Silicone polyether copolymers, sealants containing same, and related methods

Abstract

The composition has the average formula X g [Z j Y o ] c where each X is an independently selected silicone moiety having a particular structure, each Y is an independently selected polyether moiety, each Z is an independently selected organosilicon moiety, subscript c is 1 to 150, subscript g is greater than 1, subscript j is independently 0 or 1, and subscript o is independently 0 or 1, with the proviso that in each moiety denoted by subscript c, 1≦j+o≦2, and there is at least one moiety denoted by subscript c where subscript o is 1. Methods of preparing the compositions are also disclosed, along with sealants formed therewith.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the full benefit of U.S. Provisional Patent Application No. 63 / 338,198, filed May 04, 2022, the contents of which are incorporated herein by reference.

[0002] The present invention relates generally to compositions and copolymers, and more particularly to compositions comprising at least one silicone-polyether copolymer, methods for preparing same, and sealants containing same. [Background technology]

[0003] Sealants are known in the art and are utilized in numerous end-use applications and environments. The physical and performance properties of a sealant, as well as its associated specific cure mechanism, are generally selected based on the specific end-use and environment in which the sealant will be utilized. Sealants can be based on a variety of different chemistries and cure mechanisms. For example, a sealant can be silicone-based and include organopolysiloxanes. Alternatively, a sealant can be organic and include organic components, for example, to form urethanes. Increasingly, hybrid materials are being utilized in sealants, which can combine the benefits traditionally associated with silicone-based and organic sealants.

[0004] For example, silane-modified polyethers are increasingly being used in sealants as hybrid materials. However, existing silane-modified polyethers have limitations. For example, sealants containing conventional silane-modified polyethers have undesirable cure rates or cure rates that cannot be selectively controlled or adjusted based on desired properties. In addition, maximizing the cure rate of conventional sealants may require high catalyst concentrations or otherwise affect the performance properties of the resulting cured product. Therefore, it is difficult or impossible to simultaneously optimize cure rate and performance properties. Summary of the Invention

[0005] Average formula g [Z j Y o ] c Disclosed is a composition comprising at least one silicone-polyether copolymer having the formula: wherein each X is independently a silicone moiety having one of formulas (I) or (II): (R 1 ) a (R 2 O) 3-a Si-D-SiR 1 2-O-SiR 1 2-D 1 - (I) (R 1 ) a (R 2 O) 3-a Si-D 1 - (II) wherein each Y is an independently selected polyether moiety, each Z is an independently selected organosilicon moiety, and each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having 1 to 18 carbon atoms, and each R 2 is an independently selected alkyl group having 1 to 8 carbon atoms, each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms, and each D 1are independently divalent hydrocarbon radicals having 2 to 18 carbon atoms, each subscript a is independently 0 or 1, subscript c is 1 to 150, subscript g is greater than 1, each subscript j is independently 0 or 1, and each subscript o is independently 0 or 1, with the proviso that in each moiety denoted by subscript c, 1≦j+o≦2, and there is at least one moiety denoted by subscript c where subscript o is 1. The composition is subject to at least one of the following conditions: (i) the silicone-polyether copolymer comprises at least one silicone moiety X of Formula (I) and at least one silicone moiety X of Formula (II), and / or (ii) the composition comprises at least one silicone-polyether copolymer (A), wherein each silicone moiety X is of Formula (I), and at least one silicone-polyether copolymer (B), wherein each silicone moiety X is of Formula (II).

[0006] A method for preparing silicone-polyether copolymers is disclosed, which comprises reacting a polyether compound having an average of more than one terminal unsaturated group, an optionally chain-extended organosilicon compound, a first end-capped organosilicon compound, and a second end-capped organosilicon compound different from the first end-capped organosilicon compound in the presence of a hydrosilylation catalyst to prepare a composition comprising at least one silicone-polyether copolymer.

[0007] Also disclosed is a sealant, which comprises a composition including at least one silicone-polyether copolymer and a condensation reaction catalyst.

[0008] Cured products are also disclosed. The cured products are formed from the sealant. Also disclosed are composite articles and methods of preparing the composite articles. The composite article includes a substrate and a cured product disposed on the substrate. The method includes disposing the sealant on the substrate and curing the sealant to obtain a cured product on the substrate, thereby preparing the composite article. [Brief explanation of the drawings]

[0009] Various advantages and aspects of the present disclosure may be understood by consideration of the following detailed description when considered in conjunction with the accompanying drawings. [Figure 1] 1 shows the tack free time (TFT) of sealants from certain examples of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] Average formula g [Z j Y o ] c Disclosed is a composition comprising at least one silicone-polyether copolymer having the formula: wherein each X is independently a silicone moiety having one of formulas (I) or (II): (R 1 ) a (R 2 O) 3-a Si-D-SiR 1 2-O-SiR 1 2-D 1 - (I) (R 1 ) a (R 2 O) 3-a Si-D 1 - (II) wherein each Y is an independently selected polyether moiety, each Z is an independently selected organosilicon moiety, and each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having 1 to 18 carbon atoms, and each R 2 is an independently selected alkyl group having 1 to 8 carbon atoms, each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms, and each D 1are independently divalent hydrocarbon radicals having 2 to 18 carbon atoms, each subscript a is independently 0 or 1, subscript c is 1 to 150, subscript g is greater than 1, each subscript j is 0 or 1, and each subscript o is independently 0 or 1, with the proviso that in each moiety denoted by subscript c, 1≦j+o≦2, and there is at least one moiety denoted by subscript c where subscript o is 1. The composition is subject to at least one of the following conditions: (i) the silicone-polyether copolymer comprises at least one silicone moiety X of Formula (I) and at least one silicone moiety X of Formula (II), and / or (ii) the composition comprises at least one silicone-polyether copolymer (A), wherein each silicone moiety X is of Formula (I), and at least one silicone-polyether copolymer (B), wherein each silicone moiety X is of Formula (II). In one embodiment, the composition may comprise at least one silicone-polyether copolymer where each silicone moiety X is of formula (II), but where the subscript a is different for each silicone moiety X of formula (II).

[0011] Each R 1 are independently selected and may be linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. "Substituted" means that one or more hydrogen atoms may be replaced with an atom other than hydrogen (e.g., a halogen atom such as chlorine, fluorine, or bromine), or R 1 The carbon atoms in the chain may be replaced by atoms other than carbon, i.e., R 1may contain one or more heteroatoms such as oxygen, sulfur, or nitrogen within the chain. Suitable alkyl groups are exemplified by, but not limited to, 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, and branched-chain saturated hydrocarbon groups having 6 carbon atoms. Suitable aryl groups are exemplified by, but not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, halogenated alkyl groups having 1 to 6 carbon atoms or halogenated aryl groups having 6 to 10 carbon atoms. Suitable halogenated alkyl groups are exemplified by, but not limited to, the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. For example, 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 are examples of suitable halogenated alkyl groups. Suitable halogenated aryl groups are exemplified, but not limited to, by the aryl groups described above in which one or more hydrogen atoms have been replaced with a halogen atom, such as F or Cl. For example, chlorobenzyl and fluorobenzyl are suitable halogenated aryl groups.

[0012] In certain embodiments, R1 Each of R is an independently selected alkyl group. In certain embodiments, each R 1 is methyl.

[0013] Each R 2 is an independently selected alkyl group having 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 or 2, alternatively 1 carbon atom.

[0014] For silicone-polyether copolymers, the subformula [Z j Y o ] c It should be understood that "Z" does not imply a linear structure of the silicone-polyether copolymer moiety denoted by ZY. Rather, as is understood in the art, the silicone-polyether copolymer ZY can be linear or branched, with each moiety denoted by the subscript c being independently selected. As such, the silicone-polyether copolymer comprises c copolymer moieties ZY, each of which comprises o polyether moieties Y and j organosilicon moieties Z. Additionally, as will be understood in light of the following discussion, each polyether moiety Y and organosilicon moiety Z is independently selected both within and between each moiety denoted by the subscript c, and each may be linear or branched.

[0015] Each subscript c is between 1 and 150, e.g., between 1 and 100, alternatively between 1 and 50, alternatively between 1 and 25, alternatively between 1 and 10, alternatively between 1 and 5. Subscript g is greater than 1, e.g., between 1.1 and 10, alternatively between 1.1 and 8, alternatively between 1.1 and 6, alternatively between 1.1 and 4, alternatively between 1.1 and 3, alternatively between 1.1 and 2, alternatively between 1.1 and 1.9, alternatively between 1.2 and 1.8, alternatively between 1.2 and 1.7, alternatively between 1.3 and 1.7, alternatively between 1.4 and 1.7, alternatively about 1.4, 1.5, 1.6, or 1.7. Each subscript j is independently 0 or 1, and each subscript o is independently 0 or 1, with the proviso that in each moiety denoted by subscript c, 1≦j+o≦2, and there is at least one moiety denoted by subscript c where subscript o is 1. Thus, the silicone-polyether copolymer comprises at least one polyether moiety Y, but the organosilicon moiety Z is optional. Because each subscript j and each subscript o are independently selected, there may be moieties denoted by subscript c in which the polyether moiety Y is present but the organosilicon moiety Z is absent, moieties denoted by subscript c in which the polyether moiety Y is absent but the organosilicon moiety Z is present, and so on. In certain embodiments, subscript j is 0. In other embodiments, subscript j is 1. In these or other embodiments, subscript j may be 0 if the silicone-polyether copolymer is branched, while subscript j may be 1 if the silicone-polyether copolymer is linear. In certain embodiments, the subscript o is 0. In other embodiments, the subscript o is 1. The subscripts j and o can be considered as mole fractions; for example, when j=1 and o=1, the molar ratio of organosilicon moiety Z to polyether moiety Y in the moiety indicated by subscript c is 0.5:0.5. Of course, the molar ratio of Z to Y in each moiety indicated by subscript c is not limited and only applies when both organosilicon moiety Z and polyether moiety Y are present in each moiety indicated by subscript c.For example, when the moiety Z is present, the molar ratio of Z:Y can be, independently, from about 1000:1 to about 1:1000, alternatively from about 100:1 to about 1:100, alternatively from about 10:1 to about 1:100, alternatively from about 5:1 to about 1:5, alternatively from about 2:1 to about 1:2, at each moiety designated by subscript c. As noted above, the moiety [Z. j Y o ] c is not intended to imply a linear structure of the silicone-polyether copolymer moiety represented by ZY. Similarly, the subformula does not require any particular structure of the silicone-polyether copolymer moiety ZY. Rather, depending on the values selected for the subscripts j and o, the subformula [Z j Y o ] c The silicone-polyether copolymer segment represented by may comprise the organosilicon moieties Z and polyether moieties Y in block form (e.g., Y, ZY, YZ, YZY, ZYZY, YY-ZZ, ZZ-YY, etc.) or in random form. In certain embodiments, the silicone-polyether copolymer comprises the polyether moieties Y and the organosilicon moieties Z in a 2:1 ratio. In specific embodiments, when the subscript j is 1, the silicone-polyether copolymer comprises a total of one more polyether moiety Y than the organosilicon moiety X. In some such embodiments, the polyether moieties Y and the organosilicon moieties Z are present in the silicone-polyether copolymer in block form, such that the silicone-polyether copolymer has the average formula X g Y[ZY] c where the subscripts c and g are defined above. In some of these embodiments, the silicone-polyether copolymer comprises a linear polyether moiety Y and a linear organosilicon moiety Z, end-capped with a silicone moiety X, such that the silicone-polyether copolymer has the average formula X g’ Y[ZY] c X g’’ where c is defined above and each of g′ and g″ is greater than or equal to 0, with the proviso that g′+g″ is greater than 1.

[0016] Generally, for each X, each subscript a is independently 0 or 1. Typically, subscript a is 0. In some embodiments, each subscript a is 0. In certain embodiments, the silicone-polyether copolymer comprises at least one X where subscript a is 1.

[0017] Each D is an independently selected divalent hydrocarbon group having 2 to 18 carbon atoms, alternatively 2 to 16 carbon atoms, alternatively 2 to 14 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 8 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, alternatively 2 or 3 carbon atoms, or alternatively 2 carbon atoms. Each D may independently be linear or branched. For example, if D has 2 carbon atoms, D has the formula CH and may be linear (CHCH) or branched (CHCH). In certain embodiments, D is linear. When a composition comprising a silicone-polyether copolymer is prepared in bulk, in certain embodiments, at least 90 mol%, alternatively at least 95 mol%, alternatively at least 98 mol%, or alternatively 100 mol% of D is linear. In a specific embodiment, each D is CH.

[0018] Each D 1 is also an independently selected divalent hydrocarbon radical having 2 to 18 carbon atoms, alternatively 2 to 16 carbon atoms, alternatively 2 to 14 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 8 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, alternatively 2 or 3 carbon atoms, alternatively 2 carbon atoms. 1 can be independently linear or branched. For example, D 1 If has two carbon atoms, D 1 has the formula C2H4 and may be straight chain (CH2CH2) or branched chain (CHCH3). In certain embodiments, D is straight chain. Each D 1is typically formed via a hydrosilylation reaction when preparing a composition comprising at least one silicone-polyether copolymer, and is therefore a function of the silicon-bonded alkenyl groups available in the hydrosilylation reaction.

[0019] Each Y is a polyether moiety. Each Y is independently selected and can be any polyether moiety containing at least one, alternatively at least two, ether moieties. Each Y can be the same as either or each other Y. Alternatively, the silicone-polyether copolymer can contain at least two Ys that are different from each other. Y can be linear or branched. Y can be divalent, trivalent, tetravalent, or have a valence greater than four. Valence refers to the number of YX bonds present in the silicone-polyether copolymer in the context of the polyether moiety Y. In certain embodiments, the polyether moiety Y is divalent, such that the silicone-polyether copolymer has the formula XYX. In other embodiments, the valence of the polyether moiety can be greater than two, in which case the polyether moiety Y is typically branched.

[0020] Each Y is typically a group of the general formula -O-(C n H 2n O) w-, where subscript n is independently selected from 2 to 4 in each moiety denoted by subscript w, and subscript w is 1 to 1000. In certain embodiments, Y comprises multiple polyethers of such general formula, which may be present in linear or branched chain form with other polyethers to form a polyether moiety Y comprising multiple oxyalkylene-based polyethers. In such embodiments, Y may comprise oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene or oxytetramethylene units (C4H8O), or mixtures thereof, which may be in block form or randomized in Y. The oxyalkylene units in Y may independently be linear or branched. For example, oxyethylene units, if present, may be of formula -CH2CHO- or -CHCHO-. Similarly, the oxypropylene units may be of the formula -CH2CH2CH2O-, -CH2CHCH3O-, or -CHCH3CH2O-.

[0021] For example, Y can be a group of the general formula -O-(C2H4O) x (C3H6O) y (C4H8O) z -, where subscript x is 0 to 999, subscript y is 1 to 1000, and subscript z is 0 to 999, and the units represented by subscripts x, y, and z may be in a random or block form in Y. In certain embodiments, x and z are such that the polyether of Y has the general formula -O-(CHO) y -, where y is defined above.

[0022] In some embodiments, Y is a group of formula -D 2 -O-(C n H 2n O) w -D 2 In such an embodiment, each D 2is an independently selected divalent hydrocarbon group having 1 to 6 carbon atoms, alternatively 1 to 5 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 or 2 carbon atoms. 2 can be independently linear or branched. For example, D 2 If has two carbon atoms, D 2 has the formula C2H4 and may be straight chain (CH2CH2) or branched chain (CHCH3). In certain embodiments, D 2 is a linear chain. Any D 2 is any particular D 1 In specific embodiments, each D 2 is CH2. Each subscript n is independently selected from 2 to 4 in each moiety indicated by the subscript w, where subscript w is defined above.

[0023] For example, in such embodiments, Y is a group of formula -D 2 -O-(C2H4O) x (C3H6O) y (C4H8O) z -D 2 -, where subscript x is 0 to 999, subscript y is 1 to 1000, and subscript z is 0 to 999, and the units represented by subscripts x, y, and z may be in random or block form in Y. In certain embodiments, x and z are such that Y has the formula -D 2 -O-(C3H6O) y -D 2 -, where D 2 and y are defined above. In a specific embodiment, each D 2 is also C3H6. x and z are each 0 and each D 2 is C3H6, Y is a group of the formula -C3H6-O-(C3H6O) y -C3H6-, where y is defined above.

[0024] In certain embodiments, Y has the general formula -CH2-CH(R3 )-[D 2 ] m -O-[C2H4O] x [C3H6O] y [C4H8O] z -[D 2 ] m -CH(R 3 )-CH2-, In the formula, each R 3 are independently a hydrocarbyl group having 1 to 6 carbon atoms, an alkoxy group, a silyl group, or H, and each D 2 is an independently selected divalent group having 1 to 6 carbon atoms, the subscript m is 0 or 1, the subscript x is 0 to 999, the subscript y is 1 to 1000, and the subscript z is 0 to 999, and the units represented by the subscripts x, y, and z may be in a random or block form in the polyether moiety Y.

[0025] Each R 3 are independently selected and may be any of the C1-C6 hydrocarbyl groups described herein. 3 is any particular R 1 and / or R 2 For example, R 3 can be methyl, propyl, etc. In certain embodiments, each R 3 is methyl. Alternatively, or in addition, R 3 may be H, an alkoxy group, or a silyl group.

[0026] Each subscript m is independently 0 or 1, such that Y is 0, 1, or 2 divalent hydrocarbon groups D 2 Typically, each subscript m is 1. However, in certain embodiments, at least one subscript m is 0.

