Isocyanate-reactive components, compositions containing same, and foams formed therewith

Abstract

The isocyanate-reactive composition includes (A) a polyol, (B) a polysiloxane, and (C) a polyether alcohol compound. The foam-forming composition includes the isocyanate-reactive composition, (D) a polyisocyanate, (E) a catalyst, and (F) a blowing agent. The composition forms a foam upon reaction of at least components (A) and (D) in the presence of components (E) and (F).

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the entire benefit of U.S. Provisional Patent Application No. 63 / 122,932, filed December 8, 2020, and U.S. Provisional Patent Application No. 63 / 122,929, filed December 8, 2020, the contents of which are incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present disclosure relates generally to compositions, and more particularly to isocyanate-reactive components, compositions containing same for preparing foams, and foams formed therewith. [Background technology]

[0003] Foams are well known in the art and are utilized in a variety of end uses, including thermal insulation. Foams can be formed from a variety of chemical compositions and may utilize physical and / or chemical blowing agents. For example, polyurethane (PUR) and polyisocyanurate (PIR) foams are generally formed by reacting an isocyanate with a polyol in the presence of a blowing agent. Performance characteristics of foams, including hardness, density, flexibility, etc., are a function of the compositions utilized in their preparation. In many end uses of foams, it is desirable to minimize thermal conductivity without adversely affecting density. For example, thermal conductivity can be minimized simply by reducing the density of the foam. However, reducing density can render the foam unsuitable for various end uses. Summary of the Invention

[0004] An isocyanate-reactive composition for preparing foams is disclosed, which comprises (A) a polyol, (B) a polysiloxane, and (C) a polyether alcohol compound, wherein the (B) polysiloxane has the following formula: (R 1 3SiO 1 / 2 ) a (R2 2SiO 2 / 2 ) b (R’R 2 SiO 2 / 2 ) b’ (R 2 SiO 3 / 2 ) c (R’SiO 3 / 2 ) c’ (SiO 4 / 2 ) d where the subscripts a, b, b’, c, c’, and d are molar fractions such that a + b + b’ + c + c’ + d = 1, provided that 0 < a < 1, 0 ≤ b < 0.2, 0 ≤ b’ ≤ 0.1, 0 < c < 0.2, 0 ≤ c’ ≤ 0.1, 0 < d < 1, 0 ≤ b’ + c’ ≤ 0.1, and the ratio of subscript a to subscript d is 0.5 to 1.5 (a:d), and each R 1 is independently selected from a hydrocarbyl group having 1 to 30 carbon atoms, -OH, and H, and each R 2 is independently selected from R 1 and -OX, where each X is independently H, a hydrocarbyl group R having 1 to 30 carbon atoms, or a polyether moiety having the general formula -Y-R 3 (-[Y] j -Z) i where R 3 is a substituted or unsubstituted hydrocarbon segment, each Y is an independently selected oxyalkylene segment of the general formula (C n H 2n O) m where the subscript m is 1 to 50, the subscript n is independently selected from 2 to 4 in each part indicated by the subscript m, each Z is independently H or a resinous silicone moiety, the subscript i is 0 to 8, the subscript j is independently 0 or 1 in each part indicated by the subscript i, and each R’ contains an independently selected amino group. The polyether alcohol compound (C) has the general formula HO-Y-R 3 (-[Y] j -H) i where each Y, R 3 , subscript i, and subscript j are as defined above.

[0005] Also disclosed is a composition for preparing a foam. The composition includes an isocyanate-reactive composition, (D) a polyisocyanate, (E) a catalyst, and (F) a blowing agent. The composition forms a foam upon reaction of at least components (A) and (D) in the presence of components (E) and (F).

[0006] Foams formed using the compositions and methods for their preparation are also disclosed. DETAILED DESCRIPTION OF THE INVENTION

[0007] An isocyanate-reactive composition for preparing a foam is disclosed. Also disclosed are compositions that are curable and include the isocyanate-reactive composition. For clarity, the isocyanate-reactive composition may be referred to herein as the isocyanate-reactive component, to distinguish it from compositions that are curable and include an isocyanate-reactive component. Also disclosed are methods for preparing the foam and foams formed therefrom.

[0008] The isocyanate-reactive component comprises (A) a polyol. The polyol (A) is not limited so long as the isocyanate-reactive component and polyol (A) are capable of forming a foam, which is typically a function of the isocyanate index of the composition rather than the particular selection of polyol (A).

[0009] In certain embodiments, the polyol (A) comprises a polyether polyol. Suitable polyether polyols for the isocyanate-reactive component include, but are not limited to, products obtained by the polymerization of cyclic oxides, such as ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), tetrahydrofuran, or epichlorohydrin, in the presence of a multifunctional initiator. Suitable initiators contain multiple active hydrogen atoms. Catalysis for this polymerization can be either anionic or cationic, using catalysts such as KOH, CsOH, boron trifluoride, or double metal cyanide (DMC) catalysts such as zinc hexacyanocobaltate, or quaternary phosphazenium compounds. Initiators include, for example, neopentyl glycol; 1,2-propylene glycol; water; trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerol; amino alcohols such as ethanolamine, diethanolamine, and triethanolamine; 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 The initiator may be selected from alkanediols such as cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 2,5-hexanediol; ethylene glycol; diethylene glycol, triethylene glycol; bis-3-aminopropylmethylamine; ethylenediamine; diethylenetriamine; 9(1)-hydroxymethyloctadecanol, 1,4-bishydroxymethylcyclohexane; hydrogenated bisphenols; 9,9(10,10)-bishydroxymethyloctadecanol; 1,2,6-hexanetriol; and combinations thereof. Other initiators include other linear and cyclic amine-containing compounds.Exemplary polyamine initiators include ethylenediamine, neopentyldiamine, 1,6-diaminohexane; bisaminomethyltricyclodecane; bisaminocyclohexane; diethylenetriamine; bis-3-aminopropylmethylamine; 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-dimethyldipropylenetriamine; aminopropylimidazole; and combinations thereof. As understood in the art, the initiator compound or combinations thereof are generally selected based on the desired functionality of the resulting polyether polyol. For purposes of this disclosure, polyol (A) can be formed using any of the above-mentioned initiators or combinations of initiators. Additionally, polyol (A) can include any of these initiators, including glycerol.

[0010] 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 and propylene oxide to difunctional or trifunctional initiators. Polyether polyols with higher functionality than triols can also be used in place of or in addition to the polyether diols and / or triols. Copolymers having an oxyethylene content of 5 to 90 wt.%, based on the weight of the polyol component, can also be used, and these polyols can be block copolymers, random / block copolymers, or random copolymers. Still other suitable polyether polyols include polytetramethylene glycol obtained by the polymerization of tetrahydrofuran.

[0011] In these or other embodiments, polyol (A) comprises a polyether polyol. Suitable polyester polyols for the isocyanate-reactive component include, but are not limited to, hydroxyl-functional reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, glycerol, trimethylolpropane, pentaerythritol, sucrose, or polyether polyols, or mixtures of such polyhydric alcohols, and polycarboxylic acids, particularly dicarboxylic acids, or their ester-forming derivatives, such as succinic acid, glutaric acid, and adipic acid, or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, dimethyl terephthalate, or mixtures thereof. Polyester polyols obtained by the polymerization of lactones, such as caprolactone, in combination with polyols, or the polymerization of hydroxycarboxylic acids, such as hydroxycaproic acid, can also be used. In certain embodiments, polyol (A) comprises a mixture of polyester and polyether polyols.

[0012] Suitable polyesteramide polyols can be obtained by including amino alcohols such as ethanolamine in the polyesterification mixture. Suitable polythioether polyols include products obtained by condensing thiodiglycol alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino alcohols, or aminocarboxylic acids. Suitable polycarbonate polyols include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or tetraethylene glycol with diaryl carbonates, e.g., diphenyl carbonate, or phosgene. Suitable polyacetal polyols include those prepared by reacting glycols such as diethylene glycol, triethylene glycol, or hexanediol with formaldehyde. Other suitable polyacetal polyols can also be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers.

[0013] In certain embodiments, the polyol (A) comprises a polymer polyol. In certain embodiments, the polymer polyol is a graft polyol. The graft polyol may also be referred to as a graft dispersion polyol or a graft polymer polyol. The graft polyol often includes one or more vinyl monomers, such as styrene monomers and / or acrylonitrile monomers, and a product, i.e., polymer particles, obtained by in situ polymerization of a macromer, such as a polyether polyol, in the polyol.

[0014] It should be understood that 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.

[0015] In various embodiments, polyol (A) has a hydroxyl (OH) equivalent weight of greater than 0 to 2,000 g / mol, alternatively greater than 0 to 1,700 g / mol, alternatively greater than 0 to 1,000 g / mol, alternatively greater than 0 to 700 g / mol, alternatively greater than 0 to 400 g / mol, alternatively greater than 0 to 350 g / mol, alternatively greater than 0 to 325 g / mol, alternatively greater than 0 to 300 g / mol, alternatively greater than 0 to 275 g / mol, alternatively greater than 0 to 250 g / mol, alternatively greater than 0 to 225 g / mol, or alternatively greater than 0 to 200 g / mol. In certain embodiments, including the above ranges, polyol (A) has an OH equivalent weight of at least 30 g / mol. Methods for determining OH equivalent weight are known in the art, based on the functionality and molecular weight of a given polyol.

[0016] In these or other embodiments, the polyol has a functionality of 2-10, alternatively 2-9, alternatively 2-8, alternatively 2-7, alternatively 3-6.

[0017] In certain embodiments, polyol (A) comprises, consists essentially of, or consists of one or more polyether polyols, optionally in combination with one or more polyester polyols.

[0018] It should be understood that when polyol (A) comprises a blend of two or more different polyols, the above properties may be based on the overall polyol (A), i.e., averaging the properties of the individual polyols in polyol (A), or may relate to a specific polyol in the blend of polyols. Typically, the above properties relate to the overall polyol (A).

[0019] The isocyanate-reactive component further comprises (B) a polysiloxane, (C) a polyether alcohol compound, and optionally an amino silicon compound, which are described in order below.

[0020] As will be appreciated by those skilled in the art, siloxanes can be characterized in terms of the [M], [D], [T], and / or [Q] units / siloxy groups therein. More specifically, these [M], [D], [T], and [Q] siloxy groups each represent the structural units of individual functional groups present in polysiloxanes, such as organosiloxanes and organopolysiloxanes. Specifically, [M] is a siloxane having the general formula R"SiO 1 / 2 [D] represents a monofunctional unit of the general formula R''2SiO 2 / 2 [T] represents a difunctional unit of the general formula R''SiO 3 / 2 and [Q] represents a trifunctional unit of the general formula SiO 4 / 2 and is represented by the following general structural moiety:

[0021] [ka]

[0022] In these general structural moieties, each R" is independently a monovalent or polyvalent substituent. As understood in the art, the specific substituents suitable for each R" are not particularly limited and can be monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, and combinations thereof. Typically, each R" is independently selected from hydrocarbyl groups, alkoxy and / or aryloxy groups, and siloxy groups, such as those represented by any one or combination of the [M], [D], [T], and / or [Q] units described above.

[0023] As introduced above, the isocyanate-reactive component comprises polysiloxane (B). As will be understood in light of the present description, polysiloxane (B) may be classified as or otherwise referred to as an MQ resin, where M, as introduced above, is a monofunctional siloxy unit (i.e., R ” 3SiO 1 / 2 indicates R ” represents a silicon-bonded substituent), and Q represents a tetrafunctional siloxy unit (i.e., SiO4 / 2 ) is shown. Such MQ resins are known in the art as high molecular weight polymers mainly composed of M units and Q units, and optionally a limited number of D units and / or T units (e.g., a total of ≤ 20 mol %), and typically exist in solid (e.g., powder or flakes) form / as such unless placed in a solvent. MQ resins are often represented by the general formula [M] x [Q] (where the subscript x refers to the molar ratio of M siloxy units to Q siloxy units when the molar number of Q siloxy units is normalized to 1). In such cases, the higher the value of x, the lower the crosslink density of the MQ resin. As the value of x decreases, the number of M siloxy units decreases, and thus more Q siloxy units form a network without terminating with M siloxy units, and vice versa. However, it should be understood that the normalized content of Q siloxy units does not imply or limit the MQ resin to only one Q unit. Rather, MQ resins typically contain multiple Q siloxy units clustered or bonded together as will be understood from the following description.

[0024] Typically, polysiloxane (B) has the following general formula: (R 1 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R’R 2 SiO 2 / 2 ) b (R 2 SiO 3 / 2 )<​​​​​​​​​​​1 are independently selected from hydrocarbyl groups having 1 to 30 carbon atoms, —OH, and H; and each R 2 are independently 1 and -OX, where each X is independently H, a hydrocarbyl group R having 1 to 30 carbon atoms, or a polyether moiety as described below, and each R' comprises an independently selected amino group.

[0025] Referring to the general formula of polysiloxane (B) above, R 1Suitable hydrocarbyl groups include monovalent hydrocarbon moieties and derivatives and modifications thereof, which may be independently substituted or unsubstituted, linear, branched, cyclic, or combinations thereof, and saturated or unsaturated. With respect to such hydrocarbyl groups, the term "unsubstituted" refers to a hydrocarbon moiety composed of carbon and hydrogen atoms, i.e., containing no heteroatom substituents. The term "substituted" refers to a hydrocarbon moiety in which at least one hydrogen atom is replaced with an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a pendant or terminal substituent), a carbon atom in the hydrocarbon chain / backbone is replaced with an atom other than carbon (e.g., a heteroatom such as oxygen, sulfur, nitrogen, etc.) (i.e., as part of the chain / backbone), or both. As such, suitable hydrocarbyl groups may include or be a hydrocarbon moiety having one or more substituents within and / or on (i.e., attached to and / or integral with) its carbon chain / backbone, such that the hydrocarbon moiety may include or be an ether, ester, etc. The linear and branched hydrocarbon groups can be independently saturated or unsaturated, and if unsaturated, can be conjugated or non-conjugated. The cyclic hydrocarbyl groups can be independently monocyclic or polycyclic and include cycloalkyl groups, aryl groups, and heterocycles, which can be aromatic, saturated and non-aromatic, and / or non-conjugated, etc. Examples of combinations of linear and cyclic hydrocarbyl groups include alkaryl groups, aralkyl groups, etc. Typical examples of hydrocarbon moieties suitable for use in or as hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, alkynyl groups, halocarbon groups, etc., as well as derivatives, modifications, and combinations thereof. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, etc. (i.e., other linear or branched saturated hydrocarbon groups, e.g., having more than 6 carbon atoms).Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethylphenyl, etc., and derivatives and modifications thereof, which may overlap with alkaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethylphenyl, etc.). Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl, etc., and derivatives and modifications thereof. Common examples of halocarbon groups include halogenated derivatives of the hydrocarbon moieties listed above, such as halogenated alkyl groups (e.g., any of the alkyl groups listed above in which one or more hydrogen atoms have been replaced with a halogen atom such as F or Cl), aryl groups (e.g., any of the aryl groups listed above in which one or more hydrogen atoms have been replaced with a halogen atom such as F or Cl), and combinations thereof. 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, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, and the like, as well as derivatives and modifications thereof. Examples of halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl, and the like, as well as derivatives and modifications thereof.

