Silicone-modified polyurea coating compositions

Abstract

Coating compositions may combine durability with reduced environmental emissions and health risks. A coating composition may comprise an isocyanate component, an amine-functional resin comprising an aspartic amine, a reactive silicone component having a molecular weight of at least of 500 amu, a pre-polymer comprising silicone and including primary amine terminal groups, an organometallic catalyst, and a difunctional, trifunctional, or tetrafunctional chain extender.

Description

SILICONE-MODIFIED POLYUREA COATING COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of United States Provisional Patent Application No. 63 / 607,370, filed December 7, 2023, the entirety of which is incorporated herein by reference.FIELD

[0002] Described herein are coating compositions for applying to a substrate and methods of coating substrates.BACKGROUND

[0003] Precast concrete, prefabricated construction components, turbine blades, marine components, fiber and fiberglass composites, and the like may be susceptible to damage such as cracking and chipping due to the brittle nature of some polymeric materials used in one or more layers of the substrate. The appearance of substrates made from conventional polymeric materials may stain or otherwise be diminished from exposure to chemical materials and environmental conditions.SUMMARY

[0004] The present disclosure is directed to coating compositions. A coating composition may comprise an isocyanate component; an amine-functional resin comprising an aspartic acid ester; a reactive silicone component having a molecular weight of at least 500 amu; optionally, TiCh; a pre-polymer comprising silicone and primary amine terminal groups; an organometallic catalyst; and a difunctional, trifunctional, or tetrafunctional chain extender.

[0005] A coating composition may comprise an isocyanate component; and a mixture comprising: a B-pack for a polyurea coating comprising an amine compound and a hydroxyl compound; a pre-polymer comprising silicone and primary amine terminal groups; an organometallic catalyst; and a difunctional, trifunctional, or tetrafunctional chain extender.

[0006] Also disclosed are methods of making a coating composition and methods of applying a coating composition. A method of making a coating composition may comprise combining a B-pack for a polyurea coating comprising an amine compound and a hydroxylcompound, a pre-polymer comprising silicone and primary amine terminal groups, an organometallic catalyst, and a difunctional chain extender to form a first mixture; and adding an isocyanate component to the first mixture; and combining the first mixture and isocyanate component to produce the coating composition.

[0007] A coating composition may comprise an isocyanate component; an amine-functional resin comprising an aspartic amine; a reactive silicone component having a molecular weight of at least of 500 amu; TiCh; a cure retardant in an amount of at least 5 wt. %; a solvent in an amount of up to 20 wt. %; and a rheology modifier in an amount of up to 15 wt. %.

[0008] The present disclosure is further directed to methods for coating a substrate. A method may comprise applying to at least a portion of the substrate a coating composition described herein.DETAILED DESCRIPTION

[0009] Provided herein are coating compositions and methods that can be applied to substrates for improved performance. The present disclosure relates to polyurea coating compositions that can combine durability and stain resistance with reduced environmental emissions and health risks. Unlike conventional unsaturated polyester coatings, the coating compositions described herein may be free of peroxide and free of volatile organic chemicals (VOCs). In some cases, the coating compositions described herein can form quickly and enable application using automated processes, which can result in lower costs and improved product quality.

[0010] Conventional coatings such as polyester and epoxy coatings can have poor impact resistance, experience high levels of shrinkage, and / or fail to prevent or minimize staining. The polyurea coating compositions described herein may demonstrate extended durability and desirable properties such as stain resistance, impact resistance, and low shrinkage, while providing a high gloss finish with UV protection. The stain resistance may provide an easy to clean coating surface.

[0011] Described herein are polyurea coating compositions that may comprise an isocyanate component; an amine-functional resin comprising an aspartic acid ester; a reactive silicone component having a molecular weight of at least 500 amu; TiCh; a pre-polymer comprisingsilicone and primary amine terminal groups, an organometallic catalyst; and a difunctional, trifunctional, or tetrafunctional chain extender.

[0012] The coating compositions may further comprise a reactive diluent. The coating compositions may further comprise a non-reactive surface additive. The coating compositions may have an equivalent weight ratio of the isocyanate component to the active hydrogen of the amine-functional resin that ranges from 0.85:1 to 1.4:1. The amine-functional resin may comprise a primary and / or secondary amine. The amine-functional resin may comprise an aromatic amine or an aliphatic amine. The isocyanate component may comprise a prepolymer formed from hexamethylene diisocyanate, isophorone diisocyanate, or both, and a polyether polyol and / or polyetheramine. The coating compositions may be 2K, with the isocyanate component separated from the amine-functional resin until ready to be applied to a substrate. The coating composition may be a gelcoat.

[0013] The coating compositions described herein may comprise an amine-functional resin comprising an aspartic acid ester. The coating compositions may comprise an amine-hydroxyl- functional resin. Suitable polyamines are numerous and can vary widely. Such polyamines can include those that are known in the art. Non-limiting examples of suitable polyamines can comprise but are not limited to primary and secondary amines, and mixtures thereof, such as any of those listed herein. Amine terminated polyureas may also be used. Amines comprising a hydroxyl group may be included. Amines comprising tertiary amine functionality can be used provided that the amine further comprises at least two primary and / or secondary amino groups. In some cases, the isocyanate functional prepolymer may comprise a polyamine and the ratio of equivalents of isocyanate groups (NCOs) to equivalents of amine groups (NHs) and any hydroxyl groups (OHs) can be greater than 0.85. In some cases, the isocyanate functional prepolymer may comprise a polyamine and the ratio of equivalents of isocyanate groups (NCOs) to equivalents of amine groups (NHs) can be greater than 1.

[0014] The amine may include, for example, monoamines, or polyamines having at least two functional groups such as di-, tri-, or higher functional amines; and mixtures thereof. The amine may be aromatic or aliphatic such as cycloaliphatic, or mixtures thereof. Non-limiting examples of suitable monoamines can include aliphatic polyamines such as, but not limited to, ethylamine, isomeric propylamines, butylamines, pentylamines, hexylamines, cyclohexylamine, and benzylamine. Suitable primary polyamines include, but are not limited to, ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3 -diaminopentane (DYTEK® EP, Invista), 1,6- diaminohexane, 2-methy 1-1, 5 -pentane diamine (DYTEK® A, Invista), 2,5-diamino-2,5- dimethylhexane, 2,2,4- and / or 2,4, 4-trimethyl-l,6-diamino-hexane, 1,11 -diaminoundecane, 1,12- diaminododecane, 1,3- and / or 1,4-cyclohexane diamine, l-amino-3,3,5-trimethyl-5- aminomethyl-cyclohexane, 2,4- and / or 2,6-hexahydrotoluoylene diamine, 2,4'- diaminodicyclohexyl methane, 4,4'-diaminodicyclohexyl methane (PACM-20, Air Products) and 3,3'-dialkyl-4,4'-diaminodicyclohexyl methanes (such as 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane (DIMETHYL DICYKAN or LAROMIN® C260, BASF; ANCAMINE® 2049, Air Products) and 3,3'-diethyl-4,4'-diaminodicyclohexyl methane), 2,4- and / or 2,6-diaminotoluene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5-dimethylthio-2,4- toluenediamine, 3,5-dimethylthio-2,4-toluenediamine, 2,4'- and / or 4,4'-diaminodiphenyl methane, dipropylene triamine, bis hexamethylene triamine, or combinations thereof.Polyoxyalkyleneamines are also suitable. Polyoxyalkyleneamines comprise two of more primary or secondary amino groups attached to a backbone, derived, for example, from propylene oxide, ethylene oxide, butylene oxide or a mixture thereof. Examples of such amines include those available under the designation JEFF AMINE®, such as, without limitation, JEFF AMINE® D- 230, D-400, D-2000, HK-511, ED-600, ED-900, ED-2003, T-403, T-3000, T-5000, SD-231, SD- 401, SD-2001, and ST-404 (Huntsman Corporation). Such amines may have an approximate molecular weight ranging from 200 to 7500.

