Curable compositions, articles made therefrom, and methods for making and using same

Abstract

The curable composition includes a polyol component including one or more polyols, a functionalized butadiene component, and a thermally conductive filler. The thermally conductive filler is present in an amount of at least 20 wt. % based on the total weight of the curable composition. The curable composition has a thermal conductivity of at least 0.5 W / (mK) after curing.

Description

[Technical Field]

[0001] The present invention relates generally to curable compositions. Such curable compositions may be used, for example, as thermally conductive gap fillers, which may be suitable for use in electronic applications such as battery assemblies. [Background technology]

[0002] Curable compositions useful as thermally conductive gap fillers have been disclosed in the art, such as those described in EP 3352290, JP 4848782, CN 101235277, and WO 2011 / 019719. Summary of the Invention

[0003] In some embodiments, a curable composition is provided. The curable composition includes a polyol component including one or more polyols, a functional butadiene component, and a thermally conductive filler. The thermally conductive filler is present in an amount of at least 20 wt %, based on the total weight of the curable composition. The curable composition has a thermal conductivity of at least 0.5 wt % (mK) after curing.

[0004] It is to be understood that those skilled in the art can devise many other modifications and embodiments that fall within the scope and spirit of the principles of the present disclosure. All scientific and technical terms used herein have meanings commonly used in the art unless otherwise specified. The definitions provided herein are intended to aid in understanding certain terms used frequently herein and are not intended to limit the scope of the present disclosure. As used in this specification and the appended claims, the singular forms "a," "an," and "the" include embodiments having plural referents unless the context clearly dictates otherwise. As used in this specification and the appended claims, the word "or" is generally used in its sense including "and / or" unless the context clearly dictates otherwise. [Brief explanation of the drawings]

[0005] [Figure 1] 1 illustrates an exemplary battery module assembly according to some embodiments of the present disclosure. [Figure 2] 2 shows an assembled battery module corresponding to FIG. 1. [Figure 3] 1 illustrates an exemplary battery subunit assembly according to some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0006] Thermal management plays a key role in many electronic applications, such as electric vehicle (EV) battery assemblies, power electronics, electronic packaging, LEDs, solar cells, electrical grids, etc. Certain thermally conductive materials (e.g., adhesives) can be attractive choices for these applications due to their ability to efficiently dissipate heat while possessing good electrical insulation, feasibility in processing into integrated parts or complex geometries, and good conformability / wetability to different surfaces, especially good adhesion to different substrates for assembly.

[0007] One such application currently utilizing thermally conductive materials in EV battery assemblies is gap filler applications. Generally, gap filler applications require high thermal conductivity, good overlap shear adhesive strength, good tensile strength, good elongation at break for toughness, and good vibration-damping performance, as well as low viscosity / high injectability before curing and reworkability in the event that the battery assembly needs to be replaced during the service life of the EV. However, to achieve high thermal conductivity, large amounts of inorganic thermally conductive fillers are typically added to the composition. However, adding large amounts of thermally conductive fillers has detrimental effects on adhesive performance, toughness, vibration-damping performance, and viscosity.

[0008] Many current compositions used in EV thermal adhesive gap filler applications are based on polyurethane cure chemistry. While these polyurethane-based materials exhibit many beneficial properties at high filler loadings, they have poor stability at high temperatures, and the isocyanates used in such products pose safety concerns.

[0009] Silicone-containing compositions are also used in EV thermal adhesive gap filler applications, however, such materials are slow to cure and are incompatible with many components within the battery (e.g., foam, polyester, aluminum).

[0010] Alternatives to polyurethane and silicone-based compositions, such as flexible epoxy-amine and epoxythiol compositions, have also been developed, but such compositions have proven inadequate because they exhibit poor reworkability, injectability, or elongation properties, at least at high filler loadings. Furthermore, many of these compositions are incompatible with certain common, low-cost, flame-retardant filler materials.

[0011] To address the performance issues and safety concerns discussed above, curable compositions have been discovered that provide a good balance of the desirable properties discussed above. More specifically, the filled compositions of the present disclosure have good and tunable thermal conductivity, overlap shear bond strength, tensile strength, toughness elongation at break, and vibration damping performance. In addition, the curable compositions also exhibit reworkability, injectability within a wide temperature range, and are compatible with a wide range of filler materials. Furthermore, the curable compositions of the present disclosure need not be based on polyurethane curing chemistries or contain silicones. Furthermore, the curable compositions can be formed from natural / plant-based ingredients.

[0012] As used herein, The term "room temperature" refers to a temperature between 22°C and 25°C.

[0013] The terms "cure" and "curable" refer to the joining of polymer chains together, typically by covalent chemical bonds via crosslinking molecules or groups, to form a network polymer. Thus, in this disclosure, the terms "cure" and "crosslink" can also be used interchangeably. Cured or crosslinked polymers are generally characterized by insolubility, although they may become swellable in the presence of an appropriate solvent.

[0014] The term "unfilled composition" refers to all components of the composition other than the thermally conductive filler component.

[0015] The term "backbone" refers to the main continuous chain of a polymer.

[0016] The term "alkyl" refers to a monovalent group that is a radical of an alkane and includes straight-chain, branched-chain, cyclic, and bicyclic alkyl groups and groups that are combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups typically contain 1 to 30 carbon atoms. In some embodiments, alkyl groups have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of "alkyl" groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.

[0017] The term "alkylene" refers to a divalent group that is a radical of an alkane, and includes groups that are straight-chained, branched, cyclic, bicyclic, or combinations thereof. Unless otherwise specified, alkylene groups typically have 1 to 30 carbon atoms. In some embodiments, alkylene groups have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Examples of "alkylene" groups include methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,4-cyclohexylene, and 1,4-cyclohexyldimethylene.

[0018] The term "alkenyl" refers to an unsaturated branched, straight-chain, or cyclic hydrocarbon group having at least one carbon-carbon double bond. The group may be in either the cis or trans conformation about the double bond. Typical alkenyl groups include, but are not limited to, ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, and the like. Unless otherwise specified, an alkenyl group typically has 1 to 30 carbon atoms. In some embodiments, an alkenyl group has 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

[0019] The term "aromatic" refers to aromatic groups of C3 to C40, preferably C3 to C30, including both carbocyclic aromatic groups and heterocyclic aromatic groups containing one or more heteroatoms, O, N, or S, and fused ring systems in which one or more of these aromatic groups are fused together.

[0020] The term "aryl" refers to an aromatic, and optionally carbocyclic, monovalent group. An aryl has at least one aromatic ring. Any additional rings may be unsaturated, partially saturated, saturated, or aromatic. Optionally, the aromatic ring may have one or more additional carbocyclic rings fused to it. Unless otherwise specified, aryl groups typically have 6 to 30 carbon atoms. In some embodiments, aryl groups have 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.

