Compositions, silicone polyether surfactants formed therefrom, and related methods and articles

Abstract

Disclosed is a composition comprising (A) an organohydrogensiloxane having cyclic siloxane moieties containing silicon-bonded hydrogen atoms. The composition further comprises (B) a polyether compound having aliphatically unsaturated groups. Finally, the composition comprises (C) a hydrosilylation catalyst. Disclosed is a silicone polyether surfactant prepared by reacting components (A) and (B) in the presence of component (C). Additionally, disclosed is an isocyanate-reactive component comprising a polyol and a silicone polyether surfactant. Disclosed is a composition comprising an isocyanate-reactive component, an isocyanate component comprising a polyisocyanate, and a catalyst. Finally, disclosed is a method for preparing an article comprising a polyurethane and / or polyisocyanurate foam, as well as an article formed from the composition and / or the method.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and all benefits of U.S. Provisional Patent Application No. 63 / 043,295, filed June 24, 2020, the contents of which are incorporated herein by reference.

[0002] FIELD OF THE INVENTION The subject disclosure relates generally to compositions, and more specifically to compositions for preparing silicone polyether surfactants. Silicone polyether surfactants and various uses thereof are also disclosed. [Background technology]

[0003] Silicones are polymeric materials used in many commercial applications, primarily because of the distinct advantages they offer over their carbon-based analogues. More specifically called polymerized siloxanes or polysiloxanes, silicones have an inorganic silicon-oxygen backbone (...-Si-O-Si-O-Si-O-...) with organic side groups attached to the silicon atoms.

[0004] Some silicones are polyether-modified silicones, sometimes called silicone polyethers (SPEs). Many SPEs are commercially available to reduce the surface tension of aqueous solutions / dispersions. However, traditional SPEs can suffer from one or more problems.

[0005] Foams are known in the art and are used in a variety of end uses, including cushioning, support articles, encapsulants / pottants, and thermal insulation. Foams can be formed from a variety of chemical compositions and may use physical and / or chemical blowing agents. For example, polyurethane foams are generally formed by reacting an isocyanate with a polyol in the presence of a blowing agent. Often, foams are formed using SPEs to stabilize the isocyanate-reactive components, including the polyol and / or blowing agent, and prevent phase separation prior to use. Summary of the Invention

[0006] (A) the following structure:

[0007] [ka] wherein the subscript n is 1 to 1,000, each subscript p is independently 1 to 10, each R is an independently selected substituted or unsubstituted hydrocarbyl group, and one or more silicon-bonded hydrogen atoms are represented by the formula:

[0008] [ka] wherein the subscript n is independently selected and defined above, the subscript p is independently selected and defined above, and each R 1 are independently selected substituted or unsubstituted hydrocarbyl groups. The composition further comprises (B) a polyether compound having aliphatically unsaturated groups, and (C) a hydrosilylation catalyst. Also disclosed is a silicone polyether surfactant prepared by reacting components (A) and (B) in the presence of component (C).

[0009] The following structure:

[0010] [ka] Disclosed is a compound having the formula 4 are independently a hydrogen atom, a substituted or unsubstituted hydrocarbyl group, a polyether group, or a group of the formula:

[0011] [ka] wherein R 4at least one of is a polyether group; each subscript p is independently 1 to 10; each subscript n is independently 1 to 2,000; each R is an independently selected substituted or unsubstituted hydrocarbyl group; and each R 1 are independently selected and are defined above.

[0012] Additionally, an isocyanate-reactive component is disclosed that includes a polyol and a silicone polyether surfactant. Further disclosed are compositions that include an isocyanate-reactive component, an isocyanate component that includes a polyisocyanate, and a catalyst. Finally, methods for preparing articles that include polyurethane and / or polyisocyanurate foams, as well as articles and / or methods formed from the compositions, are disclosed. DETAILED DESCRIPTION OF THE INVENTION

[0013] Disclosed is a composition. The composition is a hydrosilylation-curable composition that can be cured to give a reaction product, which can be referred to as a silicone polyether surfactant, and is described in more detail below. The composition comprises (A) a compound having the following structure:

[0014] [ka] wherein the subscript n is 1 to 1,000, each subscript p is independently 1 to 10, each R is an independently selected substituted or unsubstituted hydrocarbyl group, and one or more silicon-bonded hydrogen atoms have the formula:

[0015] [ka] wherein the subscript n is independently selected and defined above, the subscript p is independently selected and defined above, and each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group.

[0016] Generally, R (and R 1Suitable hydrocarbyl groups for (R) may be independently linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, variations, and combinations thereof. Examples of suitable 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, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups or substituted hydrocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl.Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of halogenated aryl groups include the above-mentioned aryl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0017] In certain embodiments, no more than 3, alternatively no more than 2, or alternatively no more than 1 H is substituted with the immediately preceding group comprising the cyclic siloxane moiety. In one particular embodiment, one such group replaces one silicon-bonded hydrogen atom in each cyclic siloxane moiety of component (A).

[0018] In certain embodiments, each R is an unsubstituted hydrocarbyl group and component (A) includes only two cyclic siloxane moieties. In these embodiments, the formula of component (A) is:

[0019] [ka] In the formula, each R 1 and the subscripts p and n are defined above. In a further embodiment, each R and R 1 does not contain aliphatic unsaturation (i.e., aliphatic carbon-carbon double or triple bonds). Aliphatic unsaturation does not include aromatic unsaturation. In various embodiments, each R and R 1is selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, or alternatively 1 carbon atom.

[0020] The subscript n is from 1 to 2,000, alternatively from 2 to 2,000, alternatively from 1 to 1,000, alternatively from 1 to 900, alternatively from 1 to 800, alternatively from 1 to 700, alternatively from 1 to 600, alternatively from 1 to 500, alternatively from 1 to 400, alternatively from 1 to 300, alternatively from 1 to 200. In other embodiments, the subscript n is from 2 to 1,000, alternatively from 2 to 900, alternatively from 2 to 800, alternatively from 2 to 700, alternatively from 2 to 600, alternatively from 2 to 500, alternatively from 2 to 400, alternatively from 2 to 300, alternatively from 2 to 200.

[0021] Each subscript p is independently selected and defines the number of Si—O moieties in each cyclic siloxane moiety of (A) organohydrogensiloxane. Each subscript p is 1 to 10. Thus, each cyclic siloxane moiety of (A) organohydrogensiloxane independently has 3 to 12 siloxy units. In certain embodiments, each subscript p is the same. In other embodiments, each subscript p is different. In certain embodiments, each subscript p is independently 1 to 10, alternatively 1 to 9, alternatively 1 to 8, alternatively 1 to 7, alternatively 1 to 6, alternatively 1 to 5, or alternatively 1 to 4.

[0022] (A) organohydrogensiloxanes can be prepared by different techniques. For example, (A) organohydrogensiloxanes can be prepared by: 1) i) boron-containing Lewis acids, ii) Equation

[0023] [ka] hydroxyl-functional organosilicon compounds of the formula: wherein each subscript n is 1 to 2,000, alternatively 2 to 2,000, and each R is independently selected and is a hydroxyl-functional organosilicon compound as defined above; iii) Formula (RHSiO 2 / 2 ) v wherein the subscript v is 3 to 12, and each R is independently selected and can be synthesized by combining starting materials comprising a cyclic polyorganohydrogensiloxane, as defined above.

[0024] The starting material i) in the method for preparing component (A) is a boron-containing Lewis acid. The boron-containing Lewis acid may be a trivalent boron compound having at least one perfluoroaryl group per molecule, alternatively one to three perfluoroaryl groups per molecule, alternatively two to three perfluoroaryl groups per molecule, or alternatively three perfluoroaryl groups per molecule. The perfluoroaryl groups may have 6 to 12 carbon atoms, alternatively 6 to 10 carbon atoms, or alternatively 6 carbon atoms. Boron-containing Lewis acids include (C5F4)(C6F5)2B; (C5F4)3B; (C6F5)BF2; BF(C6F5)2; B(C6F5)3; BCl2(C6F5); BCl(C6F5)2; B(C6H5)(C6F5)2; B(C6H5)2(C6F5); [C6H4(mCF3)]3B; [C6H4(pOCF3)]3B; (C6F5)B(OH)2; (C6F5)2BOH; (C6F5)2BH; (C6F5)BH2; (C7H 11 )B(C6F5)2;(C8H 14 (CF)B(OCH); or (CF)B-CHCHSi(CH). Alternatively, the boron-containing Lewis acid can be tris(pentafluorophenyl)borane of formula B(CF). Such boron-containing Lewis acids are commercially available, for example, from Millipore Sigma (St. Louis, Missouri, USA).

