Compositions containing furan-functional compounds and isocyanate-functional compounds and expandable materials

Abstract

Disclosed are compositions comprising a first component comprising a first compound comprising a furan functional group and an isocyanate functional group; a second component comprising a dienophile-containing compound; and a heat-expandable material. Also disclosed herein are methods of coating a substrate comprising contacting a portion of a surface of the substrate with any of the compositions disclosed herein. Also disclosed are methods of forming an article comprising extruding any of the compositions disclosed herein. Also disclosed herein are substrates comprising a coating formed on a portion of a surface of the substrate from any of the compositions disclosed herein.

Description

[0001] Cross-referencing

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 557,854, filed February 26, 2024, and U.S. Provisional Patent Application Serial No. 63 / 691,201, filed September 5, 2024, both entitled “Compositions Containing Furan-Functional and Isocyanate-Functional Compounds and Expandable Material,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention discloses thermally expanding compositions and their uses. Background Technology

[0004] Coating compositions, including sealants and adhesives, are used in a variety of applications to treat a variety of substrates or to bond two or more substrate materials together. Summary of the Invention

[0005] This document discloses compositions comprising: a first component comprising a first compound having furan functional groups and isocyanate functional groups; a second component comprising a dienophile compound; and a thermally expanding material.

[0006] This document also discloses methods for coating substrates, which include contacting a portion of the surface of the substrate with any of the compositions disclosed herein.

[0007] Methods for forming articles are also disclosed, including extruding any of the compositions disclosed herein.

[0008] This document also discloses a substrate comprising a thermally expanding coating formed on a portion of the surface of the substrate by any of the compositions disclosed herein.

[0009] This article also discloses batteries, including any of the battery cells disclosed herein.

[0010] This article also discloses a vehicle, which includes any of the batteries disclosed herein.

[0011] This document also discloses self-supporting membranes formed from any of the compositions disclosed herein. Attached Figure Description

[0012] Figure 1 This is a schematic diagram of a top view of a cylindrical battery cell.

[0013] Figure 2 This is a schematic diagram of an exploded isometric view of an array of prismatic battery cells.

[0014] Figure 3 This is a schematic diagram of the front view of an array of pouch cell units.

[0015] Figure 4 This is a schematic diagram of an isometric view of a cylindrical battery cell located within a battery module.

[0016] Figure 5 It is a schematic diagram of an exploded perspective view of a battery pack that includes multiple battery cells.

[0017] Figure 6 is a schematic diagram of isometric views of (A) battery cell, (B) battery module and (C) battery pack.

[0018] Figure 7 This is a schematic diagram of the battery pack's perspective view.

[0019] Figure 8 This is a schematic diagram of the cell-to-battery pack configuration.

[0020] Figure 9 It is a schematic diagram of an equidistant cross-section of the unit to the chassis battery assembly. Detailed Implementation

[0021] For the purposes of this detailed description, it should be understood that alternative variations and sequences of steps may be taken in this disclosure, except where expressly stated otherwise.

[0022] The numerical values ​​presented in the specific examples are reported as accurately as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its corresponding test measurement.

[0023] Furthermore, any range of values ​​described herein is intended to include all subranges contained therein. For example, the range “1 to 10” is intended to include all subranges between (and including) the stated minimum value of 1 and the stated maximum value of 10, that is, a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0024] As used herein, the terms “comprising,” “containing,” and similar 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 unstated 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 elements, ingredients, or method steps. As used herein, “generally consisting of” is understood in the context of this application to include the specified elements, materials, ingredients, or method steps “as well as elements, materials, ingredients, or method steps that do not materially affect the essential and novel characteristics of the described content.” As used herein, open-ended terms include closed-ended terms such as “generally consisting of” and “consisting of”.

[0025] Furthermore, in this application, unless otherwise expressly stated, the use of “or” means “and / or”, even if “and / or” can be explicitly used in certain situations.

[0026] As used herein, the terms “on,” “to,” “applied on,” “applied to,” “formed on,” “deposited on,” “deposited on,” etc., mean to form, cover, deposit, or be disposed on a substrate surface, but not necessarily in contact with the substrate surface. For example, a composition “applied to” a substrate surface does not exclude the presence of one or more other intermediate coatings of the same or different compositions located between the composition and the substrate surface.

[0027] As used in this article, "liquid" means liquid with a pressure of less than 100,000 Pa at 25°C. The viscosity of the material is s, which is achieved with a plate diameter of 25 mm, a gap of 0.5 mm, and a shear rate of 1 s. -1 The values ​​were measured using a parallel plate rheometer under the specified conditions.

[0028] As used herein, "solid" means having a strength of at least 100,000 Pa at 25°C. The viscosity of the material is s, which is achieved with a plate diameter of 25 mm, a gap of 0.5 mm, and a shear rate of 1 s. -1 The values ​​were measured using a parallel plate rheometer under the specified conditions.

[0029] As used herein, “part” refers to a portion of the chemical structure of a molecule or compound, which may include substructures such as functional groups or bonds.

[0030] As used herein, “composition” or “coating composition” refers to a solution, mixture or dispersion capable of producing a coating on a substrate surface.

[0031] As used herein, “coating” refers to a coating composition applied to a substrate and cured.

[0032] As used herein, “self-supporting film” refers to an extrudable coating composition or a coating that can be peeled off from a substrate after curing.

[0033] As used herein, “article” refers to a cured composition as a solid being molded or manufactured.

[0034] As used herein, "sealant composition" refers to a coating composition that forms a sealant in its cured state.

[0035] As used herein, "sealant" refers to a coating or self-supporting membrane that provides a protective barrier against moisture, chemicals and other environmental factors, thereby preventing corrosion and extending the service life of the component.

[0036] As used herein, "adhesive composition" refers to a coating composition that forms an adhesive in its cured state.

[0037] As used herein, “adhesive” refers to a cured coating or self-supporting film that forms a load-bearing joint having an lap shear strength of at least 0.5 MPa and less than 5 MPa, which is determined according to ASTM D1002-10 using an Instron 5567 machine in tensile mode at a pulling rate of 1.3 mm / min at room temperature.

[0038] As used herein, “structural adhesive composition” refers to a coating composition that produces a structural adhesive in a cured state.

[0039] As used herein, “structural adhesive” refers to a cured coating or self-supporting film that forms a load-bearing joint having an lap shear strength of at least 5 MPa, measured in tensile mode at room temperature and at a pull rate of 1.3 mm / min according to ASTM D1002-10 using an Instron 5567 machine.

[0040] As further defined herein, “ambient conditions” generally refer to room temperature (e.g., 25°C) and humidity conditions, or temperature and humidity conditions typically found in the area where the composition is applied to the substrate, for example, at 10°C to 40°C and 5% to 80% relative humidity; while “microthermal conditions” are temperatures slightly above ambient conditions, such as greater than 40°C to 60°C.

[0041] As used herein, the terms "two-component" or "2K" refer to compositions in which, when mixed, the reactive components readily associate to form interactions or react to form bonds (physically or chemically) and thus cure without activation from an external energy source, such as under ambient or microthermal conditions. Those skilled in the art will understand that the two components of the composition are stored separately and mixed just before application.

[0042] As used herein, the term “hot melt” refers to a composition that (i) cures to form a solid under ambient conditions, (ii) begins to reflow to form a liquid upon exposure to a reflow initiation temperature, (iii) begins to reform to a solid upon cooling to below the reflow initiation temperature, and (iv) reforms to a solid under ambient conditions.

[0043] As used herein, the term "reflux initiation temperature" refers to the temperature at which the storage modulus of the composition drops below 20,000,000 Pa, which can be determined by dynamic mechanical analysis (DMA) at a frequency of 1.0 Hz and a heating rate of 3 °C / min. The reflux initiation temperature may be the result of dynamic covalent chemistry, softening (i.e., heating above the glass transition temperature of the composition), and / or melting (i.e., conversion from solid to liquid).

[0044] As used herein, the term “glass transition temperature” (“Tg”) refers to the temperature at which an amorphous material, such as a glass or polymer, changes from a brittle glassy state to a plastic state or from a plastic state to a brittle glassy state. As used herein, the term “hot melt application” means applying a hot melt to a substrate surface under thermal conditions. As used herein, “thermal conditions” include (i) hot extrusion, (ii) heating the composition to a temperature above the reflow initiation temperature of the composition, and / or (iii) heating a substrate containing the composition to a temperature above the reflow initiation temperature of the composition.

[0045] As used herein, the term “cohesiveness” when applied to coatings means that an expanded coating (a coating that has been exposed to at least the expansion initiation temperature of a thermally expanding material) remains as a whole, i.e., the expanded coating does not break apart.

[0046] As used herein, the term “non-cohesive” when applied to coatings means that an expanded coating (a coating that has been exposed to at least the expansion initiation temperature of a thermally expanding material) does not remain as a whole, i.e., the expanded coating will break apart.

[0047] As used herein, the terms “cured,” “cured,” and similar terms mean that the reactive components forming the composition interact, react, and / or crosslink to form a coating, self-supporting film, or bond. In the case of 2K compositions, the composition begins to cure when the components are mixed, causing the reactive components of the composition to react and / or physically interact. As used herein, “cured” means the composition is placed under curing conditions that lead to curing. As used herein, a “curable” composition means a composition that can be cured. As used herein, a curable composition is considered “cured” if it has an lap shear strength of at least 0.5 MPa (measured according to ASTM D1002-10) and a tensile strength of at least 0.5 MPa under ambient conditions (measured according to ISO-37 TYPE 2 using an Instron 4443 machine in tensile mode at a pull rate of 10 mm / min). “Complete” curing is achieved when the curable composition is placed under curing conditions without any significant increase in lap shear strength.

[0048] As used herein, the term "furan equivalent weight" is the theoretical molecular weight of a compound containing furan functional groups divided by the theoretical number of furan functional groups.

[0049] As used herein, the term "isocyanate equivalent weight" is the theoretical molecular weight of a compound containing isocyanate functional groups divided by the theoretical number of isocyanate functional groups.

[0050] As used herein, the term "maleimide equivalent weight" is the theoretical molecular weight of a compound containing maleimide functional groups divided by the theoretical number of maleimide functional groups.

[0051] As used herein, the term "promoter" refers to a substance that increases the rate of a chemical reaction or lowers the activation energy of a chemical reaction compared to the same reaction in the absence of a promoter. A promoter can be a "catalyst" (that is, one that does not undergo any permanent chemical change itself) or it can be reactive (that is, one that undergoes a permanent chemical change).

[0052] As used herein, a "latent" accelerator refers to a molecule or compound that reacts (i.e., crosslinks) or has a catalytic effect only upon activation by an external energy source, and may vary as appropriate. Latent accelerators may be in solid form at room temperature and do not exhibit a accelerating effect until heated and melted. Latent accelerators may be end-capped or encapsulated. An "end-capped" accelerator is one that undergoes a reversible reaction with a second compound, preventing any accelerator effect until the reversible reaction is reversed by applying heat and the second compound is removed, thereby releasing the accelerator to increase the rate of the chemical reaction or lower the activation energy of the chemical reaction. An "encapsulated" accelerator may be encapsulated within a thermoplastic material that melts upon heating, releasing the accelerator to increase the rate of the chemical reaction or lower the activation energy of the chemical reaction.

[0053] As used herein, the term "carbamate bond" refers to a bond formed between two molecules that links RNHC(O)OR.

[0054] As used herein, the term "urea bond" refers to a bond formed between two molecules that links RNHC(O)NHR.

[0055] As used herein, the term "thiocarbamate bond" refers to the bond formed between molecules that links RNHC(O)SR.

[0056] As used herein, “reprocessability” means that the composition can be reprocessed, in which articles containing the cured composition are processed into different articles by mechanical or chemical methods. In some cases, “reprocessing” can refer to mechanical processes in which articles containing the cured composition are ground, chopped, pulverized, or processed by mechanical means, and then the composition is molded into new articles by means of molding, extrusion, etc. (i.e., material recycling). Reprocessing may further include heating.

[0057] As used in this article, "reprocessing efficiency" refers to the ratio of the mechanical properties of a reprocessed material to the mechanical properties of the original material, usually defined as a percentage. Reprocessing efficiency can refer to the recovery efficiency of properties such as tensile strength, Young's modulus, fracture strain, and lap shear strength after reprocessing.

[0058] As used herein, “remolding” means that material previously molded into a fixed physical form or shape can be molded into a different fixed physical form or shape. In some cases, remolding will involve heating the material to above the material’s reflow initiation temperature to permanently fix the new shape.

[0059] As used herein, "self-healing" means that a material is capable of repairing itself, such as repairing cracks, scratches, or abrasions in the material. A self-healing process may include heating the material to a temperature above its reflow initiation temperature.

[0060] As used in this article, "monosubstituted" refers to a compound or functional group in which one of the hydrogen atoms is replaced by a different atom or functional group.

[0061] As used herein, “terminal” when referring to a functional group means a functional group located at the end of the polymer backbone or prepolymer backbone, or a monosubstituted functional group relative to the monomer or nonpolymerizable molecule.

[0062] As used herein, "monomer" refers to a molecule capable of polymerization, thereby contributing repeating units to the structure of a prepolymer or polymer. Pure and Applied Chemistry , 1996, 68 As defined in , 2287 (2289), “Glossary of basic terms in polymer science (IUPAC Recommendations 1996)”.

[0063] As used herein, a “prepolymer” refers to a molecule containing two or more molecules of a reaction product that can be further polymerized or crosslinked.

[0064] As used herein, “polymer” means a molecule having more than one repeating unit and includes oligomers and homopolymers.

[0065] As used herein, unless otherwise stated, the term "substantially free" means that the particular material is not intentionally added to the mixture or composition, and that the particular material is present only as a trace impurity of less than 0.05% by weight, based on the total weight of the mixture or composition. As used herein, unless otherwise stated, the term "largely free" means that the particular material is present only in an amount of less than 0.01% by weight, based on the total weight of the mixture or composition. As used herein, unless otherwise stated, the term "completely free" means that the mixture or composition does not contain the particular material, i.e., the mixture or composition contains 0% by weight of such material.

[0066] As used herein, the terms "non-thermal conductive filler" or "NTC filler" refer to fillers with a thermal conductivity of less than 5 W / m at 25°C. . Pigments, fillers, or inorganic powders with K (measured according to ASTM D7984).

[0067] As used herein, the terms "electrically insulating filler" or "EI filler" refer to fillers with a dielectric strength of at least 1 Ω. · Pigments, fillers, or inorganic powders with a volume resistivity of m (measured according to ASTM D257).

[0068] As used herein, the terms "conductive filler" or "EC filler" refer to fillers with a conductivity of less than 1 Ω. · Pigments, fillers, or inorganic powders with a volume resistivity of m (measured according to ASTM D257).

[0069] As used herein, the term "thermal expansion" refers to pigments, fillers, encapsulating agents, thermoplastics, inorganic powders, capsules, microcapsules, etc., that undergo volume increase in at least one dimension when heated.

[0070] As used herein, the term "expansion temperature" refers to the temperature at which a thermally expanding material begins to experience an increase in volume in at least one dimension, i.e., the temperature at which a thermally expanding material begins to expand.