[0021] The term "arylene" refers to a divalent group that is aromatic and optionally carbocyclic. An arylene has at least one aromatic ring. Optionally, the aromatic ring can have one or more additional carbocyclic rings fused to it. Any additional rings can be unsaturated, partially saturated, or saturated. Unless otherwise specified, arylene groups often have 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

[0022] The term "aralkyl" refers to a monovalent group that is an alkyl group substituted with an aryl group (e.g., benzyl). The term "alkaryl" refers to a monovalent group that is an aryl group substituted with an alkyl group (e.g., tolyl). Unless otherwise specified, in either group, the alkyl portion often has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, and the aryl portion often has 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

[0023] The term (meth)acrylate means acrylate or methacrylate.

[0024] Repeat use of reference characters in the specification is intended to represent the same or similar features or elements of the disclosure. As used herein, the symbol "~," when applied to a numerical range, includes the endpoints of the range unless otherwise stated. The recitation of numerical ranges by endpoints includes all numbers within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within that range.

[0025] In some embodiments, the present disclosure provides a filled, thermally conductive, curable composition formulated by blending at least a polyol component and a functional butadiene component.

[0026] In some embodiments, the curable composition may include a polyol component comprising one or more polyols, such as one or more polyols comprising two or more primary or secondary aliphatic hydroxyl groups (i.e., the hydroxyl groups are directly bonded to non-aromatic carbon atoms). The hydroxyl groups of the polyol may be terminally located or pendant from a polymer or copolymer. In some embodiments, the polyol may include any polyol that is compatible with (i.e., does not phase separate when mixed with) the functional butadiene component.

[0027] In some embodiments, the polyol may comprise a monomeric polyol. Representative examples of useful monomeric polyols include alkylene glycols (e.g., 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,18-dihydroxyoctadecane, and 3-chloro-1,2-propanediol), polyhydroxyalkanes (e.g., glycerin, trimethylolethane, pentaerythritol, and sorbitol), and other polyhydroxy compounds such as castor oil.

[0028] In some embodiments, the polyol may include one or more dimer diols, one or more trimer triols, or a combination thereof.

[0029] In some embodiments, suitable dimer diols may contain at least one alkyl or alkenyl group and may be characterized by having two hydroxyl groups. The dimer diols may be saturated or unsaturated. The dimer diols may be relatively high molecular weight or may be composed of mixtures containing various ratios of various large or relatively high molecular weight diols. The constituent structures may be acyclic, cyclic (e.g., monocyclic or bicyclic), or aromatic. In some embodiments, a suitable commercially available dimer diol is available from Croda under the trade name Pripol 2033.

[0030] In some embodiments, suitable trimer triols may contain at least one alkyl or alkenyl group and may be characterized by having three hydroxyl groups. The trimer triols may be saturated or unsaturated. The trimer triols may be relatively high molecular weight or may be composed of mixtures containing various ratios of large or relatively high molecular weight triols. The constituent structures may be acyclic, cyclic (e.g., monocyclic or bicyclic), or aromatic. In some embodiments, a suitable commercially available trimer triol is available from DowDuPon under the trade name Tone 0301 Polyol.

[0031] In some embodiments, other high molecular weight diols for the polyol may include polybutadiene diols and hydrogenated polybutadiene diols, such as G-1000, GI-1000 manufactured by Nippon Soda Co., and Krasol F3000 and Krasol F3100 manufactured by Total.

[0032] In some embodiments, the number average molecular weight of the polyol can be 100 g / mol to 3000 g / mol, 250 g / mol to 2000 g / mol, or 400 g / mol to 1000 g / mol. In some embodiments, the number of carbon atoms in the polyol can be 12 to 100, 20 to 100, 30 to 100, 12 to 80, 20 to 80, 30 to 80, 12 to 60, 20 to 60, or 30 to 60.

[0033] In some embodiments, the polyol component may further comprise one or more monofunctional alcohols. In some embodiments, suitable monofunctional alcohols include alkyl, alkylene, alkynyl, aromatic, heteroaromatic, branched, unbranched, substituted, and unsubstituted alcohols, alkoxylation products of alkyl alcohols, alkyl ester alcohols, and mixtures thereof. In some embodiments, the monofunctional alcohol may comprise an alkyl alcohol having 4 to 18 carbon atoms, 8 to 16 carbon atoms, or 12 to 16 carbon atoms, and a molecular weight of 74 g / mol to 1000 g / mol, or 130 g / mol to 500 g / mol.

[0034] In some embodiments, the functional butadiene component can include any functional butadiene that can react with the polyol of the polyol component. In some embodiments, the functional butadiene component can be of the following general structural formula: [ka] (wherein a is 30 to 150, or 30 to 120, and n is 1 to 30, or 2 to 15).

[0035] In some embodiments, the functionalized butadiene component may be comprised of a mixture of functionalized butadienes having various molecular weights.

[0036] In some embodiments, the functionalized butadiene component may comprise a maleated polyalkyldiene, a maleated liquid rubber, a maleated liquid isoprene, a liquid polyfarnesene, a maleated styrene-butadiene rubber (SBR), or a combination thereof. In some embodiments, the functionalized butadiene component may comprise or consist essentially of a maleated polybutadiene, such as, for example, the Ricon series of maleated butadienes available from Cray Valley.

[0037] In some embodiments, the curable compositions of the present disclosure may include reactive and non-reactive diluents compatible with the functionalized butadiene component. Examples of reactive diluents include maleic acid-modified soybean oil, dodecyl succinic anhydride, octenyl succinic anhydride, and octadecyl succinic anhydride. Examples of non-reactive diluents include liquid butadiene (e.g., Ricon 130, Ricon 131, and Ricon 134 manufactured by Cray Valley), soybean oil, hydrogenated petroleum distillates, or other vegetable oils compatible with the functionalized butadiene component.

[0038] In some embodiments, the curable compositions of the present disclosure may include one or more resins capable of reacting with the acid of the acid / ester formed when an alcohol (of a polyol or monofunctional alcohol) reacts with a functional butadiene component (e.g., maleic anhydride group). Suitable resins of this type may include epoxidized vegetable oils, epoxidized fatty acid esters, or alpha olefins, and epoxidized polybutenes. Commercially available examples of these resins include Vikoflex 5075, Vikoflex 7170, Vikoflex 7190, Vikolox 16, and Vikopol 24, all available from Arkema.

[0039] In some embodiments, the resin may be incorporated into the curable composition via either or both of the polyol and functional butadiene components. Alternatively, the resin may be incorporated into the curable composition after the polyol and functional butadiene components are combined. In either case, the resin may be present in the curable composition in an amount of 0.1 wt.% to 10 wt.%, 0.5 wt.% to 5 wt.%, or 1 wt.% to 3 wt.%, based on the total weight of the filled curable composition.