[0026] In certain embodiments, at least one R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms. For example, in certain embodiments, at least one R 1is an independently selected substituted or unsubstituted alkyl group, such as an alkyl group having 1 to 24, alternatively 1 to 18, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, or alternatively 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and iso-propyl), butyl (e.g., n-butyl, sec-butyl, iso-butyl, and tert-butyl), pentyl, hexyl, heptyl, and the like, as well as derivatives and / or modifications thereof. Examples of derivatives and / or modifications of such alkyl groups include substituted versions thereof. For example, R 1 It will be understood that R may contain or be a hydroxylethyl group, which is a derivative and / or modification of the ethyl group described above. 1 can include, or be, an independently selected substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, e.g., 2 to 5, alternatively, 2 to 4, alternatively, 2 to 3 carbon atoms. In certain embodiments, polysiloxane (B) includes at least two R groups that include alkenyl functional groups. 1 groups (i.e., at least two R 1 is selected from substituted or unsubstituted alkenyl groups. In these or other embodiments, each R 1 are independently selected from H, —OH, a C1-C6 alkyl group, an aryl group, an alkenyl group, a phenyl group, a vinyl group, and combinations thereof. 1 At least 50 mole percent, alternatively at least 60 mole percent, alternatively at least 70 mole percent, alternatively at least 80 mole percent, alternatively at least 90 mole percent of the groups are hydrocarbyl groups.

[0027] Continuing to refer to the general formula of polysiloxane (B) above, each R 2 is independently R 1 and -OX, where each X is independently H (i.e., R 2 is a hydroxy group), the hydrocarbyl group R has 1 to 30 carbon atoms (i.e., R2 is a hydrocarbyloxy group of formula -OR), or a polyether moiety. When X is a hydrocarbyloxy group, the hydrocarbyl group R can be selected from any of the hydrocarbyl groups having 1 to 30 carbon atoms described above. Thus, examples of hydrocarbyloxy groups suitable for X include alkoxy groups and aryloxy groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, benzyloxy, etc., as well as derivatives and modifications thereof. Examples of aryloxy groups include phenoxy, tolyloxy, pentafluorophenoxy, etc., as well as derivatives and modifications thereof. In some embodiments, each R 2 are independently 1 and -OR, where each R 1 are independently selected from H, —OH, and alkyl and aryl groups containing 1 to 30 carbon atoms, and each R is independently selected from alkyl and aryl groups containing 1 to 30 carbon atoms. In these or other embodiments, each R 2 is independently selected from -OH and -OR, where each R is independently selected from alkyl and aryl groups containing 1 to 30 carbon atoms.

[0028] As introduced above, in certain embodiments, at least one R 2 is of the formula -OX, where X is a polyether moiety. In these embodiments, the polyether moiety is not particularly limited and generally has the general formula (C n H 2n O) mwherein the subscript m is 1 to 50, and the subscript n is independently 2, 3, or 4 in each moiety represented by the subscript m. In certain embodiments, the subscript m is 1 to 45, e.g., 1 to 40, alternatively 1 to 30, alternatively 1 to 25, alternatively 1 to 20, or alternatively 1 to 15. In certain embodiments, the subscript m is at least 2, such that the polyoxyalkylene moiety can include one or more oxyalkylene units selected from oxyethylene units (e.g., —(C2H4O)—, i.e., the subscript n is 2), oxypropylene units (e.g., —(C3H6O)—, i.e., the subscript n is 3), and oxybutylene units (e.g., —(C4H8O)—, i.e., the subscript n is 4). When the oxyalkylene segment comprises one or more oxyalkylene units (i.e., is a polyoxyalkylene), the oxyalkylene units may be arranged in any manner, such as in a block form (e.g., an ordered block and / or a random block), a randomized form, or a combination thereof. In certain embodiments, the oxyalkylene segment comprises both oxyethylene units and oxypropylene units. In some such embodiments, the oxyalkylene segment is an oxyethylene-oxypropylene block copolymer.

[0029] The polyether portion may include one or more oxyalkylene segments. For example, in certain embodiments, X may be of the general formula -YR 3 (-[Y] j -Z) i wherein R 3 is a substituted or unsubstituted hydrocarbon segment, and each Y is a group having the general formula (C n H 2n O) m where Z is a terminal group, the subscript i is 0 to 8, and the subscript j is independently 0 or 1 in each moiety designated by the subscript i. 3is an at least divalent hydrocarbon linking group. More specifically, as used herein in this context, the hydrocarbon segment R 3 The valence of the oxyalkylene segment Y plus the subformula (-[Y] j -Z). Therefore, the hydrocarbon segment R 3 The valence of may be written as the subscript i+1.

[0030] Typically, each hydrocarbon segment R 3 independently comprise one or more substituted or unsubstituted hydrocarbon groups, i.e., hydrocarbon groups optionally modified or substituted with, for example, pendant alkoxy, carbonyl, siloxy, silyl, amino, amido, acetoxy, or aminoxy groups and / or internal O, N, or S atoms (i.e., in the backbone). For example, in some embodiments, polysiloxane (B) comprises at least one X corresponding to the general polyether moiety formula above, where the hydrocarbon segment R 3 In some such embodiments, the hydrocarbon segment R comprises, or is, a straight or branched chain hydrocarbon group having 3 to 30 carbon atoms, optionally containing one or more aromatic groups, ether groups, amine groups, or combinations thereof. 3 is a C1 to C20 hydrocarbon group. In these or other embodiments, each hydrocarbon segment R 3 independently comprise an aromatic group, an ether group, an amine group, or a combination thereof. As understood from the description herein, the hydrocarbon segment R 3 The ether and amine groups can be internal (e.g., containing an O atom or an N atom in the backbone of a straight or branched chain hydrocarbon group) or pendant (e.g., containing an alkoxy group or an amine group attached to the backbone of a straight or branched chain hydrocarbon group).

[0031] Each hydrocarbon segment R 3 may independently be linear or branched. More specifically, as will be understood from the description herein, R 3typically contains up to i branches (i.e., 0 to 8 branches), and the subscript j is a 3 1 for each branch from to the terminal group Z. In certain embodiments, each hydrocarbon segment R 3 comprises a branched chain hydrocarbon group having 3 to 16 carbon atoms. In some embodiments, each oxyalkylene segment Y independently has the formula -(CHO) x (C3H6O) y (C4H8O) z wherein the subscript x is 1 to 50, the subscript y is 0 to 50, and the subscript z is 0 to 50, and wherein the units represented by the subscripts x, y, and z can be in a random or block form in the oxyalkylene segment.

[0032] In some embodiments, polysiloxane (B) comprises at least one X corresponding to the general polyether moiety formula above, where the subscript i is 0 and each hydrocarbon segment R 3 are independently selected from linear or branched hydrocarbon groups having 3 to 30 carbon atoms. For example, if polysiloxane (B) contains at least one X corresponding to the general polyether moiety formula above, polysiloxane (B) may be reactive with isocyanate functional groups, as described below. However, polysiloxane (B) may be utilized in the compositions of the present disclosure even if it is not reactive with isocyanate functional groups. In these or other embodiments, polysiloxane (B) contains at least one X where the subscript i is 1, and the hydrocarbon segment R 3 comprises at least one group selected from linear or branched hydrocarbon groups having 3 to 30 carbon atoms, phenols, tetrahydrofurans, and alkylamines, each optionally substituted with one or more alkoxy groups. In these or other embodiments, polysiloxane (B) comprises at least one X where the subscript i is at least 2, and the hydrocarbon segment R 3contains at least one group selected from a linear or branched hydrocarbon group having 3 to 30 carbon atoms, an alkylamine, a polyamine, a polyamide, a polyaziridine, a polyphenol, and a polyester.

[0033] Typically, each terminal group Z is independently selected from H (i.e., such that the polyether moiety is terminal hydroxy-functional) or a resinous silicone moiety (i.e., from the condensation of a terminal hydroxy functionality with a condensable silicon-bonded moiety of polysiloxane (B)). For example, when subscript i is at least 1, terminal group Z may represent a crosslink to another silanol group of polysiloxane (B). Similarly, when i>1, polysiloxane (B) may contain one or more crosslinks. Those skilled in the art will understand that the presence of such crosslinks in polysiloxane (B) in the isocyanate-reactive component, as well as the crosslink density, will depend on many factors, such as the hydroxyl (e.g., silanol) functionality of the selected silicone resin, the functionality of the selected polyether alcohol compound (C), the ratio of silicone resin to polyether alcohol compound (C) utilized to prepare the isocyanate-reactive component, and the degree of conversion, as described below with respect to the method. Similarly, the presence of such crosslinking can be confirmed by methods known in the art, for example, by rheological measurements of the gel point due to the increase in average molecular weight in response to crosslinking (i.e., the gel point indicates a weight average molecular weight that diverges toward infinity). For example, a rheometer (e.g., a rheometrics mechanical spectrometer using parallel plate geometry) can be used to perform frequency sweep experiments to determine changes in dynamic storage modulus, equilibrium modulus, and elastic modulus during preparation of the isocyanate-reactive component. The full range of end groups Z, as well as the crosslinking potential of polysiloxane (B), will be better understood in view of the methods described herein.

[0034] Each R' independently comprises an amino group. In certain embodiments, each R' is an amino group. The amino group of R' has the formula -N(H) f R 2-fwherein each R is independently selected and defined above, i.e., each R is an independently selected hydrocarbyl group, and the subscript f is independently 0, 1, or 2. In other embodiments, each R' independently comprises a hydrocarbon group substituted with an amino group. Suitable hydrocarbon groups are those described above. In certain embodiments, each R' independently comprises an aliphatic hydrocarbon group substituted with an amino group. The aliphatic hydrocarbon group may be linear or cyclic and is typically saturated. In certain embodiments, each R' comprises an alkylamino group. For example, each R' is a group of the formula -(CH2) g N(H) f R 2-f where each subscript g is independently 1 to 30, alternatively 1 to 25, alternatively 1 to 20, alternatively 1 to 15, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 2 to 4, and R' and subscript f are defined above. In certain embodiments, subscript g is 3 and subscript f is 2, such that each R' is of the formula -(CH)N(H).

[0035] With continued reference to the general formula for polysiloxane (B) above, the subscripts a, b, b', c, c', and d each represent a mole fraction such that a+b+b'+c+c'+d=1. As will be understood by those skilled in the art, the subscripts a, b, c, d, and e correspond to M, D, T, and Q siloxy units, respectively. The subscripts b and b' in the general formula above both refer to D siloxy units, and the subscripts c and c' in the general formula above both refer to T siloxy units, each with a different silicon-bonded substituent (R 2to R'). Generally, the ratio of each siloxy unit is selected such that 0 < a < 1, 0 ≤ b < 0.2, 0 ≤ b' ≤ 0.1, 0 < c < 0.2, 0 ≤ c' ≤ 0.1, 0 < d < 1, and 0 ≤ b' + c' ≤ 0.1, that is, polysiloxane (B) does not optionally contain D siloxy units (including those represented by subscripts b and / or b'), does not optionally contain T siloxy represented by subscript c', but contains at least one M, T, and Q siloxy unit each (represented by subscripts a, c, and d). However, in such an embodiment, polysiloxane (B) generally has, in at least one, or most, or substantially all of the T siloxy units represented by subscript c, R 2 is configured to be -OX. Similarly, polysiloxane (B) does not optionally contain D siloxy units, but may contain a limited proportion of D siloxy units. However, typically, subscripts b and c together are less than 0.2 (i.e., b + c ≤ 0.2). In certain embodiments, subscript a is selected to be 0.3 to 0.6. In these or other embodiments, subscript d is selected to be 0.4 to 0.7. In certain embodiments, subscript c' is 0. In other embodiments, subscript c' is greater than 0 to 0.1, or greater than 0 to 0.05, or greater than 0 to 0.04, or 0.01 to 0.04. In other specific embodiments, subscript b' is 0. In still other embodiments, subscript b' is greater than 0 to 0.1, or greater than 0 to 0.05, or greater than 0 to 0.04, or 0.01 to 0.04. In another embodiment, b' and c' are each 0. In other embodiments, (b' + c') is greater than 0 to 0.1, or greater than 0 to 0.05, or greater than 0 to 0.04, or 0.01 to 0.04.

[0036] It will be understood that the subscripts a and d generally refer to the MQ resin portion of polysiloxane (B), and therefore the ratio of subscript a to subscript d can be used to characterize polysiloxane (B). For example, in some embodiments, the ratio of M siloxy units designated by subscript a to Q siloxy units designated by subscript d is 0.5 to 1.5 (a:d). In these or other embodiments, the ratio of M siloxy units designated by subscript a to Q siloxy units designated by subscript d is 0.7 to 1.2 (a:d).

[0037] As will be further understood from consideration of the methods below, the characteristics and properties of polysiloxane (B) are selected and controlled by the particular components utilized in preparing the isocyanate-reactive component as a whole.

[0038] As introduced above, the isocyanate-reactive component also includes a polyether alcohol compound (C). Typically, the polyether alcohol compound (C) has the general formula HO-YR 3 (-[Y] j -H) i wherein each Y, R 3 , the subscript i, and the subscript j are as defined above. More specifically, R 3 is a substituted or unsubstituted hydrocarbon segment, each Y is an independently selected oxyalkylene segment, the subscript i is 0 to 8, and the subscript j is independently 0 or 1 in each moiety designated by the subscript i. Further description and examples of polyether alcohol compounds (C) are provided below. However, as will be understood in more detail in view of the methods described herein, the Y and R in the general formula of polyether alcohol compounds (C) 3 are the same groups (i.e., in terms of range) shown above for the polyether portion of polysiloxane (B). Thus, each Y and R 3 The descriptions of the moieties designated by the subscripts j and i apply equally to the conserved moieties of the formulas of both the polyether portion of the polysiloxane (B) and the polyether alcohol compound (C).

[0039] Generally, the polyether alcohol compound (C) comprises an alkoxylation reaction product of (b-1) a compound containing at least one alkoxylatable group (e.g., a functional group containing a labile hydrogen atom bonded to a nucleophilic O, N, or S atom, such as an -OH, -NH, or SH group) (i.e., an alkoxylatable compound (b-1)) and (b-2) an alkoxylating agent (e.g., an alkylene oxide, a polyoxyalkylene compound, etc.), which are described in order below. As will be understood by those skilled in the art, the alkoxylation reaction is not limited and is selected taking into consideration the specific alkoxylatable compound (b-1) and alkoxylating agent (b-2) used.