[0027] In some embodiments, Y is branched, as described above. In such embodiments, Y is a group represented by the general formula [D 2 ]m’ [P], wherein D 2 is defined above, the subscript m' is 3 or greater (e.g., 3, 4, 5, 6, 7, 8, 9, 10, etc.), and P is a polyether comprising at least one of the above-mentioned polyethers. For example, in some such embodiments, P is a polyether formed from a polyol (e.g., butanediol, glycerol, sorbitol, etc.) and a polyoxyalkylene (e.g., polyoxypropylene), and m' D 2 In such a case, the number of alcohol functional groups constituting the polyol will correspond to the maximum value of m'. However, if all polyoxyalkylene chains extending from the polyol are not end-capped, m' will be less than the number of alcohol functional groups constituting the polyol.

[0028] Each Y typically has a number average molecular weight (M n In certain embodiments, at least one Y has an M of at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700. n In these or other embodiments, each Y has an M of at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700, alternatively at least 1,000, alternatively at least 2,000, alternatively at least 4,000, alternatively at least 8,000, alternatively at least 12,000, alternatively at least 16,000, alternatively at least 25,000, alternatively at least 50,000. n Each Y is typically selected based on the presence or absence of Z. For example, when Z is present, M of Y n may be smaller than when Z is absent. Z can be utilized as a chain extender in the silicone-polyether copolymer, and thus the M of each Y nThe molar ratio of Z to Y can be selected by one skilled in the art based on the desired performance characteristics and synthesis techniques. The number average molecular weight can be readily determined using gel permeation chromatography (GPC) techniques based on polystyrene standards.

[0029] Each Z is an independently selected organosilicon moiety. Each organosilicon moiety Z can independently comprise a linear organosilicon moiety, a branched organosilicon moiety, or both. Similarly, any particular organosilicon moiety Z can itself comprise a linear or branched chain segment, or can comprise both a linear or branched chain segment. Thus, Z can be a linear organosilicon moiety, a branched chain organosilicon moiety, or an organosilicon moiety comprising at least one linear chain segment and at least one branched chain segment. In certain embodiments, Z is branched (i.e., comprises at least one branched chain segment).

[0030] In certain embodiments, each polyether moiety Y is linear, such that the silicone-polyether copolymer may have one of the following structures (when Z is present):

[0031] [ka] Each X, Y, Z, and subscript c are defined above. Alternatively, each polyether moiety Y can be branched. For example, the silicone-polyether copolymer may have one of the following structures (when Z is present):

[0032] [ka] Each X, Y, Z, and subscript c are defined above. As shown in these structures, each organosilicon moiety Z can be linear or branched. In certain embodiments, both the polyether moiety Y and the organosilicon moiety Z can be branched, such that the silicone-polyether copolymer can have one of the following structures:

[0033] [ka] Each of X, Y, Z, and the subscript c is defined above.

[0034] In one embodiment, each organosilicon moiety, Z, independently has the formula:

[0035] [ka] In the formula, each R 1 is independently selected and defined above, and each d is independently 0 to 999 in each organosilicon moiety, Z. In these embodiments, the organosilicon moiety, Z, is a siloxane moiety.

[0036] In some embodiments, each polyether moiety Y and each organosilicon moiety Z is linear, the organosilicon moiety Z is a siloxane moiety, and the silicone-polyether copolymer has the following structure (when Z is present):

[0037] [ka] In the formula, each Y, R 1 , subscript c, and subscript d are as defined above.

[0038] In one embodiment, each organosilicon moiety Z is not a siloxane moiety. For example, each organosilicon moiety Z may be a silyl-terminated organic compound. In a specific embodiment, the organosilicon moiety Z has the formula -R 12Si-R 5 -SiR 1 2-, wherein each R 1 are independently defined above, and R 5 is a divalent linking group. 5 may be a divalent hydrocarbon group. Typically, the divalent hydrocarbon group is free of aliphatic unsaturation. The divalent hydrocarbon group may be linear, cyclic, branched, aromatic, etc., or may have a combination of such structures. For example, R 5 may be a divalent aryl group. When present, the organosilicon moiety Z is formed using a chain-extended organosilicon compound, which is described in more detail below.

[0039] The composition satisfies at least one of the following conditions: (i) the silicone-polyether copolymer comprises at least one silicone moiety X of Formula (I) and at least one silicone moiety X of Formula (II), and / or (ii) the composition comprises at least one silicone-polyether copolymer (A), each silicone moiety X of Formula (I), and at least one silicone-polyether copolymer (B), each silicone moiety X of Formula (II). Advantageously, the composition comprises at least one silicone moiety X of Formula (I) and at least one silicone moiety X of Formula (II), regardless of whether the at least one silicone moiety X of Formula (I) and the at least one silicone moiety X of Formula (II) are present in the same or different silicone-polyether copolymers. In light of the description herein, one skilled in the art can selectively adjust the cure rate of a composition by selectively controlling the molar ratio of the silicone moiety X of Formula (I) to the silicone moiety X of Formula (II) in compositions having different cure rates.

[0040] In certain embodiments, condition (i) is true, and the silicone-polyether copolymer comprises at least one silicone moiety X of Formula (I) and at least one silicone moiety X of Formula (II). In other embodiments, condition (ii) is true, and the composition comprises at least one silicone-polyether copolymer (A), wherein each silicone moiety X is of Formula (I), and at least one silicone-polyether copolymer (B), wherein each silicone moiety X is of Formula (II). In other embodiments, condition (i) is true and condition (ii) is not true, or condition (ii) is true and condition (i) is not true, or both conditions (i) and (ii) are true.

[0041] In specific embodiments where condition (i) applies, the silicone-polyether copolymer has the formula: X 1 g’ [Z j Y o ] c X 2 g’’ In the formula, X 1 is the silicone moiety X of formula (I), and X 2 is the silicone moiety X of formula (II), where subscript g' is greater than 1, subscript g" is greater than 1, and Z, Y, and subscripts j, o, and c are defined above. In more specific embodiments including this formula, g' and g" are each 1. In other specific embodiments including this formula, g' is 1 or 2 and g" is 1 or 2, with the proviso that g'+g"=3.

[0042] In these or other specific embodiments where condition (i) is true and subscript j is greater than 0, the silicone-polyether copolymer has the formula: (R 1 ) a (R 2 O) 3-a -Si-D-SiR 1 2-O-SiR 1 2-D1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OR 2 ) 3-a (R 1 ) a In the formula, each Y, R 1 , R 2 , subscript a, D, D 1 , subscript d, and subscript c are defined above.

[0043] In these or other specific embodiments where condition (i) is true and subscript j is greater than 0, the silicone-polyether copolymer has the formula: (R 2 O)3-Si-D-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OR 2 )2(R 1 ) In the formula, each Y, R 1 , R 2 , D, D 1 , subscript d, and subscript c are defined above.

[0044] In these or other specific embodiments where condition (i) is true and subscript j is greater than 0, the silicone-polyether copolymer has the formula: (MeO)3-Si-D-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OMe)2(Me) In the formula, each Y, R1 , R 2 , D, D 1 , subscript d, and subscript c are defined above, and Me represents methyl.

[0045] In these or other specific embodiments where condition (i) is true and subscript j is greater than 0, the silicone-polyether copolymer has the formula: (MeO)3-Si-C2H4-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OMe)2(Me) In the formula, each Y, R 1 , R 2 , D, D 1 , subscript d, and subscript c are defined above, and Me represents methyl.

[0046] In these or other specific embodiments where condition (i) is true and subscript j is greater than 0, the silicone-polyether copolymer has the formula: (MeO)3-Si-C2H4-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OMe)3 In the formula, each Y, R 1 , R 2 , D, D 1 , subscript d, and subscript c are defined above, and Me represents methyl.

[0047] In a specific embodiment where condition (i) applies, the molar ratio of the silicone moiety X of formula (I) to the silicone moiety X of formula (II) is 2:98 to 98:2(I):(II). Surprisingly, it has been found that by increasing the content of the silicone moiety X of formula (I), the curing rate can be maximized, and by increasing the content of the silicone moiety X of formula (II), the mechanical properties of the cured product, such as modulus and elongation, can be optimized (i.e., minimized). Typically, the focus in the industry is on maximizing the curing rate, which also undesirably increases the modulus of the resulting cured product. However, by maintaining an appropriate molar ratio of the silicone moiety X of formula (I) to the silicone moiety X of formula (II), the curing rate can be dramatically increased without sacrificing mechanical properties such as modulus. In certain embodiments when condition (i) applies, the mol % of silicone moieties X, which are of formula (I), based on the total number of moles of silicone moieties X, is from greater than 0 to 50, alternatively from 1 to 40, alternatively from 2 to 28, alternatively from 3 to 27, alternatively from 4 to 26, alternatively from 5 to 25, alternatively from 6 to 24, alternatively from 7 to 23, alternatively from 8 to 22, alternatively from 9 to 21, alternatively from 10 to 20, alternatively from 11 to 19, alternatively from 12 to 18, alternatively from 13 to 17, alternatively from 14 to 16. In other embodiments when condition (i) applies, the mol % of silicone moieties X, which are of formula (I), based on the total number of moles of silicone moieties X, is from greater than 0 to 50, alternatively from 1 to 40, alternatively from 1 to 35, alternatively from 1 to 30, alternatively from 1 to 25, alternatively from 1 to 20, alternatively from 2 to 15.

[0048] In a specific embodiment when condition (ii) applies, the composition comprises at least one silicone-polyether copolymer (A), wherein each silicone moiety X is of formula (I), and at least one silicone-polyether copolymer (B), wherein each silicone moiety X is of formula (II).

[0049] In this specific embodiment where condition (ii) applies, the silicone-polyether copolymer (A) has the formula: X 1 g’’’ [Z j Y o ] c The silicone-polyether copolymer (B) has the formula: X 2 g’’’’ [Z j Y o ] c In the formula, X 1 is the silicone moiety X of formula (I), and X 2 is the silicone moiety X of formula (II), where subscript g''' is greater than 1, subscript g'''' is greater than 1, and Z, Y, and subscripts j, o, and c are defined above. In other specific embodiments comprising this formula, each of g''' and g'''' is 2 or 3.

[0050] In these or other specific embodiments where condition (ii) applies and subscript j is greater than 0, at least one silicone-polyether copolymer (A) has the formula: (R 1 ) a (R 2 O) 3-a -Si-D-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -SiR 1 2-O-SiR 1 2-D-Si-(OR 2 ) 3-a (R 1 ) a, The at least one silicone-polyether copolymer (B) has the formula: (R 1 ) a (R 2 O) 3-a -Si-D 1 -Y-[(SiR 12O) d -SiR 1 2-Y] c -D 1 -Si-(OR 2 ) 3-a (R 1 ) a , In the formula, each Y, R 1 , R 2 , subscript a, D, D 1 , subscript d, and subscript c are defined above.

[0051] In these or other specific embodiments where condition (ii) applies and subscript j is greater than 0, at least one silicone-polyether copolymer (A) has the formula: (R 2 O)3-Si-D-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -SiR 1 2-O-SiR 1 2-D-Si-(OR 2 )3, The at least one silicone-polyether copolymer (B) has the formula: (R 1 )(R 2 O)2-Si-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OR 2 )2(R 1 ), In the formula, each Y, R 1 , R 2 , D, D 1 , subscript d, and subscript c are defined above.

[0052] In these or other specific embodiments where condition (ii) applies and subscript j is greater than 0, at least one silicone-polyether copolymer (A) has the formula: (MeO)3-Si-D-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -SiR 1 2-O-SiR 1 2-D-Si-(OMe)3, The at least one silicone-polyether copolymer (B) has the formula: (Me)(MeO)2-Si-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OMe)2(Me), In the formula, each Y, R 1 , R 2 , D, D 1 , subscript d, and subscript c are defined above, and Me represents methyl.

[0053] In these or other specific embodiments where condition (ii) applies and subscript j is greater than 0, at least one silicone-polyether copolymer (A) has the formula: (MeO)3-Si-D-SiR 1 2-O-SiR 1 2-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -SiR 1 2-O-SiR 1 2-D-Si-(OMe)3, The at least one silicone-polyether copolymer (B) has the formula: (MeO)3-Si-D 1 -Y-[(SiR 1 2O) d -SiR 1 2-Y] c -D 1 -Si-(OMe)3, In the formula, each Y, R 1 , R 2 , D, D 1 , subscript d, and subscript c are defined above, and Me represents methyl.

[0054] When condition (ii) applies, the molar ratio of silicone-polyether copolymer (A) to silicone-polyether copolymer (B) is 2:98 to 98:2 (A):(B). This molar ratio can be selected based on the desired cure rate and performance properties of the composition and its cured product. Generally speaking, increasing the content of silicone moieties X of formula (I) compared to the content of silicone moieties X of formula (II) increases the cure rate. The composition can also contain three or more different silicone-polyether copolymers that differ in terms of viscosity, molecular weight, structure, etc. In certain embodiments when condition (ii) applies, the mol % of the silicone-polyether copolymer (A) in the composition, based on the total amount of silicone-polyether copolymers (A) and (B) in the composition, is from greater than 0 to 50, alternatively from 1 to 40, alternatively from 2 to 28, alternatively from 3 to 27, alternatively from 4 to 26, alternatively from 5 to 25, alternatively from 6 to 24, alternatively from 7 to 23, alternatively from 8 to 22, alternatively from 9 to 21, alternatively from 10 to 20, alternatively from 11 to 19, alternatively from 12 to 18, alternatively from 13 to 17, alternatively from 14 to 16. In other embodiments when condition (ii) is true, the mol % of silicone-polyether copolymer (A) in the composition is from greater than 0 to 50, alternatively from 1 to 40, alternatively from 1 to 35, alternatively from 1 to 30, alternatively from 1 to 25, alternatively from 1 to 20, alternatively from 2 to 15, based on the total amount of silicone-polyether copolymers (A) and (B) in the composition.

[0055] The above exemplary structures are based on the assumption that each X, each Y, and / or each Z in the silicone-polyether copolymer is the same. However, as described above, each X, each Y, and each Z is independently selected. Therefore, one skilled in the art will readily understand the structure associated with the silicone-polyether copolymer based on the selection of each X, each Y, and / or each Z. In addition, the above exemplary structures are generally linear. As will be readily understood in the art in light of the description herein, the silicone-polyether copolymer, as well as the silicone-polyether copolymer (A) and the silicone-polyether copolymer (B), may be branched. For example, in certain embodiments, the silicone-polyether copolymer contains three X moieties. The same conditions and explanations apply to such embodiments, and one skilled in the art will readily understand the structure of such a branched silicone-polyether copolymer in light of the broad description herein.

[0056] Also disclosed is a method for preparing a silicone-polyether copolymer, comprising reacting a polyether compound having an average of more than one terminal unsaturated group, an optionally chain-extended organosilicon compound, a first end-capped organosilicon compound, and a second end-capped organosilicon compound different from the first end-capped organosilicon compound in the presence of a hydrosilylation catalyst to prepare a composition comprising at least one silicone-polyether copolymer.

[0057] As will be understood by those skilled in the art in light of the present disclosure, the polyether compound utilized in this method forms part of the silicone-polyether copolymer corresponding to polyether moiety Y; the chain-extended organosilicon compound, when utilized in this method, forms part of the silicone-polyether copolymer corresponding to organosilicon moiety Z; and the first and second end-capped organosilicon compounds utilized in this method form part of the silicone-polyether copolymer corresponding to silicone moiety X (based on Formulas I and II above for X).

[0058] Typically, the polyether compound has the formula Y1 [R 4 ] i wherein each R 4 is an independently selected unsaturated group having 2 to 14 carbon atoms, the subscript i is greater than 1, and Y 1 is a polyether moiety containing at least one polyether group.

[0059] Each R 4 is an independently selected unsaturated group having 2 to 14 carbon atoms. Typically, R 4 includes or is alternatively an alkenyl or alkynyl group, specific examples of which include H2C=CH-, H2C=CHCH2-, H2C=CHCH2CH2-, H2C=CH(CH2)3-, H2C=CH(CH2)4-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=C(CH3)CH2CH2-, H2C=C(CH3)CH2CH(CH3)-, H2C=C(CH3)CH(CH3)CH2-, H2C=C(CH3)C(CH3)2-,

[0060] [ka] Examples include:

[0061] In certain embodiments, each R 4 is the compound of the formula CH2C(R 3 )-[D 2 ] m wherein each R 3 are independently a hydrocarbyl group having 1 to 6 carbon atoms, an alkoxy group, a silyl group, or H, and each D 2 is an independently selected divalent group having 1 to 6 carbon atoms, and the subscript m is 0 or 1. In certain embodiments, R 3 In these or other embodiments, D 2 is -CH-. In specific embodiments, each R 4 is H2C=C(CH3)CH2-.

[0062] The subscript i is greater than 1, e.g., 2, 3, 4, 5, 6, etc. Generally, polyether compounds are those in which the subscript i is Y 1 Y 1 R at each end of 4 Contains Y 1 is at least 2, but may be 3, 4, 5, or more depending on its branching. In specific embodiments, subscript i is 2. In other specific embodiments, subscript i is 3.

[0063] Each Y 1 is a polyether moiety comprising at least one polyether group, such as any of the polyether groups described above. Typically, Y 1 The polyether group has the general formula -O-(C n H 2n O) w -, where subscript n is independently selected from 2 to 4 in each moiety designated by subscript w, and subscript w is 1 to 1000. In certain embodiments, Y 1 At least one polyether group of the formula -O-[C2H4O] x [C3H6O] y [C4H8O] z wherein each subscript x is independently 0 to 999, each subscript y is independently 1 to 1000, and each subscript z is independently 0 to 999, and the units represented by the subscripts x, y, and z may be in a random or block form in the polyether group.

