Curable compositions

Abstract

Disclosed are compositions including a first component and a second component. The first component includes an isocyanate-functional polyurethane prepolymer. The second component includes a first difunctional polyol and an aromatic diamine. The composition also may include an accelerator. Also disclosed are substrates comprising a coating formed from one of the compositions disclosed herein on a surface thereof. Also disclosed are armor assemblies comprising one of the substrates disclosed herein.

Description

CURABLE COMPOSITIONSGOVERNMENT CONTRACT

[0001] This disclosure was made with Government support under Government Contract No. NCMS FY2020 Ambient Cure Adhesives 2021007 awarded by the GVSC. The United States Government may have certain rights in the subject matter disclosed herein.CROSS-REFERENCE TO RELATED APPLICATION

[0002] This application claims priority to U.S. Provisional Application No. 63 / 696,071, filed on September 18, 2024, and entitled “Curable Compositions,” incorporated herein in its entirety.FIELD

[0003] Compositions and uses thereof arc disclosed.BACKGROUND

[0004] Compositions, including adhesives, are utilized in a wide variety of applications to treat a variety of substrates or to bond together two or more substrate materials.SUMMARY

[0005] Disclosed are compositions comprising: a first component comprising an isocyanate-functional polyurethane prepolymer; a second component comprising (a) a first difunctional polyol; and (b) an aromatic diamine; where the composition comprises the first difunctional polyol in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition; and / or wherein the composition comprises the aromatic diamine in an amount sufficient to provide an active hydrogen equivalents of greater than 42 percent to 95 percent of the total active hydrogen equivalents in the second component; and / or wherein the composition comprises an accelerator.

[0006] Also disclosed are substrates comprising a coating formed from one of the compositions disclosed herein on a surface thereof.

[0007] Also disclosed are armor assemblies comprising one of the substrates disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 is a schematic of a top-down view of cylindrical battery cells.

[0009] FIG. 2 is a schematic of an exploded isometric view of an array of prismatic battery cells.

[0010] FIG. 3 is a schematic of a front view of an array of pouch battery cells.

[0011] FIG. 4 is a schematic of an isometric view of cylindrical cells positioned in a battery module.

[0012] FIG. 5 is a schematic of an exploded perspective view of a battery pack comprising multiple battery cells.

[0013] FIG. 6 is a schematic of an isometric view of (A) a battery cell, (B) a battery module, and (C) a battery pack.

[0014] FIG. 7 is a schematic of a perspective view of a battery pack.

[0015] FIG. 8 is a schematic of a cell to battery pack configuration.

[0016] FIG. 9 is a schematic of an isometric cut-out view of a cell to chassis battery assembly.

[0017] FIG. 10A is a graph showing the storage modulus and FIG. 10B is a graph showing the tangent delta of compositions across temperatures for Examples IV and XVI in the Examples.

[0018] FIG. 11 is a graph showing lap shear strength and lap shear displacement for Examples XXXIV to XLV.

[0019] FIG. 12 is a graph showing tensile strength and tensile elongation for Examples XXXIV to XLV.DETAILED DESCRIPTION

[0020] Disclosed are compositions comprising a first component and a second component. The first component comprises an isocyanate-functional polyurethane prepolymer. The second component comprises a diructional polyol in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition. The second component also comprises an aromatic diamine. The composition may comprises the aromatic diamine in an amount sufficient to provide an active hydrogen equivalents of greater than 42 percent to 95 percent of the total active hydrogen equivalents in the second component. The composition may comprise an accelerator in an amount of 0.03 percent by weight to 0.3 percent by weight based on total weight of the composition.Isocyanate-Functional Polyurethane Prepolymer

[0021] The first component may comprise an isocyanate-functional polyurethane prepolymer.

[0022] The isocyanate-functional polyurethane prepolymer may comprise an aliphatic isocyanate, such as cyclic aliphatic isocyanate, and / or an aromatic isocyanate-functional polyurethane prepolymer.

[0023] Commercially available isocyanate-functional polyurethane prepolymers that may be used in the present disclosure include isocyanate-functional polyurethane prepolymers available under the Desmodur® trade name from Covestro AG, prepolymers available under the Adiprene® trade name from Lanxess, and prepolymers available under the Lupranat® trade name from BASF.

[0024] The isocyanate-functional polyurethane prepolymer may comprise an Mn of at least 500 g / mol, such as at least 750 g / mol. The isocyanate-functional polyurethane prepolymer may comprise an Mn of no more than 5,000 g / mol, such as no more than 2,000 g / mol. The isocyanate-functional polyurethane prepolymer may comprise an Mn of 500 g / mol to 5,000 g / mol, such as 750 g / mol to 2,000 g / mol. As used herein, Mn may be measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran (THF) as the eluent at a flow rate of 1ml min"1. For example, Mn may be measured by Gel Permeation Chromatography using Waters 2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, tetrahydrofuran (THF) used as the eluent at a flow rate of 1 ml min"1, and two PL Gel Mixed C columns used for separation.

[0025] The isocyanate-functional polyurethane prepolymer may comprise an isocyanate equivalent weight of at least 250 g / eq, such as at least 375 g / eq. The isocyanate-functional polyurethane prepolymer may comprise an isocyanate equivalent weight of no more than 2,500 g / eq, such as no more than 1000 g / eq. The isocyanate-functional polyurethane prepolymer may comprise an isocyanate equivalent weight of 250 g / eq to 2,500 g / eq, such as 375 g / eq to 1,000 g / eq.

[0026] The isocyanate-functional polyurethane prepolymer comprises one or more free isocyanate functional groups (“NCO”). The free isocyanate functional group may be terminal and / or pendant. The isocyanate-functional polyurethane prepolymer may be pre-formed or may be formed in situ.

[0027] The composition may comprise the isocyanate-functional polyurethane prepolymer in an amount of at least 30 percent by weight based on total weight of thecompositions, such as at least 40 percent by weight. The composition may comprise the isocyanate-functional polyurethane prepolymer in an amount of no more than 70 percent by weight based on total weight of the composition, such as no more than 60 percent by weight. The composition may comprise the isocyanate-functional polyurethane prepolymer in an amount of 30 percent by weight to 70 percent by weight based on total weight of the composition, such as 40 percent by weight to 60 percent by weight.

[0028] The isocyanate-functional polyurethane prepolymer may comprise a difunctional isocyanate-functional polyurethane prepolymer. As used herein, “difunctional isocyanate- functional polyurethane prepolymer” refers to an isocyanate-functional polyurethane prepolymer containing two isocyanate functional groups. The difunctional isocyanate-functional polyurethane prepolymer may comprise a functional group in addition to the two isocyanate functional groups.

[0029] The isocyanate-functional polyurethane prepolymer may comprise a reaction product of reactants comprising a difunctional polyol and a diisocyanate. Optionally, the difunctional polyol may comprise a polyurethane backbone. As used herein, the term “difunctional polyol” refers to a molecule having two hydroxyl-functional groups and does not preclude the presence of functional groups in addition to the hydroxyl-functional groups. As used herein, the term “diisocyanate refers to a molecule containing two isocyanate functional groups.

[0030] Suitable difunctional polyols useful in forming the isocyanate-functional polyurethane prepolymer include polyhydric alcohols such as ethylene glycol, propanediol, neopentyl glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, cyclohexanediol, benzenedimethanol, 4,4’-isopropylidenedicyclohexanol. Suitable difunctional polyols may also include polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, and / or polysiloxane polyols. Polyamines corresponding to polyols may also be used, and in this case, urea linkages will be formed with the isocyanates.

[0031] The difunctional polyol may comprise a polycaprolactone-based polyol. The polycaprolactone-based polyols may comprise diols terminated with primary hydroxyl groups. Commercially available polycaprolactone-based polyols include those sold under the trade nameCapa™ from Perstorp Group, such as, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205.

[0032] The difunctional polyol may comprise a polyether polyol. The polyols may be based on a polyether chain derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and the like, and mixtures thereof. The polyol may comprise a tetrahydrofuran- based polyol. The polytetrahydrofuran-based polyols may comprise diols terminated with primary hydroxyl groups. Commercially available polytetrahydrofuran-based polyols include those sold under the trade name Terathane®, such as Terathane® PTMEG 250, Terathane® PTMEG 650, and Terathane® PTMEG 1000 which are blends of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups, available from Invista. In addition, polyols based on dimer diols sold under the trade names Pripol®, Solvermol™ and Empol®, available from Cognis Corporation, or bio-based polyols, available from BioBased Technologies, may also be utilized.

[0033] The difunctional polyol used to make the isocyanate-functional polyurethane prepolymer may have an Mn of at least 500 g / mol, such as at least 1,500 g / mol. The difunctional polyol used to make the isocyanate-functional polyurethane prepolymer may have an Mn of no more than 4,000 g / mol, such as no more than 3,500 g / mol. The difunctional polyol used to make the isocyanate-functional polyurethane prepolymer may have an Mn of 500 g / mol to 4,000 g / mol, such as 1,500 g / mol to 3,500 g / mol. Mn of the difunctional polyol may be measured as described herein above.

[0034] As discussed above, the difunctional isocyanate-functional polyurethane prepolymer may comprise a reaction product of reactants comprising a diisocyanate and a difunctional polyol. Suitable diisocyanates useful in forming the isocyanate-functional polyurethane prepolymer can be polymeric. As used herein, “diisocyanate” refers to a molecule containing two isocyanate functional group. For example, the diisocyanates may comprise Ci to C20 linear', cyclic, aliphatic, and / or aromatic diisocyanates, or mixtures thereof.

[0035] Aliphatic diisocyanates may include alkylene isocyanates, such as: trimethylene diisocyanate, tetramethylene diisocyanate, such as 1 ,4-tetramethylene diisocyanate; pentamethylene diisocyanate, such as 1,5 -pentamethylene diisocyanate and 2-methyl-l,5- pentamethylene diisocyanate; hexamethylene diisocyanate (“HDI”), such as 1,6-hexamethylene diisocyanate and 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, or mixtures thereof;heptamethylene diisocyanate, such as 1 ,7-heptamethylene diisocyanate; propylene diisocyanate, such as 1 ,2-propylcnc diisocyanatc; butylene diisocyanatc, such as 1 ,2-butylcnc diisocyanatc,2.3-butylene diisocyanate, 1,3-butylene diisocyanate, and 1,4-butylene diisocyanate; ethylene diisocyanate; decamethylene diisocyanate, such as 1,10-decamethylene diisocyanate; ethylidene diisocyanate; butylidene diisocyanate; and hexamethylene diisocyanate (“HD I”). Aliphatic diisocyanates may also include cycloalkylene isocyanates, such as: cyclopentane diisocyanate such as 1,3-cyclopentane diisocyanate; cyclohexane diisocyanate such as 1 ,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate (“IPDI”), IPDI trimer (commercially available as Desmodur® Z 4470 SN); methylene bis(4-cyclohexylisocyanate) (“HMDP’); polymeric methylene diphenyl diisocyanate (“MDI”); and mixed aralkyl diisocyanates such as tetramethylxylyl diisocyanates, such as meta-tetramethylxylylene diisocyanate (commercially available as TMXDI® from Allnex SA).

[0036] Aromatic diisocyanates may include arylene isocyanates, such as: phenylene diisocyanate, such as m-phenylene diisocyanate, p-phenylene diisocyanate, and chlorophenylene2.4-diisocyanate; naphthalene diisocyanate, such as 1,5 -naphthalene diisocyanate and 1,4- naphthalene diisocyanate. Aromatic polyisocyanates may also include alkarylene isocyanates, such as: methylene-interrupted aromatic diisocyanates, such as 4,4’ -diphenylene methane diisocyanate (“MDI”), and alkylated analogs such as 3,3’-dimethyl-4,4’-diphenylmethane diisocyanate, and polymeric methylenediphenyl diisocyanate; toluene diisocyanate (“TDI”), such as 2,4-tolylene or 2,6-tolylene diisocyanate, or mixtures thereof, bitoluene diisocyanates; and4.4-toluidine diisocyanate; xylene diisocyanate; dianisidine diisocyanate; xylylene diisocyanate; and other alkylated benzene diisocyanates.

