Compositions and foamed polyurethane articles formed therefrom

Abstract

A composition for preparing a foamed polyurethane article is disclosed. The composition comprises (1) an isocyanate-reactive component and (2) an isocyanate component. The (1) isocyanate-reactive component comprises (A) an organopolysiloxane having an average of at least two methanol functional groups per molecule and (B) a polyol. The (A) organopolysiloxane is present in an amount of > 10 wt% to < 99 wt% based on the total weight of the (A) organopolysiloxane and the (B) polyol. The (2) isocyanate component comprises (C) a polyisocyanate. The composition further comprises (D) a blowing agent and (E) a catalyst. Also disclosed is a foamed polyurethane article comprising a reaction product of the composition, and a use of the foamed polyurethane article.

Description

[0001] Cross-references to related applications

[0002] This application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 028,638, filed May 22, 2020 and U.S. Provisional Patent Application No. 63 / 048,628, filed July 6, 2020, the contents of which are incorporated herein by reference. Technical Field

[0003] This subject matter disclosure generally relates to a composition, and more specifically to an isocyanate reactive composition, a composition comprising the isocyanate reactive composition for preparing foamed polyurethane articles, and related methods. Background Technology

[0004] Foams are known in the art and used in a variety of end-use applications, including mats, support articles, encapsulants / potting agents, and insulation materials. Foams can be formed from a variety of chemical compositions and can utilize physical and / or chemical blowing agents. For example, polyurethane foams are typically formed by reacting isocyanates and polyols in the presence of a blowing agent. Foams can also be formed from or with silicone compositions. The performance properties of a foam (including hardness, density, flexibility, etc.) are a function of the compositions used in its preparation. For example, unlike polyurethane foams, reducing the density of silicone foams typically results in a significant reduction in hardness due to the lack of hard segments. Furthermore, reducing the density of silicone foams also leads to a decrease in tear strength. These effects on performance properties can be undesirable, especially when certain performance characteristics of silicone foams, along with reduced density, are required. For example, reduced density and weight are particularly important in the transportation and automotive industries, as lightweighting improves efficiency and maneuverability. Summary of the Invention

[0005] A reactive isocyanate composition is disclosed, comprising (A) an organopolysiloxane having an average of at least two methanol functional groups per molecule and (B) a polyol. Based on the total weight of (A) the organopolysiloxane and (B) the polyol, (A) the organopolysiloxane is present in an amount of >10% by weight to <99% by weight.

[0006] A composition for preparing foamed polyurethane articles is also disclosed. The composition comprises (1) an isocyanate reactive component, which is an isocyanate reactive composition, and (2) an isocyanate component. The (2) isocyanate component comprises (C) a polyisocyanate. The composition also comprises (D) a blowing agent and (E) a catalyst. Components (D) and (E) may be present independently in the (1) isocyanate reactive component and the (2) isocyanate component, or may be present separately from the (1) isocyanate reactive component and the (2) isocyanate component.

[0007] Also disclosed is a foamed polyurethane article comprising the reaction product of the composition, and use of the foamed polyurethane article as a potting agent, a pouring encapsulant, a thermal insulation layer, and / or in automotive applications.

[0008] Further, a method of making a composite article with the composition is disclosed. The method includes disposing the composition on a substrate, and curing the composition to obtain a foamed polyurethane article on the substrate and make the composite article. Also disclosed is a composite article formed according to the method. DETAILED DESCRIPTION

[0009] An isocyanate-reactive composition and a composition comprising the isocyanate-reactive composition for making a foamed polyurethane article are disclosed. The foamed polyurethane article, which is a reaction product of the composition, is suitable for use in a variety of end-use applications, including those involving conventional foamed polyurethanes and / or conventional foamed silicone elastomers. For example, the foamed polyurethane article can be used as a potting agent, a pouring encapsulant, or a thermal insulation layer. As described below, the foamed polyurethane article has superior performance for use in automotive applications. However, the end-use applications of the foamed polyurethane article are not limited thereto.

[0010] The composition comprises (1) an isocyanate-reactive component and (2) an isocyanate component, each of which is described below. The disclosure also provides (1) the isocyanate-reactive component, and when separate from the composition comprising (1) the isocyanate-reactive component and (2) the isocyanate component, can be referred to as an isocyanate-reactive composition. All references and disclosures relating to (1) the isocyanate-reactive component also apply to the isocyanate-reactive composition.

[0011] The (1) isocyanate-reactive component comprises (A) an organopolysiloxane having an average of at least two methanol functional groups per molecule. The methanol functional groups can be the same as or different from each other. The methanol functional groups on the organopolysiloxane are different from silanol groups, where the methanol functional group includes a carbon-bonded hydroxyl group, while the silanol functional group includes a silicon-bonded hydroxyl group. In other words, the methanol functional group has the formula -COH, while the silanol functional group has the formula -SiOH. These functional groups behave differently; for example, the silanol functional group can readily condense to obtain a siloxane (-Si-O-Si-) bond, which does not typically occur with the methanol functional group (at least under the same catalysis of the hydrolysis of the silanol functional group).

[0012] In certain embodiments, the methanol functional group independently has the general formula -D-O a -(C b H 2b O) c- H, where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each moiety indicated by subscript c, and subscript c is 0 to 500, with the proviso that subscripts a and c are not simultaneously 0.

[0013] In one embodiment, subscript c is at least one, such that at least one of the carbinol functional groups has the general formula:

[0014] - D-O a - [C2H4O] x [C3H6O] y [C4H8O] z - H.

[0015] where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, 0 < x < 500, 0 < y < 500, and 0 < z < 500, with the proviso that 1 < x + y + z < 500. In these embodiments, the carbinol functional group can alternatively be referred to as a polyether group or moiety, but the polyether group or moiety is in the -COH rather than -COR 0 end-capped, where R 0 is a monovalent hydrocarbon group. As understood in the art, the moieties indicated by subscript x are ethylene oxide (EO) units, the moieties indicated by subscript y are propylene oxide (PO) units, and the moieties indicated by subscript z are butylene oxide (BO) units. The EO, PO, and BO units, if present, can be in block or random form in the polyether group or moiety. The relative amounts of the EO, PO, and BO units, if present, can be selectively controlled based on the desired properties of (A) the organopolysiloxane, the composition, and the resulting foamed polyurethane article. For example, the molar ratio of such alkylene oxide units can affect hydrophilicity and other properties.

[0016] In another embodiment, subscript c is 0 and subscript a is 1, such that at least one of the carbinol functional groups has the general formula: -D-OH, where D is as described above. In these embodiments, the carbinol functional group having this general formula is not a polyether group or moiety.

[0017] Regardless of the independent selection of the carbinol functional groups of component (A), component (A) is generally substantially linear. Substantially linear means that component (A) comprises, consists essentially of, or consists solely of M and D siloxy units. As readily understood in the art, the M siloxy units have the formula [R3SiO 1 / 2 ] and the D siloxy units have the formula [R2SiO 2 / 2] Conventionally, the M and D siloxy nomenclature is used in conjunction with methyl substitution only. However, for the purposes of the present disclosure, in the M and D siloxy units described above, R is independently selected from substituted or unsubstituted hydrocarbyl or a carbinol functional group, with the proviso that at least two of R are independently selected carbinol functional groups. When the M siloxy unit comprises at least one carbinol functional group, the carbinol functional group is an end group. When the D siloxy unit comprises at least one carbinol functional group, the carbinol functional group is a pendant group. The substantially linear organopolysiloxane can have an average formula: R a′ SiO (4-a′) / 2 where each R is independently selected and defined as above, including the proviso that at least two of R are independently selected carbinol functional groups, and where subscript a' is selected such that 1.9 < a' < 2.2.

[0018] Generally, hydrocarbyl groups suitable for R can independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups as well as saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be saturated or unsaturated. One example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and the like, as well as derivatives, modifications, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., iso-butyl, n-butyl, t-butyl, and / or sec-butyl), pentyl (e.g., iso-pentyl, neopentyl, and / or t-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbyl groups having from 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl groups. Examples of suitable alkenyl groups include ethenyl, allyl, propenyl, iso-propenyl, butenyl, iso-butenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halocarbon groups (i.e., halocarbon groups or substituted hydrocarbyl groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include alkyl groups described above in which one or more hydrogen atoms are replaced with a halogen atom such as F or CI. Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of halogenated aryl groups include aryl groups described above in which one or more hydrogen atoms are replaced with a halogen atom such as F or CI. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0019] In particular embodiments, each R that is not a carbinol functionality is independently selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, alternatively 1 carbon atom.

[0020] (A) The organopolysiloxane can include at least some branching attributable to the presence of T or Q siloxy units. As understood in the art, T units have the formula [RSiO 3 / 2] and Q siloxy units have the formula [SiO 4 / 2 ] wherein R is as defined above. However, (A) organopolysiloxane typically does not contain such T and Q siloxy units. By "at least some" it is meant that (A) organopolysiloxane can contain up to 5 mole %, alternatively up to 4 mole %, alternatively up to 3 mole %, alternatively up to 2 mole %, alternatively up to 1 mole %, alternatively 0 mole % of T and Q siloxy units based on all siloxy units present in (A) organopolysiloxane. If such branching is present in (A) organopolysiloxane, it can typically be attributed to T siloxy units rather than O siloxy units. Typically, (A) organopolysiloxane is a flowable liquid at room temperature, including in the absence of any solvent or carrier vehicle, rather than a gum or resin, taking into account the desired viscosity. While a gum or resin can be liquid at room temperature when present in a solvent or carrier vehicle, such solvents can be undesirable in certain end use applications as the solvent is typically volatilized or otherwise removed during the curing process.