[0015] Secondary cycloaliphatic diamines may also be used in the coating composition described herein. Suitable cycloaliphatic diamines include, without limitation, JEFFLINK® 754 (Huntsman Corporation), CLEARLINK® 1000 (Dorf-Ketal Chemicals, LLC), and aspartic ester functional amines, such as those available under the name DESMOPHEN® such as DESMOPHEN® NH1220, DESMOPHEN® NH 1420, and DESMOPHEN® NH 1520 (Covestro LLC, Pittsburgh, PA). Other suitable secondary amines include the reaction products of materials comprising primary amine functionality, such as those described herein, with acrylonitrile. For example, the secondary amine can be the reaction product of 4,4'- diaminodicyclohexylmethane and acrylonitrile. Alternatively, the secondary amine can be the reaction product of isophorone diamine and acrylonitrile, such as POLYCLEAR™ 136 (available from BASF / Hanson Group LLC).

[0016] The coating composition may comprise a B-pack for a polyurea coating, where the B- pack comprises an amine compound and a hydroxyl compound. A pre-polymer comprising silicone and primary amine terminal groups, an organometallic catalyst, and a difunctional, trifunctional, or tetrafunctional chain extender may be added to the commercially available B- pack component.

[0017] The coating compositions described herein may comprise an isocyanate component. As used herein, the term “isocyanate” includes unblocked isocyanate compounds capable of forming a covalent bond with a reactive group such as a hydroxyl, thiol or amine functional group. Thus, isocyanate can refer to “free isocyanate”, which will be understood to those skilled in the art. The isocyanate may be monofunctional (containing one isocyanate functional group (NCO)). The isocyanate may be polyfunctional (containing two or more isocyanate functional groups (NCOs)). The isocyanate may be blocked. Combinations of any isocyanates and / or isocyanate functional prepolymers can be used in the coating compositions described herein.

[0018] Suitable isocyanates are numerous and can vary widely. Such isocyanates can include those that are known in the art. Non-limiting examples of suitable isocyanates can include monomeric and / or polymeric isocyanates. The isocyanates can be selected from monomers, prepolymers, oligomers, or blends thereof. The isocyanate may be C2-C20 linear, branched, cyclic, aromatic, aliphatic, or combinations thereof.

[0019] Suitable isocyanates may include but are not limited to isophorone diisocyanate (IPDI), which is 3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate; hydrogenated materials such as cyclohexylene diisocyanate, 4,4'-methylenedicyclohexyl diisocyanate (H12MDI); mixed aralkyl diisocyanates such as tetramethylxylyl diisocyanates, OCN — C(CH3)2 — C6H4C(CH3)2 — NCO; polymethylene isocyanates such as 1,4-tetramethylene diisocyanate, 1,5 -pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,7- heptamethylene diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, 1,10- decamethylene diisocyanate and 2-methy 1-1, 5 -pentamethylene diisocyanate; and mixtures thereof.

[0020] Non-limiting examples of aromatic isocyanates for use in the coating compositions described herein may include but are not limited to phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, 1,5 -naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate, bitoluene diisocyanate, dianisidine diisocyanate, tolidine diisocyanate, alkylated benzenediisocyanates, methylene-interrupted aromatic diisocyanates such as methylenediphenyl diisocyanate, 4,4'-isomer (MDI) including alkylated analogs such as 3, 3'-dimethyl-4, d'diphenylmethane diisocyanate, polymeric methylenediphenyl diisocyanate; and mixtures thereof.

[0021] An isocyanate monomer may be used. Without wishing to be bound by theory, it is believed that the use of an isocyanate monomer (i.e., residual-free monomer from the preparation of prepolymer) may decrease the viscosity of the polyurea composition thereby improving its flowability and may provide improved adhesion of the polyurea coating to a previously applied coating and / or to an uncoated substrate. In some cases, at least 1 wt. %, or at least 2 wt. % or at least 4 wt. % of the isocyanate component may comprise at least one isocyanate monomer.

[0022] The isocyanate can include an oligomeric isocyanate such as but not limited to dimers such as the uretdione of 1,6-hexamethylene diisocyanate, trimers such as the biuret and isocyanurate of 1,6-hexanediisocyanate and the isocyanurate of isophorone diisocyanate, allophonates and polymeric oligomers. Modified isocyanates can be used, including but not limited to carbodiimides and uretone-imines, and mixtures thereof. Suitable materials include, without limitation, those available under the designation DESMODUR® (Covestro LLC, Pittsburgh, PA) and include DESMODUR® N 3200, DESMODUR® N 3300, DESMODUR® N 3400, DESMODUR® XP 2410 and DESMODUR® XP 2580.

[0023] The isocyanate component may comprise an isocyanate functional prepolymer formed from a reaction mixture comprising an isocyanate and another material. Any isocyanate known in the art, such as any of those described above, can be used in the formation of the prepolymer. For example, the isocyanate component may comprise a prepolymer formed from isophorone diisocyanate and a polyether polyol and / or polyetheramine according to the process described in US 8,691,929, which is incorporated herein by reference. See, for example, Example 1 of US 8,691,929. As used herein, an “isocyanate functional prepolymer” refers to the reaction product of isocyanate with polyamine and / or other isocyanate reactive group such as polyol; the isocyanate functional prepolymer has at least one isocyanate functional group (NCO).

[0024] The coating compositions may comprise an equivalent weight ratio of the isocyanate component to the active hydrogen of the amine-functional resin of from 0.85:1 to 1.4:1 (e.g., 0.95:1, 1.1:1 or 1.25:1). The compositions may comprise an equivalent weight ratio of the isocyanate component to the active hydrogen of the amine-functional resin of 0.85:1, 0.88:1, 0.9:1, 0.92:1, 0.94:1, 0.95:1, 0.96:1, 0.98:1, 1:1, 1.01:1, 1.02:1, 1.04:1, 1.05:1, 1.06:1, 1.08:1,1.1:1, 1.12:1, 1.14:1, 1.15:1, 1.16:1, 1.18:1, 1.2:1, 1.22:1, 1.24:1, 1.25:1, 1.26:1, 1.28:1, 1.3:1, 1.32:1, 1.34:1, 1.35:1, 1.36:1, 1.38:1, or 1.4:1, or be within a range that includes any two of the foregoing values as endpoints.

[0025] The coating compositions described herein may comprise a reactive silicone component in an amount of up to 7 wt. % (e.g., up to 4 wt. %, up to 5 wt. %, or up to 6 wt. %). The compositions may include 0.5 %, 1 %, 1.5 %, 2 %, 2.5 %, 3 %, 3.5 %, 4 %, 4.5 %, 5 %, 5.5 %, 6 %, 6.5 % or 7 % of a reactive silicone component, or within a range that includes any two of the foregoing values as endpoints. All percentages of reactive silicone component are expressed in wt. % based on the total solid weight of the composition. The reactive silicone component may comprise an amine functional silicone, a hydroxyl functional silicone, or combinations thereof. The reactive silicone component may comprise an amino-functional methyl phenyl silicone resin. The reactive silicone component may comprise a hydroxy alkyl polydimethylsiloxane. The reactive silicone component may have molecular weight of at least 500 atomic mass units (amu) (e.g., at least 1000 amu, at least 2500 amu, at least 4300 amu). The reactive silicone component may have molecular weight of at least 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2250, 2500, 2750, 3000, 3250, 3500, 3750, 4000, 4250, 4500, 4750, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10,000, 10,500, 11,000, 11,500 or 12,000 amu, or be within a range that includes any two of the foregoing values as endpoints. The reactive silicone component may include a plurality of functional groups. For example, the reactive silicone component may include at least two functional groups, three functional groups, or four functional groups. Non-limiting examples include Silmer® OHT Di- 10 and Silmer® HS 2000 (Siltech Corporation), and Tego® Protect 5000N (Evonik Industries). The reactive silicone component may have at least one reactive functional group that is reactive toward isocyanate, amine, and / or hydroxy groups. The reactive silicone component may have at least one reactive functional group that is reactive toward isocyanate, amine, and / or hydroxy groups and have a functional group equivalent weight that is greater than 500 amu. The reactive silicone component may have at least two reactive moieties / groups (e.g., at least 2, at least 3, or at least 4 reactive moieties).