[0040] In some embodiments, the curable compositions of the present disclosure may include one or more thermally conductive fillers. Any known thermally conductive filler can be used, although electrically insulating fillers may be preferred when breakthrough voltage is a concern. Suitable electrically insulating thermally conductive fillers can include ceramics such as oxides, hydroxides, oxyhydroxides, silicates, borides, carbides, and nitrides. Suitable ceramic fillers include, for example, silicon oxide (e.g., fumed silica), aluminum oxide, aluminum trihydroxide (ATH), boron nitride, silicon carbide, and beryllium oxide. In some embodiments, the thermally conductive filler may include or consist essentially of ATH. While ATH is not commonly used in many common thermal management materials due to its reactivity with certain species and the resulting formulation challenges, it should be understood that the curable compositions of the present disclosure can incorporate such inorganic fillers without drawbacks. In some embodiments, the thermally conductive filler includes fumed silica. Other thermally conductive fillers include carbon-based materials such as graphite, and metals such as aluminum, copper, gold, and silver.

[0041] Thermally conductive filler particles are available in a number of shapes, including spherical, irregular, plate-like, and acicular. Through-plane thermal conductivity can be important in certain applications. Therefore, in some embodiments, generally symmetrical (e.g., spherical or hemispherical) fillers may be used. To facilitate dispersion and increase filler loading, in some embodiments, the thermally conductive filler may be surface treated or coated. Generally, any known surface treatment and coating may be suitable, including those based on silanes, titanates, zirconates, aluminates, and organic acid chemistries. In some embodiments, the thermally conductive filler particles may include silane-surface-treated particles (i.e., particles with surface-bound organosilanes). For powder handling purposes, many fillers are available as polycrystalline agglomerates or aggregates, with or without binders. To facilitate high thermal conductivity formulations, some embodiments may include a mixture of particles and aggregates in various sizes and mixtures.

[0042] In some embodiments, the thermally conductive filler particles comprise spherical alumina, hemispherical alumina, or irregularly shaped alumina. In some embodiments, the thermally conductive filler particles comprise spherical alumina and hemispherical alumina.

[0043] The curable compositions of the present disclosure may include one or more fillers (e.g., thermally conductive inorganic fillers) in an amount of at least 25 wt%, at least 35 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the filled curable composition. In some embodiments, the filler loading may be 25 wt% to 95 wt%, 35 wt% to 90 wt%, 55 wt% to 85 wt%, or 70 wt% to 85 wt%, based on the total weight of the filled curable composition.

[0044] In some embodiments, curable compositions according to the present disclosure may include one or more dispersing agents. Generally, dispersing agents may act to stabilize inorganic filler particles in compositions without the dispersing agent, which may cause the particles to aggregate and thus adversely affect the benefits of the particles in the composition. Suitable dispersing agents may depend on the specific identity and surface chemistry of the filler. In some embodiments, suitable dispersing agents according to the present disclosure may include at least a linking group and a compatibilizing segment. The linking group may be ionically bonded to the particle surface. Examples of linking groups for alumina particles include phosphate, phosphonate, sulfonic acid, carboxylic acid, and amine. In some embodiments, the dispersing agent may be present in the curable composition in an amount of 0.1 wt % to 10 wt %, 0.1 wt % to 5 wt %, 0.5 wt % to 3 wt %, or 0.5 wt % to 2 wt %, based on the total weight of the filled curable composition.

[0045] In some embodiments, the dispersing agent may be premixed with the inorganic filler prior to incorporation into the curable composition. Such premixing can facilitate a filled system that is Newtonian-like or allows for shear-thinning behavior.

[0046] In some embodiments, the curable composition may include one or more rheology modifiers.

[0047] In some embodiments, curable compositions according to the present disclosure may include one or more catalysts. Generally, a catalyst may act to accelerate the curing of a curable composition.

[0048] In some embodiments, the curable composition may include an amine catalyst capable of catalyzing the reaction between the maleated butadiene and the polyol. The amine catalyst may be any compound containing one to four basic nitrogen atoms with lone pairs of electrons. The amine catalyst may include primary, secondary, or tertiary amine groups, or a combination thereof. The nitrogen atom in the amine catalyst may be bonded to an alkyl group, an aryl group, an arylalkylene group, an alkylarylene group, an alkylarylenealkylene group, or a combination thereof. The amine catalyst may be a cyclic amine, which may contain one or more rings and may be aromatic or non-aromatic (e.g., saturated or unsaturated). One or more of the nitrogen atoms in the amine may be part of a carbon-nitrogen double bond. In some embodiments, the amine catalyst contains only carbon-nitrogen, nitrogen-hydrogen, carbon-carbon, and carbon-hydrogen bonds, while in other embodiments, the amine catalyst may contain other functional groups (e.g., hydroxyl or ether groups). However, those skilled in the art will understand that compounds containing a nitrogen atom bonded to a carbonyl group are amides rather than amines and have different chemical properties than amines. Amine catalysts can contain carbon atoms bonded to two or more nitrogen atoms. Thus, amine catalysts can be guanidines or amidines. As those skilled in the art will understand, the lone electron pair on one or more nitrogens of amine catalysts distinguishes them from quaternary ammonium compounds, which have a permanent positive charge regardless of pH. Amine catalysts can include a combination of one or more amines as described above. In some embodiments, the amine catalyst includes at least one of a tertiary amine, an amidine, an imidazole, or a guanidine.

[0049] Examples of useful amine catalysts include propylamine, butylamine, pentylamine, hexylamine, triethylamine, tris-(2-ethylhexyl)amine (TEHA), dimethylethanolamine, benzyldimethylamine, dimethylaniline, dimethylundecylamine, tribenzylamine, triphenylamine, tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[5.4.0]undec-7-ene (DBN ...4-diazabicyclo[5.4.0]undec-7-ene (DBN), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[5.4.0]undec-7-ene (DBN), 1,4-diazabicyclo[5.4.0]undec-7-ene (DBN), 1,4-diazabicyclo[5.4.0]undec-7-ene (DBN), 1,4-diazabicyclo[5.4. Examples of suitable amine catalysts include bicyclo[2.2.2]octane (DABCO), quinuclidine, diphenylguanidine (DPG), dimethylaminomethylphenol, tris(dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol tri(2-ethylhexoate), dicyandiamide (DICY), and imidazoles (e.g., imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole), and combinations thereof. In some embodiments, the amine catalyst comprises at least one of tetramethylguanidine, diphenylguanidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, or 1,5-diazabicyclo[4.3.0]non-5-ene.

[0050] Compositions according to the present disclosure typically have open and cure times that can be useful for assembling battery modules and do not require heating above ambient conditions to cure.

