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

Abstract

The present invention discloses a composition comprising (A) an organohydrogensiloxane having a cyclic siloxane portion containing silicon-bonded hydrogen atoms. The composition also comprises (B) a polyether compound having an aliphatic unsaturated group. Finally, the composition comprises (C) a hydrosilylation catalyst. The present invention also discloses an organosilicon polyether surfactant prepared by reacting components (A) and (B) in the presence of component (C). In addition, an isocyanate-reactive component comprising a polyol and the organosilicon polyether surfactant is disclosed. A composition comprising the isocyanate-reactive component, an isocyanate component containing a polyisocyanate, and a catalyst is also disclosed. Finally, a method for preparing an article comprising polyurethane and / or polyisocyanurate foam, and an article formed by the composition and / or the method are disclosed.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and all advantages of U.S. Provisional Patent Application No. 63 / 043,295 filed on June 24, 2020, the contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to a composition, and more particularly to a composition for preparing a silicone polyether surfactant. The silicone polyether surfactant and various uses thereof are also disclosed. Background Art

[0004] Silicones are polymeric materials used in many commercial applications, primarily due to the significant advantages they possess over their carbon-based analogs. More precisely, silicones, known as polymeric siloxanes or polysiloxanes, have an inorganic silicon-oxygen backbone (…-Si-O-Si-O-Si-O-…) with organic side groups attached to the silicon atoms.

[0005] Some silicones are polyether-modified silicones, which may also be referred to as silicone polyethers (SPEs). Many SPEs are commercially available for use in reducing the surface tension of aqueous solutions / dispersions. However, conventional SPEs may face one or more problems.

[0006] Foam is known in the art and is used in various end-use applications, including cushions, support articles, encapsulants / potting agents, and insulating materials. Foam can be formed from various chemical compositions, and physical and / or chemical blowing agents can be utilized. For example, polyurethane foam is typically formed by reacting isocyanates and polyols in the presence of a blowing agent. Typically, foam is formed with SPE to stabilize the isocyanate-reactive components comprising polyols and / or blowing agents and to prevent phase separation prior to use. Summary of the invention

[0007] The present invention discloses a composition comprising (A) an organohydrogensiloxane having the following structure:

[0008]

[0009] wherein subscript n is 1 to 1,000; each subscript p is independently 1 to 10; and each R is an independently selected substituted or unsubstituted hydrocarbyl group in which one or more silicon-bonded hydrogen atoms can be replaced by a group having the formula:

[0010]

[0011] wherein subscript n is independently selected and as defined above, subscript p is independently selected and as defined above, and each R1 is an independently selected substituted or unsubstituted hydrocarbon group. The composition further comprises (B) a polyether compound having an aliphatic unsaturated group; and (C) a hydrosilylation catalyst. The present invention also discloses an organosilicon polyether surfactant prepared by reacting components (A) and (B) in the presence of component (C).

[0012] The present invention discloses a compound having the following structure:

[0013]

[0014] Each R 4 are independently selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a polyether group or a group of the formula:

[0015] The condition is that at least one R 4 is a polyether group; each subscript p is independently 1 to 10; each subscript n is independently 1 to 2,000; and each R is an independently selected substituted or unsubstituted hydrocarbon group, and each R 1 are independently selected and as defined above.

[0016] In addition, an isocyanate reactive component comprising a polyol and the silicone polyether surfactant is disclosed. Also disclosed is a composition comprising the isocyanate reactive component, an isocyanate component containing a polyisocyanate, and a catalyst. Finally, a method for preparing an article comprising a polyurethane and / or polyisocyanurate foam is disclosed, as well as an article formed by the composition and / or the method. DETAILED DESCRIPTION

[0017] The present invention discloses a composition. The composition is a hydrosilylation-curable composition that can be cured to obtain a reaction product, which can be referred to as an organosilicon polyether surfactant and is described in more detail below. The composition comprises (A) an organohydrogensiloxane having the following structure:

[0018]

[0019] wherein subscript n is 1 to 1,000; each subscript p is independently 1 to 10; and each R is an independently selected substituted or unsubstituted hydrocarbyl group in which one or more silicon-bonded hydrogen atoms can be replaced by a group having the formula:

[0020]

[0021] wherein subscript n is independently selected and as defined above, subscript p is independently selected and as defined above, and each R 1are independently selected substituted or unsubstituted hydrocarbyl groups.

[0022] Generally speaking, it is applicable to R (and R 1 ) can be independently linear, branched, cyclic or a combination thereof. Cyclic hydrocarbon groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbon groups can be independently monocyclic or polycyclic. Straight and branched hydrocarbon groups can be independently saturated or unsaturated. An example of a combination of straight and cyclic hydrocarbon groups is an aralkyl group. General examples of hydrocarbon groups include alkyl groups, aryl groups, alkenyl groups, halogenated carbon groups, etc., and their derivatives, modifications and combinations. 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 a branched saturated hydrocarbon group having 6 to 18 carbon atoms. The example of suitable non-conjugated cyclic group includes cyclobutyl, cyclohexyl and cycloheptyl groups. The example of suitable aryl group includes phenyl, tolyl, xylyl, naphthyl, benzyl and dimethylphenyl. The example of suitable alkenyl group includes vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecene, octadecene and cyclohexenyl groups. The example of suitable monovalent halogenated hydrocarbon group (that is, halogenated hydrocarbon group or substituted hydrocarbon group) includes halogenated alkyl group, aryl group and their combination. The example of halogenated alkyl group includes the above-mentioned alkyl group in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. The specific example of haloalkyl group includes 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 their derivatives. The example of halogenated aryl group includes the above-mentioned aryl group in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. The specific example of halogenated aryl group includes chlorobenzyl and fluorobenzyl groups.

[0023] In certain embodiments, no more than three, alternatively no more than two, alternatively no more than one H is replaced by a group comprising a cyclic siloxane moiety as described above. In a specific embodiment, there is one such group replacing one silicon-bonded hydrogen atom in each cyclic siloxane moiety of component (A).

[0024] In specific embodiments, each R is an unsubstituted hydrocarbyl group and component (A) contains only two cyclic siloxane moieties. In these embodiments, component (A) has the formula:

[0025]

[0026] Where R 1 and subscripts p and n are as defined above. In another embodiment, each of R and R 1 does not contain aliphatic unsaturated groups (i.e., aliphatic carbon-carbon double or triple bonds). Aliphatic unsaturated groups do not include aromatic unsaturated groups. In various embodiments, each of R and R 1 Selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, alternatively 1 carbon atom.

[0027] Subscript n is 1 to 2,000, alternatively 2 to 2,000, alternatively 1 to 1,000, alternatively 1 to 900, alternatively 1 to 800, alternatively 1 to 700, alternatively 1 to 600, alternatively 1 to 500, alternatively 1 to 400, alternatively 1 to 300, alternatively 1 to 200. In other embodiments, subscript n is 2 to 1,000, alternatively 2 to 900, alternatively 2 to 800, alternatively 2 to 700, alternatively 2 to 600, alternatively 2 to 500, alternatively 2 to 400, alternatively 2 to 300, alternatively 2 to 200.

[0028] 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. Therefore, 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 specific 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, alternatively 1 to 4.

[0029] (A) Organohydrogensiloxane can be prepared by different techniques. For example, (A) Organohydrogensiloxane can be synthesized by:

[0030] 1) The starting materials are combined as follows:

[0031] i) Boron-containing Lewis acids;

[0032] ii) Formula A hydroxy-functional organosilicon compound of wherein each subscript n is from 1 to 2,000, alternatively from 2 to 2,000, and each R is independently selected and as defined above; and

[0033] iii) Formula (RHSiO 2 / 2 ) v A cyclic polyorganohydrogensiloxane of wherein subscript v is 3 to 12; and each R is independently selected and as defined above.

[0034] The starting material i) in the method for preparing component (A) is a boron-containing Lewis acid. The boron-containing Lewis acid can be a trivalent boron compound having at least one perfluoroaryl group per molecule, alternatively 1 to 3 perfluoroaryl groups per molecule, alternatively 2 to 3 perfluoroaryl groups per molecule, and alternatively 3 perfluoroaryl groups per molecule. The perfluoroaryl group can have 6 to 12 carbon atoms, alternatively 6 to 10 carbon atoms, and alternatively 6 carbon atoms. The boron-containing Lewis acid can be selected from (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 )B(C6F5), (C6F5)2B(OC2H5) or (C6F5)2B-CH2CH2Si(CH3). Alternatively, the boron-containing Lewis acid may be tris(pentafluorophenyl)borane of formula B(C6F5)3. Such boron-containing Lewis acids are commercially available, for example, from MilliporeSigma (St. Louis, Missouri, USA).

[0035] Alternatively, the boron-containing Lewis acid may have the formula:

[0036] Each R o is an ortho substituent, each R m is a meta-substituent, and each R p is a para-substituent, R L is optional and includes a functional group or a functional polymer group; and the subscript x is 0 or 1. In the above formula, R o1-6 Each of R m1-6 Each of the R p1-3 Each of R is independently selected from H, F or CF3; provided that: not all Ro1-6 , R m1-6 and R p1-3 can be H at the same time, and when R o1-4 When two or more of them are CF3, then R o5 and R o6 are each independently selected from H or F. L is optional, that is, when the subscript x = 1, R L exists, and when the subscript x=0, R L Does not exist. L It 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 containing at least one electron pair that can be used to form a coordinate bond with the Lewis acid, and may be as described in paragraphs

[0024] to

[0025] of WO2019 / 055740 for R 4 R L Examples of include cyclic ethers such as tetrahydrofuran or tetrahydropyran. L It may be tetrahydrofuran (THF).

[0037] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 and R o6 Each of may be H. Alternatively, R o1 , R o2 , R o3 and R o4 Each of may be H. Alternatively, R o5 and R o6 Each of can be F.

[0038] Alternatively, R m1 , R m2 , R m3 , R m4 , R m5 and R m6 Each of may be CF3. Alternatively, R m1 , R m2 , R m3 and R m4 Each of may be CF3. Alternatively, R m5 and R m6 Each of may be F. Alternatively, R m5 and R m6 Each of can be H.