[0025] Alternatively, the boron-containing Lewis acid has the formula:

[0026] [ka] wherein each R o is an ortho substituent, and each R m is a meta-substituent, and each R p is a para substituent and R L is optional and comprises a functional group or functional polymer group, and the subscript x is 0 or 1. o1~6 Each of R m1~6 and R p1~3 are independently selected from H, F, or CF, with the proviso that R o1~6 , R m1~6 , and R p1~3 cannot all be H at the same time, and R o1~4 If two or more of the are CF3, R o5 and R o6 are each independently selected from H or F. L is optional, i.e., if the subscript x=1, then R L exists and subscript x=0, then R L does not exist. R L may be a Lewis base that forms a complex with the boron-containing Lewis acid of the above formula, and / or a molecule or moiety that contains at least one electron pair available to form a dative bond with the Lewis acid, and R 4 R L Examples of R include cyclic ethers such as tetrahydrofuran or tetrahydropyran. L can be tetrahydrofuran (THF).

[0027] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , and R o6 Each of R can be H. Alternatively, o1 , R o2 , Ro3 , and R o4 Each of R can be H. Alternatively, o5 and R o6 Each of may be F.

[0028] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 , and R m6 Each of R can be CF. m1 , R m2 , R m3 , and R m4 Each of R can be CF. m5 , and R m6 Each of may be F. Alternatively, R m5 and R m6 Each of may be H.

[0029] Alternatively, R p1 , R p2 , and R p3 Each of R can be H. Alternatively, p1 and R p2 can be H. Alternatively, R p3 can be F. Alternatively, R p3 can be CF3.

[0030] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5、 R o6、 R p1 , R p2 , and R p3 Each of the may be H and R m1 , R m2 , R m3、 R m4 , R m5 , and R m6 Each of can be CF. Subscript x can be 1. Alternatively, starting material i) can include tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0031] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5、 R o6、 R m5 , R m6 , R p1 , and R p2 can be H, R m1 , R m2 , R m3、 R m4 , and R p3 can be CF. Subscript x can be 1. Alternatively, starting material i) can include bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0032] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , and R p2 Each of the may be H and R o5 , R o6 , and R p3 Each of the following can be F and R m1 , R m2 , R m3 , R m4 Each of can be CF. Subscript x can be 1. Alternatively, starting material i) can include bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0033] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 , and R p3 Each of the may be H and R o5 and R o6Each of the following can be F and R m1 , R m2 , R m3 , and R m4 Each of can be CF. Subscript x can be 1. Alternatively, starting material i) can include bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0034] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5、 R m6、 R p1 , R p2 , and R p3 Each of the may be H and R m1 , R m2 , R m3、 R m4 , R m5 , and R o6 Each of can be CF. The subscript x can be 0. Alternatively, the starting material i) can include bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0035] Alternatively, R m1 , R p1 , R o2 , R o3 , R o4、 R p2、 R p3 , R o5 , and R m6 Each of the may be H and R o1 , R m2 , R m3、 R m4 , R o6 , and R m5 Each of can be CF. The subscript x can be 0. Alternatively, the starting material i) can include (3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0036] Alternatively, R o1 , Ro2 , R o3 , R o4 , R p1 , and R p2 Each of the may be H and R o5 , R o6 , R m5 , and R m6 Each of the following can be F and R m1 , R m2 , R m3 , R m4 , and R p3 Each of can be CF. Subscript x can be 1. Alternatively, starting material i) can include bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0037] Suitable boron-containing Lewis acids for starting material i) are known in the art and can be prepared by known methods, for example, the methods disclosed in WO 2019 / 055740, specifically in paragraphs

[0052] to

[0096] , by changing the appropriate starting materials.

[0038] The amount of starting material i) will vary depending on the types and amounts of other starting materials used, but starting material i) may be present in an amount of 50 ppm to 6000 ppm, based on the combined weight of starting materials i), ii), and iii), or the amount may be 50 ppm to 600 ppm on the same basis.

[0039] The starting material ii) in the process for preparing component (A) is a compound of the formula:

[0040] [ka] wherein each subscript n is 1 to 2,000, and each R is independently selected and defined above. Alternatively, subscript n can have a value such that 2≦n≦2,000, alternatively 2≦n≦1,000, alternatively 5≦n≦900, alternatively 5≦n≦50, alternatively 5≦n≦15. When subscript n=1, starting material B) can be a hydroxyl-functional silane, such as dimethyldisilanol. Hydroxyl-functional silanes are commercially available.

[0041] Alternatively, when the subscript n is greater than or equal to 2, the starting material ii) can be a hydroxyl-terminated polydiorganosiloxane. Suitable hydroxyl-terminated polydiorganosiloxanes for use as starting material ii) can be prepared by methods known in the art, such as the hydrolysis and condensation of the corresponding organohalosilanes or the equilibration of cyclic polydiorganosiloxanes. An exemplary hydroxyl-terminated polydiorganosiloxane is hydroxyl-terminated polydimethylsiloxane. Suitable hydroxyl-terminated polydimethylsiloxanes are also commercially available from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S41, DMS-S32, DMS-S33, DMS-S35, DMS-S42, and DMS-S45.

[0042] The starting material iii) in the process for preparing component (A) is (RHSiO 2 / 2 ) v where the subscript v is 3 to 12, and each R is an independently selected monovalent hydrocarbon radical. Alternatively, the subscript v may be 4 to 10, or 4 to 8. Alternatively, the subscript v may have an average value of 4 to 6, or 4 to 5, or 4. Suitable cyclic polyorganohydrogensiloxanes are known in the art and are commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA).

[0043] The amounts of starting materials ii) and iii) will vary depending on various factors, including the OH content of ii) the hydroxyl-functional organosilicon compound and the silicon-bonded hydrogen (SiH) content of iii) the cyclic polyorganohydrogensiloxane. However, these amounts are sufficient to provide a molar ratio of SiH in starting material iii) to OH in starting material ii) (SiH:OH ratio) of 4:1 to 40:1, alternatively 5:1 to 20:1, alternatively 5:1 to 10:1. A solvent may be used in this process.

[0044] The composition further comprises (B) a polyether compound having an aliphatic unsaturated group. Typically, the aliphatic unsaturated group is terminal to (B) the polyether compound.

[0045] In certain embodiments, the (B) polyether compound has the formula R 2 O(C m H 2m O) q R 3 wherein R 2 is an aliphatic unsaturated group, subscript m is independently selected from 2 to 4 in each moiety designated by subscript q, subscript q being 1 to 200; R 3 is R 1 , H, and -C(O)R 1 wherein R 1 are independently selected and are defined above.

[0046] In certain embodiments, the (B) polyether compound has the formula R 2 O(C2H4O) x (C3H6O) y (C4H8O) z R 3 wherein R 2 is an aliphatic unsaturated group, 0≦x≦200, 0≦y≦200, and 0≦z≦200, provided that the subscripts x, y, and z are not simultaneously 0, and the units represented by the subscripts x, y, and z can be in a random or block form in the (B) polyether compound; R3 is R 1 , H, and -C(O)R 1 wherein R 1 are independently selected and defined above. As understood in the art, the moieties designated by subscript x are ethylene oxide (EO) units, the moieties designated by subscript y are propylene oxide (PO) units, and the moieties designated by subscript z are butylene oxide (BO) units. When present, EO units, PO units, and BO units can be in block or random form in the (B) polyether compound. When present, the relative amounts of EO units, PO units, and BO units can be selectively controlled based on the desired properties of the reaction product of the composition. For example, the molar ratio of such alkylene oxide units can affect hydrophilicity and other properties.

[0047] The oxyalkylene units in the (B) polyether compound may independently be linear or branched. For example, oxyethylene units, if present, may be of the formula -CH2CHO- or -CHCHO-. Similarly, oxypropylene units, if present, may be of the formula -CH2CH2CHO-, -CH2CHCHO-, or -CHCH3CHO-.

[0048] It is understood that the (B) polyether compound can have one or more moieties selected from the group of EO, PO, and BO, alone or in combination. For example, the (B) polyether compound can have one or more moieties selected from the group of [EO] x Partial only, [PO] y Partial or [BO] z The moiety alone or a combination of these moieties, e.g., [EO] x [PO] y Part, [EO] x [BO] z Part, [PO] y [BO] z Part, or [EO] x [PO] y [BO]z As described above, the units denoted by the subscripts x, y, and z can be in random or block form in the (B) polyether compound. In addition, the units denoted by the subscripts x, y, and z need not be in the order specifically shown herein. For example, one skilled in the art will understand that a polymerization mixture of two or more alkylene oxides (AOs) can be used to form random polyethers, and that appropriate addition order and / or timing of two or more AOs during the polymerization reaction can be used to form block polyethers, and that different orders of AOs, their chain lengths, or combinations of random and block polyethers can be formed.