[0040] Typically, the alkoxylatable compound (b-1) is an organic alcohol, i.e., an organic compound comprising a carbon backbone and at least one hydroxyl (i.e., —OH) group. In such embodiments, the alkoxylatable compound (b-1) may be more specifically referred to as an alcohol compound (b-1). As will be understood in light of the following examples and explanations, the alcohol compound (b-1) may be a monool (i.e., containing only one hydroxyl functional group) or a polyol (i.e., containing at least two hydroxyl groups), such as a diol, triol, or the like. The carbon backbone of the alcohol compound (b-1) may be substituted or unsubstituted, for example, with any of the functional groups described herein. If substituted, the carbon backbone of the alcohol compound (b-1) may include pendant substitutions (i.e., in place of hydrogen atoms bonded to the carbon backbone) or substitutions of carbon atoms within the backbone itself (e.g., with other heteroatoms such as O, S, N, etc.). Thus, while alcohol compound (b-1) may be characterized or otherwise referred to as an organic alcohol, it should be understood that it may alternatively or further be defined in consideration of additional functional groups, if any, (e.g., as an amino alcohol, etc.) Furthermore, the carbon backbone may be linear or branched, and thus may include linear, branched, and / or cyclic hydrocarbon segments.

[0041] As will be understood in light of the present disclosure, the alcohol compound (b-1) is typically represented by the general formula HO-R 3 (-OH) i where R corresponds to 3 and the index i is as defined above. More specifically, R 3 is a hydrocarbon segment, and the subscript i is 0 to 8. In such embodiments, the hydrocarbon segment R 3 It will be understood that represents the carbon skeleton of the alcohol compound (b-1), which may contain 0 to 8 hydroxyl groups in addition to the required hydroxyl group, as indicated by the subscript i.

[0042] In certain embodiments, the subscript i is 0, such that the alcohol compound (b-1) has the general formula HO-R 3 In some such embodiments, R 3 may comprise or be a straight or branched chain hydrocarbon group having 3 to 30 carbon atoms. For example, in some embodiments, R 3 is a branched chain hydrocarbon group having 3 to 30 carbon atoms. In some such embodiments, the alcohol compound (b-1) has the formula:

[0043] [ka] In the formula, R 5 , R 6 , and R 7 are independently selected from C1 to C13 alkyl groups. For example, in some such embodiments, R 5 and R 6 are each independently selected from C1-4 alkyl groups, and R 7 is H or a C1-C13 alkyl group. In some of these embodiments, R 3 In some embodiments, R contains a total of 7 to 16 carbon atoms, e.g., 9 to 12 carbon atoms. 3contains a branching degree of at least 3. In this context, the term "branching degree" as used herein refers to the total number of methyl (-CH) groups minus 1. For example, an R 3 comprises a branching degree of 3. In some embodiments, R 5 is an alkyl group containing 3 to 12 carbon atoms, e.g., a C3-C8 alkyl group, or a C4-C6 alkyl group. In such embodiments, R 5 In these or other embodiments, R 6 is an alkyl group containing 3 to 12 carbon atoms, e.g., a C4 to C10 alkyl group, or a C6 to C8 alkyl group. In some embodiments, R 7 contains at least two methyl groups. For example, in certain embodiments, R 7 is a C1-C3 alkyl group. In another embodiment, R 7 is H. In some embodiments, R 5 is CH3(CH2)2CH(CH3)(CH2)2CH(CH3), and R 6 is H and R 7 is CH3. In certain embodiments, the alcohol compound (b-1) is (3-methyl-6-ethyl)-2-nonanol.

[0044] In certain embodiments, the subscript i is 1, such that the alcohol compound (b-1) has the general formula HO-R 3 -OH, where the hydrocarbon segment is a divalent linking group. In certain embodiments, for example, R 3 comprises or is an alkyl group (i.e., when the alcohol compound (b-1) is a glycol) or a substituted alkyl group (e.g., a diethylamino group when the alcohol compound (b-1) is diethanolamine), an aryl group (e.g., phenyl, benzyl, tolyl, etc.), a tetrahydrofuran group, or other difunctional materials such as those derived from epoxy adducts or ring opening of alkoxydiols.

[0045] In certain embodiments, the subscript i is ≧2, and thus the alcohol compound (b-1) may be further defined as a polyol, such as a triol, a tetraol, etc. In such embodiments, the alcohol compound (b-1) is exemplified by glycerol, pentaerythritol, sugar alcohols (e.g., sorbitol, xylitol, mannitol, etc.), and the like. In some such embodiments, R 3 includes or is selected from alkylamines, polyamines, polyamides, polyaziridines, polyphenols, and polyesters. 3 includes or is a phenol formaldehyde resin, an epoxy adduct of a glycidyl ether and a polyol, or an epoxy adduct of a glycidyl ether and a diamine or polyamine (e.g., a secondary diamine). In any of these embodiments, the subscript i can be from 2 to 8, such that the alcohol compound (b-1) contains from 2 to 8 hydroxyl groups, e.g., from 3 to 8, alternatively from 3 to 6, or alternatively from 3 to 5 hydroxyl groups.

[0046] It should be understood that other polyols and alcohols can be used as the alcohol compound (b-1) to similarly prepare the polyether alcohol compound (C). For example, in certain embodiments, the alcohol compound (b-1) is selected from polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyols derived from isocyanate prepolymers (e.g., those having a functionality of 2 to 8), and the like.

[0047] The alkoxylating agent (b-2) is not limited and may be or include any alkoxylating compound suitable for replacing the alkoxylatable compound (b-1) to obtain the polyether alcohol compound (C) described herein. Typically, the alkoxylating agent (b-2) is selected from alkylene oxides, polyoxyalkylene compounds, and combinations thereof. For example, in certain embodiments, the alkoxylating agent (b-2) is selected from ethylene oxide, propylene oxide, butylene oxide, and combinations thereof. In other embodiments, the alkoxylating agent (b-2) is selected from polyoxyethylene, polyoxypropylene, polyoxybutylene, and combinations thereof (e.g., in the form of a random or block polymer). Those skilled in the art will understand that the term "alkoxylated" as used herein, for example, with respect to the precursors (b-1) and (b-2) of the polyether alcohol compound (C), can be considered functional and / or descriptive and also includes ether / etherified products.

[0048] It will be understood by those skilled in the art that the number of hydroxyl groups present on the alkoxylatable compound (b-1) will affect the overall structure of the polyether alcohol compound (C) itself. In particular, the polyether alcohol compound (C) may contain polyoxyalkylene groups up to i=1, i.e., polyoxyalkylene groups from the alkoxylation of the alkoxylatable group(s) of the alcohol compound (b-1) with the alkoxylating agent (b-2).

[0049] For example, the general formula HO-YR 3 (-[Y] j -H) i With respect to the polyether alcohol compound (C) itself, each oxyalkylene segment Y independently corresponds to the formula (C2H4O) x (C3H6O) y (C4H8O) zwherein the subscript x is 1 to 50, the subscript y is 0 to 50, and the subscript z is 0 to 50, and the units represented by the subscripts x, y, and z may independently be in a randomized or block form in each oxyalkylene segment. In certain embodiments, in each oxyalkylene segment Y, the subscript x is 1 to 20, the subscript y is 0 to 20, and the subscript z is 0 to 20. In some such embodiments, x+y+z=1 to 50, e.g., 1 to 20, or alternatively, 10 to 20. In certain embodiments, the subscript x is 2 to 20, and the subscripts y and z are both 0, such that the polyether alcohol compound (C) may be further defined as a polyoxyethylene alcohol.

[0050] In certain embodiments, the polyether alcohol compound (C) is a nonionic surfactant.For example, in some such embodiments, the polyether alcohol compound (C) can be selected from linear linear ethoxylates, branched ethoxylates (e.g., polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether), amine ethoxylates (e.g., tertiary amine ethoxylates, fatty amine ethoxylates and / or propoxylates), ethoxylated, propoxylated, and / or butoxylated glycols, etc.

[0051] From the above description, in some embodiments, the polyether alcohol compound (C) has the general formula HO—(CHO) x (C3H6O) y (C4H8O) z -CR 5 R 6 R 7 wherein R 5 , R 6 , R 7 , and the subscripts x, y, and z are understood to be as defined above. In some such embodiments, for example, the subscript x is 1 to 40, the subscripts y and z are selected such that y+z=1 to 6, and R 5 and R 6 are independently selected C1-C4 alkyl groups, and R7 is H or C1-C13 alkyl. In some such embodiments, the subformula -CR 5 R 6 R 7 The moiety represented by the formula: contains a total of 7 to 16 carbon atoms and a degree of branching of at least 3.

[0052] In some embodiments, the polyether alcohol compound (C) has the formula:

[0053] [ka] In the formula, R 8 is H or isopropyl, and R 9 is CH3 or CH2CH3, the subscript y' is 1 to 5, for example 1 to 4, alternatively 2 to 4, and the subscript x is 2 to 30, such as 2 to 20, alternatively 2 to 10, alternatively 2 to 9, alternatively 5 to 9. In some of these embodiments, R 8 is H and R 9 is CH3, so that the polyether alcohol compound (C) has the formula:

[0054] [ka] where the subscripts y' and x are as defined above. In other embodiments, R 8 is isopropyl, so that the polyether alcohol compound (C) has the formula:

[0055] [ka] where the subscripts y' and x are as defined above.

[0056] Generally, the polyether alcohol compound (C) can be prepared or otherwise obtained to have a narrow molecular weight distribution, expressed as the polydispersity index (PDI) (i.e., weight average molecular weight / number average molecular weight (Mw / Mn), as measured, for example, by gel permeation chromatography). For example, in certain embodiments, the polyether alcohol compound (C) comprises a PDI of 1.15 or less, alternatively 1.1 or less. In these or other embodiments, the polyether alcohol compound (C) comprises a low level of residual unreacted alkoxylatable compound (b-1), e.g., alcohol compound (b-1) (i.e., non-alkoxylated alcohol). For example, in some embodiments, the polyether alcohol compound (C) contains less than 3 wt. %, alternatively less than 2 wt. %, alternatively 1 wt. % or less, alternatively 0.5 wt. % of residual / unreacted alcohol compound (b-1). In certain embodiments, the isocyanate-reactive component comprises one or more polyether alcohol compounds (C), e.g., a mixture of two, three, four, five, or more independently selected individual polyether alcohol compounds (B).

[0057] The isocyanate-reactive component can be formed via any order of addition of the components. In certain embodiments, polysiloxane (B) is combined with polyether alcohol compound (C) and, optionally, an aminosilicon compound to form a mixture, and the mixture is combined with polyol (A) to provide the isocyanate-reactive component. The amounts of components (B) and (C), and the aminosilicon compound (if utilized in the mixture), can vary. In some embodiments, for example, the mixture comprises 10 to 80 weight percent polysiloxane (B), based on the total weight of the mixture. Similarly, in these or other embodiments, the mixture comprises 10 to 95 weight percent polyether alcohol compound (C), based on the total weight of the mixture. In certain embodiments, the mixture comprises 10 to 80, alternatively 20 to 80, alternatively 20 to 70, alternatively 30 to 70 weight percent polysiloxane (B), based on the total weight of the mixture. In these embodiments, the remainder of the mixture may comprise polyether alcohol compound (C). Typically, the mixture will have the isocyanate-reactive component present in an amount of from greater than 0 to 25 wt%, alternatively from greater than 0 to 20 wt%, alternatively from 0 to 15 wt%, alternatively from 0 to 10 wt%, based on the total weight of polyol (A) used.

[0058] In certain embodiments, the mixture utilized to prepare the isocyanate-reactive component and / or the isocyanate-reactive component itself further comprises an aminosilicon compound. Generally, the aminosilicon compound is utilized to provide D siloxy units, designated by subscript b', if present, and / or T siloxy units, designated by subscript c', if present, in polysiloxane (B), as described below with respect to the method of preparing the composition. The use of an aminosilicon compound in preparing polysiloxane (B) and / or the mixture is optional. If used, some residual amount of aminosilicon compound may be present in the mixture and / or the isocyanate-reactive component, i.e., the aminosilicon compound may not be completely consumed in preparing polysiloxane (B) and / or the mixture.

[0059] The aminosilicon compound, when present, contains silicon-bonded substituents including amino groups which can be the substituents represented by R' in the polysiloxane (B). Typically, the aminosilicon compound also contains silicon-bonded hydroxyl groups and / or hydrolyzable groups, such as alkoxy groups.

[0060] In certain embodiments, the amino silicon compound is an amino silane, for example, a compound of the formula R'R 10 h Si(OR 10 ) 3-h wherein the subscript h is 0 or 1, R′ is defined above, and each R 10 is an independently selected alkyl group having 1 to 18, alternatively 1 to 16, alternatively 1 to 14, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4 carbon atoms. In one embodiment, the subscript h is 0 and the amino silicon compound has the formula R'Si(OR 10 )3. One specific example of such an aminosilane is 3-propylaminotriethoxysilane. In another embodiment, the subscript h is 1 and the aminosilicon compound (C) is of the formula R'R 10 Si(OR 10 ) 2. One specific example of such an aminosilane is 3-propylamino(diethoxy)methylsilane.

[0061] Amino silicon compounds are used, having the formula R'Si(OR 10 ) 3, at least a portion of the amino silicon compound used is generally hydrolyzed and condensed to form T siloxy units in polysiloxane (B) designated by subscript c', i.e., the formula R'SiO 3 / 2 Typically, each alkoxy group of the aminosilicon compound is completely hydrolyzed and condensed to give such T siloxy units in the polysiloxane (B). When an aminosilicon compound is used in preparing the polysiloxane (B), a partial condensate may be formed in the reaction intermediate of the polysiloxane (B). When an aminosilicon compound is used, a compound having the formula R'Si(OR 10)3, the partial condensation product is of the formula (R'(OZ) q SiO 3-q / 2 ) wherein the subscript q is independently 0, 1, or 2, and each Z is independently H or R 10 is.

[0062] Amino silicon compounds are used, having the formula R'R 10 Si(OR 10 )2, at least a portion of the amino silicon compound used is generally hydrolyzed and condensed to form D siloxy units in polysiloxane (B) designated by subscript b', i.e., D siloxy units of the formula R'R 2 SiO 2 / 2 Typically, each alkoxy group of the aminosilicon compound is completely hydrolyzed and condensed to give such D-siloxy units in the polysiloxane (B). When an aminosilicon compound is used in preparing the polysiloxane (B), a partial condensate may be formed in the reaction intermediate of the polysiloxane (B). When an aminosilicon compound is used, a compound having the formula R'R 10 Si(OR 10 )2, the partial condensation product has the formula R'R 10 (OZ)rSiO 2-r / 2 wherein the subscript r is independently 0 or 1 and each Z is independently H or R 10 is.