[0039] Alternatively, R p1 , R p2 and R p3 Each of may be H. Alternatively, Rp1 and R p2 It can be H. Alternatively, R p3 It can be F. Alternatively, R p3 It can be CF3.

[0040] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R p1 , R p2 and R p3 Each of may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R m6 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material i) may comprise tris(3,5-bis(trifluoromethyl)phenyl)borane THF adduct.

[0041] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R o6 , R m5 , R m6 , R p1 and R p2 Each of may be H; and R m1 , R m2 , R m3 , R m4 and R p3 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material i) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane THF adduct.

[0042] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 and R p2 Each of can be H; R o5 , R o6 and R p3 Each of may be F; and R m1 , R m2 , R m3 , R m4Each of may be CF3. The subscript x may be 1. Alternatively, the starting material i) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane THF adduct.

[0043] Alternatively, R o1 , R o2 , R o3 , R o4 , R m5 , R m6 , R p1 , R p2 and R p3 Each of can be H; R o5 and R o6 can be F; and R m1 , R m2 , R m3 and R m4 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material i) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane THF adduct.

[0044] Alternatively, R o1 , R o2 , R o3 , R o4 , R o5 , R m6 , R p1 , R p2 and R p3 Each of may be H; and R m1 , R m2 , R m3 , R m4 , R m5 and R o6 Each of may be CF3. The subscript x may be 0. Alternatively, the starting material i) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane.

[0045] Alternatively, R m1 , R p1 , R o2 , R o3 , R o4 , R p2 , R p3 , R o5 and R m6 Each of may be H; and R o1 , R m2 , R m3 , R m4 , R o6 and R m5Each of may be CF3. The subscript x may be 0. Alternatively, the starting material i) may comprise (3,5-bis(trifluoromethyl)phenyl)bis(2,5-bis(trifluoromethyl)phenyl)borane.

[0046] Alternatively, R o1 , R o2 , R o3 , R o4 , R p1 and R p2 Each of can be H; R o5 , R o6 , R m5 and R m6 Each of may be F; and R m1 , R m2 , R m3 , R m4 and R p3 Each of may be CF3. The subscript x may be 1. Alternatively, the starting material i) may comprise bis(3,5-bis(trifluoromethyl)phenyl)(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)borane THF adduct.

[0047] Boron-containing Lewis acids suitable for starting material i) are known in the art and can be prepared by known methods, for example, the methods disclosed in WO2019 / 055740, in particular in paragraphs

[0052] to

[0096] , by varying the appropriate starting material.

[0048] The amount of starting material i) will depend on the type and amount of other starting materials used, however, 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). Alternatively, the amount may be 50 ppm to 600 ppm based on the same basis.

[0049] The starting material ii) in the process for preparing component (A) is of the formula A hydroxy-functional organosilicon compound wherein each subscript n is 1 to 2,000 and each R is independently selected and as defined above. Alternatively, the subscript n may have a value such that 2≤n≤2,000, alternatively 2≤n≤1,000, alternatively 5≤n≤900, alternatively 5≤n≤50, and alternatively 5≤n≤15. When the subscript n=1, the starting material B) may be a hydroxy-functional silane, such as dimethyldisilanol. Hydroxy-functional silanes are commercially available.

[0050] Alternatively, when the subscript n ≥ 2, the starting material ii) can be a hydroxy-terminated polydiorganosiloxane. Suitable hydroxy-terminated polydiorganosiloxanes for use as starting material ii) can be prepared by methods known in the art, such as hydrolysis and condensation of corresponding organohalosilanes or the balance of cyclic polydiorganosiloxanes. Exemplary hydroxy-terminated polydiorganosiloxanes are hydroxy-terminated polydimethylsiloxanes. Suitable hydroxy-terminated polydimethylsiloxanes can also be commercially available, 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, from Gelest, Inc. (Morrisville, Pennsylvania, USA).

[0051] The starting material iii) in the process for preparing component (A) is of the formula (RHSiO 2 / 2 ) v A cyclic polyorganohydrogensiloxane wherein subscript v is 3 to 12 and each R is an independently selected monovalent hydrocarbon group. Alternatively, subscript v may be 4 to 10, alternatively 4 to 8. Alternatively, subscript v may have an average value of 4 to 6, alternatively 4 to 5, and alternatively 4. Suitable cyclic polyorganohydrogensiloxanes are known in the art and are commercially available, for example, from Dow Silicones Corporation (Midland, Michigan, USA).

[0052] The amount of starting materials ii) and iii) depends on various factors, including ii) the OH content of the hydroxy-functional organosilicon compound and iii) the silicon-bonded hydrogen (SiH) content of the cyclic polyorganohydrogensiloxane. However, the amount is sufficient to provide a molar ratio of SiH in the starting material iii) to OH in the starting material ii) (SiH:OH ratio) of 4:1 to 40:1, alternatively 5:1 to 20:1, and alternatively 5:1 to 10:1. A solvent may be used in the process.

[0053] The composition further comprises (B) a polyether compound having an aliphatic unsaturated group. Typically, the aliphatic unsaturated group is at the terminal of the (B) polyether compound.

[0054] In certain embodiments, the (B) polyether compound has the formula R 2 O(C m H 2m O) q R 3 , where R 2 is an aliphatic unsaturated group, subscript m is independently selected from 2 to 4 in each portion represented by subscript q; subscript q is 1 to 200; and R3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above.

[0055] In a specific embodiment, the (B) polyether compound has the formula R 2 O(C2H4O) x (C3H6O) y (C4H8O) z R 3 , where 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 0 at the same time, and the units represented by the subscripts x, y and z can be in random or block form in the (B) polyether compound; and R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 The moieties indicated by the subscript x are ethylene oxide (EO) units, the moieties indicated by the subscript y are propylene oxide (PO) units, and the moieties indicated by the subscript z are butylene oxide (BO) units, as understood in the art. EO, PO and BO units (if present) may be in block or random form in (B) polyether compound. The relative amounts of EO, PO and BO units (if present) may 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 may affect hydrophilicity and other properties.

[0056] The oxyalkylene units in the (B) polyether compound may independently be linear or branched. For example, if present, the oxyethylene units may have the formula -CH2CH2O- or the formula -CHCH3O-. Similarly, if present, the oxypropylene units may have the formula -CH2CH2CH2O-, the formula -CH2CHCH3O-, or the formula -CHCH3CH2O-.

[0057] It should be understood that the (B) polyether compound may have one or more moieties selected from EO, PO and BO, alone or in combination. For example, the (B) polyether compound may have only [EO] x Partial, only [PO] y Partial or only [BO] z part, or a combination of such parts, such as [EO] x [PO] y Partial, [EO] x [BO] z Part, [PO] y [BO]z Partial or [EO] x [PO] y [BO] z As described above, the units represented by the subscripts x, y and z may be in random or block form in the (B) polyether compound. In addition, the units indicated by the subscripts x, y and z do not have to be in the order specifically shown herein. For example, it will be understood by those skilled in the art that a polymerized mixture of two or more alkylene oxides (AO) can be used to form a randomized polyether, and the order of addition and / or timing of the two or more AOs during the polymerization reaction can be used to form a block polyether with different AO sequences and their chain lengths, or a combination of a randomized polyether and a block polyether can be formed.

[0058] In certain embodiments, subscript x is (and includes) 1 to 200, alternatively 1 to 50, alternatively 2 to 40, alternatively 3 to 30, alternatively 4 to 25, alternatively 5 to 20. In further embodiments, subscript x is (and includes) 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript x is (and includes) 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In other embodiments, subscript x is (and includes) 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0059] In certain embodiments, subscript y is (and includes) 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 (and includes) 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript y is (and includes) 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In other embodiments, subscript y is (and includes) 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0060] In certain embodiments, subscript z is (and includes) 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 (and includes) 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript z is (and includes) 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In other embodiments, subscript z is (and includes) 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0061] R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above. In certain embodiments, R 3 is selected from substituted or unsubstituted hydrocarbyl groups disclosed above for R, such as R 3 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, alternatively 1 carbon atom. In a specific embodiment, R 3 is a methyl group. In other embodiments, R 3 is H. In other embodiments, R 3 -C(O)R 1 When R 3 -C(O)R 1 When R 1 Typically, it 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, alternatively 1 carbon atoms, for example R 3 An acyl group.

[0062] R 2It is an aliphatic unsaturated group, which is typically an alkenyl and / or alkynyl group with 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, alternatively 2 carbon atoms. "Alkenyl" means an acyclic, branched or unbranched monovalent hydrocarbon group with one or more carbon-carbon double bonds. Its specific examples include vinyl groups, allyl groups, hexenyl groups and octenyl groups. "Alkynyl" means an acyclic, branched or unbranched monovalent hydrocarbon group with one or more carbon-carbon triple bonds. Its specific examples include ethynyl, propynyl and butynyl groups. Various examples of ethylenically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=CHCH2CH2-, H2C=CHCH2CH2-, HC≡C-, HC≡CCH2-, HC≡CCH(CH3)-, HC≡CC(CH3)2-, and HC≡CC(CH3)2CH2-. Typically, the ethylenically unsaturated group is in R 2 As understood in the art, ethylenically unsaturated groups may be referred to as aliphatic unsaturated groups.

[0063] The relative amounts of components (A) and (B) in the composition are a function of the desired reaction product. For example, the value of each subscript p generally determines the number of silicon-bonded hydrogen atoms in component (A), and if silicon-bonded hydrogen atoms are not required in the reaction product, a molar excess of component (B) relative to the moles of silicon-bonded hydrogen atoms in component (A) may be used. Alternatively, residual silicon-bonded hydrogen atoms may be required, or other components containing ethylenically unsaturated groups may be utilized to consume the silicon-bonded hydrogen atoms of component (A) without imparting polyether functionality in the reaction product. Those skilled in the art will readily understand how to determine the desired amounts of components (A) and (B) in the composition. Component (A) may optionally comprise a blend of different compounds, e.g., having different subscript p and / or n values, and component (B) may optionally comprise a blend of different polyether compounds.