[0049] In certain embodiments, the subscript x is between 1 and 200, alternatively between 1 and 50, alternatively between 2 and 40, alternatively between 3 and 30, alternatively between 4 and 25, alternatively between 5 and 20. In further embodiments, the subscript x is between 10 and 20, alternatively between 12 and 18, alternatively between 14 and 16, alternatively between 16. In further embodiments, the subscript x is between 20 and 30, alternatively between 22 and 28, alternatively between 24 and 26, alternatively between 24 or 26. In still other embodiments, the subscript x is between 30 and 40, alternatively between 32 and 38, alternatively between 34 and 36.

[0050] In certain embodiments, subscript y is 0 to 50, alternatively 1 to 50, alternatively 0 to 40, alternatively 1 to 40, alternatively 0 to 30, alternatively 1 to 30, alternatively 0 to 25, alternatively 1 to 25, alternatively 0 to 20, alternatively 1 to 20. In further embodiments, subscript y is 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript y is 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In yet other embodiments, subscript y is 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0051] In certain embodiments, subscript z is 0 to 50, alternatively 1 to 50, alternatively 0 to 40, alternatively 1 to 40, alternatively 0 to 30, alternatively 1 to 30, alternatively 0 to 25, alternatively 1 to 25, alternatively 0 to 20, alternatively 1 to 20. In further embodiments, subscript z is 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript z is 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In yet other embodiments, subscript z is 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0052] R 3 is R 1 , H, and -C(O)R 1 Selected from R 1 are independently selected and defined above. In certain embodiments, R 3 is selected from the substituted or unsubstituted hydrocarbyl groups disclosed above for R, for example, R 3 is an alkyl group. In certain embodiments, R 3 is an 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, alternatively 1 to 3, alternatively 1 to 2, or alternatively 1 carbon atom. 3 is a methyl group. In other embodiments, R 3 is H. In yet another embodiment, R 3 is -C(O)R 1 R 3 -C(O)R 1 If R 1 is typically an 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, alternatively 1 to 3, alternatively 1 to 2, or alternatively 1 carbon atom, e.g., R 3 is an acyl group.

[0053] R2 is an aliphatic unsaturated group, typically an alkenyl and / or alkynyl group having 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, or alternatively 2 carbon atoms. "Alkenyl" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, and hexenyl. "Alkynyl" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethynyl, propynyl, and butynyl. Various examples of ethylenically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, HC=C(CH3)-, HC=C(CH3)-, HC=C(CH3)CH2-, HC=CHCH2CH2-, HC=CHCH2CH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-. Typically, the ethylenic unsaturation is represented by R 2 As is understood in the art, ethylenic unsaturation is sometimes referred to as aliphatic unsaturation.

[0054] The relative amounts of components (A) and (B) in a composition are a function of the desired reaction product. For example, the value of each subscript p generally indicates the number of silicon-bonded hydrogen atoms in component (A); if silicon-bonded hydrogen atoms are undesirable in the reaction product, a molar excess of component (B) relative to the moles of silicon-bonded hydrogen atoms in component (A) can be used. Alternatively, residual silicon-bonded hydrogen atoms may be desired, or an additional component containing ethylenic unsaturation can be used to consume the silicon-bonded hydrogen atoms of component (A) without imparting polyether functionality to the reaction product. Those skilled in the art will readily understand how to determine the desired content of components (A) and (B) in a composition. Component (A) can optionally comprise a blend of different compounds, e.g., having different values ​​of subscripts p and / or n, and component (B) can optionally comprise a blend of different polyether compounds.

[0055] The composition further comprises (C) a hydrosilylation catalyst. The (C) hydrosilylation catalyst is not limited and may be any known hydrosilylation catalyst for catalyzing a hydrosilylation reaction. A combination of different hydrosilylation catalysts may also be used.

[0056] In certain embodiments, the (C) hydrosilylation catalyst comprises a Group VIII-Group XI transition metal. For the Group VIII-Group XI transition metals, reference is made to the latest IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations of these, complexes of these (e.g., organometallic complexes), and other forms of such metals may be used as the (C) hydrosilylation catalyst.

[0057] Additional examples of suitable catalysts for (C) hydrosilylation catalyst include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g., those containing calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations of these, complexes of these (e.g., organometallic complexes), and other forms of such metals may be used as (C) hydrosilylation catalyst.

[0058] The (C) hydrosilylation catalyst may be in any suitable form. For example, the (C) hydrosilylation catalyst may be solid, and examples thereof include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts containing multiple metal combinations. Further examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts.

[0059] The (C) hydrosilylation catalyst can be present in or on a solid support. Examples of supports include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate). The (C) hydrosilylation catalyst can also be disposed in, for example, a solvent that solubilizes the hydrosilylation reaction catalyst, or simply in a vehicle that supports but does not solubilize the (C) hydrosilylation catalyst. Such vehicles are known in the art.

[0060] In certain embodiments, (C) the hydrosilylation catalyst comprises platinum. In these embodiments, (C) the hydrosilylation catalyst is exemplified by, for example, platinum black, platinum compounds (such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid with monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated within matrices or core-shell compounds. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art, as exemplified by U.S. Pat. Nos. 4,766,176 and 5,017,654, the entire contents of which are incorporated herein by reference.

[0061] Platinum complexes with organopolysiloxanes suitable for use as (C) hydrosilylation catalysts include platinum complexes of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane. These complexes may be microencapsulated in a resin matrix. Alternatively, the (C) hydrosilylation catalyst may include a platinum complex of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane. The hydrosilylation catalyst may be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane, or an alkene-platinum-silyl complex. The alkene-platinum-silyl complex may be prepared, for example, by mixing 0.015 moles of (COD)PtCl with 0.045 moles of COD and 0.0612 moles of HMeSiCl, where COD represents cyclooctadiene.

[0062] Further examples of suitable hydrosilylation catalysts for component (C) are described, for example, in U.S. Pat. Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,784,879, 5,036,117, and 5,175,325, the disclosures of which are incorporated herein by reference in their entireties.

[0063] (C) The hydrosilylation catalyst may also, or instead, comprise a photoactivatable hydrosilylation catalyst capable of initiating curing by irradiation and / or heating. The photoactivatable hydrosilylation catalyst may be any hydrosilylation catalyst capable of catalyzing a hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of 150 to 800 nanometers (nm).

[0064] Specific examples of photoactivatable hydrosilylation catalysts suitable for (C) hydrosilylation catalyst include platinum(II) bis(2,4-pentanedioate), platinum(II) bis(2,4-hexanedioate), platinum(II) bis(2,4-heptanedioate), platinum(II) bis(1-phenyl-1,3-butanedioate, platinum(II) bis(1,3-diphenyl-1,3-propanedioate), platinum(II) bis(1,1,1,5,5,5-heptanedioate), and platinum(II) bis(1,1,1,5,5,5-heptanedioate). platinum(II) β-diketonate complexes such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl-Cp)trimethylplatinum, where Cp represents cyclopentadienyl; (η-cyclopentadienyl)trialkylplatinum complexes such as [Pt[C6H5NNNOCH3]4, Pt[p-CN-C6H4NNNOCH6H 11 ]4, Pt[p-H3COC6H4NNNOC6H 11 ]4, Pt[p-CH3(CH2) x -C6H4NNNOCH3]4, 1,5-cyclooctadienePt[p-CN-C6H4NNNOC6H 11 ]2, 1,5-cyclooctadiene Pt[p-CH3O-C6H4NNNOCH3]2, [(C6H5)3P]3Rh[p-CN-C6H4NNNOC6H 11 ], and Pd[p-CH3(CH2) x triazene oxide-transition metal complexes such as (η 4 -1,5-cyclooctadienyl)diphenylplatinum, (η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η4 -2,5-norborazienyl)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum, and (η 4 and (η-diolefin)(σ-aryl)platinum complexes such as (η-diolefin)(σ-aryl)platinum complexes, such as (η-diolefin)(σ-aryl)platinum complexes, (η-diolefin)(σ-aryl)platinum complexes, and (η-diolefin)(σ-aryl)platinum complexes.

[0065] The present disclosure also provides a method for producing a compound having the following structure:

[0066] [ka] wherein each R 4 are independently a hydrogen atom, a substituted or unsubstituted hydrocarbyl group, a polyether group, or a group of the formula

[0067] [ka] wherein R 4 at least one of is a polyether group; each subscript p is independently 1 to 10; each subscript n is independently 1 to 2,000; each R is an independently selected substituted or unsubstituted hydrocarbyl group; and each R 1 are independently selected substituted or unsubstituted hydrocarbyl groups. In certain embodiments, the compounds are prepared by reacting components (A) and (B) in the presence of component (C) of the composition.

[0068] In certain embodiments, R 4 In one particular embodiment, no more than three, alternatively no more than two, or alternatively no more than one of the groups immediately above comprises a cyclic siloxane moiety. 4 Each cyclic siloxane moiety contains one such group as

[0069] In certain embodiments, the compound has the following structure:

[0070] [ka] wherein each R 1 , R 4 , and the subscripts x and y are each defined above.