[0026] The coating compositions described herein may comprise TiCh. TiO may be present in an amount of at least 1 wt. % (e.g., at least 8 wt. %, at least 15 wt. %, at least 25 wt. %). The compositions may include 1 %, 1.5 %, 2 %, 2.5 %, 3 %, 3.5 %, 4 %, 4.5 %, 5 %, 5.5 %, 6 %, 6.5%, 7 %, 7.5 %, 8 %, 8.5 %, 9 %, 9.5 %, 10 %, 11 %, 12 %, 13 %, 14 %, 15 %, 16 %, 17 %, 18 %, 19 %, 20 %, 21 %, 22 %, 23 %, 24 %, 25 %, 26 %, 27 %, 28 %, 29 %, or 30 % of TiO2, or within a range that includes any two of the foregoing values as endpoints. All percentages of TiCh are expressed in wt. % based on the total solid weight of the composition.

[0027] The coating compositions described herein may comprise a pre-polymer comprising silicone and including primary amine terminal groups in an amount of up to 5 wt. % (e.g., up to 3 wt. %, up to 4 wt. %, or up to 5 wt. %). The compositions may include 0.5 %, 1 %, 1.5 %, 2 %, 2.5 %, 3 %, 3.5 %, 4 %, 4.5 %, or 5 % of the pre-polymer, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of pre-polymer are expressed in wt. % based on the total solid weight of the composition. The pre-polymer may have molecular weight of 500 to 15,000 atomic mass units (amu) (e.g., 600 amu, 2500 amu, 6300 amu). The pre-polymer may have molecular weight of 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2250, 2500, 2750, 3000, 3250, 3500, 3750, 4000, 4250, 4500, 4750, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10,000, 10,500, 11,000, 11,500, 12,000, 12,500, 13,000, 13,500, 14,000, 14,500, or 15,000 amu, or be within a range that includes any two of the foregoing values as endpoints.

[0028] The coating compositions may comprise a catalyst compound comprising a metal compound, a mixed metal compound, an organometallic compound, or combinations thereof. The metal compound, mixed metal compound, and / or organometallic compound may comprise tin, zinc, bismuth, zirconium, manganese, titanium, cobalt, iron, or lead. The coating compositions may further comprise a catalyst compound comprising an organic compound. The organic compound may comprise bicycloguanidine, an imidazole, an acid, an aliphatic amine, cyclic amine, a phosphonium salt, a phenolic acid, a phenolic salt, a sulphonic acid, a sulphonic salt, a tertiary amine or a quaternary ammonium salt. In some examples, the coating compositions may comprise more than one catalyst, for example, the composition may comprise and organobismuth catalyst and a second catalyst compound comprising a metal compound, a mixed metal compound, an organic compound, an organometallic compound, or combinations thereof. Optionally, the organometallic compound may comprise dibutyltin dilaurate (DBDL) and / or dibutyltin diacetate (DBDA). In some examples, the composition may be free of an organotin compound. In some examples, the organic catalyst may comprise a tertiary amine such as 1,8 diazabicylco-5,4,0-undecene-7 (DBU) and / or an acid such as acetic acid. In someexamples, the catalyst compound may comprise less than 1 wt. % of the composition based on total solid weight of the composition (e.g., up to 0.8 wt. %, up to 0.5 wt. %, or up to 0.2 wt. %). The compositions may include 0.1 %, 0.2 %, 0.3 %, 0.4 %, 0.5 %, 0.6 %, 0.7 %, 0.8 %, 0.9 %, or up to 1 % of the catalyst compound, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of the catalyst compound are expressed in wt. % based on the total solid weight of the composition. In some examples, the catalyst may be used to adjust the curing rheology of the coating composition.

[0029] The coating compositions described herein may comprise a chain extender. A chain extender is a compound with reactive functional groups capable of participating in crosslinking or extending of a polymer chain in the coating matrix of the coating composition. The chain extender may be a difunctional, trifunctional, or tetrafunctional chain extender. The chain extender may be present in an amount of up to 5 wt. % (e.g., up to 3 wt. %, up to 4 wt. %, or up to 5 wt. %). The compositions may include 0.5 %, 1 %, 1.5 %, 2 %, 2.5 %, 3 %, 3.5 %, 4 %, 4.5 %, or 5 % of a difunctional, trifunctional, or tetrafunctional chain extender, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of chain extender are expressed in wt. % based on the total solid weight of the composition. The chain extender may have a molecular weight range from 90 to 6000 atomic mass units (amu) (e.g., 100 amu, 500 amu, 2500 amu). The chain extender may have molecular weight of 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2250, 2500, 2750, 3000, 3250, 3500, 3750, 4000, 4250, 4500, 4750, 5000, 5500, or 6000 amu, or be within a range that includes any two of the foregoing values as endpoints. The chain extender may comprise from 2 to 4 active hydrogens of the amine- functional groups and / or hydroxyl functional groups. In some examples, the chain extender may comprise an aliphatic hydrocarbon. In some examples, the chain extender may comprise an aliphatic diol. A chain extender with suitable equivalent weight may provide stronger impact resistance and adhesion to the coating composition while maintaining effective surface hardness. Non-limiting examples of chain extenders for use in the coating compositions described herein include but are not limited to neopentyl glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, cyclohexane dimethanol, trimethylolpropane, dimethylolpropionic acid, poly(tetramethylene ether) glycol, poly(proplyene ether) diol, polyoxypropylene diamine, polyoxypropylene triamine, or combinations thereof.

[0030] The coating compositions described herein may further comprise a reactive diluent. Reactive diluents may include 1 to 4 functional groups comprising amine, epoxy, carbonate, acrylate and / or silane functional groups. The reactive diluent may comprise 2-ethylhexyl glycidyl ether, glycidyl esters of neodecanoic acids, 3, 4-epoxycyclohexylmethyl-3', 'epoxycyclohexane carboxylate, a cardanol-based diluent, an epoxy bio-based oil reactive diluent, propylene carbonate, 1,6-hexanediol diacrylate, butylacrylate, ethyhexylacrylate, methacrylate, methyl methacrylate, vinyltrimethoxy silane, dimethylsiloxane-vinylmethylsiloxane-(propylene oxide-ethylene oxide) block copolymer, tetraethyl orthosilicate, or combinations thereof. The reactive diluent may be added to the amine-functional resin or the isocyanate component. In some examples, the reactive diluent may help balance the rheology and the stoichiometry ratio of Part A and Part B in the coating system for improved curing time and mechanical performance.

[0031] The reactive diluent can modify the viscosity of the coating components to provide a low pressure differential for intermittent application (start / stop) processes applying a 2K coating composition with substantially equal mixing, including automated or robotic operations having trigger on / off spray. For example, the reactive diluent can be added to the amine-functional resin to modify the viscosity to provide for similar spray conditions for the amine and isocyanate portions of the polyurea coating. The isocyanate component can be used alone or optionally diluted with a reactive diluent to achieve the optimal spray pressure. In some cases, the pressure differential may be less than 400 psi (e.g., less than 350 psi, less than 300 psi, or less than 250 psi).