[0071] This disclosure relates to a composition comprising, substantially comprising, or consisting of: a first component comprising a first compound comprising a furan functional group and an isocyanate functional group; a second component comprising a dienophile-containing compound; a thermally expanding material; and a thermally conductive filler.

[0072] First component

[0073] The first component may comprise, consist substantially of, or consist of the following: a first compound comprising a furan functional group and an isocyanate functional group. The first compound may further comprise a carbamate bond, a urea bond, and / or a thiocarbamate bond.

[0074] The first compound may contain a general formula structure:

[0075]

[0076] (I)

[0077] Wherein X contains O, N, or S; m ≥ 1; n ≥ 1; the sum of m+n ≥ 2; R1 contains a substituted or unsubstituted alkyl group, alkylene group, (cyclo)alkyl group, aromatic group, isocyanurate moiety, biuret moiety, urethane moiety, glycourea moiety, benzoguanamine moiety, iminooxadiazinedione moiety, or polymer moiety other than urethane bond, urea bond, and / or thiourethane bond; and R2 contains a substituted or unsubstituted alkyl group, ester moiety, ether moiety, or urethane moiety. Optionally, m ≤ 12; n ≤ 12; and / or m+n ≤ 13.

[0078] The first compound may comprise the reaction product of a reactant comprising a furan-containing compound (containing an active hydrogen-containing functional group) and a polyisocyanate-containing compound. As used herein, "furan-containing compound" means a compound containing a furan functional group. As used herein, "polyisocyanate-containing compound" means a compound containing more than one isocyanate functional group, including diisocyanates, triisocyanates, or higher. The active hydrogen-containing functional group on the furan-containing compound may comprise a hydroxyl functional group, an amine functional group, and / or a thiol functional group. The active hydrogen-containing functional group of the furan-containing compound may react with the isocyanate group of the polyisocyanate. The first compound comprises at least one unreacted isocyanate group, thereby imparting isocyanate functionality to the first compound.

[0079] The substoichiometry of the active hydrogen-containing functional groups on furan-containing compounds can react with the isocyanate functional groups on polyisocyanate-containing compounds. For example, the active hydrogen-containing functional groups of furan-containing compounds can react with the isocyanate groups on polyisocyanate-containing compounds in an equivalence ratio of less than 1:1, such as not exceeding 1:2, not exceeding 1:3, not exceeding 1:5. As used herein, "substoichiometry" means that the number of active hydrogen-containing functional groups from furan-containing compounds is less than the amount required to react with all the isocyanate groups on the polyisocyanate-containing compounds, such that the reaction product contains isocyanate functionality from the polyisocyanate.

[0080] Suitable furan-containing compounds suitable for forming the first compound disclosed herein include, but are not limited to, furfuryl alcohol, furfurylamine, furfuryl thiol, furfuryl glycidyl ether, bis(hydroxymethyl)furan, their derivatives and / or combinations thereof.

[0081] Suitable polyisocyanate-containing compounds for forming the first compound disclosed herein can be polymeric compounds containing two or more isocyanate functional groups. For example, polyisocyanates may contain 2 to 20 carbon atoms and may be linear, cyclic, aliphatic and / or aromatic polyisocyanates, or mixtures thereof.

[0082] Suitable aliphatic polyisocyanates 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-1,5-pentamethylene diisocyanate; hexamethylene diisocyanate (“HDI”), such as 1,6-hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Methyl hexamethylene diisocyanate, or mixtures thereof; heptamethylene diisocyanate, such as 1,7-heptamethylene diisocyanate; propylene diisocyanate, such as 1,2-propylene diisocyanate; butene diisocyanate, such as 1,2-butene diisocyanate, 2,3-butene diisocyanate and 1,3-butene diisocyanate; ethylene diisocyanate; decamethylene diisocyanate, such as 1,10-decamethylene diisocyanate; ethylene diisocyanate; and butylene diisocyanate. Aliphatic polyisocyanates may also include cycloalkylene isocyanates, such as: cyclopentane diisocyanates, such as 1,3-cyclopentane diisocyanate; cyclohexane diisocyanates, such as 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate (“IPDI”), IPDI trimer (commercially available from Desmodur® Z 4470 SN); methylene bis(4-cyclohexyl isocyanate) (“HMDI”); polymeric methylene diphenyl diisocyanate (“MDI”); and mixed aralkyl diisocyanates, such as tetramethylxylyl diisocyanate, such as m-tetramethylxylyl diisocyanate (commercially available from Allnex SA as TMXDI®).

[0083] Suitable aromatic polyisocyanates may include arylene isocyanates, such as: phenylene diisocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate and chlorophenylene 2,4-diisocyanate; naphthalene diisocyanates, such as 1,5-naphthalene diisocyanate and 1,4-naphthalene diisocyanate. Aromatic polyisocyanates may also include arylene alkyl isocyanates, such as: methylene-block aromatic diisocyanates, such as 4,4'-diphenylmethane diisocyanate (“MDI”), and alkylated analogs, such as 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate and polymeric methylene diphenyl diisocyanate; toluene diisocyanates (“TDI”), such as 2,4-methylphenylene or 2,6-methylphenylene diisocyanate or mixtures thereof, bitoluene diisocyanate; and 4,4-toluidine diisocyanate; xylene diisocyanate; o-anisidine diisocyanate; xylene diisocyanate; and other alkylated phenyl diisocyanates.

[0084] Suitable polyisocyanates include dimers, trimers, oligomers, or prepolymers containing any of the isocyanates listed herein.

[0085] The first compound may comprise, consist generally of, or consist of monomers, prepolymers, or polymers.

[0086] The first compound may contain one, two, three or more furan functional groups. The furan functional groups may be linked to the first compound via urethane bonds, urea bonds and / or thiourethane bonds. The furan functional groups of the first compound may be terminal.

[0087] The first compound disclosed herein may be substantially free of, substantially free of, or completely free of ether bonds.

[0088] The first compound may contain at least 100 g / eq of furan equivalent weight, such as at least 200 g / eq. The first compound may contain no more than 3,000 g / eq of furan equivalent weight, such as no more than 1,500 g / eq. The first compound may contain between 100 g / eq and 3,000 g / eq of furan equivalent weight, such as between 200 g / eq and 1,500 g / eq.

[0089] Second component

[0090] The second component may comprise, consist substantially of, or consist of the following: a dienophile compound. As used herein, “dienophile” means any unsaturated functional group capable of undergoing Diels-Alder [4+2] cycloaddition with a conjugated diene. As used herein, “conjugated diene” means a compound containing two double bonds separated by a single covalent bond.

[0091] Suitable dienophiles may contain maleimide functional groups, maleate functional groups and / or fumarate functional groups.

[0092] Dienephile compounds may contain maleimide functional groups. The general formulas of dienophile compounds containing maleimide functional groups include:

[0093]

[0094] R3 may contain hydrogen, alkyl, (cyclo)alkyl, aryl, aromatic or polymeric structures (including polyester, polyurethane, polyether, acrylic or siloxane).

[0095] Suitable maleimide-containing compounds can be prepared by reacting maleic anhydride with a difunctional or polyfunctional amine-containing compound. The amine-containing compound may be selected such that the maleimide-containing compound or mixture of maleimide-containing compounds does not crystallize. Examples of suitable maleimide-containing compounds include the reaction product of maleic anhydride with a dimeric fatty acid diamine (such as commercially available from Designer Molecules, Inc. as BMI-689). Additional maleimide-containing compounds include the reaction product of amine-terminated polyethers or polysiloxanes with maleic anhydride. Other suitable maleimide-containing compounds include maleimide-terminated polyimides available from Designer Molecules, Inc., or the reaction product of maleimide-functionalized carboxylic acids with epoxy resins, hydroxyl groups, or other carboxylic acid reactive functional groups.

[0096] The dienophile may contain a maleate functional group. The general formula of dienophile-containing compounds containing a maleate functional group includes:

[0097]

[0098] Each X independently contains O, N, or S; R4 contains hydrogen, alkyl, (cyclo)alkyl, aryl, aromatic, or polymeric structures (including polyesters, polyurethanes, polyethers, acrylics, or siloxanes); and R5 contains hydrogen, alkyl, (cyclo)alkyl, aryl, aromatic, or polymeric structures (including polyesters, polyurethanes, polyethers, acrylics, or siloxanes). Dienephilic compounds containing maleate functional groups may contain unsaturated polyesters comprising the reaction product of maleic acid (or its anhydride or ester) with a polyol. Suitable polyols include any polyols described below. Dienephilic compounds containing maleate functional groups may also contain unsaturated polyesters containing maleate functional groups synthesized by other methods, such as copolymerization of epoxides with maleic anhydrides. Unsaturated polyesters may further contain other functional groups, such as hydroxyl groups. Unsaturated polyesters may be liquids.

[0099] Compounds containing a dienophile may include a fumarate functional group. The general formula of dienophile-containing compounds containing a fumarate functional group includes:

[0100]

[0101] Each X independently contains O, N, or S; R6 contains hydrogen, alkyl, (cyclo)alkyl, aryl, aromatic, or polymeric structures (including polyesters, polyurethanes, polyethers, acrylics, or siloxanes); and R7 contains hydrogen, alkyl, (cyclo)alkyl, aryl, aromatic, or polymeric structures (including polyesters, polyurethanes, polyethers, acrylics, or siloxanes). Dienophilic compounds containing fumarate functional groups may contain unsaturated polyesters comprising the reaction product of fumaric acid (or its anhydride or ester) with a polyol. Suitable polyols include any polyols described below. Dienophilic compounds containing fumarate functional groups may also contain unsaturated polyesters containing fumarate functional groups synthesized by other methods, such as copolymerization of epoxides with maleic anhydride. Unsaturated polyesters may further contain other functional groups, such as hydroxyl groups. Unsaturated polyesters may be liquids.

[0102] Compounds containing a dienophile may contain at least 100 g / eq of dienophilic equivalent weight, such as at least 200 g / eq. Compounds containing a dienophile may contain no more than 3,000 g / eq of dienophilic equivalent weight, such as no more than 1,500 g / eq. Compounds containing a dienophile may contain between 100 g / eq and 3,000 g / eq of dienophilic equivalent weight, such as between 200 g / eq and 1,500 g / eq.

[0103] The composition may comprise a furan functional group on the first compound and a dienophilic functional group on the dienophile-containing compound, in an equivalent ratio of at least 0.5:1, such as at least 0.6:1. The composition may comprise a furan functional group on the first compound and a dienophilic functional group on the dienophile-containing compound, in a molar ratio not exceeding 2:1, such as not exceeding 1.5:1. The composition may comprise a furan functional group on the first compound and a dienophilic functional group on the dienophile-containing compound, in a molar ratio of 0.5:1 to 2:1, such as 0.6:1 to 1.5:1.

[0104] thermal expansion materials

[0105] The compositions disclosed herein may comprise a thermally expanding material. The thermally expanding material may be present in the first component, the second component, and / or the third component.

[0106] Examples of suitable thermally expanding materials may include inorganic salts and / or thermally expanding graphite, such as thermally expanding graphite available from ACSMaterial.

[0107] Thermally expanding materials may include thermally expanding capsules. Thermally expanding capsules may include thermally expanding hollow capsules. Thermally expanding capsules may contain thermoplastic resins and / or volatile materials, such as volatile hydrocarbons and / or volatile gases. Thermally expanding capsules may contain a thermoplastic resin shell with a core of volatile material. Suitable thermally expanding materials include: Expancel, available from Nouryon, Advancell, available from Sekisui, etc.

[0108] The thermally expandable material may have an average initial (i.e., before expansion) particle size of at least 0.5 μm, as measured by methods known to those skilled in the art, such as laser diffraction or small-angle laser light scattering (LALLS), such as at least 1 μm, at least 2 μm, at least 3 μm, at least 5 μm, or at least 10 μm. The thermally expandable material may have an average initial particle size of no more than 100 μm, as measured by methods known to those skilled in the art, such as laser diffraction or small-angle laser light scattering (LALLS), such as no more than 80 μm, at least 60 μm, or at least 50 μm. The thermally expandable material may have an average initial particle size of 0.5 μm to 100 μm, as measured by methods known to those skilled in the art, such as laser diffraction or small-angle laser light scattering (LALLS), such as 1 μm to 80 μm, at least 2 μm to 60 μm, at least 3 μm to 50 μm, at least 5 μm to 50 μm, or at least 10 μm to 50 μm.

[0109] The thermally expandable material may have an expansion temperature of at least 60°C, such as at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, at least 170°C, at least 180°C, at least 190°C, at least 200°C, or not exceeding 250°C. In the case of thermally expandable capsules, the increase in particle size may be a result, for example, of the volatile material beginning to expand and the thermoplastic resin shell softening. For example, the expansion temperature can be achieved by heating the coating containing the thermally expandable material and / or heating the substrate on which the coating is formed. The coating and / or substrate can be heated by direct thermal exposure, and / or indirectly heated in a substrate containing ferromagnetic, ferrimagnetic and / or superparamagnetic materials, or in a coating formed from a composition containing ferromagnetic, ferrimagnetic and / or superparamagnetic materials by applying a magnetic field that causes ferromagnetic heating, ferrimagnetic heating and / or superparamagnetic heating.

[0110] The composition may contain at least 0.1% by weight of a thermally expanding material, such as at least 1% by weight, based on the total weight of the composition. The composition may contain no more than 20% by weight of a thermally expanding material, such as no more than 10% by weight, such as less than 10% by weight, such as no more than 5% by weight, based on the total weight of the composition. The composition may contain from 0.1% to 20% by weight of a thermally expanding material, such as 1% to 10% by weight, such as 1% to less than 10% by weight, such as 1% to 5% by weight, based on the total weight of the composition.

[0111] filler

[0112] The compositions disclosed herein may further comprise fillers. The fillers may be present in the first component, the second component, and / or the third component. The fillers may comprise particles of a single type of filler material, or particles of two or more types of filler materials. That is, the fillers may comprise particles of a first filler material, and may further comprise particles of a second (and third, fourth, etc.) filler material different from the first filler material. As used herein with respect to the type of filler material, references to “first,” “second,” etc., are for convenience only and do not refer to the order in which they are added to the composition.

[0113] The composition may contain at least 1% by weight of filler, such as not more than 50% by weight, based on the total weight of the composition. The composition may contain at least 50% by weight of filler, such as not more than 90% by weight, based on the total weight of the composition. The composition may contain up to 90% by weight of filler, such as from 1% to not more than 50% by weight, or from 50% to 90% by weight, based on the total weight of the composition.

[0114] The filler may include thermally conductive and electrically insulating fillers (referred to herein as “TC / EI fillers” and described in more detail below) and / or thermally conductive and electrically conductive fillers (referred to herein as “TC / EC fillers” and described in more detail below). TC / EI and / or TC / EC (collectively, “thermally conductive fillers”) may be present in the first component, the second component, and / or the third component. The thermally conductive filler may comprise organic or inorganic materials and may comprise particles of a single type of filler material, or particles of two or more types of TC / EI fillers and / or two or more types of TC / EC fillers. That is, the filler may include a first TC / EI filler, and may further include at least a second (i.e., second, third, fourth, etc.) TC / EI filler in addition to the first TC / EI filler. Similarly, the filler may include a first TC / EC filler, and may further include at least a second (i.e., second, third, fourth, etc.) TC / EC filler in addition to the first TC / EC filler. As used herein with respect to the type of filler, references to “first,” “second,” etc., are for convenience only and do not refer to the order in which they are added to the composition, etc.