[0037] As further described below, the difunctional polyol may comprise a polymer repeat unit comprising an unsubstituted polyether, an unsubstituted polyester, and / or an unsubstituted polycarbonate. Each polymer repeat unit may comprise an uninterrupted chain of at least 3 methylene units, such as no more than 6 methylene units.

[0038] The isocyanate-functional polyurethane prepolymer may comprise the diisocyanate functional prepolymer in an amount of at least 50 percent by weight based to total weight of the isocyanate-functional polyurethane prepolymer, such as at least 60 percent by weight, such as at least 70 percent by weight, such as at least 80 percent by weight, such as at least 90 percent by weight, such as 100 percent by weight, such as 50 percent by weight to 100percent by weight, such as 70 percent by weight to 100 percent by weight, such as 60 percent by weight to 90 percent by weight.

[0039] The isocyanate-functional polyurethane prepolymer may further comprise a monofunctional isocyanate-functional small molecule and / or a monofunctional isocyanate- functional prepolymer. The first component may further comprise a polyfunctional small molecule and / or a polyfunctional isocyanate-functional prepolymer. As used herein, “monofunctional isocyanate-functional small molecule” refers to an isocyanate-functional small molecule containing one isocyanate functional group. As used herein, “polyfunctional isocyanate-functional small molecule” refers to an isocyanate-functional small molecule containing more than two isocyanate functional groups. As used herein, “monofunctional isocyanate-functional prepolymer” refers to an isocyanate-functional prepolymer containing one isocyanate functional group. As used herein, “polyfunctional isocyanate-functional prepolymer” refers to an isocyanate-functional prepolymer containing more than two isocyanate functional groups. The monofunctional isocyanate-functional small molecule, monofunctional isocyanate- functional prepolymer, polyfunctional isocyanate-functional small molecule, and / or polyfunctional isocyanate-functional prepolymer each may comprise a functional group in addition to the isocyanate-functional group(s).

[0040] Optionally, the isocyanate-functional polyurethane prepolymer may comprise the monofunctional isocyanate-functional small molecule, the monofunctional isocyanate-functional prepolymer, the polyfunctional isocyanate-functional small molecule, and / or the polyfunctional isocyanate-functional prepolymer in a combined amount of no more than 50 percent by weight based on total weight of the isocyanate-functional pre-polymer, such as no more than 40 percent by weight, such as no more than 30 percent by weight, such as no more than 20 percent by weight, such as no more than 10 percent by weight, such as 10 percent by weight to 40 percent by weight, such as 20 percent by weight to 30 percent by weight.

[0041] Optionally, the composition may be substantially free, essentially free, or completely free of monofunctional isocyanate-functional small molecule, monofunctional isocyanate-functional prepolymer, polyfunctional isocyanate-functional small molecule, and / or polyfunctional isocyanate-functional prepolymer.Polyols

[0042] The second component may comprise a difunctional polyol.

[0043] The composition may comprise the difunctional polyol in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight based on total weight of the composition. The composition may comprise the difunctional polyol in an amount of less than 50 percent by weight based on total weight of the composition, such as no more than 40 percent by weight. The composition may comprise the difunctional polyol in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition, such as 5 percent by weight to 40 percent by weight.

[0044] The difunctional polyol may comprise any of the difunctional polyols described above.

[0045] The difunctional polyol may comprise a polymer repeat unit comprising an unsubstituted polyether, an unsubstituted polyester, and / or an unsubstituted polycarbonate. The polymer repeat unit of the unsubstituted polyether, polyester, or polycarbonate may comprise an uninterrupted chain of at least 3 methylene units (ie. -CH2CH2CH2-), such as no more than 6 methylene units. Suitable unsubstituted polyether diols include polytrimethylene glycol diols (commercially available from Gantrade or under the Velvetol® trade name from WeylChem), polytetramethylene glycol / polytetrahydrofuran diols, polypentamethylene glycol diols, and polyhexamethylene glycol diols. Suitable unsubstituted polyester diols include polyester diols made from the ring-opening of unsubstituted cyclic esters, such as poly(butyrolactone), poly valerolactone, and polycaprolactone (available under the Capa® trade name from Ingevity). Additional suitable polyesters include polyesters comprising 1,3-propylene glycol, 1,4- butanediol, 1,5 -pentanediol, and 1,6-hexanediol. Suitable unsubstituted polycarbonate diols include polycarbonate diols comprising 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0046] The difunctional polyol may comprise a hydroxyl-terminated polyurethane prepolymer. The difunctional hydroxyl-terminated polyurethane prepolymer may comprise the reaction product of reactants comprising a difunctional isocyanate and any difunctional polyol described above. In some cases, the difunctional isocyanate used to generate the hydroxyl- terminated polyurethane prepolymer may comprise an aromatic isocyanate, such as toluenediisocyanate or methylene diphenyldiisocyanate. The difunctional polyol used to generate the hydroxyl-terminated polyurethane prepolymer may comprise an unsubstituted polyether, an unsubstituted polyester, and / or an unsubstituted polycarbonate; the polymer repeatunit of the unsubstituted diol may comprise an uninterrupted chain of at least 3 methylene units, such as no more than 6 methylene units. Suitable diols include polytetrahydrofuran diols and polycaprolactone diols.

[0047] The difunctional polyol may have an Mn as described above.

[0048] The difunctional polyol may be present in the composition in an amount sufficient to provide at least 50 percent of the hydroxy equivalents based on total number of hydroxy equivalents in the second component.

[0049] The composition may further comprise a second polyol in addition to the difunctional polyol. The second polyol may be present in the second component, a third component, or a higher component. The second polyol may be a monofunctional alcohol and / or a polyfunctional polyol, including any of the triols, tetraols, and / or higher functional polyols described above. As used herein, “monofunctional alcohol” refers to a molecule containing one hydroxyl-functional group. As used herein, “polyfunctional polyol” refers to a molecule containing more than two hydroxyl-functional groups. The monofunctional alcohol and / or the polyfunctional polyol may comprise a functional group in addition to the hydroxyl-functional group(s).

[0050] The composition may comprise the second polyol in an amount up to 50 percent by weight based on total weight of the total polyol, such as no more than 40 percent by weight. The composition may comprise the second polyol in an amount of at least 1 percent by weight based on total weight of the total polyol, such as at least 5 percent by weight. The composition may comprise the second polyol in an amount of 1 percent by weight to 50 percent by weight based on total weight of the total polyol, such as 5 percent by weight to 40 percent by weight.Aromatic Diamine

[0051] The second component may comprise an aromatic diamine in an amount sufficient to provide an active hydrogen equivalent of greater than 42 percent to 95 percent of the total active hydrogen equivalents in the second component, such as 45 percent to 95 percent, such as 50 percent to 90 percent, such as 60 percent to 80 percent. As used herein, “aromatic diamine” refers to a compound comprising one or more aromatic rings and two amine functional groups bonded to the aromatic ring.

[0052] The aromatic diamine may be a sterically hindered aromatic diamine. As used herein, a “sterically hindered aromatic diamine” refers to (i) an aromatic diamine that comprisesa substituent, such as a C1-C4 alkyl, C1-C4 alkoxy, or C1-C4 alkylthio group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, see -butyl, tert-butyl, isobutyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n- butylthio, or isobutylthio, wherein the substituent is in at least one position ortho to each amino group, and / or (ii) an aromatic diamine in which the amine nitrogen additionally comprises a substituent such as an alkyl substituent.

[0053] The aromatic diamine may comprise a liquid at ambient conditions.

[0054] Suitable aromatic diamines include phenylene diamine, diaminodiphenylmethane, 2,4-diaminomesitylene, l,3,5-triethyl-2,6-diaminobenzene, l-methyl-3,5-diethyl-2,4- diaminobenzene, isobutyl 4-chloro-3,5-diaminobenzoate, methylene bis(methylanthranilate), trimethylene glycol di-p-aminobenzoate, dimethylthiotoluenediamine, available as Ethacure 300, diethyltoluenediamine, available as Ethacure 100, 4,4’ -bis(sec-butylamino)diphenyl methane, available as Ethacure 420, or combinations thereof.

[0055] The aromatic diamine may comprise an Mn of at least 100 g / mol, such as at least 125 g / mol. The aromatic diamine may comprise an Mn of no more than 750 g / mol, such as no more than 500 g / mol. The aromatic diamine may comprise an Mn of 100 g / mol to 750 g / mol, such as 125 g / mol to 500 g / mol. As used herein, Mn of the aromatic diamine may be measured by mass spectrometry as set forth in Mass Spectrometry: A Textbook (3rdEdition, 2018, edited by Jurgen Gross).Accelerator

[0056] The composition may comprise an accelerator. As used herein, “accelerator” refers to a substance that increases the rate or decreases the activation energy of a chemical reaction in comparison to the same reaction in the absence of an accelerator. An accelerator may be either a “catalyst,” that is, without itself undergoing any permanent chemical change, or may be reactive, that is, capable of chemical reactions and includes any level of reaction from partial to complete reaction of a reactant.

[0057] The accelerator may comprise a nitrogen-based catalyst in addition to the aromatic diamine described above, such as an amine catalyst. That is, the accelerator does not comprise an aromatic diamine. The accelerator may comprise a tertiary amine, an N- heterocyclic carbene, or an amidine / guanidine. Suitable accelerators that may be used in the present disclosure include N, A-dimethylcyclohexylamine, A,A-dimethylethanolamine, A-methylmorpholine, 2,2’ -dimorpholinodiethylether, dimethylaminoethoxyethanol, triethylenediamine, bis(2-dimcthylaminocthyl)cthcr, N,N,N’ -trimcthy laminocthylcthanolaminc, N,N,N ’,N’- tetramethyl- 1 ,6-hexanediamine, 1 ,3,5-tris(dimethylaminopropyl)-hexahydro-s-triazine, 1,8- diazabicyclo[5.4.0]undec-7-ene, A4(3-aminopropyl)imidazole, 1 ,2-dimethylimidazole, 1,5,7- triazabicyclo[4.4.0]dec-5-ene, or 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0058] The accelerator may be an organic acid, such as diphenyl phosphate, methanesulfonic acid, or triflic acid.

[0059] The accelerator may be an inorganic accelerator, such as an organometallic complex. Suitable inorganic accelerators include titanates, such as tetrabutyl titanate or tetrapropyl titanate, tin compounds, such as dibutyltin dilaurate, dibutyltin diacetate, tin octoate, or dibutyl tin oxide, or other metal compounds, such as bismuth, zirconium, titanium, aluminum, or iron, or chelates thereof, such as zirconium acetylacetonate or iron acetylacetonate.

[0060] The composition may comprise the accelerator in an amount of at least 0.0001 percent by weight based on total weight of the composition, such as at least 0.001 percent by weight, such as at least 0.01 percent by weight, such as at least 0.03 percent by weight. The composition may comprise the accelerator in an amount of no more than 5 percent by weight based on total weight of the composition, such as no more than 1 percent by weight, such as no more than 0.3 percent by weight, such as no more than 0.25 percent by weight. The composition may comprise the accelerator in an amount of 0.0001 percent by weight to 5 percent by weight based on total weight of the composition, such as 0.001 percent by weight to 1 percent by weight, such as 0.01 percent by weight to 0.25 percent by weight, such as 0.03 percent by weight to 0.3 percent by weight.Filler

[0061] The composition may comprise filler. Useful filler that may be included in the composition include cellulose, starch, acrylics, fiberglass, fibrous titanium dioxide, whisker type calcium carbonate (aragonite), carbon fiber (which includes graphite and carbon nanotubes), borosilicate, aluminosilicate, calcium carbonate, and the like. Fillers may be a thermally conductive filler such as, for example, boron nitride, aluminum trihydrate, metal oxide, metal hydroxide, graphite, graphene, and the like. Fillers may be non-thermally conductive filler, such as, for example, mica, wollastonite, calcium carbonate, glass microspheres, clay, silicon dioxide, and the like.