[0032] The coating compositions may further comprise a non-reactive surface additive in an amount up to 3 wt. % (e.g., up to 1.5 wt. % or up to wt. 2 %). The composition may include 0.05 %, 0.1 %, 0.2 %, 0.3 %, 0.4 %, 0.5 %, 0.6 %, 0.7 %, 0.8 %, 0.9 %, 1 %, 1.1 %, 1.2 %, 1.3 %, 1.4 %, 1.5 %, 1.6 %, 1.7 %, 1.8 %, 1.9 %, 2 %, 2.1 %, 2.2 %, 2.3 %, 2.4 %, 2.5 %, 2.6 %, 2.7 %, 2.8 %, 2.9 %, or 3 % a non-reactive surface additive, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of the non-reactive surface additive are expressed in wt. % based on the total solid weight of the composition. The non-reactive surface additive may comprise a defoamer, a wetting agent, a dispersing agent, or combinations thereof. In some cases, the coating composition may be free of a non-reactive surface additive.

[0033] The coating compositions may further comprise a polysiloxane, a UV absorber, a hindered amine light stabilizer (HALS), an inorganic filler, an organic filler, a reinforcing agent,a pigment, a flame retardant, a biocide, an antimicrobial, or combinations thereof. The coating compositions may comprise silicate minerals, metal oxides, metal salts, clay, natural and synthetic fibrous minerals, carbon black, melamine, rosin, cyclopentadienyl resins, or combinations thereof. For example, the coating composition may comprise calcium carbonate, silica, fumed silica, mica, glass, glass beads, aluminum tri-hydrate, gypsum, wollastonite, phosphorus, calcium sulfate, magnesium hydroxide, an organic clay derivative or combinations thereof.

[0034] The coating compositions described herein may optionally comprise a cure retardant and a solvent. The coating compositions described herein may optionally comprise a rheology modifier. The coating compositions described herein may be a IK composition. A blocked isocyanate and / or blocked amine may be used to make a IK composition. The cure retardant and solvent may provide for a longer work time by slowing the reaction of the polyurea coating composition. In some cases, the composition may have a potlife of greater than 15 min (e.g., greater than 20 min, greater than 30 min, greater than 40 min). As used herein, potlife is the time from when the components of the composition are combined to the time at which the mixed composition is no longer workable, or in the context of a IK composition, the time from when the blocked isocyanate and / or blocked amine is unblocked. The compositions may have a potlife greater than 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 min, or a potlife within a range that includes any two of the foregoing values as endpoints.

[0035] The cure retardant may be present in an amount of at least 5 wt. % (e.g., at least 5 wt. %, at least 10 wt. % or at least 25 wt. %). The compositions may include at least 5 %, 6 %, 7 %, 8 %, 9 %, 10 %, 11 %, 12 %, 13 %, 14 %, 15 %, 16 %, 17 %, 18 %, 19 %, 20 %, 25 %, 30 %, 35 %, 40 %, 45 %, 50 %, 55 %, 60 %, 65 %, 70 %, or 75 % cure retardant, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of cure retardant are expressed in wt. % based on the total solid weight of the composition. The cure retardant may comprise a ketone, a pyrazole, a polyol, or combinations thereof. For example, the cure retardant may comprise acetone, acetylacetone, 3,5-dimethylpyrazole, or combinations thereof. The cure retardant may comprise tetra (2-hydroxypropyl) ethylenediamine, polytetramethylene ether glycol, or combinations thereof.

[0036] The solvent may be present in an amount of up to 20 wt. % (e.g., up to 5 wt. %, up to 13 wt. %, or up to 17 wt. %). The compositions may include up to 1 %, 2 %, 3 %, 4 %, 5 %, 6 %, 7 %, 8 %, 9 %, 10 %, 11 %, 12 %, 13 %, 14 %, 15 %, 16 %, 17 %, 18 %, 19 %, or 20 % solvent, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of solvent are expressed in wt. % based on the total solid weight of the composition. The solvent may comprise an aromatic hydrocarbon, a carboxylic acid ester, or combinations thereof. For example, the solvent may comprise naptha, butyl acetate, xylene, or combinations thereof.

[0037] The rheology modifier may be present in an amount of up to 15 wt. % (e.g., up to 5 wt. %, up to 8 wt. %, or up to 12 wt. %). The compositions may include up to 1 %, 2 %, 3 %, 4 %, 5 %, 6 %, 7 %, 8 %, 9 %, 10 %, 11 %, 12 %, 13 %, 14 %, or 15 % rheology modifier, or include it within a range that includes any two of the foregoing values as endpoints. All percentages of rheology modifier are expressed in wt. % based on the total solid weight of the composition. The rheology modifier may comprise castor oils derivatives, clays, silicas, silicates, carbon blacks, calcium carbonates, microgels, nanogels, ureas, polyamides, bentonites, baking soda, acrylic thickeners, wax, or combinations thereof. Rheology modifiers, which may be referred to as sag control agents, controll flow and sag of the coating. The rheology modifiers can allow for the deposition of the coating with sufficient thickness to impart the necessary durability while maintaining the desired appearance, i.e., gloss, distinctness of image, and smoothness.

[0038] A substrate may include a coating composition as described herein. An article may comprise a substrate including a coating composition as described herein. Non-limiting examples of an article include industrial and commercial products such as turbine blades, prefabricated components, and other products used in marine, transportation, wind energy, and construction sectors. Other non-limiting examples of an article include parts and accessories for transportation and automotive sectors, such as recharging stations for electrical vehicles. Other non-limiting examples include modular building blocks and various 3D printed articles.

[0039] Also disclosed herein are methods for coating a substrate. Examples of suitable substrates may include metal, plastic, concrete, cement, stone, bricks, asphalt, wood, geotextile, a fiberglass composite, carbon fiber composite, and / or synthetic fiber composite. In some examples, the metal substrate may comprise iron, steel, steel alloys, galvanized metals, and / oraluminum. In some examples, the plastic substrate may comprise a polyurethane, an epoxy, and / or a polyurea. In some examples, a moisture cured polyurethane primer may improve adhesion of the coating compositions described herein on a plastic substrate. In some examples, the synthetic fibers may comprise acetate, acrylic, nylon, aramide, polyolefin, ceramic, and / or polyester fibers. In some examples, substrates comprising fabrics and fiberglass may be prewoven or machine aligned before the coating composition is applied to create polyurea composites. Fabric and fiberglass type composites comprising the coating composition described herein have desirable strength properties without the high temperature curing necessary for traditional fabric and fiberglass composites. Non-limiting examples of fabric, fiber, and fiberglass composites include panels, poles and construction parts manufacturing as well as parts for automotive, marine, or transportation sectors. A traditional pre-knitted or machine-aligned fabric and fiberglass composites may be sprayed or dipped in slow-curing coatings that require high-temperature curing to make the composite, which can generate in some cases large amounts of waste, high VOCs and high energy consumption. The slow cure of traditional fabric and fiberglass composites may lead to appearance problems, such as sagging and pinholes in the applied coating. The fast-curing polyurea coating compositions described herein may overcome these disadvantages when sprayed or otherwise applied onto pre-knitted or machine-aligned fabrics and fiberglass, cement, or concrete articles of manufacture. The coating compositions described herein may be substantially cured less than 5 min after application. The fast-curing polyurea coating compositions described herein may significantly increase the productivity and sustainability of articles used in various industrial sectors, in particular those that utilize automatic or semi-automatic manufacturing lines.