[0064] In some embodiments, Y 1 is a branched chain having the general formula [R 4 ] i’ [P], wherein R 4is defined above, subscript i' is 3 or greater (e.g., 3, 4, 5, 6, 7, 8, 9, 10, etc.), and P is a branched polyether comprising at least one of the above-mentioned polyethers. For example, in some such embodiments, P is a polyether formed from a polyol (e.g., butanediol, glycerol, sorbitol, etc.) and two, three, or more polyoxyalkylenes (e.g., polyoxypropylene), and i' R 4 In such a case, the number of alcohol functional groups constituting the polyol will correspond to the maximum value of i'. However, if all polyoxyalkylene chains extending from the polyol are not end-capped, i' will be less than the number of alcohol functional groups constituting the polyol.

[0065] In certain embodiments, the polyether compound is linear and i=2, such that the polyether compound has the formula R 4 -Y 1 -R 4 wherein Y 1 and each R 4 is as defined above. For example, in some such embodiments, the polyether compound has the formula: CH2C(R 3 )-[D 2 ] m -O-[C2H4O] x [C3H6O] y [C4H8O] z -[D 2 ] m -C(R 3 )CH2 In the formula, each R 3 , D 2 , subscript m, subscript x, subscript y, and subscript z are as defined above. In specific embodiments, each R 3 is methyl, and each D 2is CH2 and each subscript m is 1. In these or other embodiments, subscripts x and z are each 0, such that the polyether portion of the polyether compound contains only oxypropylene units.

[0066] Chain-extended organosilicon compounds are typically organosilicon compounds having at least two terminal silicon-bonded H groups. However, chain-extended organosilicon compounds may also be branched and have three, four, or more terminal silicon-bonded H groups. For example, chain-extended organosilicon compounds may have one of the following formulas:

[0067] [ka] where Z' is a siloxane moiety and each R 1 is as defined above. Thus, the chain-extended organosilicon compound typically comprises a linear silicon hydride-functional organosilicon compound, a branched silicon hydride-functional organosilicon compound, or both.

[0068] In a specific embodiment, the chain-extended organosilicon compound is a linear organohydrogensiloxane having the formula:

[0069] [ka] In the formula, each R 1 is as defined above, and the subscript d is 1 to 999.

[0070] In other embodiments, each Z' is not a siloxane moiety. For example, the chain-extended organosilicon compound has the formula HR 1 2Si-R 5 -SiR 1 2H, wherein each R 1 are independently defined above, and R 5 is a divalent linking group. 5may be a divalent hydrocarbon group. Typically, the divalent hydrocarbon group is free of aliphatic unsaturation. The divalent hydrocarbon group may be linear, cyclic, branched, aromatic, etc., or may have a combination of such structures. For example, R 5 may be a divalent aryl group.

[0071] R 5 is a divalent aryl group, specific examples of chain-extended organosilicon compounds include:

[0072] [ka] Examples include:

[0073] As introduced above, the first and second end-capped organosilicon compounds utilized in this method form the silicone moiety X of formulas (I) and (II) above. Thus, the first and second end-capped organosilicon compounds may be any organosilicon compound suitable for forming silicone-polyether copolymers, including silicone-polyether copolymer (A) and silicone-polyether copolymer (B), as understood in the art. Typically, each of the first and second end-capped organosilicon compounds is an organohydrogensiloxane compound containing at least one silicon-bonded hydrogen atom. The silicon-bonded hydrogen atom of each organohydrogensiloxane compound is converted to the unsaturated group R of the polyether compound via a hydrosilylation reaction in the presence of the hydrosilylation catalyst utilized in this method. 4 and reacts.

[0074] In certain embodiments, the first capped organosilicon compound has the formula: (R 1 ) a (R 2 O) 3-a Si-D-SiR 1 2-O-SiR 1 2H In the formula, each R 1are independently selected and defined above, and each R 2 is an independently selected alkyl group having 1 to 8 carbon atoms, each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms, and the subscript a is 0 or 1. The first endcapped organosilicon compound provides X of formula (I) in the silicone-polyether copolymer.

[0075] In a specific embodiment, the first capped organosilicon compound has the formula: (R 2 O)3Si-D-SiR 1 2-O-SiR 1 2H In the formula, R 1 and R 2 are independently selected and defined above, and D is defined above.

[0076] In these and other specific embodiments, the first capped organosilicon compound has the formula: (MeO)3Si-D-SiR 1 2-O-SiR 1 2H In the formula, R 1 are independently selected and defined above, and D is defined above.

[0077] In these and other specific embodiments, the first capped organosilicon compound has the formula: (MeO)3Si-C2H4-SiR 1 2-O-SiR 1 2H In the formula, R 1 are independently selected and defined above.

[0078] In these and other specific embodiments, the first capped organosilicon compound has the formula: (MeO)3Si-CH2CH2-Si(Me)2-O-Si(Me)2H

[0079] In these and other embodiments, the second capped organosilicon compound has the formula: (R 1 ) a (R 2 O) 3-a SiH In the formula, each R 1 are independently selected and defined above, and each R 2 is independently selected and is defined above, each D is independently a divalent hydrocarbon group having from 2 to 18 carbon atoms, and the subscript a is 0 or 1. The second end-capping organosilicon compound provides X of formula (II) in the silicone-polyether copolymer.

[0080] In a specific embodiment, the second capped organosilicon compound has the formula: (R 1 )(R 2 O)2SiH In the formula, R 1 and R 2 are independently selected and defined above.

[0081] In these and other specific embodiments, the second capped organosilicon compound has the formula: (Me)(MeO)SiH In the formula, Me represents methyl.

[0082] In other specific embodiments, the second capped organosilicon compound has the formula: (R 2 O)3SiH In the formula, R 2 are independently selected and defined above. In these specific embodiments, R 2 is typically independently methyl or ethyl.

[0083] Organohydrogensiloxane compounds suitable for use as the first and second endcapped organosilicon compounds can be made by any suitable technique.

[0084] A third or additional end-capped organosilicon compound may also be utilized in the present method. For example, a third end-capped organosilicon compound may be included within formula (I) or (II) of silicone moiety X, yet be distinct from other end-capped organosilicon compounds included within the same general formula (I) or (II).

[0085] Still further, in certain embodiments, the method may include a transalkoxylation reaction involving one or more of the silicon-bonded alkoxy groups of the first or second endcapped organosilicon compound. By way of example, the second endcapped organosilicon compound may be a compound of the formula (R 2 O)3SiH, wherein each R 2 is ethyl. In such embodiments, the ethoxy groups present in the resulting silicone-polyether copolymer can be converted to methoxy groups by reacting the ethoxy groups with methanol.

[0086] As understood in the art, the polyether compound, the optional chain-extended organosilicon compound, and the first and second end-capped organosilicon compounds can be reacted in any order or combination to obtain a composition comprising at least one silicone-polyether copolymer. In addition, the order of addition or method can depend on whether condition (i) or (ii) applies. For example, when condition (i) applies, the polyether compound, the optional chain-extended organosilicon compound, and the first and second end-capped organosilicon compounds can be reacted together in any order in a single pot. Alternatively, when condition (ii) applies, the silicone-polyether copolymer (A) can be prepared in the absence of the second end-capped organosilicon compound, and the silicone-polyether copolymer (B) can be prepared in the absence of the first end-capped organosilicon compound, and then the silicone-polyether copolymer (A) and the silicone-polyether copolymer (B) can be combined to obtain a composition. Furthermore, if utilized, the chain-extending organosilicon compound can be utilized before the first and / or second end-capping organosilicon compounds, such that chain extension occurs before end-capping. When both the first and second organosilicon compounds are used together in the present process, i.e., when condition (i) applies, they may be combined with the other ingredients at the same time or at different times.

[0087] In certain embodiments, the method comprises: reacting a polyether compound and a chain-extended organosilicon compound in the presence of a hydrosilylation catalyst to obtain a siloxane-polyether compound (i.e., a chain-extended silicone-polyether compound); and reacting a siloxane-polyether compound and a first and / or second end-capped organosilicon compound in the presence of a hydrosilylation catalyst to obtain a composition comprising at least one silicone-polyether copolymer. The siloxane-polyether compound can be prepared by any suitable technique. For example, in certain embodiments, the siloxane-polyether compound is prepared by reacting a polyether compound having two terminal unsaturated groups and a chain-extended organosilicon compound in the presence of a hydrosilylation catalyst to obtain a composition comprising at least one silicone-polyether compound.

[0088] The siloxane-polyether compounds utilized in such embodiments have the formula [Z j Y o ] c where Z, Y, subscript c, subscript j, and subscript o are defined above. For example, if the polyether moiety Y and the organosilicon moiety Z are present and linear, the siloxane-polyether compound may have the formula:

[0089] [ka] In the formula, each Y, R 1 , subscript c, and subscript d are as defined above. Thus, the siloxane-polyether compound utilized can be selected based on the desired structure of the silicone-polyether copolymer, for example, based on molecular weight, the particular structure of each Y (i.e., the units within each Y), the degree of polymerization of the siloxy units represented by subscript d, etc.

[0090] In certain embodiments, the siloxane-polyether compound has the formula:

[0091] [ka]

[0092] In such an embodiment, each Y 1 , R 1 , and R 4 is as defined above, and subscript c is typically 1 to 150, for example 1 to 100, alternatively 1 to 50, alternatively 1 to 25, alternatively 1 to 10, alternatively 1 to 5. Typically, each subscript d is 1 to 1000, for example 1 to 500, alternatively 1 to 300, alternatively 1 to 100, alternatively 1 to 50, alternatively 1 to 10.

[0093] When utilized, the polyether compound and the chain-extended organosilicon compound are typically reacted in a molar ratio of 1.001:1 to 2:1, alternatively 1.4:1 to 1.7:1, alternatively 1.05:1 to 1.5:1, alternatively 1.1:1 to 1.2:1, alternatively 1.2:1 to 1.5:1. The siloxane-polyether compound is typically formed by a molar ratio of polyether compound and chain-extended organosilicon compound such that the desired value of subscript c is reached.

[0094] The silicone-polyether compound and the first and / or second endcapped organosilicon compounds are typically reacted in a molar ratio between the unsaturated groups of the silicone-polyether compound and the silicon hydride groups of the first and second endcapped organosilicon compounds of 1.5:1 to 1:1.5, alternatively 1.4:1 to 1:1.4, alternatively 1.3:1 to 1:1.3, alternatively 1.2:1 to 1:1.2, alternatively 1.1:1 to 1:1.1, alternatively 1.1:1 to 1:1. When the silicone-polyether compound is difunctional, the silicone-polyether copolymer is typically formed by a 1:2 molar ratio of the silicone-polyether compound and the first and second endcapped organosilicon compounds, although a molar excess of one over the other may be utilized.

[0095] In certain embodiments, the method comprises reacting a polyether compound with a first and / or second end-capped organosilicon compound in the presence of a hydrosilylation catalyst to obtain a terminally capped silicone-polyether compound, and reacting the terminally capped silicone-polyether compound and a chain-extended organosilicon compound in the presence of a hydrosilylation catalyst to obtain a composition comprising at least one silicone-polyether copolymer. In these or other embodiments, the method comprises reacting at least a portion of the polyether compound with at least a portion of the first and / or second end-capped organosilicon compounds to obtain a composition comprising at least one terminally capped silicone-polyether compound, and also reacting at least a portion of the polyether compound with at least a portion of the chain-extended organosilicon compounds to obtain a composition comprising at least one silicone-polyether compound, each as described above. In still other embodiments, when a chain-extended organosilicon compound is not used, the method comprises reacting a polyether compound with a first and / or second end-capped organosilicon compound in the presence of a hydrosilylation catalyst to obtain a composition comprising at least one silicone-polyether copolymer.

[0096] The hydrosilylation catalyst is not limited and can be any known hydrosilylation catalyst for catalyzing hydrosilylation reactions. Combinations of different hydrosilylation catalysts may also be used.

[0097] In certain embodiments, the hydrosilylation catalyst comprises a Group VIII-XI transition metal. For Group VIII-XI transition metals, reference is made to the latest IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Combinations, complexes (e.g., organometallic complexes), and other forms of such metals can be used as hydrosilylation catalysts.

[0098] Additional examples of catalysts suitable for hydrosilylation reaction catalysis include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g., those containing calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals can be used as hydrosilylation reaction catalysts.

[0099] The hydrosilylation catalyst may be in any suitable form. For example, the hydrosilylation catalyst may be solid, including platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts containing multiple metal combinations. Further examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts.

[0100] The 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). The hydrosilylation catalyst may also be placed in a vehicle, such as a solvent that solubilizes the hydrosilylation catalyst, or alternatively, a vehicle that simply carries but does not solubilize the hydrosilylation catalyst. Such vehicles are known in the art.

[0101] In specific embodiments, the hydrosilylation catalyst comprises platinum. In these embodiments, the hydrosilylation catalyst is exemplified by compounds such as platinum black, chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid with monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in matrices or core-shell compounds. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art, as exemplified by U.S. Pat. Nos. 4,766,176 and 5,017,654, which are incorporated herein by reference in their entireties.

[0102] Platinum complexes with organopolysiloxanes suitable for use as hydrosilylation catalysts include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. These complexes may be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst may include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. The hydrosilylation catalyst may be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane, or an alkene-platinum-silyl complex. For example, an alkene-platinum-silyl complex may be prepared by mixing 0.015 moles of (COD)PtCl with 0.045 moles of COD and 0.0612 moles of HMeSiCl, where COD represents cyclooctadiene.

[0103] Further examples of hydrosilylation catalysts suitable for the component 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.

[0104] The hydrosilylation catalyst may also or alternatively be a photoactivatable hydrosilylation catalyst that can initiate curing upon irradiation and / or heating. The photoactivatable hydrosilylation catalyst may be any hydrosilylation catalyst that can catalyze a hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of 150 to 800 nanometers (nm).

[0105] In certain embodiments, the silicone-polyether copolymer can be prepared in the absence of any solvent or vehicle. In other embodiments, the silicone-polyether copolymer is generally formed in the presence of a diluent that is non-reactive with the silicone-polyether copolymer or the components used to prepare it. The diluent can be a solvent or vehicle, examples of which are described below with reference to the sealant formed using the composition. In such embodiments, the solvent or vehicle can be removed from the composition after preparing the silicone-polyether copolymer, or can remain. In other embodiments, the diluent can be considered a plasticizer, particularly when the composition is used to prepare a sealant. For example, conventional sealants often contain plasticizers, and therefore, the plasticizer can provide benefits in terms of reducing the viscosity of the reaction mixture when preparing the silicone-polyether copolymer and can remain in the composition for sealant purposes, thereby reducing an additional formulation step for the sealant.

[0106] The composition can be utilized in a variety of end-use applications. In certain embodiments, the composition is further defined as a sealant. When the composition is a sealant, the sealant includes a condensation reaction catalyst. Embodiments including the composition as a sealant are as follows:

[0107] Condensation reaction catalysts are not limited and in some embodiments are exemplified by tin catalysts, titanium catalysts, zirconate catalysts, and zirconium catalysts. Common examples of suitable tin catalysts include organic compounds in which the tin valency is either +4 or +2 (i.e., tin(IV) compounds or tin(II) compounds). Specific examples of tin(IV) compounds include stannic salts of carboxylic acids, such as dibutyltin dilaurate, dimethyltin dilaurate, di-(n-butyl)tin bis-ketonate, dibutyltin diacetate, dibutyltin maleate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, carbomethoxyphenyltin tris-uberate, dibutyltin dioctanoate, dibutyltin diformate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodeconoate, dibutyltin di-neodeconoate, triethyltin tartrate, dibutyltin dibenzoate, butyltin 3-2-ethylhexanoate, dioctyltin diacetate, tin octoate, tin oleate, tin butyrate, tin naphthenate, dimethyltin dichloride, and the like, combinations thereof, and / or partial hydrolysis products thereof. Additional examples of tin(IV) compounds are known in the art and are commercially available, for example, as Metatin® 740 and Fascat® 4202 from Acima Specialty Chemicals, Switzerland, Europe, a division of The Dow Chemical Company, and Formrez® UL-28 from Galata Chemicals, Hahnville, Louisiana. Specific examples of tin(II) compounds include tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctoate, tin(II) diethylhexanoate, tin(II) dilaurate, stannous salts of carboxylic acids, such as tin octoate, tin oleate, tin acetate, tin didodecanoate, tin stearate, tin naphthenate, tin hexanoate, tin succinate, tin caprylate, and combinations thereof.Examples of suitable titanium catalysts include titanium esters such as tetra-n-butyl titanate, tetraisopropyl titanate, tetra-2-ethylhexyl titanate, tetraphenyl titanate, triethanolamine titanate, organosiloxy titanium compounds, and dicarbonyl titanium compounds such as titanium ethylacetoacetate and diisopropoxydi(ethoxyacetoacetyl)titanium and bis(acetoacetonyl)-diisopropoxytitanium(IV). Many of these titanium catalysts are commercially available from Dorf Ketal Specialty Catalysts LLC of Houston, Texas, such as Tyzor™ DC, Tyzor™ TnBT, and Tyzor™ 9000. In certain embodiments, the condensation reaction catalyst is a titanium catalyst, such as one of those exemplified above, for example, such that the sealant is or can be formulated as a room-temperature vulcanizing sealant composition. The amount of condensation reaction catalyst present in the sealant depends on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or types of any additional materials present in the sealant, etc.) and can be readily determined by one of ordinary skill in the art. In one embodiment, the sealant includes the condensation reaction catalyst in an amount of 0.2 to 6, alternatively 0.5 to 3 parts by weight, based on the total weight of the at least one silicone-polyether copolymer present in the sealant. In other embodiments, the sealant includes the condensation reaction catalyst in an amount of greater than 0 to 0.2 parts by weight, alternatively greater than 0 to 0.15 parts by weight, alternatively greater than 0 to 0.125 parts by weight, or alternatively greater than 0 to 0.10 parts by weight, based on the total weight of the at least one silicone-polyether copolymer present in the sealant.