[0071] When the compound is formed from the composition, i.e., by hydrosilylation of components (A) and (B) in the presence of component (C), R 4 The polyether groups of component (A) are formed by hydrosilylation of silicon-bonded hydrogen atoms. 4 is formed by hydrosilylation of (B) a polyether compound with certain silicon-bonded hydrogen atoms of component (A). However, R 4 R may be unreacted hydrogen or a hydrocarbyl group other than a polyether group. 4 When a compound contains two or more polyether groups represented by R, the polyether groups are independently selected and may be the same or different from one another. 4 When R is a hydrocarbyl group other than a polyether group, 4 can be formed from the hydrosilylation of any unsaturated compound with certain silicon-bonded hydrogen atoms of component (A), such as alkenes, dienes, alkynes, and / or functionalized or substituted forms thereof. In certain embodiments, at least 10 mol%, alternatively at least 20 mol%, alternatively at least 30 mol%, alternatively at least 40 mol%, alternatively at least 50 mol%, alternatively at least 60 mol%, alternatively at least 70 mol%, alternatively at least 80 mol%, alternatively at least 90 mol%, alternatively at least 100 mol% of the R 4 is a polyether group.

[0072] In certain embodiments, R 4 The polyether group has the formula -DO(C m H 2m O) q R3 wherein D is a divalent linking group; subscript m is independently selected from 2 to 4 in each moiety designated by subscript q, subscript q being 1 to 200; and R 3 is R 1 , H, and -C(O)R 1 wherein R 1 are independently selected and defined above. D is generally selected from R 4 (B) R in the polyether compound, resulting in a polyether group of 2 The structure of D is therefore a function of the ethylenically unsaturated groups in the (B) polyether compound. D can be branched or linear, and the R of the (B) polyether group 2 When is an alkynyl group, it may further contain ethylenic unsaturation. In certain embodiments, D is a group of formula -C j H 2j -, where j is 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 8, alternatively 2 to 6, alternatively 2 to 4.

[0073] In certain embodiments, R 4 The polyether group has the formula -DO(C2H4O) x (C3H6O) y (C4H8O) z R 3 wherein D is a divalent linking group, 0≦x≦200, 0≦y≦200, and 0≦z≦200, with the proviso that the subscripts x, y, and z are not simultaneously 0, and the units denoted by the subscripts x, y, and z are R 4 (Polyether groups may be in random or block form, R 3 is R 1 , H, and -C(O)R 1 wherein R 1are independently selected and defined above. When present, EO units, PO units, and BO units can be in block or random form in the (B) polyether compound. When present, the relative amounts of EO units, PO units, and BO units can be selectively controlled based on the desired properties of the compound. D is described above.

[0074] R 4 The oxyalkylene units in the polyether group may independently be linear or branched. For example, oxyethylene units, if present, may be of the formula -CH2CHO- or -CHCHO-. Similarly, oxypropylene units, if present, may be of the formula -CH2CH2CHO-, -CH2CHCHO-, or -CHCH3CHO-.

[0075] R 4 It is understood that the polyether group of R may have one or more moieties selected from the group EO, PO, and BO, either alone or in combination. For example, R 4 The polyether group is [EO] x Partial only, [PO] y Partial or [BO] z The moiety alone or a combination of these moieties, e.g., [EO] x [PO] y Part, [EO] x [BO] z Part, [PO] y [BO] z Part, or [EO] x [PO] y [BO] z As noted above, the units denoted by the subscripts x, y, and z can be R 4The polyether groups may be in random or block form. In addition, the units denoted by the subscripts x, y, and z need not be in the order specifically depicted herein. For example, one skilled in the art will understand that a polymerization mixture of two or more alkylene oxides (AOs) can be used to form random polyethers, and that appropriate addition order and / or timing of two or more AOs during the polymerization reaction can be used to form block polyethers, with different AOs, chain lengths, or combinations of random and block polyethers.

[0076] In certain embodiments, the subscript x is between 1 and 200, alternatively between 1 and 50, alternatively between 2 and 40, alternatively between 3 and 30, alternatively between 4 and 25, alternatively between 5 and 20. In further embodiments, the subscript x is between 10 and 20, alternatively between 12 and 18, alternatively between 14 and 16, alternatively between 16. In further embodiments, the subscript x is between 20 and 30, alternatively between 22 and 28, alternatively between 24 and 26, alternatively between 24 or 26. In still other embodiments, the subscript x is between 30 and 40, alternatively between 32 and 38, alternatively between 34 and 36.

[0077] In certain embodiments, subscript y is 0 to 50, alternatively 1 to 50, alternatively 0 to 40, alternatively 1 to 40, alternatively 0 to 30, alternatively 1 to 30, alternatively 0 to 25, alternatively 1 to 25, alternatively 0 to 20, alternatively 1 to 20. In further embodiments, subscript y is 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript y is 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In yet other embodiments, subscript y is 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0078] In certain embodiments, subscript z is 0 to 50, alternatively 1 to 50, alternatively 0 to 40, alternatively 1 to 40, alternatively 0 to 30, alternatively 1 to 30, alternatively 0 to 25, alternatively 1 to 25, alternatively 0 to 20, alternatively 1 to 20. In further embodiments, subscript z is 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript z is 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In yet other embodiments, subscript z is 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0079] R 3 is R 1 , H, and -C(O)R 1 Selected from R 1 are independently selected and defined above. In certain embodiments, R 3 is selected from the substituted or unsubstituted hydrocarbyl groups disclosed above for R, for example, R 3 can be an alkyl group. In certain embodiments, R 3 is an 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, alternatively 1 to 3, alternatively 1 to 2, or alternatively 1 carbon atom. 3 is a methyl group. In other embodiments, R 3 is H. In yet another embodiment, R 3 is -C(O)R 1 R 3 -C(O)R 1 If R 1 is typically an 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, alternatively 1 to 3, alternatively 1 to 2, or alternatively 1 carbon atom, e.g., R 3 is an acyl group.

[0080] The subscript n is from 1 to 1,000, alternatively from 1 to 900, alternatively from 1 to 800, alternatively from 1 to 700, alternatively from 1 to 600, alternatively from 1 to 500, alternatively from 1 to 400, alternatively from 1 to 300, alternatively from 1 to 200. In other embodiments, the subscript n is from 2 to 1,000, alternatively from 2 to 900, alternatively from 2 to 800, alternatively from 2 to 700, alternatively from 2 to 600, alternatively from 2 to 500, alternatively from 2 to 400, alternatively from 2 to 300, alternatively from 2 to 200.

[0081] Each subscript p is independently selected and defines the number of Si—O moieties in each cyclic siloxane moiety of the compound. Each subscript p is 1 to 9. Thus, each cyclic siloxane moiety of the compound independently has 3 to 12 siloxy units. In certain embodiments, each subscript p is the same. In other embodiments, each subscript p is different. In certain embodiments, each subscript p is independently 1 to 9, alternatively 1 to 8, alternatively 1 to 7, alternatively 1 to 6, alternatively 1 to 5, or alternatively 1 to 4.

[0082] The above compounds have excellent physical properties for use as surfactants. For example, the compounds are particularly suitable for use as surfactants in polyurethane and / or polyisocyanurate compositions, as described below. However, the compounds are not limited to such. For example, the compounds can be used as surfactants in cosmetic compositions, coating compositions, textile compositions, lignocellulose compositions, and any other compositions or emulsions that typically use surfactants.

[0083] The present disclosure also provides an isocyanate-reactive component. The isocyanate-reactive component is typically used to react with isocyanates, for example, in forming polyurethanes and / or polyisocyanurates. The isocyanate-reactive component includes the compounds described above as surfactants. The isocyanate-reactive component further includes a polyol.

[0084] The isocyanate-reactive component typically comprises compounds in an amount of from greater than 0 to 10, alternatively from 0.1 to 10, alternatively from 0.1 to 9, alternatively from 0.1 to 8, alternatively from 0.1 to 7, alternatively from 0.1 to 6, alternatively from 0.1 to 5, alternatively from 1 to 4, alternatively from 1.5 to 3.5, alternatively from 2 to 3 parts by weight, based on 100 parts by weight of the total amount of polyol in the isocyanate-reactive component.

[0085] 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, involving catalysts such as KOH, CsOH, boron trifluoride, or double cyanide complex (DMC) catalysts such as zinc hexacyanocobaltate or quaternary phosphazenium compounds. Initiators include, for example, neopentyl glycol; 1,2-propylene glycol; 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, polyols can be formed using any of the initiators described above or a combination of initiators. The polyol is not limited to those formed by any particular preparation method.

[0086] 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.

[0087] 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, the polyol comprises a mixture of polyester and polyether polyols.

[0088] 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, and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.

