Aldehyde – diamine curable polyorganosiloxane composition and methods for the preparation and use thereof

Abstract

A curable composition includes an alpha-beta diamine compound and an aldehyde-functional organosilicon compound. The composition may cure at room temperature without the use of a tin catalyst. The composition may be used to prepare a sealant or elastomer.

Description

ALDEHYDE – DIAMINE CURABLE POLYORGANOSILOXANE COMPOSITION AND METHODS FOR THE PREPARATION AND USE THEREOF CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefits of U.S. Provisional Patent Application No. 63 / 655,636 and U.S. Provisional Patent Application No.63 / 655,635 both filed June 4, 2024 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application No.63 / 655,636 and U.S. Provisional Patent Application No.63 / 655,635 are hereby incorporated by reference. FIELD

[0002] An aldehyde – diamine curable polyorganosiloxane composition and method for its preparation are provided. More particularly, the composition includes an alpha-beta diamino- functional organosilicon compound and an aldehyde-functional organosilicon compound. INTRODUCTION

[0003] Room temperature vulcanizing (RTV) silicone compositions are useful in a myriad of applications, such as mold making, preparing adhesives, sealants, or elastomers, and forming gaskets (formed in place). RTV silicone compositions are known in the art and can be prepared from one-part compositions, or two-part (base and curing agent) compositions, where the two parts are mixed before use. Typically, RTV silicone compositions contain condensation reaction catalysts, such as dibutyl tin dilaurate, that catalyze condensation reaction cure of the RTV silicone composition. There is an ongoing need in the silicones industry to provide RTV silicone compositions that are free of organotin compounds.

[0004] Catalyst free silicone sealants that cure underwater have been disclosed. Aqueous solutions of glutaraldehyde, glyoxal or formaldehyde react without catalysts with a variety of aminopropyl modified silicone polymers to give silicone elastomers, even underwater. However, these sealants may suffer from the drawbacks of including toxic, volatile aldehydes, which are not compatible with the aminopropyl modified silicone polymers. SUMMARY

[0005] An aldehyde – diamine curable polyorganosiloxane composition comprises: (A) an alpha-beta diamino-functional organosilicon compound, and (B) an aldehyde-functional organosilicon compound. Methods for preparation and use of this composition are provided. DETAILED DESCRIPTION

[0006] The aldehyde – diamine curable polyorganosiloxane composition (composition) introduced above comprises a cure package. The cure package comprises, alternatively consists essentially of, alternatively consists of (A) the alpha-beta diamino-functional organosilicon compound and (B) the aldehyde-functional organosilicon compound. At least one of startingmaterial (A) and starting material (B) may be a polyorganosiloxane. Without wishing to be bound by theory, it is thought that the composition can cure sufficiently even without the presence of a conventional bis-hydroxyl-terminated polydiorganosiloxane. Furthermore, it is thought that the reaction of the amino moiety from starting material (A) and the aldehyde moiety from starting material (B) will generate water as a side product, which can enhance cure, particularly deep section cure of the composition, particularly when starting material (A), or starting material (B), or an additional starting material (when present), includes a hydrolyzable moiety (such as an alkoxy group). (A) Alpha-Beta Diamino-Functional Organosilicon Compound

[0007] Starting material (A) in the composition is the alpha-beta diamino-functional organosilicon compound. The alpha-beta diamino-functional organosilicon compound has, per molecule, at least one alpha-beta diamino-functional group. Alternatively, the alpha-beta diamino-functional organosilicon compound may have, per molecule, more than one alpha-beta diamino-functional group, alternatively at least two alpha-beta diamino-functional groups per molecule. The alpha-beta diamino-functional group may have formula: , wherein G1and G2are each independently selected divalentdivalent hydrocarbyl groups may be free of aliphatic unsaturation. The divalent hydrocarbyl groups may have 1 to 8 carbon atoms. The divalent hydrocarbyl groups may be linear or branched. Examples of divalent hydrocarbyl groups for G1and G2include alkane-diyl groups of empirical formula -CrH2r-, where subscript r is 1 to 8. The alkane- diyl group may be a linear alkane-diyl, e.g., -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkane-. Alternatively, each G1and each G2may be an alkane-of 2 to 4 carbon atoms. In the formula for the alpha-beta diamino-functional group, G1and G2may be the same or different, e.g., G1may have 2 or 3 carbon atoms, and G2may have 3 or 4 carbon atoms. Alternatively, suitable alpha-betadiamino-functional groups includ , ,or more that differ from one another may be used herein. For example, the alpha-beta diamino- functional organosilicon compound may comprise one or both of an alpha-beta diamino- functional silane and an alpha-beta diamino-functional polyorganosiloxane.