[0108] In some embodiments, the sealant further comprises one or more additives. Examples of suitable additives that may be present in the sealant include fillers, treatments (e.g., filler treatments), crosslinkers, adhesion promoters, surface modifiers, driers, extenders, biocides, flame retardants, plasticizers, end-capping agents, binders, anti-aging additives, water release agents, pigments, rheology modifiers, carriers, tackifiers, corrosion inhibitors, catalyst inhibitors, viscosity modifiers, UV absorbers, antioxidants, light stabilizers, and the like, and combinations thereof.

[0109] In certain embodiments, the sealant includes a filler. The filler may be or include a reinforcing filler, an extending filler, a conductive filler (e.g., electrically conductive, thermally conductive, or both), or the like, or a combination thereof. Examples of suitable reinforcing fillers include precipitated calcium carbonate and reinforcing silica fillers (e.g., fumed silica, silica aerogel, silica xerogel, and precipitated silica). Particularly suitable precipitated calcium carbonates include Winnofil® SPM from Solvay, and Ultrapflex® and Ultrapflex® 100 from Specialty Minerals, Inc. Examples of fumed silica are known in the art and commercially available, including that sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, USA. Examples of suitable extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate (e.g., ground calcium carbonate, precipitated calcium carbonate), zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, or combinations thereof. Examples of extending fillers are known in the art and are commercially available, such as quartz powder sold under the name MIN-U-SIL by US Silica of Berkeley Springs, West Virginia. Other examples of commercially available extending fillers include calcium carbonate sold under the names CS-11 by Imerys, G3T by Huber, Pfinyl 402 by Specialty Minerals, Inc., and Omyacarb 2T by Omya. The amount of filler present in the sealant will depend on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or types of any additional materials present in the sealant, etc.) and can be readily determined by one of ordinary skill in the art. The exact amount of filler utilized in a particular implementation of the sealant will also depend on whether two or more types of filler are utilized.Typically, when present, the sealant comprises filler in an amount of from 0.1 to 95, alternatively from 1 to 60, alternatively from 1 to 20 wt %, based on the weight of the sealant.

[0110] In certain embodiments, the sealant includes a treating agent. The treating agent may be any agent suitable for use in treating (e.g., surface treating) sealant additives, such as, but not limited to, fillers and other additives that may be present in the sealant (e.g., physical drying agents, flame retardants, pigments, and / or water-releasing agents). More specifically, solid and / or particulate additives may be treated with the treating agent before being added to the sealant. Alternatively, or in addition, solid and / or particulate additives may be treated with the treating agent in situ. General examples of suitable treating agents include those containing alkoxysilanes, alkoxy-functional oligosiloxanes, cyclic polyorganosiloxanes, hydroxyl-functional oligosiloxanes (e.g., dimethylsiloxane or methylphenylsiloxane), fatty acids (e.g., stearates such as calcium stearate), and the like, as well as combinations thereof. Specific examples of treating agents include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and the like, as well as combinations thereof.

[0111] In some embodiments, the treating agent is or includes an organosilicon filler treating agent. Examples of such organosilicon filler treating agents include organochlorosilanes, organosiloxanes, organodisilazanes (e.g., hexaalkyldisilazanes), and organoalkoxysilanes (e.g., CH3Si(OCH3)3, CH6 ... 13 Si(OCH3)3, C8H 17 Si(OC2H5)3, C 10 H 21 Si(OCH3)3, C 12 H 25 Si(OCH3)3, C 14 H 29In these or other embodiments, the treating agent has the formula (X): R 10 A Si(OR 11 ) 4-A In formula (X), the subscript A is an integer from 1 to 3, such as 1, 2, or 3. Each R 10 R is an independently selected monovalent organic group such as, for example, a monovalent hydrocarbon group having 1 to 50 carbon atoms, or 8 to 30 carbon atoms, or 8 to 18 carbon atoms, or 1 to 5 carbon atoms. 10 may be saturated or unsaturated, branched or unbranched. 10 R may be saturated and unbranched. 10 are exemplified by alkyl groups such as methyl, ethyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; alkenyl groups such as vinyl; and aromatic groups such as benzyl and phenylethyl. 11 are independently selected saturated hydrocarbon groups having 1 to 4 carbon atoms or 1 to 2 carbon atoms. Specific examples of organosilicon filler treating agents also include hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof.

[0112] In some embodiments, the treating agent is or includes an alkoxy-functional oligosiloxane. For example, suitable alkoxy-functional oligosiloxanes include those having the general formula (XI): (R 12 O) B Si(OSiR 13 2nd Round 14 ) (4-B) In formula (XI), the subscript B is 1, 2, or 3. In some embodiments, the subscript B is 3. Each R12 are independently selected alkyl groups. 13 are independently selected unsaturated monovalent hydrocarbon groups having 1 to 10 carbon atoms. 14 is an independently selected unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.

[0113] In certain embodiments, the treating agent is or includes a hydrogen-bonding capable polyorganosiloxane. Such treating agents utilize clustered and / or dispersed multiple hydrogen bonds as a means of tethering compatibilizing moieties to the surface of the treated sealant component (e.g., filler). Suitable hydrogen-bonding capable polyorganosiloxanes have, on average, at least one silicon-bonded group capable of hydrogen bonding per molecule, and are typically selected from organic groups having multiple hydroxyl functional groups, organic groups having at least one amino functional group, and combinations thereof. In other words, hydrogen-bonding capable polyorganosiloxanes typically utilize hydrogen bonding as the primary mode of bonding to the filler. Thus, in some embodiments, the polyorganosiloxane is incapable of forming covalent bonds with the filler. The polyorganosiloxane may be free of condensable silyl groups (e.g., silicon-bonded alkoxy groups, silazanes, and silanols). Examples of polyorganosiloxanes suitable for use in or as a sealant include saccharide-siloxane polymers, amino-functional polyorganosiloxanes, and combinations thereof. In a specific embodiment, the sealant comprises a polyorganosiloxane comprising a saccharide-siloxane polymer.

[0114] The amount of treating agent present in the sealant depends on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or type of any additional materials present in the sealant (e.g., those to be treated with a treating agent), etc.) and can be readily determined by one of ordinary skill in the art. Typically, the amount of treating agent will vary depending on the type of treating agent selected, the type and / or amount of particulates to be treated, and whether the particulates are treated before being added to the sealant or are treated in situ. Typically, when present, the sealant will include an amount of treating agent of 0.01 to 20, alternatively 0.1 to 15, alternatively 0.5 to 5 wt. %, based on the weight of the sealant.

[0115] In some embodiments, the sealant includes a polymer additive such as a crosslinker, a chain extender, a plasticizer, an end-capping agent, or the like, or a combination thereof. Generally, suitable polymer additives include compounds having functional groups reactive with functional groups present in at least one silicone-polyether copolymer of the sealant or reactive with functional groups present in another polymer additive that has reacted therewith. Particular polymer additives may be named based on their intended function (e.g., crosslinking, chain extending, end-capping, etc.). However, it should be understood that certain polymer additives described herein may have more than one function, as would be readily understood by one of ordinary skill in the art, and therefore there may be overlap in functionality between types of polymer additives. For example, suitable crosslinkers include those containing compounds having, on average, two or more substituents per molecule reactive with alkoxy groups present in at least one silicone-polyether copolymer, and suitable chain extenders include those containing compounds having, on average, two substituents per molecule reactive with alkoxy groups present in at least one silicone-polyether copolymer or reactive with groups present in another polymer additive that has reacted with at least one silicone-polyether copolymer. Thus, as will be appreciated by those skilled in the art, a variety of compounds may be used as crosslinkers and / or chain extenders. Similarly, a variety of plasticizers, exemplified by the specific plasticizers described below, may also be utilized in, or interchangeably as, crosslinkers and / or chain extenders in the sealant.

[0116] In some embodiments, the sealant includes a crosslinker. Some examples of suitable crosslinkers include silane crosslinkers having hydrolyzable groups, or their partial or complete hydrolysis products. Examples of such silane crosslinkers include those having the general formula (XII): R 15 C Si(R 16 ) (4-C) wherein each R 15 are independently selected monovalent hydrocarbon groups such as alkyl groups; 16is a hydrolyzable substituent, such as a halogen atom, an acetamido group, an acyloxy group (e.g., acetoxy), an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group, and the subscript C is 0 to 3, e.g., 0, 1, 2, or 3. The subscript C has an average value greater than 2. Alternatively, the subscript C may have a value in the range of 3 to 4. Typically, each R 16 are independently selected from hydroxyl, alkoxy, acetoxy, amide, or oxime. Specific examples of suitable silane crosslinkers include methyldiacetoxymethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydiethoxysilane, and combinations thereof.

[0117] In some embodiments, the crosslinker comprises an acyloxysilane, an alkoxysilane, a ketoximosilane, an oximosilane, or the like, or a combination thereof.

[0118] Examples of suitable acetoxysilane crosslinkers include tetraacetoxysilane, organotriacetoxysilane, diorganodiacetoxysilane, and combinations thereof. The acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3-trifluoropropyl. Exemplary acetoxysilanes include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane, octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane, tetraacetoxysilane, and combinations thereof. In some embodiments, the crosslinker comprises an organotriacetoxysilane, for example, a mixture comprising methyltriacetoxysilane and ethyltriacetoxysilane.

[0119] Examples of suitable amino-functional alkoxysilanes suitable for use in or as a crosslinker are HN(CH)Si(OCH), HN(CH)Si(OCHCH), HN(CH)Si(OCH), HN(CH)Si(OCHCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH). 5Si(OCH2CH3)3, H2N(CH2)2NH(CH2)3Si(OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3, CH 3NH(CH2)2NH(CH2)3Si(OCH2CH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2 SiCH3(OCH3)2, H2N(CH2)2SiCH3(OCH2CH3)2, H2N(CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3 (OCH3)2, CH3NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)5SiCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2) 3SiCH3(OCH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, and combinations thereof.

[0120] Examples of suitable oximosilane crosslinkers include structural units selected from alkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanes such as methoxytrioximosilane, ethoxytrioximosilane, and propoxytrioximosilane; or alkenyltrioximosilanes such as propenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanes such as vinyloximosilane; alkenylalkyldioximosilanes such as vinylmethyldioximosilane, vinylethyldioximosilane, vinylmethyldioximosilane, or vinylethyldioximosilane; or combinations thereof.

[0121] Examples of suitable ketoximo silane crosslinkers include methyl tris(dimethyl ketoximo) silane, methyl tris(methyl ethyl ketoximo) silane, methyl tris(methyl propyl ketoximo) silane, methyl tris(methyl isobutyl ketoximo) silane, ethyl tris(dimethyl ketoximo) silane, ethyl tris(methyl ethyl ketoximo) silane, ethyl tris(methyl propyl ketoximo) silane, ethyl tris(methyl isobutyl ketoximo) silane, vinyl tris(dimethyl ketoximo) silane, vinyl tris(methyl ethyl ketoximo) silane, and vinyl tris(methyl propyl ketoximo) silane. vinyltris(methylisobutylketoximo)silane, tetrakis(dimethylketoximo)silane, tetrakis(methylethylketoximo)silane, tetrakis(methylpropylketoximo)silane, tetrakis(methylisobutylketoximo)silane, methylbis(dimethylketoximo)silane, methylbis(cyclohexylketoximo)silane, triethoxy(ethylmethylketoxime)silane, diethoxydi(ethylmethylketoxime)silane, ethoxytri(ethylmethylketoxime)silane, methylvinylbis(methylisobutylketoximo)silane, or combinations thereof.

[0122] In certain embodiments, the crosslinker comprises a dialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, such as an alkyltrialkoxysilane; an alkoxysilane, exemplified by a tetraalkoxysilane, its partial or complete hydrolysis product, or a combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and combinations thereof. Examples of suitable tetraalkoxysilanes include tetraethoxysilane. In a specific embodiment, the crosslinker comprises methyltrimethoxysilane, or alternatively, is methyltrimethoxysilane.

[0123] In certain embodiments, the crosslinker is polymeric. For example, the crosslinker may include dipodal silanes such as bis(triethoxysilyl)hexane), 1,4-bis[trimethoxysilyl(ethyl)]benzene, bis[3-(triethoxysilyl)propyl]tetrasulfide, bis(trimethoxysilyl)hexane), bis(triethoxysilyl)ethane, bis(trimethoxysilyl)ethane, and combinations thereof. In these or other embodiments, the crosslinker may include hydrolyzable substituents and other silicon-bonded organic groups, and, if a polymeric crosslinker is used, the crosslinker may be a single crosslinker or a combination of two or more crosslinkers that differ from each other, for example, based on siloxane units, structure, molecular weight, sequence, etc.

[0124] The amount of crosslinker present in the sealant will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials (e.g., other polymeric additives) present in the sealant, the type of crosslinker utilized, etc.) and can be readily determined by one of ordinary skill in the art. Generally, the sealant includes the crosslinker, when present, in an amount of 0.5 to 15 wt %, alternatively 1 to 10 wt %, alternatively 3 to 10 wt %, based on the weight of the at least one silicone-polyether copolymer.

[0125] In some embodiments, the sealant includes a plasticizer. Examples of suitable plasticizers include organic plasticizers such as those containing carboxylic acid esters (e.g., esters), phthalates (e.g., phthalates), carboxylates (e.g., carboxylates), adipates (e.g., adipates), or combinations thereof. Specific examples of suitable organic plasticizers include bis(2-ethylhexyl) terephthalate, bis(2-ethylhexyl)-1,4-benzenedicarboxylate, 2-ethylhexylmethyl-1,4-benzenedicarboxylate, 1,2 cyclohexanedicarboxylic acid, dinonyl esters (branched and linear), bis(2-propylheptyl) phthalate, diisononyl adipate, and combinations thereof.

[0126] In certain embodiments, the plasticizer has an average per molecule of the formula:

[0127] [ka] [In the formula, R 17 represents a hydrogen atom or a monovalent organic group (e.g., a branched or straight chain monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms). In these or other embodiments, the plasticizer has an average of at least two groups of the above formula per molecule, each bonded to a carbon atom in the cyclic hydrocarbon. In such cases, the plasticizer has the following general formula:

[0128] [ka] may have: In this formula, D is a carbocyclic group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms, and may be unsaturated, saturated, or aromatic. The subscript E is 1 to 12. Each R 18 are independently a branched or straight-chain monovalent hydrocarbon group such as an alkyl group having 4 to 15 carbon atoms (e.g., an alkyl group such as a methyl group, an ethyl group, or a butyl group). 19 are independently a hydrogen atom or a branched or straight chain, substituted or unsubstituted monovalent organic group. For example, in some embodiments, at least one R 19 is a moiety containing an ester functionality.

[0129] In a specific embodiment, the sealant includes a polymer plasticizer. Examples of the polymer plasticizer include alkenyl polymers (e.g., alkenyl polymers obtained by polymerizing vinyl or allylic monomers by various methods); polyalkylene glycol esters (e.g., diethylene glycol dibenzoate, triethylene glycol, dibenzoate pentaerythritol ester, etc.); polyester plasticizers (e.g., polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol); polyesters containing polyester polyols each having a molecular weight of 500 or more (e.g., polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.); polystyrenes (e.g., polystyrene, poly-α-methylstyrene, etc.); polybutenes and polybutadienes (e.g., polyisobutylene, butadiene acrylonitrile, etc.); and polychloroprene. In various embodiments, a combination of low molecular weight plasticizers and high molecular weight polymeric plasticizers may be present in the sealant.

[0130] Suitable plasticizers are known in the art and commercially available. Such plasticizers may be present in the sealant alone or in combination. For example, plasticizers may include phthalates, such as dialkyl phthalates, for example, dibutyl phthalate (Eastman™ DBP Plasticizer), diheptyl phthalate, diisononyl phthalate, di(2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate (BASF Palatinol® DPHP), di(2-ethylhexyl) phthalate (Eastman™ DOP Plasticizer), dimethyl phthalate (Eastman™ DMP Plasticizer); diethyl phthalate (Eastman™ DMP Plasticizer); butyl benzyl phthalate, and bis(2-ethylhexyl) terephthalate (Eastman™ 425 Plasticizer); dicarboxylates, for example, benzyl, C7-C9 straight and branched chain alkyl esters, 1,2, benzyl dicarboxylic acid (Ferro SANTICIZER® 261A), 1,2,4-benzenetricarboxylic acid (BASF Palatinol® TOTM-I), bis(2-ethylhexyl)-1,4-benzenedicarboxylate (Eastman™ 168 Plasticizer); 2-ethylhexylmethyl-1,4-benzenedicarboxylate; branched and linear 1,2 cyclohexanedicarboxylic acid dinonyl ester (BASF Hexamoll® DINCH); diisononyl adipate; trimellitates, such as trioctyl trimellitate (Eastman™ TOTM Plasticizer); triethylene glycol bis(2-ethylhexanoate) (Eastman™ TEG-EH Plasticizer); triacetin (Eastman™ Triacetin);These may include non-aromatic dibasic acid esters such as dioctyl adipate, bis(2-ethylhexyl) adipate (Eastman™ DOA Plasticizer and Eastman™ DOA Plasticizer, Kosher), di-2-ethylhexyl adipate (BASF Plastomoll® DOA), dioctyl sebacate, dibutyl sebacate, and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylresinoleate; phosphates such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils, epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; tris(2-ethylhexyl) esters; fatty acid esters; and combinations thereof. Other suitable plasticizers and their commercial products include BASF Palamoll® 652 and Eastman 168 Xtreme™ plasticizers;

[0131] The amount of plasticizer present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials (e.g., other polymer additives) present in the sealant, the type of crosslinker utilized, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant comprises plasticizer in an amount of 5 to 150 parts by weight, based on the combined weight of all components in the sealant. In a specific embodiment, the sealant comprises plasticizer in an amount of 0.1 to 10% by weight, based on the total weight of the sealant.

