyamine is reacted with diethylmaleate in relative amounts such that there is at least one, in some cases one, olefinic double bond present for each primary amino group to produce a polyetheraspartic ester comprising three secondary amino groups, three diethylmaleate residues, and no primary amino groups. Such a polyetheraspartic ester corresponds to formula (VII) wherein: n is 3; s is 0; m is independently an integer of 1 to 5; T represents a 1 ,1 ,1 -tris(methyl)propyl residue; R 1 and R 2 represent ethyl residues; and R 3 represents isopropyl (1-methylethyl) residues. This

wherein x, y, and z are independently an integer of 1 to 5. In various embodiments, polyetheraspartic ester component (B2) may comprise a polyetheraspartic ester corresponding to formula (VI I -A). In formula (VII- A), x+y+z may be an integer of 3 to 15, and in some embodiments, 4 to 8 or 5 to 6.

[0053] Alternatively, an equivalent of the resulting polyether polyamine may be reacted with two equivalents of diethylmaleate to produce a polyetheraspartic ester comprising two secondary amino groups, two diethylmaleate residues, and one primary amino group. Such a polyetheraspartic ester corresponds to formula (VII) wherein: n is 2; s is 1 ; m is independently an integer of 1 to 5; Z' represents a 1 ,1 ,1- tris(methyl)propyl residue; R 1 and R 2 represent ethyl residues; and R 3 represents isopropyl ( -methyiethy!) residues. This polyetheraspartic ester may correspond to formula (VIII): Mil)

wherein x, y, and z are independently an integer of 1 to 5. In various embodiments, polyetheraspartic ester component (B2) may comprise a polyetheraspartic ester corresponding to formula (VIII). In formula (VIII), x+y+z may be an integer of 3 to 15, and in some embodiments, 4 to 8 or 5 to 6.

[0054] In some embodiments of the present invention, the polyetheraspartic ester, such as the polyetheraspartic ester shown in Formula (Vll-A), is present in component (B) in an amount of 10 to 50 percent by weight, such as 10 to 30, or 15 to 30 percent by weight, based on the total weight of reactants in component (B).

[0055] In addition to a polyisocyanate (A), a polyaspartic ester (B1), and a polyetheraspartic ester (B2), the two-component coating systems and compositions described in this specification may also comprise (B3) an aliphatic imine. Suitable aliphatic imines may have at least two structural units per molecule corresponding to formula (IX): FormuSg (IX|

[0056] These optional components with capped amino functions, which are referred in this specification as polyaldimines and polyketimines, may have a molecular weight M n of 112 g/mol to 6500 g/mol, in some embodiments 140 g/mol to 2500 g/mol, and in some embodiments 140 g/mol to 458 g/mol. If the molecular weight cannot readily be determined as the sum of the atomic weights of the individual elements, it may, for example, be calculated from the functionality and the content of functional groups (established, for example, by determining the primary amino groups present after hydrolysis) or, in the case of higher molecular weight compounds, it may be determined by gel permeation chromatography using polystyrene as the standard.

[0057] The polyaldimines and polyketimines suitable for use in the coating systems and compositions disclosed in this specification may include compounds corresponding to formula (X):

Formula (X)

wherein: R 4 and R 5 are the same or different and represent hydrogen or a hydrocarbon group with up to 20 carbon atoms, or R 4 and R 5 form a 5- membered or 6-membered cycloaliphatic ring together with the carbon atom, R 6 is a (p+1 )-valent residue obtained by removing the primary amino groups from a corresponding polyamine optionally containing oxygen and/or nitrogen atoms, and p is an integer from 1 to 3. R 4 and R 5 , independently of one another, may be alkyl residues with 1 to 8 carbon atoms. The polyamine from which R 6 is obtained may have a number- average molecular weight Mn of 88 g/mol to 2000 g/mol.

[0058] In various embodiments, an imine component (B3) may comprise one or more compounds of formula (X) in which all R 4 groups represent hydrogen, all R 5 groups represent a hydrocarbon residue with up to 8 carbon atoms, and p=1.

[0059] The aldehydes and ketones that may be used for the production of the polyaldimines and polyketimines, respectively, may correspond to formula (XI):

Formula (XI)

and may have a molecular weight of 44 g/mol to 128 g/mol (aldehydes) and 58 g/mol to 198 g/mol (ketones).

[0060] Suitable aldehydes include, for example, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde,

trimethylacetaldehyde, 2,2-dimethylpropanal, 2-ethylhexanal, 3- cyclohexane-1 -carboxaldehyde, hexanal, heptanal, octanal,

valeraldehyde, benzaldehyde, tetrahydrobenzaldehyde,

hexahydrobenzaldehyde, propargyl-aldehyde, p-toluylaldehyde, phenylethanal, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, sorbinaldehyde, and combinations of any thereof.