[0089] In certain embodiments, the polyol is 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. Graft polyols often include products obtained by in situ polymerization of one or more vinyl monomers, such as styrene monomers and / or acrylonitrile monomers, i.e., polymer particles, and macromers in the polyol, such as polyether polyols.

[0090] In other embodiments, the polymer polyol is selected from polyharnstoff (PHD) polyols, polyisocyanate polyaddition (PIPA) polyols, and combinations thereof. It should be understood that the isocyanate-reactive component can include any combination of the aforementioned polymer polyols. PHD polyols are typically formed by the in-situ reaction of a diisocyanate with a diamine in a polyol to provide a stable dispersion of polyurea particles. PIPA polyols are similar to PHD polyols, except that the dispersion is typically formed by the in-situ reaction of an alkanolamine with a diisocyanate instead of a diamine to provide a polyurethane dispersion in a polyol.

[0091] 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.

[0092] In various embodiments, the polyol 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, alternatively greater than 0 to 200 g / mol. In certain embodiments, including the above ranges, the OH equivalent weight of the polyol is 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.

[0093] 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.

[0094] In certain embodiments, the polyol comprises, consists essentially of, or consists of one or more polyether polyols. In other words, in these embodiments, the polyol typically does not include any polyols that are not polyether polyols. In other certain embodiments, the polyol comprises, consists essentially of, or consists of one or more polyester polyols. In other words, in these embodiments, the polyol typically does not include any polyols that are not polyester polyols.

[0095] As understood in the art, polyurethanes contain organic units linked by carbamate (urethane) linkages. Polyurethanes are generally formed by reacting polyisocyanates with polyols, typically polyether polyols. Because polyurethanes contain two types of monomers that polymerize alternately, they are generally classified as alternating copolymers. Both the isocyanates and polyols used to make polyurethanes contain, on average, two or more functional groups per molecule. Polyisocyanurates can also be prepared by reacting polyisocyanates with polyols. However, in the preparation of polyisocyanurates, the proportion of methylene diphenyl diisocyanate ("MDI") used is typically high, and polyester-derived polyols are used in the reaction instead of polyether polyols. The resulting chemical structure differs significantly from that of polyurethanes, with the isocyanate groups of the MDI trimers forming isocyanurate groups and the polyols linking together to form complex polymeric structures. Thus, the selection of polyol in the isocyanate-reactive component is typically a function of the end use of the isocyanate-reactive component, for example, to obtain a polyurethane, a polyisocyanurate, or a hybrid polyurethane / polyisocyanurate.

[0096] In certain embodiments, the isocyanate-reactive component further comprises a blowing agent. If 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 reaction of the isocyanate-reactive component with the polyisocyanate. If a blowing agent is used, the blowing agent 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.

[0097] 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.

[0098] In various embodiments, the chemical blowing agent is 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 to 5,000 mPa·s, alternatively 10 to 2,500 mPa·s, alternatively 10 to 1,000 mPa·s, alternatively 10 to 500 mPa·s, alternatively 10 to 100 mPa·s. Alternatively, the chemical blowing agent may include formic acid.

[0099] In certain embodiments, the physical blowing agent comprises, or is, water. In one embodiment, the amount of water present in the isocyanate-reactive component provides a concentration of 0.02 to 5 wt. %, alternatively 0.02 to 4 wt. %, alternatively 0.02 to 3 wt. %, alternatively 0.02 to 2 wt. %, 0.02 to 1 wt. %, alternatively 0.03 to 0.9 wt. %, alternatively 0.05 to 0.8 wt. %, alternatively 0.1 to 0.7 wt. %, based on the total weight of the isocyanate-reactive component and polyisocyanate, as further described below.

[0100] In various embodiments, the isocyanate-reactive component comprises a physical blowing agent, which may be used in addition to or instead of a chemical blowing agent.

[0101] In various embodiments, the physical blowing agent is one that undergoes a phase change from a liquid to a gaseous state upon exposure to atmospheric pressure and a temperature of ≥ 10°C, alternatively ≥ 20°C, alternatively ≥ 30°C, alternatively ≥ 40°C, alternatively ≥ 50°C, alternatively ≥ 60°C, alternatively ≥ 70°C, alternatively ≥ 80°C, alternatively ≥ 90°C, or alternatively ≥ 100°C. The boiling point temperature generally varies depending on the particular type of physical blowing agent.

[0102] 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.

[0103] 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.

[0104] 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 above 30°C, such as HFC-365mfc, may be desirable because they do not require liquefaction during foam processing.

[0105] 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.

[0106] In certain embodiments, the isocyanate-reactive component includes a hydrocarbon-containing physical blowing agent. In various embodiments in which the isocyanate-reactive component includes a physical blowing agent, the physical blowing agent is present in the isocyanate-reactive component in an amount of from greater than 0 to 60 parts by weight, alternatively from 5 to 55 parts by weight, alternatively from 10 to 50 parts by weight, alternatively from 15 to 45 parts by weight, alternatively from 20 to 45 parts by weight, alternatively from 25 to 45 parts by weight, based on 100 parts by weight of polyol in the isocyanate-reactive component. The surfactants of the present invention have superior properties in stabilizing isocyanate-reactive components containing such physical blowing agents. Conventional surfactants experience phase separation prior to end-use of isocyanate-reactive components containing similar amounts of physical blowing agent.

[0107] In some embodiments, the isocyanate-reactive component further comprises a catalyst. The isocyanate-reactive component generally reacts with the polyisocyanate in the presence of a catalyst, but the catalyst can be present in a separate portion from the isocyanate-reactive component and combined during the reaction, or, for example, in the case of a two-component (2k) system, can be present in the isocyanate-reactive component.

[0108] In one embodiment, the catalyst comprises a tin catalyst. Suitable tin catalysts include tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, and tin(II) laurate. In one embodiment, the catalyst 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 can also include other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate.

[0109] Examples of other suitable catalysts include iron(II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines such as tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine; 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.

[0110] Further examples of other suitable catalysts, specifically trimerization catalysts, include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, potassium 2-ethylhexanoate N,N,N-trimethylisopropylamine / formate, and combinations thereof.

[0111] 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. (E) The catalyst may include a delayed action tertiary amine based on 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU"). Alternatively or additionally, the catalyst may include N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether and / or ethylenediamine. 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.

[0112] The catalyst 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 isocyanate-reactive component. When a carrier vehicle is used to dissolve the catalyst, the carrier vehicle can be referred to as a solvent. The carrier vehicle can be an isocyanate-reactive, e.g., an alcohol-functional carrier vehicle such as dipropylene glycol.

[0113] The catalyst can be used in various amounts and can include any combination of different catalysts.

[0114] The isocyanate-reactive component 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, fire retardants, smoke suppressants, antistatic agents, antimicrobial agents, and combinations thereof.

[0115] One or more of the additives can be present in any suitable weight percentage (wt%) of the isocyanate-reactive component, such as 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 isocyanate-reactive component. Those skilled 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.

[0116] Suitable carrier vehicles include silicones, both linear and cyclic, organic oils, organic solvents, and mixtures thereof.

[0117] 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.

[0118] 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. Additional suitable surfactants may include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, or mixtures of such surfactants. The compound is present as a surfactant in the isocyanate-reactive component. Thus, any additional or optional surfactant may be referred to as a co-surfactant.

[0119] Co-surfactant can comprise fluorocarbon surfactant or fluorinated surfactant.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, fluorinated organic surfactants can be perfluorinated polyethers, such as those represented by 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, adding a fluorinated surfactant to the isocyanate-reactive component reduces the cured foam density of articles formed therefrom. Generally, increasing the amount of fluorinated surfactant in the isocyanate-reactive component reduces the foam density. This is especially true for slow-cure systems where the surfactant stabilizes the cells while the network forms and cures.

[0124] In various embodiments, the isocyanate-reactive component further comprises an organopolysiloxane resin ("resin"). Suitable resins are described above. In certain embodiments, the resin is an MQ resin. The resin can help stabilize the foam.

[0125] Suitable pigments are known in the art. In various embodiments, the isocyanate-reactive component further comprises carbon black, for example, acetylene black.

[0126] The isocyanate-reactive component 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 family, garnet family; aluminosilicates; cyclic aluminosilicates; linear aluminosilicates; and layered aluminosilicates. In certain embodiments, the isocyanate-reactive component includes at least one filler, including hollow particles, e.g., hollow spheres. Such fillers may be useful for contributing to the porosity and / or overall porosity of the foam. If a filler is used, it may be used in the isocyanate-reactive component in an amount of 0.01 to 50 wt%, alternatively 0.05 to 40 wt%, alternatively 0.1 to 35 wt%, based on the total weight of the isocyanate-reactive component. Further, if fumed silica is used, it may be used in an amount of 0.01 to 5 wt%, alternatively 0.05 to 3 wt%, alternatively 0.1 to 2.5 wt%, alternatively 0.2 to 2.2 wt%, based on the total weight of the isocyanate-reactive component.