[0040] A method of coating a substrate may comprise applying to at least a portion of a substrate the coating composition described herein. Optionally, the method may further comprise adding a primer to the substrate prior to applying the coating composition. The primer may comprise an isocyanate pre-polymer that can be moisture cured. Optionally, the primer may comprise zinc. In some examples, the primer may comprise greater than 80 % zinc in dry film. In some examples, the primer may be a two-component, moisture curing urethane primer. The primer may comprise a polyurethane.

[0041] The methods for applying the coating compositions may comprise extrusion, spraying, troweling, brushing, and / or rolling. The coating compositions may be applied with aspray gun by air purge spray, mechanical purge spray, atomized air spray, non-atomized air spray, atomized airless spray, non-atomized airless spray, and / or low-pressure static-mix spray, or other means known to those skilled in the art. In some cases, a static mixer may be used during spraying, extrusion, spraying, troweling, brushing, and / or rolling. The static mixer may allow the application pressure to be reduced and improve mixing, which could reduce operating costs and improve product quality.

[0042] A spray gun used to apply the coating compositions may have a reciprocator speed of 300-1000 mm / sec (e.g., 350 mm / sec, 500 mm / sec, 700 mm / sec). The reciprocator speed may be 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, or 1000 mm / sec. The coating compositions may be applied at a rate of 4-20 Ibs / min (e.g., 5 Ibs / min, 10 Ibs / min, 15 Ibs / min). The application rate may be 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 Ibs / min. The coating compositions may be applied at a pressure of greater than 1500 psi (e.g., 2000 psi, 3000 psi, 3500 psi). The application pressure may be greater than 1500, 1750, 2000, 2250, 2500, 2750, 3000, 3500, or 4000 psi. For a 2K application, the pressure differential may be less than 400 psi (e.g., less than 350 psi, less than 300 psi, or less than 250 psi). The pressure differential may be less than 400, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, or 25 psi. The coating compositions may be applied at a temperature of greater than 120 °F (e.g., greater than 120 °F, greater than 135 °F, greater than 150 °F). The application temperature may greater than 120 °F, 125 °F, 130 °F, 135 °F, 140 °F, 145 °F, 150 °F, 155 °F, 160 °F, 165 °F, 170 °F, 175 °F, or 180 °F. The coating compositions may be applied at a thickness of up to 500 mil (e.g., up to 20 mil, up to 85 mil, up to 140 mil). The coating compositions may be applied at a thickness of 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 mil.

[0043] The coating compositions described herein may have a tack-free time of less than 250 sec according to ASTM D1640-03 (e.g., 200 sec, 75 sec, or 25 sec). The tack-free time may be less than 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 20, 15, 10, or 5 sec. The coating compositions may have a dry-through time of less than 1100 sec according to ASTM D 1640-03 (e.g., 500 sec, 200 sec, or 100 sec). The dry-through time may be less than 1100, 1075, 1050, 1025, 1000, 975, 950, 925, 900, 875, 850, 825, 800, 775, 750, 725, 700, 675, 650, 625, 600, 575,550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, or 50 sec.

[0044] The coating compositions described herein may have a Shore D hardness value of greater than 60, according to ASTM D2240- 15(2021) (e.g., greater than 65, greater than 70, or greater than 75). The Shore D hardness value may be greater than 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80. The Shore D hardness value may be determined at 7 days according to ASTM D2240- 15(2021). The coating compositions may have a cycloaliphatic ring equivalent weight greater than 127 meq / lOOg (e.g., greater than 136 meq / lOOg, greater than 172 meq / lOOg, or greater than 254 meq / lOOg). The cycloaliphatic ring equivalent weight may be greater than 127, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, or 370 meq / lOOg. In some cases, the coating composition may have a Shore D hardness value of greater than 65 at 7 days, according to ASTM D2240- 15(2021), and a cycloaliphatic ring equivalent weight greater than 127 meq / lOOg.

[0045] The coating compositions may have a contrast ratio (CR) value at 10 mil of at least 50, according to ASTM D2805 (e.g., at least 72, at least 83, or at least 94). The CR value at 10 mil may be at least 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95. The coating compositions may have a stain resistant value of less than 60, according to ANSI Z124.1.2-2005 5.2 (e.g., 60, 50, or 45). The stain resistant value may be less than 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, or 40 according to ANSI Z 124.1.2-2005 5.2.

[0046] The coating compositions may have an elongation from 4 to 100%, according to ASTM D638-14 (e.g., 10 %, 30 %, or 70 %). The elongation may be 4%, 6 %, 8 %, 10 %, 15 %, 20 %, 25 %, 30 %, 35 %, 40 %, 45 %, 50 %, 55 %, 60 %, 65 %, 70 %, 75 %, 80 %, 85 %, 90 %, 95 %, or 100 %.

[0047] The coating compositions described herein may protect a substrate and reduce damage to the substrate due to impact with an object. In some examples, a coated substrate may be free of scratches or cracks to the coating after an impact with an object (e.g., according to ASTM D2794(2019)) . In some examples, a coated substrate may have only minor scratches to the coating after an impact with an object. A stronger impact resistance may reduce product defects caused by post-processing handling, transportation, and end uses. The reduction indefects can lower overall costs. The stronger impact resistance can improve product quality and extend the product lifetime.

[0048] The coating compositions described herein may have strong adhesion to a substrate. The coating compositions may have an adhesion value to dry cement of at least 400 psi, according to ISO 4624:2016 (e.g., at least 400, at least 800, at least 1100 psi). The adhesion may be at least 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, or 1600 psi. In some examples, a substrate may still be wet if a premix of concrete or cement is not fully dried prior to the application of the coating composition. In some examples, a substrate may remain wet or moist if the surrounding humidity level is high or after weather-related precipitation. The coating composition described herein may be applied to a wet or moist substrate. The coating compositions may have an adhesion value to moist / wet cement of at least 200 psi, according to ISO 4624:2016 (e.g., at least 200 psi, at least 500 psi, at least 750 psi.) Moist / wet cement refers to cement with a moisture content greater than 3 wt. %. Moisture content can be measured with a non-destructive moisture meter calibrated with gravimetric testing, such as those sold by Tramex Ltd. (Brooklyn, NY), including the Tramex Concrete Moisture Encounter. The adhesion may be 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, or 1200, psi. Without wishing to be bound by theory, it is believed that when the moisture cured isocyanate prepolymer contacts water, urea moieties may be created. The urea and isocyanate moieties may provide adhesion improvement of coating composition on the wet substrate.

[0049] The coating compositions may be rust resistant. The coating compositions may be chlorine resistant. Rust resistance and chlorine resistance tests may be performed by placing 1" diameter chemical spots of a rust solution or chlorine solution on a sample and covering with a watch glass for 24 hours following ASTM D1308-20, Test Method 3.1.1 Spot Test, Covered, Procedure 7.2, at ambient conditions (75+ / - 2 degrees F). The sample may be considered to pass if no deterioration, softening, cracking or color changing occurs. A rust solution may be prepared by using tin snips or other appropriate cutting tool to remove the head from a rusty nail and trim the other end as necessary to result in a segment 2.54 cm in length. The piece of rusty nail may be placed on the test panel and using a pipette, 1 mL of deionized water may be transferred directly onto the piece of nail that may be covered by a watch glass for observation.

[0050] The coating compositions may have a fire test value of less than 30 sec, excluding the edges, according to ANSI Z124.1.2-2005 5.6. The center of the coating composition samples can remain undamaged after two 30 second burning intervals. The center of the coating composition samples may self-extinguish if they were burned after two 30 second burning intervals.