[0021] In specific embodiments where component (A) is linear, component (A) can have the following general formula:

[0022]

[0023] where each R is independently selected and as defined above, including the proviso that at least two of R independently comprise a carbinol functional group, and subscript n is from 0 to 100. Subscript n can alternatively be referred to as the degree of polymerization (DP) of component (A). Typically, DP is inversely proportional to viscosity, all other things being equal (e.g., substituents and branching). Subscript n is alternatively greater than 0 to 95, alternatively greater than 0 to 90, alternatively greater than 0 to 85, alternatively greater than 0 to 80, alternatively greater than 0 to 75, alternatively greater than 0 to 70, alternatively greater than 0 to 65. Alternatively, subscript n is from 5 to 70, alternatively from 10 to 65. In one specific embodiment, subscript n is from 10 to 20. In alternative specific embodiments, subscript n is from 28 to 32, alternatively from 29 to 31, alternatively 30. In alternative specific embodiments, subscript n is from 48 to 52, alternatively from 49 to 51, alternatively 50. In alternative specific embodiments, subscript n is from 58 to 62, alternatively from 59 to 61, alternatively 60.

[0024] In specific embodiments, each carbinol functional group has the formula -D-OH, and (A) organopolysiloxane has the following general formula:

[0025]

[0026] where D and subscript n are as defined above, and where each R1is an independently selected substituted or unsubstituted hydrocarbyl group, as described above for R. In these embodiments, the methanol functional groups are end groups in component (A). These methanol functional groups can be the same as or different from one another, based on D. This formula can alternatively be written as [(OHD-)R 1 2SiO 1 / 2 ]2[Si 1 2O 2 / 2 ] n .

[0027] In other embodiments, each methanol functional group has the general formula -D-O a -(C b H 2b O) c -H, where D and subscripts a-c are as defined above, and the methanol functional groups are pendant groups, such that (A) organopolysiloxane has the following general formula:

[0028]

[0029] where each R 1 is independently selected and as defined above, each subscript Z is -D-O a -(C b H 2b O) c -H, where D and subscripts a-c are as defined above, each subscript R 2 is independently selected from R 1 and Z, and subscripts p and q are each 1 to 99, with the proviso that p+q < 100. In the above general formula, the siloxy units represented by subscripts q and p can be in random or block form. The above general formula is intended to represent the average unit formula for component (A) in this embodiment, based on the number of R 1 2SiO 2 / 2 units represented by subscript q and the number of R 2 ZSiO 2 / 2 units represented by subscript p, without requiring a specific order thereof. Thus, this formula can alternatively be written as [(R 1 )3SiO 1 / 2 ]2[(R 1 )2SiO 2 / 2 ] q [(R 1 )ZSiO 2 / 2 ] p where subscripts q and p are as defined above. In these embodiments, the methanol functional groups are polyether groups, and the polyether groups are pendant groups in component (A). When each R 1When R is methyl, this embodiment of Component (A) is trimethylsiloxy-terminated, and includes dimethylsiloxy units (denoted by subscript q).

[0030] While specific structures of Component (A) are exemplified above, Component (A) can include terminal polyether groups that are methanol functional groups, or pendant methanol functional groups that are not polyether groups, or any combination of independently selected methanol functional groups.

[0031] D is generally a function of the (A) organopolysiloxane being prepared. For example, the (A) organopolysiloxane can be formed by a hydrosilylation reaction between an organohydrogenpolysiloxane and an unsaturated methanol compound. In such embodiments, the organohydrogenpolysiloxane includes silicon-bonded hydrogen atoms at positions (e.g., terminal and / or pendant groups) where methanol functional groups are desired. The unsaturated methanol compound can have the formula Y-O a -(C b H 2b O) c -H, where Y is an olefinically unsaturated group, and subscripts a, b, and c are as defined above.

[0032] In the above hydrosilylation reaction, the olefinically unsaturated group represented by Y can be an alkenyl and / or alkynyl group having 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, alternatively 2 carbon atoms. “Alkenyl” means an acyclic, branched, or unbranched, monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples thereof include ethenyl groups, allyl groups, hexenyl groups, and octenyl groups. “Alkynyl” means an acyclic, branched, or unbranched, monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples thereof include ethynyl, propynyl, and butynyl groups. Various examples of olefinically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-. Typically, the olefinic unsaturation is at the terminal end of Y. As is understood in the art, the olefinically unsaturated group can be referred to as an aliphatic unsaturated group. Thus, when D is, for example, -CH2CH2-, the unsaturated methanol compound can have the formula CH2=CH-O a -(C b H 2b O) cThe number of carbon atoms in -H.D is a function of the number of carbon atoms in the olefinically unsaturated group, and remains constant even after the hydrosilylation reaction to make Component (A).

[0033] In certain embodiments, the hydrosilylation reaction catalyst used to form Component (A) comprises a Group VIII to Group XI transition metal. Reference to Group VIII to Group XI transition metals is based on the modern IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hafnium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals can be used as hydrosilylation reaction catalysts.

[0034] Additional examples of catalysts suitable for use as hydrosilylation reaction catalysts include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g., including complexes of calcium (Ca), potassium (K), strontium (Sr), and the like). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals can be used as hydrosilylation reaction catalysts.

[0035] The hydrosilylation reaction catalyst can be in any suitable form. For example, the hydrosilylation reaction catalyst can be a solid, examples of which include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts including combinations of multiple metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-Al, Cu-Zn-Ti, and similar copper-containing catalysts, and the like.

[0036] The hydrosilylation reaction catalyst can be located in or on a solid support. Examples of supports include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate), and the like. The hydrosilylation reaction catalyst can also be disposed in a vehicle, such as a solvent that dissolves the hydrosilylation reaction catalyst, or alternatively a vehicle that merely carries but does not dissolve the hydrosilylation reaction catalyst. Such vehicles are known in the art.

[0037] In specific embodiments, the hydrosilylation reaction catalyst includes platinum. In these embodiments, the hydrosilylation reaction catalyst is exemplified by, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid and monohydric alcohols, bis(acetylacetone) platinum, bis(acetylacetone) platinum, platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, and platinum compounds microencapsulated in a matrix or core-shell type compounds. Microencapsulated hydrosilation catalysts and methods for their preparation are also known in the art.

[0038] Complexes of platinum with organopolysiloxanes suitable for use as hydrosilylation reaction catalysts include complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum. These complexes can be microencapsulated in a resin matrix. Alternatively, the hydrosilylation reaction catalyst can include complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum. The hydrosilation reaction catalyst can be prepared by a method including reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane or an olefin-platinum-silyl complex. The olefin-platinum-silyl complex can be prepared, for example, by mixing 0.015 moles (COD) PtCl2with 0.045 moles COD and 0.0612 moles HMeSiCl2, where COD is cyclooctadiene.

[0039] The hydrosilation reaction catalyst is used in the composition in catalytic amounts, i.e., in amounts or quantities sufficient to promote curing thereof under the desired conditions. The hydrosilation reaction catalyst can be a single hydrosilation reaction catalyst or a mixture including two or more different hydrosilation reaction catalysts.

[0040] Alternatively, when component (A) is formed by a reaction other than hydrosilylation, e.g., a condensation reaction or a ring-opening reaction, D can be a covalent bond.

[0041] In certain embodiments, component (A) has a capillary viscosity (kinematic viscosity via a glass capillary) at 25 °C of 1 mPa-s to 1,000 mPa-s, alternatively 1 mPa-s to 900 mPa-s, alternatively 10 mPa-s to 700 mPa-s, alternatively 10 mPa-s to 600 mPa-s. Capillary viscosity can be measured according to Dow Corning Corporate Test Method CTM0004, July 20, 1970. CTM0004 is known in the art and is based on ASTM D445, IP 71. Generally, when component (A) has polyether side groups as the methyl alcohol functional groups, component (A) has a higher viscosity than when component (A) includes terminal methyl alcohol functional groups that are not polyether groups (as shown in the exemplary structures above). For example, when component (A) includes polyether side groups, the capillary viscosity at 25 °C is generally 200 mPa-s to 900 mPa-s, alternatively 300 mPa-s to 800 mPa-s, alternatively 400 mPa-s to 700 mPa-s, alternatively 500 mPa-s to 600 mPa-s. In contrast, when component (A) includes only terminal methyl alcohol functional groups that are not polyether groups, component (A) can have a capillary viscosity at 25 °C of greater than 0 mPa-s to 250 mPa-s, alternatively greater than 0 mPa-s to 100 mPa-s, alternatively greater than 0 mPa-s to 75 mPa-s, alternatively 10 mPa-s to 75 mPa-s, alternatively 25 mPa-s to 75 mPa-s.

[0042] In these or other embodiments, component (A) can have an OH equivalent weight of 100 g / mol to 2,000 g / mol, alternatively 200 g / mol to 1,750 g / mol, alternatively 300 g / mol to 1,500 g / mol, alternatively 400 g / mol to 1,200 g / mol. Methods for determining OH equivalent weight based on functionality and molecular weight are known in the art.

[0043] (1) The isocyanate-reactive component further comprises (B) a polyol.