[0009] The alpha-beta diamino-functional organosilicon compound may be a silane (A-1), which may have , wherein G1and G2are as described above,1, each R2is an independently selected monovalent hydrocarbyl group, and each X has formula -OR2. Alternatively, subscript y may be 0. R2may be an alkyl group with 1 to 18 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, isobutyl, sec-butyl and tert-butyl), and branched and linear saturated hydrocarbyl groups of 5 to 18 carbon atoms. Alternatively R2may be selected from methyl, ethyl, propyl or butyl; alternatively methyl or ethyl. Examples of alpha-beta diamino-functional trialkoxysilanes suitable for use as starting material (A) include 3-aminoethylaminopropyltrimethoxysilane (CAS# 1760-24-3, which is commercially available as XIAMETER™ OFS-6020 Silane from Dow Silicones Corporation) or N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (also with CAS# 1760-24-3 available from Sigma Aldrich and also as S1A0591.0 from Gelest); N1-(3- (triethoxysilyl)propyl)ethane-1,2-diamine (with CAS # 5089-72-5); N-(6- amniohexyl)aminomethyltriethoxysilane (with CAS#15129-36-9, available as SIA0592.6 from Gelest); and N-(6-aminohexyl)aminopropyltrimethoxysilane (with CAS#518-58-0, available as SIA0594.0 from Gelest).

[0010] Alternatively, (A) the alpha-beta diamino-functional organosilicon compound may be(A-2) a polyorganosiloxane. The alpha-beta diamino-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. Alternatively, the alpha-beta diamino-functional polyorganosiloxane may be cyclic, linear, or branched; alternatively linear. The alpha-beta diamino-functional polyorganosiloxane may have at least 1, alternatively at least 2, and alternatively at least 3 alpha-beta diamino-functional groups per molecule. Said alpha-beta diamino-functional polyorganosiloxane may comprise unit formula (A2-1): (R23SiO1 / 2)a(R22RNHSiO1 / 2)b(R22SiO2 / 2)c(R2RNHSiO2 / 2)d(R2SiO3 / 2)e(RNHSiO3 / 2)f(SiO4 / 2)g(ZO1 / 2)h; wherein R2is as described above, each RNHis an independently selected alpha-beta diaminofunctional group of formula , wherein G1and G2are as described above, and each Z isgroup consisting of a hydrogen atom and R5, wherein each R5is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms. Subscripts a, b, c, d, e, f, and g represent average numbers, per molecule, of each siloxy unit in the unit formula. Subscript h represents an average number of hydrolyzable groups per molecule. Subscripts a, b, c, d, e, f, g, and h and have values such that subscript a ≥ 0, subscript b ≥ 0, subscript c ≥ 0, subscript d ≥ 0, subscript e ≥ 0, subscript f ≥ 0, subscript g ≥ 0, and subscript h ≥ 0; and subscript h has a value such that 0 ≤ h / (e + f + g) ≤ 1.5. Furthermore, the subscripts have values such that 10,000 ≥ (a + b + c + d + e + f + g) ≥ 2, and a quantity (b + d + f) ≥ 1, alternatively (b + d + f) ≥ 2, and alternatively (b + d + f) ≥ 3. Alternatively, each R2may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms. Alternatively, each Z is independently selected from the group consisting of a hydrogen atom and R5, where each R5is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms. Alternatively, each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen.