[0063] A combination of different aminosilicon compounds may be utilized together as the aminosilicon compound.

[0064] The amino silicon compound is typically present in the mixture in an amount of from 0 to 25 wt %, alternatively from 0 to 20 wt %, alternatively from 0 to 15 wt %, based on the total weight of the mixture.

[0065] The mixture, when utilized in preparing an isocyanate-reactive component, generally has a tunable liquid viscosity. In particular, the mixture generally comprises a viscosity of 100 to 800,000 cps at 25°C. For example, in certain embodiments, the mixture comprises a viscosity of 185 cps to 700,000 cps at 25°C, depending, for example, on the specific polyether alcohol compound (C) selected, the ratio of polysiloxane (B) to polyether alcohol compound (C) used, the presence or absence of an amino silicon compound, and the like. Furthermore, as will be understood from the following method, the ratio of -OX=polyether moieties to -OX=H moieties (i.e., capping ratio) within polysiloxane (B) can also be independently selected and controlled to provide a liquid mixture. Because the mixture has a tunable liquid viscosity, the viscosity can be selectively controlled based on the desired end use and its properties.

[0066] The mixture comprises (I) combining a solid silicone resin, a polyether alcohol compound (C), and optionally an aminosilicon compound together to obtain a mixture comprising polysiloxane (B), a polyether alcohol compound (C), and optionally an aminosilicon compound. The method also comprises (II) liquefying the mixture comprising polysiloxane (B), a polyether alcohol compound (C), and optionally an aminosilicon compound. As described below, in certain embodiments utilizing an aminosilicon compound, the aminosilicon compound is incorporated during and / or after the step of liquefying the mixture.

[0067] As can be understood from the description herein, the polyether alcohol compound (C) can liquefy the solid silicone resin, optionally without reacting with the solid silicone resin.Therefore, the solid silicone resin is typically solid when combined with the polyether alcohol compound (C), as described below, optionally in the presence of a carrier vehicle.The term "solid" is used herein with respect to the solid silicone resin to describe a silicone that has a softening point and / or melting point higher than room temperature, so that the silicone resin is solid or substantially solid at room temperature in the absence of an organic solvent.

[0068] 1. A solid silicone resin having the general formula: (R 1 3SiO 1 / 2 ) a (R 4 2SiO 2 / 2 ) b (R 4 SiO 3 / 2 ) c (SiO 4 / 2 ) d , In the formula, each R 4 is R 1 and -OR, with the proviso that R 4 is selected from —OH and —OR in at least one T siloxy unit designated by subscript c, and each R 1 , R, and the subscripts a, b, c, and d are as defined above.

[0069] With respect to the foregoing formula, as will be understood by those skilled in the art in light of the description herein, the solid silicone resin utilized in the present method forms the siloxane backbone of polysiloxane (B). Accordingly, the above description of the M, D, T, and Q siloxy units, designated by the subscripts a, b, c, and d, respectively, of polysiloxane (B) applies equally to the solid silicone resin of the present method. For example, in certain embodiments, the solid silicone resin comprises an MQ ratio of 0.5 to 1.5, i.e., the ratio of M siloxy units designated by the subscript a to Q siloxy units designated by the subscript d (a:d). In these or other embodiments, the ratio of M siloxy units designated by the subscript a to Q siloxy units designated by the subscript d in the solid silicone resin is 0.7 to 1.2 (a:d). However, as is readily understood in the art, the ranges for the subscripts a, b, c, and d are applicable to both the solid silicone resin and the polysiloxane (B), but each of the subscripts a, b, c, and d can independently vary between the solid silicone resin and the polysiloxane (B). For example, when the method for preparing the composition includes liquefaction, certain siloxane bonds can be cleaved to obtain SiOZ moieties (where Z is independently H or alkyl). For this reason, the polysiloxane (B) may have, for example, fewer Q siloxy units than the solid silicone resin on a mole fraction basis. Alternatively or additionally, the polysiloxane (B) may also have fewer M siloxy groups than the solid silicone resin, depending on the use and selection of the polyether alcohol compound (C) and, optionally, the amino silicon compound (if used).

[0070] Typically, the solid silicone resin has a weight average molecular weight of 2,000 to 30,000, for example, 3,000 to 30,000, alternatively 4,000 to 30,000, alternatively 4,000 to 25,000, alternatively 5,000 to 25,000, alternatively 5,000 to 20,000, alternatively 6,000 to 20,000. As will be appreciated by those skilled in the art, weight average molecular weights can be readily determined in Daltons using triple detector gel permeation chromatography (e.g., with light scattering, refractive index, and viscosity detectors) against polystyrene standards.

[0071] It will be understood that the polyether alcohol compound (C) utilized in the mixture (e.g., to cap and / or liquefy the polysiloxane (B)) is the same component as described above with respect to the polyether alcohol compound (C) of the mixture and the isocyanate-reactive component. Accordingly, the above discussion of polyether alcohol compound (C) and its various moieties applies equally to the present method.

[0072] As introduced above, the mixture is formed by combining the solid silicone resin, the polyether alcohol compound (C), and, optionally, any other components utilized (collectively, "process components"). As will be understood by those skilled in the art, generally, no prior steps are required other than combining the reaction components together, although the specific processes described below may be used. Furthermore, while one embodiment of the method involves reacting the solid silicone resin with the polyether alcohol compound (C) (e.g., via a condensation reaction) to prepare the polysiloxane (B), thereby obtaining the mixture, it will be understood that in another embodiment, the method may be utilized to prepare the mixture by simply liquefying the polysiloxane (B) (or solid silicone resin) in the presence of the polyether alcohol compound (C) without reacting / capping.

[0073] Furthermore, as mentioned above, an aminosilicon compound may optionally be utilized in the present method. If used, the aminosilicon compound can be incorporated at any point in the process of preparing the mixture. For example, in one embodiment, the aminosilicon compound is combined with the solid silicone resin and the polyether alcohol compound (C) so that the aminosilicon compound is present in the mixture. Alternatively, or in addition, the aminosilicon compound can be combined with the mixture after its formation. Furthermore, the aminosilicon compound can be combined during and / or after liquefaction of the mixture, as described below.

[0074] Regarding the process components, the solid silicone resin may be prepared or obtained by other methods, i.e., as a prepared resin. Methods for preparing MQ resins, such as solid silicone resins, are known in the art, and suitable precursors and suitable starting materials are commercially available from various suppliers. When the solid silicone resin is part of the process, the preparation is typically carried out before combining the solid silicone resin with the polyether alcohol compound (C). The polyether alcohol compound (C) may also be prepared as part of the process, or may be obtained for use in the process by other methods. In certain embodiments, the polyether alcohol compound (C) is prepared by reacting (e.g., alkoxylating) an alkoxylatable compound (b-1) with an alkoxylating agent (b-2). When selecting an alkoxylating agent (b-2), for example, when an alkylene oxide is utilized, one skilled in the art will understand that propylene oxide and / or butylene oxide may be used to modify the viscosity by increasing the flexibility of the product of the alkoxylation and / or condensation reaction of the present method, thereby increasing the flowability of the polyether alcohol compound (C) and, optionally, the polysiloxane (B) prepared therewith.

[0075] Typically, the process components are combined in a vessel or reactor to prepare a mixture. The process components may be fed into the vessel together or separately, as exemplified below, or may be dispensed into the vessel in any additional order and in any combination. The process may further include, for example, stirring the mixture to promote mixing and contact of the process components when combined. Such contact may independently use other conditions with (e.g., simultaneously or sequentially) or without (i.e., independent of or in place of) stirring, and are typically carried out to aid in the preparation of polysiloxane (B) in the mixture and / or liquefaction of the mixture. Other conditions may be utilized in addition to or in place of the conditions described herein, and may be consequently effective conditions for promoting condensation, liquefaction, etc., during the course of the process.

[0076] The present method can utilize any amount of the method components, and more specifically, can involve combining the solid silicone resin, polyether alcohol compound (C), and optionally the aminosilicon compound in various amounts or ratios depending on the desired properties of the resulting mixture and / or the characteristics of the starting materials used. For example, the solid silicone resin and polyether alcohol compound (C) and optionally the aminosilicon compound can be utilized in amounts configured to provide a specific capping ratio (i.e., the molar ratio of silanol functional groups of the MQ resin to the hydroxyl functional groups of the polyether alcohol compound (C)) of the polysiloxane (B) prepared therewith (e.g., a capping ratio of 0.25 to 1.0, e.g., 0.5 to 0.75). Thus, as will be appreciated by those skilled in the art, the solid silicone resin and polyether alcohol compound (C) can be utilized in any amount, regardless of whether the molar ratio is 1 or greater. A molar ratio of 1 or greater is advantageous for either component. For example, the solid silicone resin and polyether alcohol compound (C) can be utilized in a molar ratio of 1:10 to 10:1, alternatively 1:5 to 5:1, alternatively 1:2 to 2:1, alternatively 1:1.1 to 1.1:1. As indicated, an excess (e.g., a slight excess, a moderate excess, or a total excess) of either component can also be utilized.

[0077] The solid silicone resin, polyether alcohol compound (C), and optionally the aminosilicon compound can be combined in any order, optionally under shear or mixing. For example, in some embodiments, a mixture is prepared by combining the solid silicone resin, polyether alcohol compound (C), and optionally the aminosilicon compound, along with any additional components that are optionally used. The components can be combined in any order, simultaneously, or in any combination thereof (e.g., in various multi-part compositions that are ultimately combined with each other). Similarly, the mixture can be prepared in a batch, semi-batch, semi-continuous, or continuous process, unless otherwise specified herein. Typically, once combined, the components of the mixture are homogenized, for example, by mixing, which can be carried out by any of a variety of techniques known in the art using any equipment suitable for mixing. Examples of suitable mixing techniques generally include ultrasonication, dispersive mixing, planetary mixing, three-roll milling, etc. Examples of mixing equipment include stirred batch kettles for relatively high fluidity (low dynamic viscosity) compositions, ribbon blenders, solution blenders, co-kneaders, twin rotor mixers, Banbury-type mixers, pulverizers, extruders, and the like, which may be batch-type or continuous compounding type equipment, utilized alone or in combination with one or more mixers of the same or different types.

[0078] In some embodiments, the solid silicone resin, the polyether alcohol compound (C), and optionally the amino silicon compound are combined in the presence of a carrier vehicle. The carrier vehicle is not limited and is typically selected based on the particular solid silicone resin and / or polyether alcohol compound (C) used, the desired end use of the mixture, etc. Generally, the carrier vehicle includes or is a solvent, a fluid, an oil (e.g., an organic oil and / or a silicone oil), etc., or a combination thereof.

[0079] In some embodiments, the carrier vehicle comprises a silicone fluid. The silicone fluid is typically a low viscosity and / or volatile siloxane. In some embodiments, the silicone fluid is a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methylethyl siloxane, or the like, or a combination thereof. Typically, the silicone fluid has a viscosity of 1 to 1,000 mm at 25°C. 2 Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexademethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,

[0033] Further examples of suitable silicone fluids include 5x10 methylsiloxane, 5x10 methylsiloxane, 5x10 methyloctyltrisiloxane, 5x10 methyltrimethicone ... -7 ~1.5x10 -6 m 2 Examples of suitable polyorganosiloxanes include polyorganosiloxanes having a suitable vapor pressure of 1000 psi / sec.

[0080] In certain embodiments, the carrier vehicle comprises an organic fluid, typically comprising organic oils containing volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. Common examples of such organic fluids include C6-C8 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8 to C 16Included are volatile hydrocarbon oils such as branched esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), as well as derivatives, modifications, and combinations thereof. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having four or more carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, aromatic halides, and combinations thereof. Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 ~C 13 ), Isopar H(C 11 ~C 12 ), and hydrogenated polydecene. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, octyl palmitate, and combinations thereof. It will be understood that some of the above examples of organic fluids (e.g., glycol ethers) may overlap with the polyether alcohol compound (C), which may be utilized as a carrier vehicle by itself or in combination with another carrier vehicle described herein. In some embodiments, the method is carried out in the absence or substantially the absence of organic fluids meeting the description of polyether alcohol compound (C) (i.e., other than polyether alcohol compound (C) itself).

[0081] In some embodiments, the carrier vehicle comprises an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and n-propanol; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran, white spirit; mineral spirits, naphtha; n-methylpyrrolidone, and the like, as well as derivatives, modifications, and combinations thereof. In certain embodiments, the carrier vehicle comprises a polar organic solvent, such as a water-compatible solvent. Specific examples of such polar organic solvents utilized in certain embodiments include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-butanone, tetrahydrofuran, acetone, and combinations thereof. Other carrier vehicles may also be utilized instead of, in addition to, or in combination with those described herein. In certain embodiments, the carrier vehicle comprises or is an aliphatic and / or aromatic hydrocarbon solvent such as xylene, a siloxane solvent such as hexamethylenedisiloxane (HMDSO), D4 or D5 cyclics or other such siloxanes, or a combination thereof. In other embodiments, the method is carried out substantially free of certain solvents. For example, in some embodiments, the method is carried out free of, or substantially free of, hexamethylenedisiloxane (HMDSO), D4 cyclics, and / or D5 cyclics. In these or other embodiments, the method is carried out free of, or substantially free of, benzene, toluene, ethylbenzene, and xylene (i.e., BTEX solvents). In these or other embodiments, the method is carried out free of, or substantially free of, aromatic solvents.

[0082] In certain embodiments, the solid silicone resin is combined with the carrier vehicle before being combined with the polyether alcohol compound (C) and optionally the aminosilicon compound. However, in other embodiments, the polyether alcohol compound (C) is combined with the carrier vehicle and optionally the aminosilicon compound before being combined with the solid silicone resin, or the components are combined substantially simultaneously to form the mixture. Parameters related to the conditions under which these components are combined (e.g., temperature, pressure, etc.) can also be controlled. However, the method can also be carried out at ambient conditions. Typically, the solid silicone resin, polyether alcohol compound (C), optionally the aminosilicon compound, and the carrier vehicle are combined together at a temperature below 45°C (i.e., low-temperature processing) to form the mixture. However, in some embodiments, the solid silicone resin, polyether alcohol compound (C), optionally the aminosilicon compound, and the carrier vehicle are combined together at a temperature below 40°C, alternatively below 35°C, alternatively below 30°C, or at or near ambient temperature.