[0044] Suitable for (1) isocyanate-reactive components, polyether polyols include, but are not limited to, products obtained by polymerization of cyclic oxides (e.g., ethylene oxide ("EO"), propylene oxide ("PO"), butylene oxide ("BO"), tetrahydrofuran, or epichlorohydrin) in the presence of a multifunctional initiator. Suitable initiators contain more than one (i.e., multiple) active hydrogen atoms. Catalysts for the polymerization can be anionic or cationic, suitable catalysts include KOH, CsOH, boron trifluoride, or double metal cyanide complex (DMC) catalysts, such as zinc hexacyanocobaltate or quaternary phosphonium compounds. Initiators can be selected from, for example, neopentyl glycol; 1,2-propanediol; water; trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerol; amino alcohols such as ethanolamine, diethanolamine, and triethanolamine; alkanediols such as 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,2-propanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,5-hexanediol; ethylene glycol; diethylene glycol; triethylene glycol; bis-3-aminopropyl methylamine; ethylenediamine; diethylenetriamine; 9(1)-hydroxymethyloctadecanol, 1,4-bishydroxymethylcyclohexane; hydrogenated bisphenol; 9,9(10,10)-bishydroxymethyloctadecanol; 1,2,6-hexanetriol; and combinations thereof. Other initiators include other linear and cyclic compounds containing amine groups. Exemplary polyamine initiators include ethylenediamine; neopentanediamine; 1,6-diaminohexane; bisaminomethyltricyclodecane; bisaminocyclohexane; diethylenetriamine; bis-3-aminopropyl methylamine; triethylenetetramine; various isomers of toluenediamine; diphenylmethanediamine; N-methyl-1,2-ethanediamine, N-methyl-1,3-propanediamine; N,N-dimethyl-1,3-diaminopropane; N,N-dimethylethanolamine; 3,3'-diamino-N-methyldipropylamine; N,N-dimethyldipropylene triamine; aminopropyl-imidazole; and combinations thereof. As understood in the art, the initiator compound or combination thereof is typically selected based on the desired functionality of the resulting polyether polyol. For purposes of the present disclosure, the (B) polyol can be formed with any of the initiators or combinations of initiators described above. In addition, the (B) polyol can comprise any of these initiators, including glycerol.

[0045] Other suitable polyether polyols include polyether diols and triols such as polyoxypropylene diols and triols and poly(oxyethylene-oxypropylene) diols and triols obtained by the simultaneous or sequential addition of ethylene oxide and propylene oxide to a di- or tri-functional initiator. Polyether polyols having a functionality higher than triols can also be used in place of or in addition to polyether diols and / or triols. Copolymers having an oxyethylene content of 5 to 90 weight percent can be used based on the weight of the copolymer. When the (B) polyol is a copolymer, the (B) polyol can be a block copolymer, a random / block copolymer, or a random copolymer. The (B) polyol can also be a terpolymer. Other suitable polyether polyols also include polytetramethylene glycols obtained by polymerization of tetrahydrofuran.

[0046] Suitable polyester polyols for (1) isocyanate-reactive components include, but are not limited to, the hydroxyl functional reaction products (including mixtures thereof) of polyols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, glycerol, trimethylolpropane, pentaerythritol, sucrose, polyether polyols; and polycarboxylic acids, especially dicarboxylic acids or their ester-forming derivatives, for example succinic acid, glutaric acid, and adipic acid or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, terephthalic acid dimethyl ester, or mixtures thereof. Polyester polyols obtained by polymerization of lactones (e.g., caprolactone) with polyols or by polymerization of hydroxycarboxylic acids (e.g., hydroxylhexanoic acid) can also be used. In certain embodiments, the (B) polyol comprises a mixture of a polyester and a polyether polyol.

[0047] Suitable polyester amide polyols can be obtained by including an amino alcohol such as ethanolamine in the polyesterification mixture. Suitable polythioether polyols include products obtained by condensing thiodiglycol alone or with other diols, alkylene oxides, dicarboxylic acids, formaldehyde, amino alcohols, or aminocarboxylic acids. Suitable polycarbonate polyols include products obtained by reacting a diol (e.g., 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or tetraethylene glycol) with a diaryl carbonate (e.g., diphenyl carbonate) or with phosgene. Suitable polyacetal polyols include those prepared by reacting a diol (e.g., diethylene glycol, triethylene glycol, or hexanediol) with formaldehyde. Other suitable polyacetal polyols can also be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols include hydroxyl-terminated butadiene homopolymers and copolymers, and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.

[0048] In certain embodiments, the (B) polyol is a polymeric polyol. In specific embodiments, the polymeric polyol is a grafted polyol. A grafted polyol can also be referred to as a grafted dispersion polyol or a grafted polymeric polyol. A grafted polyol generally includes a product (i.e., a polymeric particle) obtained by in situ polymerization of one or more vinyl monomers (e.g., styrene monomers and / or acrylonitrile monomers) with a macromonomer in a polyol (e.g., a polyether polyol).

[0049] In other embodiments, the polymeric polyol is selected from the group consisting of a polyharnstoff (PHD) polyol, a polyisocyanate polyaddition (PIPA) polyol, and combinations thereof. It is understood that (1) the isocyanate-reactive component can include any combination of the foregoing polymeric polyols. A PHD polyol is generally formed by in situ reaction of a diisocyanate with a diamine in a polyol to give a stable dispersion of polyurea particles. A PIPA polyol is similar to a PHD polyol, except that the dispersion is generally formed by in situ reaction of a diisocyanate with a chain alkanolamine rather than a diamine to give a polyurethane dispersion in a polyol.

[0050] It is understood that (1) the isocyanate-reactive component can include any combination of two or more polyols that differ from one another based on functionality, molecular weight, viscosity, or structure.

[0051] In various embodiments, the (B) polyol has a hydroxyl (OH) equivalent weight of greater than 0 g / mol to 2,000 g / mol, alternatively greater than 0 g / mol to 1,700 g / mol, alternatively greater than 0 g / mol to 1,000 g / mol, alternatively greater than 0 g / mol to 700 g / mol, alternatively greater than 0 g / mol to 400 g / mol, alternatively greater than 0 g / mol to 350 g / mol, alternatively greater than 0 g / mol to 325 g / mol, alternatively greater than 0 g / mol to 300 g / mol, alternatively greater than 0 g / mol to 275 g / mol, alternatively greater than 0 g / mol to 250 g / mol, alternatively greater than 0 g / mol to 225 g / mol, alternatively greater than 0 g / mol to 200 g / mol. In certain embodiments, including the ranges described above, the (B) polyol has an OH equivalent weight of at least 30 g / mol. Methods for determining OH equivalent weight based on functionality and molecular weight of a given polyol are known in the art.

[0052] In these or other embodiments, the (B) polyol has a functionality of 2 to -10, alternatively 2 to 9, alternatively 2 to 8, alternatively 2 to 7, alternatively 3 to 6.

[0053] In specific embodiments, the (B) polyol comprises, alternatively consists essentially of, or yet further consists of one or more polyether polyols. In other words, in these embodiments, the (B) polyol typically does not contain any polyol that is not a polyether polyol. Specific examples of specific polyether polyols include sucrose / glycerol initiated polyether polyols of 4.9 functionality, propoxylated glycerol (polyether triol), and sucrose / glycerol initiated polyether polyols of 7.0 functionality.

[0054] It will be appreciated that when the (B) polyol comprises a blend of two or more different polyols, the above properties can be based on the overall (B) polyol, i.e., the properties of the individual polyols averaged over the (B) polyol, or can relate to a specific polyol in the polyol blend. Typically, these properties relate to the overall (B) polyol.

[0055] In certain embodiments, the (A) organopolysiloxane is present in the (1) isocyanate-reactive component in an amount of > 10 to < 99, alternatively > 15 to < 99, alternatively > 20 to < 99, alternatively > 25 to < 99, alternatively > 30 to < 99, alternatively > 35 to < 99, alternatively > 40 to < 99, alternatively > 45 to < 99, alternatively > 50 to < 99, alternatively > 10 to < 98, alternatively > 10 to < 71, alternatively > 51 to < 98, alternatively > 52 to < 96, alternatively > 53 to < 94, optionally > 54 to < 92, alternatively > 55 to < 90, alternatively > 56 to < 88, alternatively > 57 to < 86, alternatively > 58 to < 84, alternatively > 59 to < 82, alternatively > 60 to < 80 weight percent based on the total weight of the (A) organopolysiloxane and the (B) polyol. In other embodiments, the (A) organopolysiloxane is present in the (1) isocyanate-reactive component in an amount of > 10 to < 30, alternatively > 10 to < 25, alternatively > 10 to < 20, alternatively > 11 to < 19, alternatively > 12 to < 18, alternatively > 13 to < 17, alternatively > 14 to < 16 weight percent based on the total weight of the (A) organopolysiloxane and the (B) polyol. Thus, component (B) makes up the remainder of the total weight of components (A) and (B) within these ranges. In specific embodiments, the (A) organopolysiloxane is present in the (1) isocyanate-reactive component in an amount of 60 to 75, alternatively 65 to 75, alternatively 70 to 75 weight percent based on the total weight of components (A) and (B). In certain embodiments, the (A) organopolysiloxane is present in the composition in an amount of 15 to 80 weight percent based on the total weight of the composition.