[0064] The composition further comprises (C) a hydrosilylation catalyst. The (C) hydrosilylation catalyst is not limited and can be any known hydrosilylation reaction catalyst for catalyzing a hydrosilylation reaction. A combination of different hydrosilylation catalysts can be used.

[0065] In certain embodiments, the (C) hydrosilylation catalyst comprises a Group VIII to Group XI transition metal. Group VIII to Group XI transition metals refer to the modern IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hafnium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals may be used as (C) hydrosilylation catalysts.

[0066] Additional examples of catalysts suitable for (C) hydrosilylation catalysts include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr) and / or hafnium (Hf)), lanthanides, actinides, and Group I and Group II metal complexes (e.g., those containing calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals can be used as (C) hydrosilylation catalysts.

[0067] (C) The hydrosilylation catalyst may be in any suitable form. For example, the (C) hydrosilylation catalyst may be a solid, examples of which include platinum-based catalysts, palladium-based catalysts and similar noble metal-based catalysts, and nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum and similar catalysts including combinations of multiple metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-Al, Cu-Zn-Ti and similar copper-containing catalysts, etc.

[0068] The (C) hydrosilylation catalyst may be 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), etc. The (C) hydrosilylation catalyst may also be disposed in a vehicle, such as a solvent that dissolves the hydrosilylation reaction catalyst, or alternatively a vehicle that only carries but does not dissolve the (C) hydrosilylation catalyst. Such vehicles are known in the art.

[0069] In specific embodiments, the (C) hydrosilylation catalyst comprises platinum. In these embodiments, examples of the (C) hydrosilylation catalyst include, for example, platinum black, compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid and monohydric alcohols, bis(ethyl acetoacetate) platinum, bis(acetylacetonate) platinum, platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, and platinum compounds microencapsulated in a matrix or core-shell compound. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art, as exemplified in U.S. Pat. Nos. 4,766,176 and 5,017,654, which are incorporated herein by reference in their entirety.

[0070] The complex of platinum and organopolysiloxane suitable for use as (C) hydrosilylation catalyst includes a complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum. These complexes can be microencapsulated in a resin matrix. Alternatively, (C) hydrosilylation catalyst may include a complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum. Hydrosilylation reaction catalysts can be prepared by a method including reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane or an olefin-platinum-silyl complex. Olefin-platinum-silyl complexes can be prepared, for example, by mixing 0.015 mol (COD) PtCl2 with 0.045 mol COD and 0.0612 mol HMeSiCl2, wherein COD represents cyclooctadiene.

[0071] Additional examples of hydrosilylation catalysts suitable 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.

[0072] (C) The hydrosilylation catalyst may also include or alternatively be a photoactivatable hydrosilylation catalyst that can initiate curing via radiation and / or heating. The photoactivatable hydrosilylation catalyst may be any hydrosilylation catalyst capable of catalyzing a hydrosilylation reaction, particularly when exposed to radiation having a wavelength of 150 nanometers to 800 nanometers (nm).

[0073] Specific examples of photoactivatable hydrosilylation reaction catalysts suitable for (C) hydrosilylation catalysts include, but are not limited to, β-diketone platinum (II) complexes, such as bis(2,4-pentanedioate) platinum (II), bis(2,4-hexanedioate) platinum (II), bis(2,4-heptanedioate) platinum (II), bis(1-phenyl-1,3-succinate) platinum (II), bis(1,3-diphenyl-1,3-propanedioate) platinum (II), bis(1,1,5,5-tetramethylol) platinum (II), and bis(1,5-diphenyl-1,3-propanedioate). ,5-hexafluoro-2,4-pentanedioic acid) platinum (II); (η-cyclopentadienyl) trialkyl platinum complexes, such as (Cp) trimethyl platinum, (Cp) ethyldimethyl platinum, (Cp) triethyl platinum, (chloro-Cp) trimethyl platinum and (trimethylsilyl-Cp) trimethyl platinum, wherein Cp represents a cyclopentadienyl group; triazene oxide-transition metal complexes, such as Pt[C6H5NNNOCH3]4, Pt[p-CN-C6H4NNNOC6H 11 ]4. Pt[p-H3COC6H4NNNOC6H 11 ]4. Pt[p-CH3(CH2) x -C6H4NNNOCH3]4,1,5-cyclooctadiene.Pt[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 —C6H4NNNOCH3]2, wherein x is 1, 3, 5, 11 or 17; (η-diolefin)(σ-aryl)platinum complexes such as (η 4 -1,5-cyclooctadienyl)diphenylplatinum, (η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η 4 -2,5-norbornene)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl) platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum and (η 4 -1,5-cyclooctadienyl)bis-(4-trifluoromethylphenyl)platinum.

[0074] The present disclosure also provides a compound having the following structure:

[0075]

[0076] Each R 4 independently selected from hydrogen atoms, substituted or unsubstituted hydrocarbon groups, polyether groups or group, provided that at least one R 4 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 hydrocarbon group, and each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group. In certain embodiments, the compound is prepared by reacting components (A) and (B) in the presence of component (C) of the composition.

[0077] In certain embodiments, no more than three, alternatively no more than two, alternatively no more than one R 4 In a specific embodiment, the compound contains one such group as R in each cyclic siloxane moiety. 4 .

[0078] In other embodiments, the compound has the structure:

[0079]

[0080] Where R 1 , R 4 and subscripts p and n are each as defined above.

[0081] When the compound is formed from the composition, i.e., via hydrosilylation of components (A) and (B) in the presence of component (C), R 4 The polyether groups are formed by hydrosilylation of silicon-bonded hydrogen atoms of component (A). 4 It is formed by hydrosilylation of the (B) polyether compound with specific silicon-bonded hydrogen atoms of component (A). 4 It may be unreacted hydrogen or a hydrocarbon group other than the polyether group. 4 When R represents a polyether group, the polyether groups are independently selected and may be the same as or different from each other. 4 When R is a hydrocarbon group different from the polyether group, 4 The hydrosilylation of any unsaturated compound with a specific silicon-bonded hydrogen atom of component (A) may be formed, for example, olefins, 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 100 mol% of the R 4 The group is a polyether group.

[0082] In certain embodiments, R 4 The polyether group has the formula -DO(C m H 2m O) q R 3 , wherein D is a divalent linking group, subscript m is independently selected from 2 to 4 in each portion represented by subscript q; subscript q is 1 to 200; and R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above. D is generally a polyether compound (B) consisting of R 2 The hydrosilylation forms a divalent hydrocarbon group, which produces R 4 Therefore, the structure of D is a function of the ethylenically unsaturated groups of the (B) polyether compound. D may be branched or linear, and when R of the (B) polyether group is 2 When D is an alkynyl group, D may also contain an ethylenically unsaturated group. In certain embodiments, D has the formula -C j H 2j -, wherein 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.

[0083] In a specific embodiment, 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; provided that the subscripts x, y and z are not 0 at the same time, and the units represented by the subscripts x, y and z are in R 4 The polyether groups of R may be in random or block form; and R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above. EO, PO and BO units (if present) may be in block or random form in (B) polyether compound. The relative amounts of EO, PO and BO units (if present) may be selectively controlled based on the desired properties of the compound. D is as described above.

[0084] R 4The oxyalkylene units in the polyether group of can be independently linear or branched. For example, if present, the oxyethylene units can have the formula -CH2CH2O- or have the formula -CHCH3O-. Similarly, if present, the oxypropylene units can have the formula -CH2CH2CH2O-, the formula -CH2CHCH3O-, or the formula -CHCH3CH2O-.

[0085] It should be understood that R 4 The polyether group may have one or more moieties selected from EO, PO and BO, alone or in combination. 4 The polyether groups may have only [EO] x Partial, only [PO] y Partial or only [BO] z part, or a combination of such parts, such as [EO] x [PO] y Partial, [EO] x [BO] z Part, [PO] y [BO] z Partial or [EO] x [PO] y [BO] z As mentioned above, the units represented by the subscripts x, y and z are in R 4 The polyether groups of can be in random or block form. In addition, the units indicated by the subscripts x, y and z do not have to be in the order specifically shown herein. For example, it will be understood by those skilled in the art that a polymerized mixture of two or more alkylene oxides (AOs) can be used to form a randomized polyether, and the order of addition and / or timing of the two or more AOs during the polymerization reaction can be used to form a block polyether with different AO sequences and their chain lengths, or a combination of randomized polyethers and block polyethers can be formed.

[0086] In certain embodiments, subscript x is (and includes) 1 to 200, alternatively 1 to 50, alternatively 2 to 40, alternatively 3 to 30, alternatively 4 to 25, alternatively 5 to 20. In further embodiments, subscript x is (and includes) 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript x is (and includes) 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In other embodiments, subscript x is (and includes) 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0087] In certain embodiments, subscript y is (and includes) 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 (and includes) 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript y is (and includes) 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In other embodiments, subscript y is (and includes) 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0088] In certain embodiments, subscript z is (and includes) 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 (and includes) 10 to 20, alternatively 12 to 18, alternatively 14 to 16, alternatively 16. In further embodiments, subscript z is (and includes) 20 to 30, alternatively 22 to 28, alternatively 24 to 26, alternatively 24 or 26. In other embodiments, subscript z is (and includes) 30 to 40, alternatively 32 to 38, alternatively 34 to 36.

[0089] R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above. In certain embodiments, R 3 is selected from substituted or unsubstituted hydrocarbon groups disclosed above for R, such as R 3 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, alternatively 1 carbon atom. In a specific embodiment, R 3 is a methyl group. In other embodiments, R 3 is H. In other embodiments, R 3 -C(O)R 1 When R 3 -C(O)R 1 When R 1Typically, it 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, alternatively 1 carbon atoms, for example R 3 An acyl group.