[0051] In some applications, it may be useful to increase the open time of the compositions of the present disclosure. To increase the open time, in some embodiments, at least a portion of the amine catalyst is a latent amine or amine that phase-separates from the composition at ambient temperature. The phase-separated second amine may be present as a solid, in a solid adduct, or sequestered within a solid in a composition where the reactive component is generally a liquid.

[0052] In some embodiments, at least some of the amines are solids in the composition. In these embodiments, the solids are insoluble in the composition at ambient temperature but dissolve in the composition at elevated temperatures (e.g., at least 50°C, 60°C, 70°C, 75°C, 80°C, 90°C, 95°C, or 100°C). In some embodiments, the amine catalyst comprises dicyandiamide (DICY). In some embodiments, the amine catalyst comprises an adduct of an amine and an epoxy resin. The adduct can comprise any of the amines described above and any of the epoxy resins. Suitable adducts of amines and epoxy resins are commercially available, for example, from Hexion, Inc., Columbus, Ohio, under the trade name "EPIKURE," and from Ajinomoto Fine-Techno Co., Inc., Kawasaki, Japan, under the trade name "AJICURE."

[0053] In some embodiments, at least some of the amine catalyst is sequestered within the solid in the composition. Such amine catalysts can be encapsulated and can be made by various microencapsulation techniques (e.g., coacervation, interfacial addition and condensation, emulsion polymerization, microfluidic polymerization, reverse micellar polymerization, air suspension encapsulation, centrifugal extrusion, spray drying, prilling, pan coating, other processes, and any combination thereof). The amine catalyst can be contained in one single cavity or reservoir within the solid, or can be present in multiple cavities within the solid. The loading level of the amine catalyst can be 5% to 90%, 10% to 90%, or 30% to 90%, based on the total weight of the amine catalyst and solid. In these embodiments, the amine catalyst is sequestered within the solid at ambient temperature, but is released into the composition at elevated temperatures (e.g., at least 50°C, 60°C, 70°C, 75°C, 80°C, 90°C, 95°C, or 100°C) when the solid at least partially dissolves. The time required to at least partially dissolve the solids may be up to 5, 4, 3, 2, or 1 minute.

[0054] In some embodiments, the catalyst may include a Lewis acid such as SnCl4 or paratoluenesulfonic acid.

[0055] In some embodiments, the curable compositions of the present disclosure may be provided (e.g., packaged) as two-part compositions, where a first part comprises the polyol component described above and a second part comprises the functionalized butadiene component described above. Other components of the curable composition (e.g., fillers, crosslinkers, dispersants, catalysts, etc.) may be included in one or both of the first and second parts. The present disclosure further provides a dispenser comprising a first chamber and a second chamber. The first chamber comprises the first part and the second chamber comprises the second part.

[0056] In addition to the additives described above, one or both of the first and second parts may contain additional additives, such as any or all of antioxidants / stabilizers, colorants, abrasive granules, thermal degradation stabilizers, light stabilizers, conductive particles, tackifiers, flow agents, thickeners, matting agents, inert fillers, binders, foaming agents, fungicides, bactericides, surfactants, plasticizers, and other additives known to those skilled in the art. These additives, if present, are added in amounts effective for their intended purpose.

[0057] In some embodiments, the polyol component (excluding any filler) may be present in the curable composition of the present disclosure in an amount of 0.1 wt.% to 20 wt.%, 0.5 wt.% to 10 wt.%, 1 wt.% to 8 wt.%, 1.5 wt.% to 5 wt.%, or 2 wt.% to 4 wt.%, based on the total weight of the filled curable composition. In some embodiments, the polyol component (excluding any filler) may be present in the curable composition of the present disclosure in an amount of at least 0.1 wt.%, at least 0.5 wt.%, at least 1 wt.%, at least 1.5 wt.%, at least 2 wt.%, or at least 2.5 wt.%, based on the total weight of the filled curable composition. In some embodiments, the functional butadiene component (excluding any filler) may be present in the curable composition of the present disclosure in an amount of 1 wt.% to 40 wt.%, 2 wt.% to 30 wt.%, 3 wt.% to 20 wt.%, or 4 wt.% to 10 wt.%, based on the total weight of the filled curable composition. In some embodiments, the functional butadiene component (not including any filler) may be present in the curable compositions of the present disclosure in an amount of at least 1 wt %, at least 2 wt %, at least 3 wt %, or at least 4 wt %, based on the total weight of the filled curable composition.

[0058] In some embodiments, the polyol and functional butadiene components may be present in the curable composition based on the stoichiometric ratio of the functional groups of each component.

[0059] In some embodiments, after curing (i.e., the cured composition that is the reaction product of the curable composition), the curable compositions of the present disclosure may exhibit thermal, mechanical, and rheological properties that make them particularly useful as thermally conductive gap fillers. The curable compositions of the present disclosure are believed to provide an optimal blend of tensile strength, elongation at break, and lap shear strength for certain EV battery assembly applications. Furthermore, the curable compositions of the present disclosure are believed to offer strong reworkability and injectability at conventional operating temperatures and to be compatible with certain common, low-cost, flame-retardant filler materials (e.g., ATH).

[0060] In some embodiments, the cured composition may have an elongation at break in the range of 0.1% to 200%, 0.5% to 175%, 1% to 160%, or 5% to 160% at a tensile rate of 0.8 mm / min to 1.5 mm / min for a fully cured system (for purposes of this application, elongation at break values ​​are those measured in accordance with ASTM D638-03, "Standard Test Method for Tensile Properties of Plastics"), or at least 5%, at least 5.5%, at least 6%, at least 7%, at least 10%, at least 50%, at least 100%, or at least 150% at a tensile rate of 0.8 mm / min to 1.5 mm / min for a fully cured system.

[0061] In some embodiments, the cured composition has a viscosity of 1 N / mm on a bare aluminum substrate for a fully cured system. 2 ~30N / mm 2 , 2N / mm 2 ~30N / mm 2 , 1N / mm 2 ~25N / mm 2 , 4N / mm 2 ~20N / mm 2 , 6N / mm 2 ~20N / mm 2 , 2N / mm 2 ~16N / mm 2 , or 3N / mm 2 ~8N / mm 2 (For purposes of this application, lap shear strength values ​​are those measured on untreated aluminum substrates (i.e., aluminum substrates having no surface treatments or coatings other than a native oxide layer) in accordance with EN 1465 Adhesives—Determination of tensile lap-shear strength of bonded assemblies.) Furthermore, it should be noted that when performing lap shear strength measurements, the cured composition may exhibit adhesive failure (as opposed to cohesive failure), making the cured composition more susceptible to peeling from the aluminum substrate.