[0056] In certain embodiments, the weight % of silicone in the backbone of the foamed polyurethane article formed from the composition based on the components of the (1) isocyanate-reactive component used (i.e., not considering (C) polyisocyanate described below) is from 5 wt % to 80 wt %, alternatively from 5 wt % to 70 wt %. An organopolysiloxane having terminal methyl alcohol functionality that is not a polyether group will have 100 wt % of a silicone backbone, and thus the remainder of the backbone in the foamed polyurethane article will be attributed to (B) polyol. However, when (A) organopolysiloxane comprises polyether pendant groups as the methyl alcohol functionality, the backbone in the foamed polyurethane article from (1) isocyanate-reactive component is not 100 wt %, but is a function of the chain length of the polyether groups as the methyl alcohol functionality. Typically, in such embodiments, (A) organopolysiloxane having polyether pendant groups as the methyl alcohol functionality has at least 25 wt % of a silicone backbone based on the total weight of (A) organopolysiloxane.

[0057] In specific embodiments, (1) isocyanate-reactive component consists essentially of (A) organopolysiloxane, (B) polyol, and optionally any chain extender or crosslinker. In this context, "consists essentially of" means that (1) isocyanate-reactive component is free of components other than (A) organopolysiloxane and (B) polyol that react with isocyanate to produce urethane (urethane) linkages. Thus, even when (1) isocyanate-reactive component consists essentially of (A) organopolysiloxane and (B) polyol, (1) isocyanate-reactive component can include other components or additives, such as any of the other components or optional additives described below, so long as such other components or optional additives do not themselves react with isocyanate to produce urethane linkages.

[0058] The composition also includes (2) an isocyanate component comprising (C) a polyisocyanate. Suitable (C) polyisocyanates have two or more isocyanate functional groups and include conventional aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. The (C) polyisocyanate can be selected from the group consisting of diphenylmethane diisocyanate ("MDI"), polymeric diphenylmethane diisocyanate ("pMDI"), toluene diisocyanate ("TDI"), hexamethylene diisocyanate ("HDI"), dicyclohexylmethane diisocyanate ("HMDI"), isophorone diisocyanate ("IPDI"), cyclohexyl diisocyanate ("CHDI"), naphthalene diisocyanate ("NDI"), phenyl diisocyanate ("PDI"), and combinations thereof. In certain embodiments, the (C) polyisocyanate comprises, consists essentially of, or is pMDI. In one embodiment, the (C) polyisocyanate has the formula OCN-R-NCO, where R is an alkyl moiety, an aryl moiety, or an aralkyl moiety. In this embodiment, the (C) polyisocyanate can comprise any number of carbon atoms, typically 4 to 20 carbon atoms.

[0059] Specific examples of suitable (C) polyisocyanates include alkylene diisocyanates having 4 to 12 carbons in the alkylene moiety, such as 1,12-dodecane diisocyanate, 2-ethyl-1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, and 1,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates such as 1,3- and 1,4-cyclohexane diisocyanate and any mixture of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures; and aromatic diisocyanates and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, mixtures of 4,4'-, 2,4'- and 2,2-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates, and mixtures of MDI and toluene diisocyanate (TDI).

[0060] (C) Polyisocyanate can include modified polyvalent isocyanate, i.e. products obtained by partial chemical reaction of organic diisocyanates and / or polyisocyanates. Examples of suitable modified polyvalent isocyanates include diisocyanates and / or polyisocyanates containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups and / or urethane groups. Specific examples of suitable modified polyvalent isocyanates include organic polyisocyanates containing urethane groups and having an NCO content of 15 to 33.6 parts by weight based on the total weight, such as low molecular weight diols, triols, dialkylene glycols, trialkylene glycols or polyoxyalkylene glycols having a molecular weight of up to 6000; modified 4,4'-diphenylmethane diisocyanate or 2,4- and 2,6-toluene diisocyanate, examples of which dialkylene and polyalkylene glycols can be used individually or as mixtures include diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol and polyoxypropylene polyoxyethylene glycol or triol. Prepolymers containing NCO groups having an NCO content of 3.5 to 29 parts by weight based on the total weight of the (C) polyisocyanate and prepared from polyester polyols and / or polyether polyols; mixtures of 4,4'-diphenylmethane diisocyanate, 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate or polymeric MDI are also suitable. Furthermore, liquid polyisocyanates having an NCO content of 15 to 33.6 parts by weight based on the total weight of the (2) isocyanate component containing carbodiimide groups, such as based on 4,4'- and 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4'- and / or 2,6-toluene diisocyanate can also be suitable. Modified polyisocyanates can optionally be mixed together or with unmodified organic polyisocyanates such as 2,4'- and 4,4'-diphenylmethane diisocyanate, polymeric MDI, 2,4'- and / or 2,6-toluene diisocyanate.

[0061] It will be appreciated that (C) polyisocyanate can include any combination of two or more polyisocyanates that differ from one another based on functionality, molecular weight, viscosity, or structure. In particular embodiments, (C) polyisocyanate comprises, consists essentially of, or is pMDI.

[0062] (C) polyisocyanate typically has a functionality of 2.0 to 5.0, alternatively 2.0 to 4.5, alternatively 2.0 to 4.0, alternatively 2.0 to 3.5.

[0063] In these or other embodiments, (C) the polyisocyanate has 15 to 60 weight percent, alternatively 15 to 55 weight percent, alternatively 20 to 48.5 weight percent NCO. Methods for determining the NCO weight content are known in the art based on the functionality and molecular weight of the particular isocyanate.

[0064] (C) the polyisocyanate is typically present in the composition in an amount to provide an isocyanate index of 80 to 200, alternatively 80 to 130, alternatively 85 to 125, alternatively 90 to 120, alternatively 95 to 120, alternatively 100 to 120, alternatively 105 to 115. The isocyanate index is the molar ratio of NCO to isocyanate-reactive hydrogen functionality multiplied by 100. Isocyanate index and methods for its calculation are well known in the art.

[0065] The composition also includes (D) a blowing agent. Where a blowing agent is already present (e.g., water) or is generated during the reaction (e.g., carbon dioxide), the blowing agent can be referred to as a supplemental blowing agent, but the supplemental blowing agent can provide most or all of the blowing during the curing of the composition. (D) the blowing agent can be selected from chemical blowing agents, physical blowing agents, and combinations thereof. Examples of such blowing agents are described below.

[0066] The amount of blowing agent used can vary depending on the desired result. For example, the amount of blowing agent can be varied to adjust the final foam density and foam rise profile in the foamed polyurethane article, as well as the cell size.

[0067] In various embodiments, (D) the blowing agent comprises a chemical blowing agent, and the chemical blowing agent is selected from Si-OH compounds, which can be monomeric, oligomeric, or polymeric. In certain embodiments, the chemical blowing agent is selected from the group consisting of organosilanes and organosiloxanes having at least one silanol (Si-OH) group. Examples of suitable OH-functional compounds include dialkylsiloxanes, such as OH-terminated dimethylsiloxane. Such siloxanes can have a relatively low viscosity, such as 10 to 5,000 mPa-s, 10 to 2,500 mPa-s, 10 to 1,000 mPa-s, 10 to 500 mPa-s, or 10 to 100 mPa-s at 25 °C.

[0068] In particular embodiments, the chemical blowing agent comprises water, alternatively is water. The amount of water present in the total mass of the composition (prior to reaction) is typically 0.02 to 1.00 weight percent, alternatively 0.03 to 0.9 weight percent, alternatively 0.05 to 0.8 weight percent, alternatively 0.1 to 0.7 weight percent, based on the total weight of the composition.

[0069] In various embodiments, the composition includes a physical blowing agent. The physical blowing agent can be used with or in place of a chemical blowing agent.

[0070] In various embodiments, the physical blowing agent is a blowing agent that undergoes a phase change from a liquid to a gas during exposure to atmospheric pressure and a temperature of > 10°C, or > 20°C, or > 30°C, or > 40°C, or > 50°C, or > 60°C, or > 70°C, or > 80°C, or > 90°C, or > 100°C. The boiling temperature generally depends on the specific type of physical blowing agent.

[0071] Useful physical blowing agents include hydrocarbons such as pentane and hexane; halogenated (e.g., chlorinated and / or fluorinated) hydrocarbons such as dichloromethane, chloroform, trichloroethane, chlorofluorocarbons, and hydrochlorofluorocarbons ("HCFCs"); ethers; ketones; and esters such as methyl formate, ethyl formate, methyl acetate, or ethyl acetate. The physical blowing agent can be a liquid or a gas, and the above examples are generally used as liquids that volatilize during foam production. Examples of physical blowing agents that can be gases at room temperature include air, nitrogen, and / or carbon dioxide. In particular embodiments, the physical blowing agent comprises or is n-pentane and / or cyclopentane. In certain embodiments, the physical blowing agent comprises a compound selected from the group consisting of propane, butane, isobutane, isobutene, isopentane, cyclopentane, n-pentane, dimethyl ether, or mixtures thereof. In many embodiments, the blowing agent comprises a compound that is inert, i.e., does not react with other components of the composition. In this context, inert refers to reactivity, not volatility.

[0072] In various embodiments, the physical blowing agent comprises a hydrofluorocarbon ("HFC"). "Hydrofluorocarbon" and "HFC" are interchangeable terms and refer to an organic compound containing hydrogen, carbon, and fluorine. The organic compound is substantially free of halogens other than fluorine.