[0011] Alternatively, (A-2) the alpha-beta diamino-functional polyorganosiloxane may comprise (A2-2) a linear polydiorganosiloxane having, per molecule, at least one alpha-beta diamino-functional group; alternatively at least two alpha-beta diamino-functional groups (e.g., when in the formula (A2-1) for the alpha-beta diamino-functional polyorganosiloxane above, subscripts e = f = g = 0). For example, said polydiorganosiloxane may comprise unit formula (A2-3): (R23SiO1 / 2)a(RNHR22SiO1 / 2)b(R22SiO2 / 2)c(RNHR2SiO2 / 2)d(ZO1 / 2)h, wherein RNHand R2are as described above, subscript a is 0, 1, or 2; subscript b is 0, 1, or 2; subscript h is 0, 1, or 2; subscript c ≥ 0, subscript d ≥ 0, with the provisos that a quantity (b + d) ≥ 1, a quantity (a + b +h) = 2, and a quantity (a + b + c + d) ≥ 2. Alternatively, in the unit formula (A2-3) for the linear alpha-beta diamino-functional polydiorganosiloxane, above, the quantity (a + b + c + d) may be at least 3, alternatively at least 4, and alternatively > 50. At the same time said formula, the quantity (a + b + c + d) may be less than or equal to 10,000; alternatively less than or equal to 4,000; alternatively less than or equal to 2,000; alternatively less than or equal to 1,000; alternatively less than or equal to 500; alternatively less than or equal to 250. Alternatively, subscript c ≥ 0, subscript d ≥ 0, with the provisos that a quantity (b + d) ≥ 1, and a quantity 1 ≤ (c + d) ≤ 180. Alternatively, in the unit formula for the linear alpha-beta diamino-functional polyorganosiloxane, each R2may be independently selected from the group consisting of alkyl and aryl; alternatively methyl and phenyl. Alternatively, each R2in said formula may be an alkyl group; alternatively each R2may be methyl.

[0012] Alternatively, (A-2) the alpha-beta diamino-functional polyorganosiloxane may be oligomeric, e.g., when in unit formula (A2-1) above the quantity (a + b + c + d + e + f + g) ≤ 50, alternatively ≤ 40, alternatively ≤ 30, alternatively ≤ 25, alternatively ≤ 20, alternatively ≤ 10, alternatively ≤ 5, alternatively ≤ 4, alternatively ≤ 3. Examples of linear alpha-beta diamino- functional polyorganosiloxane oligomers may have formula (A2-4): , where R4is as described above, each R3’isof R4and RNH, with the proviso that at least one R3’, per molecule, is RNH, and subscript Z is 0 to 48.

[0013] Starting material (A-2) may comprise an alpha-beta diamino-functional polydiorganosiloxane such as: i) bis(trimethylsiloxy-terminated) poly(dimethyl / aminoethylaminoisobutyl,methyl)siloxane with CAS# 106842-44-8, which is commercially available as DOWSIL™ 2-8566; ii) bis(alkoxy- terminated)poly(dimethyl / aminoethylaminoisobutyl,methyl)siloxane; iii) dimethyl, methyl aminoethylaminoisobutyl siloxane, methoxy and hydroxy terminated with CAS# 831241-93-1, which is commercially available as DOWSIL™ AP 8041 Fluid; iv) dimethyl, (aminoethylaminopropyl)methyl siloxane, trimethylsiloxy-terminated with CAS# 71750-79-3, which is commercially available as DOWSIL™ FZ-3710 Fluid; v) dimethyl siloxane, 3-(2- aminoethyl)aminopropyl dimethoxysiloxy-terminated (with CAS# 71750-80-6, which is commercially available as XIAMETER™ OFX-0531 Fluid); and combinations of two or more thereof. Other alpha-beta diamino-functional polyorganosiloxanes such as DOWSIL™ AP-8568Amino Fluid, XIAMETER™ OFX-8220 Fluid, XIAMETER™ OFX-8417 Fluid, XIAMETER™ OFX-8166 Fluid are also commercially available. All of these DOWSIL™ and XIAMETER™ branded products are commercially available from The Dow Chemical Company of Midland, Michigan, USA. Alpha-beta diamino-functional organosilicon compounds are known in the art and may be made by known methods, such as those disclosed in US Patents 7238768, 11028229, and 11028233. (B) Aldehyde-Functional Organosilicon Compound

[0014] Starting material (B) in the composition is an aldehyde-functional organosilicon compound. The aldehyde-functional organosilicon compound has, per molecule, at least one aldehyde-functional group covalently bonded to silicon. Alternatively, the aldehyde-functional organosilicon compound may have, per molecule, more than one aldehyde-functional group covalently bonded to silicon, alternatively at least two aldehyde-functional groups per molecule, and alternatively at least aldehyde-functional groups per molecule. The aldehyde-functional group covalently bonded to silicon may have a divalent hydrocarbon group free of aliphatic unsaturation that be linearor branched. Examples of divalent hydrocarbyl groups for G include alkane-diyl groups of empirical formula -CrH2r-, where subscript r is 2 to 8. The alkane-diyl group may be a linear alkane-diyl, e.g., -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkane- or. Alternatively, each G may be an alkane-diyl group of 2 to 6 carbon atoms;2, 3, or 6 carbon atoms. The aldehyde-functional organosilicon compound may be one aldehyde-functional organosilicon compound. Alternatively, two or more aldehyde- functional organosilicon compounds that differ from one another may be used in the process described herein. For example, the aldehyde-functional organosilicon compound may comprise one or both of an aldehyde-functional silane and an aldehyde-functional polyorganosiloxane.