[0062] The filler may be present in the composition in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight. The filler may be present in the composition in an amount of less than 50 percent by weight based on total weight of the composition, such as no more than 30 percent by weight, such as no more than 20 percent by weight. The filler may be present in the composition in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition, such as 5 percent by weight to 20 percent by weight.Moisture Scavengers

[0063] The composition may optionally comprise a moisture scavenger.

[0064] Examples of suitable moisture scavengers that may be used in the present disclosure include physical and chemical moisture scavengers. As used herein, “moisture scavenger” refers to a material capable of absorbing water or reacting with water to prevent its reaction with other components of the composition. Suitable physical moisture scavengers include zeolites / molecular sieves. Suitable chemical moisture scavengers include oxazolidines, tosyl isocyanates, orthoformates, or vinyl silanes.

[0065] The composition may comprise the moisture scavenger in an amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight. The composition may comprise the moisture scavenger in an amount of no more than 10 percent by weight based on total weight of the composition, such as no more than 5 percent by weight. The composition may comprise the moisture scavenger in an amount of 0.1 percent by weight to 10 percent by weight based on total weight of the composition, such as 1 percent by weight to 5 percent by weight.Additives

[0066] The composition may optionally comprise an additive. The additive(s) may be present in the first component, the second component, and / or a third or higher components so long as the additive is not reactive with any of the other ingredients in such components. As used herein, an “additive” includes a rheology modifier including a thixotrope, a tackifier, a thermoplastic polymer, a surfactant, a dispersant, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, a plasticizer, an adhesion promoter, an antioxidant, a silane, a stabilizer, an oil, and / or a blowing agent. Certain thermally conductive materials such as aluminum hydroxide and magnesium hydroxide, for example, also may be flame retardants.As used herein, “flame retardant” refers to a material that slows down or stops the spread of fire or reduces its intensity. Flame retardants may be available as a powder that may be mixed with a composition, a foam, or a gel. In examples, when the compositions disclosed herein include a flame retardant, such compositions may form a coating on a substrate surface and such coating may function as a flame retardant. A flame retardant can include a mineral, an organic compound, an organohalogen compound, an organophosphorus compound, or a combination thereof. As used herein, the term “plasticizer” refers to a molecule or a compound that does not have a functional group capable of reacting with molecules or compounds in a composition, does not volatilize under ambient conditions, and that is added to the composition to decrease viscosity, decrease glass transition temperature (Tg), and impart flexibility.

[0067] Additive(s), if present at all, may be present in the composition in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight. Additive(s), if present at all, may be present in the composition in a combined amount of no more than 10 percent by weight based on total weight of the composition, such as no more than 5 percent by weight. Additive(s), if present at all, may be present in the composition in a combined amount of 0.1 percent by weight to 10 percent by weight based on total weight of the composition, such as 1 percent by weight to 5 percent by weight.Compositions

[0068] The composition may comprise a ratio of isocyanate equivalents to active hydrogen equivalents (“NCO:OH+NH2”) of at least 0.75:1, such as at least 1:1. The composition may comprise a ratio of isocyanate equivalents to active hydrogen equivalents of no more than 1.7:1, such as no more than 1.4:1. The composition may comprise a ratio of isocyanate equivalents to active hydrogen equivalents of 0.75:1 to 1.7:1, such as 1:1 to 1.4:1.

[0069] The compositions disclosed herein may be formulated, for example, as a coating composition such as an adhesive composition, such as a structural adhesive composition, a sealant composition, a pottant composition, a foam, a pre-preg, a liquid shim composition, a sealant composition, or a gap filler composition.

[0070] The composition may be substantially free, essentially free, or completely free, of unreacted small molecule aromatic diisocyanate, such as phenylene diisocyanates; toluene diisocyanates p- and m-phenylene diisocyanate, xylene diisocyanates, 2,4 and / or 2,6toluene diisocyanates (TD1), 1 ,5-naphthalene diisocyanate; carbodimide modified methylene diisocyanatc, 4, 4'-diphcnyl-mcthanc diisocyanatc (MDI) and, if appropriate, its higher homologues (polymeric MDI), modified MDI compounds, naphthalene diisocyanates (NDI), isomer mixtures of individual aromatic diisocyanates or combinations thereof.Methods and Cured Coatings

[0071] The compositions described above may be applied alone or as part of a system that can be deposited in a number of different ways onto a number of different substrates. Accordingly, disclosed herein are methods for treating a substrate comprising, or consisting essentially of, or consisting of, contacting a surface of the substrate with any of the compositions disclosed herein. Optionally, the method may comprise mixing the first component and the second component to form the composition. The composition can be applied to the surface of a substrate in any number of different ways by depositing, applying, or contacting the compositions to a substate surface to form a coating thereon, non-limiting examples of which include brushes, rollers, films, pellets, trowels, spatulas, dips, spray guns, and applicator guns.

[0072] After application to the substrate(s), the composition may be cured. For example, the composition may be allowed to cure at ambient conditions or slightly thermal conditions, and for any desired time period (e.g., from 5 minutes to 1 hour) sufficient to cure the composition on the substrate(s). Optionally, the composition may be further cured by heating at an elevated temperature following the contacting of the substrate surface with the composition, such as at a temperature of less than 90°C, such as less than 80°C, such as less than 70°C, such as less than 60°C, but greater than ambient, such as greater than 40°C, such as greater than 50°C, and for any desired time period (e.g., from 5 minutes to 1 hour) sufficient to cure the composition on the substrate(s). Upon cure, the composition may form a coating on the substrate surface. The coating may be, for example, an adhesive such as a structural adhesive, a sealant, a pottant, a prepreg, a liquid shim, a seal, or a gap filler. The composition may be cured to form an article, such as by additive manufacturing, such as 3D printing as described below.

[0073] The method optionally may further comprise contacting a surface of a second substrate to the composition such that the composition is between the first substrate and the second substrate. For example, the composition may be applied to either one or both of the substrate materials such that the composition is positioned between the first and the secondsubstrates. Tn examples, the substrates may be aligned, and pressure and / or spacers may be added to control bond thickness.

[0074] The composition may be applied to cleaned or uncleaned (i.e., including oil or oiled) substrate surfaces. The compositions disclosed herein may also be applied to a substrate that has been pretreated, coated with an electrodepo sitable coating, and / or coated with additional coatings such as a primer, basecoat, or topcoat. That is, “contacting a surface of the substrate” encompasses contacting a surface of a substrate that has been treated with other coatings, as described herein.

[0075] The composition may be injected or otherwise placed in a die caster or a mould and dried or cured under ambient conditions or by exposure to an external energy source, for example, such as by heating to a temperature of less than 180°C, such as less than 130°C, such as less than 90°C to form a pail or a member and optionally may be machined to a particular configuration.

[0076] The compositions disclosed herein may be applied to a substrate surface and cured as described above to form a coating.

[0077] The coatings surprisingly demonstrate at least one of the following:(a) a gradual decrease in storage modulus from -50°C to 150°C, resulting in a tangent delta less than 0.5 across this temperature range, such as a tangent delta less than 0.4, such as a tangent delta less than 0.3, as shown in FIG. 10A and FIG. 10B (Example IV vs. comparative example XVI); and / or(b) a lap shear strength greater than 14 MPa, such as greater than 15 MPa, such as greater than 17 MPa and a lap shear displacement of at least 3.0 mm, such as at least 3.5 mm, such as at least 4.0 mm, both measured according to ASTM D1002- 10 (2019) using 2024 T3 aluminum and a pull rate of 13 mm / min; and or(c) an ultimate tensile strength at break of greater than 9 MPa, such as at least 11 MPa, such as at least 14 MPa, and at least 250% elongation at break, such as at least 350%, such as at least 500% measured according to ISO 527-1:2019.3-D Printing

[0078] The compositions disclosed herein may be casted, extruded, molded, or machined to form a part or a member in a cured state.

[0079] The compositions may be used in any suitable additive manufacturing technology, such as three-dimensional (3D) printing, extrusion, jetting, and binder jetting. “Additive manufacturing” refers to a process of producing a part or member by constructing it in layers, such as one layer at a time. “3D printing” refers to a computerized process, optionally including artificial intelligence modulation, by which materials are printed or deposited in successive layers to produce a 3D pail or member.

[0080] The present disclosure is also directed to the production of structural articles, such as by way of a non-limiting example, sound damping pads, print gaskets, or seals, using an additive manufacturing process, such as 3D printing. A 3D part or member may be produced by depositing successive portions or layers over a base of any spatial configuration and thereafter depositing additional portions or layers over the underlying deposited portion or layer and / or adjacent to the previously deposited portion or layer to produce the 3D printed part or member.

[0081] It will be appreciated that the configuration of the 3D printing process, including the selection of suitable deposition equipment, depends on a number of factors such as the deposition volume, the viscosity of the composition and the complexity of the part being fabricated. Any suitable mixing, delivery, and 3D printing equipment as known to those skilled in the art, may be used. Compositions may be printed or deposited in any size and / or shape of droplets or extrudate, and in any patterns to produce the 3D structure.

[0082] Compositions as disclosed herein may be applied or deposited by any suitable 3D printing method as known to those skilled in the art.

[0083] The first component and the second component may be premixed, i.e., mixed together, prior to application, and then deposited. The mixture may be reacted or thermoset when the material is deposited; the deposited reaction mixture may react after deposition and may also react with previously deposited portions and / or subsequently deposited portions of the article such as underlying layers or overlying layers of the article.

[0084] In a non-limiting example, the first and second components may be released from their individual storage containers and pushed, such as pumped through conduits, such as hoses, to a mixer, such as a static or dynamic mixer, wherein the composition may be mixed for a time sufficient to homogenize the composition, wherein the composition may then be released through an outlet. The outlet may be a deposition device, such as a printing head, and / or the materials may exit the mixing unit and be pushed, such as by a pump, through a conduit, such asa hose, to the printing head. The printing head may optionally be mounted on a 3D rotational robotic ami to allow delivery of 3D print compositions to any base in any spatial configuration and / or the base may be manipulated in any spatial configuration during the 3D printing process.

[0085] Alternatively, the first component and the second component may be deposited independently from different printing heads. The first component may be deposited from one printing head and the second component may be deposited from a second printing head sequentially or simultaneously. The first and second components may be deposited in any pattern such that the first and second components comprising any deposited layer can react together as well as react with underlying and / or overlying layers to produce the 3D printed part or member.

[0086] Methods provided by the present disclosure include printing the composition on a fabricated part. Methods provided by the present disclosure include directly printing parts. The entire part can be formed from one of the compositions disclosed herein, one or more portions of a part can be formed from one of the compositions disclosed herein, one or more different portions of a part can be formed using the compositions disclosed herein, and / or one or more surfaces of a part can be formed from a composition provided by the present disclosure. In addition, internal regions of a part can be formed from a composition provided by the present disclosure.Dielectric Coating Compositions and Dielectric Coatings and Dielectric Systems and Kits

[0087] Also disclosed herein are dielectric coating systems. The dielectric coating system may comprise: a first composition for application to a first portion of a substrate surface, the first composition comprising a dielectric coating composition; and a second composition for application to a second portion of a substrate surface, the second composition comprising any of the compositions disclosed above that, in a cured state, may form a second coating. The first portion and the second portion may be on a single substrate or may be on a first substrate and a second substrate, respectively.

[0088] Also disclosed herein are dielectric coating kits. The dielectric coating kit may comprise: a first composition for application to a first portion of a substrate surface, the first composition comprising a dielectric coating composition; and a second composition for application to a second portion of a substrate surface, the second composition comprising any ofthe compositions disclosed above that, in a cured state, may form a second coating. The first portion and the second portion may be on a single substrate or may be on a first substrate and a second substrate, respectively. The kit optionally may comprise instructions for applying the first composition and the second composition to the first portion and the second portion of the substrate surface, respectively.