[0073] Examples of suitable HFCs include aliphatic compounds such as 1,1,1,3,3- pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1- fluorobutane, nonafluorocyclopentane, perfluoro-2-methylbutane, 1-fluorohexane, perfluoro-2,3-dimethylbutane, perfluoro-1,2-dimethylcyclobutane, perfluorohexane, perfluoroisohexane, perfluorocyclohexane, perfluoroheptane, perfluoroethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and perfluorooctane, 1,1,1,2-tetrafluoroethane (HFC-134a); and aromatic compounds such as fluorobenzene, 1,2-difluorobenzene; 1,4-difluorobenzene, 1,3-difluorobenzene; 1,3,5-trifluorobenzene; 1,2,4,5-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,3,4-tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, and 1-fluoro-3-(trifluoromethyl)benzene. In certain embodiments, HFC-365mfc and HFC-245fa can be preferred due to their increased availability and ease of use, with HFC-365mfc having a higher boiling point than HFC-245fa, which can be useful in certain applications. For example, HFCs with a boiling point higher than 30 °C, such as HFC-365mfc, can be desirable because they do not need to be liquefied during foam processing.

[0074] Another example of a physical blowing agent is a hydrofluoroolefin (HFO) such as trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze, available from Honeywell under the trade name Solstice ze), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd, available from Arkema under the trade name Forane), 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf, available from Honeywell under the trade name Solstice yf, and from Chemours under the trade name Opteon YF), cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z, available from Chemours under the trade name Opteon MZ), and Opteon 1150.

[0075] In certain embodiments, the (D) blowing agent and the composition are free of any physical blowing agent that is added discretely in or to the composition. In other words, a nominal amount of gas can be inherently formed during curing of the composition, which gas is not considered a physical blowing agent for purposes of the present disclosure because it is not included as a discrete component in the composition or the (D) blowing agent. In specific embodiments, water is the only (D) blowing agent present in the composition.

[0076] (D) The blowing agent can be present with components (A) and (B) in (1) the isocyanate-reactive component, or can be a separate component in the composition.

[0077] The composition further comprises (E) a catalyst.

[0078] In one embodiment, the (E) catalyst comprises a tin catalyst. Suitable tin catalysts include tin (II) salts of organic carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate, and tin (II) laurate. In one embodiment, the (E) catalyst comprises dibutyltin dilaurate, which is a dialkyl tin (IV) salt of an organic carboxylic acid. Specific examples of suitable organometallic catalysts, such as dibutyltin dilaurate, are available from Air Products and Chemicals, Inc., Allentown, PA, under the trademark Organometallic catalysts can also include other dialkyl tin (IV) salts of organic carboxylic acids, such as dibutyl tin diacetate, dibutyl tin maleate, and dioctyl tin diacetate.

[0079] Examples of other suitable catalysts include iron (II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines, including tris(N,N-dimethylaminopropyl)-hexahydrotriazine; tetraalkylammonium hydroxides, including tetramethylammonium hydroxide; alkali metal hydroxides, including sodium hydroxide and potassium hydroxide; alkali metal alkoxides, including sodium methoxide and potassium isopropoxide; and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and / or pendant OH groups.

[0080] Other examples of other suitable catalysts, particularly trimerization catalysts, include N,N,N-dimethylaminopropyl hexahydrotriazine, potassium, potassium acetate, N,N,N-trimethylisopropylamine / formate salt, and combinations thereof.

[0081] Other suitable catalysts, particularly tertiary amine catalysts, include dimethylaminoethanol, dimethylaminoethoxyethanol, triethylamine, N,N,N',N'-tetramethylethylenediamine, triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane), N,N-dimethylaminopropylamine, N,N,N',N',N"-pentamethyldipropylenetriamine, tris(dimethylaminopropyl)amine, N,N-dimethylpiperazine, tetramethyliminobis(propylamine), dimethylbenzylamine, trimethylamine, triethanolamine, N,N-diethylethanolamine, N-methylpyrrolidone, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylamino-ethyl)ether, N,N-dimethylcyclohexylamine ("DMCHA"), N,N,N',N',N"-pentamethyldiethylenetriamine, 1,2-dimethylimidazole, 3-(dimethylamino)propylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and combinations thereof. (E) Catalysts can include tertiary amines based on 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU") that are delayed action. Alternatively or additionally, (E) catalysts can include N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethylether and / or ethylenediamine. Tertiary amine catalysts can be further modified for use as delayed action catalysts by the addition of approximately the same stoichiometric amount of an acid containing acidic protons such as phenol or formic acid. Such delayed action catalysts are commercially available from Air Products and Evonik.

[0082] (E) Catalysts can be used alone or in a carrier vehicle. Carrier vehicles are known in the art and are further described below as an optional component of the composition. If a carrier vehicle is used and (E) catalyst is dissolved, the carrier vehicle can be referred to as a solvent. The carrier vehicle can be isocyanate-reactive, for example, an alcohol-functional carrier vehicle such as dipropylene glycol.

[0083] (E) Catalysts can be used in various amounts. (E) Catalysts can include any combination of different catalysts. (E) Catalysts can be present with components (A) and (B) in (1) the isocyanate-reactive component, or can be a separate component in the composition.

[0084] The composition can optionally further comprise an additive component. The additive component can be selected from the group consisting of catalysts, blowing agents, plasticizers, crosslinking agents, chain extenders, chain terminators, wetting agents, surface modifiers, surfactants, waxes, foam stabilizers, moisture scavengers, desiccants, viscosity reducers, cell size reducing compounds, reinforcing agents, dyes, pigments, colorants, fillers, flame retardants, mold release agents, antioxidants, compatibilizers, ultraviolet light stabilizers, thixotropic agents, anti-aging agents, lubricants, coupling agents, solvents, rheology promoters, adhesion promoters, thickening agents, flame retardants, smoke suppressants, antistatic agents, antimicrobials, and combinations thereof.

[0085] One or more of the additives can be present in any suitable weight percent (wt.%) of the composition, such as from about 0.1 wt.% to about 15 wt.%, from about 0.5 wt.% to about 5 wt.%, or about 0.1 wt.% or less, about 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, or about 15 wt.% or more of the composition. A person skilled in the art can readily determine a suitable amount of an additive depending on, for example, the type of additive and the desired result. Certain optional additives are described in more detail below.

[0086] Suitable carrier vehicles include linear and cyclic organosilicon, organic oils, organic solvents, and mixtures of these.

[0087] The carrier vehicle can also be a low viscosity organopolysiloxane or volatile methylsiloxane or volatile ethylsiloxane or volatile methyl ethyl siloxane having a viscosity in the range of 1 mm 2 / second to 1,000 mm 2 / second at 25°C, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, and polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, octanoyl polymethylsiloxane, and any mixture thereof.

[0088] Suitable surfactants (or "foaming aids") include silicone polyethers, oxirane polymers, oxetane polymers, copolymers of oxirane and oxetane, other nonionic surfactants, and combinations thereof. When the composition comprises a silicone polyether as a surfactant, the surfactant is different from component (A), which is (1) a reactive component of the isocyanate-reactive component other than a surfactant. Moreover, component (A) is present in the composition at a concentration much higher than the surfactant. Additional suitable surfactants can include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, or mixtures of such surfactants.

[0089] In various embodiments, the composition comprises a fluorocarbon surfactant or a fluorinated surfactant. The fluorinated surfactant can be any of those compounds known in the art that contain a fluorine atom on carbon and are also surface active. These fluorinated surfactants can be organic or silicon-containing. For example, the fluorinated organic surfactant can be a perfluorinated polyether, such as those having repeating units of the formula:

[0090] or -CF2CF2O- and mixtures of such units.

[0091] The silicon-containing fluorinated surfactant can be, for example, a siloxane containing organic groups bonded to fluorine, such as a siloxane having repeating units of the formula:

[0092]

[0093] In various embodiments, the addition of the fluorinated surfactant to the composition reduces the density of the cured foam. Generally, increasing the amount of fluorinated surfactant in the composition reduces the density of the foamed polyurethane article. This is particularly true for slow-cure systems, where the surfactant stabilizes the bubbles while the network is forming and curing.

[0094] In various embodiments, the composition further comprises an organopolysiloxane resin ("resin"). Suitable resins are as described above. In certain embodiments, the resin is an MQ resin. The resin can be used to stabilize the foamed polyurethane article, i.e., the resin can be a foam stabilizer.

[0095] Suitable pigments are known in the art. In various embodiments, the composition further comprises carbon black, for example acetylene black.

[0096] The composition can include one or more fillers. The fillers can be one or more reinforcing fillers, non-reinforcing fillers, extending fillers, or mixtures thereof. Examples of finely divided reinforcing fillers include high surface area fumed and precipitated silicas, including rice hull ash and to some extent calcium carbonate. Fumed silicas can include surface functionalized types, such as hydrophilic or hydrophobic, and are available from Cabot Corporation under the CAB-O-SIL tradename. Examples of finely divided non-reinforcing fillers include ground quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, and carbon black, talc, and wollastonite. Other fillers that can be used alone or in addition to the above include carbon nanotubes, e.g., multi-walled carbon nanotubes, aluminite, hollow glass spheres, alumina, calcium sulfate (plaster of paris), gypsum, calcium sulfate, magnesium carbonate, clays such as kaolin, alumina trihydrate, magnesium hydroxide (brucite), graphite, copper carbonate such as malachite, nickel carbonate such as zarachite, barium carbonate such as witherite, and / or strontium carbonate such as strontianite. Additional alternative fillers include aluminum oxides, silicates selected from the group consisting of olivine group, garnet group; aluminosilicates; cyclosilicates; chain silicates; and sheet silicates. In certain embodiments, the composition includes at least one filler that includes hollow particles, e.g., hollow spheres. Such fillers can be used to help the porosity and / or overall void content of the foamed polyurethane article. When used, the fillers can be used in the composition in an amount of 0.01 to 50 weight percent, alternatively 0.05 to 40 weight percent, alternatively 0.1 to 35 weight percent, based on the total weight of the composition. Further, the fumed silica, if used, can be used in an amount of 0.01 to 5 weight percent, alternatively 0.05 to 3 weight percent, alternatively 0.1 to 2.5 weight percent, alternatively 0.2 to 2.2 weight percent, based on the total weight of the composition.