[0127] If a filler is 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 using, for example, a fatty acid or a fatty acid ester such as a stearate, or 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 isocyanate-reactive component. 5 e Si(OR 6 ) 4-e [In the formula, R 5 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 6 is 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.

[0128] In various embodiments, the isocyanate-reactive component further comprises an adhesion promoter. The adhesive 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.

[0129] 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.

[0130] In certain embodiments, the isocyanate-reactive component, particularly the isocyanate-reactive component, may further comprise a chain extender. Suitable chain extenders include any of the components listed above as initiators for the polyol, which may be used alone or in combination as chain extenders, when present, separately from and in addition to the polyol.

[0131] If optional additives are used in the isocyanate-reactive component, any of these can be present in the isocyanate-reactive component or as separate components in the composition. Alternatively, optional additives that are not isocyanate-reactive (e.g., fillers, etc.) can be included with the polyisocyanate in the isocyanate component described below. Typically, the composition is a 2k (two-component) composition, where the isocyanate component consists of a polyisocyanate and an isocyanate-reactive component with the remaining ingredients used.

[0132] 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, alternatively less than 850 centipoise. The dynamic viscosity is measured at 10 s with a temperature ramp rate of 3° C. / min from 20 to 80° C. -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. This viscosity range allows the isocyanate-reactive component to flow freely, which is advantageous for certain end-use applications where foaming is desired in or on certain substrates or articles, such as those that define voids and / or orifices.

[0133] The present disclosure also provides a composition comprising (1) an isocyanate-reactive component, (2) an isocyanate component comprising a polyisocyanate, and a catalyst. As described above, the catalyst is typically present in the (1) isocyanate-reactive component of the composition. However, the catalyst can alternatively be present in the (2) isocyanate component, or can be separate from the (1) isocyanate-reactive component and the (2) isocyanate component.

[0134] Suitable polyisocyanates have two or more isocyanate functional groups and include conventional aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. The polyisocyanate component 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 comprises, consists essentially of, or is pMDI. In one embodiment, the isocyanate component is of the formula OCN-R-NCO, where R is an alkyl, aryl, or arylalkyl moiety. In this embodiment, the polyisocyanate can contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0135] Specific examples of suitable polyisocyanates include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, 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).

[0136] The polyisocyanate may include modified polyisocyanates, i.e., products 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 isocyanates; 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 components, 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.

[0137] It is understood that the polyisocyanate may comprise any combination of two or more polyisocyanates that differ from one another based on functionality, molecular weight, viscosity, or structure, hi certain embodiments, the polyisocyanate comprises, consists essentially of, or is pMDI.

[0138] The polyisocyanates typically have 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.

[0139] In these or other embodiments, the polyisocyanate has an NCO weight percent of 15 to 60, alternatively 15 to 55, alternatively 20 to 48.5 wt %. Methods for determining NCO content are known in the art, based on the functionality and molecular weight of the particular isocyanate.

[0140] In certain embodiments, the polyisocyanate is typically present in the composition in an amount to provide an Isocyanate Index of from 80 to 200, alternatively from 80 to 130, alternatively from 85 to 125, alternatively from 90 to 120, alternatively from 95 to 120, alternatively from 100 to 120, alternatively from 105 to 115. In other embodiments, the polyisocyanate is typically present in the composition in an amount to provide an Isocyanate Index of from 80 to 800, alternatively from 90 to 700, alternatively from 100 to 600, alternatively from 150 to 500, alternatively from 200 to 300. The Isocyanate Index is the molar ratio of NCO to isocyanate-reactive hydrogen functional groups multiplied by 100. Isocyanate Index and methods for its calculation are well known in the art.

[0141] The composition can be prepared by combining (1) an isocyanate-reactive component, (2) an isocyanate component, and, if no optional components are present in the (1) isocyanate-reactive component, any optional components in any order of addition. As described in more detail below, the composition can be a one-part composition, a two-component (2K) composition, or a multi-part composition. When the (1) isocyanate-reactive component and the (2) isocyanate component are combined, particularly in the presence of a catalyst, a reaction is initiated and a foamed article results. The foamed article can be formed at room temperature and ambient conditions. Alternatively, at least one condition, such as temperature, humidity, pressure, etc., can be selectively changed during the formation of the foamed article.

[0142] Also disclosed is a foamed article comprising the reaction product of the composition. The foamed article can be a foamed polyurethane, a foamed polyisocyanurate, or a foamed polyurethane / polyisocyanurate, depending on the selection of the polyol in the isocyanate-reactive component and the polyisocyanate in the isocyanate component.

[0143] In many embodiments, the foam article is a closed-cell foam, however, the foam article can be an open-cell foam, or both a closed-cell and an open-cell foam.

[0144] In various embodiments, the foam article has pores that are generally uniform in size and / or shape and / or distribution.

[0145] 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 greater than 15 cells is scribed.

[0146] Foam articles, and composite articles comprising a substrate and a foam article together, can be formed by disposing the composition on a substrate and allowing the composition to cure.

[0147] 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).

[0148] The substrate is not limited and may be any substrate. The foam article 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, depending on the choice. The substrate may optionally have continuous or non-continuous shape, size, dimensions, surface roughness, and other properties.

[0149] 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.

[0150] 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. Composite materials 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.

[0151] In certain embodiments, the substrate defines at least one gap, and disposing the composition comprises disposing the composition within the at least one gap such that the foamed article resides within the gap in the composite article. In some embodiments, the composition is generally flowable and conforms to the shape of the substrate at ambient conditions, such as room temperature and atmospheric pressure.

[0152] 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.

[0153] Reference example 1 The basic procedure for Reference Example 1 is to prepare (A) organohydrogensiloxane, which is one type of component (A).

[0154] In Reference Example 1, bulk reaction solvents were dried by passage through columns of alumina and Q5 reactive scavenger (known as Cu-0226 S and supplied by BASF). All other solvents were purchased as anhydrous grades from Aldrich and stored over activated 3 Å molecular sieves before use. NMR solvents (CDCl3, CD2Cl2, and CD6D6) obtained from Cambridge Isotope Laboratories, Inc. were dried over activated 3 Å molecular sieves or, in the case of CD6D6, dried using Na / K alloy. 1-Bromo-2,5-bis(trifluoromethyl)benzene was purchased from Oakwood Chemical. Prior to use, n-butyllithium (solution in hexane) was titrated with 1.00 M decanol in toluene containing 1,10-phenanthroline as indicator. 1

[0155] Multinuclear NMR spectrum ( 1 H, 13 C. 19 F, 29 Si, 11 B) were collected on one of the following instruments: a Varian MR-400 or a Varian VNMRS-500. 11 B NMR spectra were collected only on a Varian VNMRS-500. 1H and 13C NMR chemical shifts are in parts per million relative to the residual solvent peak, i.e., 1 5.32 ppm for H-CD2Cl2, 7.15 ppm for C6D6, and 7.25 ppm for CDCl3; 13 The reference values ​​were 54.00 ppm for C-CD2Cl2, 128.00 ppm for C6D6, and 77.00 ppm for CDCl3. 11 B NMR chemical shifts are externally referenced to BF3(Et2O) (0 ppm). 19F NMR chemical shifts were externally referenced to CFCl (0 ppm). Subambient reaction temperatures were measured using an Extech Instruments EasyView™ 10 Dual K model EA 10 thermometer equipped with a fine JKEM sensor PTFE wire K 36INJ, except when dry ice or ice was the only cooling means.

[0156] The catalysts used to prepare certain types of component (A) were synthesized as follows. __________________ 1 Watson, SC; Eastham, JF "Colored indicators for simple direct titration of magnesium and lithium reagents", J. Organomet. Chem., 1967, 9, 165-168.

[0157] [ka]

[0158] n-Butyllithium (4.00 mL, 2.535 M in hexane, 10.14 mmol) was slowly added to a cold (-78 °C, CO2(s) bath) solution of 1-bromo-2,5-bis(trifluoromethyl)benzene (3.00 g, 10.24 mmol) in diethyl ether (200 mL). The reaction mixture was stirred at -78 °C for 1 hour. Isopropoxy-bis(3,5-bis(trifluoromethyl)phenyl)borane (5.036 g, 10.15 mmol) in ether (18 mL) was slowly added. The reaction mixture was stirred at -78 °C for several hours. The solution was allowed to warm to ambient temperature with stirring overnight, giving a pale yellow, clear solution. The reaction mixture was stripped of volatiles to give a yellow oil. The oil was extracted with benzene. No insoluble material was found. The reaction mixture was stripped of volatiles to give a yellow oil. The yield was 7.88 g (98.3%).