[0089] When used with respect to the dielectric coating systems and kits disclosed herein, the first portion and the second portion may be the same or different, provided that the first portion and the second portion overlap to form a coating stack, e.g., a second coating on a dielectric coating. Such a coating stack does not preclude the possibility of coatings in addition to the dielectric coating and the second coating, wherein such additional coatings may or may not be between the dielectric coating and the second coating. Optionally, the coating stack may be formed between two substrates.

[0090] The dielectric coating may be formed on a first portion of a surface of a first substrate and the second coating may be formed on a second portion of a surface of a second substrate and the substrates may be positioned such that the first portion and the second portion overlap to form a coating stack as described above.

[0091] As used herein, “dielectric” refers to a coating composition or coating comprising a dielectric strength of at least 10 kV / mm measured using a Sefelec Dielectric Strength Tester (RMG12AC-DC; voltage limit 12.0 kV, Imax Limit 0.1 mA, 19 sec ramp, 20 sec dwell, 2 sec fall) according to ASTM D149-09, such as at least 12 kV / mm, such as at least 15 kV / mm.

[0092] The dielectric coating composition may comprise a binder comprising a filmforming resin. As used herein, “film-forming resin” refers to one or more monomers, oligomers, prepolymers and / or polymers, such as homopolymers and / or copolymers, that can form a coating upon reaction with a curing agent or crosslinker, upon evaporation of a solvent, and / or upon photo or thermal activation. The dielectric coating composition may comprise any suitable filmforming resin, including organic film-forming resins and / or inorganic film-forming resins, such as silicon-based film-forming resins. Examples of suitable film-forming resins include but are not limited to polyester, alkyd, urethane, isocyanate, polyurea, epoxy, acrylic, polyether, polysulfide, polyamine, polyamide, polyvinyl chloride, polyolefin, polyvinylidene fluoride, polyolefin, polysiloxane, amine-aldehydes, resinous polyols, phosphatized polyepoxides, phosphatized acrylic polymers, and / or aminoplasts.

[0093] The dielectric coating composition may optionally comprise a curing agent and / or crosslinker that is capable of crosslinking with the film-forming resin to cure the dielectric coating composition. Any suitable curing agent and / or crosslinker that is capable of crosslinking with the film-forming resin may be used. Examples of suitable curing agents include but are not limited to amines, aminoplasts, phenoplasts, polyisocyanates, including blocked polyisocyanates, polyepoxides, beta-hydroxyalkylamides, polyacids, organometallic acid-functional materials, polyamines, polyamides, polysulfides, polythiols, polyenes such as polyacrylates, polyols, polysilanes and the like, or combinations thereof.

[0094] The dielectric coating composition may optionally further comprise colorants, pigments, additives, and / or fillers. Suitable fillers that may be used in the dielectric coating composition includeTC / EI filler materials, TC / EC filler materials, and / or NTC / EI filler materials.

[0095] The dielectric coating composition may comprise a thermoset coating composition, wherein the coating composition is cured upon crosslinking of a film-forming resin and a curing agent and / or crosslinker. Alternatively, the dielectric coating composition may comprise a thermoplastic coating composition, wherein the coating composition comprises a film-forming resin that cures upon evaporation of water and / or solvent. Alternatively, the dielectric coating composition may comprise a thermoset or thermoplastic coating composition that cures upon exposure to actinic radiation, such as ultraviolet light.

[0096] The dielectric coating composition may comprise a liquid coating composition or a powder coating composition. As used herein, when referring to a dielectric coating composition, “liquid” means a material having a viscosity less than 100,000 Pa-s at 25°C as measured by parallel plate rheology with a plate diameter of 25 mm, a gap of 0.5 mm, and a shear rate of 1 s’1.

[0097] Suitable liquid coating compositions include but are not limited to electrodepositable coating compositions, one-component coating compositions, and / or multicomponent coating compositions.

[0098] For example, the liquid dielectric coating composition may comprise an electrodepositable coating composition. The electrodepositable coating composition may comprise one or more cationic or anionic salt group-containing film-forming resins that may bedeposited onto a metal or other conductive substrate under the influence of an applied electrical potential, i.c., by clcctrodcposition.

[0099] In other examples, the liquid dielectric coating composition may comprise a UV- curable coating composition comprising film-forming resins capable of curing upon exposure to UV radiation. Any suitable UV-curable film-forming resin may be used, such as free radical polymerizable resins containing ethylenic unsaturation or olefinic double bonds and / or filmforming resins that may react through a cationic photopolymerization mechanism. Examples of suitable UV-curable coating compositions that may be used include but are not limited to the RAYCRON line of UV-curable coatings, commercially available from PPG Industries, Inc.

[0100] Other suitable liquid dielectric coating compositions include but are not limited to the SPECTRACRON line of solvent-based coating compositions and the AQUACRON line of water-based coating compositions, all commercially available from PPG Industries, Inc. The liquid dielectric coating may also be applied as a two-component composition where the filmforming resins and the reactive curing agent and / or crosslinker are mixed just before application of the coating composition and may optionally cure under ambient conditions without any external energy source.

[0101] Alternatively, the dielectric coating composition may comprise a powder coating composition. “Powder coating composition” as used herein refers to any dielectric coating composition in the form of a co-reactable solid in particulate form which may be substantially free, essentially free, or completely free of water and / or solvent. Suitable film-forming resins useful in dielectric powder coating compositions include those discussed in PCT Publ. No. WO 2021 / 173941A1, pars.

[0006] to

[0042] ,

[0057] to

[0068] ,

[0088] to

[0105] and

[0128] to

[0139] , incorporated herein by reference. Non-limiting examples of suitable powder compositions that may be used in the present disclosure include the polyester-based ENVIROCRON line of powder coating compositions (commercially available from PPG Industries, Inc.), silicon modified polyester compositions, epoxy-polyester hybrid compositions, and / or UV-curable powder compositions.

[0102] The dielectric coating composition may be applied to a substrate by any suitable method known in the art, including but not limited to electrodeposition, coil coating, spraying, such as electrostatic spraying, flow coating, spin coating, curtain coating, brushing, dipping, hot- melt extrusion, application of a film, and / or by the use of a fluidized bed. Once applied to thesubstrate, the dielectric coating composition may be cured by any method known in the art, such as baking, induction heating, infrared heating, and / or exposure to actinic radiation such as UV.

[0103] A dielectric coating may be formed from the dielectric coating compositions described herein.

[0104] The dielectric coating may comprise a dielectric strength of at least 10 kV / mm measured using a Sefelec Dielectric Strength Tester (RMG12AC-DC; voltage limit 12.0 kV DC, Imax Limit 0.1 mA, 19 sec ramp, 20 sec dwell, 2 sec fall) according to ASTM D149-09, such as at least 12 kV / mm, such as at least 15 kV / mm. The dielectric coating may comprise a dielectric strength of no more than 120 kV / mm measured using a Sefelec Dielectric Strength Tester (RMG12AC-DC; voltage limit 12.0 kV DC, Imax Limit 0.1 mA, 19 sec ramp, 20 sec dwell, 2 sec fall) according to ASTM D149-09, such as no more than 100 kV / mm. The dielectric coating may comprise a dielectric strength of 10 kV / mm to 120 kV / mm measured using a Sefelec Dielectric Strength Tester (RMG12AC-DC; voltage limit 12.0 kV DC, Imax Limit 0.1 mA, 19 sec ramp, 20 sec dwell, 2 sec fall) according to ASTM DI 49-09, such as 12 kV / mm to 100 kV / mm, such as 15 kV / mm to 100 kV / mm.

[0105] The dielectric coating may be formulated as a hot-melt or a film. As used herein, a “film” refers to a sheet comprising a cured composition that may be formed independent of a substrate surface. The film may optionally comprise an adhesive layer, such as a pressure sensitive adhesive layer.

[0106] Compositions of the present disclosure may be applied or deposited using any suitable method, including those aforementioned. Using the methods provided by the present disclosure articles may be formed from one of the compositions disclosed herein.Substrates

[0107] Compositions described herein may be coated or deposited on, or otherwise contacted with, any substrate or surface, such as, but not limited to, metals or metal alloys, polymeric materials, such as plastics including filled and unfilled thermoplastic or thermoset materials, and / or composite materials. The substrate may comprise a composite material such as a plastic, a fiberglass, and / or a carbon fiber composite. Other suitable substrates include, but are not limited to, glass or natural materials such as wood. Substrates may include two or more of any different materials in any combination, such as, but not limited to, two different metals, or a metal and a metal alloy, or a metal and a metal alloy and one or more composite materials.

[0108] Suitable substrates may include, but are not limited to, both flexible and rigid metal substrates such as ferrous metals, aluminum, aluminum alloys, magnesium, titanium, copper, and other metal and alloy substrates. The ferrous metal substrates may include, for example, iron, steel, and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, nickel plated cold rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, pickled steel, zinc-iron alloy such as GALV ANNEAL, and combinations thereof. Aluminum alloys, such as those, for example, of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX, or 8XXX series as well as clad aluminum alloys and cast aluminum alloys, such as those, for example, of the A356, 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, or 8XX.X series also may be used as the substrate. The substrate also may comprise, for example, magnesium, such as magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series, titanium and / or titanium alloys, such as those of grades 1-36 including H grade valiants, copper and copper alloys, or other non-ferrous metals, as well as alloys of these materials.

[0109] It will also be understood that the substrate may comprise a bare substrate or the substrate may be pretreated or pre-coated, at least in part, with one or more layers. Suitable pretreatment solutions may include but are not limited to a zinc phosphate pretreatment solution such as, for example, those described in U.S. Pat. Nos. 4,793,867 and 5,588,989, or a zirconium containing pretreatment solution such as, for example, those described in U.S. Pat. Nos. 7,749,368 and 8,673,091, all of which are incorporated herein by reference.

[0110] The substrate may be in any form, such as, without limitation, a sheet, a foil, a laminate foil, a pad, a fabricated part, a component, or an article.

[0111] In examples, the substrate may be a multi-metal article. As used herein, the term “multi-metal article” refers to (1) an article that has at least one surface comprised of a first metal and at least one surface comprised of a second metal that is different from the first metal, (2) a first article that has at least one surface comprised of a first metal and a second article that has at least one surface comprised of a second metal that is different from the first metal, or (3) both (1) and (2).

[0112] The compositions disclosed herein are not limited and may be particularly suitable for use in various industrial or transportation applications including automotive applications, commercial applications, rail locomotive, marine applications, and / or aerospaceapplications. Suitable substrates for use in the present disclosure include those that are used in the assembly of vehicular bodies (for example, without limitation, door, body panel, trunk deck lid, roof panel, hood, roof, and / or stringers, rivets, landing gear components, and / or skins used on an aircraft), vehicular frames, vehicular parts, motorcycles, wheels, and industrial structures and components. As used herein, “vehicle” or variations thereof includes, but is not limited to, civilian vehicles, light and heavy commercial vehicles, civilian and military aircraft, and / or land vehicles such as cars, motorcycles, and / or trucks. Other suitable substrates include armor assemblies such as those on a tank and / orto protective clothing such as body armor, personal armor, suits of armor, and the like.

[0113] FIGS. 1 to 9 illustrate non-limiting examples of battery assembly components and constructions as well as non-limiting applications or use of compositions as disclosed herein in said battery assemblies. Although FIGS. 1 to 9 illustrate specific examples of cell shapes and cell arrangements, cells may be arranged in any configuration known to those skilled in the art. Additionally, the compositions disclosed herein, in an at least partially cured state, may be used to form pads, adhesives, coatings, pottants and the like, to provide thermal protection between battery cells, within battery modules and / or within battery packs. These materials may be used on any surface or in any space within such battery assemblies. For example, compositions disclosed herein also may be useful in battery assemblies including, but not limited to, cell to module (FIGS. 3, 4, 6B), module to pack (FIGS. 6C, 7), cell to pack (FIG. 8), and cell to chassis battery assemblies (FIG. 9). Such battery assemblies may be used in, but not limited to, any aforementioned application.