[0097] The fillers, if present, can optionally be surface treated with a treating agent. Treating agents and treating methods are understood in the art. Surface treatment of fillers is typically performed, for example, with fatty acids or fatty acid esters such as stearates or with organosilanes, organosiloxanes, or organosilazanes such as hexaalkyldisilazanes or short-chain siloxane diols. Typically, surface treatment renders the fillers hydrophobic and thus more easily handled and obtain a uniform mixture with other components in the composition. Silanes such as those of the formula R 4 e Si(OR 5 ) 4-e where R 4 is a substituted or unsubstituted monovalent hydrocarbon radical of 6 to 20 carbon atoms, for example, alkyl radicals such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, and aralkyl radicals such as benzyl and phenylethyl, R 5alkyl of 1 to 6 carbon atoms, and the subscript "e" is equal to 1, 2, or 3.

[0098] In various embodiments, the composition further comprises an adhesion promoter or adhesion imparting agent. The adhesion imparting agent can improve the adhesion of the foamed polyurethane article to the base material with which it is in contact during curing. In certain embodiments, the adhesion imparting agent is selected from organosilicon compounds having at least one alkoxy group bonded to a silicon atom in the molecule. Examples of the alkoxy group are a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. In addition, examples of non-alkoxy groups bonded to the silicon atom of the organosilicon compound are: substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, haloalkyl groups, and the like; epoxy group-containing monovalent organic groups such as a 3-glycidyloxypropyl group, a 4-glycidyloxybutyl group, or a similar glycidoxyalkyl group; a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, or a similar epoxycyclohexylalkyl group; and a 4-oxiranylbutyl group, an 8-oxiranyloctyl group, or a similar oxiranylalkyl group; acryl group-containing monovalent organic groups such as a 3-methacryloyloxypropyl group, and the like; and a hydrogen atom.

[0099] In specific embodiments in which the adhesion imparting agent comprises an organosilicon compound, the organosilicon compound has a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom. In addition, due to the ability to impart good adhesion with respect to various types of base materials, the organosilicon compound can have at least one epoxy group-containing monovalent organic group in the molecule. Examples of this type of organosilicon compound are organosilane compounds, organosiloxane oligomers, and alkyl silicate. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate are linear structures, partially branched linear structures, branched structures, cyclic structures, and network structures. Linear structures, branched structures, and network structures are typical. Examples of this type of organosilicon compound are: silane compounds such as a 3-glycidyloxypropyltrimethoxysilane, a 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, a 3-methacryloyloxypropyltrimethoxysilane, and the like; siloxane compounds having at least one silicon-bonded alkenyl group or a silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group in the molecule; mixtures of a silane compound or a siloxane compound having at least one silicon-bonded alkoxy group and a siloxane compound having at least one silicon-bonded hydroxyl group and at least one silicon-bonded alkenyl group in the molecule; and methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate.

[0100] In particular embodiments, the composition, particularly the (1) isocyanate-reactive component, can also include a chain extender. Suitable chain extenders include any of the components listed above as initiators for the (B) polyol, which can be used alone or in combination as a chain extender, when present, separate and apart from the (B) polyol. Chain extenders typically include hydroxyl groups at each terminus.

[0101] Any optional additives, if used in the composition, can be present in the (1) isocyanate-reactive component or as a separate component in the composition. Alternatively, non-isocyanate-reactive optional additives, such as fillers and the like, can be included in the (2) isocyanate component. Typically, the composition is a 2k (two-component) composition, where the (2) isocyanate component consists of the (C) polyisocyanate, and the (1) isocyanate-reactive component includes components (A), (B), (D), (E), and any optional components used in the composition.

[0102] In certain embodiments, the (1) isocyanate-reactive component has a viscosity of less than 1,500 centipoise, alternatively less than 1,400 centipoise, alternatively less than 1,300 centipoise, alternatively less than 1,200 centipoise, alternatively less than 1,100 centipoise, alternatively less than 1,000 centipoise, alternatively less than 900 centipoise, alternatively less than 875 centipoise, alternatively less than 850 centipoise, at 25 °C. Dynamic viscosity can be measured via a TA Instruments AR 2000 rheometer with 45 mm cone and plate geometry at a constant shear rate of 10 s -1 Motion viscosity can be measured according to ASTM D445. These ranges apply even when the composition is a 2k composition and the (1) isocyanate-reactive component includes all of the materials in the composition except for the (C) polyisocyanate. This viscosity range allows the (1) isocyanate-reactive component to flow freely, which is advantageous for certain end-use applications that require foaming in or on certain substrates or articles, including those that define a gap and / or orifice.

[0103] The composition can be prepared by combining (1) the isocyanate-reactive component and (2) the isocyanate component, and components (D) and (E) and any optional components, if not present in the (1) isocyanate-reactive component, in any order of addition. As described in greater detail below, the composition can be a one-component composition, a two-component or 2K composition, or a multi-component composition. When the (1) isocyanate-reactive component and (2) isocyanate component are combined, particularly in the presence of the (E) catalyst, a reaction is initiated, which produces a foamed polyurethane article. The foamed polyurethane article can form at room temperature and ambient conditions. Alternatively, at least one condition, such as temperature, humidity, pressure, etc., can be selectively varied during the formation of the foamed polyurethane article.

[0104] Also disclosed is a foamed polyurethane article comprising the reaction product of the composition.

[0105] In many embodiments, the foamed polyurethane article is a closed-cell foam. In various embodiments, the foamed polyurethane article has a density < 1.5 grams per cubic centimeter (g / cm 3 , alternatively < 1.4 g / cm 3 , alternatively < 1.3 g / cm 3 , alternatively < 1.2 g / cm 3 , alternatively < 1.1 g / cm 3 , alternatively < 1.0 g / cm 3 , alternatively < 0.9 g / cm 3 , alternatively < 0.8 g / cm 3 , alternatively < 0.7 g / cm 3 , alternatively < 0.6 g / cm 3 , alternatively > 0.1 g / cm 3 to < 0.6 g / cm 3 .

[0106] If the density is too high, the foamed polyurethane article can be too heavy or too hard for certain applications. If the density is too low, the foamed polyurethane article can lack the structural integrity required for certain applications. The density of the foamed polyurethane article can be determined by methods understood in the art. For example, the density of the foamed polyurethane article can be measured by the Archimedes principle, using a balance and a density kit and following the standard instructions associated with such a balance and kit. An example of a suitable balance is a Mettler-Toledo XS205DU balance with density kit.

[0107] In various embodiments, the foamed polyurethane article has substantially uniform sized and / or shaped and / or distributed cells. In certain embodiments, the foamed polyurethane article has an average cell diameter of < 5 millimeters, alternatively < 2.5 millimeters, alternatively < 1 millimeter, alternatively < 0.75 millimeters, alternatively 0.3 to 0.7 millimeters, alternatively 0.4 to 0.6 millimeters.

[0108] The average cell diameter can be determined by methods known in the art. For example, ATSM Method D3576-15 can be used with the following modifications: (1) image the foam using an optical or electronic microscope instead of projecting the image on a screen; and (2) draw a line of known length that spans greater than 15 cells instead of a 30 mm line.

[0109] In these or other embodiments, the foamed polyurethane article is substantially resistant to shrinkage after formation. By substantially resistant to shrinkage is meant that the foamed polyurethane article does not shrink by more than 20%, alternatively not more than 18%, alternatively not more than 16%, alternatively not more than 14%, alternatively not more than 12%, alternatively not more than 10%, alternatively not more than 8%, alternatively not more than 6%, alternatively not more than 4%, alternatively not more than 2% in any dimension over a period of time. The period of time can be one hour, one day, one week, one month, one year, or more. The foamed polyurethane article typically has one or more glass transition temperatures (T g ), where the highest value of the one or more T g is at least 15 °C, alternatively at least 20 °C, alternatively at least 25 °C, alternatively at least 30 °C. The T g is evaluated as the peak value of the tan delta peak, where tan delta is the ratio of loss modulus to storage modulus, as measured from a dynamic mechanical thermal analysis (DMTA) experiment at a strain cycling frequency of 1 Hz and a temperature scan of 3 °C / min over a range covering at least 0 °C to 70 °C or more.

[0110] The foamed polyurethane article, as well as the composite article comprising the substrate and the foamed polyurethane article together, can be formed by disposing the composition on the substrate and curing the composition.

[0111] The composition can be disposed or distributed on the substrate in any suitable manner. Typically, the composition is applied in wet form by wet coating techniques. The composition can be applied by i) spin coating; ii) brushing; iii) drop coating; iv) spraying; v) dip coating; vi) roller coating; vii) flow coating; viii) slot coating; ix) gravure coating; x) Meyer bar coating; or xi) a combination of any two or more of i) to x).

[0112] The substrate is not limited and can be any substrate. The foamed polyurethane article can be separated from the substrate, for example if the substrate is a mold, or can be physically and / or chemically bonded to the substrate according to its selection. The substrate can optionally have a continuous or discontinuous shape, size, dimension, surface roughness, and other characteristics.