[0132] In some embodiments, the sealant includes an extender. Examples of suitable extenders include non-functional polyorganosiloxanes, such as those of the formula R 20 2SiO 2 / 2 and a bifunctional unit of formula R 21 3SiD'-, wherein each R 20 and each R 21are independently monovalent organic groups, such as monovalent hydrocarbon groups exemplified by the following: alkyl, such as methyl, ethyl, propyl, and butyl; alkenyl, such as vinyl, allyl, and hexenyl; aryl, such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups, such as phenylethyl; and D' is an oxygen atom or a divalent group. Non-functional polyorganosiloxanes are known in the art and are commercially available. Suitable non-functional polyorganosiloxanes are exemplified, but not limited to, by polydimethylsiloxane. Such polydimethylsiloxanes include DOWSIL® 200 Fluids, commercially available from DOW Silicones Corporation of Michigan, USA, and contain 5×10 -5 ~0.1, or 5×10 -5 ~0.05, or 0.0125~0.06m 2 The sealant may have a viscosity ranging from 0.1 to 10 wt. % based on the total weight of the sealant. The amount of extender present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials (e.g., other polymeric additives) present in the sealant, the type of crosslinker utilized, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include extender in an amount of 0.1 to 10 wt. % based on the total weight of the sealant.

[0133] In some embodiments, the sealant comprises an end-capping agent. Suitable end-capping agents include M units, i.e., end-capping agents of the formula R 22 3SiO 1 / 2 wherein each R 22each independently represents a monovalent organic group, such as a monovalent hydrocarbon group. Typical examples of such endblockers include those containing polyorganosiloxanes (e.g., polydiorganosiloxanes, such as polydimethylsiloxanes) terminated at one end with a triorganosilyl group, e.g., (CH3)3SiO—, and at the other end with a hydroxyl group. Other examples of suitable endblockers include polydiorganosiloxanes containing both hydroxyl and triorganosilyl endgroups, which may have more than 50%, or alternatively, more than 75%, of all endgroups as hydroxyl groups. The amount of triorganosilyl groups present in such endblockers can vary and is typically used to adjust the modulus of the reaction product prepared by the sealant condensation reaction. While not wishing to be bound by theory, it is believed that a higher concentration of triorganosilyl endgroups may result in a lower modulus in a particular cured product. In some embodiments, the sealant endblocker comprises a single endblocking compound. However, in other embodiments, the end-capping agent of the sealant comprises two or more different end-capping compounds that differ from one another by properties including, for example, structure, viscosity, average molecular weight, polymer units, sequence, etc., or a combination thereof. The amount of end-capping agent present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials (e.g., other polymer additives) present in the sealant, the type of end-capping agent utilized, etc.) and can be readily determined by one of ordinary skill in the art. Generally, the sealant comprises the end-capping agent, when present, in an amount of 0 to 50 wt %, alternatively 0 to 30 wt %, alternatively 0 to 15 wt %, based on the total weight of the at least one silicone-polyether copolymer.

[0134] In certain embodiments, the sealant includes a surface modifier. Suitable surface modifiers include adhesion promoters, release agents, and the like, as well as combinations thereof. Typically, surface modifiers are utilized to modify the surface appearance of the sealant's reaction product. For example, surface modifiers can be used to increase the surface gloss of the reaction product. Specific examples of suitable surface modifiers include polydiorganosiloxanes having alkyl and aryl groups. For example, DOWSIL® 550 Fluid is commercially available from Dow Silicones Corporation and has a viscosity of 0.000125 m. 2 A trimethylsiloxy-terminated poly(dimethyl / methylphenyl)siloxane having a viscosity of 1 / s. These and other examples of suitable surface modifiers include natural oils (e.g., obtained from vegetable or animal sources), such as linseed oil, tung oil, soybean oil, castor oil, fish oil, hemp seed oil, cottonseed oil, oiticica oil, rapeseed oil, and the like, and combinations thereof.

[0135] In some embodiments, the surface modifier is an adhesion promoter. Suitable adhesion promoters may include hydrocarbon oxysilanes such as alkoxysilanes, combinations of alkoxysilanes with hydroxy-functional polyorganosiloxanes, amino-functional silanes, epoxy-functional silanes, mercapto-functional silanes, or combinations thereof. Adhesion promoters are known in the art and can be represented by the formula R 23 F R 24 G Si(OR 25 ) 4-(F+G) wherein each R 23 are independently a monovalent organic group having at least 3 carbon atoms, and R 24 contains at least one SiC-bonded substituent having an adhesion-promoting group such as an amino group, an epoxy group, a mercapto group, or an acrylate group, and each R 25are independently monovalent organic groups (e.g., methyl, ethyl, propyl, butyl, etc.), the subscript F has a value ranging from 0 to 2, the subscript G is either 1 or 2, and the sum of (F+G) is 3 or less. In certain embodiments, the adhesion promoter comprises a partial condensate of the above-described silanes. In these or other embodiments, the adhesion promoter comprises a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0136] In some embodiments, the adhesion promoter comprises an unsaturated or epoxy-functional compound. In such embodiments, the adhesion promoter comprises an unsaturated or epoxy-functional alkoxysilane, such as a compound represented by formula (XIII): R 26 H Si(OR 27 ) (4-H) where the subscript H is 1, 2, or 3, or the subscript H is 1. Each R 26 are independently a monovalent organic group, provided that at least one R 26 R is an unsaturated organic group or an epoxy-functional organic group. 26 Epoxy-functional organic groups of R are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. 26 The unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl, and the like. 27 are independently saturated hydrocarbon groups having 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. 27 is exemplified by methyl, ethyl, propyl, and butyl.

[0137] Specific examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

[0138] In some embodiments, the adhesion promoter comprises an epoxy-functional siloxane (e.g., any of those described above), such as the reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane, or a physical blend of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane. The adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the adhesion promoter is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane with the reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane / dimethylsiloxane copolymer.

[0139] In certain embodiments, the adhesion promoter is an amino-functional silane, such as HN(CH)Si(OCH, HN(CH)Si(OCHCH), HN(CH)Si(OCH, HN(CH)Si(OCH), HN(CH)Si(OCHCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), HN(CH) NH(CH2)3Si(OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH2CH3 )3, C4H9NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH3(OCH3)2, H2N(CH2)2SiCH3(OCH 2CH3)2, H2N(CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)3SiCH3(OCH2CH3)2, C H3NH(CH2)5SiCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH 2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, N-(3-(trimethoxysilyl)propyl)ethylenediamine, and the like, and combinations thereof. In these or other embodiments, the adhesion promoter comprises a mercapto-functional alkoxysilane, such as 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

[0140] Additional examples of surface modifiers include adhesion promoters that are the reaction products of epoxyalkylalkoxysilanes, such as 3-glycidoxypropyltrimethoxysilane, and amino-substituted alkoxysilanes, such as 3-aminopropyltrimethoxysilane, optionally with an alkylalkoxysilane, such as methyltrimethoxysilane.

[0141] In some embodiments, the surface modifier includes or is a release agent. Suitable release agents are exemplified by fluorinated compounds (e.g., fluorofunctional silicones or fluorofunctional organic compounds). In specific embodiments, the sealant includes multiple surface modifiers, such as one or more adhesion promoters, one or more release agents, one or more natural oils, or combinations thereof.

[0142] The amount of surface modifier present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials present in the sealant, the cure conditions to which the sealant is intended to be exposed, etc.) and can be readily determined by one of ordinary skill in the art. Generally, if present, the sealant comprises the surface modifier in an amount of 0.01 to 50, alternatively 0.01 to 10, alternatively 0.01 to 5 parts by weight, based on the total weight of all components in the sealant.

[0143] In certain embodiments, the sealant includes a desiccant, such as a physical desiccant (e.g., an adsorbent), a chemical desiccant, or the like. Generally, desiccants bind water and low molecular weight alcohols from various sources. For example, a desiccant may bind to by-products of a condensation reaction involving at least one silicone-polyether copolymer, such as water and alcohol. Physical desiccants typically trap and / or adsorb such water and / or by-products, while chemical desiccants typically bind to water and / or other by-products by chemical means (e.g., via covalent bonds). Examples of desiccants suitable for use in the sealant include adsorbents, such as those comprising inorganic particulates. Such adsorbents typically have a particle size of 10 micrometers or less or 5 micrometers or less and an average pore size sufficient to adsorb water and low molecular weight alcohols (e.g., an average pore size of 10 Å (angstroms) or less, or 5 Å or less, or 3 Å or less). Specific examples of such adsorbents include zeolites (e.g., chabazite, mordenite, and analcime), and molecular sieves, including alkali metal aluminosilicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof. Examples of commercially available desiccants include molecular sieves such as the 3 Å (angstrom) sold under the trade name SYLOSIV® by Grace Davidson and Zeochem of Lousville, Kentucky, USA, and the 4 Å molecular sieve sold under the trade name Doucil zeolite 4A by Ineos Silicas of Warrington, UK. Other examples of suitable desiccants include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A molecular sieves (all commercially available from UOP, Illinois, USA); SILIPORITE NK 30AP and 65xP from Atofina, Philadelphia, Pennsylvania, USA; and molecular sieves commercially available from W.R. Grace. Examples of chemical desiccants include silanes, such as those described above with respect to crosslinkers.For example, alkoxysilanes suitable as desiccants include vinyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof. As will be appreciated by those skilled in the art, a chemical desiccant can be added to a sealant or a portion of a sealant (e.g., if the sealant is a multi-part composition) to render the sealant or portion thereof water-free. Thus, the desiccant can be added to a portion of the sealant (e.g., the dry portion) before the sealant is formed, thereby rendering that portion storable. Alternatively, or in addition, the desiccant can render the sealant water-free after formulation (e.g., after the sealant portions are mixed together). The amount of desiccant present in a sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials present in the sealant, the curing conditions to which the sealant is intended to be exposed, etc.) and can be readily determined by one skilled in the art. Generally, when present, the sealant will contain a desiccant in an amount of 0.1 to 5 parts by weight, based on the total weight of all components in the sealant.

[0144] In some embodiments, the sealant includes a biocide. Typical examples of suitable biocides include fungicides, herbicides, insecticides, antimicrobial agents, and the like, as well as combinations thereof. For example, in certain embodiments, the biocide includes or is a fungicide. Specific examples of fungicides include N-substituted benzimidazole carbamates, benzimidazolyl carbamates (e.g., methyl 2-benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate, isopropyl 2-benzimidazolylcarbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, methyl N-{2-[1-(N-methylcarbamoyl)benzimidazolyl]}carbamate, bamate, methyl N-{2-[1-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methyl N-{2-[1-(N-methylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, ethyl N-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[2-(N-methylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, ethyl N-{2-[1-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, isopropyl N-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, isopropyl N-{2-[1-(N-methylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate methyl N-{1-(N,N-dimethylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[N-methylcarbamoyloxy] ... methyl N-{2-[1-(N-butylcarbamoyloxy)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1-(N-butylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-chlorobenzimidazolyl]}carbamate carbamate, and methyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-nitrobenzimidazolyl]}carbamate; 10,10'-oxybisphenoxarsine (trade name: Vinyzene, OBPA); di-iodomethyl-para-tolyl sulfone; benzothiophene-2-cyclohexylcarboxamide-S,S-dioxide; N-(fluorodichloridemethylthio)phthalimide (trade name: Fluor-Folper, Preventol A3); methyl-benzimidazol-2-ylcarbamate (trade name: Carbendazim, Preventol BCM); zinc-bis(2-pyridylthio-1-oxide); zinc pyrithione; 2-(4-thiazolyl)-benzimidazole; N-phenyl-iodopropargyl carbamate; N-octyl-4-isothiazolin-3-one; 4,Examples of fungicides include 5-dichlorido-2-n-octyl-4-isothiazolin-3-one; N-butyl-1,2-benzisothiazolin-3-one; triazolyl compounds such as tebuconazole, and combinations thereof. In certain embodiments, such fungicides are used in combination with one or more inorganic materials, such as minerals (e.g., zeolites), metals (e.g., copper, silver, platinum, etc.), and combinations thereof.