[0083] In some embodiments, the method includes reacting a solid silicone resin with a polyether alcohol compound (C) to prepare a polysiloxane (B) in the mixture. In these or other embodiments, in methods utilizing an aminosilicon compound, the method may further include reacting the solid silicone resin or a reaction intermediate formed by reacting the solid silicone resin with the polyether alcohol compound (C) with the aminosilicon compound to prepare polysiloxane (B). Generally, the aminosilicon compound hydrolyzes and condenses to provide T siloxy units having amino functionality in polysiloxane (B). As introduced above, the reaction in the method can be generally defined as a condensation reaction or can be otherwise characterized, and certain parameters and conditions of the reaction can be selected by one skilled in the art taking into account the specific components utilized. For example, in some such embodiments, the method includes disposing a catalyst (i.e., a condensation catalyst) in the mixture. Condensation catalysts, such as those based on tin (e.g., Sn octoate) or bases (e.g., NaOAc, KOH, etc.), are known in the art and are selected based on the process components utilized. However, in other embodiments, the process is carried out in the absence of any tin catalyst, for example, to provide the mixture as a tin-free product, thereby avoiding limitations associated with tin being carried over into the final composition.

[0084] When carried out in the present method, the catalyst can be used in any amount, which can be selected by those skilled in the art and is based on, for example, the specific catalyst selected, the concentration / amount of its active catalytic species, the nature / type of the selected solid silicone resin and / or polyether alcohol compound (C), the reaction parameters used, the scale of the reaction (e.g., the total amount of process components used, etc.). The molar ratio of catalyst to process components can affect the rate and / or amount of condensation to prepare polysiloxane (B) in the mixture. Therefore, the amount of catalyst relative to the process components and the molar ratio therebetween can vary. Typically, these relative amounts and molar ratios are selected to maximize the reaction of the process components while minimizing the catalyst loading (e.g., to increase the economic efficiency of the reaction, increase the ease of purifying the reaction product formed, etc.).

[0085] In certain embodiments, the catalyst is utilized in an amount of 0.000001 to 50 weight percent (i.e., weight / weight), based on the total amount of solid silicone resin utilized. For example, the catalyst may be used in an amount of 0.000001 to 25, alternatively 0.00001 to 10, alternatively 0.0001 to 5 weight percent, based on the total amount of solid silicone resin utilized. In some embodiments, the catalyst is utilized in an amount sufficient to provide a ratio of catalytic tin to hydrolyzable groups of the solid silicone resin compound of 1:10 to 1:1,000,000, alternatively 1:50 to 1:1,000, alternatively 1:100 to 1:500. Such ratios may be weight ratios (i.e., weight / weight) or may be molar ratios between the components. It will be understood that amounts and ratios outside the ranges recited above may also be utilized. For example, the catalyst may be utilized in a stoichiometric amount (i.e., a supercatalytic amount), based, for example, on the total amount of polyether alcohol compound (C) used in the mixture.

[0086] The catalyst can be prepared or obtained otherwise (i.e., as a prepared compound). Methods for preparing condensation catalysts (e.g., tin catalysts, acetate catalysts, etc.) using commercially available compounds from various suppliers are known in the art. Thus, the catalyst can be prepared before the reaction of the solid silicone resin with the polyether alcohol compound (C) (and optionally the aminosilicon compound) or in situ (i.e., during the reaction of these components, for example, by combining the catalyst components with a mixture comprising the solid silicone resin and the polyether alcohol compound (C) and optionally the aminosilicon compound). As such, in certain embodiments, the catalyst is prepared as part of the preparation method, i.e., the preparation method includes preparing the catalyst.

[0087] If a condensation reaction is desired, the method typically further includes exposing the mixture to one or more condensation conditions (e.g., elevated temperature, reduced pressure, reflux, etc.). As such, the vessel or reactor can be heated or cooled in any suitable manner (e.g., via a jacket, mantle, exchanger, bath, coil, etc.) to allow the reaction to be carried out at elevated or reduced temperatures, pressures, etc., as described below. For example, depending on the nature of the condensation reaction, the condensation conditions may include heating the mixture to an elevated temperature, such as 100°C, to promote condensation of the polyether alcohol compound (C) and the solid silicone resin (and optionally the amino silicon compound). Similarly, the condensation conditions may include drawing a vacuum on the reactor, which is utilized to subject the mixture to reduced pressure (e.g., 35 to 300 mbar). In combination, the reduced pressure and elevated temperature may be utilized to distill water from the reaction, thereby driving the condensation toward completion by preventing the reverse reaction. Those skilled in the art will appreciate that the particular temperature and pressure utilized will be selected based on the process components and carrier vehicle present in the mixture, e.g., to provide efficient reflux conditions without overheating the mixture. For example, in various embodiments, the reaction is carried out at a reaction / condensation temperature of 23-200°C, e.g., from above ambient temperature (e.g., above 25°C) to 200°C, alternatively from above 25-180°C, alternatively from above 25-165°C, alternatively from above 25-150°C, alternatively from 30-150°C, alternatively from 50-150°C, alternatively from 70-150°C, alternatively from 60-150°C, alternatively from 85-150°C, alternatively from 100-150°C, alternatively from 110-150°C. In certain embodiments, the reaction temperature is selected and / or controlled based on the boiling point of any one solvent or volatile diluent, such as when reflux conditions are utilized. Additionally, a co-solvent, such as toluene, may be used to azeotrope water from the mixture.

[0088] Generally, the reaction rate of the components in the mixture (i.e., condensation of the polyether alcohol compound (C) and the solid silicone resin, and optionally the amino silicon compound) increases as i) the reaction temperature increases and ii) water is removed from the reaction system. Therefore, the required reaction time is selected taking into account the specifics of the mixture being reacted. In exemplary embodiments, the reaction time (i.e., the condensation / capping time, which may be monitored by visual inspection, spectroscopy (e.g., NMR, FT-IR, etc.), or other methods known in the art) may be on the order of one to several hours, such as 1 to 10 hours, alternatively 2 to 10 hours, alternatively 3 to 10 hours, alternatively 4 to 10 hours, alternatively 4 to 8 hours, or alternatively 4 to 6 hours. However, both longer and shorter reaction times may be selected taking into account, for example, the scale of the reaction and any particular components utilized in the mixture.

[0089] In certain embodiments, the method includes dissolving a solid silicone resin in a carrier vehicle (i.e., a solvent) to obtain a silicone resin solution, and combining the silicone resin solution with a polyether alcohol compound (C) and, optionally, an aminosilicon compound to form a mixture. In these embodiments, for example, if a carrier vehicle is utilized, the method typically further includes removing the carrier vehicle from the mixture once the polysiloxane (B) has been prepared therein. More specifically, in such embodiments, liquefying the mixture includes solvent-exchanging the solid silicone resin from the solvent / carrier vehicle into the polyether alcohol compound (C) and, optionally, the aminosilicon compound, thereby preparing the mixture. The solvent exchange is not particularly limited and may simply include removing the carrier vehicle from the reactor (e.g., by distillation). For example, in certain embodiments, the method includes heating the mixture to a temperature of 60-150°C under reduced pressure (i.e., about 35 mbar) to remove the solvent and obtain the mixture.

[0090] As can be seen from the above description and the examples herein, the mixture prepared by the present method provides a liquefied combination of polysiloxane (B), polyether alcohol compound (C), and, if utilized but not completely consumed, optionally an aminosilicon compound. Polysiloxane (B) may comprise the condensation reaction product of a solid silicone resin with polyether alcohol compound (C) (and optionally an aminosilicon compound), or may simply be a liquefied form of a solid silicone resin (e.g., in the absence of capping / condensation with polyether alcohol compound (C) and optionally an aminosilicon compound). The mixture is then typically placed in or combined with polyol (A) to provide the isocyanate-reactive component.

[0091] The isocyanate-reactive component may optionally include various other components. For example, the isocyanate-reactive component is utilized to form a foam. As understood in the art, the isocyanate-reactive component typically reacts with the isocyanate component to provide a foam (e.g., in a two-component (2k) system). Various components, such as catalysts, blowing agents, surfactants, flame retardants, etc., may be included in the isocyanate-reactive component, the isocyanate component, or additional components overall (such that a multi-component composition is utilized to form a foam). While such components are described below with respect to compositions including an isocyanate-reactive component, it should be understood that any of the components described below with respect to the composition, except for any polyisocyanate or isocyanate-functional compound, may be included in the isocyanate-reactive component.

[0092] As introduced above, a composition for preparing a foam is also disclosed. The composition is curable and can be referred to as a curable composition or a foam composition. The composition includes the isocyanate-reactive component disclosed above, (D) a polyisocyanate, (E) a catalyst, and (F) a blowing agent. In certain embodiments, the foam includes or is a polyurethane foam. In other certain embodiments, the foam includes or is a polyisocyanurate foam. In still other embodiments, the foam includes both polyurethane and polyisocyanurate segments or moieties. The composition forms a foam upon reaction of at least components (A) and (D) in the presence of components (E) and (F). The composition is typically a multi-part (i.e., two or more) composition in which the polyisocyanate (D) is present in the isocyanate component. Catalyst (E) is typically present in the isocyanate-reactive component described above, but may alternatively be present in the isocyanate component and / or in a third component separate from the isocyanate-reactive component and the isocyanate component.

[0093] Suitable polyisocyanates for the composition have two or more isocyanate functional groups and include conventional aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. The polyisocyanate (D) may 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 polyisocyanate (D) comprises, consists essentially of, or is pMDI. In one embodiment, polyisocyanate (D) is of the formula OCN-R-NCO, where R is an alkyl, aryl, or arylalkyl moiety. In this embodiment, polyisocyanate (D) can contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0094] Specific examples of suitable polyisocyanates include alkylene diisocyanates having 4 to 12 carbon atoms 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 preferably 1,6-hexamethylene diisocyanate; alicyclic diisocyanates, such as 1,3- and 1,4-cyclohexane diisocyanate, and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydro- and the corresponding isomeric mixtures, 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomeric mixtures, and aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomeric mixtures, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate and the corresponding isomeric mixtures, mixtures of 4,4'-, 2,4'-, and 2,2-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates, and mixtures of MDI and toluene diisocyanate (TDI).

[0095] The polyisocyanate (D) may comprise a modified polyisocyanate, i.e., a product obtained by partial chemical reaction of organic diisocyanates and / or polyisocyanates. Examples of suitable modified polyisocyanates 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 polyisocyanates 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 di- and polyoxyalkylene glycols that can be used individually or in mixtures include diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene polyoxyethylene glycol or -triol. Also suitable are NCO group-containing prepolymers produced from polyester polyols and / or polyether polyols, having an NCO content of 3.5 to 29 parts by weight based on the total weight of the polyisocyanate (D); 4,4'-diphenylmethane diisocyanate, a mixture of 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, or polymeric MDI. Furthermore, (2) liquid polyisocyanates containing carbodiimide groups, having an NCO content of 15 to 33.6 parts by weight based on the total weight of the isocyanate component, for example, 4,4'- and 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4'- and / or 2,6-toluene diisocyanate, may also be suitable.The modified polyisocyanates may 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.

[0096] It is understood that polyisocyanate (D) can comprise any combination of two or more polyisocyanates that differ from one another based on functionality, molecular weight, viscosity, or structure. In certain embodiments, polyisocyanate (D) comprises, consists essentially of, or is pMDI.

[0097] The polyisocyanate (D) typically has a functionality from 2.0 to 5.0, alternatively from 2.0 to 4.5, alternatively from 2.0 to 4.0, alternatively from 2.0 to 3.5.

[0098] In these or other embodiments, polyisocyanate (D) has an NCO weight percent of 15 to 60, alternatively 15 to 55, alternatively 20 to 48.5 wt. %. Methods for determining NCO content by weight are known in the art, based on the functionality and molecular weight of the particular isocyanate.

[0099] As noted above, polyisocyanate (D) is typically present in the composition in an amount to provide an Isocyanate Index based on whether polyurethane and / or polyisocyanurate foams are desired. As is known in the art, when the Isocyanate Index is less than 130, the composition cures to provide primarily polyurethane foams. In contrast, when the Isocyanate Index is greater than 130, the composition cures to provide primarily polyisocyanurate foams. For example, when catalyst (E) includes or is a trimerization catalyst, as described below, the composition forms cyanurate compounds. In certain embodiments, polyisocyanate (D) is present in the composition in an amount to provide an Isocyanate Index of from 100 to less than 130, alternatively from 105 to 125. In other embodiments, polyisocyanate (D) is present in the composition in an amount to provide an Isocyanate Index of from 130 to 350, alternatively from 150 to 350, alternatively from 180 to 350. Isocyanate Index is the molar ratio of NCO to isocyanate reactive hydrogen functional groups multiplied by 100. Isocyanate Index and methods for calculating it are well known in the art.

[0100] The composition additionally comprises (E) a catalyst.

[0101] In one embodiment, catalyst (E) 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, catalyst (E) comprises dibutyltin dilaurate, a dialkyltin(IV) salt of an organic carboxylic acid. Specific examples of suitable organometallic catalysts, such as dibutyltin dilaurate, are commercially available from Air Products and Chemicals, Inc. (Allentown, PA) under the trademark DABCO®. Organometallic catalysts may also include other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate.

[0102] Examples of other suitable catalysts include iron(II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines, including tris(N,N-dimethylaminopropyl)-s-hexahydrotriazone, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium isopropoxide; and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and / or OH pendant groups.

[0103] Further examples of other suitable catalysts, particularly trimerization catalysts, include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, N,N,N-trimethylisopropylamine / formate, and combinations thereof.

[0104] Still further examples of 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, tetramethylimino-bis(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. Catalyst (E) may include a delayed-action tertiary amine based on 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU"). Alternatively or additionally, catalyst (E) may include N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether and / or ethylenediamine. The tertiary amine catalysts can be further modified for use as delayed action catalysts by adding approximately the same stoichiometric amount of an acidic proton-containing acid such as phenol or formic acid. Such delayed action catalysts are commercially available from Air Products and Evonik.

[0105] The catalyst (E) can be used as is or can be placed in a carrier vehicle. Carrier vehicles are known in the art and are further described below as optional components of the composition. When a carrier vehicle is used to dissolve the catalyst (E), the carrier vehicle can be referred to as a solvent. The carrier vehicle can be an isocyanate-reactive, for example, an alcohol-functional carrier vehicle such as dipropylene glycol.

[0106] The catalyst (E) can be used in various amounts. The catalyst (E) can include any combination of different catalysts. As noted above, the catalyst (E) is typically present in the isocyanate-reactive component, but may alternatively be present in the isocyanate component and / or in a third component separate from the isocyanate-reactive component and the isocyanate component.

[0107] The composition further comprises (F) a blowing agent. When the blowing agent is already present (e.g., water) or is generated during the reaction (e.g., carbon dioxide), the blowing agent may be referred to as a co-blowing agent, which may provide most or all of the foaming during the curing of the composition. The blowing agent (F) may be selected from the group consisting of chemical blowing agents, physical blowing agents, and combinations thereof. Examples of such blowing agents are described below.

[0108] The amount of blowing agent used can be varied depending on the desired results, for example, the amount of blowing agent can be varied to adjust the final foam density and foam rise profile, as well as the final foam cell size.