[0015] The aldehyde-functional organosilicon compound may comprise an aldehyde-functional silane of formula (B1): RAldxSiR4(4-x), where each RAldis an independently selected group of the , as described above; and each R4is independently selected from the an alkyl group of 1 to 18 carbon atoms, an aryl group of 6to 18 carbon atoms, an group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and subscript x is 1 to 4. Alternatively, subscript x may be 1 or 2, alternatively 2, and alternatively 1. Alternatively, each R4may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an alkoxy-functional group of 1 to 18 carbon atoms. Alternatively, in formula (B1) each R4may be an alkoxy-functional group of 1 to 18 carbon atoms or an acyloxy group of 2 to 18 carbon atoms; alternatively, methoxy, ethoxy, or acetoxy. Alternatively, in formula (B1), when subscript x = 1, at least one instance of R4may be a hydrocarbonoxy group or an acyloxy group, alternatively at least two instances of R4, and alternatively 2 instances of R4.

[0016] Suitable aldehyde-functional silanes are exemplified by aldehyde-functional trialkoxysilanes such as (butyl-aldehyde)trimethoxysilane, (propyl-aldehyde)-trimethoxysilane, (propyl-aldehyde)-triethoxysilane, (propyl-aldehyde)-triisopropoxysilane, and (propyl- aldehyde)-tris(methoxyethoxy)silane; aldehyde-functional dialkoxysilanes such as (propyl- aldehyde)-phenyldiethoxysilane, (propyl-aldehyde)-methyldimethoxysilane, and (propyl- aldehyde)-methyldiethoxysilane; aldehyde-functional monoalkoxysilanes such as tri(propyl- aldehyde)-methoxysilane; aldehyde-functional triacyloxysilanes such as (propyl-aldehyde)- triacetoxysilane, and aldehyde-functional diacyloxysilanes such as (propyl-aldehyde)- methyldiacetoxysilane.

[0017] Alternatively, the aldehyde-functional organosilicon compound may comprise (B2) an aldehyde-functional polyorganosiloxane. Said aldehyde-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. Said aldehyde- functional polyorganosiloxane may have at least 1, alternatively at least 2, and alternatively at least 3 aldehyde groups per molecule. Said aldehyde-functional polyorganosiloxane may comprise unit formula (B2-1): (R43SiO1 / 2)a(R42RAldSiO1 / 2)b(R42SiO2 / 2)c(R4RAldSiO2 / 2)d(R4SiO3 / 2)e(RAldSiO3 / 2)f(SiO4 / 2)g(ZO1 / 2)h; where each RAldis an independently selected aldehyde group of the , as described above, and R4, Z, and subscripts a, b, c, d, e, f, g, and h areAlternatively, each R4may be independently selected from the group consisting of an alkylgroup of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and a hydrocarbonoxy group of 1 to 18 carbon atoms. Alternatively, in formula (B2-1) each R4may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms. Each Z is independently selected from the group consisting of a hydrogen atom and R5, where each R5is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms. Subscripts a, b, c, d, e, f, and g represent average numbers, per molecule, of each siloxy unit in the unit formula. Subscript h represents an average number of hydrolyzable groups per molecule. Subscripts a, b, c, d, e, f, g, and h and have values such that subscript a ≥ 0, subscript b ≥ 0, subscript c ≥ 0, subscript d ≥ 0, subscript e ≥ 0, subscript f ≥ 0, subscript g ≥ 0, and subscript h ≥ 0; and subscript h has a value such that 0 ≤ h / (e + f + g) ≤ 1.5, 10,000 ≥ (a + b + c + d + e + f + g) ≥ 2, and a quantity (b + d + f) ≥ 1. At the same time, the quantity (a + b + c + d + e + f + g) may be ≤ 10,000. Alternatively, in the unit formula (B2-1) for the aldehyde-functional polyorganosiloxane, each R4may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18 carbon atoms. Alternatively, in the unit formula (B2-1) each R4may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an alkoxy-functional group of 1 to 18 carbon atoms. Alternatively, in the unit formula (B2-1) each R4may be independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms and an aryl group of 6 to 18 carbon atoms. Alternatively, in the unit formula (B2-1) each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen.