[0051] The methods described herein may further comprise preparing at least a portion of the article prior to applying the coating composition. In some cases, preparing at least a portion of the article may comprise sanding or scrubbing at least a portion of the article.

[0052] The substrate can comprise a vehicle, a structure, marine components, automotive body parts, aerospace components, wind turbine components, roofing structure components, transportation components, construction components, consumer goods, and / or infrastructure components. An article of manufacture may comprise a substrate comprising the coating composition described herein.

[0053] ‘Consumer goods” as used herein refers to a bathtub, spa, swimming pool, vanity, sink, shower pan, battery container, sporting equipment, music equipment / speaker, shoe soles, golf ball, electronic protective cover / case, wall panel, flooring, doors, tables, chairs, or other item that is exposed to a corrosive environment, harsh environmental conditions, or an environment vulnerable to impact. “Vehicle” refers to in its broadest sense all types of vehicles, such as but not limited to cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, railcars, airplanes, helicopters, boats of all sizes and the like.“Infrastructure” as used herein refers to a building interior, building exterior, bridge, food production facility, beverage facility, pharmaceutical plant, battery plants, EV charging station, gas station, concrete deck, pipe structure, roofing, pedestrian walkway, fence, art installation, restaurant / kitchen interior, and the like.

[0054] Molecular weight values disclosed herein can be determined using gel permeation chromatography (GPC) such as according to ASTM D5296 - 19.

[0055] Any numerical range recited herein is intended to include all subranges subsumed therein. When ranges are given, any endpoints of those ranges and / or numbers within those ranges can be combined with the scope of the present disclosure. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resultingfrom the standard variation found in their respective testing measurements. “Including” and like terms mean “including but not limited to”. The word “comprising” and forms of the word “comprising” as used in this description and in the claims do not limit the disclosure claimed to exclude any variants or additions.

[0056] As used herein, the terms “on” and “applied on / over” mean formed or provided on but not necessarily in contact with the surface. Each of the characteristics and examples described above and below, and combinations thereof, may be said to be encompassed by the present disclosure.

[0057] As used herein, the meaning of “a,” “an,” and “the” includes singular and plural references unless the context clearly dictates otherwise.

[0058] As used herein, the terms “disclosure,” “the disclosure,” “this disclosure” and “the present disclosure” are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise noted.

[0059] Although the disclosure has been described in terms of “comprising”, “consisting essentially of’ or “consisting of’ are also within the scope of the present disclosure. In this context, “consisting essentially of’ means that any additional components will not materially affect the viscosity or other properties of the composition.

[0060] The following working examples are intended to further describe the disclosure. It is understood that the disclosure described in this specification is not necessarily limited to the examples described in this section. Components that are mentioned elsewhere in the specification as suitable alternative materials for use in the disclosure, but which are not demonstrated in the working examples below, are expected to provide results comparable to their demonstrated counterparts.Example Aspects

[0061] The following clauses represents a non-exhaustive list of example aspects of the disclosed silicone-modified polyurea coating compositions.

[0062] Clause 1. A coating composition comprising: an isocyanate component; an amine- functional resin comprising an aspartic acid ester; a reactive silicone component having a molecular weight of at least of 500 amu; a pre-polymer comprising silicone and primary amine terminal groups; an organometallic catalyst; and a chain extender.

[0063] Clause 2. The coating composition of clause 1, further comprising a reactive diluent.

[0064] Clause 3. The coating composition clause 1 or 2, wherein the pre-polymer has a molecular weight from 500 to 15,000 amu.

[0065] Clause 4. The coating composition of any one of clauses 1-3, wherein the chain extender comprises a difunctional, trifunctional, or tetrafunctional compound.

[0066] Clause 5. The coating composition of any one of clauses 1-4, further comprising an additional polysiloxane, a UV absorber, a hindered amine light stabilizer (HALS), an inorganic filler, an organic filler, a reinforcing agent, a pigment, a flame retardant, a biocide, an antimicrobial, or combinations thereof.

[0067] Clause 6. The coating composition of any one of clauses 1-5, wherein an equivalent weight ratio of the isocyanate component to active hydrogen of the amine-functional resin ranges from 0.85:1 to 1.4:1.

[0068] Clause 7. The coating composition of any one of clauses 1-6, wherein the chain extender has a molecular weight range from 90 to 6000 atomic mass units.

[0069] Clause 8. The coating composition of any one of clauses 1-7, further comprising TiO2, optionally present in an amount of at least 5 wt. %.

[0070] Clause 9. The coating composition of any one of clauses 1-8, wherein the isocyanate component comprises a prepolymer formed from hexamethylene diisocyanate, isophorone diisocyanate, or both and a polyether polyol and / or polyetheramine.

[0071] Clause 10. The coating composition of any one of clauses 1-9, further comprising a catalyst comprising zinc, manganese, zirconium, titanium, cobalt, iron, lead, bismuth, or tin.

[0072] Clause 11. A substrate comprising the coating composition of any one of clauses 1- 10.

[0073] Clause 12. An article comprising the substrate of clause 11.

[0074] Clause 13. The article of clause 12 comprising a precast concrete component, a prefabricated construction component, a turbine blade, fiber composite, fiberglass composite, pre-woven fiber, or machine aligned fiber.

[0075] Clause 14. A method comprising applying to at least a portion of a substrate the coating composition according to any one of clauses 1-10.

[0076] Clause 15. The method of clause 14, further comprising adding a primer composition to the substrate prior to applying the coating composition.

[0077] Clause 16. The method of clause 14 or 15, wherein the primer comprises a moisture cure isocyanate prepolymer.

[0078] Clause 17. The method of any one of clauses 14-16, wherein the coating composition is applied with a spray gun by air purge spray, mechanical purge spray, atomized air spray, nonatomized air spray, atomized airless spray, non-atomized airless spray, air-assisted airless spray, and / or low pressure static-mix spray.

[0079] Clause 18. The method of clause 17, wherein the spray gun has a reciprocator speed of 300-1000 mm / sec.

[0080] Clause 19. The method of clause 17 or 18, wherein the coating composition is applied at a rate of 4-20 Ibs / min.

[0081] Clause 20. The method of any one of clauses 14-19, wherein the coating composition has a tack-free time of less than 250 sec according to ASTM DI 640-03.

[0082] Clause 21. The method of any one of clauses 14-20, wherein the coating composition has a dry-through time of less than 1100 sec according to ASTM DI 640-03.

[0083] Clause 22. The method of any one of clauses 14-21, wherein the coating composition has an adhesion value to dry cement of at least 400, according to ISO 4624:2016.

[0084] Clause 23. The method of any one of clauses 14-22, wherein the coating composition has an adhesion value to moist cement of at least 200, according to ISO 4624:2016.

[0085] Clause 24. The method of any one of clauses 14-23, wherein the substrate comprises plastic, fabric, fiber, geotextile, concrete, cement, fiberglass composite, carbon fiber composite, and / or synthetic fiber composite.

[0086] Clause 25. The substrate of clause 11, wherein the substrate comprises metal, plastic, fabric, fiber, geotextile, concrete, cement, fiberglass composite, carbon fiber composite, and / or synthetic fiber composite.

[0087] Clause 26. The article of clause 12, wherein the substrate comprises plastic, fabric, fiber, geotextile, concrete, cement, fiberglass composite, carbon fiber composite, and / or synthetic fiber composite.

[0088] Clause 27. A coating composition comprising: an isocyanate component; and a mixture comprising: a B-pack for a polyurea coating comprising an amine compound and a hydroxyl compound; a pre-polymer comprising silicone and primary amine terminal groups; an organometallic catalyst; and a difunctional, trifunctional, or tetrafunctional chain extender.