[0109] In various embodiments, the blowing agent (F) comprises a chemical blowing agent selected from the group of Si-OH compounds, which may 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 may have a relatively low viscosity at 25°C, such as 10 mPa·s to 5,000 mPa·s, 10 mPa·s to 2,500 mPa·s, 10 mPa·s to 1,000 mPa·s, 10 mPa·s to 500 mPa·s, or 10 mPa·s to 100 mPa·s.

[0110] In certain embodiments, the chemical blowing agent comprises or is water. The amount of water present in the total mass of the composition (before reaction) is typically from 0.02 wt. % to 1.00 wt. %, alternatively from 0.03 wt. % to 0.9 wt. %, alternatively from 0.05 wt. % to 0.8 wt. %, alternatively from 0.1 wt. % to 0.7 wt. %, based on the total weight of the composition.

[0111] In various embodiments, the composition includes a physical blowing agent, which may be used in addition to or instead of a chemical blowing agent.

[0112] In various embodiments, the physical blowing agent is one that undergoes a phase change from a liquid to a gaseous state during exposure to atmospheric pressure and a temperature of 10° C. or greater, alternatively 20° C. or greater, alternatively 30° C. or greater, alternatively 40° C. or greater, alternatively 50° C. or greater, alternatively 60° C. or greater, alternatively 70° C. or greater, alternatively 80° C. or greater, alternatively 90° C. or greater, or alternatively 100° C. or greater. The boiling point temperature generally varies depending on the particular type of physical blowing agent.

[0113] Useful physical blowing agents include hydrocarbons, such as pentane, hexane, halogenated, more particularly chlorinated and / or fluorinated hydrocarbons, such as methylene chloride, chloroform, trichloroethane, chlorofluorocarbons, hydrochlorofluorocarbons ("HCFCs"), ethers, ketones, and esters, such as methyl formate, ethyl formate, methyl acetate, or ethyl acetate, in liquid form, or air as a gas, and nitrogen or carbon dioxide. In certain embodiments, the physical blowing agent includes or is n-pentane. In certain embodiments, the physical blowing agent includes 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 includes an inert compound.

[0114] In various embodiments, the physical blowing agent comprises a hydrofluorocarbon ("HFC"). "Hydrofluorocarbon" and "HFC" are interchangeable terms and refer to organic compounds containing hydrogen, carbon, and fluorine, which are substantially free of halogens other than fluorine.

[0115] Examples of suitable HFCs include 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, and perfluoro-1,3-dimethylcyclohexane. Aliphatic compounds such as cyclohexane, perfluorooctane, and 1,1,1,2-tetrafluoroethane (HFC-134a); and aromatic compounds such as fluorobenzene and 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 may be preferred due to their increased availability and ease of use, with HFC-365mfc having a higher boiling point than HFC-245fa, which may be useful in certain applications. For example, HFCs with boiling points higher than 30°C, such as HFC-365mfc, may be desirable because they do not require liquefaction during foam processing.

[0116] Further examples of physical blowing agents are hydrofluoroolefins (HFOs) such as trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze, available from Honeywell under the tradename Solstice ze), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd, available from Arkema under the tradename Forane), 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf, available from Honeywell under the tradename Solstice yf and available from Chemours under the tradename Opteon YF), cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z, available from Chemours under the tradename Opteon MZ), and Opteon 1150.

[0117] The blowing agent (F) can be present in the isocyanate-reactive component, the isocyanate component, or can be a separate component in the composition.

[0118] In certain embodiments, the composition further comprises (G) a surfactant. The surfactant (G) may be present in the isocyanate-reactive component, the isocyanate component, or a component separate from the isocyanate-reactive component and the isocyanate component. Suitable surfactants (or "foaming aids") include silicone polyethers, ethylene oxide polymers, propylene oxide polymers, copolymers of ethylene oxide and propylene oxide, other nonionic surfactants, and combinations thereof. When the composition comprises a silicone polyether as a surfactant, the surfactant is distinguished from the polysiloxane (B), which is not a surfactant, as understood in the art. Typically, such silicone polyether surfactants are non-resinous. Additional suitable surfactants may include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, or mixtures of such surfactants.

[0119] In various embodiments, the composition comprises a fluorocarbon surfactant or a fluorinated surfactant.The fluorinated surfactant can be any compound known in the art that contains fluorine atoms on carbon and is also a surfactant.These fluorinated surfactants can be organic or silicon-containing.For example, the fluorinated organic surfactant can be a perfluorinated polyether, such as the formula:

[0120] [ka] and mixtures of such units.

[0121] The silicon-containing fluorinated surfactant may be a siloxane, for example, a siloxane containing an organic radical having fluorine bonded thereto, such as a siloxane having the following formula:

[0122] [ka] The repeating unit may be a siloxane having the following repeating unit.

[0123] In various embodiments, the addition of a 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 foam. This is especially true for slow-cure systems where the surfactant stabilizes the cells while the network forms and cures.

[0124] The composition may optionally further comprise an additive component selected from the group consisting of catalysts, blowing agents, plasticizers, crosslinkers, chain extenders, chain terminators, wetting agents, surface modifiers, waxes, foam stabilizers, moisture scavengers, drying agents, viscosity reducers, cell size reducing compounds, toughening agents, dyes, pigments, colorants, fillers, flame retardants, mold release agents, antioxidants, compatibilizers, UV stabilizers, thixotropic agents, anti-aging agents, lubricants, coupling agents, solvents, rheology promoters, adhesion promoters, thickeners, smoke suppressants, antistatic agents, antimicrobial agents, and combinations thereof.

[0125] One or more of the additives can be present in any suitable weight percent (wt%) of the composition, for example, 0.1 wt% to 15 wt%, 0.5 wt% to 5 wt%, or 0.1 wt% or less, 1 wt%, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt% or more of the composition. One of ordinary skill in the art can readily determine suitable amounts of additives depending, for example, on the type of additive and the desired result. Certain optional additives are described in more detail below.

[0126] Suitable carrier vehicles include silicones, both linear and cyclic, organic oils, organic solvents, and mixtures thereof.

[0127] The carrier vehicle may also have a viscosity of 1 to 1,000 mm at 25°C. 2

[0039] The organopolysiloxane may also be a low viscosity organopolysiloxane, or a volatile methylsiloxane, or a volatile ethylsiloxane, or a volatile methylethylsiloxane, having a viscosity in the range of 1 / sec, 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, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof.

[0128] Suitable pigments are known in the art. In various embodiments, the composition further comprises carbon black, such as acetylene black.

[0129] The composition may include one or more fillers. The filler may be one or more reinforcing fillers, non-reinforcing fillers, or a mixture thereof. Examples of finely divided reinforcing fillers include high surface area fumed and precipitated silicas, such as rice husk ash, and some calcium carbonate. Fumed silica may include surface functionalized types, such as hydrophilic or hydrophobic, and is available from Cabot Corporation under the trade name CAB-0-SIL. Examples of finely divided non-reinforcing fillers include crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, carbon black, talc, and wollastonite. Other fillers that may be used alone or in combination with the above fillers include carbon nanotubes, e.g., multi-walled carbon nanotubes, aluminite, hollow glass spheres, clays such as calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesium carbonate, kaolin, aluminum trihydroxide, magnesium hydroxide (brucite), graphite, copper carbonates, e.g., malachite, nickel carbonates, e.g., zarachite, barium carbonates, e.g., witherite, and / or strontium carbonates, e.g., strontium sulphite. Further alternative fillers include silicates from the group consisting of aluminum oxide, olivine, garnet; aluminosilicates; cyclic silicates; chain silicates; and layered silicates. In certain embodiments, the composition includes at least one filler comprising hollow particles, e.g., hollow spheres. Such fillers may be useful for contributing to the porosity and / or overall porosity of the foam. Fillers, when utilized, may be used in the composition in an amount of 0.01 wt.% to 50 wt.%, alternatively 0.05 wt.% to 40 wt.%, alternatively 0.1 wt.% to 35 wt.%, based on the total weight of the composition. Additionally, fumed silica, when utilized, may be used in an amount of 0.01 wt.% to 5 wt.%, alternatively 0.05 wt.% to 3 wt.%, alternatively 0.1 wt.% to 2.5 wt.%, alternatively 0.2 wt.% to 2.2 wt.%, based on the total weight of the composition.

[0130] If present, the filler may optionally be surface-treated with a treating agent. Treating agents and treatment methods are understood in the art. Surface treatment of the filler is typically carried out with, for example, a fatty acid or a fatty acid ester such as a stearate, or with an organosilane, organosiloxane, or organosilazane, such as a hexaalkyldisilazane or a short-chain siloxanediol. Generally, the surface treatment renders the filler hydrophobic, thus facilitating handling and obtaining a homogeneous mixture with the other components in the composition. R 4 e Si(OR 5 ) 4-e [In the formula, R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 6 to 20 carbon atoms, e.g., alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, and aralkyl groups such as benzyl and phenylethyl; R 5 is an alkyl having 1 to 6 carbon atoms and the subscript "e" is 1, 2, or 3] can also be used as a filler treating agent.

[0131] In various embodiments, the composition further comprises an adhesion promoter. The adhesion promoter can improve the adhesion of the foam to the substrate it comes into contact with during curing. In certain embodiments, the adhesion promoter is selected from organosilicon compounds having at least one alkoxy group bonded to a silicone atom in the molecule. The alkoxy group is exemplified by methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy groups. Further, the non-alkoxy groups bonded to the silicon atom of the organosilicon compound are exemplified by substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated alkyl groups; epoxy group-containing monovalent organic groups such as 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, or similar glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl groups, 3-(3,4-epoxycyclohexyl)propyl groups, or similar epoxycyclohexylalkyl groups; and 4-oxiranylbutyl groups, 8-oxiranyloctyl groups, or similar oxiranylalkyl groups; acryl group-containing monovalent organic groups such as 3-methacryloxypropyl groups; and hydrogen atoms.

[0132] This organosilicon compound generally has a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom. Furthermore, due to its ability to provide good adhesion to various types of substrates, this organosilicon compound generally has at least one epoxy-containing monovalent organic group in the molecule. This type of organosilicon compound is exemplified by organosilane compounds, organosiloxane oligomers, and alkyl silicates. The molecular structure of the organosiloxane oligomer or alkyl silicate is exemplified by a linear structure, a partially branched linear structure, a branched structure, a cyclic structure, and a net structure. The linear structure, the branched structure, and the net structure are typical. Organosilicon compounds of this type are exemplified by silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like; siloxane compounds having at least one silicon-bonded alkenyl group or silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group in the molecule; mixtures of silane or siloxane compounds having at least one silicon-bonded alkoxy group in the molecule and siloxane compounds 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.

[0133] In specific embodiments, the composition, particularly the isocyanate-reactive component, may further comprise a chain extender. Suitable chain extenders include any of the components listed above as initiators for polyol (A), which may be used alone or in combination as chain extenders, when present, separately from and in addition to polyol (A).

[0134] When utilized in the composition, any of the optional additives may be present in the isocyanate-reactive component or as separate components in the composition. Alternatively, optional additives that are not isocyanate-reactive, such as fillers, may be included in the isocyanate component. Typically, the composition is a 2k (two-component) composition, where the isocyanate component consists of polyisocyanate (D) and the isocyanate-reactive component comprises the remaining ingredients.

[0135] In certain embodiments, the isocyanate-reactive component has a viscosity at 25°C 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, or alternatively less than 850 centipoise. The dynamic viscosity is measured at 10 s from 20 to 80°C with a temperature ramp rate of 3°C / min. -1 The kinematic viscosity can be measured using a TA Instruments AR 2000 rheometer with a 45 mm cone-and-plate geometry at a constant shear rate of 100 rpm. Kinematic viscosity can be measured according to ASTM D445. These ranges apply even when the composition is a 2k composition and the isocyanate-reactive component comprises everything in the composition except the polyisocyanate (D). This viscosity range allows the isocyanate-reactive component to flow freely, which is advantageous for certain end-use applications where foaming in or on certain substrates or articles is desired, such as those defining voids and / or orifices.

[0136] The composition may be prepared by combining the isocyanate-reactive component and the isocyanate component, as well as any optional components not present in the isocyanate-reactive component, in any order of addition. As described in more detail below, the composition may be a one-part composition, a two-component or 2K composition, or a multi-part composition. When the isocyanate-reactive component and the isocyanate component are combined, particularly in the presence of catalyst (E), a reaction is initiated to produce a foam. The foam may be formed at room temperature and ambient conditions. Alternatively, at least one condition, such as temperature, humidity, pressure, etc., may be selectively changed during foam formation.

[0137] A foam comprising the reaction product of the composition is also disclosed.

[0138] In many embodiments, the foam is a closed-cell foam. In many embodiments, the foam is an open-cell foam. In various embodiments, the foam has a modulus of elasticity of 20 to 70, alternatively 30 to 60, alternatively 30 to 50, alternatively 30 to 45 kg / m 3 The density of the foam can be determined via methods understood in the art. For example, the density of the foam can be measured via Archimedes' principle using a balance and density kit and following standard instructions associated with such balance and kit. An example of a suitable balance is a Mettler-Toledo XS205DU balance with a density kit.

[0139] In various embodiments, the foam has pores that are generally uniform in size and / or shape and / or distribution. In certain embodiments, the foam has an average pore size of 5 millimeters or less, alternatively 2.5 millimeters or less, alternatively 1 millimeter or less, alternatively 0.75 millimeters or less, alternatively 0.1 to 0.7 millimeters, alternatively 0.2 to 0.6 millimeters.

[0140] The average pore size can be determined by methods understood in the art, for example, ATSM Method D3576-15 with the following modifications: (1) rather than projecting an image onto a screen, the foam is imaged using an optical or electron microscope; (2) rather than scribing a 30 mm line, a line of known length is scribed over 15 cells.

[0141] In various embodiments, the foam has a k-factor of 15 to 28 mW / m K. As understood in the art, k-factor can be measured according to ASTM C 518 and as described below in connection with the Examples.

[0142] Foams and composite articles comprising a substrate and a foam together can be formed by disposing the composition on a substrate and allowing the composition to cure.

[0143] The composition can be disposed or distributed on the substrate in any suitable manner. Typically, the curable composition is applied in wet form by a wet coating technique. The curable composition can be applied by i) spin coating, ii) brush coating, iii) drop coating, iv) spray coating, v) dip coating, vi) roll coating, vii) flow coating, viii) slot coating, ix) gravure coating, x) Mayer bar coating, or xi) a combination of any two or more of i)-x).

[0144] The substrate is not limited and may be any substrate, for example, a mold, a sheet, a panel, etc. The foam may be separable from the substrate, for example, if the substrate is a mold, or may be physically and / or chemically bonded to the substrate as desired. The substrate may optionally have continuous or non-continuous shapes, sizes, dimensions, surface roughness, and other properties.