[0115] Optionally, the filler may include a surface coating. The surface coating may include silanes, aminosilanes, and / or polymers having multiple functional groups that can bind to or interact with the filler.

[0116] The filler may have an average particle size of at least 0.01 μm in at least one dimension, such as at least 2 μm, such as at least 10 μm, as reported by the manufacturer or measured below; and may have an average particle size of no more than 500 μm in at least one dimension, such as no more than 400 μm, such as no more than 300 μm, such as no more than 100 μm, as reported by the manufacturer or measured below. The filler may have an average particle size of 0.01 μm to 500 μm in at least one dimension, such as 0.1 μm to 400 μm, such as 2 μm to 300 μm, such as 10 μm to 100 μm, as reported by the manufacturer or measured below. The particle size can be measured by methods known to those skilled in the art, such as using a scanning electron microscope (SEM), such as a Quanta 250FEG SEM or equivalent instrument. For example, the powder can be dispersed on a carbon ribbon fragment attached to an aluminum rod and coated with Au / Pd for 20 seconds. The sample can then be analyzed in SEM under high vacuum (accelerating voltage 10 kV and spot size 3.0) to measure 30 particles from three different regions to provide the average particle size for each sample. Those skilled in the art will recognize that variations in the fundamental elements preserving microscopic imaging and average representative size are possible in this procedure.

[0117] Thermally conductive fillers may comprise particles and their agglomerates, each of which has, for example, a plate-like, spherical, or needle-like shape. As used herein, “plate-like” refers to a two-dimensional material having a substantially flat surface and a thickness in one direction less than 25% of its maximum dimension.

[0118] The thermally conductive filler can have at least 5 W / m at 25°C. · The thermal conductivity of K (measured according to ASTM D7984-21) is, for example, at least 18 W / m. · K, such as at least 55 W / m · K; and can have a strength of no more than 3,000 W / m at 25°C. · The thermal conductivity of K, such as not exceeding 1,400 W / m · K, such as not exceeding 450 W / m · K. The thermally conductive filler can achieve 5 W / m at 25°C. · K up to 3,000W / m · The thermal conductivity of K, such as 18 W / m · K up to 1,400 W / m · K, such as 55 W / m · K up to 450 W / m · K. Thermal conductivity can be measured according to ASTM D7984-21.

[0119] The filler (TC / EI and / or NTC / EI) can be electrically insulating. The electrically insulating filler may have a strength of at least 1 Ω. · The volume resistivity of m, such as at least 10 Ω · m, such as at least 100 Ω · m. Electrical insulation can be measured according to ASTM D257-19.

[0120] The filler can be conductive. Conductive fillers can have a conductivity of less than 1 Ω. . The volume resistivity (measured according to ASTM D257-19) is, for example, less than 0.1 Ω. . m.

[0121] Suitable TC / EI fillers include: boron nitride (e.g., available from Saint-Gobain as CarboTherm, from Momentive as CoolFlow and PolarTherm, and from Panadyne as hexagonal boron nitride powder), silicon nitride or aluminum nitride (e.g., available from Micron Metals Inc. as aluminum nitride powder, and from Toyal as Toyalnite); metal oxides, such as boehmite, pseudoboehmite, alumina (e.g., available from Micron Metals Inc. as aluminum nitride powder, and from Toyal as Toyalnite); and metal oxides such as gibbsite, boehmite, and alumina (e.g., available from Micron Metals Inc. as aluminum nitride powder). Abrasives are commercially available from Microgrit, Nabaltec (Nabalox), Evonik (Aeroxide), and Imerys (Alodur); magnesium oxide, beryllium oxide, titanium oxide, zinc oxide, nickel oxide, copper oxide, or tin oxide; metal hydroxides, such as aluminum hydroxide or magnesium hydroxide; arsenides, such as boron arsenide; carbides, such as silicon carbide; minerals, such as agate and corundum; ceramics, such as ceramic microspheres (e.g., available from Zeeospheres Ceramics or 3M); silicon carbide; and diamond. These fillers can also be surface-modified, such as PYROKISUMA 5301K available from Kyowa Chemical Industry Co., Ltd. Thermally conductive fillers can be used alone or in combination of two or more. TC / EI fillers can also be ferromagnetic, ferrimagnetic, and / or superparamagnetic.

[0122] Suitable TC / EC fillers include metals such as silver, zinc, copper, gold, or metal-coated hollow particles; carbon compounds such as graphite (e.g., Timrex available from Imerys or ThermoCarb available from Asbury Carbons), carbon black (e.g., Vulcan available from Cabot Corporation), carbon fibers (e.g., milled carbon fibers available from Zoltek), graphene and graphene carbon particles (e.g., xGnP graphene nanosheets and / or graphene carbon particles available from XG Sciences, as described below); carbonyl iron; copper (e.g., spherical powder available from Sigma Aldrich); zinc (e.g., Ultrapure available from PurityZinc Metals and Alexzinc available from US...). Zinc powders (such as XL and XLP) obtained from zinc (zinc). Examples of “graphene carbon particles” include carbon particles having a structure of one or more single-atom-thick planar sheets containing sp2-bonded carbon atoms, which are closely packed in a honeycomb lattice. The average number of stacked layers can be less than 100, for example less than 50. The average number of stacked layers can be 30 or less, such as 20 or less, such as 10 or less, such as 5 or less. Graphene carbon particles can be substantially flat; however, at least a portion of the planar sheet can be substantially curved, curled, wrinkled, or buckled. The particles generally do not have a spherical or isometric morphology. Suitable graphene carbon particles are described in paragraphs

[0059] to

[0065] of U.S. Publication No. 2012 / 0129980, the referenced portion of which is incorporated herein by reference. Other suitable graphene carbon particles are described in U.S. Patent No. 9,562,175, 6:6 through 9:52, the referenced portion of which is incorporated herein by reference. As used herein, the term “substantially flat” means planar; “curved” or “curved” means a material that deviates from planarity due to having a non-zero curvature; and “wrinkled” or “bent” means that at least a portion of the region is thicker than a sheet, such that the plane is folded or folded itself. TC / EC fillers can also be ferromagnetic, ferrimagnetic, and / or superparamagnetic.

[0123] As discussed above, the thermally conductive filler may be present in the first component, second component, third component, and / or higher components. The compositions disclosed herein may contain at least 14.5% by weight of the thermally conductive filler, such as at least 25% by weight, based on the total weight of the composition. The compositions disclosed herein may contain no more than 90% by weight of the thermally conductive filler, such as no more than 60% by weight, based on the total weight of the composition. The compositions disclosed herein may contain from 14.5% by weight to 90% by weight of the thermally conductive filler, such as from 25% by weight to 60% by weight, based on the total weight of the composition.

[0124] The composition may contain 100% by volume of thermally conductive filler based on the total volume of the filler. The composition may contain no more than 90% by volume of thermally conductive filler, such as no more than 80% by volume. The composition may contain at least 20% by volume of thermally conductive filler based on the total volume of the filler, such as at least 50% by volume. The composition may contain from 20% to 90% by volume of thermally conductive filler based on the total volume of the filler, such as from 50% to 80% by volume.

[0125] The filler may include a non-thermally conductive, electrically insulating filler (referred to herein as "NTC / EI" filler). As used herein, the NTC / EI filler is a complement to the aforementioned thermally expanding material. The NTC / EI filler may be present in the first component, the second component, and / or the third component. The NTC / EI filler may contain organic or inorganic materials and may contain particles of a single type of filler material, or particles of two or more types of NTC / EI fillers. That is, the composition may contain a first NTC / EI filler, and in addition to the first NTC / EI filler, may further contain at least a second (i.e., second, third, fourth, etc.) NTC / EI filler.

[0126] NTC / EI fillers may include any of the surface coatings and may have the particle size described above for thermally conductive fillers. NTC / EI fillers may include particles and their agglomerates, each of which has, for example, a plate-like, spherical, or needle-like shape, as described above for thermally conductive fillers.

[0127] NTC / EI packing can achieve less than 5 W / m at 25℃. · The thermal conductivity of K (measured according to ASTM D7984-21), such as not exceeding 3 W / m · K, such as not exceeding 1 W / mK, such as not exceeding 0.1 W / mK, such as not exceeding 0.05 W / mK, such as 0.02 W / m at 25°C · K up to 5 W / m at 25℃ · K. Thermal conductivity can be measured as described above.

[0128] NTC / EI can have at least 1 Ω · The volume resistivity (measured according to ASTM D257-19) is, for example, at least 10 Ω. · m, such as at least 100 Ω · m.

[0129] Suitable NTC / EI fillers include, but are not limited to: mica, wollastonite, calcium carbonate, glass microspheres, clay, silica, or combinations thereof.

[0130] As used herein, the term "mica" generally refers to a flaky silicate (layered silicate) mineral. Mica can include muscovite. Muscovite is a layered silicate mineral containing aluminum and potassium, with the chemical formula KAl2(AlSi3O3). 10 (F,OH)2 or (KF)2(Al2O3)3(SiO2)6(H2O). Exemplary, non-limiting, commercially available muscovite includes products sold under the trade name DakotaPURE™ from Pacer Minerals, such as DakotaPURE™ 700, DakotaPURE™ 1500, DakotaPURE™ 2400, DakotaPURE™ 3000, DakotaPURE™ 3500, and DakotaPURE™ 4000. Wollastonite comprises calcium silicate minerals (CaSiO3) that may contain small amounts of iron, aluminum, magnesium, manganese, titanium, and / or potassium. Wollastonite may have a thickness of 1.5 to 2.1 m. 2 BET surface area per g, such as 1.8 m² 2 / g, and the median particle size can be 6 micrometers to 10 micrometers, such as 8 micrometers. Non-limiting examples of commercially available wollastonite include NYAD 400, which is available from NYCO Minerals, Inc.

[0131] Calcium carbonate (CaCO3) can include precipitated calcium carbonate or heavy calcium carbonate. Calcium carbonate may or may not undergo surface treatment, such as treatment with stearic acid, such as Socal® 312, commercially available from IMERYS. Non-limiting examples of commercially available precipitated calcium carbonate include Ultra-Pflex®, Albafil®, and Albacar HO®, available from Specialty Minerals, and Winnofil® SPT, available from Solvay. Non-limiting examples of commercially available heavy calcium carbonate include Duramite, available from IMERYS. TM And Marblewhite®, available from Specialty Minerals.

[0132] Useful clay minerals include nonionic plate-like fillers such as talc, pyrophyllite, chlorite, vermiculite, or combinations thereof.

[0133] Glass microspheres can be hollow borosilicate glass. Non-limiting examples of commercially available glass microspheres include 3M glass bubble types VS, K series, and S series, which are available from 3M.

[0134] As discussed above, NTC / EI fillers may be present in the first component, second component, third component, and / or higher components. The compositions disclosed herein may contain at least 0.5% by weight of NTC / EI filler, such as at least 1% by weight, such as at least 1.5% by weight, based on the total weight of the composition. The compositions disclosed herein may contain no more than 30% by weight of NTC / EI filler, such as no more than 20% by weight, such as no more than 10% by weight, based on the total weight of the composition. The compositions disclosed herein may contain up to 30% by weight of NTC / EI filler, such as from 0.5% to 30% by weight, such as from 1% to 20% by weight, such as from 1.5% to 10% by weight, based on the total weight of the composition.

[0135] Third compound

[0136] The composition may further comprise a third compound that reacts with the isocyanate functional group. The third compound may be present in the second and / or third or higher components. The third compound may comprise a hydroxyl functional group, such as a polyol.

[0137] As used in this article with respect to compounds, references to "first," "second," "third," "fourth," etc., are for convenience only and do not refer to the order in which they are added to the composition.

[0138] Suitable polyols include diols, triols, tetraols, and polyols with higher functionality. Combinations of such polyols can also be used. Polyols may include, for example, ethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentylene glycol, hexanediol, cyclohexanediol, phenylenediol, 4,4'-isopropylidene dicyclohexanol, glycerol, trimethylolpropane, pentaerythritol, bis(trimethylolpropane) or bis(pentaerythritol). Suitable polyols may also include polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof.

[0139] Polyols may include polycaprolactone-based polyols. Polycaprolactone-based polyols may include diols capped with primary hydroxyl groups. Commercially available polycaprolactone-based polyols include those marketed under the trade name Capa™ from the Perstorp Group, such as, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091, and Capa 4101.

[0140] Polyols may include polyether polyols. Polyols may be based on polyether chains derived from ethylene glycol, propylene glycol, butanediol, hexanediol, or mixtures thereof. Polyols may include tetrahydrofuran-based polyols. Polytetrahydrofuran-based polyols may include diols, triols, or tetraols terminated with primary hydroxyl groups. Commercially available polytetrahydrofuran-based polyols include those sold under the trade name Terathane® from Invista, such as Terathane® PTMEG 250, Terathane® PTMEG 650, and Terathane® PTMEG 1000, which are blends of linear diols in which hydroxyl groups are separated by repeating tetramethylene ether groups. In addition, dimerized glycol-based polyols available from Cognis Corporation under the trade names Pripol®, Solvermol™, and Empol®, or bio-based polyols such as the tetrafunctional polyol Agrol 4.0 available from BioBased Technologies, can be used. The polyols may contain amine-containing polyols, such as Quadrol PM, commercially available from BASF.

[0141] The composition may comprise an isocyanate functional group on the first compound and a hydroxyl functional group on the third compound, in an equivalent ratio of at least 0.2:1, such as at least 0.4:1, such as at least 0.6:1. The composition may comprise an isocyanate functional group on the first compound and a hydroxyl functional group on the third compound, in an equivalent ratio not exceeding 3:1, such as not exceeding 2:1, such as not exceeding 1.5:1. The composition may comprise an isocyanate functional group on the first compound and a hydroxyl functional group on the third compound, in an equivalent ratio of 0.2:1 to 3:1, such as 0.4:1 to 2:1, such as 0.6:1 to 1.5:1.

[0142] Fourth compound

[0143] The composition may further comprise a fourth compound containing a furan functional group, different from the compounds disclosed herein. The fourth compound may be present in the first component and / or the third component or higher components. This statement is not intended to be limiting and does not preclude the possibility that the composition may contain more than two furan functional group compounds, such as three compounds, such as four compounds.

[0144] The fourth compound may contain at least 68 g / eq of furan equivalent weight, such as at least 80 g / eq. The fourth compound may contain no more than 1,500 g / eq of furan equivalent weight, such as no more than 1,000 g / eq. The fourth compound may contain between 68 g / eq and 1,500 g / eq of furan equivalent weight, such as between 80 g / eq and 1,000 g / eq.

[0145] The composition may optionally contain one or more additives. As used herein, “additive” means rheology modifier, tackifier, thermoplastic polymer, surfactant, flame retardant, corrosion inhibitor, UV stabilizer, colorant, dye, solvent, plasticizer, adhesion promoter, antioxidant, silane and / or dehumidifier.