[0061] Suitable ketones include, for example, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, methyl heptyl ketone, methyl undecyl ketone, diethyl ketone, ethyl butyl ketone, ethyl amyl ketone, diisopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methylcyclohexanone, isophorone, 5-methyl-3-heptanone, 1-phenyl-2- propanone, acetophenone, methyl nonyl ketone, dinonyl ketone, 3,3,5- trimethylcyclohexanone, and combinations of any thereof.

[0062] Mixtures of different ketones or aldehydes, as well as mixtures of ketones with aldehydes may also be used.

[0063] The polyamines used in the production of the polyaldimines and polyketimines are organic compounds having at least two, and in some embodiments 2 (p=1 ), aliphatically and/or cycloaliphatically bound primary amino groups. The polyamines generally have a number average molecular weight of 60 g/mol to 6,000 g/mol, in some embodiments 88 g/mol to 2000 g/mol, and in some embodiments 88 g/mol to 238 g/mol. Suitable polyamines for the production of the polyaldimines and

polyketimines include the compounds previously mentioned for preparing polyaspartic esters (B1 ). Different polyamines can be used for the production of polyaspartic esters (B1 ) and the optional polyaldimines and polyketimines (B3), respectively.

[0064] The production of the polyaldimines and polyketimines may take place by reacting the starting components while maintaining a stoichiometric ratio of amino groups to aldehyde or keto groups of 1 :1 to 1 : 1.5. To accelerate the reaction, catalytic quantities of acidic substances, such as, for example, p-to!uenesulfonic acid, hydrogen chloride, sulfuric acid, or aluminum chloride, can be incorporated.

[0065] The reaction generally takes place within the temperature range of 20°C to 180°C, and is optionally carried out using an entrainer (e.g. toluene, xylene, cyclohexane, and/or octane) to remove the water of reaction until the calculated quantity of water (1 mole of water per mole of primary amino group) has been eliminated or until no more water is eliminated. The phases may then be separated or the entrainer and any un-reacted compounds present may be removed by distillation. The products thus obtained may be used together with components (B1 ) and (B2) without any further purification. [0066] When polyaldimines and/or polyketimines are incorporated together with the aspartic esters, the weight ratio of aspartic esters

(B1 +B2) to the optional aliphatic imine (B3) may be 99: 1 to 5:95, such as 80:20 to 20:80. In certain embodiments, the aliphatic imine (B3) is included in component (B) in an amount of up to 10 percent by weight, such as up to 5 percent by weight, or in some cases, 4 to 5 percent by weight, based on the total weight of reactants in component (B).

[0067] In certain embodiments, the sum of (B1 ), (B2) and (B3) is 100% of the reactants in component (B).

[0068] The two-component coating systems or compositions described in this specification may comprise conventional auxiliary agents or additives appropriate for the system or composition end use. For example, auxiliary agents or additives may include, but are not limited to, defoamers, rheology modifiers (e.g., thickeners), leveling agents, flow promoters, pigments, dispersing agents, catalysts, anti-skinning agents, anti-sedimentation agents, and/or emulsifiers.

[0069] The two-component coating systems or compositions may further comprise organic solvents. Such solvents are known to those skilled in the art.

[0070] The two-component coating systems disclosed and described in this specification may be formulated by preparing a

crosslinker component comprising the polyisocyanate (A) and by preparing a separate binder component comprising the polyaspartic ester (B1 ), the polyetheraspartic ester (B2), and, optionally, an aliphatic imine (B3). The crosslinker component and the binder component of the two-component coating systems are mixed together to form the two-component coating compositions, which may be applied to a substrate as a coating film and cured to form a coating.

[0071] The two-component coating systems and compositions described in this specification may be formulated so that the isocyanate-to- amine (NCO:NH x ) ratio of the polyisocyanate component (A) to the amino- functional components (B1), (B2), and optionally (B3) is 1 :5 to 5:1 , and in some embodiments, 1 :3 to 3:1 , 1 :2 to 2:1 , 1 :1.5 to 1 .5:1 , 0.5: 1 to 5:1 , 1.5:1 to 3:1 , or 1 :1 to 1.5:1. The two-component coating systems and

compositions described in this specification may be formulated so that an approximately 1 :1 mixture by volume of a crosslinker component comprising polyisocyanate (A) and binder component comprising the amino-functional components (B1 ), (B2), and optionally (B3), forms a coating composition having an NCO:NHx ratio as described above, for example, in some embodiments 1 :1 , and in other embodiments, ranging from 1 :1 to 1.5:1 or 1 :1 to 1.3:1.