[0145] Alternatively, the substrate may comprise a plastic, which may be thermosetting and / or thermoplastic. However, the substrate may alternatively be or comprise glass, ceramic, metal such as titanium, magnesium, aluminum, carbon steel, stainless steel, nickel-coated steel, or an alloy of such metals, or a combination of different materials. Because the composition may cure at ambient conditions, high temperatures that may damage some substrates are not required for curing to occur.

[0146] Specific examples of suitable substrates include polymer substrates such as polyamide (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 / acid monomer copolymers such as those available from Dow under the trade name Surlyn, polypropylene (PP), and polybutylene; other styrenic resins such as polystyrene (PS) and SB rubber; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resin; phenoxy resin; cellulose such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene;Thermoplastic elastomers include polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluoropolymers, as well as copolymers and combinations thereof. Thermosetting resins include epoxy, polyurethane, polyurea, phenol-formaldehyde, urea-formaldehyde, or combinations thereof. The substrate may have a coating, film, or layer disposed thereon. Coatings made from polymer latexes, such as latexes from acrylic acid, acrylate, methacrylate, methacrylic acid, other alkyl acrylates, other alkyl acrylic acids, styrene, isoprene, butylene monomers, or alkyl esters of the aforementioned acid monomers, or latexes from copolymers of the aforementioned monomers, can be used. Composites based on any of these resins can be used as substrates by combining them with glass fiber, carbon fiber, or solid fillers, such as calcium carbonate, clay, aluminum hydroxide, aluminum oxide, silicon dioxide, glass spheres, sawdust, wood fiber, or combinations thereof.

[0147] In one particular embodiment, the foam can be utilized in insulation applications, such as commercial or residential insulation, insulated metal panels for roofing applications, structural insulating panels (SIPs), e.g., for post and beam construction, or tank and / or pipe insulation. Alternatively, in another particular embodiment, the foam can be used in cladding applications. The end use of the foam is not so limited, and the foam can be utilized in place of any conventional rigid foam.

[0148] The following examples, which represent embodiments of the present disclosure, are intended to illustrate, but not limit, the invention. Unless otherwise specified, all reactions were carried out under air and all components were purchased or otherwise obtained from various commercial suppliers.

[0149] The following instruments and characterization procedures / parameters are used to evaluate various physical properties of the compounds and compositions prepared in the examples below.

[0150] Instrumentation and Characterization Parameters The following instruments and characterization procedures / parameters are used to evaluate various physical properties of the compounds and foams prepared in the examples below.

[0151] Gel Permeation and Size Exclusion Chromatography (GPC / SEC) SEC Instrumentation SEC is performed on a Waters 2695 LC pump and autosampler with a flow rate set at 1 mL / min and an injection volume set at 100 μL. SEC separation is performed on two Agilent Plgel Mixed-D columns, each held at 35°C, using a Shodex RI-201 refractive index detector.

[0152] Sample preparation Samples are prepared in THF eluent at a concentration of approximately 5 mg / mL polymer. The solutions are shaken on a flat-bed shaker at ambient temperature for approximately 2 hours and then filtered through a 0.45 μm PTFE syringe filter before injection.

[0153] Processing the data Agilent GPC software Cirrus version 3.3 was used for data collection and data reduction. A total of 16 polystyrene (PS) linear narrow molecular weight standards from Agilent with Mp values ​​ranging from 3752 to 0.58 kg / mol were used for molecular weight calibration. A third-order polynomial was used for calibration curve fitting, providing reference to all molecular weight averages, distributions, and molecular weights as PS equivalent values.

[0154] Brookfield Viscosity Measurement Brookfield Instrumentation A Brookfield DV3T cone / plate rheometer maintained at 25° C. by water recirculation is utilized with a CPA-40Z spindle and 0.50 mL material volume for the measurements.

[0155] Sample preparation and procedures A method based on ASTM D 4287 is utilized using a horizontal viscometer. For each series of samples, the required parameters are entered into the digital viscometer and the position of the sample cup is adjusted relative to the spindle (cone) as specified by the manufacturer to maintain the required clearance. The sample cup is removed and 0.5 mL of sample is added to the center of the cup using a 1 mL syringe, ensuring all air bubbles are excluded from the material. The sample is allowed to equilibrate at 25 + / - 0.1°C. The motor is started at a specific speed and the digital readout of viscosity is recorded. Prior to taking samples, the instrument is calibrated using Standard 200 Fluid (with a viscosity close to that of the sample, if possible) as a control.

[0156] 29 Si NMR 29 For Si NMR, 2.5-3 g of each product prepared below and approximately 5 g of solvent (CDCl3 + Cr(acac)3) were loaded into a 16 mm silicon-free NMR tube, and spectra were obtained according to the conditions and instruments in Table 2 below.

[0157] [Table 1]

[0158] Foam cell size of the foams formed below was measured according to modified ASTM D3576, while bubble counts were performed from images obtained by using a Hitachi SU-8230 scanning electron microscope in low magnification mode. Cross sections of the foam samples were cut with a scalpel and coated with a 15 nm Pt / Pd coating.

[0159] The foam density of the foams is measured by modified ASTM D 1622. For this purpose, a 2 inch x 2 inch x 2 inch cube was cut from each foam.

[0160] K-factor testing The thermal conductivity of the foams was measured according to ASTM C 518, measuring the lambda value (k-factor) at an average of 10°C (top plate 2°C, bottom plate 18°C) using a TA LaserComp Fox 200 instrument. 200 x 200 x 25 mm samples of each foam were cut with a band saw for this measurement.

[0161] LOI (Limiting Oxygen Index) Testing LOI was tested with the FTT Oxygen Index (Model No. FTT0077), an instrument from Fire Testing Technology (FTT) for measuring the minimum percentage of oxygen in a test atmosphere required to slightly support combustion according to ISO 4589 Part 3 or UK Naval Engineering Standard NES 715 or GB / T 2406, GB / T 5454. LOI is a common index for judging the flammability of different materials. It is defined as the minimum oxygen concentration (adjusted by oxygen-nitrogen mixture) required to sustain combustion of a vertically mounted test specimen. A lower LOI indicates worse flame retardancy.

[0162] Test specimens measuring 150 x 10 x 10 mm were cut from the same location on the mold foam and marked with a top and bottom mark relative to the foaming direction. The specimens were placed in the test area of ​​the instrument. The oxygen level was adjusted by controlling the nitrogen level. Typically, two to three specimens were initially burned to estimate the range of LOI (lower and upper limits). Starting at the lower oxygen level, the specimens were burned, and the burning behavior was monitored using the criterion of specimen burning heights below or above 5 cm under a given oxygen level. The oxygen level was adjusted up or down by 0.1 to 0.2% each time to find the maximum oxygen level that could burn specimens close to but below 5 cm.

[0163] MSD (Maximum Smoke Density) Test MSD testing was performed using a ShineRay smoke density tester (JCY-2) in accordance with GB / T 8627-2007. Test specimens were cut from the same location on a molded foam (25 x 25 x 25 mm) and marked with a top and bottom mark relative to the foaming direction. The specimen was placed in the test area of ​​the instrument. A lighter was lit and the flame was adjusted to the desired height. The specimen was then burned under the flame, and the smoke density vs. time curve was monitored to obtain a smoke density vs. time curve from which the MSD (maximum smoke density) could be read. After the test, the chamber was cleaned, and a second specimen was tested according to the same procedure. The test was repeated on three to five specimens, and the average MSD was used.

[0164] Ignition potential of products subjected to direct flame impingement Direct flame tests according to standard EN 11925-2 were performed on selected foam samples. Test specimens were cut from the same location on the molded foam (90 x 190 x 25 mm in size). The specimens were conditioned for one week before testing. The specimens were placed on a specimen holder suspended in a test cabinet. The burner was positioned vertically with a flame height of 20 mm and then tilted at a 45° angle. The flame was applied to the bottom edge of each specimen at the center of its width and thickness for 15 seconds, and then the burner was retracted. The flame height was recorded. If present, the final droplets on the filter foil were recorded. The test was repeated on two specimens, and the maximum recorded value during the test on a different specimen was used for each sample.

[0165] Compression strength The bidirectional compressive strength (CS) at 10% deflection (kPa) was measured according to EN 826. The compressive strength was measured perpendicular and parallel to the growth of the foam.

[0166] Test specimens were cut from the same location on the mold foam, and the compressive strength was measured in triplicate in each direction. The test specimens for measuring CS were 40 × 40 × 25 mm.

[0167] material Table 3 below provides a brief summary and provides information about certain abbreviations, shorthand notations, and components used in the examples.

[0168] [Table 2-1]

[0169] [Table 2-2]

[0170] Preparation Example 1 482.59 g of MQ Resin 1 and 283.46 g of Surfactant 1 were placed in a 500 mL pear-shaped flask. The contents of the flask were adjusted to 75 wt. % solids (resin + surfactant) by the addition of xylene. The total weight was 988.3 g. The flask was mixed at 200 rpm using an overhead stirrer and then heated to 90°C for 20 minutes. The contents of the flask were then heated to 100°C for 20 minutes, and then the temperature was increased to 110°C for approximately 3 hours. The temperature was increased to 130°C over approximately 1 hour, and the flask was cooled to room temperature and rotary evaporated under vacuum at 100°C to remove the xylene. The resulting product was clear and had a Brookfield viscosity of 8400 cps at 25°C.

[0171] Preparation Example 2 58.6 g of MQ Resin 2, 57.4 g of Surfactant 2, and 25.6 g of Surfactant 3 were placed in a 500 mL pear-shaped flask. 0.2 grams of Sn octoate was added to the flask, and the contents of the flask were adjusted to 70 wt. % solids (resin + surfactant) by the addition of xylene. The total weight was 141.9 g. The contents of the flask were then heated to 125°C and held for 5 hours. The flask was cooled to room temperature and rotary evaporated under vacuum at 100°C to remove the xylene. The resulting product was clear and had a Brookfield viscosity of 185 cps at 25°C.

[0172] Preparation Examples 3-4 The product of Preparative Example 2 was placed in two different polyols to determine shelf life stability, which was greater than six months. The relative amounts of ingredients in Examples 3 and 4 are shown in Table 4 below.

[0173] [Table 3]

[0174] Preparation Example 5 273.5 g of MQ Resin 2 and 161.6 g of Surfactant 5 were placed in a 1000 mL four-neck flask. 0.15 g of Sn octoate was added, and the contents of the flask were adjusted to 70 wt. % solids (resin + surfactant) by the addition of xylene. The total weight was 507.5 g. The flask was mixed with an overhead stirrer at 200 rpm and heated to 80°C for 15 minutes. A Dean-Stark trap was attached to the flask, and the contents were refluxed at 140°C for 4 hours, collecting the reaction water. The flask was cooled to room temperature and rotary evaporated under vacuum at 100°C to remove the xylene. The resulting product was clear and had a Brookfield viscosity at 25°C of 1595 cps and a density of 1.084 g / cc. The product was analyzed by GPC. The resulting product had a resin content of approximately 54%.

[0175] Preparation Example 6 246.7 g of MQ Resin 2 and 79.93 g of Surfactant 1 were placed in a 1000 mL four-neck flask. 0.15 g of Sn octoate was added, and the contents of the flask were adjusted to 50 wt. % solids (resin + surfactant) by adding xylene. The total weight was 506.7 g. The flask was mixed with an overhead stirrer at 200 rpm and heated to 80°C for 15 minutes. A Dean-Stark trap was attached to the flask, and the contents were refluxed at 140°C for 4 hours, collecting the reaction water. The flask was cooled to room temperature and rotary evaporated under vacuum at 100°C to remove the xylene. The resulting product was clear and had a Brookfield viscosity of 1800 cps and a density of 1.088 g / cc. The product was analyzed by GPC and Si NMR. The resulting product had a resin content of approximately 68%.

[0176] Preparation Example 7 226.0 g of MQ Resin 2 and 93.75 g of Surfactant 4 were placed in a 1000 mL four-neck flask. 0.15 g of Sn octoate was added, and the contents of the flask were adjusted to 50 wt. % solids (resin + surfactant) by adding xylene. The total weight was 506.1 g. The flask was mixed with an overhead stirrer at 200 rpm and heated to 80°C for 15 minutes. A Dean-Stark trap was attached to the flask, and the contents were refluxed at 140°C for 4 hours, collecting the reaction water. The flask was cooled to room temperature and rotary evaporated under vacuum at 100°C to remove the xylene. The resulting product was clear and had a Brookfield viscosity of 1386 cps and a density of 1.27 g / cc. The product was analyzed by GPC. The resulting product had a resin content of approximately 63%.

[0177] Preparation Example 8 291 g of MQ Resin 2 and 718.2 g of Surfactant 6 were placed in a 2000 mL four-neck flask. 0.4 g of Sn octoate was added, and the contents of the flask were adjusted to 90 wt. % solids (resin + surfactant) by adding xylene. The total weight was 1008 g. The flask was mixed with an overhead stirrer at 200 rpm and heated to 80°C for 15 minutes. A Dean-Stark trap was attached to the flask, and the contents were refluxed at 140°C for 4 hours, collecting the reaction water. The flask was cooled to room temperature and rotary evaporated under vacuum at 100°C to remove the xylene. The resulting product was clear and had a Brookfield viscosity of 5884 cps and a density of 1.046 g / cc. The product was analyzed by GPC-IR. The resulting product had a resin content of approximately 20%.

[0178] GPC analysis of preparation examples 5 to 8 The results of GPC analysis for the compositions / products obtained in Preparative Examples 5-8 are shown in Table 5 below.

[0179] The GPC composition was obtained by deconvolution of the GPC spectrum and calibration of free MQ resin and free surfactant.

[0180] [Table 4]

[0181] Examples 1 to 3 and Comparative Examples 1 to 2 Compositions and foams were prepared using the products of Preparative Examples 1 and 3-4. The compositions were three-part compositions, with (1) Part (A) containing Isocyanate 1 or 2 and (2) Part (B) containing the remaining ingredients. Table 6 shows the relative amounts of the components in each composition of Examples 1-3 and Comparative Examples 1-2. Unless otherwise indicated, values ​​in Table 6 are in grams. PE indicates a Preparative Example, so "PE 1" indicates the relative amount of product, for example, from Preparative Example 1. CE indicates a Comparative Example. To form the foam, Part B of each composition was mixed in a cup for 1 minute. Part A was then combined with Part B and mixed for 5 seconds to obtain a raised foam. The open cell content of the final foam was measured according to ASTM D 2856-94.