[0062] In some embodiments, the cured composition exhibits a strain of 0.5 N / mm at a strain rate of 1% strain / min to 10% strain / min for the fully cured system. 2 ~16N / mm 2 , 1N / mm 2 ~10N / mm 2 , or 2N / mm 2 ~8N / mm 2 (For the purposes of this application, tensile strength values ​​are those measured according to the tensile test of EN ISO 527-2).

[0063] In some embodiments, the cured compositions are sufficiently "reworkable" in the sense that they can be used to bond subsequent battery assemblies if the original batteries need to be replaced during the life of the EV. In this regard, the cured compositions may have a peel strength of at least 0.01 N / mm on aluminum substrates and at least 0.01 N / mm on PET substrates. For purposes of this application, peel strength is determined in accordance with ASTM D1876.

[0064] In some embodiments, the viscosity of the at least partially cured composition may be in the range of 100 poise to 50,000 poise measured at room temperature within 10 minutes of combining the polyol component and the functionalized butadiene component, and may be in the range of 100 poise to 50,000 poise at 60° C. Further, with respect to viscosity, the viscosity of the polyol component (before combining and including any filler) may be in the range of 100 poise to 100,000 poise measured at room temperature and may be in the range of 10 poise to 10,000 poise at 60° C., and the viscosity of the functionalized butadiene composition (before combining and including any filler) may be in the range of 100 poise to 100,000 poise measured at room temperature and may be in the range of 10 poise to 10,000 poise at 60° C. For the purposes of this application, viscosity values ​​were measured using a 40 mm parallel plate geometry at 1% strain on an ARES rheometer (TA Instruments, Wood Dale, IL, US) equipped with a forced convection oven attachment at angular frequencies ranging from 10 rad / s to 500 rad / s.

[0065] In some embodiments, the curable composition may have a cure speed ranging from 10 minutes to 240 hours, 30 minutes to 72 hours, or 1 hour to 24 hours to fully cure at room temperature, or from 10 minutes to 6 hours, 10 minutes to 3 hours, or 30 minutes to 60 minutes to fully cure at 100°C, or from 1 hour to 24 hours to fully cure at room temperature, or from 10 minutes to 6 hours, 10 minutes to 3 hours, or 30 minutes to 60 minutes to fully cure at 120°C.

[0066] In some embodiments, the composition may have a green strength cure rate of less than 10 minutes, less than 11 minutes, less than 15 minutes, less than 20 minutes, or less than 30 minutes at room temperature. For purposes of this application, the green strength cure rate may be approximated based on the lap shear strength rate of rise. In this regard, in some embodiments, after 10 minutes of cure at room temperature, the composition may have an lap shear strength of at least 0.2 MPa, at least 0.3 MPa, at least 0.5 MPa, or at least 0.8 MPa. For purposes of this application, lap shear strength values ​​are those measured in accordance with EN 1465.

[0067] In some embodiments, after curing, the curable compositions of the present disclosure have a viscosity of 1 W / (m * K)~5W / (m * K), 1W / (m * K)~2W / (m * K), or 1.4W / (m * K)~1.8W / (m * K), or at least 0.5 W / (m * K), or at least 1 W / (m * For purposes of this application, thermal conductivity values ​​are first determined by ASTM E1461-13, "Standard Test Method for Thermal Diffusivity by the Flash Method," and then calculated from the measured thermal diffusivity, heat capacity, and density measurements using the following formula: k = α·cp·ρ [where k is the thermal conductivity (W / (mK)) and α is the thermal diffusivity (mm 2 / s), cp is the specific heat capacity (J / Kg), and ρ is the density (g / cm 3 The thermal conductivity is determined by calculating the thermal conductivity according to the following formula: The thermal diffusivity of a sample can be measured directly using a Netzsch LFA467 "HYPERFLASH" and relative to a standard, respectively, according to ASTM E1461-13. The sample density can be measured using geometric methods, while the specific heat capacity can be measured using differential scanning calorimetry.

[0068] The present disclosure further relates to methods for producing the curable compositions. In some embodiments, the curable compositions of the present disclosure can be prepared by first mixing the components of the polyol component (including the filler and any optional additives) and separately mixing the components of the functional butadiene component (including the filler and any optional additives). Both the polyol and functional butadiene components can be mixed using any conventional mixing technique, including the use of a speed mixer. In embodiments in which a dispersant is used, the dispersant can be premixed with the filler before being incorporated into the composition. The polyol component and the functional butadiene component can then be mixed using any conventional mixing technique to form the curable composition.

[0069] In some embodiments, the curable compositions of the present disclosure can be cured without the use of catalysts or other curing agents. Generally, the curable compositions can be cured at room temperature without the need for typical application conditions, such as high temperatures or actinic radiation (e.g., ultraviolet light). In some embodiments, the first curable composition cures at room temperature or below. In some embodiments, flash heating (e.g., IR light) can be used.

[0070] In some embodiments, the curable composition of the present disclosure may be provided as a two-component composition. Generally, the two components of the two-component composition may be mixed before being applied to the substrate to be bonded. After mixing, the two-component composition can reach a desired handling strength and ultimately achieve a desired final strength. Applying the curable composition can be performed, for example, by dispensing the curable composition from a dispenser including a first chamber, a second chamber, and a mixing tip, where the first chamber includes a first portion and the second chamber includes a second portion, and the first and second chambers are connected to the mixing tip to allow the first and second portions to flow through the mixing tip.

[0071] The curable compositions of the present disclosure may be useful in coatings, molded articles, adhesives (including structural and semi-structural adhesives), magnetic media, filled or reinforced composites, caulking and sealing compounds, molding and molding compounds, potting and encapsulating compounds, impregnation and coating compounds, conductive adhesives for electronic devices, protective coatings for electronic devices, primers or adhesion promoting layers, and other applications known to those of ordinary skill in the art. In some embodiments, the present disclosure provides an article comprising a substrate having a cured coating of the curable composition.

[0072] In some embodiments, the curable composition may function as a structural adhesive, i.e., the curable composition can bond a first substrate to a second substrate after curing. Generally, the bond strength (e.g., peel strength, lap shear strength, or impact strength) of a structural adhesive continues to build sufficiently after an initial cure period. In some embodiments, the present disclosure provides an article comprising a first substrate, a second substrate, and a cured composition disposed between the first substrate and the second substrate and adhering the first substrate to the second substrate, wherein the cured composition is a reaction product of any one of the curable compositions of the present disclosure. In some embodiments, the first and / or second substrate may be at least one of a metal, a ceramic, and a polymer, such as a thermoplastic resin.