[0114] Battery assemblies may be any combination of one or more battery cells, the interconnects which provide electrical conductivity between them, as well as ancillary components such as, in non-limiting examples, control electronics and components that ensure the necessary structural, mechanical, and environmental requirements for the operation of a specific battery (for example, without limitation, cell interconnectors such as wires, battery pack enclosures including trays and lids, module enclosures, module frames and frame plates, module racking, cooling and heating components including cooling plates, cooling fins, and cooling tubes, electrical busbars, battery management systems, battery thermal management systems, chargers, inverters and converters).

[0115] As illustrated in FIG. 4, battery cells 10 may be connected by interconnector wires 5 with other battery cells 10 in series or in parallel to enable an electric current to flow between cells 10. Battery cells may be any suitable size or shape known to those skilled in the art, such as but not limited to, cylindrical (FIGS. 1, 4 and 9), prismatic (FIGS. 2, 5-8) and / or pouch (FIG. 3). Battery cells 10 may be enclosed to provide desired mechanical protection and environmental isolation of the cell. For example, cylindrical and prismatic cells may be encased in metal cans, cases, and lids, while pouch cells may be enclosed in multilayer laminate foils. Battery terminals 1 connect the electrodes inside the battery cell to the electrical circuit outside the battery cell, with one being a positive terminal and the other being a negative terminal.

[0116] As illustrated in FIGS. 3 and 4, battery cells 10 may be arranged in modules 100. The modules 100 may include a partial enclosure of the arranged cells 10. Ancillary components, such as those disclosed above, may be included. Spaces of any dimensions may be located between the plurality of cells, ancillary components, base, and / or any interior surface of the module wall or other enclosure 120.

[0117] FIG. 1 illustrates a top-down view of cylindrical battery cells 10 having terminals 1. As shown, the cells are arranged in rows with either cooling tubes 3 or dielectric insulation paper (e-paper) 4 between them. As shown, materials, such as adhesive 6 and / or pottants 7 optionally formed from one of the cured compositions disclosed herein may be positioned between the cells 10, cooling tubes 3 and / or e-paper 4.

[0118] FIG. 2 illustrates an exploded isometric view of an array of prismatic battery cells 10. As shown, each prismatic cell 10 may comprise a top 11, a bottom, and walls 13 positioned between the top and bottom and each having a surface. As shown, materials, such as pads 8 formed from one of the cured compositions disclosed herein may be positioned between surfaces of cell walls 13 of adjacent cells 10.

[0119] FIG. 3 illustrates a cut-out front view of an array of pouch battery cells 10 in a module 100. The module walls 120 at least partially encase the cells 10. As shown, materials, such as pads 8 formed from one of the cured compositions disclosed herein may be positioned between surfaces of cells 10.

[0120] FIG. 4 illustrates an isometric view of cylindrical cells 10 in a battery module 100. Each cell may comprise a top 11, a bottom 12, and walls 13 positioned between the top and bottom and each having a surface. The top 11 and the bottom 12 may be oppositely chargedterminals with one being a positive terminal 1 and the other being a negative terminal (not shown). The battery cells may be connected at their terminals by interconnectors such as wires 5 and the like to enable an electric current to flow between the electric cells. The module 100 or module walls 120 may form a space having a volume. The cells 10 may be positioned within the space to consume a portion of the volume. The material, such as a pottant 7 formed from one of the cured compositions disclosed herein may be positioned within the space to consume a portion of the volume such that the material is adjacent to a surface of a cell wall 13 and / or an interior surface of at least one of the walls 120 of the module 100.

[0121] FIG. 5 illustrates an exploded perspective view of a battery module 100 comprised of an array of battery cells 10, a cooling fin 230, and a cooling plate 240. Materials, such as pads 8 formed from one of the cured compositions disclosed herein may be positioned between cells 10. Additional pads 8 may be positioned between the cells 10, the cooling fin 230, the cooling plate 240, and / or an interior surface of walls 120. Other pads 8 may be positioned adjacent an exterior surface of the walls 120.

[0122] FIG. 6 illustrates an isometric view of a battery cell 10 (FIG. 6A) to battery module 100 (FIG. 6B) to battery pack 200 (FIG. 6C) battery assembly. The battery module 100 comprises a plurality of battery cells 10 and the battery pack 200 comprises a plurality of battery modules 100.

[0123] FIG. 7 illustrates a perspective view of a battery pack 200 cutout. The battery pack includes a plurality of battery modules 100 and cells 10 within each module 100. The base of the battery pack 200 comprises a cooling plate 240. Materials, such as adhesives, 9 formed from one of the cured compositions disclosed herein may be positioned between the cooling plate 240 and interior surface of a wall of the battery pack 200. Materials, such as pads 8 formed from one of the cured compositions disclosed herein may be positioned between cells 10 within modules 100.

[0124] FIG. 8 illustrates an isometric view of a cell 10 to pack battery 200 assembly. Cells 10 are arranged within the pack 200 (without being in separate modules).

[0125] In other cases, the battery cells may be arranged on or within an article such as, but not limited to, a cell to chassis battery assembly, as illustrated in FIG. 9, wherein a cell is used to construct the battery assembly without prior assembly of the cells into modules and / or packs. FIG. 9 illustrates an isometric cut-out view of a cell to chassis battery assembly 300.Cells 10 are arranged on a base comprising the undercarriage 55 and supported by the vehicle frame 45 and under the vehicle interior floor 35.

[0126] Any battery assembly may further comprise a thermal management system comprising air or fluid circuits which may be liquid based (for example glycol solutions) or direct refrigerant based.Uses of the Compositions and Coatings

[0127] The compositions disclosed herein may be used to form coatings having the following properties:(a) a gradual decrease in storage modulus from -50°C to 150°C, resulting in a tangent delta less than 0.5 across this temperature range, such as a tangent delta less than 0.4, such as a tangent delta less than 0.3, as shown in FIG. 10A and FIG. 10B (Example IV vs. comparative example XVI); and / or(b) a lap shear strength greater than 14 MPa, such as greater than 15 MPa, such as greater than 17 MPa and a lap shear displacement of at least 3.0 mm, such as at least 3.5 mm, such as at least 4.0 mm, both measured according to ASTM D1002-10 (2019) using 2024 T3 aluminum and a pull rate of 13 mm / min; and or(c) an ultimate tensile strength at break of greater than 9 MPa, such as at least 11 MPa, such as at least 14 MPa, and at least 250% elongation at break, such as at least 350%, such as at least 500% measured according to ISO 527-1:2019.

[0128] The combination of properties described above was surprising and unexpected.

[0129] The coating may be used to form an adhesive such as a structural adhesive, a sealant, a pottant, a pre-preg, a liquid shim, a seal, and / or a gap filler, and / or may be used in additive manufacturing, such as 3D printing, to form an article.Definitions

[0130] For purposes of this detailed description, it is to be understood that the disclosure may assume alternative variations and step sequences, except where expressly specified to the contrary.

[0131] The numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0132] Also, any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0133] As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, ingredients or method steps. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, ingredient or method step. As used herein, “consisting essentially of’ is understood in the context of this application to include the specified elements, materials, ingredients or method steps “and those that do not materially affect the basic and novel characteristic(s)” of what is being described.

[0134] In addition, in this application, the use of “or” means “and / or” unless specifically stated otherwise, even though “and / or” may be explicitly used in certain instances.

[0135] As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” and the like mean formed, overlaid, deposited, or provided on, but not necessarily in contact with, a substrate surface. For example, a composition “applied onto” a substrate surface does not preclude the presence of one or more other intervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0136] As used herein, a “composition” or a “coating composition” refers to a solution, mixture, or a dispersion that is capable of producing a coating on a substrate surface. “Coating” as used herein includes films, layers and the like.

[0137] As used herein, a “sealant composition” refers to a coating composition that forms a sealant in its cured state.

[0138] As used herein, a “sealant” refers to a coating that has a tensile strength of at least 0.05 MPa measured according to ISO-37 TYPE 2 using an Instron 4443 machine in tensile mode with a pull rate of 10 mm per minute.

[0139] As used herein, a “gap filler composition” refers to a coating composition that forms a gap filler in its cured state.

[0140] As used herein, a “gap filler” refers to a coating that fills a gap and that has a butt joint strength of at least 0.001 N / mm2 measured according to ASTM D2095.

[0141] As used herein, an “adhesive composition” refers to a coating composition that forms an adhesive in its cured state.

[0142] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint, such as a load-bearing joint having a lap shear strength of at least 0.05 MPa, as determined according to ASTM DI 002- 10 using an Instron 5567 machine in tensile mode with a pull rate of 1 mm per minute.

[0143] As used herein, a “structural adhesive” refers to produces a load-bearing joint, such as a load-bearing joint having a lap shear strength of at least 10 MPa, as determined according to ASTM D1002-10 using an Instron 5567 machine in tensile mode with a pull rate of 1 mm per minute.

[0144] As used herein, a “pottant composition” refers to a curable composition that, when cured, forms a pottant.

[0145] As used herein, a “pottant” refers to a material that encapsulates a substrate or a component.

[0146] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0147] As used herein, a “liquid shim composition” refers to a curable composition that, when cured, forms a liquid shim.

[0148] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0149] As further defined herein, ambient conditions generally refer to room temperature (e.g. 23°C) and humidity conditions or temperature and humidity conditions that are typically found in the area in which the composition is applied to a substrate, e.g., at 10°C to 40°C and 5% to 80% relative humidity, while slightly thermal conditions are temperatures that are slightly above ambient temperature, but are generally below the curing temperature for the composition (i.e., in other words, at temperatures and humidity conditions below which the reactive components will readily react and cure, e.g., > 40°C and less than 220°C at 20% to 80% relative humidity).

[0150] As used herein, the term “two-component” or “2K” refers to a composition in which the reactive components readily associate to form an interaction or react to form a bond (physically or chemically), i.e., cure, without activation from an external energy source, such as at ambient or slightly thermal conditions, when mixed. One of skill in the art understands that the two components of the composition are stored separately from each other and mixed just prior to application of the composition. Two-component compositions may optionally be heated or baked, as described below.

[0151] As used herein, “reactive components” refer to components of the final composition containing isocyanate or active hydrogen functional groups, including di-functional isocyanate-containing prepolymer, the first and second difunctional polyols, monofunctional isocyanate-containing molecules, polyfunctional isocyanate-containing molecules, monofunctional alcohols, polyfunctional polyols, and aromatic amine.

[0152] As used herein, the term “cure,” “curing,” and similar terms, means that the components that form the composition are crosslinked (i.e., interact and / or react) to form a coating or a bond. In the case of a 2K composition, the composition begins to cure when the components of the composition are mixed, resulting in the reaction of the reactive functional groups of the components of the composition and / or the physical interaction of the components of the composition.

[0153] The term “curable,” as used in connection with a coating composition, means that the composition is able to be cured under ambient and / or slightly thermal conditions.

[0154] As used herein, “Mn” refers to the number average molecular weight measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran (THF) as the eluent at a flow rate of 1ml min'1.

[0155] As used herein, “isocyanate equivalent weight” refers to the total weight of isocyanate-containing components divided by the molar equivalents of isocyanate functionality. The value may be determined from the isocyanate content as measured in accordance with ASTM D2572-19.

[0156] As used herein, “active hydrogen” refers to a hydrogen that can be displaced when a nitrogen-containing functional group, an oxygen-containing functional group, and / or a sulfur-containing functional group reacts as a nucleophile with an appropriate electrophile andcan be determined, for example, by the Zerewitinoff test. Examples of functional groups including an active hydrogen include amines, hydroxyls, and thiols.