[0089] Clause 28. A method of making a coating composition comprising: combining a B- pack for a polyurea coating comprising an amine compound and a hydroxyl compound, a prepolymer comprising silicone and primary amine terminal groups, an organometallic catalyst, and a difunctional, trifunctional, or tetrafunctional chain extender to form a first mixture; adding an isocyanate component to the first mixture; and combining the first mixture and isocyanate component to produce the coating composition.

[0090] Clause 29. A coating composition comprising: an isocyanate component; an amine- functional resin comprising an aspartic amine; a reactive silicone component having a molecular weight of at least of 500 amu; TiO2; a cure retardant in an amount of at least 5 wt. %; a solvent in an amount of up to 20 wt. %; and a rheology modifier in an amount of up to 15 wt. %.

[0091] Clause 30. The coating composition of clause 29, further comprising a reactive diluent.

[0092] Clause 31. The coating composition of clause 29 or 30, wherein the cure retardant comprises a ketone, a pyrazole, a polyol, or combinations thereof.

[0093] Clause 32. The coating composition of any one of clauses 29-31, wherein the cure retardant comprises acetone, acetylacetone, 3,5-dimethylpyrazole, or combinations thereof.

[0094] Clause 33. The coating composition of any one of clauses 29-31, wherein the cure retardant comprises tetra (2-hydroxypropyl) ethylenediamine, polytetramethylene ether glycol or combinations thereof.

[0095] Clause 34. The coating composition of any one of clauses 29-33, wherein the solvent comprises an aromatic hydrocarbon, a carboxylic acid ester, or combinations thereof.

[0096] Clause 35. The coating composition of any one of clauses 29-33, wherein the solvent comprises naptha, xylene, butyl acetate, or combinations thereof.

[0097] Clause 36. The coating composition of any one of clauses 29-35, wherein the composition has a potlife of greater than 15 minutes.

[0098] Clause 37. The coating composition of any one of clauses 29-35, wherein the composition has a potlife of greater than 30 minutes.

[0099] Clause 38. A method for repairing an article comprising a first coating, the method comprising applying to at least a portion of the article the coating composition according to any one of clauses 1-10 or 29-37.

[0100] Clause 39. The method of clause 38, wherein the first coating comprises a polyurea composition, a polyaspartic composition, a polyurethane composition, or combinations thereof.

[0101] Clause 40. The method of clause 38 or 39, further comprising preparing at least the portion of the article prior to applying the coating composition.

[0102] Clause 41. The method of clause 40, wherein preparing at least the portion of the article comprises sanding or scrubbing at least a portion of the article.

[0103] Clause 42. The method of clause 40 or 41, wherein preparing at least the portion of the article comprises adding a filler material and / or a base layer comprising a second coating composition to at least a portion of the article.

[0104] Clause 43. The method any one of clauses 38-42, wherein applying the coating composition comprises extrusion, spraying, troweling, brushing, and / or rolling.

[0105] Clause 44. The method of clause 43, wherein spraying comprises air purge spray, mechanical purge spray, atomized air spray, non-atomized air spray, atomized airless spray, nonatomized airless spray, air-assisted airless spray, and / or low-pressure static-mix spray.

[0106] Clause 45. The method of clause 43, wherein applying further comprises using a static mixer.

[0107] Clause 46. The method any one of clauses 38-45, further comprising smoothing and / or polishing the coating composition after the coating composition gels on the article according to “dry hard time” as defined by ASTM DI 640-03.

[0108] Clause 47. The method any one of clauses 38-46, wherein the coating composition has a potlife greater than 15 minutes.

[0109] Clause 48. The method of any one of clauses 38-47, wherein the coating composition is applied to a void or damaged area of the first coating of the article.

[0110] Clause 49. The method of any one of clauses 38-48, wherein the article comprises a plastic, wood, concrete, cement, fiber, geotextile, fiberglass composite, carbon fiber composite, and / or synthetic fiber composite.

[0111] Clause 50. The method any one of clauses 38-49, further comprising contacting the coating composition with a second solvent after the coating composition gels on the article.

[0112] Clause 51. The method of clause 50, wherein the second solvent comprises an aromatic hydrocarbon, a carboxylic acid ester, or combinations thereof.

[0113] Clause 52. The method of clause 50 or 51, wherein the second solvent blends a portion of the gelled coating composition with a portion of article to reduce visual contrast between the gelled coating composition and the article.

[0114] Clause 53. A kit comprising: a first part comprising an isocyanate component; and a second part comprising: an amine-functional resin comprising an aspartic amine; a reactive silicone component having a molecular weight of at least of 500 amu; TiO2; a cure retardant; and a rheology modifier.

[0115] Clause 54. The kit of clause 53, further comprising a solvent.

[0116] Clause 55. A kit comprising: a first part comprising: an isocyanate component; a reactive silicone component having a molecular weight of at least of 500 amu; TiO2; a cure retardant; and a rheology modifier; and a second part comprising an amine-functional resin comprising an aspartic amine.

[0117] Clause 56. The kit of clause 55, further comprising a solvent.EXAMPLES

[0118] Working Examples of coating compositions described herein were prepared and evaluated for performance.Example 1

[0119] Desmodur N 3300 (hexamethylene diisocyanate trimer) and propylene carbonate were transferred to a container equipped with a Cowles blade. The mixture was mixed in the container for 10 min at room temperature. This mixture was used as the A-pack (i.e., Part A) in the formulations of Examples 2 and 3.Example 2

[0120] The B-pack (i.e., Part B) samples were prepared according to the compositions in Table 1. The B-pack (amine) samples were prepared by first combining 50 wt% of the amine / hydroxy functional compounds with all additives, excluding pigments, where applicable. Under agitation at room temperature, the pigment, where applicable, was added to the resin blend and ground with a horizontal mill until Hegman > 5. Upon completion of the grind phase,any remaining material listed in the composition table were added, where applicable, under low shear and mixed for 10 min with a Cowles blade to complete the B-pack formulation. Samples were shaken for 10 min prior to all application work to ensure a homogenous sample.Table 1Table 1, cont.Table 1, cont.

[0121] The “Pigment I Additives Blend” included one or more weather additives in an amount from 0.3 - 2.5 wt. %; TiCh from 5 to 30 wt. %; one or more pigments from 1 to 8 wt. %; one or more surface active additives from 0.04 - 3 wt. %; and one or more alkoxy silane additives up to 2 wt. %, based on the total weight of Part B. The total amount of pigment excluded TiCh for film properties and rheology control. Quadrol PM is available from BASF. HXA CE 425 is available from BASF / Hanson Group LLC.Example 3

[0122] The product Aliphatic White Polyurea Amine BDL95663G, available from PPG Industries (Pittsburgh, PA) was used to create additional Example formulations. The components of BDL95663G, as listed in the corresponding safety data sheet for the product, are shown in Table 2A. The B-Packs of Example formulations 1-18 shown in Table 1 are alternatives to BDL95663G that are expected to perform similarly.Table 2 A

[0123] The additional Example formulations are shown in Table 2B. The B-pack (amine) samples of Example formulations 20-23 were prepared by adding a reactive silicone component to the amine / hydroxy functional compound (BDL95663G). SILMER® reactive silicone products are available from Siltech Corporation (Toronto, Ontario, Canada). According to the manufacturer: Silmer OHT AO is a hydroxyalkyl modified silicone with two-functional hydroxyl attached to a silicone backbone; Silmer OHT Di- 10, Silmer OHT Di-50, Silmer OHT Di- 100 are tetra-functional hydroxyl silicones; Silmer OH Di- 10 is a linear di-functional hydroxylterminated silicone pre-polymer; and Silmer NH C50 is a tri-functional silicone with amine groups. The molecular weight and equivalent weight of the reactive silicone component additives are listed in Table 3.Table 2BTable 2B, Cont.Table 3