[0159] 1 H NMR(400MHz,benzene-d6)δ 8.06(s,1H),8.00(s,4H),7.70(dt,J=1.8,0.9Hz,2H),7.40(d,J=8.3Hz,1H),7.19(d,J=8.4Hz,1 H),3.79(hept,J=6.1Hz,1H),2.78(q,J=7.1Hz,4H),0.73(d,J=6.1Hz,6H),0.54(t,J=7.1Hz,6H). 13 C NMR(101MHz,benzene-d6)δ 158.31,153.97,135.44(q,J=3.7Hz),135.23,133.55(t,J=4.1Hz),133.25,133.18,132.37(d,J=97.8Hz),130.92(q,J=32.0Hz),127.8 0(q,J=273.9Hz),124.92(q,J=272.5Hz),124.66(q,J=272.8Hz),123.86(q,J=3.8Hz),119.86(p,J=3.9Hz),66.24,66.17,25.60,13.94. 19 F NMR (376 MHz, benzene-d6) δ -55.30--55.51 (m), -62.82, -63.61. 11 B NMR (160 MHz, benzene-d6) δ 2.16.

[0160] In a nitrogen-purged glovebox, a 1 wt% catalyst solution was prepared in a glass vial by dissolving the catalyst prepared immediately above in anhydrous toluene. A cyclic polyorganohydrogensiloxane (a crude (unpurified after production) cyclic polymethylhydrogensiloxane mixture with a DP of 4-6, 11.2 g) and a Teflon-coated stir bar were placed in the glass vial. To the stirred solution, the catalyst solution (e.g., 225 μL) was added via micropipette, followed by the slow addition of a silanol-terminated polydimethylsiloxane with an average DP of 10.8 (e.g., 8.4 g) over 1 h. An aliquot of the reaction mixture was taken, quenched with one drop of phenylacetylene, and analyzed by NMR spectroscopy in CDCl3 (approximately 1 g / 100 mL) containing Cr(acac)3 as an NMR relaxation agent. 29Analysis was performed by Si NMR. Conversion was established by comparing the signal of HOSi(Me)2O-(MOH) with that of MeSiO3(T). Conversion was 99% over 1.3 hours.

[0161] The stability of the above general procedure was monitored as follows: In a nitrogen-purged glovebox, a 1 wt. % solution of the above catalyst was prepared in a glass vial by dissolving the solid catalyst sample in anhydrous toluene. A cyclic polyorganohydrogensiloxane (5 g) and a Teflon-coated stir bar were placed in the glass vial. To the stirred solution, the catalyst solution (e.g., 100.5 μL) was added via micropipette. Samples were taken from aliquots over time and quenched with a phenylacetylene / toluene mixture so that toluene could serve as an internal standard. The aliquots were then analyzed by GC. The relative amounts of reactants were compared by monitoring the ratio of cyclic polyorganohydrogensiloxane to the toluene standard. The cyclic polyorganohydrogensiloxane was monitored over time before the addition of the silanol-terminated polydimethylsiloxane.

[0162] [ka]

[0163] [ka]

[0164] The melting point and freezing point temperatures shown below are measured as follows. Use a 5-place analytical balance to obtain the mass of a Tzero Pan equipped with a Tzero Hermetic Lid. Place 7-12 mg of the specific sample into the pan and, using tweezers, place the pan into the blue lower sealing die and cover with the sealing lid. Place the lower die into the pan press and move the press lever to seal the lid onto the pan. Remove the pan with tweezers and place it in the autosampler. The autosampler uses the following test scheme: Sampling interval: 0.20s / pt Data storage: Off Equilibrate at 60°C Isothermal for 5.00 min Data storage: On Cool to -90°C at -10,000°C / min Isothermal for 10.00 min Marking the end of cycle 1 Heat to 60°C at 10,000°C / min Marking the end of Cycle 2 Data storage: Off Equilibrate at 40.00°C The various ingredients used in the preparation of Preparative Examples 1-4 and Comparative Preparative Examples 1-2 are set out in Table 1 below.

[0165] [Table 1]

[0166] Preparation Example 1 A 250 mL three-necked round-bottom flask was charged with 54.94 g of component (B3) and 30.14 g of the carrier. The flask was then equipped with an overhead mechanical stirrer (glass rod with a Teflon paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. The contents of the flask were heated to 78°C using an aluminum heating block under a slight nitrogen sweep and vigorous stirring (275 rpm). 0.16 g of component (C) (0.5 wt% Pt) was then added to the flask. 15.11 g of component (A1) was then added incrementally to the flask. Specifically, 1 mL of component (C) was added at a time until the flask temperature stabilized and the contents of the flask became optically clear, and this was repeated until a total of 15.11 g of component (A1) had been added to the flask. During the incremental addition of component (A1), an additional 0.17 g of component (C) was added to the flask. After the entire amount of component (A1) used was added to the flask, the contents of the flask were heated under reflux (about 84°C) for about 1.5 hours to obtain a clear, amber solution. Volatile materials were stripped from the resulting clear, amber solution under heating and vacuum (6 Torr, 100°C for 1 hour) to obtain a reaction product. The reaction product was transferred to a jar and measured to have a freezing point of -15.7°C and a melting point of 18.1°C.

[0167] Preparation Example 2 A 250 mL three-necked round-bottom flask was charged with 16.94 g of component (A2) and 30.9 g of the support. The flask was then equipped with an overhead mechanical stirrer (glass rod with a Teflon paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. The contents of the flask were heated to 75°C using an aluminum heating block under a slight nitrogen sweep and vigorous stirring (275 rpm). 43.08 g of component (B1) was diluted with 10 g of the support to obtain a mixture. 25 g of the mixture was then added to the flask via syringe, and the contents of the flask were then catalyzed with 0.191 mL of component (C) (1 wt. % Pt). After the remaining amount of the mixture was added to the flask, an additional 76 μL of component (C) (to obtain 10 ppm Pt) was added. The contents of the flask were heated at reflux (approximately 84°C) for approximately 1.5 hours to obtain a clear, amber solution. The amber-colored, clear solution was stripped of volatiles under heat and vacuum (6 Torr, 100°C for 1 hour) to yield a reaction product. The reaction product was transferred to a jar. Upon cooling to room temperature, the reaction product thickened to a honey-like consistency. The reaction product was transferred to a jar and determined to have a freezing point of 5.5°C and a melting point of 30.6°C.

[0168] Preparation Example 3 A 250 mL three-necked round-bottom flask was charged with 33.89 g of component (B4) and 30 g of the carrier. The flask was then equipped with an overhead mechanical stirrer, a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. The contents of the flask were heated to 78 °C using an aluminum heating block under a slight nitrogen sweep and vigorous stirring (275 rpm). 2 g of component (A2) was then added to the flask via syringe, and the contents of the flask were then catalyzed with 0.12 mL of component (C) (1 wt. % Pt). While maintaining a temperature of 80–81 °C, the remainder of component (A2) (i.e., 24.17 g) was added in 1–2 mL increments over approximately 60 minutes, with additional amounts of component (C) (5 ppm Pt) added midway to obtain a pale yellow, clear solution. The pale yellow, clear solution was stripped of volatiles under heating and vacuum (6 Torr, 100°C for 1 hour) to give the reaction product in the form of a viscous yellow liquid, which was transferred to a jar and measured to have a freezing point of -25.9°C and a melting point of -2.2°C.

[0169] Preparation Example 4 A 250 mL three-necked round-bottom flask was charged with 8.30 g of component (A3), 32 g of support, and 51.94 g of component (B5). The flask was then equipped with an overhead mechanical stirrer (glass rod with a Teflon paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. The contents of the flask were heated to approximately 70°C using a heating mantle under a slight nitrogen sweep and vigorous stirring (275 rpm). The reaction in the flask was catalyzed with 0.32 mL of component (C) (0.5 wt% Pt relative to 20 ppm Pt). The reaction in the flask was continued for 3 hours to obtain a reaction mixture, after which the reaction mixture was stripped under vacuum with heating (to 30 Torr, 80°C for 1 hour).

[0170] Comparative Preparation Example 1 A 250 mL three-neck round-bottom flask was charged with 30.1 g of support, 46.19 g of component (B1), and 17.61 g of component (A1'). The flask was then equipped with an overhead mechanical stirrer (glass rod with a Teflon paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. The contents of the flask were heated to approximately 68.0°C using a heating mantle under a slight nitrogen sweep and vigorous stirring (275 rpm). The reaction was then catalyzed with 0.122 mL of component (C) (1 wt.% Pt relative to 15 ppm Pt). The temperature of the flask from the reaction increased from 68.0°C to 79.7°C and became clear near 79.5°C. The contents of the flask were then heated to reflux for 1 hour and then cooled to room temperature overnight, resulting in a yellow solution. The yellow solution was stripped of volatiles under vacuum (6 Torr, warmed to 100°C, held for 1 hour) to give a yellow liquid which was determined to have a freezing point of 13.1°C and a melting point of 30.8°C.