[0145] In certain embodiments, the biocide comprises or is a herbicide. Specific examples of herbicides include amide herbicides such as allidochlor or N,N-diallyl-2-chloroacetamide; CDEA 2-chloro-N,N-diethylacetamide; ethanipromide (RS)-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-N-ethylpropionamide; anilide herbicides such as cis-anilide cis-2,5-dimethylpyrrolidine-1-carboxyanilide; flufenacet 4'-fluoro-N-isopropyl-2-[5-(trifluoromethyl)-1,3,4-thiadiazol-2-yloxy]acetanilide; naproanilide (RS)-α-2-naphthoxypropionanilide; arylalanine herbicides such as benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine; and flamprop-M. N-benzoyl-N-(3-chloro-4-fluorophenyl)-D-alanine; chloroacetanilide herbicides such as butachlor or N-butoxymethyl-2-chloro-2',6'-diethylacetanilide; metazachlor or 2-chloro-N-(pyrazol-1-ylmethyl)aceto-2',6'-xylide; prinachlor (RS)-2-chloro-N-(1-methylprop-2-ynyl)acetanilide; sulfonanilide herbicides such as cloransulam 3-chloro-2-(5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidin-2-ylsulfonamido)benzoic acid; metoslam 2',6'-dichloro-5,7-dimethoxy-3'-methyl[1,2,4 ]Triazolo[1,5-a]pyrimidine-2-sulfonanilide; antibiotic herbicides such as bilanafos 4-[hydroxy(methyl)phosphinoyl]-L-homoalanyl-L-alanyl-L-alanine; benzoic acid herbicides such as chloramben 3-amino-2,5-dichlorobenzoic acid; 2,3,6-TBA 2,3,6-trichlorobenzoic acid; pyrimidinyloxybenzoic acid herbicides such as bispyribac 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid; pyrimidinylthiobenzoic acid herbicides such as pyrithiobac 2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid; phthalic acid herbicides such as chlorthal tetrachloroterephthalic acid;Picolinic acid herbicides such as aminopyralid 4-amino-3,6-dichloropyridine-2-carboxylic acid; quinoline carboxylic acid herbicides such as quinclorac 3,7-dichloroquinoline-8-carboxylic acid; arsenical herbicides such as CMA calcium bis(hydrogen methylarsonate); MAMA ammonium hydrogen methylarsonate; sodium arsenite; benzoylcyclohexanedione herbicides such as mesotrione 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione; benfuresate 2,3-dihydro-3,3-dimethylbenzofuran-5-yl Benzofuranyl alkylsulfonate herbicides such as ethanesulfonate; carbamate herbicides such as carboxazole methyl 5-tert-butyl-1,2-oxazol-3-ylcarbamate; fenasulam methyl 4-[2-(4-chloro-o-tolyloxy)acetamido]phenylsulfonylcarbamate; carbanilate herbicides such as BCPC(RS)-sec-butyl 3-chlorocarbanilate; desmedipham ethyl 3-phenylcarbamoyloxyphenylcarbamate; SWEP methyl 3,4-dichlorocarbanilate; Butro Cyclohexene oxime herbicides such as oxydim (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-en-1-one; tepraloxydim (RS)-(EZ)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one; cyclohexene oxime herbicides such as isoxachlorthol 4-chloro-2-mesylphenyl 5-cyclopropyl-1,2-oxazol-4-yl ketone; dicarboxyimide herbicides such as flumezin 2-methyl-4-(α,α,α-trifluoro-m-tolyl)-1,2,4-oxadiazinan-3,5-dione; dinitroaniline herbicides such as ethalfluralin N-ethyl-α,α,α-trifluoro-N-(2-methylallyl)-2,6-dinitro-p-toluidine; prodiamine 5-dipropylamino-α,α,α-trifluoro-4,6-dinitro-o-toluidine; dinitrophenol herbicides such as dinoprop 4,6-dinitro-o-cymen-3-ol;Diphenyl ether herbicides such as ethinofen α-ethoxy-4,6-dinitro-o-cresol; ethoxyphen O-[2-chloro-5-(2-chloro-α,α,α-trifluoro-p-tolyloxy)benzoyl]-L-lactic acid; nitrophenyl ether herbicides such as aclonifen 2-chloro-6-nitro-3-phenoxyaniline; nitrofen 2,4-dichlorophenyl 4-nitrophenyl ether; dithiocarbamate herbicides such as dazomet 3,5-dimethyl-1,3,5-thiadiazinan-2-thione; halogenated aliphatic herbicides such as dalapon 2,2-dichloropropionic acid; chloroacetic acid; imidazolinone herbicides such as imazapyr (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid. Herbicides; inorganic herbicides such as disodium tetraborate decahydrate; nitrile herbicides such as sodium azide and chloroxynil 3,5-dichloro-4-hydroxybenzonitrile; ioxynil 4-hydroxy-3,5-diiodobenzonitrile; organophosphate herbicides such as anilophos S-4-chloro-N-isopropylcarbanyloxymethyl O,O-dimethylphosphorodithioate; glufosinate 4-[hydroxy(methyl)phosphinyl]-DL-homoalanine; phenoxy herbicides such as clomeprop (RS)-2-(2,4-dichloro-m-tolyloxy)propionanilide; fenteracol 2-(2,4,5-trichlorophenoxy)ethanol; phenoxyacetic acid herbicides such as MCPA (4-chloro-2-methylphenoxy)acetic acid; MCPB Phenoxybutyric acid herbicides such as 4-(4-chloro-o-tolyloxy)butyric acid; phenoxypropionic acid herbicides such as fenoprop (RS)-2-(2,4,5-trichlorophenoxy)propionic acid; aryloxyphenoxypropionic acid herbicides such as isoxapyrifop (RS)-2-[2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionyl]isoxazolidine; phenylenediamine herbicides such as dinitramine N1,N1-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine; pyrazolyloxyacetophenone herbicides such as pyrazoxyfen 2-[4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yloxy]acetophenone;Pyrazolylphenyl herbicides such as pyraflufen 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl)-4-fluorophenoxyacetic acid; pyridazine herbicides such as pyridafol 6-chloro-3-phenylpyridazin-4-ol; pyridazinone herbicides such as chloridazon 5-amino-4-chloro-2-phenylpyridazin-3(2H)-one; oxapyrazon 5-bromo-1,6-dihydro-6-oxo-1-phenylpyridazin-4-yloxamic acid; pyridine herbicides such as fluroxypyr 4-amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid; thiazopyrmethyl 2- Pyrimidinediamine herbicides such as difluoromethyl-5-(4,5-dihydro-1,3-thiazol-2-yl)-4-isobutyl-6-trifluoromethylnicotinate; iprimidam 6-chloro-N4-isopropylpyrimidine-2,4-diamine; quaternary ammonium herbicides such as diethamquat 1,1'-bis(diethylcarbamoylmethyl)-4,4'-bipyridinium; paraquat 1,1-dimethyl-4,4'-bipyridinium; thiocarbamate herbicides such as cyclolate S-ethylcyclohexyl(ethyl)thiocarbamate; thiocarbazyl S-benzyl di-sec-butylthiocarbamate, EXD Thiocarbonate herbicides such as O,O-diethyldithiobis(thioformate); thiourea herbicides such as methyluron 1,1-dimethyl-3-m-tolyl-2-thiourea; triazine herbicides such as triaziflam (RS)-N-[2-(3,5-dimethylphenoxy)-1-methylethyl]-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine; chlorotriazine herbicides such as ciprazine 6-chloro-N2-cyclopropyl-N4-isopropyl-1,3,5-triazine-2,4-diamine; propazine 6-chloro-A2,N4-diisopropyl-1,3,5-triazine-2,4-diamine; methoxytriazine herbicides such as prometon N2,N4-diisopropyl-6-methoxy-1,3,5-triazine-2,4-diamine;Methylthiotriazine herbicides such as Cyanatrin 2-(4-ethylamino-6-methylthio-1,3,5-triazin-2-ylamino)-2-methylpropionitrile; triazinone herbicides such as Hexazinone 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4(1H,3H)-dione; triazole herbicides such as Epronaz N-ethyl-N-propyl-3-propylsulfonyl-1H-1,2,4-triazole-1-carboxamide; carfentrazone (RS) Triazolone herbicides such as 2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propionic acid; triazolopyrimidine herbicides such as florasulam 2',6',8-trifluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonanilide; flupropacyl isopropyl 2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6- Uracil herbicides such as dioxo-4-trifluoromethylpyridin-1-yl)benzoic acid; urea herbicides such as cycluron 3-cyclooctyl-1,1-dimethylurea; monisouron 1-(5-tert-butyl-1,2-oxazol-3-yl)-3-methylurea; phenylurea herbicides such as chloroxuron 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea; siduron 1-(2-methylcyclohexyl)-3-phenylurea; fura Pyrimidinesulfonylurea herbicides such as zasulfuron 1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl)urea; pyrazosulfuron 5-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-1-methylpyrazole-4-carboxylic acid; triazinylsulfonylurea herbicides such as thifensulfuron 3-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)thiophene-2-carboxylic acid;Thiadiazolyl ureas such as tebuthiuron 1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea, and / or unclassified herbicides such as chlorfenac (2,3,6-trichlorophenyl)acetic acid; methazole 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione; Tritac (RS)-1-(2,3,6-trichlorobenzyloxy)propan-2-ol; 2,4-D, chlorimuron, and fenoxaprop, and combinations thereof.

[0146] In some embodiments, the biocide includes or is an insecticide. Specific examples of insecticides include insect repellents (e.g., N,N-diethyl-meta-toluamide) and pyrethroids (e.g., pyrethrins). Specific examples of insecticides include atrazine, diazinon, and chlorpyrifos. In these or other embodiments, the biocide includes or is an antimicrobial. The type and nature of the antimicrobial can vary and can be readily determined by one of ordinary skill in the art. Specific antimicrobials are commercially available, including DOWSIL® 5700 and DOWSIL® 5772, manufactured by Dow Silicones Corporation of Midland, Michigan, USA. In certain embodiments, the biocide includes or is a boron-containing material, such as boric anhydride, borax, or disodium octaborate tetrahydrate. In various embodiments, the sealant comprises two or more biocides, each independently selected from the fungicides, herbicides, antimicrobial agents, and other biocidal components exemplified herein.

[0147] The amount of biocide present in the sealant will vary depending on a variety of factors (e.g., the type of biocide utilized, the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the curing conditions to which the sealant is intended to be exposed, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include a biocide or combination of biocides in an amount of 0.01 to 10, alternatively 0.1 to 5, weight percent, based on the total weight of the sealant.

[0148] In certain embodiments, the sealant includes a flame retardant. Examples of suitable flame retardants include organic / carbonaceous flame retardants (e.g., carbon black, etc.), inorganic / mineral flame retardants (e.g., aluminum hydroxide hydrate, silicates such as wollastonite, platinum and / or platinum metal complexes, etc.), and combinations thereof.Additional examples of suitable flame retardants include halogen-based flame retardants (e.g., decabromodiphenyl oxide, octabromodiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenyloxybenzene, ethylene bis-tetrabromophthalamide, pentabromoethylbenzene, pentabromobenzyl acrylate, tribromophenylmaleimide, tetrabromobisphenyl A, bis-(tribromophenoxy)ethane, bis-(pentabromophenoxy)ethane, polydibromophenylene oxide, tribromophenyl aryl ether, bis-dibromopropyl ether, tetrabromophthalic anhydride, dibromoneopentyl glycol, dibromoethyldibromocyclohexane, pentabromodiphenyl oxide, tribromostyrene, pentabromochlorocyclohexane, tetrabromoxylene, hexabromocyclododecane, brominated polystyrene, tetradecabromodiphenoxybenzene, trifluoropropene, and PVC. phosphorus-based flame retardants such as (2,3-dibromopropyl)phosphate, phosphorus, cyclic phosphates, triaryl phosphate, bis-melaminium pentate, pentaerythritol bicyclic phosphate, dimethylmethyl phosphate, phosphine oxide diol, triphenyl phosphate, tris-(2-chloroethyl)phosphate, phosphate esters such as triclayl-, trixylenyl-, isodecyldiphenyl-, ethylhexyldiphenyl-, trioctyl-, tributyl-, and tributoxyethyl phosphate esters, and phosphate salts of various amines (e.g., ammonium phosphate); tetraalkyl lead compounds such as tetraethyl lead; iron pentacarbonyl; manganese methylcyclopentadienyl tricarbonyl; melamine and its derivatives, such as melamine salts; guanidine; dicyandiamide; ammonium sulfonate; alumina trihydrate; magnesium hydroxide alumina trihydrate, and the like, as well as derivatives, modifications, and combinations thereof.The amount of flame retardant present in the sealant will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the cure conditions to which the sealant is intended to be exposed, the presence / absence of a vehicle / solvent, etc.) and can be readily determined by one of ordinary skill in the art. Generally, if present, the sealant will include flame retardant in an amount of 0.01 to 15, alternatively 0.1 to 10, weight percent, based on the total weight of the sealant.

[0149] In certain embodiments, the sealant includes a binder. Typically, the binder is a non-reactive, elastomeric organic polymer, i.e., an elastomeric organic polymer that does not react with the at least one silicone-polyether copolymer. In addition, the binder is typically compatible with the at least one silicone-polyether copolymer, i.e., the binder does not form a two-phase system when formulated into a sealant with the at least one silicone-polyether copolymer. In general, suitable binders have low gas and moisture permeability and typically have a number average molecular weight (Mn) of 30,000 to 75,000. However, the binder may also include a blend of various non-reactive elastomeric organic polymers (e.g., polymers having low molecular weights and polymers having high molecular weights). In this case, the high molecular weight polymer may typically have an Mn of 100,000 to 600,000, and the low molecular weight polymer may typically have an Mn of 900 to 10,000, or 900 to 3,000. The lower end of the Mn range is typically selected so that the binder is compatible with at least one silicone-polyether copolymer and the other components of the sealant, as will be understood by those skilled in the art. The binder may include or be one non-reactive elastomeric organic polymer, or it may include two or more non-reactive elastomeric organic polymers that differ from one another based on, for example, structure, viscosity, average molecular weight (Mn or Mw), polymer units, sequence, etc., or a combination thereof.

[0150] Examples of suitable binders include polyisobutylenes, which are known in the art and commercially available. Specific examples of polyisobutylenes include those sold under the trade name OPPANOL® by BASF Corporation of Germany and various grades of hydrogenated polyisobutene sold under the trade name PARLEAM® by NOF Corp. of Japan. Further examples of suitable polyisobutylenes are sold under the trade name VISTANEX® by ExxonMobil Chemical Co. of Baytown, Texas, USA. These include VISTANEX® MML-80, MML-100, MML-120, and MML-140, which are paraffinic hydrocarbon polymers composed of long-chain linear macromolecules containing only chain-end olefinic bonds. VISTANEX® MM polyisobutylene has a viscosity average molecular weight of 70,000 to 90,000, and VISTANEX® LM polyisobutylene (e.g., LM-MS) is a low molecular weight polyisobutylene having a viscosity average molecular weight of 8,700 to 10. Further examples of polyisobutylenes include VISTANEX LM-MH (viscosity average molecular weight 10,000 to 11,700); Soltex PB-24 (Mn 950), Indopol® H-100 (Mn 910), Indopol® H-1200 (Mn 2100) from Amoco Corp. of Chicago, Illinois, USA; and NAPVIS® and HYVIS® (e.g., NAPVIS® 200, D10, and DE3; and HYVIS® 200) from BP Chemicals, London, UK. NAPVIS® polyisobutylene may typically have an Mn of 900 to 1300. In addition to or instead of the polyisobutylene(s), the binder may include butyl rubber, styrene-ethylene / butylene-styrene (SEBS) block copolymer, styrene-ethylene / propylene-styrene (SEPS) block copolymer, polyolefin plastomer, or combinations thereof.SEBS and SEPS block copolymers are known in the art and are commercially available as Kraton® G polymers from Kraton Polymers US LLC, Houston, Texas, USA, and Septon polymers from Kuraray America, Inc., New York, New York, USA. Polyolefin plastomers are known in the art and are commercially available as AFFINITY® GA 1900 compositions and AFFINITY® GA 1950 compositions from Dow Chemical Company, Elastomers & Specialty Products Division, Midland, Michigan, USA.

[0151] The amount of bonding agent present in the sealant will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the cure conditions to which the sealant is intended to be exposed, the presence / absence of a vehicle / solvent, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include bonding agent in an amount of 1 to 50, alternatively 5 to 40, alternatively 5 to 35 parts by weight, based on the total weight of all components in the sealant.

[0152] In some embodiments, the sealant includes an anti-aging additive. Examples of anti-aging additives include antioxidants, UV absorbers, UV and / or light stabilizers, heat stabilizers, and combinations thereof. The anti-aging additive may be or include one type of anti-aging additive, or may include two or more different types of anti-aging additives. Furthermore, some anti-aging additives may serve multiple functions (e.g., as both a UV absorber and a UV stabilizer, or as both an antioxidant and a UV absorber). Many suitable anti-aging additives are known in the art and commercially available. For example, suitable antioxidants include phenolic antioxidants (e.g., fully sterically hindered phenols and partially sterically hindered phenols) and combinations of phenolic antioxidants and stabilizers (e.g., sterically hindered amines such as tetramethylpiperidine derivatives, also known as "hindered amine light stabilizers" (HALS)). Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 from BASF. IRGANOX® 1010 contains pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). Examples of UV absorbers include branched and linear phenols, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-(TINUVIN® 571). Examples of UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate; and combinations thereof (TINUVIN® 272). These and other TINUVIN® additives, such as TINUVIN® 765, are commercially available from BASF. Other UV and light stabilizers are commercially available and exemplified by LowLite from Chemtura, OnCap from PolyOne, Light Stabilizer 210 from EI du Pont de Nemours and Company (Delaware, USA).Oligomeric (high molecular weight) stabilizers may also be utilized in or as the anti-aging additive, for example, to minimize the potential for migration of the anti-aging additive from the sealant or its cured product. Examples of such oligomeric antioxidant stabilizers include TINUVIN® 622, the dimethyl ester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol. Examples of heat stabilizers include iron oxide, carbon black, iron carboxylates, cerium hydrate, barium zirconate, cerium and zirconium octoate, porphyrins, and the like, as well as combinations thereof.

[0153] The amount of anti-aging additive present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the curing conditions to which the sealant is intended to be exposed, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include the anti-aging additive in an amount of from greater than 0 to 5, alternatively 0.1 to 4, alternatively 0.5 to 3 wt. %, based on the total weight of the sealant.

[0154] In certain embodiments, the sealant includes a water-release agent, i.e., a component that releases water over time (e.g., in response to application conditions such as temperature and / or pressure). Typically, the water-release agent contains a sufficient amount of water to partially, or alternatively, fully react the sealant and is therefore selected to release that amount of water when exposed to the applied conditions (e.g., the sealant's use temperature) for a sufficient period of time. However, in general, the water-release agent is selected to bind water sufficiently to prevent too much water from being released during the manufacture and / or storage of the sealant. For example, the water-release agent typically binds water sufficiently during the formulation / compounding of the sealant so that sufficient water is available for the condensation reaction of the at least one silicone-polyether copolymer during or after the application process in which the sealant is used. This "controlled release" property can also provide the advantage of preventing too much water from being released during the application process and / or from being released too quickly, which could result in foaming or voids in the reaction composition formed by the condensation reaction of the at least one silicone-polyether copolymer of the sealant. The particular water-release agent selected will depend on a variety of factors (e.g., the other components of the sealant, the amount / type of at least one silicone-polyether copolymer, the type of condensation reaction catalyst, the process conditions under which the sealant is formulated, etc.) and can be readily determined by one of ordinary skill in the art. Examples of suitable water-release agents are exemplified by metal salt hydrates, hydrated molecular sieves, and precipitated carbonates. A particular example includes precipitated calcium carbonate available from Solvay under the trade name WINNOFIL® SPM. In certain embodiments, the water-release agent is selected to include or be precipitated calcium carbonate. The water-release agent can be selected to ensure that not all water is released during formulation, while at the same time releasing a sufficient amount of water for the condensation reaction of the at least one silicone-polyether copolymer upon exposure to the applicable temperature range for a sufficient period of time.The amount of water-releasing agent present in the sealant will vary depending on a variety of factors (e.g., the water permeability of the at least one silicone-polyether copolymer, the presence / absence of a vehicle / solvent, the presence / absence of a desiccant, the manner in which the sealant is formulated / prepared, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include a water-releasing agent in an amount of 1 to 50, alternatively 5 to 40, alternatively 5 to 30 parts by weight, based on the total weight of all components in the sealant.

[0155] In some embodiments, the sealant includes a pigment (i.e., a component that imparts color to the sealant and / or its reaction products). Such pigments may include any inorganic compound, e.g., metallic, such as chromium oxide, titanium oxide, cobalt pigments, as well as those not based on such metals, e.g., non-metallic inorganic compounds. Examples of suitable pigments include indigo, titanium dioxide, carbon black, and combinations thereof, as well as other commercially available pigments, such as Stan-Tone 505P01 Green, available from PolyOne. In certain embodiments, the pigment includes carbon black. Specific examples of carbon black include Shawinigan acetylene black, commercially available from Chevron Phillips Chemical Company LP; SUPERJET® carbon black (e.g., LB-1011), supplied by Elementis Pigments Inc., Fairview Heights, Illinois, USA; SR511, supplied by Sid Richardson Carbon Co., Akron, Ohio, USA; and N330, N550, N762, and N990, supplied by Degussa Engineered Carbons, Parsippany, New Jersey, USA. The amount of pigment present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the presence / absence of a vehicle / solvent, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant comprises a pigment in an amount of from greater than 0 to 20, alternatively 0.001 to 10, and alternatively 0.001 to 5 weight percent, based on the total weight of the sealant.