[0090] Subscript n is 1 to 1,000, alternatively 1 to 900, alternatively 1 to 800, alternatively 1 to 700, alternatively 1 to 600, alternatively 1 to 500, alternatively 1 to 400, alternatively 1 to 300, alternatively 1 to 200. In other embodiments, subscript n is 2 to 1,000, alternatively 2 to 900, alternatively 2 to 800, alternatively 2 to 700, alternatively 2 to 600, alternatively 2 to 500, alternatively 2 to 400, alternatively 2 to 300, alternatively 2 to 200.

[0091] 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. Therefore, 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 specific 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, alternatively 1 to 4.

[0092] 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 thereto. For example, the compounds can be used as surfactants in cosmetic compositions, coating compositions, textile compositions, lignocellulosic compositions, and any other compositions or emulsions in which surfactants are commonly used.

[0093] The present disclosure also provides an isocyanate reactive component. The isocyanate reactive component is generally used to react with isocyanates, for example to form polyurethanes and / or polyisocyanurates. The isocyanate reactive component comprises the above-mentioned compound as a surfactant. The isocyanate reactive component also comprises a polyol.

[0094] The isocyanate-reactive component typically comprises greater than 0 to 10 parts by weight, alternatively 0.1 to 10 parts by weight, alternatively 0.1 to 9 parts by weight, alternatively 0.1 to 8 parts by weight, alternatively 0.1 to 7 parts by weight, alternatively 0.1 to 6 parts by weight, alternatively 0.1 to 5 parts by weight, alternatively 1 to 4 parts by weight, alternatively 1.5 to 3.5 parts by weight, alternatively 2 to 3 parts by weight of the compound, based on 100 parts by weight of the total amount of polyols in the isocyanate-reactive component.

[0095] Suitable polyether polyols for use in the isocyanate reactive component include, but are not limited to, products obtained by 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 a plurality of active hydrogen atoms. The catalyst used for the polymerization may be an anionic catalyst or a cationic catalyst, and suitable catalysts include KOH, CsOH, boron trifluoride or a dicyanide complex (DMC) catalyst, such as zinc hexacyanocobaltate or a quaternary phosphazene compound. The initiator may be selected from, for example, neopentyl glycol; 1,2-propylene glycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerol; amino alcohols such as ethanolamine, diethanolamine and triethanolamine; alkanediols such as 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, 1,5-pentanediol, 2-methylpropane-1,3-diol , 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,5-hexanediol; ethylene glycol; diethylene glycol, triethylene glycol; bis-3-aminopropylmethylamine; ethylenediamine; diethylenetriamine; 9(1)-hydroxymethyloctadecyl alcohol, 1,4-bishydroxymethylcyclohexane; hydrogenated bisphenol; 9,9(10,10)-bishydroxymethyloctadecyl alcohol; 1,2,6-hexanetriol and combinations thereof. Other initiators include other linear and cyclic compounds containing amines. 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-ethylenediamine, N-methyl-1,3-propanediamine; N,N-dimethyl-1,3-diaminopropane; N,N-dimethylethanolamine; 3,3'-diamino-N-methyldipropylamine; N,N-dimethyldipropylenetriamine; aminopropyl-imidazole; and combinations thereof. As understood in the art, the initiator compound or combination thereof is typically selected based on the desired functionality of the resulting polyether polyol. For purposes of the present disclosure, the polyol may be formed with any of the above-described initiators or combinations of initiators. The polyol is not limited to a polyol formed by any particular preparation method.

[0096] Other suitable polyether polyols include polyether diols and triols, such as polyoxypropylene diols and triols and poly(oxyethylene-oxypropylene) diols and triols, which are obtained by adding ethylene oxide and propylene oxide to difunctional or trifunctional initiators simultaneously or sequentially. Polyether polyols with higher functionality than triols can also be used instead of polyether diols and / or triols or in addition to polyether diols and / or triols. Copolymers with an oxyethylene content of 5% to 90% by weight based on the weight of the polyol component can also be used, wherein the polyol can be a block copolymer, a random / block copolymer or a random copolymer. Other suitable polyether polyols also include polytetramethylene glycol obtained by polymerization of tetrahydrofuran.

[0097] Polyester polyols suitable for isocyanate reaction components include, but are not limited to, the following hydroxyl functionalized reaction products: polyols 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 polyols; and polycarboxylic acids, particularly dicarboxylic acids or their ester 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 polymerization of lactones (e.g., caprolactone) and polyols or by polymerization of hydroxycarboxylic acids (e.g., hydroxycaproic acid) can also be used. In certain embodiments, the polyol comprises a mixture of polyester and polyether polyols.

[0098] 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 glycols (such as 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol) with diaryl carbonates (such as diphenyl carbonate) or with 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 hydroxyl-terminated butadiene homopolymers and copolymers, and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.

[0099] In certain embodiments, the polyol is a polymer polyol. In a specific embodiment, the polymer polyol is a graft polyol. Graft polyols may also be referred to as graft dispersed polyols or graft polymer polyols. Graft polyols typically include products (i.e., polymeric particles) obtained by in-situ polymerization of one or more vinyl monomers (e.g., styrene monomers and / or acrylonitrile monomers) with macromonomers in a polyol (e.g., a polyether polyol).

[0100] In other embodiments, the polymer polyol is selected from polyurea (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 above polymer polyols. PHD polyols are usually formed by the in-situ reaction of diisocyanates and diamines in polyols to obtain a stable dispersion of polyurea particles. PIPA polyols are similar to PHD polyols, except that dispersions are usually formed by the in-situ reaction of diisocyanates with alkanolamines rather than diamines to obtain polyurethane dispersions in polyols.

[0101] It should be understood that the isocyanate-reactive component may include any combination of two or more polyols that differ from one another based on functionality, molecular weight, viscosity, or structure.

[0102] In various embodiments, the hydroxyl (OH) equivalent weight of the polyol is greater than 0 g / mol to 2,000 g / mol, alternatively greater than 0 g / mol to 1,700 g / mol, alternatively greater than 0 g / mol to 1,000 g / mol, alternatively greater than 0 g / mol to 700 g / mol, alternatively greater than 0 g / mol to 400 g / mol, alternatively greater than 0 g / mol to 350 g / mol, alternatively greater than 0 g / mol to 325 g / mol, alternatively greater than 0 g / mol to 300 g / mol, alternatively greater than 0 g / mol to 275 g / mol, alternatively greater than 0 g / mol to 250 g / mol, alternatively greater than 0 g / mol to 225 g / mol, alternatively greater than 0 g / mol to 200 g / mol. In certain embodiments, including the above ranges, the OH equivalent weight of the polyol is at least 30 g / mol. Methods of determining OH equivalent weight based on the functionality and molecular weight of a given polyol are known in the art.

[0103] In these or other embodiments, the polyol has a functionality of 2 to 10, alternatively 2 to 9, alternatively 2 to 8, alternatively 2 to 7, alternatively 3 to 6.

[0104] In specific embodiments, polyol comprises one or more polyether polyols, alternatively consists essentially of one or more polyether polyols, alternatively consists of one or more polyether polyols. In other words, in these embodiments, polyol does not contain any polyol that is not a polyether polyol usually. In other specific embodiments, polyol comprises one or more polyester polyols, alternatively consists essentially of one or more polyester polyols, alternatively consists of one or more polyester polyols. In other words, in these embodiments, polyol does not contain any polyol that is not a polyester polyol usually.

[0105] As understood in the art, polyurethanes contain organic units connected by urethane (urethane) bonds. Polyurethanes are generally formed by reacting polyisocyanates with polyols (generally polyether polyols). Since polyurethanes contain two types of monomers, which polymerize with each other, they are generally classified as alternating copolymers. The isocyanates and polyols used to prepare polyurethanes contain two or more functional groups per molecule on average. Polyisocyanurates can also be prepared by reacting polyisocyanates with polyols. However, when preparing polyisocyanurates, the proportion of methylene diphenyl diisocyanate ("MDI") used is generally high, and polyester-derived polyols are used in the reaction instead of polyether polyols. The resulting chemical structure is significantly different from that of polyurethanes, in which the isocyanate groups on MDI are trimerized to form isocyanurate groups, which are linked together with the polyols to form a complex polymeric structure. Therefore, the selection of polyols in the isocyanate-reactive component is generally a function of the end use of the isocyanate-reactive component, for example to obtain polyurethanes, polyisocyanurates or mixed polyurethanes / polyisocyanurates.

[0106] In certain embodiments, the isocyanate reactive component also includes a blowing agent. In the case where the blowing agent already exists (e.g., water) or is produced (e.g., carbon dioxide) during the reaction, the blowing agent may be referred to as a supplementary blowing agent, but the supplementary blowing agent may provide most or all of the foaming during the reaction of the isocyanate reactive component with the polyisocyanate. If used, the blowing agent may be selected from a chemical blowing agent, a physical blowing agent, and a combination thereof. Examples of such blowing agents are described below.

[0107] The amount of blowing agent used can vary 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 cell size in the final foam.

[0108] In various embodiments, the chemical blowing agent is selected from Si-OH compounds, which may be monomers, oligomers or polymers. 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 dimethylsiloxanes. Such siloxanes may have a relatively low viscosity, such as 10mPa·s to 5,000mPa·s at 25°C, alternatively 10mPa·s to 2,500mPa·s, alternatively 10mPa·s to 1,000mPa·s, alternatively 10mPa·s to 500mPa·s, alternatively 10mPa·s to 100mPa·s. Alternatively, the chemical blowing agent may include formic acid.

[0109] In a specific embodiment, the chemical blowing agent comprises water, alternatively water. In one embodiment, the amount of water present in the isocyanate reactive component is 0.02 wt % to 5 wt %, alternatively 0.02 wt % to 4 wt %, alternatively 0.02 wt % to 3 wt %, alternatively 0.02 wt % to 2 wt %, 0.02 wt % to 1 wt %, alternatively 0.03 wt % to 0.9 wt %, alternatively 0.05 wt % to 0.8 wt %, alternatively 0.1 wt % to 0.7 wt %, based on the total weight of the isocyanate reactive component and the polyisocyanate, which is further described below.