[0146] The compositions provided in this disclosure may contain flame retardants or combinations of flame retardants. For example, certain thermally conductive materials such as aluminum hydroxide and magnesium hydroxide may also be flame retardants; such materials are considered thermally conductive for the purpose of calculating the weight percentage herein. As used herein, "flame retardant" means a material that slows or prevents the spread of fire or reduces its intensity. Flame retardants may be available in powder form, which may be mixed with compositions, foams, or gels. In examples, when the compositions disclosed herein contain flame retardants, such compositions may form a coating on a substrate surface, and such coating may act as a flame retardant. Flame retardants may include: minerals, organic compounds, organohalogen compounds, organophosphorus compounds, or combinations thereof.

[0147] The composition may contain at least 0.01% by weight of additives, such as at least 0.1% by weight, based on the total weight of the composition. The composition may contain no more than 15% by weight of additives, such as no more than 10% by weight, based on the total weight of the composition. The composition may contain from 0.01% by weight to 15% by weight of additives, such as from 0.1% by weight to 10% by weight, based on the total weight of the composition.

[0148] The compositions disclosed herein may further comprise elastomer particles. As used herein, “elastomer particles” refers to particles comprising one or more materials having a glass transition temperature (Tg) greater than -150°C and less than 30°C, calculated, for example, using the Fox equation.

[0149] Elastomer particles can have a core / shell structure. Suitable core-shell elastomer particles can consist of an acrylic shell and an elastomer core. The core can include natural or synthetic rubber, polybutadiene, styrene-butadiene, polyisoprene, chloroprene, acrylonitrile-butadiene, butyl rubber, polysiloxane, polysulfide, ethylene-vinyl acetate, fluorinated elastomer, polyolefin, or combinations thereof. Elastomer particles can include a polybutadiene core, a styrene-butadiene core, and / or a polysiloxane core.

[0150] Exemplary non-limiting commercial core-shell elastomer particle products (using polybutadiene rubber particles) that can be used in the compositions of this disclosure include core-shell polybutadiene rubber powder (commercially available from Dow Chemical as PARALOID™ EXL 2650A).

[0151] Exemplary non-limiting commercial core-shell elastomer particle products (using styrene-butadiene rubber particles) that can be used in compositions include core-shell styrene-butadiene rubber powder (available from Arkema as CLEARSTRENGTH). ® XT100, or commercially available as PARALOID™ EXL 2650J, and a core-shell styrene-butadiene rubber dispersion in polypropylene glycol (MW 400) (core-shell rubber 25% by weight) (commercially available from Kaneka Texas Corporation as Kane Ace MX 715).

[0152] Exemplary non-limiting commercial core-shell elastomer particle products (using polysiloxane rubber particles) that can be used in the compositions of this disclosure include core-shell polysiloxane rubber powder (available from Wacker as GENIOPERL) ® P52 (obtained through commercial purchase).

[0153] The composition may contain at least 0.1% by weight of elastomeric particles, such as at least 1% by weight, based on the total weight of the composition. The composition may contain no more than 50% by weight of elastomeric particles, such as no more than 20% by weight, based on the total weight of the composition. The composition may contain up to 25% by weight of elastomeric particles, such as from 0.1% to 50% by weight, or from 1% to 20% by weight, based on the total weight of the composition.

[0154] The composition may optionally further include a dispersant. As used herein, the term "dispersant" refers to a substance that can be added to the composition to improve particle separation by wetting the thermally conductive filler particles and breaking down agglomerates.

[0155] Dispersants suitable for use in the composition include fatty acids, phosphate esters, polyurethanes, polyamines, polyacrylates, polyalkoxylates, sulfonates, polyethers, and polyesters, or any combination thereof. Non-limiting examples of commercially available dispersants include ANTI-TERRA-U100, DISPERBYK-102, DISPERBYK-103, DISPERBYK-111, DISPERBYK-171, DISPERBYK-2151, DISPERBYK-2152, DISPERBYK-2059, DISPERBYK-2000, DISPERBYK-2117, and DISPERBYK-2118, available from BYK Company; SOLSPERSE 24000SC, SOLSPERSE 16000, and SOLSPERSE 8000 superdispersants, available from The Lubrizol Corporation; and Tegowet 270, Tegowet 500, and TEOG® Dispersants, available from Evonik. 670 and Tegowet 550.

[0156] The composition may contain at least 0.5% by weight of a dispersant, such as at least 1% by weight, based on the total weight of the composition. The composition may contain no more than 10% by weight of a dispersant, such as no more than 5% by weight, based on the total weight of the composition. The composition may contain more than 0% by weight to 10% by weight of a dispersant, such as 0.5% by weight to 10% by weight, or 1% by weight to 5% by weight, based on the total weight of the composition.

[0157] The composition may further comprise an accelerator. The accelerator may be present in the first component, second component, and / or third component, or higher components. The accelerator may comprise an amine catalyst or a nitrogen-based catalyst. The accelerator may comprise a tertiary amine, N - Heterocyclic carbenes or amidine / guanidine. Suitable promoters that can be used in this disclosure include N,N -Dimethylcyclohexylamine, N , N -Dimethylethanolamine, N 2,2'-Dimorpholine, 2,2'-Dimorpholinodiethyl ether, dimethylaminoethoxyethanol, triethylenediamine, bis(2-dimethylaminoethyl) ether, N , N , N '-Trimethylaminoethylethanolamine, N , N , N' , N'-Tetramethyl-1,6-hexanediamine, 1,3,5-tris(dimethylaminopropyl)-hexahydro-triazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N -(3-aminopropyl)imidazolium, 1,2-dimethylimidazolium, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. In some cases, the accelerator may contain an organic acid, such as diphenyl phosphate, methanesulfonic acid, or trifluoromethanesulfonic acid. The accelerator may contain an organometallic complex. Suitable organometallic complexes include titanates, such as tetrabutyl titanate or tetrapropyl titanate; tin compounds, such as dibutyltin dilaurate, dibutyltin diacetate, tin octanoate, or dibutyltin oxide; or other metal compounds, such as chelates of bismuth, zirconium, titanium, aluminum, or iron, such as zirconium acetylacetonate or iron acetylacetonate. In examples, the accelerator may be latent, end-capped, and / or encapsulated.

[0158] The composition may contain at least 0.001% by weight of an accelerator, such as at least 0.01% by weight, based on the total weight of the composition, and the accelerator may be present in the composition in an amount not exceeding 2% by weight, such as not exceeding 1% by weight, based on the total weight of the composition. The accelerator may be present in the composition in an amount from 0.001% by weight to 2% by weight, such as from 0.01% by weight to 1% by weight, based on the total weight of the composition. The composition may contain at most 2% by weight of an accelerator, such as at most 1% by weight, based on the total weight of the composition.

[0159] The first and second components can be liquids under ambient conditions, can be mixed at ambient temperature, and can be cured at ambient temperature. The composition can be formulated into a two-component composition.

[0160] The compositions disclosed herein can be formulated into self-supporting membranes, adhesives, structural adhesives, sealants, potting compounds, gap fillers, prepregs, embedding materials, encapsulating agents, etc.

[0161] The compositions disclosed herein can be formulated into hot melts. To formulate a hot melt, the reflow initiation temperature must be below the expansion temperature. Solid hot melts can be heated above their reflow initiation temperature and can be used to surround substrates or components to substantially exclude air, water, and / or moisture from the substrate, and / or increase the strength or stiffness of the substrate or component. Furthermore, the compositions can be brought into contact with surfaces or components as pre-formed films, and the system can be heated above the reflow initiation temperature of the composition and then cooled to produce a bonded or embedded system.

[0162] The composition may have a reflux initiation temperature of at least 50°C, such as at least 60°C. The composition may have a reflux initiation temperature of less than 150°C, such as less than 140°C. The composition may have a reflux initiation temperature of 50°C to 150°C, such as 60°C to 140°C.

[0163] For example, the reflow initiation temperature can be achieved by heating the coating containing the coating disclosed herein and / or heating the substrate on which the coating is formed. The coating and / or substrate can be heated by directional heat exposure, and / or indirectly heated in a substrate containing ferromagnetic, ferrimagnetic, and / or superparamagnetic materials, or in a coating formed from a composition containing ferromagnetic, ferrimagnetic, and / or superparamagnetic materials, by applying a magnetic field that causes ferromagnetic heating, ferrimagnetic heating, and / or superparamagnetic heating.

[0164] Methods and Cured Coatings

[0165] The above compositions can be applied alone or as part of a system that can be deposited onto different substrates in different ways. Therefore, methods for treating substrates are disclosed herein, comprising, or substantially comprising, either bringing a surface of a substrate into contact with any of the compositions disclosed herein. "Surface in contact with substrate" encompasses surfaces of substrates that have been treated with other coatings as described herein. Optionally, the method may include mixing a first component and a second component to form a composition. The compositions can be applied to the surface of a substrate in different ways, non-limiting examples of which include brushing, roller coating, film formation, granulation, troweling, doctor blade application, dip coating, spraying, or application with a glue gun to form a coating on the substrate surface.

[0166] After being applied to a substrate, the composition can be cured. For example, the composition can be allowed to cure at room temperature or under mild heat for any desired time (e.g., 5 minutes to 1 hour) sufficient for the composition to cure on the substrate. Optionally, after contacting the substrate surface with the composition, the composition can be further cured by heating at elevated temperatures, such as below 90°C, such as below 80°C, such as below 70°C, such as below 60°C but above ambient temperature, such as above 40°C, such as above 50°C, and for any desired time (e.g., 5 minutes to 1 hour), as long as that time is sufficient for the composition to cure on the substrate, provided that in compositions containing thermally expanding materials, the thermal conditions are below the expansion temperature of the thermally expanding material. After curing, the composition can form a coating on the substrate surface. The coating can be, for example, an adhesive such as a structural adhesive, potting compound, prepreg, liquid gasket, sealant, or gap filler. The composition can be cured to form articles, such as by additive manufacturing, such as three-dimensional (“3D”) printing as described below.

[0167] The composition may have a Tg of at least -120°C (measured using a TA Instruments Q800 DMA V21.3 in single cantilever mode). The composition may have a Tg of no more than 150°C, such as no more than 100°C, such as at most 90°C (measured using a TA Instruments Q800 DMA V21.3 in single cantilever mode). The composition may have a Tg of -120°C to 150°C, such as -120°C to 100°C (measured using a TA Instruments Q800 DMA V21.3 in single cantilever mode).

[0168] The coating disclosed herein is cured to form a thermally expandable coating before the thermally expandable material expands.

[0169] The method may optionally further include contacting the surface of the second substrate with the composition such that the composition is positioned between the first and second substrates. For example, the composition may be applied to one or both of the first and second substrates such that the composition is positioned between the first and second substrates. In examples, the substrates may be aligned, and pressure and / or spacers may be added to control the adhesive thickness.

[0170] The composition can be applied to clean or unclean (i.e., including oily or greased) substrate surfaces. The compositions disclosed herein can also be applied to substrates that have been pretreated, coated with an electrodepositable coating, and / or coated with additional coatings such as primers, undercoats, or topcoats.

[0171] The composition may be injected or otherwise placed in a die-casting machine or mold and dried or cured under ambient conditions or by exposure to an external energy source, such as by heating to temperatures below 180°C, such as below 130°C, such as below 90°C, to form a part or component and optionally may be machined into a particular configuration.

[0172] The compositions disclosed herein can be applied to a substrate surface and cured as described above to form a coating. For example, the coating can be an adhesive (such as a structural adhesive), a sealant, a gap filler, a potting compound, and / or a liquid gasket.

[0173] The thermally expandable coating disclosed herein exhibits an expansion-before thermal conductivity of at least 0.5 W / m·K at 25°C, measured using a modified transient planar source instrument according to ASTM D7984-21, such as at least 1 W / m·K, such as at least 2 W / m·K. · K, such as at least 3 W / m·K, such as at least 4 W / m·K, such as at least 5 W / m·K. Adding thermally expanding materials did not reduce the thermal conductivity of the thermally expanding coating before expansion.

[0174] The thermally expandable coatings disclosed herein may have a reduction in thermal conductivity of at least 10% after expansion (after exposure to the expansion temperature of at least the thermally expandable material) relative to their thermal conductivity before expansion (measured at 25°C using a modified transient planar source instrument according to ASTM D7984-21), such as at least 25%, at least 50%, at least 75%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%.

[0175] After exposure to thermal conditions (such as at least the expansion temperature of the thermally expanding material), the thermally expanding material, when measured at 25°C by methods known to those skilled in the art (such as SEM, laser diffraction, or LALLS), may have an expansion volume ratio (i.e., volume after expansion / volume before expansion), such as at least 1.1, at least 1.2, at least 1.5, at least 2, at least 2.5, at least 3, at least 4, at least 5, at least 10, at least 11, at least 12, at least 20, at least 50, at least 75, at least 100, at least 125, at least 175, at least 200, at least 10 to 150, at least 10 to 100.

[0176] After exposure to the expansion temperature of the thermally expanding material, the thermally expanding coating disclosed herein can be cohesive.

[0177] After exposure to the expansion temperature of the thermally expanding material, the thermally expanding coating disclosed herein can be non-cohesive / fragile.

[0178] The thermally expanding coatings disclosed herein (i.e., after curing) may have an expanded volume ratio greater than 1, such as at least 1.1, at least 1.2, at least 1.5, at least 2, at least 3, at least 5, at least 10, at least 20, wherein the expanded volume ratio = expanded volume (measured at 25°C after exposure to the expansion temperature of at least the thermally expanding material) / unexpanded volume (measured at 25°C before exposure to the expansion temperature of at least the thermally expanding material), and wherein the volume is measured using calipers, and the coating is cohesive / non-brittle.

[0179] When the disclosed composition is a high-load composition (i.e., containing 50% to 90% by weight of filler and 0.5% to 10% by weight of thermally expandable material based on the total weight of the composition), it is found that the composition is pumpable (i.e., each component has a content of no more than 10%). 6The viscosity was measured at 25°C using an AntonPaar MCR 301 rotational rheometer with parallel plates of 25 mm diameter (1 mm gap) under a shear stress of 1 Hz. This was an unexpected result.

[0180] After being exposed to the expansion temperature of a thermally expanding material, the coating can be cohesive.

[0181] After being exposed to the expansion temperature of a thermally expanding material, the coating can be non-cohesive / fragile, which can be used to remove the coating from the surface of a substrate, such as for removing battery cells from a battery pack.

[0182] The thermal expansion coating disclosed herein exhibits a V0 vertical flammability rating (measured by UL-94 Vertical Flame Test Procedure). A V0 rating means that: (1) no flammability (open flame or smoldering flame) is observed for more than 10 seconds after the flame is removed from the first and second flame exposures; (2) no smoldering flame is observed for more than 30 seconds after the flame is removed from the second flame exposure; and (3) no dripping of flame particles that could ignite the medical cotton is observed.

[0183] The thermally expandable coating disclosed herein exhibits a pre-expansion lap shear strength of at least 5 MPa at 25°C, measured using a 0.063-inch thick 2024 T3 aluminum substrate, according to ASTM D1002-10, in tensile mode using an INSTON 5567 machine at a pull rate of 1.3 mm / min, and is such as at least 10 MPa.