[0072] The coating compositions may be applied onto surfaces using various techniques, such as spraying, dipping, flow coating, rolling, brushing, pouring, squeegeeing and the like. Any solvents present in the applied coating evaporate and the coatings cure and harden due to the urea-forming crosslinking reactions between the polyisocyanate and the amino-functional components. The crosslinking reactions may occur under ambient conditions or at higher temperatures of, for example, 40°C to 200°C.

[0073] The coating compositions can be applied onto any

compatible substrate, such as, for example, metals, plastics, ceramics, glass, concrete, and other organic or inorganic materials or natural materials, and to substrates that have been subjected to any pre-treatment that may be desirable.

[0074] The non-limiting and non-exhaustive examples that follow are intended to further describe various non-limiting and non-exhaustive embodiments without restricting the scope of the embodiments described in this specification.

EXAMPLES

[0075] Unless otherwise specified, all percentages are to be understood as being percentages by weight. [0076] A polyetheraspartic ester was prepared by the Michael addition reaction of diethylmaleate with Jeffamine® T-403 (an aliphatic tri- functional polyether polyamine containing oxypropylene units available from Huntsman Corporation) using the reactants in such proportions that one olefinic double bond was present for each primary amino group. The Michael addition reaction was carried out by charging the Jeffamine® T- 403 to a stirred vessel under nitrogen, slowly charging diethylmaleate to the vessel so as to maintain the exotherm at less than 50°C, and

maintaining the reaction mixture at 53°C for approximately 18 hours. The resulting polyetheraspartic ester had a stabilized viscosity of 250 to 400 millipascals at 25°C after aging for 6-8 weeks.

[0077] Two commercially available polyaspartic esters were used for comparative purposes: Desmophen® NH 1420 and Desmophen® NH 1520, Bayer MaterialScience LLC. Desmophen® NH 1420 is obtained by the Michael addition of one molar equivalent of 4,4'- diaminodicyc!ohexylmethane and two molar equivalents of diethyl maleate. Desmophen® NH 1520 is obtained by the Michael addition of one molar equivalent of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and two molar equivalents of diethyl maleate. Desmophen® NH 1420 has a stabilized viscosity of 900 to 2,000 millipascals at 25°C after aging for 6-8 weeks, and Desmophen® NH 1520 has a stabilized viscosity of 800 to 2,000 millipascals at 25°C after aging for 16-18 weeks.

.Example.2:

[0078] The polyetheraspartic ester prepared in accordance with

Example- 1 was used to formulate a 100 g/L VOC two-component coating system. Comparative two-component coating systems are formulated with Desmophen® NH 1420, Desmophen® NH 520, and a 33/67 weight percent blend of Desmophen® NH 1420 and Desmophen® NH 1520, respectively, for comparative purposes. The formulations are presented in Table 1 (parts by weight).

Table 1

* Desmophen® XP 7076 is a polyaldimine prepared by the addition of 2 molar equivalents of isobutyraldehyde (2-methylpropanal) to 1 molar equivalent of 5-amino-1 -aminomethyl- ,3,3-trimethyl- cyclohexane (isophorone diamine, IPDA).

[0079] The pot life of the formulations was evaluated by measuring viscosity (in cPs) according to ASTM Standard D 7395-07 using a

Brookfield R/S Rheometer at 25 °C with a C50-1 spindle as a function of time. The results are presented in Table 2.

[0080] The cure time of the coating compositions was evaluated I measuring the Gardner dry times of the formulations at approximately 70°F to 72°F and 25% and 50% relative humidity (RH). The results are presented in Table 3.

Table 3

This dry time was measured at 71 °F and 40% RH.

[0081] The time-dependent viscosity and, therefore, the pot life of the coating composition formulated with the polyetheraspartic ester was similar to that of the coating composition formulated with the 33/67 weight percent blend of Desmophen® NH 1420 and Desmophen® NH 1520. However, as shown in Table 3, the cure times of the coating composition formulated with the polyetheraspartic ester were substantially and significantly less than the cure times of the coating composition formulated with the 33/67 weight percent blend of Desmophen® NH 1420 and

Desmophen® NH 1520. Accordingly, coating compositions comprising the polyetheraspartic ester may exhibit substantially and significantly decreased cure time while maintaining relatively long pot lives.

Examples 3A-3C:

[0082] The polyetheraspartic ester prepared in accordance with Example-1 was used in admixture with either Desmophen® NH 1420 and Desmophen® NH 520 or both to formulate various two-component coating systems. The formulations and results are shown below (weights in grams).