[0110] In various embodiments, the isocyanate-reactive component comprises a physical blowing agent. The physical blowing agent can be used in addition to or in place of a chemical blowing agent.

[0111] In various embodiments, the physical blowing agent is one that undergoes a phase change from liquid to gas during 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., alternatively ≥100° C. The boiling point temperature generally depends on the specific type of physical blowing agent.

[0112] Useful physical blowing agents include hydrocarbons (such as pentane, hexane, halogenated hydrocarbons, more specifically chlorinated and / or fluorinated hydrocarbons, for example methylene chloride, chloroform, trichloroethane, chlorofluorocarbons, hydrochlorofluorocarbons (HCFCs)), ethers, ketones and esters (for example methyl formate, ethyl formate, methyl acetate or ethyl acetate), air, nitrogen or carbon dioxide in liquid form or as a gas. In specific embodiments, the physical blowing agent comprises or is n-pentane. In certain embodiments, the physical blowing agent comprises a compound selected from the group consisting of propane, butane, isobutane, isobutylene, isopentane, cyclopentane, n-pentane, dimethyl ether or a mixture thereof. In many embodiments, the blowing agent comprises a compound that is inert.

[0113] 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. The compounds are substantially free of halogens other than fluorine.

[0114] Examples of suitable HFCs include aliphatic compounds such as 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1-fluorobutane, nonafluorocyclopentane, perfluoro-2-methylbutane, 1-fluorohexane, perfluoro-2,3-dimethylbutane, perfluoro-1,2-dimethylcyclobutane, perfluorohexane, perfluoroisohexane, perfluorocyclohexane, perfluoroheptane, perfluoro Ethylcyclohexane, perfluoro-1,3-dimethylcyclohexane and perfluorooctane, 1,1,1,2-tetrafluoroethane (HFC-134a); and aromatic compounds such as fluorobenzene, 1,2-difluorobenzene; 1,4-difluorobenzene, 1,3-difluorobenzene; 1,3,5-trifluorobenzene; 1,2,4,5-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,3,4-tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene and 1-fluoro-3-(trifluoromethyl)benzene. In certain embodiments, HFC-365mfc and HFC-245fa may be preferred due to their increased availability and ease of use, wherein HFC-365mfc has a higher boiling point than HFC-245fa, which may be useful in certain applications. For example, HFCs such as HFC-365mfc having a boiling point above 30°C may be desirable because they do not require liquefaction during foam processing.

[0115] Another example of a physical blowing agent is a hydrofluoroolefin (HFO), such as trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze, available under the trade name Solstice ze from Honeywell), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd, available under the trade name Forane from Arkema), 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf, available under the trade name Solstice yf from Honeywell and under the trade name Opteon YF from Chemours), cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z, available under the trade name Opteon MZ from Chemours), and Opteon 1150.

[0116] In a specific embodiment, the isocyanate-reactive component comprises a physical blowing agent containing hydrocarbon. In various embodiments in which the isocyanate-reactive component comprises a physical blowing agent, based on 100 parts by weight of polyol in the isocyanate-reactive component, the physical blowing agent is present in the isocyanate-reactive component in an amount greater than 0 to 60 parts by weight, alternatively 5 to 55 parts by weight, alternatively 10 to 50 parts by weight, alternatively 15 to 45 parts by weight, alternatively 20 to 45 parts by weight, alternatively 25 to 45 parts by weight. The surfactant of the present invention has excellent characteristics in stabilizing the isocyanate-reactive component comprising such a physical blowing agent. Conventional surfactants cause phase separation before the final use of the isocyanate-reactive component, and the isocyanate-reactive component comprises a physical blowing agent of similar load.

[0117] In various embodiments, the isocyanate-reactive component also includes a catalyst. Although the isocyanate-reactive component is typically reacted with the polyisocyanate in the presence of a catalyst, the catalyst may be in a separate portion from the isocyanate-reactive component and combined during the reaction, or may be present in the isocyanate-reactive component, such as in the case of a two-component (2k) system.

[0118] 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, which is a dialkyltin (IV) salt of an organic carboxylic acid. Specific examples of suitable organometallic catalysts (e.g., dibutyltin dilaurate) are available from Air Products and Chemicals, Inc., Allentown, PA, under the trademark The organometallic catalyst may also comprise other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate and dioctyltin diacetate.

[0119] Examples of other suitable catalysts include iron (II) chloride; zinc chloride; lead octoate; tris (dialkylaminoalkyl) -s-hexahydrotriazines, including tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine; tetraalkylammonium hydroxides, including tetramethylammonium hydroxide; alkali metal hydroxides, including sodium hydroxide and potassium hydroxide; alkali metal alkoxides, including sodium methoxide and potassium isopropoxide; and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and / or pendant OH groups.

[0120] Other examples of other suitable catalysts, particularly trimerization catalysts, include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, potassium 2-ethylhexanoate, N,N,N-trimethylisopropylamine / formates, and combinations thereof.

[0121] Other 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, tetramethyliminobis(propyl)amine, (E) The catalyst may comprise a delayed action tertiary amine based on 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU"). Alternatively or in addition, the catalyst may comprise N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether and / or ethylenediamine. The tertiary amine catalyst may be further modified by adding an acidic proton-containing acid such as phenol or formic acid in approximately the same stoichiometric amount for use as a delayed action catalyst. Such delayed action catalysts are commercially available from Air Products and Evonik.

[0122] The catalyst can be used alone or in a carrier vehicle. Carrier vehicles are known in the art and are further described below as optional components of the isocyanate-reactive component. If a carrier vehicle is used and the catalyst is dissolved, the carrier vehicle may be referred to as a solvent. The carrier vehicle may be isocyanate-reactive, for example an alcohol-functional carrier vehicle, such as dipropylene glycol.

[0123] The catalyst can be used in various amounts. The catalyst can comprise any combination of different catalysts.

[0124] The isocyanate reactive component may optionally further comprise an additive component. The additive component may be selected from catalysts, blowing agents, plasticizers, crosslinking agents, chain extenders, chain terminators, wetting agents, surface modifiers, waxes, foam stabilizers, dehumidifiers, desiccants, viscosity reducers, compounds that reduce cell size, reinforcing 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, flame retardants, smoke suppressants, antistatic agents, antimicrobial agents, and combinations thereof.

[0125] One or more additives can exist with any suitable weight percentage (wt %) of isocyanate reactive components, such as with 0.1 wt % to 15 wt %, 0.5 wt % to 5 wt % or 0.1 wt % or less, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt % or 15 wt % or more of isocyanate reactive components. Those skilled in the art can easily measure the appropriate amount of additive according to the result of for example the type of additive and expectation. Some optional additives are described in more detail below.

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

[0127] The carrier vehicle may also have a viscosity of 1 to 1,000 mm at 25°C. 2 / second range, 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, caprylylmethicone, and any mixture thereof.

[0128] 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. Other suitable surfactants may include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, or mixtures of such surfactants. The compound is present in the isocyanate reactive component as a surfactant. Therefore, any additional or optional surfactant may be referred to as a supplemental surfactant.

[0129] The supplemental surfactant may comprise a fluorocarbon surfactant or a fluorinated surfactant. The fluorinated surfactant may be any of those compounds known in the art that contain fluorine atoms on carbon and are also surfactants. These fluorinated surfactants may be organic or silicon-containing. For example, the fluorinated organic surfactant may be a perfluorinated polyether, such as those having repeating units of the formula:

[0130] or -CF2CF2O- and mixtures of such units.

[0131] The silicon-containing fluorinated surfactant may be, for example, a siloxane containing an organic group bonded to fluorine, such as a siloxane having a repeating unit of the formula:

[0132]

[0133] In various embodiments, the addition of a fluorinated surfactant to the isocyanate reactive component reduces the cured foam density of the article formed therefrom. Generally speaking, increasing the amount of fluorinated surfactant in the isocyanate reactive component reduces the density of the foam. This is particularly true for slow cure systems where the surfactant stabilizes the bubbles while the network is forming and curing.

[0134] 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 be used to stabilize the foam.

[0135] Suitable pigments are known in the art.In various embodiments, the isocyanate-reactive component further comprises carbon black, such as acetylene black.

[0136] The isocyanate reactive component may include one or more fillers. The filler may be one or more reinforcing fillers, non-reinforcing fillers, or mixtures thereof. Examples of finely divided reinforcing fillers include high surface area gas phase and precipitated silica, which include rice husk ash and a certain degree of 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-O-SIL. Examples of finely divided non-reinforcing fillers include pulverized quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide and carbon black, talc, and wollastonite. Other fillers that can be used alone or in addition to the above include carbon nanotubes such as multi-walled carbon nanotubes, alumina, hollow glass spheres, calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesium carbonate, clays such as kaolin, alumina trihydrate, magnesium hydroxide (brucite), graphite, copper carbonate such as malachite, nickel carbonate such as zarachite, barium carbonate such as witherite and / or strontium carbonate such as strontite. Additional alternative fillers include alumina, selected from the following silicates: olivine, garnet; aluminosilicates; cyclosilicates; chain silicates; and sheet silicates. In certain embodiments, the isocyanate-reactive component comprises at least one filler comprising hollow particles, such as hollow spheres. Such fillers can be used to contribute to the porosity and / or overall porosity of the foam. When used, fillers can be used in the isocyanate-reactive component in an amount of 0.01 wt % to 50 wt %, alternatively 0.05 wt % to 40 wt %, alternatively 0.1 wt % to 35 wt %, based on the total weight of the isocyanate-reactive component. In addition, fumed silica (if used) can be used in an amount of 0.01 wt % to 5 wt %, alternatively 0.05 wt % to 3 wt %, alternatively 0.1 wt % to 2.5 wt %, alternatively 0.2 wt % to 2.2 wt %, based on the total weight of the isocyanate-reactive component.