[0184] Dielectric coating compositions and dielectric coatings, as well as dielectric systems and kits

[0185] In addition to thermally expandable coatings, any substrate disclosed herein may contain a dielectric coating. The dielectric coating composition and the thermally expandable coating composition may form continuous or discontinuous coatings, provided that these coatings overlap to form a coating stack, for example, a thermally expandable coating formed by the thermally expandable coating composition situated on a dielectric coating formed by the dielectric coating composition. Such a coating stack does not preclude the possibility of coatings other than the dielectric coating and the second coating, wherein such additional coatings may or may not be situated between the dielectric coating and the second coating. Optionally, the coating stack may be formed between two substrates. As used herein, “dielectric” means a coating composition or coating comprising a dielectric strength of at least 10 kV / mm, such as at least 12 kV / mm, such as at least 15 kV / mm, as measured according to ASTM D149-09 using a Sefelec dielectric strength tester (RMG12AC-DC; voltage limit 12.0 kV, Imax limit 0.1 mA, 19-second ramp, 20-second dwell, 2-second fall).

[0186] This document also discloses coating systems. A coating system may include: a dielectric coating composition for application to a first portion of a substrate surface; and any thermally expanding coating composition disclosed herein for application to a second portion of the substrate surface. In a cured state, the dielectric coating composition may form a dielectric coating. In a cured state, the thermally expanding coating composition may form a thermally expanding coating.

[0187] This document also discloses coating kits. A coating kit may include: a dielectric coating composition for application to a first portion of a substrate surface; and any thermally expanding coating composition disclosed herein for application to a second portion of the substrate surface. The kit may optionally include instructions for applying the dielectric coating composition and the thermally expanding coating composition to the substrate surface.

[0188] As used herein with respect to dielectric coatings and thermal expansion coatings, and systems and kits comprising compositions for forming them, the first portion and the second portion may be located on a single substrate, or may be located on a first substrate and a second substrate, respectively.

[0189] The dielectric coating composition may include a binder comprising a film-forming 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 crosslinking agent, upon solvent evaporation, and / or upon light or thermal activation. The dielectric coating composition may contain any suitable film-forming resin, including organic 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: polyesters, alkyd resins, urethanes, isocyanates, polyureas, epoxy resins, acrylics, polyethers, polysulfides, polyamines, polyamides, polyvinyl chloride, polyolefins, polyvinylidene fluoride, polyvinyl chloride, polyolefins, polysiloxanes, amine-aldehydes, resin polyols, phosphorylated polyepoxides, phosphorylated acrylic polymers, amino plastics, or combinations thereof.

[0190] The dielectric coating composition may optionally include a curing agent and / or a crosslinking agent capable of crosslinking with the film-forming resin to cure the dielectric coating composition. Any suitable curing agent and / or crosslinking agent capable of crosslinking with the film-forming resin may be used. Examples of suitable curing agents include, but are not limited to: amines; amino plastics; phenolic plastics; polyisocyanates, including terminal isocyanates; polyepoxides; β-hydroxyalkylamides; polybasic acids; organometallic acid functional materials; polyamines; polyamides; polysulfides; polythiols; polyolefins, such as polyacrylates; polyols; polysilanes; and combinations thereof.

[0191] The dielectric coating composition may optionally further comprise colorants, pigments, additives, and / or fillers. Suitable fillers that can be used in the dielectric coating composition include TC / EI fillers, TC / EC fillers, and / or NTC / EI fillers.

[0192] The dielectric coating composition may comprise a thermosetting coating composition, wherein the coating composition cures upon crosslinking of a film-forming resin with a curing agent and / or a crosslinking agent. 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 thermosetting or thermoplastic coating composition that cures upon exposure to photochemical radiation, such as ultraviolet light.

[0193] 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 having a Pa value of less than 100,000 at 25°C. A material with a viscosity of s, such that when passed through a plate with a diameter of 25 mm, a gap of 0.5 mm, and a shear rate of 1 s... -1 The parallel plate rheology is used for measurement.

[0194] Suitable liquid coating compositions include, but are not limited to, electrodepositable coating compositions, single-component coating compositions, and / or multi-component coating compositions.

[0195] For example, a liquid dielectric coating composition may comprise an electrodepositable coating composition. The electrodepositable coating composition may comprise one or more film-forming resins containing cationic or anionic salt groups, which can be deposited onto a metal or other conductive substrate under the influence of an applied potential (i.e., by electrodeposition).

[0196] In other examples, the liquid dielectric coating composition may comprise a UV-curable coating composition comprising a film-forming resin capable of curing upon exposure to UV radiation. Any suitable UV-curable film-forming resin may be used, such as a radical polymerizable resin containing vinyl unsaturation or olefinic double bonds and / or a film-forming resin that can be reacted via a cationic photopolymerization mechanism. Examples of suitable UV-curable coating compositions that may be used include, but are not limited to, the RAYCRON series of UV-curable coatings commercially available from PPG Industries, Inc.

[0197] Other suitable liquid dielectric coating compositions include, but are not limited to, the SPECTRACRON series of solvent-based coating compositions and the AQUACRON series of water-based coating compositions, all of which are commercially available from PPG Industries, Inc. Liquid dielectric coatings can also be applied as two-component compositions, wherein the film-forming resin and the reactive curing agent and / or crosslinking agent are mixed immediately before the coating composition is applied, and can optionally be cured under ambient conditions without any external energy source.

[0198] Alternatively, the dielectric coating composition may comprise a powder coating composition. As used herein, “powder coating composition” means any dielectric coating composition in particulate form, in the form of a co-reactive solid, which may be substantially free of, substantially free of, or completely free of water and / or solvents. Suitable film-forming resins that may be used in dielectric powder coating compositions include those discussed in paragraphs

[0006] to

[0042] ,

[0057] to

[0068] ,

[0088] to

[0105] , and

[0128] to

[0139] of PCT Publication WO 2021 / 173941A1, which are incorporated herein by reference. Non-limiting examples of suitable powder compositions that may be used in this disclosure include: polyester-based ENVIROCRON series powder coating compositions (commercially available from PPG Industries, Inc.), silicone-modified polyester compositions, epoxy-polyester blends, and / or UV-curable powder compositions.

[0199] The dielectric coating composition can be applied to a substrate by any suitable method known in the art, including but not limited to electrodeposition, roll coating, spraying (such as electrostatic spraying), flow coating, spin coating, curtain coating, brush coating, dip coating, hot melt extrusion, application of self-supporting films, and / or fluidized bed processes. Once applied to the substrate, the dielectric coating composition can be cured by any method known in the art, such as baking, induction heating, infrared heating, and / or exposure to photochemical radiation (such as UV).

[0200] The dielectric coating formed from the dielectric coating compositions disclosed herein may have a dielectric strength of at least 10 kV / mm, such as at least 12 kV / mm, such as at least 15 kV / mm. The dielectric coating may have a dielectric strength not exceeding 120 kV / mm, such as not exceeding 100 kV / mm. The dielectric coating may have a dielectric strength from 10 kV / mm to 120 kV / mm, such as from 12 kV / mm to 100 kV / mm, such as from 15 kV / mm to 100 kV / mm. The dielectric strength may be measured according to ASTM D149-09 using a Sefelec dielectric strength tester (RMG12AC-DC; voltage limit 12.0 kV DC, Imax limit 0.1 mA, 19-second ramp, 20-second dwell, 2-second descent).

[0201] Additive manufacturing

[0202] The compositions disclosed herein can be used in any suitable additive manufacturing technology, such as three-dimensional (3D) printing, extrusion, jetting, and binder jetting. Additive manufacturing refers to the process of producing parts or components by building them layer by layer (such as one layer at a time).

[0203] This disclosure also relates to the use of additive manufacturing processes, such as 3D printing, to produce structural articles, such as acoustic damping liners, printed gaskets, or seals as non-limiting examples. 3D printing refers to a computerized process, optionally including artificial intelligence modulation, in which material is printed or deposited in successive layers to produce 3D parts or components, such as acoustic damping liners in a battery assembly as a non-limiting example. 3D parts or components can be produced by depositing successive portions or layers on a base of any spatial configuration, and then depositing additional portions or layers on and / or adjacent to the previously deposited portions or layers to produce 3D-printed parts or components.

[0204] It should be understood that the configuration of the 3D printing process (including the selection of suitable deposition equipment) depends on factors such as deposition volume, viscosity of the composition, and complexity of the part being manufactured. Any suitable mixing, conveying, and 3D printing equipment known to those skilled in the art can be used. The composition can be printed or deposited in droplets or extrusions of any size and / or shape and in any pattern to produce a 3D structure.

[0205] The compositions disclosed herein can be applied or deposited using any suitable 3D printing method known to those skilled in the art. The first and second components of the compositions disclosed herein can be mixed and then deposited, or the first and second components can be deposited separately, such as simultaneously and / or sequentially.

[0206] The first and second components can be premixed, i.e., mixed together, and then deposited. The mixture may react or become thermosetting during material deposition; the deposition reaction mixture may react after deposition and may also react with previously deposited portions of the article and / or subsequently deposited portions, such as the underlying layer or overlay of the article.

[0207] In one non-limiting example, the first and second components may be released from their respective storage containers and propelled (e.g., pumped) through conduits (e.g., hoses) to a mixer (e.g., a static or dynamic mixer), where the compositions may be mixed for a time sufficient to homogenize them, and the compositions may then be released through an outlet. The outlet may be a deposition device (e.g., a printhead), and / or the material may exit the mixing unit and be propelled (e.g., by pump) through conduits (e.g., hoses) to the printhead. The printhead may optionally be mounted on a 3D rotary robotic arm to allow the 3D printing composition to be delivered to any substrate in any spatial configuration, and / or the substrate may be manipulated in any spatial configuration during the 3D printing process.

[0208] Alternatively, the first and second components can be deposited independently from different printheads. The first component can be deposited from one printhead and the second component can be deposited from a second printhead. The first and second components can be deposited in any pattern, such that the first and second components, containing any deposited layers, can react with each other, as well as with the underlying and / or upper layers, to produce 3D printed parts or components.

[0209] The method provided in this disclosure includes printing a composition onto a manufactured part. The method provided in this disclosure also includes directly printing the part.

[0210] Using the methods provided in this disclosure, components can be manufactured. The entire component can be formed from one of the compositions disclosed herein, one or more portions of the component can be formed from one of the compositions disclosed herein, one or more distinct portions of the component can be formed using the compositions disclosed herein, and / or one or more surfaces of the component can be formed from the compositions provided in this disclosure. Additionally, internal regions of the component can be formed from the compositions provided in this disclosure.

[0211] Uses of the composition and coating

[0212] The compositions disclosed herein exhibit ambient temperature curing properties. Coatings formed from the compositions disclosed herein can also surprisingly be used as structural adhesives.

[0213] The coating formed from the compositions disclosed herein exhibits high lap shear strength at 25°C, measured according to ASTM D1002-10 using an Instron 5567 machine in tensile mode at a pull rate of 1.3 mm / min; however, it exhibits low lap shear strength at 150°C, also measured according to ASTM D1002-10 using an Instron 5567 machine in tensile mode at a pull rate of 1.3 mm / min. This is a surprising and unexpected result.

[0214] The thermal conductivity of the coating disclosed in this paper (before expansion) did not decrease significantly due to the inclusion of thermally expanding materials. This is a surprising and unexpected result.

[0215] Furthermore, the coating formed from the composition disclosed herein surprisingly exhibits high expansion when heated to 160°C. Upon expansion, the coating surprisingly shows a significant decrease in thermal conductivity.

[0216] Furthermore, articles formed from the compositions disclosed herein can surprisingly exhibit high reprocessability, remodelability, and / or self-sealing properties. To exhibit reprocessability, remodelability, and / or self-healing properties, the expansion temperature of the thermally expanding material must be greater than the reflow initiation temperature of the cured composition.

[0217] Furthermore, it was surprisingly found that adding thermally expanding materials did not reduce the thermal conductivity of the thermally expanding coating disclosed herein before expansion.

[0218] The compositions disclosed herein can be used to repair joints between two substrates.

[0219] The compositions disclosed herein can be used to form coatings having the following properties:

[0220] (a) At 25°C, and as measured in the examples, the thermal conductivity before expansion is at least 0.5 W / m·K, such as at least 1 W / m·K, such as at least 2 W / m·K, such as at least 3 W / m·K, such as at least 4 W / m·K, such as at least 5 W / m·K; and / or

[0221] (b) The thermal conductivity before expansion does not decrease significantly due to the addition of thermally expanding materials; and / or

[0222] (c) After expansion (after exposure to thermal conditions above 60°C, such as at least 70°C, such as at least 80°C, such as at least 90°C, such as at least 100°C, such as at least 110°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C, such as at least 160°C, such as at least 170°C, such as at least 180°C, such as at least 190°C, such as at least 200°C), the thermal conductivity decreases by at least 10%, such as at least 25%, such as at least 50%, such as at least 75%, such as at least 95%, such as at least 96%, such as at least 97%, such as at least 98%, such as at least 99%, relative to the thermal conductivity before expansion (measured at 25°C as described in the examples); and / or

[0223] (d) The volume ratio after expansion is greater than 1, such as at least 1.1, at least 1.2, at least 1.5, at least 2, at least 3, at least 5, at least 10, at least 20, wherein the volume ratio after expansion = volume after expansion (measured at 25°C after exposure to heat conditions above 60°C, such as at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, at least 170°C, at least 180°C, at least 190°C, at least 200°C) / volume before expansion (measured at 25°C before exposure to heat conditions), and wherein the volume is measured using calipers, and the coating is cohesive / non-brittle; and / or

[0224] (e) Vertical flaming test rating of V0 (measured according to UL-94 Vertical Flame Test Procedure) (V0 rating means: (1) no burning (open flame or smoldering flame) for more than 10 seconds is observed after the flame is removed from the first and second flame exposures; (2) no smoldering flame for more than 30 seconds is observed after the flame is removed from the second flame exposure; and (3) no dripping of flame particles that could ignite the medical cotton is observed); and / or

[0225] (f) At 25°C, using a 0.063-inch thick 2024 T3 aluminum substrate, the lap shear strength measured in tensile mode at a pull rate of 1.3 mm / min using an INSTON 5567 machine according to ASTM D1002-10, shall be at least 5 MPa; and / or

[0226] (g) At 25°C, using a 0.063-inch thick 2024 T3 aluminum substrate, the lap shear strength was measured in tensile mode at a pull rate of 1.3 mm / min using an INSTON 5567 machine according to ASTM D1002-10, and the measured lap shear strength was at least 10 MPa.

[0227] The combination of the above properties is unexpected and surprising.

[0228] Substrate

[0229] The compositions described herein can be coated or deposited on any substrate or surface, 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 thermosetting materials), and / or composite materials. Other suitable substrates include, but are not limited to, glass or natural materials (such as wood). The substrate may include two or more of any different materials in any combination, such as, but not limited to, two different metals; or metals and metal alloys; or metals and metal alloys with one or more composite materials.