[0073] The curable composition may be coated onto a substrate at a useful thickness ranging from 5 microns to 10,000 microns, 25 microns to 10,000 microns, 100 microns to 5,000 microns, or 250 microns to 1,000 microns. Useful substrates may be of any nature and composition, and may be inorganic or organic. Representative examples of useful substrates include ceramics, siliceous substrates including glass, metals (e.g., aluminum or steel), natural and man-made stone, woven and nonwoven articles, polymeric materials including thermoplastic and thermoset (e.g., polymethyl(meth)acrylate, polycarbonate, polystyrene, styrene-acrylonitrile copolymers, polyesters, styrene copolymers such as polyethylene terephthalate), silicones, paints (such as those based on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), and wood, as well as composites of the foregoing materials.

[0074] In another aspect, the present disclosure provides a coated article comprising a metal substrate comprising a coating of an uncured, partially cured, or fully cured curable composition on at least one surface thereof. When the substrate has two major surfaces, the coating can be coated on one or both major surfaces of the metal substrate and can include additional layers such as a bonding layer, a tie layer, a protective layer, and a topcoat layer. The metal substrate can be, for example, at least one of the interior and exterior surfaces of a pipe, a vessel, a conduit, a rod, a contoured article, a sheet, or a tube.

[0075] In some embodiments, the present disclosure is further directed to battery modules comprising the uncured, partially cured, or fully cured curable compositions of the present disclosure. Components of a typical battery module during assembly are shown in FIG. 1 , and an assembled battery module is shown in FIG. 2 . A battery module 50 can be formed by placing a plurality of battery cells 10 on a first base plate 20. Generally, any known battery cell may be used, including, for example, hard-case prismatic cells or pouch-type cells. The number, size, and location of cells associated with a particular battery module may be tailored to meet specific design and performance requirements. Base plate construction and design are well known, and any base plate suitable for the intended application (typically a metal base plate made from aluminum or steel) can be used.

[0076] The battery cells 10 can be connected to the first base plate 20 via a first layer 30 of a first curable composition according to any of the embodiments of the present disclosure. The first layer 30 of the curable composition can provide a first level of thermal management when the battery cells are assembled into a battery module. Because a voltage difference (e.g., up to a 2.3 volt voltage difference) can occur between the battery cells and the first base plate, breakthrough voltage can be an important safety feature of this layer. Therefore, in some embodiments, electrically insulating fillers such as ceramics (typically alumina and boron nitride) can be preferred for use in the curable composition.

[0077] In some embodiments, layer 30 may comprise a discrete pattern of the first curable composition applied to first surface 22 of first base plate 20, as shown in FIG. 1 . For example, a pattern of material corresponding to a desired layout of battery cells may be applied to the surface of the base plate (e.g., robotically). In some embodiments, the first layer may be formed as a coating of the first curable composition covering all or substantially all of the first surface of the first base plate. In an alternative embodiment, the first layer may be formed by applying the curable composition directly to the battery cells and then attaching them to the first surface of the first base plate.

[0078] In some embodiments, the curable composition may need to accommodate dimensional variations of up to 2 mm, up to 4 mm, or even more. Thus, in some embodiments, the first layer of the first curable composition may be at least 0.05 mm thick, e.g., at least 0.1 mm, or even at least 0.5 mm thick. To increase the breakthrough voltage, depending on the electrical properties of the material, a thicker layer (e.g., in some embodiments, at least 1, at least 2, or even at least 3 mm thick) may be required. Generally, to maximize heat conduction through the curable composition and minimize cost, the curable composition layer should be as thin as possible while still ensuring good contact with the heat sink. Thus, in some embodiments, the first layer is 5 mm thick or less, e.g., 4 mm thick or less, or even 2 mm thick or less.

[0079] As the first curable composition cures, the battery cells are more firmly held in place. Once curing is complete, the battery cells are finally secured in the desired position, as shown in Figure 2. Additional elements, such as bands 40, may be used to secure the cells for transport and further handling.

[0080] Generally, it is desirable for the curable composition to cure under typical application conditions, for example, without the need for elevated temperatures or actinic radiation (e.g., ultraviolet light). In some embodiments, the first curable composition cures at room temperature or at temperatures below 30°C, such as below 25°C, or even below 20°C.

[0081] In some embodiments, the time to cure is 60 minutes or less, e.g., 40 minutes or less, or even 20 minutes or less. While very rapid cure (e.g., less than 5 minutes, or even less than 1 minute) may be suitable for some applications, in some embodiments, an open time of at least 5 minutes, e.g., at least 10 minutes, or even at least 15 minutes, may be desired to allow time for placement and repositioning of the battery cells. Generally, it is desirable to achieve the desired cure time without the use of expensive catalysts such as platinum.

[0082] As shown in Figure 3, multiple battery modules 50, such as those shown and described in connection with Figures 1 and 2, are assembled to form a battery subunit 100. The number, dimensions, and location of modules associated with a particular battery subunit may be tailored to meet particular design and performance requirements. The structure and design of second base plates are well known, and any base plate (typically a metal base plate) suitable for the intended application may be used.

[0083] Individual battery modules 50 may be disposed on and connected to second base plate 120 via a second layer 130 of a curable composition according to any of the embodiments of the present disclosure.

[0084] A second layer 130 of the second curable composition can be disposed between the second surface 24 of the first base plate 20 (see FIGS. 1 and 2 ) and the first surface 122 of the second base plate 120. The second curable composition can provide a second level of thermal management where the battery module is assembled into battery subunits. At this level, breakthrough voltage may not be a requirement. Thus, in some embodiments, conductive fillers such as graphite and metal fillers can be used, alone or in combination with electrically insulating fillers such as ceramics.

[0085] In some embodiments, the second layer 130 may be formed as a coating of the second curable composition covering all or substantially all of the first surface 122 of the second base plate 120, as shown in FIG. 3. In some embodiments, the second layer may include a discrete pattern of the second curable composition applied to the surface of the second base plate. For example, a pattern of material corresponding to the desired layout of the battery modules may be applied to the surface of the second base plate (e.g., applied by a robot). In an alternative embodiment, the second layer may be formed by applying the second curable composition directly to the second surface 24 of the first base plate 20 (see FIGS. 1 and 2) and then attaching the modules to the first surface 122 of the second base plate 120.

[0086] Assembled battery subunits may be combined to form further structures. For example, as is known, battery modules may be combined with other elements, such as a battery control unit, to form a battery system, e.g., a battery system for use in an electric vehicle. In some embodiments, additional layers of a curable composition according to the present disclosure may be used in the assembly of such a battery system. For example, in some embodiments, a thermally conductive gap filler according to the present disclosure may be used to attach and aid in cooling the battery control unit.

[0087] List of embodiments 1. A curable composition comprising: a polyol component comprising one or more polyols; a functional butadiene component; a thermally conductive filler present in an amount of at least 20 wt.%, based on the total weight of the curable composition; A curable composition, wherein the curable composition has a thermal conductivity of at least 0.5 W / (mK) after curing.