[0156] In certain embodiments, the sealant includes a rheological additive, such as a rheology modifier and / or a viscosity modifier. Examples of suitable rheological additives include waxes; polyamides, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium, aluminum, and / or barium stearate, and derivatives, modifications, and combinations thereof. In certain embodiments, the rheological modifier is selected to facilitate filler incorporation, sealant blending, degassing, and / or mixing (e.g., during its preparation), as will be understood by those skilled in the art. Specific examples of rheological additives include those commercially available and known in the art. Examples of such rheological additives include Polyvest, available from Evonik; Disparlon, available from King Industries; Kevlar Fiber Pulp, available from DuPont; Rheospan, available from Nanocor; Ircogel, available from Lubrizol; Crayvallac® SLX, available from Palmer Holland, and combinations thereof.

[0157] In some embodiments, the rheology modifier comprises a wax (e.g., paraffin wax, microcrystalline wax, or a combination thereof). Waxes typically comprise non-polar hydrocarbons that may contain branched chain structures, cyclic structures, or a combination thereof. Examples of suitable waxes include petroleum microcrystalline waxes available from Strahl & Pitsch, Inc., West Babylon, NY, USA, under the designations SP 96 (melting point 62-69°C), SP 18 (melting point 73-80°C), SP 19 (melting point 76-83°C), SP 26 (melting point range 76-83°C), SP 60 (melting point 79-85°C), SP 617 (melting point 88-93°C), SP 89 (melting point 90-95°C), and SP 624 (melting point 90-95°C). Other suitable waxes include those sold under the trademark Multiwax® by Crompton Corporation of Petrolia, Pennsylvania, USA. Such waxes include Multiwax® 180-W, which contains saturated branched and cyclic non-polar hydrocarbons and has a melting point of 79°C to 87°C; Multiwax® W-445, which contains saturated branched and cyclic non-polar hydrocarbons and has a melting point of 76°C to 83°C; and Multiwax® W-835, which contains saturated branched and cyclic non-polar hydrocarbons and has a melting point of 73°C to 80°C. In certain embodiments, the wax comprises or is a microcrystalline wax that is solid at room temperature (25°C). In some embodiments, the wax is selected to have a melting point within the desired application temperature range (i.e., the temperature range over which the sealant is intended to be used / applied). It is believed that waxes, when melted, function as processing aids, greatly facilitating the incorporation of fillers in the composition during formulation, the formulation process itself, and the degassing step, if used. For example, in certain embodiments, waxes have melting temperatures below 100°C, which can facilitate mixing prior to application (e.g., if the sealant is a multi-component composition), even in a simple static mixer. In such cases, waxes can also facilitate application of the sealant with good rheology at temperatures between 80 and 110°C, alternatively between 90 and 100°C.

[0158] The amount of rheological additive present in the sealant will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the cure conditions to which the sealant is intended to be exposed, the presence / absence of a vehicle / solvent, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include the rheological additive in an amount of from greater than 0 to 20, alternatively 1 to 15, alternatively 1 to 5 parts by weight, based on the total weight of all components in the sealant.

[0159] In certain embodiments, the sealant includes a vehicle (e.g., a carrier vehicle such as a solvent and / or diluent). Depending on the selection of the various components of the sealant, the carrier vehicle may be, for example, an oil (e.g., an organic oil and / or a silicone oil), a solvent, water, or the like. As will be understood by those skilled in the art, the particular vehicle utilized, if present, is selected to facilitate (e.g., increase) the flow of the sealant or portions thereof (e.g., one or more parts of the sealant when the sealant is a multi-part composition), as well as the incorporation of certain components (e.g., at least one silicone-polyether copolymer, chain extender, end-capping agent, etc.). Accordingly, suitable vehicles vary and generally include those that aid in the flow of one or more components of the sealant but do not essentially react with any of such components. Thus, the vehicle may be selected based on the solubility, volatility, or both of one or more components of the sealant. In this context, solubility refers to the vehicle's ability to dissolve and / or disperse one or more components of the sealant, and volatility refers to the vehicle's vapor pressure. If the vehicle is too volatile (i.e., has a vapor pressure that is too high for the intended use), bubbles may form within the sealant at the application temperature, leading to cracking and / or otherwise weakening or adversely affecting the properties of the cured product formed from the sealant. However, if the vehicle is not sufficiently volatile (i.e., has a vapor pressure that is too low for the intended use), the vehicle may remain in the cured product of the sealant and / or function as a plasticizer for it. Examples of suitable vehicles generally include silicone fluids, organic fluids, and combinations thereof.

[0160] In some embodiments, the sealant vehicle includes or is a silicone fluid. The silicone fluid is typically a low viscosity and / or volatile siloxane. In some embodiments, the silicone fluid is a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methylethyl siloxane, or the like, or a combination thereof. Typically, the silicone fluid has a viscosity of 1 to 1,000 mm at 25°C. 2 In some embodiments, the silicone fluid has a viscosity in the range of 1 / 2 s / sec. 28 R 29 SiO) I wherein each R 28 and R 29 are independently selected from H and substituted or unsubstituted hydrocarbyl groups, and the subscript I is 3 to 8. Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3, bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, and polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylylmethicone, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone, and the like, as well as derivatives, modifications, and combinations thereof. Further examples of suitable silicone fluids include 5x10 -7 ~1.5×10 -6 m 2Polyorganosiloxanes having suitable vapor pressures, such as 0.15 to 1.5 vol / s, are commercially available, for example, DOWSIL® 200 Fluids® and DOWSIL® OS FLUIDS from Dow Silicones Corporation, Midland, Michigan, USA.

[0161] In certain embodiments, the vehicle of the sealant comprises or is an organic fluid, typically an organic oil containing volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. Common examples of such organic fluids include C6-C8 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8 to C 16 Branched esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), as well as derivatives, modifications, and combinations thereof. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols with more than three carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, aromatic halides, and combinations thereof. Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 ~C 13 ), Isopar H(C 11 ~C 12), hydrogenated polydecene. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, octyl palmitate, and combinations thereof.

[0162] In some embodiments, the vehicle comprises or is an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and n-propanol; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and methylene chloride; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran, white spirit; mineral spirit; naphtha; n-methylpyrrolidone, and the like, and derivatives, modifications, and combinations thereof.

[0163] Other vehicles can also be used in the sealant. For example, in some embodiments, the vehicle includes or is an ionic liquid. Examples of ionic liquids include combinations of anions and cations. Typically, the anion is selected from alkyl sulfate-based anions, tosylate anions, sulfonate-based anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, hexafluorophosphate anions, tetrafluoroborate anions, and the like, and the cation is selected from imidazolium-based cations, pyrrolidinium-based cations, pyridinium-based cations, lithium cations, and the like. However, combinations of multiple cations and anions can also be used. Specific examples of the ionic liquid include 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 3-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, N-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, and methyltrioctylammonium bis(trifluoromethanesulfonyl)imide. imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and the like, as well as derivatives, modifications, and combinations thereof.

[0164] The amount of vehicle present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the manner in which the sealant was formulated, the cure conditions to which the sealant is intended to be exposed, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant comprises vehicle in an amount of 1 to 99, alternatively 1 to 75, alternatively 2 to 60, alternatively 2 to 50 wt %, based on the total weight of the sealant.

[0165] In certain embodiments, the sealant includes a tackifier. Typical examples of suitable tackifiers include aliphatic hydrocarbon resins (e.g., hydrogenated polyolefins having 6 to 20 carbon atoms), hydrogenated terpene resins, rosin esters, hydrogenated rosin glycerol esters, or combinations thereof. Specific examples of suitable tackifiers include natural or modified rosins, such as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; glycerol and pentaerythritol esters of natural or modified rosins, such as the glycerol ester of plain wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenol-modified pentaerythritol ester of rosin; copolymers and / or terpolymers of natural terpenes, such as styrene / terpene and / or α-methylstyrene / terpene polymers; and polyols having a softening point of 60°C to 150°C as determined by ASTM Method E28. Terpene resins include, for example, polyterpene resins produced by polymerization of terpene hydrocarbons (e.g., pinene) in the presence of a Friedel-Crafts catalyst, as well as their hydrogenated products (e.g., hydrogenated polyterpenes); phenol-modified terpene resins, such as those produced by the condensation of bicyclic terpenes with phenols with acid, and their hydrogenated derivatives; aliphatic petroleum hydrocarbon resins, such as those produced by polymerization of monomers consisting primarily of olefins and diolefins, having a Ring and Ball softening point of 60°C to 135°C, and hydrogenated aliphatic petroleum hydrocarbon resins; alicyclic petroleum hydrocarbon resins and their hydrogenated derivatives; aliphatic / aromatic or alicyclic / aromatic copolymers and their hydrogenated derivatives; and combinations thereof. In some embodiments, the sealant includes a solid tackifier (i.e., a tackifier having a Ring and Ball softening point above 25°C).Other examples of suitable tackifiers include aliphatic hydrocarbon resins exemplified by ESCOREZ 1102, 1304, 1310, 1315, and 5600 from Exxon Chemical, and hydrogenated terpene resins exemplified by Eastotac H-100, H-115E, and H-130L from Eastman; Arkon P100 from Arakawa Chemical Industries, Ltd., and Wingtack 95 from Goodyear; hydrogenated rosin glycerol esters exemplified by Staybelite Ester 10 and Foral from Hercules; polyterpenes exemplified by Piccolyte A125 from Hercules; aliphatic / aromatic and / or cycloaliphatic / aromatic resins exemplified by ECR149B and ECR179A from Exxon Chemical, and the like, and commercially available equivalents, and combinations thereof. The amount of tackifier present in the sealant will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the types and / or amounts of other components of the sealant, the intended use of the sealant, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will include tackifier in an amount of 1 to 20 parts by weight, based on the total weight of all components in the sealant.

[0166] In certain embodiments, the sealant includes a corrosion inhibitor. Examples of suitable corrosion inhibitors include benzotriazole, mercaptobenzotriazole, and the like, as well as combinations thereof. Specific examples of suitable corrosion inhibitors are known in the art and commercially available, such as CUVAN® 826 (e.g., a 2,5-dimercapto-1,3,4-thiadiazole derivative) and CUVAN® 484 (an alkyl thiadiazole), available from RT Vanderbilt, Norwalk, Connecticut, USA.

[0167] The amount of corrosion inhibitor present in the sealant will vary depending on various factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the intended use of the sealant, the curing conditions to which the sealant is intended to be exposed, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the sealant will contain corrosion inhibitor in an amount of 0.05 to 0.5 wt. %, based on the total weight of the sealant.

[0168] As introduced in the various paragraphs above, various components of the sealant may serve multiple purposes, and therefore, certain additives may overlap with respect to the components described herein. For example, certain alkoxysilanes may be useful as filler treating agents, adhesion promoters, and crosslinkers. In addition, the sealant may further include additional additives not described above, such as catalyst inhibitors, cure accelerators, and discoloration additives. Such additional additives are independently selected and utilized in the sealant in an amount selected based on its intended use, as readily determined by one of ordinary skill in the art. Typically, when present, the sealant includes each of such additional additives in an amount of 0.001 to 10, alternatively 0.01 to 5, or alternatively 0.1 to 1 wt. %, based on the total weight of the sealant.

[0169] As described above, the sealant can be prepared as a one-part composition or as a multi-part composition (e.g., comprising two, three, four, or more parts). For example, in some embodiments, the sealant can be prepared as a one-part composition and prepared by combining all of the components together by any convenient means, such as by mixing. Such one-part compositions can be made by optionally combining (e.g., premixing) at least one silicone-polyether copolymer with various additives (e.g., fillers) to form an intermediate mixture, and then combining (e.g., by mixing) the intermediate mixture with a premix containing a condensation reaction catalyst and various other additives to form a sealant mixture or sealant. Other additives (e.g., anti-aging additives, pigments, etc.) can be added to the sealant at any desired stage, such as via combination with an intermediate mixture, premix, or sealant mixture. Thus, a final mixing step can be performed (e.g., under substantially anhydrous conditions) to form the sealant, which is typically stored under substantially anhydrous conditions, for example, in a sealed container, until ready for use.

[0170] In some embodiments, the sealant is prepared as a multi-part composition (e.g., when a crosslinker is utilized). In such embodiments, the condensation reaction catalyst and crosslinker are typically stored in separate portions and combined immediately prior to use of the sealant. For example, the sealant may comprise a two-component curable composition prepared by combining at least one silicone-polyether copolymer and a crosslinker to form a first (i.e., curing agent) portion by any convenient means (e.g., mixing). The second portion (i.e., base) may be prepared by combining a condensation reaction catalyst and (I) copolymer by any convenient means (e.g., mixing). The components may be combined at ambient or elevated temperatures, under ambient or anhydrous conditions, depending on various factors, for example, whether a one-part or multi-part composition is selected. The base and curing agent portions may then be combined by any convenient means, such as by mixing, immediately prior to use. The base and curing agent portions may be combined in a 1:1 ratio, or the relative amount of base:curing agent may range from 1:1 to 10:1.

[0171] The equipment used to mix the sealant components is not particularly limited and is typically selected depending on the type and amount of each component selected for use in the sealant or portion thereof (collectively, the "sealant composition"). For example, a stirred batch kettle may be used for relatively low viscosity sealant compositions, such as compositions that react to form a gum or gel. Alternatively, continuous compounding equipment (e.g., an extruder such as a twin-screw extruder) may be used for more viscous sealant compositions and sealant compositions containing a relatively large amount of particles. Exemplary methods that can be used to prepare the sealant compositions described herein include, for example, those disclosed in U.S. Patent Publication Nos. 2009 / 0291238 and 2008 / 0300358, portions of which are incorporated herein by reference.

[0172] The sealant composition prepared as described above can be stable when stored in a container that reduces or prevents exposure of the sealant composition to moisture. However, the sealant composition can react through a condensation reaction when exposed to atmospheric moisture. In addition, when a water-releasing agent is used, the sealant composition can react through a condensation reaction without being exposed to atmospheric moisture.

[0173] Cured products are also provided. The cured products are formed from the sealant. More specifically, the cured products are formed by curing the sealant, for example, via the condensation reaction described above.

[0174] Also provided is a composite article comprising the cured product. More specifically, the composite article comprises a substrate and the cured product disposed on the substrate. The composite article is formed by disposing a sealant on the substrate and curing the sealant to provide a cured product on the substrate, thereby preparing the composite article. The substrate is exemplified by, for example, an exterior building facade.

[0175] Also disclosed is a method of sealing a space defined between two elements, the method including applying a sealant to the space and allowing the sealant to cure within the space, thereby sealing the space.

[0176] As described above, the present invention makes it possible to selectively control or otherwise adjust the properties of the cured product of a composition and its curing speed. Generally speaking, it has been difficult or previously impossible to optimize modulus and tensile strength without sacrificing or affecting the curing speed and the concentration of the condensation reaction catalyst. In other words, maximizing the curing speed may require a high concentration of the condensation reaction catalyst, which may affect the properties of the cured product, such as modulus and elongation.

[0177] Surprisingly, it has been found that the use of different end-capped organosilicon compounds, which result in different silicone moieties X having formula (I) and (II) in at least one silicone-polyether copolymer of the composition, can improve modulus and elongation, for example, compared to using only the silicone moiety X of formula (I).Furthermore, by including different silicone moieties X in at least one silicone-polyether copolymer of the composition, it is possible to achieve a much faster curing time, for example, compared to using only the silicone moiety X of formula (II).In fact, these surprising advantages can be achieved with a lower concentration of condensation reaction catalyst than the conventional concentration required, which is particularly advantageous when the condensation reaction catalyst contains tin.By increasing the content of silicone moiety X of formula (I), it is possible to maximize the curing speed, and by increasing the content of silicone moiety X of formula (II), it is possible to optimize the mechanical properties of the cured product, such as modulus and elongation. Thus, depending on the desired cure rate, concentration of the condensation reaction catalyst, and performance properties of the cured product, the relative amounts of silicone moieties X of formula (I) and silicone moieties X of formula (II) allow for selective control or adjustment of reaction parameters and performance properties. Accordingly, the present invention also provides a method for selectively controlling or adjusting reaction parameters and performance properties of the composition and associated cured product.

[0178] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way.

[0179] Certain ingredients utilized in the examples are set forth in Table 1 below.

[0180] [Table 1]

[0181] General Procedure 1: Preparation Examples 1-5 Preparative Examples 1-5 follow General Procedure 1. The specific amounts of each component utilized in Preparative Examples 1-5 are detailed in Table 2 below.

[0182] In general procedure 1, a rotary flask was attached to a rotary evaporator equipped with an oil heating bath. The flask was purged with N2 and polyether compound 1 was placed in it. The rotary evaporator was set to 90 revolutions per minute (rpm) and evacuated three times with an N2 purge to remove oxygen. The heating bath was set to 115 °C and the rotary evaporator was evacuated to maximum high vacuum to dry polyether compound 1 for 2–3 h. The flask was removed from the oil heating bath, cooled to ambient temperature under high vacuum, purged with N2, and transferred to a nitrogen glove bag.

[0183] Next, polyether compound 1 was weighed into a SpeedMixer cup. The chain-extended organosilicon compound, the first end-capped organosilicon compound, and the hydrosilylation catalyst were placed in the cup and stirred with a spatula for 30 seconds. The second end-capped organosilicon compound was weighed into a syringe and placed into the contents of the cup. The cup was then closed, sealed with electrical tape, and mixed using a SpeedMixer at 3500 rpm for 3 minutes. The cup was then placed in a metal tin container with a desiccant and purged with nitrogen. The metal tin container was then placed in a 55°C oven for 6 days. The metal tin container was then removed from the oven, allowed to cool to room temperature, and the cup was removed and placed in a glove bag for analytical sampling of its contents (e.g., NMR, viscosity, GPC).

[0184] Table 2 below shows the amount of each component utilized in Preparations 1-5 following General Procedure 1.