[0137] The filler, if present, 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 performed, for example, with a fatty acid or fatty acid ester such as stearate, or with an organosilane, organosiloxane or organosilazane such as hexaalkyldisilazane or short chain siloxane diol. Typically, the surface treatment renders the filler hydrophobic and thus easier to handle and obtain a homogeneous mixture with the other components of the isocyanate reactive component. Silanes such as R 5 e Si(OR 6 ) 4-e It can also be used as a filler treatment agent, where R 5 is a substituted or unsubstituted monovalent hydrocarbon group of 6 to 20 carbon atoms, for example, an alkyl group such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and an aralkyl group such as benzyl and phenethyl, R 6 is an alkyl group of 1 to 6 carbon atoms, and the subscript "e" is equal to 1, 2 or 3.

[0138] In various embodiments, the isocyanate reactive component also includes an adhesion imparting agent. The adhesion imparting agent can improve the adhesion of the foam to the substrate material contacted during curing. In certain embodiments, the adhesion imparting agent is selected from an organosilicon compound having at least one alkoxy group bonded to a silicon atom in the molecule. The alkoxy group is exemplified by a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. In addition, examples of non-alkoxy groups bonded to the silicon atom of the organic silicon compound are: substituted or unsubstituted monovalent hydrocarbon groups, such as alkyl groups, alkenyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, etc.; epoxy-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 glycidoxyalkyl groups; and 4-oxacyclopropylbutyl groups, 8-oxacyclopropyloctyl groups or similar oxacyclopropyl groups; monovalent organic groups containing acrylic groups, such as 3-methacryloxypropyl groups, etc.; and hydrogen atoms.

[0139] The organosilicon compound generally has a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom. In addition, due to the ability to impart good adhesion to various types of substrate materials, the organosilicon compound generally has at least one monovalent organic group containing an epoxy group in the molecule. Examples of this type of organosilicon compound are organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of organosiloxane oligomers or alkyl silicates are linear structures, partially branched linear structures, branched structures, cyclic structures, and reticular structures. The linear structure, branched structure, and reticular structure are typical. Examples of this type of organic silicon compound are: silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc.; 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; a mixture of a silane compound or a siloxane compound having at least one silicon-bonded alkoxy group and a siloxane compound having at least one silicon-bonded hydroxyl group and at least one silicon-bonded alkenyl group in the molecule; and methyl polysilicate, ethyl polysilicate, and ethyl polysilicate containing an epoxy group.

[0140] In specific embodiments, the isocyanate reactive components, particularly isocyanate reactive components, may also contain a chain extender. Suitable chain extenders include any of the components listed above as initiators for the polyols, which may be used alone or in combination as chain extenders, when present, separate from and in addition to the polyols.

[0141] If used in the isocyanate-reactive component, any optional additives may be present in the isocyanate-reactive component or as a separate component in the composition. Alternatively, non-isocyanate-reactive optional additives such as fillers and the like may be included in the isocyanate component described below along with the polyisocyanate. Typically, the composition is a 2k (two-component) composition, wherein the isocyanate component consists of the polyisocyanate and an isocyanate-reactive component comprising the remaining components used.

[0142] In certain embodiments, the viscosity of the isocyanate reactive component at 25° C. is 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 can be measured via a TA Instruments AR 2000 rheometer with a 45 mm cone and plate geometry for 10 s -1The kinematic viscosity is measured at a constant shear rate of 100°C and a heating rate of 3°C / min from 20°C to 80°C. The 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 all substances 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 that require foaming in or on certain substrates or articles, including those that define gaps and / or orifices.

[0143] 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 may alternatively be present in the (2) isocyanate component, or be separate from the (1) isocyanate reactive component and the (2) isocyanate component.

[0144] Suitable polyisocyanates have two or more isocyanate functional groups and include conventional aliphatic, alicyclic, araliphatic and aromatic isocyanates. Polyisocyanates can be selected from 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 pMDI, is essentially composed of pMDI or is pMDI. In one embodiment, the polyisocyanate has the formula OCN-R-NCO, wherein R is an alkyl moiety, an aryl moiety or an aralkyl moiety. In this embodiment, the polyisocyanate may contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0145] Specific examples of suitable polyisocyanates include: alkylene diisocyanates having 4 to 12 carbons 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-hexamethylcyclohexane; Hydrogen toluene diisocyanate and its corresponding isomer mixtures, 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate and its corresponding isomer mixtures, aromatic diisocyanates and polyisocyanates (such as 2,4- and 2,6-toluene diisocyanate) and its corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and its corresponding isomer mixtures, mixtures of 4,4'-, 2,4'- and 2,2-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate, and mixtures of MDI and toluene diisocyanate (TDI).

[0146] Polyisocyanates may include modified polyvalent isocyanates, i.e. products obtained by partial chemical reactions of organic diisocyanates and / or polyisocyanates. Examples of suitable modified polyvalent isocyanates include diisocyanates and / or polyisocyanates containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups and / or urethane groups. Specific examples of suitable modified polyvalent isocyanates include organic polyisocyanates containing urethane groups and having an NCO content of 15 to 33.6 parts by weight, based on the total weight, such as low molecular weight diols, triols, dialkylene glycols, trialkylene glycols or polyoxyalkylene glycols with a molecular weight of up to 6000; modified 4,4'-diphenylmethane diisocyanate or 2,4- and 2,6-toluene diisocyanate, examples of which dioxyalkylene and polyoxyalkylene glycols that can be used alone or as a mixture include diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol and polyoxypropylene polyoxyethylene glycol or triol. Prepolymers containing NCO groups and having an NCO content of 3.5 to 29 parts by weight, based on the total weight of the isocyanate, and prepared from polyester polyols and / or polyether polyols; 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate or polymeric MDI are also suitable. In addition, liquid polyisocyanates containing carbodiimide groups and having an NCO content of 15 to 33.6 parts by weight, based on the total weight of the (2) isocyanate component, may also be suitable, for example based on 4,4'- and 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4'- and / or 2,6-toluene diisocyanate. The modified polyisocyanates can optionally be mixed together or with unmodified organic polyisocyanates such as 2,4′- and 4,4′-diphenylmethane diisocyanate, polymeric MDI, 2,4′- and / or 2,6-toluene diisocyanate.

[0147] It should be understood that the polyisocyanate may include any combination of two or more polyisocyanates that differ from one another based on functionality, molecular weight, viscosity, or structure.In specific embodiments, the polyisocyanate comprises, consists essentially of, or is pMDI.

[0148] The functionality of the polyisocyanate is typically 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.

[0149] In these or other embodiments, the polyisocyanate has 15 wt % to 60 wt %, alternatively 15 wt % to 55 wt %, alternatively 20 wt % to 48.5 wt % NCO. Methods for determining the NCO weight content based on the functionality and molecular weight of the specific isocyanate are known in the art.

[0150] In certain embodiments, the polyisocyanate is typically present in the composition in an amount to provide an isocyanate index of 80 to 200, alternatively 80 to 130, alternatively 85 to 125, alternatively 90 to 120, alternatively 95 to 120, alternatively 100 to 120, alternatively 105 to 115. In other embodiments, the polyisocyanate is typically present in the composition in an amount to provide an isocyanate index of 80 to 800, alternatively 90 to 700, alternatively 100 to 600, alternatively 150 to 500, alternatively 200 to 300. The isocyanate index is the molar ratio of NCO to isocyanate-reactive hydrogen functional groups multiplied by 100. Isocyanate indices and methods for calculating them are well known in the art.

[0151] The composition can be prepared by combining (1) an isocyanate-reactive component and (2) an isocyanate component and any optional components (if not present in (1) the isocyanate-reactive component) in any order of addition. As described in more detail below, the composition can be a one-component composition, a two-component (2K) composition, or a multi-component composition. When the (1) isocyanate-reactive component and (2) the isocyanate component are combined, particularly in the presence of a catalyst, a reaction is initiated that produces a foamed article. 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.

[0152] Also disclosed is a foamed article comprising a 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 of the isocyanate-reactive component and the polyisocyanate of the isocyanate component.

[0153] In many embodiments, the foamed article is a closed-cell foam. However, the foamed article can also be an open-cell foam or both a closed-cell and an open-cell foam.

[0154] In various embodiments, the foamed article has cells that are generally uniform in size and / or shape and / or distribution.

[0155] The average pore size can be determined by methods known in the art. For example, ATSM method D3576-15 can be used with the following modifications: (1) imaging the foam using an optical or electron microscope rather than projecting the image on a screen; and (2) drawing a line of known length spanning greater than 15 cells rather than a 30 mm line.

[0156] The foamed article and the composite article comprising the substrate and the foamed article together can be formed by disposing the composition on the substrate and curing the composition.

[0157] The composition may be arranged or distributed on the substrate in any suitable manner. Typically, the curable composition is applied in wet form via a wet coating technique. The curable composition may be applied by i) spin coating; ii) brush coating; iii) drop coating; iv) spray coating; v) dip coating; vi) roller coating; vii) flow coating; viii) slot coating; ix) concave coating; x) Meyer rod coating; or xi) a combination of any two or more of i) to x).

[0158] The substrate is not limited and can be any substrate. The foamed article can be separated from the substrate, for example if the substrate is a mold, or can be physically and / or chemically bonded to the substrate according to its choice. The substrate can optionally have a continuous or discontinuous shape, size, dimension, surface roughness and other characteristics.

[0159] Alternatively, the substrate may comprise plastics, 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-plated steel, or alloys of these metals or multiple metals, or combinations of different materials. Because the composition can cure under ambient conditions, elevated temperatures are not required to achieve curing, which would damage certain substrates.

[0160] 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; polystyrene (PS) and other styrenic resins SB rubber; polyoxymethylene (POM); polycarbonate (PC); polymethyl methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyvinyl chloride (PVC ... S); polyphenylene ether (PPE); polyimide (PI); polyamide-imide (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, such as polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type and fluorine type; and copolymers and combinations thereof. Thermosetting resins may include epoxy resins, polyurethanes, polyureas, phenolic resins, urea-formaldehyde resins, or combinations thereof. The substrate may include a coating, film or layer disposed thereon. Coatings made from polymer latexes such as latexes made from acrylic acid, acrylates, methacrylates, methacrylic acid, other alkyl acrylates, other alkyl acrylic acid, styrene, isoprene butene monomers, or latexes made from alkyl esters of the aforementioned acid monomers, or latexes made from copolymers of the aforementioned monomers can be used. Composite materials based on any of these resins can be used as a substrate by combining with glass fibers, carbon fibers, or solid fillers such as calcium carbonate, clay, aluminum hydroxide, aluminum oxide, silica, glass spheres, sawdust, wood fibers, or combinations thereof.