[0088] 2. The curable composition of embodiment 1, wherein the polyol component further comprises one or more monofunctional alcohols.

[0089] 3. The curable composition of embodiment 1 or 2, wherein the polyol component comprises a polyol having a number average molecular weight of 100 g / mol to 3000 g / mol.

[0090] 4. The curable composition of any one of embodiments 1-3, wherein the polyols are present in the curable composition in an amount of 0.5 wt.% to 30 wt.%, in total, based on the total weight of the curable composition.

[0091] 5. The curable composition of any one of embodiments 1-4, wherein the functionalized butadiene component comprises a maleated polyalkyldiene, a maleated liquid rubber, a maleated liquid isoprene, a liquid polyfarnesene, or a maleated styrene-butadiene rubber.

[0092] 6. The curable composition of any one of embodiments 1-5, wherein the functionalized butadiene component comprises a maleic acid modified polybutadiene.

[0093] 7. The curable composition of any one of embodiments 1-6, wherein the thermally conductive filler comprises aluminum trihydroxide.

[0094] 8. The curable composition of any one of embodiments 1-7, wherein the thermally conductive filler is present in an amount of at least 70 wt.%, based on the total weight of the curable composition.

[0095] 9. The curable composition of any one of embodiments 1-8, further comprising a resin capable of reacting with the acid of the acid / ester formed when the alcohol group of the polyol reacts with the functional butadiene component.

[0096] 10. The curable composition of embodiment 9, wherein the resin comprises an epoxidized vegetable oil, an epoxidized fatty acid ester, an epoxidized alpha olefin, or an epoxidized polybutene.

[0097] 11. The curable composition of any one of embodiments 9-10, wherein the resin is present in the curable composition in an amount of 0.5% to 70% by weight, based on the total weight of the curable composition.

[0098] 12. The curable composition of any one of embodiments 1 to 11, further comprising an amine catalyst.

[0099] 13. The curable composition of any one of embodiments 1-12, wherein the curable composition, after curing, provides a flame retardancy of at least UL94-HB.

[0100] 14. The curable composition of any one of embodiments 1-13, wherein the curable composition, after curing, provides an elongation at break of at least 5%.

[0101] 15. The curable composition, after curing, has a compressive strength of 0.1 N / mm on a bare aluminum substrate. 2 ~30N / mm 2 15. The curable composition of any one of embodiments 1-14, which provides an overlap shear strength in the range of

[0102] 16. The curable composition has a compressive strength of 0.5 N / mm after curing. 2 ~30N / mm 2 16. The curable composition of any one of embodiments 1 to 15, which provides a tensile strength of

[0103] 17. The curable composition of any one of embodiments 1-16, wherein the curable composition, after curing, provides a peel strength on an aluminum substrate of at least 0.01 N / mm.

[0104] 18. The curable composition of any one of embodiments 1 to 17, wherein the curable composition has a viscosity of 100 poise to 50,000 poise measured at room temperature within 10 minutes of combining the polyol component, the functional butadiene component, and the thermally conductive filler.

[0105] 19. The curable composition, after curing, has a surface roughness of at least 1 W / (m * 19. The curable composition of any one of embodiments 1-18, wherein the curable composition provides a thermal conductivity of 0.15 or less.

[0106] 20. An article comprising a cured composition, wherein the cured composition is a reaction product of the curable composition of any one of embodiments 1-13.

[0107] 21. The article of embodiment 20, wherein the cured composition has a thickness of from 5 microns to 10,000 microns.

[0108] 22. The article of any one of embodiments 20-21, further comprising a substrate having a surface, the cured composition being disposed on the surface of the substrate.

[0109] 23. The article of embodiment 22, wherein the substrate is a metal substrate.

[0110] 24. An article comprising a first substrate, a second substrate, and a cured composition disposed between the first substrate and the second substrate and adhering the first substrate to the second substrate, wherein the cured composition is a reaction product of the curable composition of any one of embodiments 1-13.

[0111] 25. A battery module comprising a plurality of battery cells connected to a first base plate by a first layer of the curable composition according to any one of embodiments 1-13.

[0112] 26. A method for manufacturing a battery module, comprising: applying a first layer of the curable composition described in any one of embodiments 1 to 13 to a first surface of a first base plate; attaching a plurality of battery cells to the first layer to connect the battery cells to the first base plate; and curing the curable composition. [Example]

[0113] Objects and advantages of the present disclosure are further illustrated by the following comparative examples and examples. Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained or are available from common chemical suppliers, such as Sigma-Aldrich Corp. (Saint Louis, MO, US), or can be synthesized by conventional methods.

[0114] The following abbreviations are used herein: in = inch, mil = 0.001 inch, m = meter, cm = centimeter, mm = millimeter, μm = micrometer (10 -6 m), min = minute, hr = hour, g = gram, °C = degree Celsius, rpm = revolutions per minute, wt% = weight %, W = watts, K = degree Kelvin, MPa = megapascals. "Room temperature" refers to ambient temperature conditions ranging from 20°C to 25°C, with an average of 23°C.

[0115] [Table 1]

[0116] Test Method 1 second -1 ~5 seconds -1 Dispensing ability was qualitatively evaluated by obtaining viscosity as a function of shear rate over a range of shear rates. Samples with viscosities below 1000 Pa.s in this shear rate range were found to be easy to dispense through cartridges with static mixer heads and were rated "good."

[0117] Thermal conductivity measurements were performed using ASTM E1461-13, "Standard Test Method for Thermal Diffusivity by the Flash Method." Disks 1.2 cm (0.47 in) in diameter and 2 mm thick were punched from cured samples prepared by curing the formulation between two glass plates lined on both sides with release liners in an oven at 90°C (194°F) for 2 hours. Thermal diffusivity α (T) was measured using an LFA 467 HYPERFLASH Light Flash Apparatus manufactured by Netzsch Instruments of Burlington, MA, US. Thermal conductivity k was calculated using the equation: k = α C p ρ (where k is the thermal conductivity in W / (mK) and α is the 2 is the thermal diffusivity in C / sec p is the specific heat capacity in J / Kg and ρ is in g / cm 3 The thermal conductivity, heat capacity, and density were calculated according to the following formula (density at 1000 K).