[0185] [Table 2]

[0186] General Procedure 2: Preparations 6-11 Preparative Examples 6-11 follow General Procedure 2. The specific amounts of each component utilized in Preparative Examples 6-11 are detailed in Table 3 below.

[0187] In general procedure 2, a rotary flask was attached to a rotary evaporator equipped with an oil heating bath. The flask was purged with N2 and polyether compound 1 was placed in it. The rotary evaporator was set to 90 revolutions per minute (rpm) and evacuated three times with an N2 purge to remove oxygen. The heating bath was set to 115 °C and the rotary evaporator was evacuated to maximum high vacuum to dry polyether compound 1 for 2-3 hours. The flask was removed from the oil heating bath, cooled to ambient temperature under high vacuum, purged with N2, and transferred to a nitrogen glove bag.

[0188] Next, polyether compound 1 was weighed into a SpeedMixer cup. The chain-extended organosilicon compound, the first and third end-capped organosilicon compounds (the third end-capped organosilicon compound is utilized in Preparative Examples 6-8, as shown in Table 3 below), and the hydrosilylation catalyst were placed in the cup and stirred with a spatula for 30 seconds. In Preparative Examples 9-11, the second end-capped organosilicon compound was weighed into a syringe and placed into the contents of the cup. The cup was then closed, sealed with electrical tape, and mixed for 3 minutes at 3,500 rpm using a SpeedMixer. The cup was then placed in a metal tin container with a desiccant and purged with nitrogen. The metal tin container was then placed in a 55°C oven for 6 days. The metal tin container was then removed from the oven, allowed to cool to room temperature, and the cup was removed and placed in a glove bag for analytical sampling (by NMR). The cup was then returned to the glove bag, and the conversion agent and a catalytic amount of hydrochloric acid were added to the cup and stirred with a spatula for 30 seconds. The cup was closed, sealed with an electric tap, and mixed in a Speedmixer at 3500 rpm for 3 minutes. The cup was left in a glove bag overnight, and the contents of the cup were transferred to a rotary flask. Residual amounts of converting agent, ethanol, and hydrochloric acid were removed by rotary evaporation, first at 80°C and then at 115°C for 1 hour. The contents of the rotary flask were returned to the glove bag for analytical sampling (NMR, viscosity, GPC, etc.).

[0189] Table 3 below shows the amount of each component utilized in Preparative Examples 6-11 following General Procedure 2. In Table 3, the amount of hydrochloric acid utilized is based on parts per million relative to the amount of converting agent utilized.

[0190] [Table 3]

[0191] Preparation 12: Preparative Example 12 follows General Procedure 1, with the only difference being that no second end-capped organosilicon compound was used. Instead, Preparative Example 12 only used the first end-capped organosilicon compound. Table 4 below shows the amount of each component utilized in Preparative Example 12.

[0192] [Table 4]

[0193] Preparation 13: Preparative Example 13 followed General Procedure 1, with the only difference being that no first end-capped organosilicon compound was used. Instead, Preparative Example 13 used only a second end-capped organosilicon compound. As in General Procedure 1, the second end-capped organosilicon compound was placed in the cup via syringe, rather than being placed in the cup with the chain-extended organosilicon compound and Polyether Compound 1. Table 5 below shows the amount of each component utilized in Preparative Example 13.

[0194] [Table 5]

[0195] Preparation 14: Preparative Example 14 followed General Procedure 2, with the only difference being that neither the first nor the second end-capped organosilicon compound was used. Instead, Preparative Example 14 used only the third end-capped organosilicon compound. In addition, in Preparative Example 14, the third end-capped organosilicon compound was weighed into a cup along with Polyether Compound 1 and the chain-extended organosilicon compound, rather than being added by syringe. Table 6 below shows the amount of each component used in Preparative Example 14. In Table 6, the content of hydrochloric acid used is based on parts per million relative to the amount of converting agent used.

[0196] [Table 6]

[0197] Preparation Examples 15-17: Preparative Examples 15-17 follow General Procedure 1, with the only difference being that no chain-extended organosilicon compound was used and Polyether Compound 2 was utilized in place of Polyether Compound 1. Table 7 below shows the amount of each component utilized in Preparative Examples 15-17.

[0198] [Table 7]

[0199] Preparation 18: Preparative Example 18 follows General Procedure 1, with the only difference being that neither a second capped organosilicon compound nor a chain-extending organosilicon compound was used, and Polyether Compound 2 was utilized in place of Polyether Compound 1. Table 8 below shows the amount of each component utilized in Preparative Example 18.

[0200] [Table 8]

[0201] Preparation 19: Preparative Example 13 follows General Procedure 1, with the only difference being that neither the first capped organosilicon compound nor the chain-extended organosilicon compound was used, and Polyether Compound 2 was utilized in place of Polyether Compound 1. Table 9 below shows the amount of each component utilized in Preparative Example 19.

[0202] [Table 9]

[0203] Example 1 to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Examples 23 to 25 and Comparative Examples 1 to 5: The compositions containing the silicone-polyether copolymers prepared in Preparation Examples 1 to 19 were used in Examples 1 to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Examples 23 to 25 and Comparative Examples 1-5. In certain examples, certain compositions consisted of a particular silicone-polyether copolymer. In other examples, certain compositions included a blend of two different silicone-polyether copolymers. Table 10 below shows the results for Example 1. to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 The silicone-polyether copolymers and relative amounts used in Table 2-25 and Comparative Examples 1-5 are shown.

[0204] [Table 10]

[0205] Table 11 below shows the results of Example 1 measured as described above. to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 Table 11 shows viscosity and GPC data for Example 1-25 and Comparative Examples 1-5. In Table 11, "n / a" indicates that a particular measurement was not performed for a given example.

[0206] Viscosity: An Anton Paar MCR-302 Rheometer was used for viscosity measurements. Samples were measured at 25°C using an 8 mm cone and a 1° cone angle plate (truncation gap = 22 μm, CP08-1) and at 25°C and 0°C using a 25 mm cone and a 2° cone angle plate (truncation gap = 106 μm, CP25-2). A constant shear technique was used for all materials. Viscosity changes were monitored to ensure that temperature equilibrium and sample volatility were not an issue with the measurements.

[0207] GPC: The chromatography system consisted of a Waters 2695 Separations Module coupled to a Waters 2410 Differential Refractometer. Separation was achieved using two (300 mm x 7.5 mm) Polymer Laboratories PLgel 5 μm Mixed-C columns (molecular weight separation range 200–2,000,000, preceded by a PLgel 5 μm guard column (50 mm x 7.5 mm)). The analysis was performed using certified-grade THF flowing at 1.0 mL / min as the eluent, and both the column and detector were controlled at 35°C. Samples were prepared in THF at approximately 5 mg / mL, solvated for approximately 2 hours with occasional shaking, and filtered through a 0.45 μm PTFE syringe filter before analysis. A 100 μL injection volume was used, and data were collected for 25 minutes. Data collection and analysis were performed using ThermoLabsystems Atlas chromatography software and Polymer Laboratories Cirrus GPC software. Average molecular weights were determined against a calibration curve (third order) generated using polystyrene standards spanning the molecular weight range of 580 to 2,300,000.

[0208] [Table 11]

[0209] Sealant Example 1 to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 ~25 and sealant comparison examples 1 to 5: Sealant Example 1 to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 In Example 1 to 25 and Comparative Sealant Examples 1 to 5, to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 The compositions of Examples 1 to 25 and Comparative Examples 1 to 5 were used to form sealants. to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 To form sealants using the compositions of Examples 1-25 and Comparative Examples 1-5, 1000 parts per million by weight (ppmw) of catalyst and 5000 ppmw of adhesion promoter were added. to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 The compositions were combined with each of the compositions of Comparative Examples 1 to 5. to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 The components of each of Sealant Example 1-25 and Comparative Sealant Examples 1-5 were mixed in a 40 g capacity polypropylene mixing cup for a Flacktek SpeedMixer® and mixed at 2000 rpm for 1 minute to obtain each sealant in the form of a homogeneous mixture. to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 Each of the sealants 1 to 25 and Comparative Sealant Examples 1 to 5 was cured to obtain a cured product, and the properties of each cured product were measured as described below.

[0210] Tensile Testing: Tensile properties were measured according to ASTM D412. Specifically, each sealant was placed on a 10 cm x 10 cm Teflon plate with edge guards. The Teflon plate was placed in a room controlled at 50% relative humidity and 23°C. After the plate was left in the room for 7 days to cure, it was transferred to an uncontrolled air-circulating oven set at 50°C and held there for 4 days. The sample was then removed from the oven and allowed to cool to room temperature. Dogbone-shaped specimens were cut from the sample with a carbon steel die to determine tensile strength, and small pieces were cut from the sample for differential scanning calorimetry (DSC).

[0211] The size of the dog-bone specimen for tensile testing was 50 mm long with a 20 mm long narrow neck. An MTS test frame equipped with a 100 N total capacity load cell was used for the tensile test. The test speed was 50.8 cm / min. The strain is calculated as the displacement of the length of the narrow neck. The stress at break is calculated by dividing the peak stress by the initial cross-sectional area of the narrow neck region.

[0212] Tack-Free Time: The tack-free time (TFT) of the sealant was determined using a Drying Time Recorder from TQC. The Drying Time Recorder is a fully digitally controlled machine operating in accordance with the Beck Koller (BK) method and conforming to ASTM D5895, ISO 9117-4, and DIN EN 14022. The Drying Time Recorder was placed in a chamber with a constant 50% humidity. The Drying Time Recorder was equipped with a carrier with six needles that could be lowered against the top of up to six 25 x 300 mm aluminum panels coated with a 4-mil thick sealant film. The needles were then slowly drawn across the panels for a set period encompassing the final cure time of each sealant. The tack-free time (TFT) was assessed by moving the carrier across the panels to the beginning of the cure phase. The TFT could then be determined by combining a visual indication of the cure process with the associated time readout by the Drying Time Recorder.

[0213] The hardness of each cured product was measured in accordance with ASTM D2240.

[0214] Tables 12 and 13 below show sealant example 1 to 16, Reference Examples 17 to 19, Examples 20 to 22, Reference Example 23 1 shows the tack-free time, tensile strength properties, and hardness of the sealants and cured products of Comparative Examples 1 to 5.

[0215] [Table 12]

[0216] [Table 13]

[0217] FIG. 1 shows the tack-free time of certain sealants (i.e., Comparative Examples 1 and 3, and Examples 1-3 and 7-8) as a function of the mole percent of silicone moiety X of the first organosilicon end-capped compound, which is silicone moiety X of Formula (I). FIG. 1 shows that Comparative Example 3, which does not contain silicone moiety X of Formula (I), had a TFT of 6638 minutes, while Comparative Example 1, which contains only silicone moiety X of Formula (I) (i.e., excluding silicone moiety X of Formula (II)), had a TFT of only 24 minutes. Surprisingly, increasing the content of silicone moiety X of Formula (I) dramatically reduced the TFT from 6638 minutes to 288 minutes, even with a relatively small amount (see Comparative Example 3 vs. Example 8). As shown in the examples, despite the significant improvement in TFT, mechanical properties were not sacrificed due to the content of silicone moiety X of Formula (II).

[0218] The invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the invention are possible in light of the above teachings. The invention may be practiced other than as specifically described. The present application also relates to the following aspects: (1) Average formula g [Z j Y o ] c wherein each X is independently a silicone moiety having one of formulas (I) or (II): (R 1 ) a (R 2 O) 3-a Si-D-SiR 1 2 -O-SiR 1 2 -D 1 - (I) (R 1 ) a (R 2 O) 3-a Si-D 1 - (II) wherein each Y is an independently selected polyether moiety and each Z is an independently selected organosilicon moiety; Each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group having 1 to 18 carbon atoms, and each R 2 is an independently selected alkyl group having 1 to 8 carbon atoms, each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms, and each D 1 are independently a divalent hydrocarbon radical having 2 to 18 carbon atoms, each subscript a is independently 0 or 1, subscript c is 1 to 150, subscript g is greater than 1, each subscript j is independently 0 or 1, and each subscript o is independently 0 or 1, with the proviso that in each moiety designated by subscript c, 1≦j+o≦2, and there is at least one moiety designated by subscript c where subscript o is 1; (i) the silicone-polyether copolymer comprises at least one silicone moiety X of formula (I) and at least one silicone moiety X of formula (II), and / or (ii) a composition, subject to at least one of the two proviso that the composition comprises at least one silicone-polyether copolymer (A) in which each silicone moiety X is of formula (I) and at least one silicone-polyether copolymer (B) in which each silicone moiety X is of formula (II). (2) The composition according to (1) above, wherein condition (i) applies. (3) The composition according to (1) above, wherein condition (ii) applies. (4) The composition according to (3) above, comprising a molar ratio of the silicone-polyether copolymer (A) to the silicone-polyether copolymer (B) of 2:98 to 98:2 (A):(B). (5) (i) each polyether moiety Y is a member of the formula —O—(C n H 2n O) w wherein the subscript n is independently selected from 2 to 4 in each moiety designated by the subscript w, and the subscript w is from 1 to 1000; (ii) each polyether moiety Y has a number average molecular weight of at least about 100; (iii) at least one polyether moiety Y is a polyhydroxyl polyether; or (vi) a combination of (i)-(iii). (6) Each polyether moiety Y has the formula: -CH 2 -CH(R 3 )-[D 2 ] m -O-[C 2 H 4 O] x [C 3 H 6 O] y [C 4H 8 O] z -[D 2 ] m -CH(R 3 )-CH 2 -、 In the formula, each R 3 are independently a hydrocarbyl group having 1 to 6 carbon atoms, an alkoxy group, a silyl group, or H, and each D 2 is an independently selected divalent group having 1 to 6 carbon atoms, the subscript m is 0 or 1, the subscript x is 0 to 999, the subscript y is 1 to 1000, and the subscript z is 0 to 999, and the units represented by the subscripts x, y, and z may be in a random or block form in the polyether moiety Y; Each organosilicon moiety, Z, independently has the formula:

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Claims

1. Average formula ｇ [Z ｊ Y ｏ ] ｃ wherein each X is independently a silicone moiety having one of formulas (I) or (II): (R １ ) ａ (R ２ O) ３－ａ Si-D-SiR １ ２ -O-SiR １ ２ -D １ - (I) (R １ ) ａ (R ２ O) ３－ａ Si-D １ - (-I) wherein each Y is an independently selected polyether moiety and each Z is an independently selected organosilicon moiety; Each R １ is an independently selected substituted or unsubstituted hydrocarbyl group having 1 to 18 carbon atoms; Each R ２ is an independently selected alkyl group having 1 to 8 carbon atoms; each D is independently a divalent hydrocarbon group having 2 to 18 carbon atoms; Each D １ are independently a divalent hydrocarbon group having 2 to 18 carbon atoms; each subscript a is independently 0 or 1; subscript c is 1 to 150; subscript g is greater than 1 and each subscript j is independently 0 or 1; each subscript o is independently 0 or 1, with the proviso that in each moiety denoted by subscript c, 1≦j+o≦2, and there is at least one moiety denoted by subscript c in which subscript o is 1; (i) the silicone-polyether copolymer comprises at least one silicone moiety X of formula (I) and at least one silicone moiety X of formula (II); and / or (ii) the composition comprises at least one silicone-polyether copolymer (A), wherein each silicone moiety X is of formula (I), and at least one silicone-polyether copolymer (B), wherein each silicone moiety X is of formula (II); The composition satisfies at least one of the following two conditions:

2. The composition of claim 1 , wherein condition (i) applies.

3. The composition of claim 1 , wherein condition (ii) applies.

4. Each polyether moiety Y has the formula: -CH ２ -CH(R ３ )-[D ２ ]m-O-[C ２ H ４ O]x[C ３ H ６ O]y[C ４ H ８ O]z-[D ２ ] ｍ -CH(R ３ )-CH ２ -、 In the formula, each R ３ are independently a hydrocarbyl group having 1 to 6 carbon atoms, an alkoxy group, a silyl group, or H, and each D ２ is an independently selected divalent radical having 1 to 6 carbon atoms, subscript m is 0 or 1, subscript x is 0 to 999, subscript y is 1 to 1000, and subscript z is 0 to 999, and the units represented by subscripts x, y, and z may be in a random or block form in said polyether moiety Y; Each organosilicon moiety, Z, independently has the formula: 【Chemical 1】 In the formula, each R １ is independently selected and defined above, and each d is independently 0 to 999 in each organosilicon moiety Z.

5. 1. A method for preparing a composition comprising at least one silicone-polyether copolymer, said method comprising: a polyether compound having an average of more than one terminal unsaturated group, optionally a chain-extended organosilicon compound, a first end-capped organosilicon compound, in the presence of a hydrosilylation catalyst; and a second endcapped organosilicon compound different from the first endcapped organosilicon compound to prepare a composition comprising the at least one silicone-polyether copolymer; The method, wherein the composition is a composition according to any one of claims 1 to 3.

6. The composition of any one of claims 1 to 3 further defined as a sealant, said sealant further comprising a condensation reaction catalyst.

7. A cured product of the composition of claim 6.

8. A composite article comprising a substrate and the cured product of claim 7 disposed on the substrate.

9. 1. A method for preparing a composite article, said method comprising: disposing the composition on a substrate; and curing the composition to obtain a cured product on the substrate, thereby forming the composite article; The method of claim 6 , wherein the composition is the composition of claim 6 .

10. 1. A method of sealing a space defined between two elements, said method comprising: applying a composition to the space; and curing the composition in the space, thereby sealing the space. The method of claim 6 , wherein the composition is the composition of claim 6 .

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