Table 3 - Exam le 3A

Total 50.00 j 5.63 45.32 5.03

Theoretical Results

Weight Solids 90.65 Wt/Gal 8.87

Volume Solids 89.34 Mix Ratio (volume) 1.90:1

P/B 0 NCO:NH 1.05

PVC 0 Theoretical VOC 0.83 Table 4 - Example 3B

Total " soToo : 5.71 40.53 " 4.50

Theoretical Results

: Weight Solids 81.05 Wt/Gal 8.76

Volume Solids 78.86 Mix Ratio (volume) 2.28: 1

P/B 0 NCO:NH 1.05

PVC 0 Theoretical VOC 1.66

Table 5 - Example 3C

Raw Material Weight Volume Weight Solids Volume Solids

Component 1

Desmophen NH 1420 88.72 10.08 88.72 10.08

Desmophen NH 1520 124.21 14.11 124.21 14,11

Polyetheraspartic Ester 106.46 TZ06 106.46 12.06

Desmophen® XP 7076 35.49 4.89 35.49 4.89

Byk-306 2.59 0.34 0.32 0.04

Byk-A 530 6.04 0 90 0.30 0.01

Eastman EEP Solvent 251.02 31.69 0 0

Subtotal 614.52 ' 74.07 355.50 41.19

Component 2

Desmodur N-39 " 248.89 25.93 248.89 25.93

Subtotal 248.89 25.93 248 89 25.93

' Total " " 863 ~ 4Ϊ 100.00 604.39 67.12

Theoretical Results

Weight Solids 70.00 Wt/Gal 8.63

Volume Solids 67.12 Mix Ratio (volume) 2.86: 1

P/B 0 NCO:NH 1.05

PVC 0 Theoretical VOC 2.59

Table 6 - Results

[0083] The results below show the viscosity (in cPs) according to ASTM Standard D 7395-07 using a Brookfield R/S Rheometer at 25°C with a C50-1 spindle as a function of time.

Example 4

[0084] A polyetheraspartic ester was prepared by the Michael addition

reaction of diethyimaleate with Jeffamine® T-403 (an aliphatic tri-functional polyether polyamine containing oxypropylene units available from Huntsman Corporation) using the reactants in such proportions so that there was a 1.00:1.01 ratio of amine equivalents to diethyl maleate. The Michael addition reaction was carried out by charging the Jeffamine® T-403 to a stirred vessel under nitrogen, slowly charging diethyimaleate to the vessel so as to maintain the exotherm at less than 50 °C, and maintaining the reaction mixture at around 50°C for approximately 6 hours. The resulting polyetheraspartic ester had a stabilized viscosity of 250 to 400 millipascals at 25°C after aging for 6-8 weeks.

Examples 5A - SAO

[0085] Coating compositions were preparing by mixing the ingredients of Component 1 in a 250 ml_ plastic container using the amounts (in grams) listed in Table 7. The mixture was mixed using a FlackTek spin mixer for 2 minutes at 2,300 rpm. Then, Component 2 was added to the mixture and mixed using a FlackTek spin mixer for 30 seconds at 2,300 rpm.

[0086] The pot-life of the mixtures was determined based on the viscosities of the formulations according to ASTM Standard D 7395-07 using a Brookfield R/S Rheometer at 25°C with a C50-1 spindle. The minutes that it took for the viscosity to reach 2,500 cPs was determined to be the pot-life of the formulation.

[0087] The compositions were drawn down on glass substrates after an acetone wipe. The thicknesses of the compositions were adjusted to 6 mils (dry film thickness). The Gardner Circular Drytimes (set-to-touch and hard-dry) were measured according to ASTM D 5895 at 24°C and 50% relative humidity.

[0088] Results are set forth in Table 7.

Table 7

3 Blocked diamine, Evonik Industries

4 Surface additive, BYK USA Inc.

5 Defoamer, BYK USA Inc.

6 Low-viscosity, aliphatic polyisocyanate resin based on hexamethylene Diisocyanate, Bayer MaterialScience LLC TabSe 7 (continued)

TabSe 7 (continued)

Table 7 (continued)

Tabe ? (coritSriuf d)

Ta fa Se 7 (conti n ued

[0089] This specification has been written with reference to various non-limiting and non-exhaustive embodiments. However, it will be recognized by persons having ordinary skill in the art that various substitutions, modifications, or combinations of any of the disclosed embodiments (or portions thereof) may be made within the scope of this specification. Thus, it is contemplated and understood that this specification supports additional embodiments not expressly set forth herein. Such embodiments may be obtained, for example, by combining, modifying, or reorganizing any of the disclosed steps, components, elements, features, aspects, characteristics, limitations, and the like, of the various non-limiting embodiments described in this speelicaiien. l : n this manner, . plicant's) reserve the right to amend the cfaims during prosecutio to add . ' features as variousiy described ir> this specification, and such amendments omply with the

requirements of 3§ U. c. 112, first paragraph, and 35 IXS.G, § 132(a).




 
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