[0161] In a specific embodiment, the substrate defines at least one gap, and disposing the composition includes disposing the composition in the at least one gap so that the foamed article is present in the gap in the composite article. In some embodiments, the composition is generally flowable and will conform to the shape of the substrate under ambient conditions (including room temperature and atmospheric pressure).

[0162] The following examples, which illustrate embodiments of the present disclosure, are intended to illustrate, not to limit, the invention. Unless otherwise noted, all reactions were conducted under air and all components were purchased or otherwise obtained from various commercial suppliers.

[0163] Reference Example 1

[0164] The general procedure of Reference Example 1 is to prepare a component (A), namely (A) an organohydrogensiloxane.

[0165] In Reference Example 1, the bulk reaction solvent was dried by passing it through a column of alumina and a Q5 reactive scavenger (referred to as Cu-0226 S, supplied by BASF). All other solvents were purchased from Aldrich as anhydrous grades and stored in activated molecular sieves. NMR solvents (CDCl3, CD2Cl2, and C6D6) were obtained from Cambridge Isotope Laboratories, Inc. and activated Molecular sieve drying or, in the case of C6D6, Na / K alloy drying. 1-Bromo-2,5-bis(trifluoromethyl)benzene was purchased from Oakwood Chemical. Prior to use, n-butyllithium (in hexanes) was titrated using 1.00 M decanol in toluene with 1,10-phenanthroline as an indicator. 1

[0166] Multinuclear NMR spectra were collected on one of the following instruments: 1 H. 13 C. 19 F. 29 4. 11 B): Varian MR-400 or Varian VNMRS-500. 11 B NMR spectra were collected only on a Varian VNMRS-500. 1 H and 13 C NMR chemical shifts are expressed in parts per million relative to the residual solvent peak: 1 H- is 5.32 ppm for CD2Cl2, 7.15 ppm for C6D6, and 7.25 ppm for CDCl3; 13 C- is 54.00 ppm for CD2Cl2, 128.00 ppm for C6D6, and 77.00 ppm for CDCl3. 11 BNMR chemical shifts were externally referenced to BF3(Et2O) (0 ppm), 19 F NMR chemical shifts were externally referenced to CFCl3 (0 ppm). Except when using dry ice or ice as the only means of cooling, subambient reaction temperatures were measured using an Extech Instruments EasyView with fine JKEM sensor PTFE wire K36INJ. TM 10Dual K model EA 10 thermometer for measurements.

[0167] The catalyst used to prepare certain types of component (A) is synthesized as follows:

[0168] Preparation of Lithium Isopropoxybis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borate

[0169]

[0170] n-Butyl lithium (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 diethyl ether (18 mL) was slowly added. The reaction mixture was stirred at -78°C for several hours. The solution was warmed to ambient temperature while stirring overnight to give a pale yellow clear solution. Volatiles were removed from the reaction mixture to give a yellow oil. The oil was extracted with benzene. There was no insoluble matter. Volatiles were removed from the reaction mixture to give a yellow oil. The yield was 7.88 g, 98.3%.

[0171] 1 H NMR (400MHz, benzene-d6) δ8.06(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, 1H), 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) δ158.31, 153.97, 135.44 (q, J = 3.7Hz), 135.23, 133.5 5(t,J=4.1Hz),133.25,133.18,132.37(d,J=97.8Hz),130.92(q,J=32.0H z),127.80(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. 11B NMR (160 MHz, benzene-d6) δ 2.16.

[0172] In a nitrogen-purged glove box, a 1 wt% catalyst solution was prepared in a glass vial by dissolving the freshly prepared catalyst above in anhydrous toluene. Cyclic polyorganohydrogensiloxane (mixture of cyclic polymethylhydrogensiloxanes with DP=4 to 6, crude material (not purified after preparation), 11.2 g) and a Teflon-coated stirring bar were placed in a glass vial. The catalyst solution (e.g., 225 μL) was added to the stirring solution via a micropipette, followed by the slow addition of silanol-terminated polydimethylsiloxane with an average DP=10.8 (e.g., 8.4 g) over 1 hour. An aliquot of the reaction mixture was removed, quenched with a drop of phenylacetylene and stirred by stirring in CDCl3 containing Cr(acac)3 as an NMR relaxation agent (~1 g / 100 mL). 29 Si NMR analysis was performed. The conversion was established by comparing the signals of HOSi(Me)2O-(MOH) and MeSiO3(T). The conversion was 99% in 1.3 hours.

[0173] The stability in the above general procedure is monitored as follows: in a nitrogen-purged glove box, by dissolving the solid catalyst sample in anhydrous toluene, a solution of 1 wt % of the above catalyst is prepared in a glass vial. Cyclic polyorganohydrogensiloxane (5 g) and a Teflon-coated stirring rod are placed in a glass vial. Catalyst solution (e.g., 100.5 μL) is added to the stirred solution via a micropipette. Aliquots are sampled over time and quenched with a phenylacetylene / toluene mixture so that toluene can serve as an internal standard. Aliquots are then analyzed by GC. The relative amount of the reaction is compared by monitoring the ratio of cyclic polyorganohydrogensiloxane to toluene standards. Cyclic polyorganohydrogensiloxane is monitored over time before adding silanol-terminated polydimethylsiloxane.

[0174]

[0175] The following melting point and freezing point temperatures were measured as follows:

[0176] Using a 5-position analytical balance, obtain the mass of a Tzero pan with a Tzero sealing lid. 7 mg-12 mg of a specific sample is placed in the pan, and using tweezers, the pan is placed in the blue sealed lower mold and covered with a sealing lid. The lower mold is placed in the pan press, and the pressing rod is moved to hermetically seal the lid to the pan. The pan is removed with tweezers and placed in the autosampler. The autosampler uses the following test protocol:

[0177] Sampling interval: 0.20s / pt

[0178] Data storage: Off

[0179] Equilibrate at 60°C

[0180] Isothermal 5.00min

[0181] Data Storage: On

[0182] Heating at a rate of -10.000℃ / min to -90℃

[0183] Isothermal 10.00 min

[0184] Marking cycle 1 ends

[0185] Heating at a rate of 10.000℃ / min to 60℃

[0186] Marking cycle 2 ends

[0187] Data storage: Off

[0188] Equilibrate at 40.00℃

[0189] Various components used in Preparation Examples 1-4 and Comparative Preparation Examples 1-2 are listed in Table 1 below.

[0190] Table 1: Components / compounds utilized

[0191]

[0192] Preparation Example 1

[0193] 54.94g component (B3) and 30.14g carrier are loaded into 250mL 3-necked round-bottom flask.Then flask is equipped with an overhead mechanical stirrer (glass rod with Teflon stirring paddle), a thermocouple with nitrogen inlet and a water-cooled condenser connected to a bubbler. Under slight nitrogen purge and vigorous stirring (275rpm), the content of flask is heated to 78 ℃ with an aluminum heating block. 0.16g component (C) (0.5 wt %Pt) is placed in flask. Then, 15.11g component (A1) is progressively placed in flask. Specifically, 1mL component (C) is added once, until the temperature of flask stabilizes and the content of flask becomes optically transparent, repeat until a total of 15.11g component (A1) is placed in flask. During the progressive addition of component (A1), another 0.17g component (C) is placed in flask. After the total amount of component (A1) used was placed in a flask, the contents of the flask were heated under reflux (about 84° C.) for about 1.5 h to obtain a clear amber solution. The volatiles of the resulting clear amber solution were stripped with heat (6 Torr, 100° C. for 1 h) under vacuum to obtain a reaction product. The reaction product was transferred to a wide-mouth bottle and measured to have a freezing point of -15.7° C. and a melting point of 18.1° C.

[0194] Preparation Example 2

[0195] 16.94 grams of component (A2) and 30.9g of carrier were loaded into a 250mL 3-necked round-bottom flask. The flask was then equipped with an overhead mechanical stirrer (glass rod with Teflon stirring paddle), a thermocouple with a nitrogen inlet, and a water-cooled condenser connected to a bubbler. Under a slight nitrogen purge and vigorous stirring (275rpm), the contents of the flask were heated to 75°C with an aluminum heating block. 43.08g of component (B1) was diluted with 10g of carrier to obtain a mixture. Then, 25g of the mixture was added to the flask via a syringe, and the contents of the flask were catalyzed with 0.191mL of component (C) (1 wt % Pt). The mixture of the remaining amount was added to the flask, and then another 76 μL (obtaining 10ppm Pt) component (C) was added. The contents of the flask were heated at reflux (about 84°C) for about 1.5h to obtain a clear amber solution. The volatiles of the clear amber solution were stripped with heat (6 torr, 100°C for 1 h) under vacuum to give the reaction product. The reaction product was transferred to a wide-mouth bottle and thickened to a honey-like consistency once cooled to room temperature. The reaction product was measured to have a freezing point of 5.5°C and a melting point of 30.6°C.

[0196] Preparation Example 3

[0197] 33.89g component (B4) and 30g carrier are loaded into 250mL 3-necked round-bottom flask.Then flask is equipped with an overhead mechanical stirrer, a thermocouple with a nitrogen inlet and a water-cooled condenser connected to a bubbler. Under slight nitrogen purge and vigorous stirring (275rpm), the contents of the flask are heated to 78°C with an aluminum heating block.Then, 2 grams of components (A2) are added to the flask via a syringe, and then the contents of the flask are catalyzed with 0.12mL component (C) (1 wt %Pt). In about 60min, remaining component (A2) (that is, 24.17g) is added halfway with the component (C) (5ppmPt.) of another amount with the part of 1-2mL, while maintaining the temperature to be 80-81°C, to obtain a clear light yellow solution. The volatile matter of the clear light yellow solution is stripped under vacuum and heating (6 Torr, 100°C for 1h), to obtain a reaction product in the form of a viscous yellow liquid. The reaction product was found to have a freezing point of -25.9°C and a melting point of -2.2°C.