[0230] Suitable substrates may include, but are not limited to, flexible and rigid metallic substrates, such as ferrous metals, aluminum, aluminum alloys, magnesium, titanium, copper, and other metallic and alloy substrates. Ferrous metal substrates may include, for example, iron, steel, and their alloys. Non-limiting examples of useful steel materials include cold-rolled steel, nickel-plated cold-rolled steel, galvanized (zinc-coated) steel, electro-galvanized steel, stainless steel, pickled steel, zinc-iron alloys (such as GALVANNEAL), and combinations thereof. Aluminum alloys (such as those in the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX, or 8XXX series, for example) as well as clad aluminum alloys and cast aluminum alloys (such as those in the A356, 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, or 8XX.X series, for example) may also be used as substrates. The substrate may also include, for example, magnesium, such as magnesium alloys of the AZ31B, AZ91C, AM60B or EV31A series, titanium and / or titanium alloys, such as titanium alloys of grades 1-36 containing H-grade variants, copper and copper alloys or other non-ferrous metals, and alloys of these materials. The substrate may include composite materials, such as plastics, glass fibers and / or carbon fiber composites.

[0231] It should also be understood that the substrate may include a bare substrate, or the substrate may be pretreated or pre-coated with one or more layers. Suitable pretreatment solutions may include, but are not limited to, zinc phosphate pretreatment solutions, such as those described, for example, in U.S. Patent Nos. 4,793,867 and 5,588,989, or zirconium-containing pretreatment solutions, such as those described, for example, in U.S. Patent Nos. 7,749,368 and 8,673,091, all of which are incorporated herein by reference.

[0232] The substrate can be in any form, such as, but not limited to, sheets, foils, laminated foils, pads, prefabricated parts, components, or articles. Compositions containing the materials disclosed herein can be used to coat substrates, such as by depositing a hot melt, applying it to a substrate surface, or contacting the composition with a substrate surface. These compositions can be used in any form in the cured state, such as, but not limited to, coatings, sealants, adhesives, potting or encapsulating agents (such as solids or gels), and gaskets (such as in-situ formed gaskets or discrete prefabricated or pre-formed gaskets).

[0233] In the examples, the substrate may be a multi-metal article. As used herein, the term “multi-metal article” means: (1) an article having a surface comprising a first metal and a surface comprising a second metal different from the first metal; (2) a first article having a surface comprising a first metal and a second article having a surface comprising a second metal different from the first metal; or (3) both (1) and (2).

[0234] The compositions disclosed herein are not limited and are particularly suitable for a wide range of industrial or transportation applications, including automotive, commercial, rail, marine, and / or aerospace applications. Suitable substrates for use in this disclosure include substrates used in assemblies of vehicle bodies (e.g., but not limited to doors, body panels, trunk lids, top panels, hoods, top and / or longitudinal beams, rivets, landing gear assemblies, and / or skins used on aircraft), vehicle frames, vehicle components, motorcycles, wheels, and industrial structures and components. As used herein, “vehicle” or variations thereof include, but are not limited to, civil vehicles, light and heavy commercial vehicles, civil and military aircraft and / or land vehicles, such as automobiles, motorcycles, and / or trucks. The compositions disclosed herein are also suitable for a wide range of industrial applications, including appliances, personal electronic devices, circuit boards, and combinations thereof.

[0235] Figures 1 to 9 Non-limiting examples of battery assembly components and constructions are shown, as well as non-limiting applications or uses of the compositions disclosed herein in said battery assemblies. Although Figures 1 to 9Specific examples of cell shapes and cell arrangements are shown, but cells can be arranged in any configuration known to those skilled in the art. Furthermore, the compositions disclosed herein, in their cured state, can be used to form gaskets, adhesives, structural adhesives, coatings, potting compounds, etc., to provide thermal protection between battery cells, within battery modules, and / or within battery packs. These materials can be used on any surface or in any space within such battery assemblies. For example, the compositions disclosed herein can also be used in battery assemblies, including but not limited to cell-to-module (C / C) modules. Figure 3 , Figure 4 , Figure 6B ), Module to Group ( Figure 6C , Figure 7 Unit to group () Figure 8 ), and the unit to chassis battery assembly ( Figure 9 Such battery assemblies can be used in, but are not limited to, any of the applications described above.

[0236] A battery assembly can be any combination of one or more battery cells, interconnects that provide conductivity between battery cells, and auxiliary components, such as control electronics and components that, in non-limiting instances, ensure the structural, mechanical, and environmental requirements necessary for the operation of a particular battery (e.g., but not limited to, cell interconnects such as wires, battery pack housings including trays and covers, module housings, module frames and frame plates, module supports, cooling and heating assemblies including cooling plates, cooling fins and cooling tubes, electrical busbars, battery management systems, battery thermal management systems, chargers, inverters, and converters).

[0237] Battery cell 10 is typically a single-cell energy storage container that can be connected in series or parallel. The battery cell can be any suitable size or shape known to those skilled in the art, such as, but not limited to, cylindrical. Figure 1 , Figure 4 and Figure 9 ), prismatic ( Figure 2 , Figures 5 to 8 ) and / or bag-shaped ( Figure 3 The battery cell 10 is enclosed to provide the desired mechanical protection and environmental isolation for the cell. For example, cylindrical and prismatic cells can be encapsulated in metal cans, housings, and caps, while pouch cells can be encapsulated in multilayer laminated foil. Battery terminals 1 connect the electrodes inside the battery cell to the circuitry outside the battery cell; one terminal is the positive terminal, and the other is the negative terminal. Figure 4 As shown, the battery cell 10 can be connected in series or in parallel with other battery cells 10 via the interconnect wire 5 so that current can flow between the cells 10.

[0238] like Figure 3 and Figure 4As shown, battery cells 10 can be arranged in a module 100 comprising multiple cells 10 connected in series or parallel. Module 100 may include a housing for the arranged cells 10. Auxiliary components, such as those described above, may be included. Spaces of any size may be located between any inner surfaces of the multiple cells, auxiliary components, base and / or module walls or other housings 120.

[0239] Figure 1 A top view of a cylindrical battery cell 10 having terminal 1 is shown. As shown, the cells are arranged in rows, with cooling tubes 3 or dielectric insulating paper (e-paper) 4 between the rows. As shown, materials optionally formed from the compositions disclosed herein in a cured state, such as adhesive 6 and / or potting compound 7, may be positioned between the cell 10, the cooling tubes 3, and / or the e-paper 4. Optionally, the e-paper 4 may be replaced by one of the compositions disclosed herein.

[0240] Figure 2 An exploded isometric view of an array of prismatic cell units 10 is shown. As shown, each prismatic cell 10 may include a top 11, a bottom, and a wall 13 positioned between the top and bottom, each having a surface. As shown, a material formed by the compositions disclosed herein in a cured state, such as a gasket 8, may be positioned between the surfaces of the cell walls 13 of adjacent cells 10.

[0241] Figure 3 A cross-sectional front view of an array of pouch cell units 10 in module 100 is shown. Module walls 120 partially or completely surround the units 10. As shown, materials formed by the compositions disclosed herein in a cured state, such as gaskets 8, may be positioned between the surfaces of the units 10.

[0242] Figure 4 An isometric view of cylindrical cells 10 in a battery module 100 is shown. Each cell may include a top 11, a bottom 12, and a wall 13 positioned between the top and bottom, each having a surface. The top 11 and bottom 12 may be terminals with opposite charges, one being a positive terminal 1 and the other a negative terminal (not shown). Battery cells may be connected at their terminals via interconnects, such as wires 5, to allow current to flow between electrical cells. Module 100 or module walls 120 may form a space with volume. Cells 10 may be positioned within the space to consume a portion of the volume. A material formed from the coating compositions disclosed herein, such as potting compound 7, may be positioned within the space to occupy a portion of the volume, such that the material is adjacent to the surface of the cell wall 13 and / or the inner surface of one or more walls 120 of module 100.

[0243] Figure 5An exploded perspective view of a battery module 100 is shown, which includes one or more arrays of battery cells 10, cooling fins 230, and a cooling plate 240. Materials formed by the compositions disclosed herein in a cured state, such as gaskets 8, may be positioned between the cells 10. Additional gaskets 8 may be positioned between the cells 10, the inner surfaces of the cooling fins 230, the cooling plate 240, and / or the wall 120. Other gaskets 8 may be positioned adjacent to the outer surface of the wall 120.

[0244] Figure 6 shows battery cell 10 ( Figure 6A ) to battery module 100 ( Figure 6B ) to battery pack 200 ( Figure 6C Isometric view of the battery assembly. Battery module 100 includes a plurality of battery cells 10, and battery pack 200 includes a plurality of battery modules 100.

[0245] Figure 7 A perspective view of a cutout in the battery pack 200 is shown. The battery pack 200 includes a plurality of battery modules 100 and cells 10 located within each module 100. The base of the battery pack 200 includes a cooling plate 240. Materials formed by the compositions disclosed herein in a cured state, such as adhesive 9, may be positioned between the cooling plate 240 and the inner surface of the wall of the battery pack 200. Materials formed by the compositions disclosed herein in a cured state, such as gasket 8, may be positioned between the cells 10 within the module 100.

[0246] Figure 8 An isometric view of the assembly of unit 10 to battery pack 200 is shown. Unit 10 is arranged within pack 200 (rather than in a separate module).

[0247] In other cases, the battery cells may be arranged on or within the article, such as, but not limited to, Figure 9 The units shown are used to construct the battery assembly from the chassis, wherein one or more units are used to build the battery assembly without prior assembly of the units into modules and / or groups. Figure 9 An isometric sectional view of the unit to the chassis battery assembly 300 is shown. The unit 10 is arranged on a base that includes a chassis 55 and is supported by a vehicle frame 45 and located below the vehicle's interior floor 35.

[0248] Any battery assembly may further include a thermal management system comprising air or fluid circuits, which may be liquid-based (e.g., ethylene glycol solution) or based on a direct refrigerant.

[0249] The substrate may comprise a coating formed on a portion of the surface of the substrate by a hot melt formed from one of the compositions disclosed herein, the coating having the following properties in the cured state: (a) at 25°C, using a 0.063-inch thick 2024 T3 aluminum substrate, measured in tensile mode at a pull rate of 1.3 mm / min according to ASTM D1002-10 using an INSTON 5567 machine, the lap shear strength is at least 15 MPa; (b) at 50°C, using a 0.063-inch thick 2024 T3 aluminum substrate, measured in tensile mode at a pull rate of 1.3 mm / min according to ASTM D1002-10 using an INSTON 5567 machine, the lap shear strength is at least 5 MPa; (c) at 150°C, using a 0.063-inch thick 2024 T3 aluminum substrate, measured in tensile mode at a pull rate of 1.3 mm / min according to ASTM D1002-10 using an INSTON 5567 machine, the lap shear strength is at least 5 MPa; The 5567 machine measures the lap shear strength at a pulling rate of 1.3 mm / min in tensile mode, with the measured lap shear strength not exceeding 2 MPa; and / or (d) by dynamic mechanical analysis (DMA) at a frequency of 1.0 Hz and a heating rate of 3 °C / min, with a glass transition temperature of 35 °C to 55 °C.

[0250] aspect

[0251] In view of the foregoing description, this disclosure relates to, but is not limited to, aspects 1 through 117.

[0252] 1. A composition comprising:

[0253] The first component comprises a first compound, which contains a furan functional group and an isocyanate functional group;

[0254] The second component comprises a dienophile-containing compound; and

[0255] Thermally expanding materials.

[0256] 2. The composition according to aspect 1, wherein the first compound comprises a carbamate bond, a urea bond and / or a thiocarbamate bond.

[0257] 3. The composition according to aspect 2, wherein the urethane bond, urea bond and / or thiourethane bond is located between the furan functional group and the isocyanate functional group.

[0258] 4. The composition according to any one of the foregoing aspects, wherein the first compound comprises structure I:

[0259]

[0260] Wherein X contains O, N or S, m ≥ 1, n ≥ 1, and the sum of m+n ≥ 2; R1 contains substituted or unsubstituted alkyl groups, alkylene groups, (cyclo)alkyl groups, aromatic groups, isocyanurate moieties, biuret moieties, urethane moieties, glycourea moieties, benzoguanamine moieties, iminooxadiazinedione moieties, or polymer moieties other than urethane bonds, urea bonds and / or thiourethane bonds; and R2 contains substituted or unsubstituted alkyl groups, ester moieties, ether moieties or urethane moieties.

[0261] 5. The composition according to aspect 4, wherein R2 comprises a carbon atom.

[0262] 6. The composition according to aspect 4 or aspect 5, wherein R1 comprises isocyanurate, urethane, or iminooxadiazine dione, R2 comprises CH2, and X comprises O.

[0263] 7. The composition according to any one of aspects 4 to 6, wherein m + n > 2.

[0264] 8. The composition according to any one of aspects 4 to 7, wherein m ≤ 12, n ≤ 12, and / or m+n ≤ 13.

[0265] 9. The composition according to any one of the foregoing aspects, wherein the first compound is substantially free of ether bonds.

[0266] 10. The composition according to any one of the foregoing aspects, wherein the first compound comprises a monomer, a prepolymer, or a polymer.

[0267] 11. The composition according to any one of the foregoing aspects, wherein the first compound comprises at least 100 g / eq of furan equivalent weight, such as at least 200 g / eq.

[0268] 12. The composition according to any one of the foregoing aspects, wherein the first compound comprises a furan equivalent weight of not more than 3,000 g / eq, such as not more than 1,000 g / eq.

[0269] 13. The composition according to any one of the foregoing aspects, wherein the composition comprises 100 g / eq to 3,000 g / eq of furan equivalent weight, such as 200 g / eq to 1,000 g / eq.

[0270] 14. The composition according to any one of the preceding aspects, wherein the first compound comprises at least 100 g / eq of isocyanate equivalent weight, such as at least 200 g / eq.

[0271] 15. The composition according to any one of the foregoing aspects, wherein the first compound comprises an isocyanate equivalent of not more than 3,000 g / eq, such as not more than 1,500 g / eq.

[0272] 16. The composition according to any one of the foregoing aspects, wherein the first compound comprises an isocyanate equivalent weight of 100 g / eq to 3,000 g / eq, such as 200 g / eq to 1,500 g / eq.

[0273] 17. The composition according to any one of the foregoing aspects, wherein the first compound comprises a reaction product of a reactant, the reactant comprising:

[0274] (a) Furan-containing compounds containing active hydrogen-containing functional groups; and

[0275] (b) Compounds containing polyisocyanates.

[0276] 18. The composition according to aspect 17, wherein the active hydrogen-containing functional group comprises a hydroxyl functional group, an amine functional group and / or a thiol functional group.

[0277] 19. The composition according to aspect 17 or aspect 18, wherein the isocyanate functional group comprises an isocyanate functional group derived from a polyisocyanate.

[0278] 20. The composition according to any one of aspects 17 to 19, wherein the active hydrogen-containing functional group is present in a substoichiometric amount relative to the isocyanate functional group.

[0279] 21. The composition according to any one of aspects 17 to 20, wherein the equivalent ratio of the active hydrogen-containing functional group to the isocyanate functional group is less than 1:1, such as not more than 1:2, such as not more than 1:3, such as not more than 1:5.