[0182] [Table 5]

[0183] Examples 4 to 9 and Comparative Examples 3 to 6 Foams were prepared using the products of Preparative Examples 5-8. Specifically, each of the foams of Examples 4-9 and Comparative Examples 3-6 was formed from a composition. The compositions were three-part compositions: (1) Part (A) was 3 parts isocyanate; (2) Part (B) was 5 parts polyol, 1 part flame retardant, 3 parts silicone surfactant, blowing agent, and the product of Preparative Examples 5-8 (if applicable), respectively; and (3) Part (C) was the catalyst. Tables 7 and 8 show the relative amounts of the components in each composition of Examples 4-9 and Comparative Examples 3-6. Values ​​in Tables 7 and 8 are in grams. PE indicates a Preparative Example, so "PE 5" indicates the relative amount of product from, for example, Preparative Example 5. CE indicates a Comparative Example.

[0184] [Table 6]

[0185] [Table 7]

[0186] To prepare each foam for each of Examples 4-9 and Comparative Examples 3-6, Part (B) was prepared and mixed with Part (A) in a plastic container for 10 seconds using a high-speed air mixer at 2000 revolutions per minute (rpm). While still stirring, Part (C) was added to the plastic container via syringe, ensuring that Part (C) was rapidly drawn into the vortex. The contents of the plastic container were stirred for an additional 5 seconds (total mixing time 15 seconds), and then the contents of the plastic container were poured into a plastic film-lined wooden box measuring 9 inches x 9 inches x 4 inches. The resulting foams were removed from the box and allowed to stand for 24 hours before further characterization.

[0187] Tables 9 and 10 below show the physical properties associated with the foams of Examples 4-9 and Comparative Examples 3-6. CE indicates Comparative Example. The indices b and t in Table 10 relate to measurements taken from samples taken from the top or bottom of the foam, respectively.

[0188] [Table 8]

[0189] [Table 9]

[0190] Examples 10 to 12 and Comparative Examples 7 to 8 Additional foams were prepared. In particular, each of the foams of Examples 10-12 and Comparative Examples 7-8 was formed from a composition. Table 11 shows the relative amounts of the components in each composition of Examples 10-12 and Comparative Examples 7-8. The values ​​in Table 11 are in grams.

[0191] [Table 10]

[0192] The compositions of Examples 10-12 and Comparative Examples 7-8 were identical except for the presence (or absence, in Comparative Example 7) of MQ Resin 3 and Surfactant 7. Examples 10-12 vary the relative amounts of MQ Resin 3 and Surfactant 7. Each of these compositions was prepared as a two-part composition in which all components except Isocyanate 4 were present in the isocyanate-reactive component, and Isocyanate 4 was present solely in the isocyanate component. In Examples 10-12, MQ Resin 3 was dissolved in Surfactant 7 to obtain a clear solution, which was then blended with the other components in each isocyanate-reactive component. Each isocyanate-reactive component was blended at 3,000 rpm for 1-2 minutes.

[0193] Foams were formed using the compositions of Examples 10-12 and Comparative Examples 7-8. Specifically, each isocyanate-reactive component was placed in a 500 mL container, followed by the addition of the isocyanate component to obtain a mixture. The mixture was vigorously stirred at 3000 rpm for 5-6 seconds and poured into a preheated mold (60°C) with dimensions of 400 x 200 x 100 mm. The mold was immediately closed and sealed for 20 minutes to allow all foams to form and expand. Each foam was then removed from the mold and evaluated as described above.

[0194] To ensure accuracy and consistency of the various tests, each side of each foam was marked and test specimens were cut from the same location on each foam in different sizes for different test purposes.

[0195] The properties measured for the foams of Examples 10-12 and Comparative Examples 7-8 are listed in Table 12 below.

[0196] [Table 11]

[0197] Example 13 291.7 g of silicone resin 4 and 140 g of surfactant 8 were placed in a 2000 mL four-neck flask. No condensation catalyst was added. The flask was rotary evaporated at 60 °C under a vacuum of 2-5 mmHg to remove 81.68 g of xylene. The resulting product was clear and had a Brookfield viscosity of 1230 cps. A sample was analyzed by GPC and Si NMR. The resulting product had a resin content of approximately 60%.

[0198] Example 14 100 g of the product formed in Example 13 and 6 g of an aminosilicon compound were cold blended at room temperature at 60 revolutions per minute (rpm) for 3 hours to provide a loading of 10% aminosilicon compound based on the resin content of the product formed in Example 13.

[0199] Example 15 100 g of the product formed in Example 13 and 6 g of an aminosilicon compound were blended for 3 hours at 60 rpm and heated at 80° C. in a rotary evaporator at 300 mm Hg vacuum.

[0200] Example 16 100 g of the product formed in Example 13 and 12 g of an amino silicon compound were blended for 3 hours at 60 rpm and heated at 80° C. in a rotary evaporator at 300 mm Hg vacuum.

[0201] Example 17 100 g of the product formed in Example 13 and 12 g of an amino silicon compound were blended at 60 rpm for 3 hours and heated at 80° C. in a rotary evaporator at 300 mm Hg vacuum to obtain the product. 14.7 g of Polyol 8 was combined with the product to obtain a clear solution.

[0202] Comparative Example 9 12.9 g of the amino silicon compound and 87.1 g of surfactant 8 were cold blended at room temperature at 60 revolutions per minute (rpm) for 3 hours.

[0203] Comparative Example 10 12.9 g of the amino silicon compound and 87.1 g of surfactant 8 were blended for 3 hours at 60 rpm and heated at 80° C. on a rotary evaporator at 300 mm Hg vacuum.

[0204] Comparative Example 11 16.8 g of amino silicon compound and 83.2 g of surfactant 8 were blended for 3 hours at 60 rpm and heated at 80° C. in a rotary evaporator at 300 mm Hg vacuum.

[0205] Comparative Example 12 12.7 g of the amino silicon compound and 63.9 g of Polyol 8 were blended at 60 rpm for 3 hours and heated at 80° C. in a rotary evaporator under a vacuum of 300 mmHg to obtain a product. 23.3 g of Polyol 2 was then cold blended with the product.

[0206] The results of GPC analysis of the product compositions obtained in Examples 13 to 17 and Comparative Examples 9 to 12 are shown in Table 13 below.

[0207] [Table 12]

[0208] The products of Examples 13 to 17 and Comparative Examples 9 to 12 were 29 The siloxy unit content was analyzed by Si NMR and the results are shown in Table 14 below. In Table 14, Z is H or alkyl, Me is methyl, neopentyl is (CH3)3CCH2, X is independently H, a hydrocarbyl group R having 1 to 30 carbon atoms, or a polyether moiety formed by polyether alcohol 9, and T' is H2NCH2CH2CH2SiO 3 / 2 The siloxy units are shown. The values ​​in Table 14 are mole fractions.

[0209] [Table 13]

[0210] Table 15 below shows the products or compositions formed in Examples 13-17 and Comparative Examples 9-12. The values ​​in Table 14 are weight percents based on the products or compositions formed in Examples 13-17 and Comparative Examples 9-12, respectively.

[0211] [Table 14]

[0212] Examples 18 to 22 and Comparative Examples 13 to 20 Isocyanate-reactive components for preparing foams were prepared using the products of Examples 13-17 and Comparative Examples 9-12. Specifically, each of the isocyanate-reactive components of Examples 18-22 and Comparative Examples 13-20 was formed using the products of Examples 13-17 or Comparative Examples 9-12, where applicable. Tables 16 and 17 show the relative amounts of components in each of the isocyanate-reactive components of 18-22 and Comparative Examples 13-20, including all components other than the polyisocyanate utilized in the composition that cures to provide the foam. The values ​​in Tables 16 and 17 are in weight percent based on the total weight of each specific isocyanate-reactive component. CE indicates a comparative example. Additionally, two different silicone surfactants were utilized in the isocyanate-reactive components of Examples 18-22 and Comparative Examples 13-20. Specifically, two isocyanate-reactive components were formed in each of Examples 18-22 and Comparative Examples 13-20: one with Silicone Surfactant 2 and the other with Silicone Surfactant 5. The concentrations are the same for all isocyanate-reactive components in Examples 18-22 and Comparative Examples 13-20. Tables 16 and 17 show that for each of Examples 18-22 and Comparative Examples 13-20, either Silicone Surfactant 2 or 5 was utilized, meaning one isocyanate-reactive component was made with Silicone Surfactant 2 and another isocyanate-reactive component was made with Silicone Surfactant 5.

[0213] [Table 15]

[0214] [Table 16]

[0215] The isocyanate-reactive components of Examples 18-22 and Comparative Examples 13-20 were prepared as follows: Polyol 9, Silicone Surfactant 2 and / or 5, Flame Retardant 2, Blowing Agent 2, and Catalyst 1 were mixed using a pneumatic mixer at 15 rpm for 60-90 seconds to obtain a masterbatch. Catalyst 5, along with the products of Examples 13-17 or Comparative Examples 9-12, if applicable, were added to the masterbatch on the day the foam was prepared and blended at 2700 rpm for 15 seconds. Blowing Agents 1 and 3 were then incorporated and mixed at 1500 rpm for 10 seconds to obtain the isocyanate-reactive components in Tables 16 and 17 above.

[0216] The isocyanate-reactive components of Examples 18-22 and Comparative Examples 13-20 were then combined with Isocyanate 4 by pouring Isocyanate 4 into the particular isocyanate-reactive component and stirring the so-formed composition at 2700 rpm for 6 seconds. After stirring, each composition was poured into a 20 x 20 x 20 cm cube box or a 20 x 20 x 8 cm mold (closed upon placement of the composition) heated at 50°C. Use of the cube box resulted in the formation of a free-rise foam. Use of the mold resulted in molded panels. The molded panels were demolded after 10 minutes.

[0217] The compositions formed using the isocyanate-reactive components and Isocyanate 4 of Examples 18-22 and Comparative Examples 13-20 were prepared at two different Isocyanate Indices: one 180 (i.e., a low index) and one 250 (i.e., a high index). Thus, the amount of Isocyanate 4 utilized in preparing the corresponding compositions of Examples 18-22 and Comparative Examples 13-20 was an amount that provided an Isocyanate Index of either 180 or 250.

[0218] The properties of the foams formed in the mold are measured according to the tests described above. Tables 18 and 19 below show the properties of the foams so formed in Examples 18-22 and Comparative Examples 13-20 based on both the type of silicone surfactant utilized and whether a particular foam was formed with a low isocyanate index (180) or a high isocyanate index (250). In Tables 18 and 19, CS Adv refers to the compressive strength in the direction of foam advance, and CS Tick refers to the compressive strength in the thickness direction of the foam. SS refers to "silicone surfactant."

[0219] [Table 17]

[0220] [Table 18]

[0221] It is to be understood that the appended claims are not limited to the specific compounds, compositions, or methods described therein for purposes of describing the Detailed Description, and that variations may occur among specific embodiments within the scope of the appended claims.

Claims

1. 1. An isocyanate-reactive composition for preparing a foam, said composition comprising: (A) a polyol; (B) a polysiloxane having the formula: (R １ ３ SiO １／２ ) ａ (R ２ ２ SiO ２／２ ) ｂ (R'R ２ SiO ２／２ ) ｂ’ (R ２ SiO ３／２ ) ｃ (R'SiO ３／２ ) ｃ’ (SiO ４／２ ) ｄ and The subscripts a, b, b', c, c', and d are mole fractions such that a+b+b'+c+c'+d=1, where 0<a<1, 0≦b<0.2, 0≦b'≦0.1, 0<c<0.2, 0≦c'≦0.1, 0.4<d<0.7, 0≦b'+c'≦0.1, and the ratio of the subscript a to the subscript d is 0.7 to 1.2 (a:d), and each R １ is independently selected from a hydrocarbyl group having 1 to 30 carbon atoms, —OH, and H; and each R ２ is R １ and —OX, where each X is independently H, a hydrocarbyl group R having 1 to 30 carbon atoms, or a group of the general formula —Y—R ３ (-[Y] ｊ -Z) ｉ where R ３ is a substituted or unsubstituted hydrocarbon segment, and each Y is a group represented by the general formula (CnH ２ nO)m independently selected oxyalkylene segments; wherein the subscript m is 1 to 50, the subscript n is independently selected from 2 to 4 in each moiety designated by the subscript m, each Z is independently H or a resinous silicone moiety, the subscript i is 0 to 8, the subscript j is independently 0 or 1 in each moiety designated by the subscript i, and each R′ comprises an independently selected amino group; and (C) General formula HO-Y-R ３ (-[Y] ｊ -H] ｉ wherein each Y, R ３ , the subscript i, and the subscript j are as defined above. and a polyether alcohol compound.

2. 1. A composition for preparing a foam, said composition comprising: The isocyanate-reactive composition of claim 1; (D) a polyisocyanate; (E) a catalyst; (F) a foaming agent, The composition comprises at least components (A) and (D) reacting in the presence of components (E) and (F) to form a foam.

3. 3. The composition of claim 2, further comprising (G) a surfactant and, optionally, an amino silicon compound.

4. 4. The composition of any one of claims 1 to 3, wherein (i) subscript a is 0.3 to 0.6; (ii) the sum of subscripts b and c is less than 0.2; (iii) the polysiloxane (B) comprises a weight average molecular weight (Mw) of 2000 to 30,000; or (iv) any combination of (i) to (iii).

5. In the polysiloxane (B), (i) each R ２ is independently of the formula -OX in said T siloxy units denoted by subscript c, and (ii) X is a group of each R of formula -OX ２ (iii) each R １ is independently selected from alkyl and aryl groups containing 1 to 30 carbon atoms and H; (iv) each R′, if present, is independently a group of the formula —(CH ２ ) ｇ N (H) ｆ R ２－ｆ wherein each g is independently 1 to 30, f is 0, 1, or 2, and R is independently selected and defined above, or any combination of (v)(i)-(iv).

6. (i) the hydrocarbon segment R ３ comprises a branched chain hydrocarbon group having 3 to 16 carbon atoms; (ii) subscript i is 1 to 8; (iii) subscript j is 1 in each portion designated by subscript i; and (iv) each oxyalkylene segment Y independently has the formula (C ２ H ４ O) x (C ３ H ６ O)y(C ４ H ８ 0) z, wherein subscript x is from 1 to 50, subscript y is from 0 to 50, and subscript z is from 0 to 50, and the units represented by subscripts x, y, and z can be in random or block form in the oxyalkylene segment, or any combination of (v)(i) to (iv).

7. 4. The composition of any one of claims 1 to 3, wherein the composition (i) is tin-free, (ii) is cyclic siloxane-free, (iii) contains less than 1 wt. % solvent based on the total weight of the composition, or (iv) any combination of (i)-(iii).

8. The composition of claim 1, wherein the polysiloxane (B) has a weight average molecular weight (Mw) of 3,000 to 30,000.

9. A foam comprising the reaction product of the composition of claim 2 or 3.

10. 10. Use of the foam of claim 9 in thermal insulation applications, insulating panels for building structures, and / or cladding.

11. 1. A method for preparing a foam, said method comprising: mixing the composition; and curing the composition to obtain a foam. The method of claim 2 or 3, wherein the composition is a composition according to claim 2 or 3.

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