[0198] Preparation Example 4

[0199] Into 250mL 3 neck round bottom flask, load 8.30g component (A3), 32g carrier and 51.94g component (B5).Then be equipped with overhead mechanical stirrer (glass rod with Teflon stirring paddle), thermocouple with nitrogen inlet and the water-cooled condenser that is connected to bubbler for flask.Under slight nitrogen purge and vigorous stirring (275rpm), the content of flask is heated to about 70 ℃ with heating jacket.With 0.32mL component (C) (for 20ppm Pt, 0.5 wt %Pt) reaction in catalytic flask.After making reaction in flask, carry out 3 hours to obtain reaction mixture, stripping reaction mixture under vacuum and heating (as low as 30 torr) 1h at 80 ℃.

[0200] Comparative Preparation Example 1

[0201] 30.1g carrier, 46.19g component (B1) and 17.61g component (A1') are loaded into a 250mL 3-necked round-bottom flask. The flask is then equipped with an overhead mechanical stirrer (glass rod with Teflon stirring paddle), a thermocouple with a nitrogen inlet and a water-cooled condenser connected to a bubbler. Under a slight nitrogen purge and vigorous stirring (275rpm), the contents of the flask are heated to 68.0°C with a heating jacket. The catalytic reaction is then performed with 0.122mL component (C) (for 15ppm Pt, 1 wt% Pt). The flask temperature from the reaction is raised from 68.0°C to 79.7°C, and clarified when approaching 79.5°C. The contents of the flask are then heated to reflux for 1 hour, then cooled to room temperature overnight to obtain a yellow solution. The volatiles of the yellow solution are stripped under vacuum (6 Torr, raised to 100°C, kept for 1 hour) to obtain a yellow liquid. The yellow liquid was found to have a freezing point of 13.1°C and a melting point of 30.8°C.

[0202] Comparative Preparation Example 2

[0203] 55.39g component (B2), 20.20g component (A2') and 39g carrier are loaded into a 250mL 3-necked round-bottom flask. The flask is then equipped with an overhead mechanical stirrer (glass rod with Teflon stirring paddle), a thermocouple with a nitrogen inlet and a water-cooled condenser connected to a bubbler. Under a slight nitrogen purge and vigorous stirring (275rpm), the contents of the flask are heated to about 70°C with an aluminum heating block. The reaction is then catalyzed with 0.05mL component (C) (1 wt % Pt, 5ppm Pt is obtained). The setting point is changed to 90°C on the heating block, and the reaction is heated under reflux for 1 hour. The reaction is clarified when approaching 83°C, and the temperature is raised simultaneously to obtain a clarified amber liquid. The clarified amber liquid is then stripped under vacuum (6 Torr, 100°C for 2h) to obtain a reaction product, which solidifies when cooled to RT.

[0204] Examples 1-3 and Comparative Examples 1-2 :

[0205] Isocyanate reactive components were prepared using some of the compounds (i.e., reaction products) formed in Preparation Examples 1-4 and Comparative Preparation Examples 1-2. Specifically, Example 1 utilized the compound of Preparation Example 1, Example 2 utilized the compound of Preparation Example 2, Example 3 utilized the compound of Preparation Example 3, Comparative Example 1 utilized the compound of Comparative Preparation Example 1, and Comparative Example 2 utilized the compound of Comparative Preparation Example 2. The compounds of Preparation Examples 1-3 and Comparative Preparation Examples 1-2 were used as surfactants in the isocyanate reactive components of Examples 1-3 and Comparative Examples 1-2.

[0206] Table 2 below lists the amount of each component utilized in the isocyanate reactive components of Examples 1-3 and Comparative Examples 1-2. Each value in Table 2 below is based on 100 parts by weight of polyol. The same components and amounts are utilized in Examples 1-3 and Comparative Examples 1-2, except for the surfactant, which is the corresponding compound prepared in each of Preparation Examples 1-3 and Comparative Preparation Examples 1-2 as described above. The surfactants in Table 2 below are different for each of the above Examples 1-3 and Comparative Examples 1-2.

[0207] Table 2 :

[0208]

[0209] General Procedure for Examples 1-3 and Comparative Examples 1-2 :

[0210] Each of the embodiments 1-3 and comparative examples 1-2 follows the same general procedure for preparing the corresponding isocyanate reactive components. Specifically, in each of the embodiments 1-3 and comparative examples 1-2, 60g samples are prepared for analysis via Turbiscan, with enough emulsions for visual observation and inspection vials. In each of the embodiments 1-3 and comparative examples 1-2, the specific surfactant utilized is mixed with polyol, blowing agent 1, flame retardant, catalyst 1, catalyst 2 and catalyst 3 in a 250mL Nalgene bottle to obtain a pre-blend. Using an air-driven mixer, blowing agent 2 is mixed into the pre-blend to avoid the ignition source of blowing agent 2. Add another 1-2 gram of blowing agent 2 to resolve volatilization / evaporation during mixing. At about 3000rpm, a small 3-blade propeller is used to obtain an emulsion of pre-blend and blowing agent 2. The emulsification time varies from thirty seconds to five minutes according to the surfactant. The emulsion is weighed, and if necessary, the amount of blowing agent 2 is adjusted to 35 ± 2% by weight of the emulsion. The emulsion is immediately transferred to a 30 mL vial for visual observation at room temperature. Once creaming or rupture in the emulsion is visually observed, the observation is stopped. The visual observation results are listed in Table 3 below. When the phase separation of the specific isocyanate reactive component (e.g., via rupture and / or creaming) is observed, stability is observed and determined to be no longer present.

[0211] Table 3: Stability of the general procedures of Examples 1-3 and Comparative Examples 1-2 .

[0212] Example Stable duration Example 1 2 days Example 2 7 days Example 3 <1h Comparative Example 1 <12h Comparative Example 2 <1h

[0213] Hypothetical Examples 1-3 and Hypothetical Comparative Examples 1-2 :

[0214] The isocyanate-reactive components of Examples 1-3 and Comparative Examples 1-2 above were used to prepare polyurethane foams. Specifically, each of the isocyanate-reactive components of Examples 1-3 and Comparative Examples 1-2 was reacted with polymethylene polyphenyl isocyanate containing MDI (pMDI) having an NCO content of 30.9% measured according to ASTM D5155 and a dynamic viscosity at 25° C. of 500 mPa·s to 1,000 mPa·s measured according to ASTM D4889. Based on 100 parts by weight of the polyol in each isocyanate-reactive component, pMDI was reacted with the isocyanate-reactive component in each of Examples 1-3 and Comparative Examples 1-2 in an amount of 350 parts by weight.

[0215] The term "comprising" and its derivatives, such as "having" and "containing", are used herein in their broadest sense, meaning and encompassing the concepts of "including", "consisting essentially of", and "consisting of". The use of "for example", "for example", "such as", and "including" to list illustrative examples is not meant to be limited to the listed examples. 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.

[0216] In general, as used herein, a hyphen "-" or dash "–" within a range of values ​​means "to" or "up to"; ">" means "higher than" or "greater than"; "≥" means "at least" or "greater than or equal to"; "<" means "lower than" or "less than"; and "≤" means "at most" or "less than or equal to". Each of the foregoing patent applications, patents, and / or patent application publications is each expressly incorporated by reference in its entirety in one or more non-limiting embodiments.

[0217] It is to be understood that the appended claims are not limited to individual and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments falling within the scope of the appended claims.

Claims

1. A composition comprising: (A) an organohydrogensiloxane having the following structure: wherein subscript n is 1 to 1,000; each subscript p is independently 1 to 10; and each R is an independently selected substituted or unsubstituted hydrocarbyl group in which one or more silicon-bonded hydrogen atoms can be replaced by a group having the formula: wherein subscript n is independently selected and as defined above, subscript p is independently selected and as defined above, and each R 1 are independently selected substituted or unsubstituted hydrocarbyl groups; (B) a polyether compound having an aliphatic unsaturated group, wherein the (B) polyether compound has a formula R 2 O(C2H4O) x (C3H6O) y (C4H8O) z R 3 , where R 2 is an aliphatic unsaturated group; 10≤x≤40; 0≤y≤200; and 0≤z≤200; provided that the subscripts x, y and z are not 0 at the same time, and the units represented by the subscripts x, y and z can be in random or block form in the (B) polyether compound; and R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above; and (C) Hydrosilylation catalyst.

2. The composition according to claim 1, wherein: (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; or (iv) any combination of (i) to (iii).

3. An organosilicon polyether surfactant obtained by reacting components (A) and (B) in the presence of component (C), wherein components (A), (B) and (C) are as described in claim 1 or 2.

4. A compound having the following structure: Each R 4 are independently selected from hydrogen, substituted or unsubstituted hydrocarbon groups, polyether groups or group, provided that at least one R 4 is the 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 hydrocarbon group; and each R 1 are independently selected substituted or unsubstituted hydrocarbon groups, wherein R 4 The polyether group has the formula -DO(C2H4O) x (C3H6O) y (C4H8O) z R 3 , wherein D is a divalent linking group; 10≤x≤40; 0≤y≤200; and 0≤z≤200; provided that x, y and z are not 0 at the same time, and the units represented by the subscripts x, y and z can be in random or block form in the polyether group; and R 3 Selected from R 1 , H and -C(O)R 1 , where R 1 are independently selected and as defined above.

5. The compound according to claim 4, wherein: (i) each R is an independently selected unsubstituted hydrocarbon 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) to (iv).

6. An isocyanate-reactive component, the isocyanate-reactive component comprising: polyols; and A surfactant, wherein the surfactant comprises the compound according to claim 4 or 5.

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

8. The composition according to 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 wt % to 10 wt % based on the total weight of the composition; or (v) any combination of (i) to (iv).

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

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

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