[0171] Comparative Preparation Example 2 A 250 mL three-necked round-bottom flask was charged with 55.39 g of component (B2), 20.20 g of component (A2'), and 39 g of support. The flask was then equipped with an overhead mechanical stirrer (glass rod with a Teflon paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. The contents of the flask were heated to approximately 70°C using an aluminum heating block under a slight nitrogen sweep and vigorous stirring (275 rpm). The reaction was then catalyzed with 0.05 mL of component (C) (1 wt% Pt, providing 5 ppm Pt). The set point on the heating block was changed to 90°C, and the reaction was heated to reflux for 1 hour. During heating, the reaction became clear near 83°C, yielding a clear, amber liquid. The clear, amber liquid was then stripped under vacuum (6 Torr, 100°C for 2 hours) to obtain the reaction product. The reaction product solidified upon cooling to room temperature.

[0172] Examples 1 to 3 and Comparative Examples 1 and 2: Isocyanate-reactive components are prepared using a portion of the compounds (i.e., reaction products) formed in Preparative Examples 1-4 and Comparative Preparative Examples 1-2. Specifically, Example 1 uses the compound of Preparative Example 1, Example 2 uses the compound of Preparative Example 2, Example 3 uses the compound of Preparative Example 3, Comparative Example 1 uses the compound of Comparative Preparative Example 1, and Comparative Example 2 uses the compound of Comparative Preparative Example 2. The compounds of Preparative Examples 1-3 and Comparative Preparative Examples 1-2 are used as surfactants in the isocyanate-reactive components of Examples 1-3 and Comparative Examples 1-2.

[0173] Table 2 below shows the amount of each component used in the isocyanate-reactive components of Examples 1-3 and Comparative Examples 1-2. Each value in Table 2 below is in parts by weight based on 100 parts by weight of polyol. The same components and amounts are used in Examples 1-3 and Comparative Examples 1-2, except for the surfactant. The surfactant is the respective compound prepared in each of Preparative Examples 1-3 and Comparative Preparative Examples 1-2 above. The reference to the surfactant in Table 2 below is different for Examples 1-3 and Comparative Examples 1-2, as described above.

[0174] [Table 2]

[0175] General Procedure for Examples 1-3 and Comparative Examples 1-2: Each of Examples 1-3 and Comparative Examples 1-2 follows the same basic procedure for preparing the respective isocyanate-reactive components. Specifically, for each of Examples 1-3 and Comparative Examples 1-2, a 60 g sample is prepared using enough emulsion to visually observe and inspect the vial for analysis by Turbiscan. In each of Examples 1-3 and Comparative Examples 1-2, the specific surfactant used is mixed with polyol, blowing agent 1, flame retardant, catalyst 1, catalyst 2, and catalyst 3 in a 250 mL Nalgene bottle to obtain a preblend. Blowing agent 2 is mixed into the preblend using an air-driven mixer to avoid an ignition source from blowing agent 2. An additional 1-2 grams of blowing agent 2 is added to account for volatilization / evaporation during mixing. A small, three-bladed propeller at approximately 3000 rpm is used to obtain an emulsion of the preblend and blowing agent 2. The emulsification time varies from 30 seconds to 5 minutes, depending on the surfactant. The emulsion was weighed and the amount of Blowing Agent 2 adjusted, if necessary, to target 35±2% by weight of the emulsion. The emulsion was immediately transferred to a 30 mL vial for visual observation at room temperature. Observation was stopped upon visual observation of creaming or breakdown of the emulsion. The results of the visual inspection are listed in Table 3 below. Stability was observed and determined to be absent upon phase separation (e.g., by breakdown and / or creaming) of certain isocyanate-reactive components.

[0176] [Table 3]

[0177] Prophetic Examples 1 to 3 and Prophetic Comparative Examples 1 to 2: Polyurethane foams were prepared using the isocyanate-reactive components of Examples 1 to 3 and Comparative Examples 1 to 2. Specifically, each of the isocyanate-reactive components of Examples 1 to 3 and Comparative Examples 1 to 2 was reacted with polymethylene polyphenylisocyanate containing MDI (pMDI) having an NCO content of 30.9% as measured in accordance with ASTM D5155 and a dynamic viscosity at 25°C of 500 to 1,000 MPa·s as measured in accordance with ASTM D4889. The isocyanate-reactive component and pMDI in each of Examples 1 to 3 and Comparative Examples 1 to 2 were reacted in an amount of 350 parts by weight based on 100 parts by weight of the polyol in each isocyanate-reactive component.

[0178] The term "comprising" and its derivatives, such as "comprise" and "comprises," are used herein in their broadest sense to mean and encompass the notions of "including," "include," "consist(ing) essentially of," and "consist(ing) of." The use of "for example," "eg," "such as," and "including" to list examples does not limit the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and encompasses other similar or equivalent examples.

[0179] Generally, as used herein, a hyphen "-" or a wavy line "~" in a range of values ​​means "to" or "through," ">" means "above" or "greater-than," "≥" means "at least" or "greater-than or equal to," "<" means "below" or "less-than," and "≤" means "at most" or "less-than or equal to." Each of the foregoing patent applications, patents, and / or patent publications is expressly incorporated herein by reference in its entirety on an individual basis in one or more non-limiting embodiments.

[0180] 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 of the Invention, and that variations may occur among specific embodiments within the scope of the appended claims.

Claims

1. 1. A composition comprising: (A) a molecule having the following structure: 【Chemistry 1】 wherein subscript n is 1 to 2,000, each subscript p is independently 1 to 10, each R is an independently selected substituted or unsubstituted hydrocarbyl group, and one or more silicon-bonded hydrogen atoms have the formula: 【Chemistry 2】 wherein the subscript n is independently selected and defined above, the subscript p is independently selected and defined above, and each R １ is an independently selected substituted or unsubstituted hydrocarbyl group; and (B) a polyether compound having an aliphatic unsaturated group; (C) a hydrosilylation catalyst.

2. (i) each R is an independently selected unsubstituted hydrocarbyl group free of aliphatic unsaturation; (ii) each subscript p is independently 1 to 4; (iii) subscript n is 1 to 200; and (iv) the (B) polyether compound has the formula R ２ O (C ｍ H ２ｍ O) ｑ R ３ wherein R ２ is an aliphatic unsaturated group, subscript m is independently selected from 2 to 4 in each moiety designated by subscript q, subscript q is 1 to 200, and R ３ is R １ , H, and —C(O)R １ wherein R １ are independently selected and defined above, or any combination of (v)(i)-(iv).

3. A silicone polyether surfactant obtained by reacting component (A) with component (B) in the presence of component (C), wherein component (A), component (B), and component (C) are as defined in claim 1 or 2.

4. The following structure: 【Transformation 3】 wherein each R ４ are independently hydrogen, a substituted or unsubstituted hydrocarbyl group, a polyether group, or a group of the formula 【Chemistry 4】 wherein R ４ at least one of is a polyether group, each subscript p is independently 1 to 10, each subscript n is independently 1 to 2,000, each R is an independently selected substituted or unsubstituted hydrocarbyl group, and each R １ are independently selected substituted or unsubstituted hydrocarbyl groups, and said polyether group of R 4 has the formula -D-O(C m H 2m O) q R 3 , where D is a divalent linking group, subscript m is independently selected from 2 to 4 at each moiety designated by subscript q, subscript q is 1 to 200, and R 3 is selected from R 1 , H, and -C(O)R 1 , where R 1 is independently selected and defined above.

5. (i) each R is an independently selected unsubstituted hydrocarbyl group free of aliphatic unsaturation; (ii) each R ４ is a polyether group; (iii) each subscript p is independently 1 to 4; (iv) subscript n is 1 to 200; or (v) any combination of (i) through (iv).

6. an isocyanate-reactive component, Polyol and and a surfactant, wherein the surfactant comprises a compound according to claim 4 or 5.

7. 1. A composition comprising: (1) an isocyanate-reactive component according to claim 6; (2) an isocyanate component including a polyisocyanate; A composition comprising:

8. 8. The composition of claim 7, wherein: (i) the polyol comprises a polyether polyol and / or a polyester polyol; (ii) the polyisocyanate comprises a polymeric diphenylmethane diisocyanate; (iii) the composition further comprises a blowing agent; (iv) the composition comprises the surfactant in an amount of 0.1 to 10 wt. %, based on the total weight of the composition; or (v) any combination of (i)-(iv).

9. 1. A method of manufacturing an article, the method comprising: reacting the isocyanate-reactive component of claim 6 with an isocyanate component comprising a polyisocyanate in the presence of a catalyst and a blowing agent to obtain the article; The method wherein the article comprises a polyurethane foam or a polyisocyanurate foam.

10. An article comprising the reaction product of the composition of claim 7.

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