[0280] 22. The composition according to any one of the foregoing aspects, wherein the furan functional group of the first compound is terminal.

[0281] 23. The composition according to any one of the foregoing aspects, wherein the dienophile-containing compound comprises at least 100 g / eq of dienophile equivalent weight, such as at least 200 g / eq.

[0282] 24. The composition according to any one of the foregoing aspects, wherein the dienophile-containing compound comprises a dienophile equivalent weight of not more than 3,000 g / eq, such as not more than 1,000 g / eq.

[0283] 25. The composition according to any one of the foregoing aspects, wherein the dienophile-containing compound comprises 100 g / eq to 3,000 g / eq of dienophile equivalent weight, such as 200 g / eq to 1,000 g / eq.

[0284] 26. The composition according to any one of the foregoing aspects, wherein the furan functional group and the dienophile are reactive under environmental conditions.

[0285] 27. The composition according to any one of the foregoing aspects, wherein the furan functional group of the first compound and the dienophile of the dienophile-containing compound are present in an equivalent ratio of at least 0.5:1, such as at least 0.6:1.

[0286] 28. The composition according to any one of the foregoing aspects, wherein the furan functional group of the first compound and the dienophile of the dienophile-containing compound are present in an equivalent ratio not exceeding 2:1, such as not exceeding 1:1.

[0287] 29. The composition according to any one of the foregoing aspects, wherein the furan functional group of the first compound and the dienophile of the dienophile-containing compound are present in an equivalent ratio of 0.5:1 to 2:1, such as 0.6:1 to 1:1.

[0288] 30. The composition according to any one of the foregoing aspects, wherein the dienophile comprises a maleimide functional group, a maleic ester functional group and / or a fumarate functional group.

[0289] 31. The composition according to any one of the foregoing aspects, wherein the second component comprises a third compound that reacts with the isocyanate functional group.

[0290] 32. The composition according to aspect 31, wherein the third compound comprises a hydroxyl functional group.

[0291] 33. The composition according to aspect 32, comprising an isocyanate functional group on a first compound and a hydroxyl functional group on a third compound, wherein the equivalent ratio is at least 0.2:1, such as at least 0.4:1.

[0292] 34. The composition according to aspect 32 or aspect 33, comprising an isocyanate functional group on a first compound and a hydroxyl functional group on a third compound, in an equivalent ratio not exceeding 3:1, such as not exceeding 2:1.

[0293] 35. The composition according to any one of aspects 32 to 34, comprising an isocyanate functional group on the first compound and a hydroxyl functional group on the third compound in an equivalent ratio of 0.2:1 to 3:1, such as 0.4:1 to 2:1.

[0294] 36. The composition according to any one of the foregoing aspects, wherein the first component further comprises a fourth compound comprising a furan functional group.

[0295] 37. The composition according to aspect 36, wherein the fourth compound comprises at least 68 g / eq of furan equivalent weight, such as at least 80 g / eq.

[0296] 38. The composition according to aspect 36 or aspect 37, wherein the fourth compound comprises a furan equivalent weight of not more than 1,500 g / eq, such as not more than 1,000 g / eq.

[0297] 39. The composition according to any one of aspects 36 to 38, wherein the fourth compound comprises 68 g / eq to 1,500 g / eq of furan equivalent weight, such as 80 g / eq to 1,000 g / eq.

[0298] 40. The composition according to any one of the foregoing aspects, wherein the thermally expanding material is present in the first component, the second component and / or the third component.

[0299] 41. The composition according to any one of the preceding aspects, wherein the thermally expanding material comprises an average initial (before expansion) particle size of at least 0.5 μm as measured by laser diffraction, such as at least 2 μm, such as at least 3 μm, such as at least 5 μm, such as at least 10 μm.

[0300] 42. The composition according to any one of the preceding aspects, wherein the thermally expanding material comprises an average initial (before expansion) particle size of not more than 100 μm as determined by laser diffraction, such as not more than 80 μm, such as not more than 60 μm, such as not more than 50 μm.

[0301] 43. The composition according to any one of the preceding aspects, wherein the thermally expanding material comprises an average initial (before expansion) particle size of 0.5 μm to 100 μm as determined by laser diffraction, such as 1 μm to 80 μm, such as 2 μm to 60 μm, such as 3 μm to 50 μm, such as 5 μm to 50 μm, such as 10 μm to 50 μm.

[0302] 44. The composition according to any one of the foregoing aspects, comprising at least 0.5% by weight of a thermally expanding material, such as at least 0.75% by weight or at least 1% by weight, based on the total weight of the composition.

[0303] 45. The composition according to any one of the preceding aspects, comprising not more than 10% by weight of thermally expanding material, such as not more than 7% by weight or not more than 3% by weight, based on the total weight of the composition.

[0304] 46. ​​The composition according to any one of the preceding aspects, comprising, by weight of the total composition, an amount of thermally expanding material, such as 0.75% to 7% by weight, or such as 1% to 3% by weight.

[0305] 47. The composition according to any one of the foregoing aspects further comprises fillers, accelerators, dispersants, additives and / or elastomer particles.

[0306] 48. The composition according to aspect 47, wherein the first component, the second component and / or the third component comprises fillers, accelerators, dispersants, additives and / or elastomer particles.

[0307] 49. The composition according to aspect 47 or aspect 48, wherein the composition comprises at least 0.5% by weight of filler, such as at least 1% by weight, based on the total weight of the composition.

[0308] 50. The composition according to any one of aspects 47 to 49, wherein the composition comprises a filler in an amount not exceeding 90% by weight, such as not exceeding 30% by weight, based on the total weight of the composition.

[0309] 51. The composition according to any one of aspects 47 to 50, wherein the composition comprises a filler in an amount of 0.5% to 90% by weight, such as 1% to 30% by weight, based on the total weight of the composition.

[0310] 52. The composition according to any one of aspects 47 to 51, wherein the filler comprises a thermally conductive filler and / or a non-thermally conductive filler.

[0311] 53. The composition according to aspect 52, comprising 100% by volume of thermally conductive filler, such as not more than 90% by volume, such as not more than 80% by volume, based on the total volume of the filler.

[0312] 54. The composition according to aspect 52 or aspect 53, comprising at least 20% by volume of thermally conductive filler, such as at least 50% by volume, based on the total volume of the filler.

[0313] 55. The composition according to any one of aspects 52 to 54, comprising, on a total volume basis of 20% to 90% thermally conductive filler, such as 50% to 80% by volume.

[0314] 56. The composition according to any one of aspects 52 to 55, comprising at least 10% by volume of a non-thermal conductive filler, such as at least 20% by volume, based on the total volume of the filler.

[0315] 57. The composition according to any one of aspects 52 to 56, comprising at most 100% by volume of a non-thermal conductive filler, such as not more than 80% by volume, such as not more than 50% by volume, based on the total volume of the filler.

[0316] 58. The composition according to any one of aspects 52 to 57, comprising 10 vol% to 80 vol% of a non-thermal-conducting filler, such as 20 vol% to 50 vol%, based on the total volume of the filler.

[0317] 59. The composition according to any one of aspects 47 to 58, comprising at least 0.001% by weight of an accelerator, such as at least 0.01% by weight, based on the total weight of the composition.

[0318] 60. The composition according to any one of aspects 47 to 59, comprising an accelerator in an amount not exceeding 2% by weight of the total weight of the composition, such as not exceeding 1% by weight.

[0319] 61. The composition according to any one of aspects 47 to 60, comprising an amount of accelerator, such as 0.01% to 1% by weight, based on the total weight of the composition, from 0.001% to 2% by weight.

[0320] 62. The composition according to any one of aspects 47 to 61, comprising at least 0.5% by weight of a dispersant, such as at least 1% by weight, based on the total weight of the composition.

[0321] 63. The composition according to any one of aspects 47 to 62, comprising a dispersant in an amount not exceeding 10% by weight of the total weight of the composition, such as not exceeding 5% by weight.

[0322] 64. The composition according to any one of aspects 47 to 63, comprising a dispersant, such as 1% to 5% by weight, in an amount of 0.5% to 10% by weight based on the total weight of the composition.

[0323] 65. The composition according to any one of aspects 47 to 64, comprising an amount of additive, such as at least 0.01% by weight, based on the total weight of the composition.

[0324] 66. The composition according to any one of aspects 47 to 65, comprising an amount of additive not exceeding 15% by weight of the total weight of the composition, such as not exceeding 10% by weight.

[0325] 67. The composition according to any one of aspects 47 to 66, comprising an amount of additive, such as 0.1% to 15% by weight, based on the total weight of the composition.

[0326] 68. The composition according to any one of aspects 47 to 67, comprising at least 0.1% by weight of elastomeric particles, such as at least 1% by weight, based on the total weight of the composition.

[0327] 69. The composition according to any one of aspects 47 to 68, comprising not more than 50% by weight of elastomeric particles, such as not more than 20% by weight, based on the total weight of the composition.

[0328] 70. The composition according to any one of aspects 47 to 69, comprising 0.1% to 50% by weight of elastomeric particles, such as 1% to 20% by weight, based on the total weight of the composition.

[0329] 71. The composition according to any one of aspects 47 to 70, wherein:

[0330] (a) The fillers include thermally conductive fillers (such as boron nitride, aluminum trihydrate and / or alumina) and / or non-thermally conductive fillers (such as fumed silica, wollastonite, calcium carbonate, mica iron oxide or combinations thereof).

[0331] (b) Additives include rheology modifiers, tackifiers, thermoplastic polymers, surfactants, flame retardants, corrosion inhibitors, UV stabilizers, colorants, dyes, solvents, plasticizers, adhesion promoters, antioxidants, silanes, silane-terminated polymers, dehumidifiers, thixotropic agents and / or sagging control agents;

[0332] (c) The elastomer particles contain a core-shell structure, such as comprising an acrylate shell and an elastomer core; and / or

[0333] (d) The promoters include amine-based catalysts and / or organometallic complexes.

[0334] 72. The composition according to any one of the foregoing aspects is formulated as a two-component composition.

[0335] 73. The composition according to any one of the foregoing aspects, wherein the composition is formulated to cure under ambient conditions.

[0336] 74. The composition according to any one of the foregoing aspects, wherein the composition is substantially free of, substantially free of or completely free of solvent.

[0337] 75. The composition according to any one of aspects 40 to 74, wherein the composition comprises 50% to 90% by weight of filler based on the total weight of the composition, and has a shear stress of not more than 10 at 25°C measured by an Anton Paar MCR 301 rotational rheometer using parallel plates with a diameter of 25 mm (1 mm gap) at 1 Hz.6 Viscosity in Pa·s.

[0338] 76. The composition according to any one of aspects 22 to 75, having a Tg of at least -120°C (measured using TAInstruments Q800 DMA V21.3 in single cantilever mode).

[0339] 77. The composition according to any one of aspects 22 to 76, having a Tg of not more than 150°C (measured using TAInstruments Q800 DMA V21.3 in single cantilever mode), such as not more than 100°C, such as at most 90°C.

[0340] 78. The composition according to any one of aspects 22 to 77, having a Tg of -120°C to 150°C (measured using TAInstruments Q800 DMA V21.3 in single cantilever mode), such as -120°C to 100°C.

[0341] 79. A method for coating a substrate, the method comprising:

[0342] The composition is brought into contact with a portion of the surface of the substrate according to any one of the foregoing aspects; and optionally (i) the composition is cured at a temperature below the expansion temperature of the expandable material and / or (ii) the composition is cured before the thermally expandable material expands.

[0343] 80. The method according to aspect 79, further comprising mixing the first component and the second component to form a composition according to any one of the preceding aspects; and optionally heating the composition after such contact.

[0344] 81. The method according to aspect 79 or aspect 80, further comprising: contacting the surface of the second substrate with the composition such that the composition is located between the first substrate and the second substrate.

[0345] 82. The method according to any one of aspects 79 to 81, wherein prior to the contact, the joint between the first substrate and the second substrate is broken, and wherein the contact forms a repair joint.

[0346] 83. A method of forming an article, comprising: extruding the composition according to any one of aspects 1 to 78.

[0347] 84. The method according to aspect 83, wherein the extrusion includes three-dimensional printing.

[0348] 85. An article formed by the method according to aspect 83 or aspect 84.

[0349] 86. The article of aspect 85, wherein when the expansion temperature of the thermally expanding material is higher than the reflow initiation temperature of the composition, the article exhibits remodelability, reprocessability and / or self-healing properties.

[0350] 87. A substrate comprising a coating formed on a portion of the surface of the substrate by the composition according to any one of aspects 1 to 78.

[0351] 88. The substrate according to aspect 87, which is coated according to the method of any one of aspects 74 to 77.

[0352] 89. The substrate according to aspect 87 or aspect 88, wherein the coating comprises a sealant, an adhesive, a gap filler, a potting compound, an encapsulating agent (such as a solid or gel) and / or a gasket (such as a pre-formed gasket, a pre-manufactured gasket, or an in-situ formed gasket).

[0353] 90. The substrate according to any one of aspects 87 to 89, further comprising a dielectric coating.

[0354] 91. The substrate according to any one of aspects 87 to 90, wherein the substrate comprises a battery cell.

[0355] 92. The substrate according to any one of aspects 87 to 91, wherein the substrate includes articles, components or combinations thereof.

[0356] 93. The substrate according to aspect 92, wherein the article of manufacture includes a vehicle, an appliance, a personal electronic device, a circuit board, a multi-metal substrate or a combination thereof.

[0357] 94. The substrate according to aspect 93, wherein the component includes a vehicle component.

[0358] 95. The substrate according to aspect 93 or aspect 94, wherein the vehicle includes a land vehicle or an aircraft.

[0359] 96. A battery comprising a battery cell according to aspect 91 and optionally a battery assembly.

[0360] 97. The battery according to aspect 96, wherein the battery cell and the thermal expansion coating are housed in a module, and / or wherein the battery and the thermal expansion coating are housed in a group.

[0361] 98. The battery according to aspect 97, wherein the module is housed in a group.

[0362] 99. The battery according to aspect 97, which is adjacent to the chassis of the vehicle.

[0363] 100. A vehicle comprising a battery according to any one of aspects 96 to 99.

[0364] 101. The vehicle according to aspect 100, wherein the vehicle includes a land vehicle or an aircraft.

[0365] 102. A self-supporting membrane formed from the composition according to any one of aspects 1 to 78.

[0366] 103. Use of the composition according to any one of aspects 1 to 78, wherein the composition is used to manufacture a substrate according to any one of aspects 88 to 96.

[0367] 104. The use according to aspect 103, wherein the coating has a thermal conductivity before expansion of at least 0.5 W / m·K, such as at least 2 W / m·K, when measured at 25°C and as described in the examples.

[0368] 105. The use according to aspect 103 or aspect 104, wherein the coating has an expansion thermal conductivity that is not significantly reduced by the addition of a thermally expanding material.

[0369] 106. The use according to any one of aspects 103 to 105, wherein the coating has a thermal conductivity reduction of at least 10%, such as at least 25%, after expansion relative to the thermal conductivity before expansion (measured at 25°C as described in the examples).

[0370] 107. The use according to any one of aspects 103 to 106, wherein the coating has an expanded volume ratio greater than 1, such as at least 2, wherein the volume is measured using calipers, and the coating is cohesive / non-brittle.