[0157] As used herein, “active hydrogen equivalent weight” refers to the total weight of active hydrogen-containing components divided by the molar equivalents of active hydrogen functionality. For clarity, it is assumed herein that a primary amine has one active hydrogen with respect to reaction with an isocyanate. The active hydrogen equivalent weight may be determined from the amine equivalent weight and the hydroxyl equivalent weight.

[0158] “Amine equivalent weight” refers to the total weight of amine-containing components divided by the molar equivalents of amine functionality, which can be determined in accordance with ASTM D6979-03.

[0159] “Hydroxyl equivalent weight” refers to the total weight of hydroxyl-containing component divided by the molar equivalents of hydroxyl functionality, which may be determined, for example, in accordance with ASTM D4247-23.

[0160] As used herein, the term “unsubstituted” when used with respect to a polyether, polyester, or polycarbonate indicates that the carbon backbone of the polymer repeat unit contains only methylene units (and therefore does not contain any higher substituted tertiary or quaternary carbons).

[0161] As used herein, a “polymer repeat unit” refers to the smallest constitutional unit whose repeated covalent bonding generates an oligomer, polymer, or portion of a polymer.

[0162] As used herein, “aromatic,” when referring to a compound, means that the compound comprises at least one aromatic ring.

[0163] As used herein, the term “monofunctional,” when used with respect to a particular functional group, refers to a molecule containing only one such functional group.

[0164] As used herein, the term “difunctional,” when used with respect to a particular functional group, refers to a molecule containing two such functional groups.

[0165] As used herein, the term “polyfunctional,” when used with respect to a particular functional group, refers to a molecule containing more than two functional groups.

[0166] As used herein, the term “multifunctional,” when used with respect to a particular functional group, refers collectively to “difunctional” molecules and “polyfunctional” molecules.

[0167] As used herein, “polymer” refers to oligomers, homopolymers, and copolymers.

[0168] As used herein, “small molecule” refers to a molecule that comprises discrete chemical structures, has a molecular weight of less than 400 g / mol and that is not a polymer (i.e., is not composed of repeating units). The molecular weight of a small molecule may be determined by mass spectrometry. Appropriate mass spectrometry methods for various types of small molecules are available in many references, such as Mass Spectrometry: A Textbook (3rdEdition, 2018, edited by Jurgen Gross).

[0169] As used herein, the term “solvent” refers to a molecule or a compound that is used to lower the viscosity of a resin, volatilizes under ambient conditions, and does not have a reactive functional group capable of reacting with molecules or compounds in a composition.

[0170] As used herein, the term “system” refers to a plurality of compositions for application to a substrate surface that results in a plurality of layers formed on the substrate surface. The system may be part of a production line (such as a factory production line) that produces a finished substrate or that produces a treated substrate suitable for use in additional production lines. Unless indicated to the contrary, reference to a “first composition,” a “second composition,” etc., when used with respect to a “system” is not intended to imply a specific order of treatment but rather is for ease of reference only.

[0171] As used herein, unless indicated otherwise, the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is only present as an impurity in a trace amount of less than 0.05% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “essentially free” means that a particular material is only present in an amount of less than 0.01% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “completely free” means that a mixture or composition, respectively, does not comprise a particular material, i.e., the mixture or composition comprises 0% by weight of such material.

[0172] In view of the foregoing description the present disclosure thus relates in particular to the following Aspects 1 to 84 without being limited thereto.

[0173] 1. A composition comprising: a first component comprising an isocyanate-functional polyurethane prepolymer; a second component comprising:(a) a first difunctional polyol; and(b) an aromatic diamine; wherein the composition comprises the first difunctional polyol in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition; and / or wherein the composition comprises the aromatic diamine in an amount sufficient to provide active hydrogen equivalents of greater than 42 percent to 95 percent of the total active hydrogen equivalents in the second component; and / or wherein the composition comprises an accelerator.

[0174] 2. The composition of aspect 1, comprising the accelerator in an amount of at least 0.0001 percent by weight based on total weight of the composition, such as at least 0.001 percent by weight.

[0175] 3. The composition of aspect 1 or aspect 2, comprising the accelerator in an amount of at least 0.01 percent by weight based on total weight of the composition, such as at least 0.03 percent by weight.

[0176] 4. The composition of any of the preceding aspects, comprising the accelerator in an amount of no more than 5 percent by weight based on total weight of the composition, such as no more than 1 percent by weight.

[0177] 5. The composition of any of the preceding aspects, comprising the accelerator in an amount of no more than 0.3 percent by weight based on total weight of the composition, such as no more than 0.25 percent by weight.

[0178] 6. The composition of any of the preceding aspects, comprising the accelerator in an amount of 0.0001 percent by weight to 5 percent by weight based on total weight of the composition, such as 0.001 percent by weight to 1 percent by weight based on total weight of the composition.

[0179] 7. The composition of any of the preceding aspects, comprising the accelerator in an amount of 0.01 percent by weight to 0.3 percent by weight based on total weight of the composition, such as 0.03 percent by weight to 0.3 percent by weight based on total weight of the composition.

[0180] 8. The composition of any of the preceding aspects, wherein the accelerator comprises an organic acid, an organometallic complex, and / or a nitrogen -based catalyst in addition to the aromatic diamine.

[0181] 9. The composition of any of the preceding aspects, wherein the accelerator comprises a tertiary amine, an / V-hctcrocyclic carbene, an amidine, and / or a guanidine.

[0182] 10. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an aliphatic isocyanate-functional polyurethane prepolymer, such as a cyclic aliphatic isocyanate prepolymer, and / or an aromatic isocyanate- functional prepolymer.

[0183] 11. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an Mn of at least 500 g / mol, such as at least 750 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydro furan as the eluent at a flow rate of 1 ml min'1.

[0184] 12. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an Mn of no more than 5,000 g / mol, such as no more than 2,000 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0185] 13. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an Mn of 500 g / mol to 5,000 g / mol, such as 750 g / mol to 2,000 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0186] 14. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an isocyanate equivalent weight of at least 250 g / eq, such as at least 375 g / eq.

[0187] 15. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an isocyanate equivalent weight of no more than 2,500 g / eq, such as no more than 1,000 g / eq.

[0188] 16. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises an isocyanate equivalent weight of 250 g / eq to 2,500 g / eq, such as 375 g / eq to 1,000 g / eq.

[0189] 17. The composition of any of the preceding aspects, comprising the isocyanate-functional polyurethane prepolymer in an amount of at least 30 percent by weight based on total weight of the composition, such as at least 40 percent by weight.

[0190] 18. The composition of any of the preceding aspects, comprising the isocyanate-functional polyurethane prepolymer in an amount of no more than 70 percent by weight based on total weight of the composition, such as no more than 60 percent by weight.

[0191] 19. The composition of any of the preceding aspects, comprising the isocyanate-functional polyurethane prepolymer in an amount of 30 percent by weight to 70 percent by weight based on total weight of the composition, such as 40 percent by weight to 60 percent by weight.

[0192] 20. The composition of any of the preceding aspects, wherein the isocyanate- functional polyurethane prepolymer comprises a difunctional isocyanate-functional prepolymer, and optionally further comprises a monofunctional isocyanate-functional small molecule, a monofunctional isocyanate-functional prepolymer, a polyfunctional small molecule, and / or a polyfunctional isocyanate-functional prepolymer.

[0193] 21. The composition of aspect 20, wherein the difunctional isocyanate- functional polyurethane prepolymer comprises a reaction product of reactants comprising a second difunctional polyol and a diisocyanate.

[0194] 22. The composition of aspect 21, wherein the second difunctional polyol comprises an Mn of at least 500 g / mol, such as at least 1,500 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0195] 23. The composition of aspect 21 or aspect 22, wherein the second difunctional polyol comprises an Mn of no more than 4,000 g / mol, such as no more than 3,500 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0196] 24. The composition of any of aspects 21 to 23, wherein the second difunctional polyol comprises an Mn of 500 g / mol to 4,000 g / mol, such as 1,500 g / mol to 3,500 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0197] 25. The composition of any of aspects 21 to 24, wherein the second difunctional polyol comprises a polymer repeat unit comprising an unsubstituted polyether, an unsubstituted polyester, and / or an unsubstituted polycarbonate, wherein each polymer repeat unit comprises an uninterrupted chain of at least 3 methylene units, such as no more than 6 methylene units.

[0198] 26. The composition of any of aspects 21 to 25, wherein the second difunctional polyol comprises a hydroxyl-functional polyurethane prepolymer formed as a reaction product of reactants comprising the unsubstituted polyether, the unsubstituted polyester, and / or the unsubstituted polycarbonate, such as polytetrahydrofuran and / or polycaprolactone.

[0199] 27. The composition of any of aspects 20 to 26, comprising the diisocyanate functional prepolymer in an amount of at least 50 percent by weight based on total weight of the isocyanate-functional polyurethane prepolymer, such as at least 60 percent by weight.

[0200] 28. The composition of any of aspects 20 to 27, comprising the diisocyanate functional prepolymer in an amount of at least 70 percent by weight based on total weight of the isocyanate-functional polyurethane prepolymer, such as at least 80 percent by weight.

[0201] 29. The composition of any of aspects 20 to 28, comprising the diisocyanate functional prepolymer in an amount of at least 90 percent by weight based on total weight of the isocyanate-functional polyurethane prepolymer, such as 100 percent by weight.

[0202] 30. The composition of any of aspects 20 to 29, comprising the diisocyanate functional prepolymer in an amount of 50 percent by weight to 100 percent by weight based on total weight of the isocyanate-functional polyurethane prepolymer, such as 70 percent by weight to 100 percent by weight.

[0203] 31. The composition of any of aspects 20 to 30, comprising the diisocyanate functional prepolymer in an amount of 60 percent by weight to 90 percent by weight based on total weight of the isocyanate-functional polyurethane prepolymer.

[0204] 32. The composition of any of aspects 20 to 31, comprising the monofunctional isocyanate-functional small molecule, the monofunctional isocyanate-functional prepolymer, the polyfunctional small molecule, and / or the polyfunctional isocyanate-functional prepolymer in a combined amount of no more than 50 percent by weight based on total weight of the isocyanate-functional prepolymer, such as no more than 40 percent by weight.

[0205] 33. The composition of any of aspects 20 to 32, comprising the monofunctional isocyanate-functional small molecule, the monofunctional isocyanate-functional prepolymer, the polyfunctional small molecule, and / or the polyfunctional isocyanate-functional prepolymer in a combined amount of no more than 30 percent by weight based on total weight of the isocyanate-functional prepolymer, such as no more than 20 percent by weight.

[0206] 34. The composition of any of aspects 20 to 33, comprising the monofunctional isocyanate-functional small molecule, the monofunctional isocyanate-functional prepolymer, the polyfunctional small molecule, and / or the polyfunctional isocyanate-functional prepolymer in a combined amount of no more than 10 percent by weight based on total weight of the isocyanate-functional prepolymer.

[0207] 35. The composition of any of aspects 20 to 34, comprising the monofunctional isocyanate-functional small molecule, the monofunctional isocyanate-functional prepolymer, the polyfunctional small molecule, and / or the polyfunctional isocyanate-functional prepolymer in a combined amount of 10 percent by weight to 40 percent by weight based on total weight of the isocyanate-functional prepolymer, such as 20 percent by weight to 30 percent by weight.

[0208] 36. The composition of any of the preceding aspects, wherein the composition is substantially free, essentially free, or completely free of a monofunctional isocyanate- functional small molecule, a monofunctional isocyanate-functional prepolymer, a polyfunctional isocyanate-functional small molecule, and / or a polyfunctional isocyanate-functional prepolymer.

[0209] 37. The composition of any of the preceding aspects, comprising the first difunctional polyol in an amount of at least 5 percent by weight to less than 50 percent by weight based on total weight of the composition.