[0113] Alternatively, the substrate can comprise a plastic, which can be thermoset and / or thermoplastic. However, the substrate can alternatively be or include glass, ceramic, metal such as titanium, magnesium, aluminum, carbon steel, stainless steel, nickel-plated steel, or alloys of these metals or multiple metals, or combinations of different materials. Because the composition can be cured at ambient conditions, elevated temperatures, which can damage certain substrates, are not required to achieve curing.

[0114] Specific examples of suitable substrates include polymeric substrates such as polyamides (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyesters; polyolefins such as polyethylene (PE), ethylene / acidic monomer copolymers (such as available under the trade designation Surlyn from Dow), polypropylene (PP), and polybutylene; polystyrene (PS) and other styrenic resins SB rubber; polyoxymethylene (POM); polycarbonates (PC); polymethyl methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (PPE); polyimides (PI); polyamide-imides (PAI); polyetherimides (PEI); polysulfones (PSU); polyether sulfones; polyketones (PK); polyether ketones; polyvinyl alcohol (PVA); polyether ether ketone (PEEK); polyether ketone ketone (PEKK); polyarylate (PAR); polyether nitrile (PEN); phenolic resins; phenoxy resins; cellulose such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene; thermoplastic elastomers such as polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluorine type; and copolymers and combinations thereof. The thermoset resin can include an epoxy resin, a polyurethane, a polyurea, a phenolic resin, a urea-formaldehyde resin, or combinations thereof. The substrate can include a coating, film, or layer disposed thereon. Coatings made from polymer latexes such as latexes made from acrylic acid, acrylate, methacrylate, methacrylic acid, other alkyl acrylates, other alkyl acrylic acids, styrene, isoprene butylene monomers, or latexes made from alkyl esters of the foregoing acid monomers, or latexes made from copolymers of the foregoing monomers can be used. Composites based on any of these resins can be used as the substrate by combination with glass fibers, carbon fibers, or solid fillers such as calcium carbonate, clay, aluminum hydroxide, aluminum oxide, silica, glass spheres, sawdust, wood fibers, or combinations thereof.

[0115] In particular embodiments, the substrate defines at least one gap, and disposing the composition includes disposing the composition in the at least one gap such that the foamed polyurethane article is present within the gap in the composite article. Due to the low viscosity of the composition, the composition is generally flowable and will conform to the shape of the substrate under ambient conditions, including room temperature and atmospheric pressure.

[0116] In one particular embodiment, the substrate includes a battery cell, and the composite article includes a battery pack. However, the composition and foamed polyurethane article can be used in other end-use applications, including as a potting or encapsulating agent in end-uses other than battery packs, such as for electrical circuits, and for purposes other than a potting or encapsulating agent.

[0117] Embodiment 1 is directed to an isocyanate-reactive composition comprising: (A) an organopolysiloxane having, on average, at least two methanol functional groups per molecule; and (B) a polyol; wherein the (A) organopolysiloxane is present in an amount of > 10 wt% to < 99 wt% based on the total weight of the (A) organopolysiloxane and the (B) polyol.

[0118] Embodiment 2 is directed to a composition for making a foamed polyurethane article, the composition comprising: (1) an isocyanate-reactive component, the (1) isocyanate-reactive component being the isocyanate-reactive component of Embodiment 1; and (2) an isocyanate component, the isocyanate component comprising (C) a polyisocyanate; wherein the composition further comprises: (D) a blowing agent; and (E) a catalyst.

[0119] Embodiment 3 is directed to the composition of Embodiment 1 or 2, wherein: (i) the methanol functional groups are the same as one another; (ii) the methanol functional groups have the general formula -D-OH, where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each moiety indicated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not both 0; or (iii) both (i) and (ii). a -(C b H 2b O) c -H, where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each moiety indicated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not both 0; or (iii) both (i) and (ii).

[0120] Embodiment 4 is directed to the composition of any one of Embodiments 1-3, wherein in at least one of the methanol functional groups: (i) subscript D is a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 1, and subscript c is 0, such that the methanol functional group has the general formula -D-OH; (ii) the methanol functional group is a terminal group; or (iii) both (i) and (ii).

[0121] Embodiment 5 relates to the composition of any one of embodiments 1-3, wherein: (i) at least one of the carbinol functional groups has the following general formula:

[0122] -D-O a -[C2H4O] x [C3H6O] y [C4H8O] z -H;

[0123] wherein D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, 0 < x < 500, 0 < y < 500, and 0 < z < 500, provided that 1 < x + y + z < 500; (ii) the carbinol functional groups are pendant; or (iii) both (i) and (ii).

[0124] Embodiment 6 relates to the composition of any one of embodiments 1-3, wherein: (i) component (A) has an OH equivalent weight of 400 g / mol to 1,200 g / mol; (ii) component (A) has a viscosity of 1 mPa-s to 1,000 mPa-s at 25 °C; (iii) component (A) is substantially linear; (iv) at least one of the carbinol functional groups is pendant; (v) at least one of the carbinol functional groups is terminal; (vi) component (A) is present in the composition in an amount of 15 wt% to 80 wt%, based on the total weight of the composition; (vii) component (A) has the following general formula:

[0125]

[0126] wherein each R is an independently selected hydrocarbyl group or comprises a carbinol functional group, provided that at least two of R independently comprise a carbinol functional group, and subscript n is 0 to 100; (viii) any combination of (i) to (vii).

[0127] Embodiment 7 relates to the composition of any one of embodiments 1-6, wherein component (B): (i) has a number average functionality of 2 to 8; (ii) has an average OH equivalent weight of greater than 0 to 2,000; (iii) is a polyether polyol; or (iv) any combination of (i) to (iii).

[0128] Embodiment 8 relates to the composition of any one of embodiments 2-7, wherein: (i) component (C) comprises polymeric MDI (pMDI); (ii) the isocyanate-reactive component has a viscosity of less than 1,000 mPa-s at 25 °C; or (iii) both (i) and (ii).

[0129] Embodiment 9 relates to a foamed polyurethane article comprising the reaction product of the composition according to any one of embodiments 1-8.

[0130] Embodiment 10 relates to the foamed polyurethane article according to embodiment 9 having: (i) a closed cell structure; (ii) a glass transition temperature (Tg) greater than 20 °C; (iii) a density of 0.1 g / cm3to 0.6 g / cm3; or (iv) any combination of (i) to (iii). g ) (iii) a density of 0.1 g / cm3to 0.6 g / cm3; or (iv) any combination of (i) to (iii). 3 ) (iii) a density of 0.1 g / cm3to 0.6 g / cm3; or (iv) any combination of (i) to (iii). 3 ) (iii) a density of 0.1 g / cm3to 0.6 g / cm3; or (iv) any combination of (i) to (iii).

[0131] Embodiment 11 relates to the use of the foamed polyurethane article according to embodiments 9 or 10 as a potting agent, a pouring agent, a thermal insulation layer, and / or in automotive applications.

[0132] Embodiment 12 relates to a method of making a composite article, the method comprising: disposing a composition on a substrate, and curing the composition to obtain a foamed polyurethane article on the substrate and make the composite article, wherein the composition is the composition according to any one of embodiments 1 to 8.

[0133] Embodiment 13 relates to the method according to embodiment 12, wherein the substrate defines at least one gap, and disposing the composition comprises disposing the composition in the at least one gap, such that the foamed polyurethane article is present within the gap in the composite article.

[0134] Embodiment 14 relates to the method according to embodiments 12 or 13, wherein the substrate comprises a battery cell, and the composite article comprises a battery pack.

[0135] Embodiment 15 relates to a composite article formed according to the method of any one of embodiments 12 to 14.

[0136] Industrial Applications

[0137] The compositions, foamed polyurethane articles, and methods of the present disclosure can be used for a variety of end applications and are not limited to a particular one. Examples of suitable applications include space-filling applications, automotive applications (e.g., for control modules), and the like. The foamed polyurethane articles can be used to at least partially cover or encapsulate articles such as batteries and other electronic components. The foamed polyurethane articles can also be used for thermal insulation. Further, the foamed polyurethane articles can be used as fire-blocking. In general, the foamed polyurethane articles of the present disclosure provide a combination of desirable physical properties relative to conventional foams, including one or more of: reduced weight, reduced density, increased heat resistance, increased stability, and the like. The foamed polyurethane articles can be formed in environments where hydrogen gas formation is of concern. Additionally, the foamed polyurethane articles can be foamed at or about room temperature, which is suitable for temperature sensitive applications.

[0138] The following examples, which illustrate embodiments of the present disclosure, are intended to illustrate and not to limit the application. Unless otherwise indicated, all reactions were conducted under air and all components were purchased from various commercial suppliers or otherwise obtained.

[0139] The following equipment and characterization procedures / parameters were used to evaluate various physical properties of the compounds and compositions prepared in the following examples.

[0140] Kinematic viscosity was measured according to ASTM D445, unless otherwise indicated.

[0141] For silicone-containing materials (components (Al), (A2), (A3), (Fl), and (F2)), capillary viscosity (kinematic viscosity through a glass capillary) was measured by Dow Corning Corporation Test Method CTM0004 Method of July 20, 1970. CTM0004 is known in the art and is based on ASTM D445, IP 71.

[0142] The dynamic viscosity of each B portion (described below) was measured on a TA Instruments AR 2000 rheometer with a 45 mm cone-plate geometry. Data were collected from 20 °C to 80 °C at a ramp rate of 3 °C / min at a constant shear rate of 10 s -1 The viscosity value at 25 °C was recorded from this measurement.