[0118] Lap shear adhesive strength was measured according to ASTM D-1002-10, "Standard Test Method for Apparent Shear Strength of Single-Lap-Joint Adhesively Bonded Metal Specimens by Tension Loading (Metal-to-Metal)," using a CRITERION Model 42 (available from MTS Systems Corporation, Eden Prairie, MN, USA) with a 5 kN load cell and a crosshead speed of 0.05 in / min (0.13 cm / min). The specimens were coated onto aluminum rods (2024, T3 wrought aluminum alloy) manufactured by Erickson Metals of Minnesota, Coon Rapids, MN, USA, cleaned with methyl ethyl ketone (MEK), and clamped together. Bond thickness was controlled with 2 mil (0.005 cm) glass beads, and the overlap area was 1.27 cm x 2.54 cm (0.5 in x 1.0 in). The samples were cured in an oven at 120°C for 1 hour before testing, which was carried out at room temperature. The average value from five replicates was recorded. The adhesive bond failure mode, cohesive or adhesive failure, was also noted. Cohesive failure was defined as failure within the adhesive layer, while adhesive failure was considered failure at the interface between the adhesive and the aluminum substrate.

[0119] Tensile strength, modulus, and elongation at break were determined using a CRITERION Model 42 (available from MTS Systems Corporation, Eden Prairie, MN, US) with a 500 N load cell and a crosshead speed of 0.05 in / min (0.13 cm / min) following the method described in ASTM D638-14, "Standard Test Method for Tensile Properties of Plastics." Type V dog bones were punched from cured films of the formulations, and tensile properties were measured at room temperature. Average values ​​from five replicates were recorded.

[0120] Hardness was measured using a Shore A durometer available from Mitutoyo, Aurora, IL, US. The hardness of the reference sample was measured first, followed by the hardness of the cured sample. Tests were performed at room temperature, and the average value from five replicates was recorded.

[0121] Cure rate was determined via rheology by measuring viscosity, storage modulus, and loss modulus as a function of time at room temperature using an ARES rheometer in parallel plate geometry with a 0.5 mm gap at a frequency of 1 Hz. The gel time was determined to be the time at which the storage and loss moduli intersect (i.e., are equal).

[0122] Sample preparation The formulations for Examples 1-4 are provided in Table 2. For each formulation, all organic components except the catalyst were mixed together in the amounts shown in the table below at 2000 rpm for 2 minutes in a SPEEDMIXER DAC 400 VAC manufactured by FlackTek, Inc. of Landrum, SC, US.

[0123] For Examples 1, 4, and 5, the inorganic fillers were added in small, multi-stage additions to ensure proper dispersion, with each portion of filler being mixed for 1 minute at 2000 rpm using a Speedmixer DAC 400 VAC. For Examples 2 and 3, which contained a trimodal size distribution of three alumina fillers, the following mixing procedure was followed: TM1250 was added first, then mixed for 2 minutes at 2000 rpm using a Speedmixer DAC 400 VAC; BAK10 was then added in two equal portions, then mixed for 2 minutes at 2000 rpm using a Speedmixer DAC 400 VAC; and BAK70 was added last in three equal portions, then mixed for 2 minutes at 2000 rpm using a Speedmixer DAC 400 VAC.

[0124] For Examples 1-4, the catalyst was then added and mixed with a Speedmixer DAC 400 VAC at 2000 rpm for 30 seconds, and the formulation was degassed at 40 Torr for 1 minute using a Speedmixer DAC 400 VAC. Films were cast between glass plates at the desired thickness for testing. The films were cured in an oven at 90°C for 1 hour and allowed to stand at room temperature for 24 hours before measurements were taken.

[0125] Comparative Examples CE1-CE4 used commercially available two-part epoxy-based formulations curable using either amine- or thiol-based cure systems and were chosen for their high flexibility. For each comparative example, 100 g of Part A and 100 g of Part B were combined with the amounts of filler and dispersant shown in Table 2 and mixed as in Examples 1-5.

[0126] [Table 2]

[0127] result The thermal and mechanical properties of Examples 1 and 2 are provided in Table 3, and hardness values ​​are listed in Table 4. Example 1, with a filler loading of 80 wt%, exhibited a breaking elongation of 24.22%, while Example 2, with a filler loading of 90 wt%, exhibited a high breaking elongation of 9.3%. When Comparative Examples CE1-CE4 were mixed, even with relatively low filler loading levels, the resulting materials were too dry and / or too incompatible with the filler to exhibit any evidence of hardening.

[0128] [Table 3]

[0129] [Table 4]

[0130] The formulations of Examples 1, 4, and 5 were identical except for the catalyst: Example 1 contained a relatively fast catalyst (ANCAMINE K61B), Example 4 contained a relatively slow catalyst (TEHA), and Example 5 contained no catalyst. The gel times for Examples 1, 4, and 5 are summarized in Table 5.

[0131] [Table 5]

[0132] Various modifications and alterations to the present disclosure will become apparent to those skilled in the art without departing from the scope and spirit of the disclosure. It is understood that the present disclosure is not intended to be unduly limited by the exemplary embodiments and examples set forth herein, and that such examples and embodiments are presented merely as examples within the scope of the present disclosure, which is intended to be limited only by the claims set forth herein as follows. All references cited in this disclosure are incorporated herein by reference in their entirety.

Claims

1. 1. A curable composition comprising: a diol component comprising one or more diols; at least one component selected from the group consisting of maleated polyalkyldiene, maleic acid modified liquid rubber, maleic acid modified liquid isoprene, or maleic acid modified styrene-butadiene rubber; a resin selected from the group consisting of epoxidized vegetable oil, epoxidized fatty acid ester, epoxidized alpha olefin, epoxidized polybutene, and combinations thereof; a thermally conductive filler present in an amount of at least 50 wt.%, based on the total weight of the curable composition; A curable composition, wherein the curable composition, after curing, has a thermal conductivity of at least 0.5 W / (mK).

2. further comprising one or more monofunctional alcohols; the thermally conductive filler comprises aluminum trihydroxide; The curable composition of claim 1.

3. 10. The curable composition of claim 1, wherein the thermally conductive filler is present in an amount of at least 70 wt%, based on the total weight of the curable composition.

4. The curable composition of claim 1 further comprising an amine catalyst.

5. The curable composition, after curing, has an elongation at break of at least 5% and a modulus of elasticity of at least 0.1 N / mm on a bare aluminum substrate. ２ ~30N / mm ２ and an overlap shear strength in the range of 0.5 N / mm ２ ~30N / mm ２ and a peel strength on an aluminum substrate of at least 0.01 N / mm.

6. The curable composition, after curing, has a viscosity of at least 1 W / (m ＊ 10. The curable composition of claim 1, wherein the curable composition provides a thermal conductivity of 0.1% or less of the diol component, a maleated polyalkyldiene, a maleic acid-modified liquid rubber, a maleic acid-modified liquid isoprene, or a maleic acid-modified styrene-butadiene rubber, and a thermally conductive filler.

7. 10. An article comprising a cured composition, said cured composition being a reaction product of the curable composition of claim 1.

8. The article of claim 7 further comprising a metal substrate having a surface, the cured composition being disposed on the surface of the substrate.

9. A battery module comprising a plurality of battery cells connected to a first base plate by a first layer of the curable composition of claim 1.

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