[0210] 38. The composition of any of the preceding aspects, comprising the first difunctional polyol in an amount of 1 percent by weight to no more than 40 percent by weight based on total weight of the composition, such as 5 percent by weight to 40 percent by weight.

[0211] 39. The composition of any of the preceding aspects, wherein the first difunctional polyol comprises an Mn of at least 500 g / mol, such as at least 1,500 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min’1.

[0212] 40. The composition of any of the preceding aspects, wherein the first difunctional polyol comprises an Mn of no more than 4,000 g / mol, such as no more than 3,500 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0213] 41. The composition of any of the preceding aspects, wherein the first difunctional polyol comprises an Mn of 500 g / mol to 4,000 g / mol, such as 1,500 g / mol to 3,500 g / mol, wherein Mn is measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1 ml min'1.

[0214] 42. The composition of any of the preceding aspects, wherein the first difunctional polyol comprises a polymer repeat unit comprising an unsubstituted polyether, an unsubstituted polyester, and / or an unsubstituted polycarbonate, wherein each polymer repeat unit comprises an uninterrupted chain of at least 3 methylene units, such as no more than 6 methylene units.

[0215] 43. The composition of any of the preceding aspects, wherein the first difunctional polyol comprises a hydroxyl-functional polyurethane prepolymer formed as a reaction product of reactants comprising the unsubstituted polyether, the unsubstituted polyester, and / or the unsubstituted polycarbonate, such as polytetrahydrofuran and / or polycaprolactone.

[0216] 44. The composition of any of the preceding aspects, comprising the first difunctional polyol in an amount sufficient to provide at least 50 percent of the hydroxy equivalents based on total number of hydroxy equivalents in the second component.

[0217] 45. The composition of any of the preceding aspects, wherein the second component further comprises a monofunctional alcohol and / or a polyfunctional polyol.

[0218] 46. The composition of aspect 45, comprising the monofunctional alcohol and / or the polyfunctional alcohol in a combined amount of no more than 50 percent by weight based on total weight of the polyol, such as no more than 40 percent by weight.

[0219] 47. The composition of aspect 45 or aspect 46, comprising the monofunctional alcohol and / or the polyfunctional alcohol in a combined amount of at least 1 percent by weight based on total weight of the polyol, such as at least 5 percent by weight.

[0220] 48. The composition of any of aspects 45 to 47, comprising the monofunctional alcohol and / or the polyfunctional alcohol in a combined amount of 1 percent byweight to 50 percent by weight based on total weight of the polyol, such as 5 percent by weight to 40 percent by weight.

[0221] 49. The composition of any of the preceding aspects, comprising the aromatic diamine in an amount sufficient to provide an active hydrogen equivalent of 45 percent to 95 percent of the total active hydrogen equivalents in the second component, such as 50 percent to 90 percent.

[0222] 50. The composition of any of the preceding aspects, comprising the aromatic diamine in an amount sufficient to provide an active hydrogen equivalent of 60 percent to 80 percent of the total active hydrogen equivalents in the second component.

[0223] 51. The composition of any of the preceding aspects, wherein the aromatic diamine comprises a liquid aromatic diamine at ambient conditions and / or a sterically hindered aromatic diamine.

[0224] 52. The composition of any of the preceding aspects, wherein the aromatic diamine comprises an Mn of at least 100 g / mol measured by mass spectrometry, such as at least 125 g / mol.

[0225] 53. The composition of any of the preceding aspects, wherein the aromatic diamine comprises an Mn of no more than 750 g / mol measured by mass spectrometry, such as no more than 500 g / mol.

[0226] 54. The composition of any of the preceding aspects, wherein the aromatic diamine comprises an Mn of 100 g / mol to 750 g / mol measured by mass spectrometry, such as 125 g / mol to 500 g / mol.

[0227] 55. The composition of any of the preceding aspects, further comprising a filler, an additive, and / or a moisture scavenger.

[0228] 56. The composition of aspect 55, comprising the filler in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight.

[0229] 57. The composition of aspect 55 or aspect 56, comprising the filler in an amount of less than 50 percent by weight based on total weight of the composition.

[0230] 58. The composition of any of aspects 55 to 57, comprising the filler in an amount of no more than 30 percent by weight based on total weight of the composition, such as no more than 20 percent by weight.

[0231] 59. The composition of any of aspects 55 to 58, comprising the filler in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition, such as 5 percent by weight to 20 percent by weight.

[0232] 60. The composition of any of aspects 55 to 59, comprising the moisture scavenger in an amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight.

[0233] 61. The composition of any of aspects 55 to 60, comprising the moisture scavenger in an amount of no more than 10 percent by weight based on total weight of the composition, such as no more than 5 percent by weight.

[0234] 62. The composition of any of aspects 55 to 61, comprising the moisture scavenger in an amount of 0.1 percent by weight to 10 percent by weight based on total weight of the composition, such as 1 percent by weight to 5 percent by weight.

[0235] 63. The composition of any of aspects 55 to 62, comprising the additive(s) in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight.

[0236] 64. The composition of any of aspects 55 to 63, comprising the additive(s) in a combined amount of no more than 10 percent by weight based on total weight of the composition, such as no more than 5 percent by weight.

[0237] 65. The composition of any of aspects 55 to 64, comprising the additive(s) in a combined amount of 0.1 percent by weight to 10 percent by weight based on total weight of the composition, such as 1 percent by weight to 5 percent by weight.

[0238] 66. The composition of any of the preceding aspects, comprising a ratio of isocyanate equivalents to active hydrogen equivalents of at least 0.75:1, such as at least 1:1.

[0239] 67. The composition of any of the preceding aspects, comprising a ratio of isocyanate equivalents to active hydrogen equivalents of no more than 1.7:1, such as no more than 1.4:1.

[0240] 68. The composition of any of the preceding aspects, comprising a ratio of isocyanate equivalents to active hydrogen equivalents of 0.75: 1 to 1.7:1 , such as 1 :1 to 1.4:1.

[0241] 69. The composition of any of the preceding aspects, wherein the composition is substantially free, or essentially free, or completely free, of unreacted aromatic diisocyanate.

[0242] 70. A substrate comprising a coating formed from the composition of any of the preceding aspects on a surface thereof.

[0243] 71. The substrate of aspect 70, further comprising a dielectric coating.

[0244] 72. A composite wall panel comprising the substrate of aspect 70.

[0245] 73. An armor assembly comprising the substrate of aspect 70, such as a tank or protective clothing.

[0246] 74. A battery comprising the substrate of aspect 70 or aspect 71.

[0247] 75. A use of the composition of any of aspects 1 to 69 to form a coating having a decrease in storage modulus from -50°C to 150°C and a tangent delta less than 0.5 from -50°C to 150°C, such as a tangent delta less than 0.4.

[0248] 76. The use of aspect 75 to form a coating having a decrease in storage modulus from -50°C to 150°C and a tangent delta less than 0.3 from -50°C to 150°C.

[0249] 77. A use of the composition of any of aspects 1 to 69 to form a coating having a lap shear strength greater than 14 MPa, such as greater than 15 MPa, measured according to ASTM DI 002- 10 (2019) using 2024 T3 aluminum and a pull rate of 13 mm / min.

[0250] 78. The use of aspect 77, to form a coating having a lap shear’ strength greater than 14 MPa, such as greater than 17 MPa, measured according to ASTM DI 002- 10 (2019) using 2024 T3 aluminum and a pull rate of 13 mm / min.

[0251] 79. A use of the composition of any of aspects 1 to 69 to form a coating having a lap shear displacement of at least 3.0 mm, such as at least 3.5 mm, measured according to ASTM D1002-10 (2019) using 2024 T3 aluminum and a pull rate of 13 mm / min.

[0252] 80. The use of aspect 79, to form a coating having a lap shear displacement of at least 4.0 mm, measured according to ASTM D1002-10 (2019) using 2024 T3 aluminum and a pull rate of 13 mm / min.

[0253] 81. A use of the composition of any of aspects 1 to 69 to form a coating having an ultimate tensile strength at break of greater than 9 MPa, such as at least 11 MPa measured according to ISO 527-1:2019.

[0254] 82. The use of aspect 81, to form a coating having an ultimate tensile strength at break of at least 14 MPa, such as at least 11 MPa measured according to ISO 527-1:2019.

[0255] 83. A use of the composition of any of aspects 1 to 69 to form a coating having an elongation at break of at least 250% elongation at break, such as at least 350%, measured according to ISO 527-1:2019.

[0256] 84. The use of aspect 83 to form a coating having an elongation at break of at least 500%, measured according to ISO 527-1:2019.

[0257] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details.ExamplesSynthesis Example 1: Synthesis of Isocyanate-Functional Polyurethane Prepolymer

[0258] To a round-bottom flask was added Mondur TD Grade 80 A (mixture of 2,4- and 2,6-toluenediisocyanate, 107.0 g, 0.410 eq. NCO) and heated to 70°C. In a separate flask, Polymeg 1000 (polytetrahydrofuran-based diol, Mw = 1000 g / mol, 124.2 g, 0.0828 eq. OH) and Arcol PPG-1025 (polypropylene oxide-based diol, Mw = 1000 g / mol, 57.3 g, 0.0382 eq. OH) were mixed. The mixture of polyols was added over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 70°C for about 1 hour, until the mixture measured an isocyanate equivalent weight of 333 g / eq. 1,4-Butanediol (11.4 g, 0.084 eq. OH) was added to the mixture over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 70°C for about 1 hour, until the mixture measured an isocyanate equivalent weight of 504 g / eq determined by titration. The titration was performed by dissolving the isocyanate sample in a solution of n-dibutylamine in the appropriate solvent (e.g., toluene) and the mixture was stirred for 20 minutes, followed by dilution with isopropanol. The excess n-dibutylamine was back-titrated with HC1 solution.Synthesis Example 2: Synthesis of Hydroxyl-functional Polyurethane Prepolymer

[0259] To a round-bottom flask was added Polymeg 1000 (90.67 g, 0.181 eq. OH) and heated to 70°C. Mondur TD Grade 80 A (9.33 g, 0.107 mol of NCO) was added over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 70°C until the isocyanate was consumed, yielding a material with a measured OH equivalent weight of 1350 g / eq.Synthesis Example 3; Synthesis of Hydroxyl-functional Polyurethane Prepolymer fromIPDI

[0260] To a 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device were added 785.1 g of IPDI (isophorone diisocyanate, commercially available from Covestro) and 1.01 g of dibutyltin dilaurate (DBTDL, commercially available from Arkema), then heated to 70°C. In a separate flask, 785.1 g of Polymeg 1000 and 362.2 g of Arcol PPG- 1025 were mixed. The mixture of polyols was added over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 75°C for about 1 hour, then 72.1 g of 1 ,4-butanediol was added to the mixture over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 75°C for about 1 hour, until the mixture measured an isocyanate equivalent weight of 534 g / eq determined by titration.Synthesis Example 4; Synthesis of Hydroxyl-functional Polyurethane Prepolymer from HDI

[0261] To a 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device were added 208.9 g of HDI (Hexamethylene diisocyanate, commercially available from Covestro) and 0.3 g of dibutyltin dilaurate (DBTDL, commercially available from Arkema), then heated to 70°C. In a separate flask, 248.4 g of Polymeg 1000 and 114.6 g of Arcol PPG- 1025 were mixed. The mixture of polyols was added over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 75 °C for about 1 hour, then 22.8 g of 1 ,4-butanediol was added to the mixture over approximately 1 hour, ensuring that the temperature of the mixture did not exceed 90°C. The mixture was held at 75°C for about 1 hour, until the mixture measured an isocyanate equivalent weight of 492.2 g / eq determined by titration.Formulation of Compositions to XVI

[0262] Unless otherwise noted, all compositions and test samples were prepared according to the following methods: Part B liquids were combined in a DAC cup and mixed on a Hauschild 600.1 FVZ SpeedMixer at 2200 rpm for one minute. If the polyol was solid at room temperature, it was heated to its melting point until liquid before mixing. The solid additives, ifused, were added one at a time and mixed at 2200 rpm for one minute between each addition. A final mix on a Hauschild SMART DAC 1100.3 VAC-P was completed using the following profile: 1. 500 rpm, 3.6 counter rpm for 45 seconds. 2. 1000 rpm, 2.0 counter rpm for 120 seconds. 3. 1000 rpm, 3.6 counter rpm for 75 seconds. 4. 1000 rpm, 8.0 counter rpm for 120 seconds while at 0 bar of pressure to degas. If the Part A had multiple resins, they were premixed in a SpeedMixer at 2200 rpm for one minute. To combine Parts A and B, both parts were combined in one cup and mixed in a SpeedMixer at 2200 rpm for one minute immediately before use.