[0124] The results indicate that inclusion of a reactive silicone component with a molecular weight of at least 500 amu can promote effective stain resistance. The results also demonstrate that a reactive silicone component comprising (i) a hydroxyl functional silicone including at least 3 reactive hydroxyl moieties and / or (ii) an amine functional silicone can promote effective stain resistance. Example 19 (negative control) did not include a reactive silicone component and resulted in a stain resistance score of 60. When a di-functional hydroxyl reactive silicone was added (Examples 20 and 21), the stain resistance score did not improve or only slightly improved. In contrast, the addition of a tetra-functional hydroxyl silicone (Examples 22-24 and 26-28) or an amine-functional silicone (Example 25) beneficially provided greater stain resistance.Example 4

[0125] The part A and part B compositions from Tables 1 and 2B were sprayed via a plural component spray system, such as Graco E-10 HP and HXP2 machines equipped with a mixing gun, such as Graco® AP Fusion, MP Fusion and AP Proconnect guns. The plural system was set to the spray parameters listed in Table 4.Table 4Example 5

[0126] A mixture of Desmodur N 3900 (hexamethylene diisocyanate) and propylene carbonate was prepared by adding the N3900 and the propylene carbonate to a vessel equipped with a Cowles blade. The mixture was mixed in the vessel for 10 min at room temperature.

[0127] The B-pack (i.e., Part B) samples were prepared according to the compositions in Table 5. The B-pack samples were prepared by combining (i) the B-pack of GelFlex M (amine functional resin available from PPG Industries, Pittsburgh, PA) with (ii) Silmer NH Di-50 prepolymer (linear silicone with primary amine terminal groups), (iii) Coscat™ 83 (bismuth-based organometallic catalyst), (iv) 1,4-butanediol as difunctional chain extender, and any remaining material listed in Table 5 under low shear and mixed for 10 min, at room temperature, with a Cowles blade to complete the B-pack formulation of Example formulations 30-32. The molecular weight, equivalent weight, and amine value of the pre-polymer is listed in Table 6. GelFlex M is a polyurea coating comprising aspartic acid ester at 40-50 wt. % and cycloaliphatic amines at 20-30 wt. %, and an amine-based polyol at 5-10 wt. %. The 1,4-butanediol is an aliphatic hydrocarbon difunctional chain extender. Coscat™ 83 Catalyst (Palmer Holland) is an organobismuth catalyst.

[0128] The B-pack formulation and the N 3900 mixture (A-pack) were combined. Samples were shaken for 10 min prior to all application work to ensure a homogenous sample. B-pack and A-pack formulation were sprayed on the substrate at the volume-mix ratio provided in Table 5.Table 5Table 6

[0129] Impact testing was performed according to ASTM D2794(2019) with a slight procedure modification. The test was carried out by dropping a 900 g weight from a lm height onto the substrate. The cycle was repeated 10 times. For the direct impact test, the weight was dropped onto the front of the substrate. The front of the substrate of Ex. 29 had no polyurea coating on it. The substrates of Ex. 30-32 were protected by a polyurea coating on the front of the substrate. For the reverse impact test, the weight was dropped onto the back of the substrate. The damages observations from impact testing on these substrates were ranked according to Table 7.Table 7

[0130] The results indicate that the inclusion of a chain extender in combination with the prepolymer can beneficially improve the impact resistance of the coating. Example 30 did not include a chain extender, whereas Examples 31 and 32 included a chain extender. As demonstrated by the results, Examples 31 and 32 exhibited greater impact resistance, with level 5 damage observations for both the direct and reverse impact testing.

[0131] Adhesion testing demonstrated that the inclusion of a chain extender can improve adhesion. Example 31 exhibited higher dry cement adhesion as compared to Example 30. To test wet adhesion performance, a coating of water was sprayed on the surface of the substrate using a cup gun followed by a 5 min waiting period for the water to penetrate the surface of the substrate under ambient conditions. A layer of primer containing moisture cured isocyanate such as DURETHANE MCZ primer part A (available from PPG Industries Inc.) was applied to Ex. 32 prior to applying the polyurea coating application, which improved wet adhesion performance.

[0132] Whereas various examples of the disclosure have been described in fulfillment of the various objectives of the disclosure, it should be recognized that these examples are merely illustrative of the principles of the present disclosure. Numerous modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the present disclosure as defined in the following claims.

Claims

CLAIMS1. A coating composition comprising: an isocyanate component; an amine-functional resin optionally comprising an aspartic acid ester; a reactive silicone component having a molecular weight of at least of 500 amu; a pre-polymer comprising silicone and including primary amine terminal groups; an organometallic catalyst; and a chain extender.

2. The coating composition of claim 1, further comprising a reactive diluent.

3. The coating composition of claim 1 or 2, wherein the pre-polymer has a molecular weight from 500 to 15,000 amu.

4. The coating composition of any one of claims 1-3, wherein the chain extender comprises a difunctional, trifunctional, or tetrafunctional compound, such as a polyol and / or polyamine, such as a neopentyl glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, cyclohexane dimethanol, trimethylolpropane, dimethylolpropionic acid, poly(tetramethylene ether) glycol, poly(proplyene ether) diol, polyoxypropylene diamine, polyoxypropylene triamine, or combination thereof.

5. The coating composition of any one of claims 1-4, further comprising an additional poly siloxane.

6. The coating composition of any one of claims 1-5, wherein an equivalent weight ratio of the isocyanate component to active hydrogen of the amine-functional resin ranges from 0.85:1 to 1.4:1.

7. The coating composition of any one of claims 1-6, wherein the chain extender has a molecular weight ranging from 90 to 6000 amu.

8. The coating composition of any one of claims 1-7, further comprising TiCh in an amount of at least 5 wt. % based on a total solid weight of the composition.

9. The coating composition of any one of claims 1-8, wherein the isocyanate component comprises a prepolymer formed from hexamethylene diisocyanate, isophorone diisocyanate, or both, and a polyether polyol and / or polyetheramine.

10. The coating composition of any one of claims 1-9, wherein the organometallic catalyst comprises zinc, manganese, zirconium, titanium, cobalt, iron, lead, bismuth, and / or tin.

11. The coating composition of any one of claims 1-10, further comprising: a cure retardant in an amount of at least 5 wt. % based on a total solid weight of the composition; a solvent in an amount of up to 20 wt. % based on a total solid weight of the composition; and / or a rheology modifier in an amount of up to 15 wt. % based on a total solid weight of the composition.

12. The coating composition of claim 11, wherein the cure retardant comprises a ketone, a pyrazole, a polyol, or combinations thereof.

13. The coating composition of claim 11 or claim 12, wherein the cure retardant comprises acetone, acetylacetone, 3,5-dimethylpyrazole, or combinations thereof.

14. The coating composition of any one of claims 11-13, wherein the cure retardant comprises tetra (2-hydroxypropyl) ethylenediamine, polytetramethylene ether glycol or combinations thereof.

15. The coating composition of any one of claims 11-14, wherein the solvent comprises an aromatic hydrocarbon, a carboxylic acid ester, or combinations thereof.

16. The coating composition of any one of claims 11-15, wherein the solvent comprises naptha, xylene, butyl acetate, or combinations thereof.

17. A substrate comprising the coating composition of any one of claims 1-16.

18. An article comprising the substrate of claim 17.

19. The article of claim 18, comprising a precast concrete component, a prefabricated construction component, a turbine blade, fiber composite, fiberglass composite, pre-woven fiber, or machine aligned fiber.

20. A method comprising applying to at least a portion of a substrate the coating composition according to any one of claims 1-16.

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