[0371] 108. The use according to any one of aspects 103 to 107, wherein the coating has a vertical flammability test rating of V0 (measured by UL-94 vertical flame test procedure).

[0372] 109. The application according to any one of aspects 103 to 108, wherein the coating has a measured lap shear strength of at least 5 MPa at 25°C, the lap shear strength being measured using a 0.063-inch thick 2024 T3 aluminum substrate, according to ASTM D1002-10, in tensile mode by an INSTON 5567 machine at a pulling rate of 1.3 mm / min.

[0373] 110. The application according to any one of aspects 103 to 109, wherein the coating has a measured lap shear strength of at least 10 MPa at 25°C, the lap shear strength being measured using a 0.063-inch thick 2024 T3 aluminum substrate, according to ASTM D1002-10, in tensile mode by an INSTON 5567 machine at a pulling rate of 1.3 mm / min.

[0374] 111. The use according to any one of aspects 103 to 110, wherein the coating is cohesive after exposure to the expansion temperature of a thermally expanding material.

[0375] 112. The use according to any one of aspects 103 to 111, wherein the coating is non-cohesive and / or brittle after exposure to the expansion temperature of a thermally expanding material.

[0376] 113. A system comprising:

[0377] A dielectric coating composition for application to a first portion of a substrate surface; and

[0378] The composition according to any one of aspects 1 to 78 is used for applying a second portion to the surface.

[0379] 114. A kit comprising:

[0380] A dielectric coating composition for application to a first portion of a substrate surface; and

[0381] The composition according to any one of aspects 1 to 78, for application to the second portion of the surface

[0382] 115. The system or kit according to aspect 113 or aspect 114, further comprising instructions for applying the dielectric coating composition and the composition.

[0383] 116. The system or kit according to any one of aspects 113 to 115, wherein the dielectric coating composition comprises:

[0384] Adhesives comprising film-forming resins such as polyesters, alkyl groups, urethanes, isocyanates, polyureas, epoxy resins, acrylics, polyethers, polysulfides, polyamines, polyamides, polyvinyl chloride, polyolefins, polyvinylidene fluoride, polyvinyl chloride, polyolefins, polysiloxanes, amine-aldehydes, resin polyols, phosphorylated polyepoxides, phosphorylated acrylic polymers, amino plastics, or combinations thereof; and / or

[0385] Curing agents and / or crosslinking agents capable of crosslinking with the film-forming resin to cure the dielectric coating composition, such as: amines; amino plastics; phenolic plastics; polyisocyanates, including end-capped isocyanates; polyepoxides; β-hydroxyalkylamides; polybasic acids; organometallic acid functional materials; polyamines; polyamides; polysulfides; polythiols; polyolefins, such as polyacrylates; polyols; polysilanes, etc.; or combinations thereof.

[0386] 117. A system or kit according to any one of aspects 113 to 116, wherein the dielectric coating composition comprises a powder coating composition and / or a liquid coating composition (such as an electrodepositable coating composition, a UV-curable coating composition, and / or a solvent-based coating composition).

[0387] The following examples illustrate the disclosed subject matter and should not be construed as limiting this disclosure to its details. Unless otherwise stated, all parts and percentages in the examples and throughout the specification are by weight.

[0388] Example

[0389] Unless otherwise stated, all quantities in the following tables are measured in grams.

[0390] Example 1

[0391] Compositions I and II were prepared using the materials and quantities listed in Table 1. Aliphatic polyisocyanate (hexamethylene diisocyanate trimer) Desmodur N3900 was placed in an appropriately sized flask and covered with nitrogen to prevent interaction with moisture. Dibutyltin dilaurate was added as a catalyst, and the mixture was heated to 60°C. At 60°C, furfuryl alcohol was then added at a rate that kept the solution temperature below 80°C. After all furfuryl alcohol had been added, the reaction was maintained at 80°C until the isocyanate equivalent (NCO EQ WT) determined by titration stabilized (using a Metrohm 888 Titrando titrator; the titration method was as follows: a sample of the mixture (~2.00 g) was dissolved in 30 mL of a solution consisting of 20 mL of dibutylamine and 980 mL of N-methylpyrrolidone, followed by titration with 0.2 N HCl solution in isopropanol titrant).

[0392]

[0393] The furan / isocyanate functional compounds in Table 1 were used to prepare compositions III and IV in Table 2. Compositions V through VIII were prepared using a FlackTek Speedmixer in a 200 max DAC cup with the materials listed in Table 2. All wet components were added to the DAC cup and mixed at 2350 RPM for 2 minutes. The dry components were then added and mixed again at 2350 RPM for 2 minutes.

[0394]

[0395] Deoxygenation composition (DEOX-1) was prepared using 18.2 L of deionized water, 180.5 g of fluorosilicic acid (23% solution), 80 g of fluorozirconic acid (45% solution), 11.61 g of potassium hydrogen fluoride, and 31.6 g of Chemfil buffer (commercially available from PPG Industries, Inc.). Compositions IX to XIV, as tested, were then prepared using compositions III to VIII. Compositions IX to XIV were prepared as Part A and Part B, respectively, in a 60 max DAC cup using the materials listed in Table 3. All wet components were added, and the mixture was stirred for 2 minutes at 2350 RPM using a dual asymmetric mixer (SpeedMixer®). The dry components were added and stirred again for 2 minutes in the same manner. Parts A and B were then blended and stirred again in the same manner. Overlap shear specimens were prepared using 0.063” 2024 T3 aluminum. All oil contaminants on the sheets were removed with acetone and methyl ethyl ketone, and the sheets were treated with DEOX-1. A primer layer was then applied to these sheets by scraping on a one-component epoxy adhesive composition PR-2930® (commercially available from PPG Industries) PR-2 to a thickness of 0.010” and baking at 180°C for 30 minutes. The overlap shear specimens (LSS) were tested using an Instron Model 5567 equipped with a 30 kN load cell. The overlap dimension of the test specimens was 1” × ½”, and the test rate was 1.3 mm / min for all three temperatures. The method for preparing lap shear specimens is as follows: Apply adhesive to one side of a primer-coated substrate, overlap the two substrates by 1 / 2" and secure them with a long-tail clip, then remove excess adhesive at the joint using a metal scraper. Allow the specimens to cure at 50°C for 24 hours. After curing, cool the specimens to room temperature for 1 hour.

[0396] The dimensions of each sample before and after expansion were measured using calipers and then used to calculate the volumetric expansion ratio. Thermal expansion was performed in an oven preheated to 160°C. Each sample was thermally expanded with a weight on top to apply a pressure of 3.2 kPa. The thermal conductivity of each sample before and after expansion was measured using a TCi thermal conductivity analyzer (commercially available from C-Therm Technologies Ltd.). The thermal conductivity samples were prepared by casting the samples into a mold to obtain samples with a diameter of at least 30 mm and a height of 5 mm, allowing the composition to cure as described above. The thermal conductivity was then measured on the samples according to ASTM D7984-21 using a modified transient planar source MTPS instrument from C-Therm Technologies Ltd. If the thermal conductivity of the sample was below the range of the polymer material calibration method, the foam material method was used without the use of a contact agent. The results are provided in Table 3.

[0397]

[0398] The results in Table 3 compare the performance of coatings formed from the compositions disclosed herein (compositions IX and X) with those formed from compositions containing epoxy-thiol chemicals (compositions XIII and XIV) and compositions containing epoxy-amine chemicals (compositions XI and XII). The coating formed from composition X exhibits superior lap shear strength compared to the coating formed from composition XII. Surprisingly, upon thermal activation, the coatings formed from compositions IX and X also exhibit the ability to expand at a ratio even greater than that of the coatings formed from compositions XIII and XIV. The coatings formed from compositions XI and XII exhibit similar strength to those formed from compositions IX and X, but without expansion. After thermal activation and expansion, the thermal conductivity of the coating formed from composition X decreased from 1.23 W / mK to 0.38 W / mK, indicating that the coating formed from this composition transitioned from thermal conductivity to thermal insulation after expansion.

[0399] Example 2

[0400] Examples A and B below provide descriptions of the synthesis of furan / isocyanate functional polymers.

[0401]

[0402] 1 DESMODUR N3900 is available commercially from Covestro.

[0403] 2Dibutyltin dilaurate is commercially available from Evonik Industries.

[0404] 3 Furfuryl alcohol is commercially available from Sigma Aldrich.

[0405] The first part was added to a 2000 mL four-necked round-bottom flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating hood with a thermometer connected via a temperature feedback control device. The reaction mixture was heated to 60 °C. The second part was then added at a rate that kept the temperature of the mixture below 80 °C. After the addition of the second part, the reaction was maintained at 80 °C until the isocyanate equivalent weight stabilized. The isocyanate equivalent weight was determined by titration of the sample. The sample was prepared by dissolving 1 g of isocyanate per 420 g / eq of the predicted isocyanate equivalent weight in 30 mL of a solution consisting of 20 mL of dibutylamine and 980 mL of N-methyl-2-pyrrolidone. The sample was then titrated with a 0.2 N HCl solution in isopropanol titrant using a Metrohm 808 or 888 Titrando. The reaction mixture was maintained at 80 °C until the isocyanate equivalent weight stabilized. The reaction mixture was then poured out at 40°C under N2 cover.

[0406] Example C below describes the synthesis of another dienophilic prepolymer.

[0407]

[0408] 1 Dipropylene glycol is commercially available from Sigma Aldrich.

[0409] 2 Maleic anhydride is commercially available from TCI America.

[0410] 3 IONOL is 2,6-di-tert-butyl-4-methylphenol and is commercially available from Sasol Chemicals (USA) LLC.

[0411] 4 Monobutyltin oxide is commercially available from Arkema Inc.

[0412] 5 2-Ethylhexyl glycidyl ether is commercially available from Negase America LLC.

[0413] Part 1 was added to a 1000 mL four-necked round-bottom flask equipped with a motor-driven stainless steel stirrer, a water-cooled condenser, and a heating hood with a thermometer connected via a temperature feedback control device. The mixture was heated to 220 °C and held until the acid value, determined by titration, stabilized at approximately 150 mg KOH / g. The mixture was then cooled to 120 °C, and Part 2 was added. The mixture was heated to 140 °C and held until the acid value, determined by titration, was less than 2 mg KOH / g. The mixture was then cooled to 80 °C and poured into a suitably sized container. The final OH equivalent weight, determined by titration, was 302 g / eq. The hydroxyl value was determined by esterification of excess acetic anhydride with imidazole as a catalyst at elevated temperature. The excess acetic anhydride was hydrolyzed to acetic acid, which was then potentiometrically titrated with a standard potassium hydroxide solution.

[0414] Example 3

[0415] DEOX-1 was prepared as described above.

[0416] Compositions XV and XVI are formed by blending the components in Table 6 in the stated proportions and mixing at 2350 RPM for 4 minutes using a dual asymmetric mixer (SpeedMixer®). Overlap shear specimens (25.6 mm × 12.8 mm) were prepared using 0.063” 2024 T3 aluminum. Oil stains on the specimens were removed with acetone and methyl ethyl ketone, and the specimens were treated with DEOX-1. The preparation method for the overlap shear specimens was as follows: Composition XV or Composition XVI was applied to one side of a primed specimen and then overlapped with a second specimen (overlap size 1” × ½”). The two specimens were secured together using a long-tail clip, and excess composition at the joint was removed using a metal scraper. The specimens were allowed to cure under ambient conditions for at least 7 days prior to testing. After 7 days of curing under ambient conditions, half of the specimens were heated to 150°C and held for one hour, then allowed to cool back to room temperature. The overlap shear strength was measured at room temperature (25°C) for all specimens. Overlap shear specimens exposed to Composition XVI at 150°C could not be tested due to bond failure. The results are provided in Table 6.

[0417]

[0418] The data in Table 6 show that composition XVI (containing a thermally expanding material) expands upon exposure to 150°C, resulting in complete adhesive detachment. However, the addition of the thermally expanding material does not affect the lap shear strength at ambient temperature. Therefore, the compositions according to this disclosure exhibit considerable lap shear strength while being able to detach upon exposure to high temperatures.

[0419] While aspects of this disclosure have been described in detail, those skilled in the art will understand that various modifications and alternatives to those details can be developed based on the general teachings of this disclosure. Therefore, the specific arrangements disclosed are intended to be illustrative only and not to limit the scope of this disclosure, which is defined by the full scope of the appended claims and aspects and any and all equivalents thereof.

Claims

1. A composition comprising: The first component comprises a first compound, the first compound comprising a furan functional group and an isocyanate functional group; The second component comprises a dienophile-containing compound; and Thermally expanding materials.

2. The composition according to claim 1, wherein the first compound comprises a carbamate bond, a urea bond, and / or a thiocarbamate bond.

3. The composition according to claim 2, wherein the urethane bond, the urea bond and / or the thiourethane bond are located between the furan functional group and the isocyanate functional group.

4. The composition according to any one of the preceding claims, wherein the first compound comprises structure I: Wherein X contains O, N or S, m ≥ 1, n ≥ 1, and the sum of m+n ≥ 2; R1 contains substituted or unsubstituted alkyl groups, alkylene groups, (cyclo)alkyl groups, aromatic groups, isocyanurate moieties, biuret moieties, urethane moieties, glycourea moieties, benzoguanidine moieties, or polymer moieties different from the urethane bonds or the urea bonds; and R2 contains substituted or unsubstituted alkyl groups, ester moieties, ether moieties, or urethane moieties.

5. The composition according to any one of the preceding claims, wherein the first compound is substantially free of ether bonds.

6. The composition according to any one of the preceding claims, wherein the first compound comprises 100 g / eq to 3,000 g / eq of furan equivalent weight and / or 100 g / eq to 3,000 g / eq of isocyanate equivalent weight.

7. The composition according to any one of the preceding claims, comprising from 0.5% to 20% by weight of the thermally expanding material based on the total weight of the composition.

8. The composition according to any one of the preceding claims further comprises fillers, accelerators, dispersants, additives and / or elastomer particles.

9. The composition according to claim 8, wherein the filler comprises a thermally conductive filler and / or a non-thermally conductive filler.

10. A method for coating a substrate, the method comprising: A portion of the surface of the substrate is brought into contact with the composition according to any one of the preceding claims.

11. A method of forming an article, the method comprising extruding a composition according to any one of claims 1 to 9.

12. A substrate comprising a thermally expanding coating formed on a first portion of the surface of the substrate by the composition according to any one of claims 1 to 9.

13. The substrate of claim 12, further comprising a dielectric coating on the surface of the substrate.

14. The substrate according to claim 12 or claim 13, wherein the substrate comprises a battery cell.

15. The substrate according to any one of claims 12 to 14, wherein the substrate comprises a component, a vehicle component, a vehicle, an appliance, a personal electronic device, a circuit board, a multi-metal substrate, or a combination thereof.

16. The substrate of claim 15, wherein the vehicle comprises a land vehicle or an aircraft.

17. A battery comprising a battery cell according to claim 16 and optionally a battery assembly.

18. A vehicle comprising the battery according to claim 17.

19. A self-supporting membrane formed from the composition according to any one of claims 1 to 9.

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