[0263] Lap shear specimens were prepared according to ASTM D1002-10 using 1”X4”X0.063” 2024 T3 aluminum ordered from BRALCO Metals. The panels were wiped clean of surface oils with methyl ethyl ketone (MEK) before being etched in ChemDeox 395 (commercially available from PPG Industries, Inc.) by first wetting the substrate in DI water for one minute, then submerging for one minute in the etching solution heated to 38 °C and finally rinsing in DI water for one minute. The cleaned substrate was fully dried in a 70°C oven. Once cooled to room temperature, the panels were wiped lightly with a gauze pad wetted with a 10% solution of Silquest Y-9627 (Momentive Performance Materials) dissolved in MEK. The wiped substrate dried at room temperature for one hour.

[0264] Freshly mixed adhesive was applied to one piece of the lap shear specimen and 30 mil glass spacer beads (MO-SCI Online) were lightly and evenly sprinkled on the adhesive surface. The adhesive and beads were sandwiched with a second piece of substrate in the desired overlap dimensions and held together using small binder clips to form a bonded dimension of 1” x * / 2” . Excess adhesive was removed from the joint using a metal spatula. All samples were cured for at least seven days at 25°C and 50% relative humidity. To form free films of the material from which tensile samples were cut, freshly mixed adhesive was poured and leveled in an open PTFE mold to a thickness of 14” and were cured under the same conditions as the lap shear specimens. Once cured, test samples were cut from the free film using an ISO 37-2 die. Lap shear and tensile testing were performed on an INSTRON 68TM-50 machine according to ASTM D1002-10 and ISO 527. It must be noted that the lap shear testing was performed at a rate of 13 mm / min. Samples (17.5 mm long x 13 mm wide x 5 mm thick) used for the measurement of storage modulus and tangent delta over a range of temperatures (FIG. 10A and FIG. 10B) were taken from the same free film samples formed as described above for makingtensile measurements. The testing was completed using a TA Instruments Q800 Dynamic Mechanical Analysis (DMA) instrument via ASTM D7028-07 (2015) running “MultiFrequency — Strain” mode with single cantilever clamps from -150 degrees Celsius to 150 degrees Celsius with a temperature ramp of 3 degrees Celsius / minute, frequency of 1 Hz, and oscillation strain of 0.1 Hz.Table 1. Compositions, lap shear and tensile results for CompositionsI-V.

[0265] The data in Table 1 show compositions with an increasing active hydrogen equivalent percent of aromatic amine relative to total active hydrogen equivalents. These results indicate that compositions with less than 45 equivalent percent of aromatic diamine fail to cure to a hai’d enough state to test. Compositions with no difunctional polyol (Composition V) form strong but inflexible samples, signified by the significant decrease in % elongation of Composition V compared to Composition IV. Composition IV shows a surprising combination of high lap shear strength and tensile strength with high lap shear displacement and tensile elongation at break, signifying a significantly tough material.Table 2. Compositions, lap shear and tensile results for Compositions VI-X.

[0266] Table 2 shows compositions which contain different polyols in the same equivalent percent. The Hydroxyl Functional Polyurethane Prepolymer (Synthesis Example 2), Polycaprolactone Polyol Diol, and Polytetramethylene Ether Glycol provide a superior combination of high lap shear and tensile strength with high lap shear displacement and tensile elongation at break. Primary Hydroxyl-functional Polypropylene Glycol and PolyethyleneGlycol provide lower strengths and elongation. In cases where the standard deviation is reported as 0, only one specimen was run. Composition X Part A was solid at room temperature, so it was melted at 60°C before the addition of the Part A to allow for complete mixing.Compositions IX and X contain extra moisture scavenger to account for high ambient humidity conditions during preparation.Table 3. Compositions, lap shear and tensile results for Compositions VI, XI-XIV.

[0267] Table 3 shows several compositions with an increasing equivalents fraction of Secondary-Hydroxyl Functional Polypropylene Glycol compared to the hydroxyl-functional polyurethane prepolymer of Synthesis Example 2. The results indicate that the composition can accept up to 10 equivalents percent of the total active hydrogens of secondary hydroxyl propylene glycol, or 50 equivalents percent of total polyol active hydrogens, while maintaining a combination of high strength and flexibility. The lap shear and tensile properties of the compositions decrease significantly with the introduction of secondary hydroxyl functional polypropylene glycol.Table 4. Compositions, lap shear and tensile results for Compositions IV, XV-XVI.

[0268] Table 4 shows compositions which contain small molecule aromatic diisocyanates (Compositions XV and XVI). Compared to Composition IV, which has no small molecule aromatic diisocyanates, Compositions XV and XVI have significantly lower strength and flexibility. Additionally, surprisingly Composition IV contains a significantly lower weight percent of polyol and has a surprisingly higher combination of lap shear strength and displacement.Table 5. Compositions and hardness results for Compositions XVII - XVIII.

[0269] Table 5 shows compositions which contain different types of accelerators. The compositions have, either, no accelerator, a tertiary amine, tin- or bismuth-based accelerator. The final hardness values of the compositions are very similar, which demonstrates that the composition will cure without accelerator or with a variety of accelerators.Table 6. Compositions, lap shear and tensile results for Compositions XXI- XXIV.

[0270] Table 6 shows compositions with carrying levels of filler, from 1 to 4- wt%. Surprisingly, the lap shear strength and displacement peak at 25 wt% filler content.Additionally, the lap shear failure mode changes from compete adhesive failure to complete cohesive failure mode with the addition of more filler. Moving to 40 wt% filler content, the lap shear properties begin to decrease. Also surprisingly, the tensile strength and elongation are highest with no filler content.Table 7. Compositions, lap shear and tensile results for Compositions XXV-XXXIII.

[0271] Table 7 shows compositions made with either an aliphatic isocyanate prepolymer or a blend of aliphatic isocyanate prepolymer with an aromatic isocyanate prepolymer. As the amount of aliphatic isocyanate prepolymer increases, the tensile strength and lap shear strength of the adhesive composition begins to decrease. However, the strength of the adhesive is equal to or better than the aromatic-only composition (Compisition XXV) with up to 25 wt% of (OH+NH2) equivalents coming from the aliphatic isocyanate prepolymer (Compositions XXVI and XXX).Table 8. Compositions, lap shear and tensile results for Compositions XXXIV-XLV.

[0272] Table 8 shows compositions which contain increasing amounts of a liquid aromatic diamine, replacing the hydroxyl functional polyurethane prepolymer from Synthesis Example 2. Compositions XXXIV-XXXVII contain a very low amount of accelerator while Compositions XXXIX-XLV have a higher amount of accelerator. These results demonstrate an interesting combination of properties even at high amounts of aromatic diamine. Compositions XLII and XLIII should that, at 60 and 8- eq% of aromatic diamine, respectively, the compositions have a high lap shear strength (> 17 MPa) while maintaining a high tensile elongation at break (> 500%), making a strong and flexible material. Data are shown graphically in FIG. 11 and FIG. 12.

[0273] Whereas specific aspects of the disclosure have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the disclosure which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Claims

We claim:

1. A composition comprising: a first component comprising an isocyanate-functional polyurethane prepolymer; a second component comprising:(a) a first difunctional polyol; and(b) an aromatic diamine; wherein the composition comprises the first difunctional polyol in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition; and / or wherein the composition comprises the aromatic diamine in an amount sufficient to provide active hydrogen equivalents of greater than 42 percent to 95 percent of the total active hydrogen equivalents in the second component.

2. The composition of claim 1, further comprising an accelerator.

3. The composition of claim 2, comprising the accelerator in an amount of 0.0001 percent by weight to 5 percent by weight based on total weight of the composition.

4. A composition comprising: a first component comprising an isocyanate-functional polyurethane prepolymer; a second component comprising:(a) a first difunctional polyol in an amount of 1 percent by weight to less than 50 percent by weight based on total weight of the composition; and(b) an aromatic diamine; and an accelerator in an amount of 0.0001 percent by weight to 5 percent by weight based on total weight of the composition.

5. The composition of any of claims 2 to 4, wherein the accelerator comprises a nitrogenbased catalyst and / or an organometallic complex.

6. The composition of any of claims 2 to 5, comprising the accelerator in an amount of 0.03 percent by weight to 0.3 percent by weight based on total weight of the composition.

7. The composition of any of the preceding claims, wherein the isocyanate-functional polyurethane prepolymer comprises a difunctional isocyanate-functional polyurethane prepolymer, and optionally further comprises a monofunctional isocyanate-functional small molecule, a monofunctional isocyanate-functional prepolymer, polyfunctional isocyanate- functional small molecule, and / or a polyfunctional isocyanate-functional prepolymer.

8. The composition of claim 7, wherein the difunctional isocyanate-functional polyurethane prepolymer comprises a reaction product of reactants comprising a second difunctional polyol and a diisocyanate.

9. The composition of any of the preceding claims, wherein:(a) the isocyanate-functional polyurethane prepolymer comprises an Mn of 500 g / mol to 5,000 g / mol measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of1ml min’1;(b) the difunctional polyol comprises an Mn of 500 g / mol to 4,000 g / mol measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran as the eluent at a flow rate of 1ml min’1; and / or(c) the aromatic diamine comprises an Mn of 100 g / mol to 750 g / mol, measured by mass spectrometry.

10. The composition of any of the preceding claims, wherein the isocyanate-functional polyurethane prepolymer comprises an isocyanate equivalent weight of 250 g / eq to 2,500 g / eq.

11. The composition of any of the preceding claims, wherein the composition comprises the isocyanate-functional polyurethane prepolymer in an amount of 30 percent by weight to 70 percent by weight based on total weight of the composition.

12. The composition of any of the preceding claims, wherein the second component further comprises a monofunctional alcohol and / or a polyfunctional polyol.

13. The composition of any of the preceding claims, wherein the first difunctional polyol comprises a polymer repeat unit comprising an unsubstituted polyether, an unsubstituted polyester, and / or an unsubstituted polycarbonate, wherein each polymer repeat unit comprises an uninterrupted chain of at least 3 methylene units, such as no more than 6 methylene units.

14. The composition of claim 13, wherein the first difunctional polyol comprises a hydroxyl- functional polyurethane prepolymer formed as a reaction product of reactants comprising the unsubstituted polyether, the unsubstituted polyester, and / or the unsubstituted polycarbonate.

15. The composition of any of the preceding claims, comprising the first difunctional polyol in an amount sufficient to provide at least 50 percent of the hydroxy equivalents based on total number of hydroxy equivalents of total polyol in the second component.

16. The composition of any of the preceding claims, wherein the aromatic diamine comprises a liquid aromatic diamine at ambient conditions or a sterically hindered aromatic diamine.

17. The composition of any of the preceding claims, wherein the composition comprises a ratio of isocyanate equivalents to active hydrogen equivalents of 0.75:1 to 1.7:1.

18. The composition of any of the preceding claims, wherein the composition is substantially free, or essentially free, or completely free of an unreacted small molecule aromatic polyisocyanate.

19. A substrate comprising a coating formed from the composition of any of the preceding claims on a surface thereof.

20. An armor assembly comprising the substrate of claim 19, such as a tank or protective clothing.

Images