[0143] The initial dynamic viscosity of each reaction mixture listed in Tables 6-8 was measured in the absence of any catalyst or blowing agent (e.g., water) to avoid damage to the metal plates due to foaming / gelation during the viscosity measurement and clean-up process. The remaining components of Parts A and B were thoroughly mixed in the appropriate ratio (mass of B:A 1 :0.63) in a SpeedMixer DAC 150.1 FVZ from FlackTek Inc. using a Max 40 Tall cup at 2500 rpm for 6 seconds. Mixing was performed adjacent to the rheometer (AR2000 from TA Instruments of Delaware) to avoid transfer time of the reaction mixture. The calibration sequence step was 15 seconds long. The first measurement was taken 5 seconds after calibration and equilibration was complete. Measurements were taken at a constant temperature of 25 °C. After initiation of the mixture of isocyanate and the remainder of the mixture with a 45 mm cone-plate geometry at a constant shear rate of 10 s -1 The first time point for recording the reactive viscosity was recorded at ~27 seconds after initiation of the mixture of isocyanate and the remainder of the mixture with a 45 mm cone-plate geometry at a constant shear rate of 10 s

[0144] The NCO content by weight of component (C) (i.e., (C1), (C2), and (C3)) was determined according to ASTM D5155.

[0145] The various components utilized in the examples are listed in Table 1 below.

[0146] Table 1 : Components / Compounds Utilized

[0147]

[0148]

[0149] Examples 1-15 and Comparative Examples 1-4

[0150] Examples 1-15 and Comparative Examples 1-4 are compositions for preparing a foamed polyurethane article according to the general procedure described below. Specifically, each of Examples 1-15 and Comparative Examples 1-4 is a composition designed to have a total composition mass of about 12 to 15 grams. Tables 2-5 below show the relative amounts of each component from Table 1 used in Examples 1-15 and Comparative Examples 1-4. The “A-Part” in Tables 2-5 is the particular component (C) (i.e., component (C1), (C2), or (C3)) used in each composition of Examples 1-15 and Comparative Examples 1-4. The “B-Part” in Tables 2-5 includes all components except the particular component (C) in the A-Part. The values for the components in the B-Part are weight percentages (wt%) based on the total weight of the B-Part. The values for the A-Part (i.e., the particular component (C) used) are based on 100 parts by weight of the B-Part.

[0151] General Procedure

[0152] Using the compositions of Examples 1-15 and Comparative Examples 1-4, foamed polyurethane articles were prepared utilizing the General Procedure, as further described below after Tables 2-5. In the General Procedure, components (A) and (B) were weighed on an analytical balance in a Max 40 Tall FlackTek cup (40 gm tall cup) to obtain a polyol mixture. The remaining components of Part B were mixed with the polyol mixture in a SpeedMixer DAC 600.1 FVZ (hereinafter SpeedMixer) at 2000 rpm for 1 minute to obtain Part B. Then, Part A (i.e., the particular component (C)) was combined with Part B in the weight % and isocyanate index listed in Tables 2-5 below to obtain a reaction mixture. The reaction mixture was mixed in the SpeedMixer at 800 rpm for 5 seconds and then at 2000 rpm for 6 seconds. Immediately after mixing, the reaction mixture was removed from the SpeedMixer and the cup lid was removed under a fume hood. After a period of time for the removal of the cup lid, the polyurethane foam began to rise in the FlackTek cup. The FlackTek cup was held in an upright position without any interference and once the reaction and foaming began, the times for cream time, rise time, green strength, and about final strength, etc. were recorded. These parameters and properties will be further described below. TM DAC 600.1 FVZ (hereinafter SpeedMixer) at 2000 rpm for 1 minute to obtain Part B. Then, Part A (i.e., the particular component (C)) was combined with Part B in the weight % and isocyanate index listed in Tables 2-5 below to obtain a reaction mixture. The reaction mixture was mixed in the SpeedMixer at 800 rpm for 5 seconds and then at 2000 rpm for 6 seconds. Immediately after mixing, the reaction mixture was removed from the SpeedMixer and the cup lid was removed under a fume hood. After a period of time for the removal of the cup lid, the polyurethane foam began to rise in the FlackTek cup. The FlackTek cup was held in an upright position without any interference and once the reaction and foaming began, the times for cream time, rise time, green strength, and about final strength, etc. were recorded. These parameters and properties will be further described below.

[0153] Table 2: Compositions of Examples 1-5

[0154]

[0155]

[0156] Table 3: Compositions of Examples 6-10

[0157]

[0158]

[0159] Table 4: Compositions of Examples 11-15

[0160]

[0161]

[0162] Table 5: Compositions of Comparative Examples 1-4

[0163]

[0164]

[0165] As described above, polyurethane foamed articles (i.e., cured products) were formed from the compositions of Examples 1-15 and Comparative Examples 1-4 by the general procedure. However, due to performance failures, the cured products formed in Comparative Examples 2-4 were not further evaluated. Specifically, in Comparative Example 2, the liquid foam collapsed prior to curing. In Comparative Example 3, a polyurethane foam was initially formed, but the polyurethane foam of Comparative Example 3 shrunk overnight, which is undesirable for many end-use applications. Finally, in Comparative Example 3, as in Comparative Example 2, the liquid foam collapsed prior to curing.

[0166] The reaction kinetics of forming polyurethane foamed articles in Examples 1-15 and Comparative Example 1 were monitored, and the properties of the resulting foamed polyurethane articles were measured. Tables 6-8 below detail the kinetics and properties of the foamed polyurethane articles formed from the compositions of Examples 1-15 and Comparative Example 1. Any time range in Tables 6-8 is based on stop watch values related to two different tests. However, Example 3 was only monitored once and does not include such a range but only a single value. N / A in Tables 6-8 indicates not measured.

[0167] Table 6: Kinetics and Properties of Foamed Polyurethane Articles Formed with Compositions of Examples 1-5 and Comparative Example 1

[0168]

[0169]

[0170] Table 7: Kinetics and Properties of Foamed Polyurethane Articles Formed with Compositions of Examples 6-10

[0171]

[0172]

[0173] Table 8: Kinetics and Properties of Foamed Polyurethane Articles Formed with Compositions of Examples 11-15 Table 9: Kinetics and Properties of Foamed Polyurethane Articles Formed with Compositions of Comparative Examples 1-4

[0174]

[0175]

[0176] It is to be understood that the following claims are in no way limited to the specific compounds, compositions or methods described in the specific embodiments, which can vary between particular embodiments falling within the scope of the following claims.

Claims

1. A composition for preparing foamed polyurethane articles, the composition comprising: (1) An isocyanate reactive component, wherein the isocyanate reactive component comprises: (A) An organopolysiloxane having, on average, at least two methanol functional groups linked to silicon per molecule, wherein the at least two methanol functional groups are located at opposite terminal positions, and the methanol functional groups have the general formula -DO. a -(C b H 2b O) c -H, where D is a covalent bond or a divalent hydrocarbon linker having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each part indicated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not simultaneously 0; and (B) Polyols; Wherein, based on the total weight of the organopolysiloxane (A) and the polyol (B), the organopolysiloxane (A) is >10% by weight and <99% by weight; and Based on all silanoxy units present in said (A) organopolysiloxane, said (A) organopolysiloxane contains up to 5 mol% of T silanoxy units and / or Q silanoxy units, wherein said T silanoxy units have the formula [RSiO 3 / 2 ], and the Q-methylsilyloxy unit has the formula [SiO] 4 / 2 ]; (2) Isocyanate component, wherein the isocyanate component comprises (C) polyisocyanate; (D) foaming agents; and (E) Catalyst.

2. The composition according to claim 1, wherein: (i) The methanol functional groups are identical to each other.

3. The composition according to claim 2, wherein in at least one of the methanol functional groups: (i) subscript D is a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 1, and subscript c is 0, such that the methanol functional group has the general formula -D-OH; (ii) the methanol functional group is a terminal group; or (iii) both of (i) and (ii).

4. The composition according to claim 1 or 2, wherein: (i) At least one of the methanol functional groups has the following general formula: -DO a -[C2H4O] x [C3H6O] y [C4H8O] z -H; Where D is a covalent bond or a divalent hydrocarbon linker with 2 to 18 carbon atoms, the subscript a is 0 or 1, 0≤x≤500, 0≤y≤500, and 0≤z≤500, and the condition is 1≤x+y+z≤500.

5. The composition according to claim 1 or 2, wherein: (i) Component (A) has an OH equivalent of 400 g / mol to 1,200 g / mol; (ii) Component (A) has a viscosity of 1 mPa·s to 1,000 mPa·s at 25 °C; (iii) Component (A) is substantially linear; (iv) at least one of the methanol functional groups is a side group; (v) based on the total weight of the composition, component (A) is present in the composition in an amount of 15 wt% to 80 wt%; (vi) Component (A) has the following general formula: Each R is an independently chosen hydrocarbon group or contains a methanol functional group, and the subscript n is 0 to 100; or any combination of (viii)(i) to (vi).

6. A foamed polyurethane article comprising the reaction product of the composition according to claim 1.

7. A method for preparing composite material articles, the method comprising: Set the composition on the substrate, and The composition is cured to obtain a foamed polyurethane article on the substrate and the composite material article is prepared. The composition thereon is the composition according to claim 1.

8. The method of claim 7, wherein the substrate comprises a battery cell, and the composite material article comprises a battery pack.

9. A composite material article formed according to the method of claim 7 or 8.

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