[0018] Alternatively, (B2) the aldehyde-functional polyorganosiloxane may comprise (B2-2) a linear polydiorganosiloxane having, per molecule, at least one aldehyde-functional group; alternatively at least two aldehyde-functional groups (e.g., when in the formula (B2-1) for the aldehyde-functional polyorganosiloxane above, subscripts e = f = g = 0). For example, said polydiorganosiloxane may comprise unit formula (B2-3): (R43SiO1 / 2)a(RAldR42SiO1 / 2)b(R42SiO2 / 2)c(RAldR4SiO2 / 2)d, where RAldand R4are as described above, subscript a is 0, 1, or 2; subscript b is 0, 1, or 2, subscript c ≥ 0, subscript d ≥ 0, with the provisos that a quantity (b + d) ≥ 1, a quantity (a + b) = 2, and a quantity (a + b + c + d) ≥ 2. Alternatively, in the unit formula (B2-3) for the linear aldehyde-functional polyorganosiloxane, above, the quantity (a + b + c + d) may be at least 3, alternatively at least 4, and alternatively > 50. At the same time said formula, the quantity (a + b + c + d) may be less than or equal to 10,000; alternatively less than or equal to 4,000; alternatively less than or equal to 2,000; alternatively less than or equal to 1,000; alternatively less than or equal to 500; alternatively lessthan or equal to 250. Alternatively, subscript c ≥ 0, subscript d ≥ 0, with the provisos that a quantity (b + d) ≥ 1, and a quantity 1 ≤ (c + d) ≤ 180. Alternatively, in the unit formula for the linear aldehyde-functional polyorganosiloxane, each R4may be independently selected from the group consisting of alkyl and aryl; alternatively methyl and phenyl. Alternatively, each R4in said formula may be an alkyl group; alternatively each R4may be methyl.

[0019] Starting material (B2) may comprise an aldehyde-functional polydiorganosiloxane such as i) bis-dimethyl(propyl-aldehyde)siloxy-terminated polydimethylsiloxane, ii) bis- dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / methyl(propyl- aldehyde)siloxane), iii) bis-dimethyl(propyl-aldehyde)siloxy-terminated polymethyl(propyl- aldehyde)siloxane, iv) bis-trimethylsiloxy-terminated poly(dimethylsiloxane / methyl(propyl- aldehyde)siloxane), v) bis-trimethylsiloxy-terminated polymethyl(propyl-aldehyde)siloxane, vi) bis-dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(propyl-aldehyde)siloxane), vii) bis- dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl,methyl,(propyl-aldehyde)-siloxy-terminated polydimethylsiloxane, x) bis- dimethyl(heptyl-aldehyde)siloxy-terminated polydimethylsiloxane, xi) bis-dimethyl(heptyl- aldehyde)siloxy-terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xii) bis- dimethyl(heptyl-aldehyde)siloxy-terminated polymethyl(heptyl-aldehyde)siloxane, xiii) bis- trimethylsiloxy-terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xiv) bis- trimethylsiloxy-terminated polymethyl(heptyl-aldehyde)siloxane, xv) bis-dimethyl(heptyl- aldehyde)-siloxy terminated poly(dimethylsiloxane / methylphenylsiloxane / methyl(heptyl- aldehyde)siloxane), xvi) bis-dimethyl(propyl-aldehyde)siloxy-terminated poly(dimethylsiloxane / methyl(heptyl-aldehyde)siloxane), xvii) bis-dimethyl(heptyl-aldehyde)- siloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), xviii) dimethyl(heptyl- aldehyde)-siloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), and xix) a combination of two or more of i) to xviii).

[0020] Alternatively, (B2) the aldehyde-functional polyorganosiloxane may be oligomeric, e.g., when in unit formula (B2-1) above the quantity (a + b + c + d + e + f + g) ≤ 50, alternatively ≤ 40, alternatively ≤ 30, alternatively ≤ 25, alternatively ≤ 20, alternatively ≤ 10, alternatively ≤ 5, alternatively ≤ 4, alternatively ≤ 3. Examples of linear aldehyde-functionalpolyorganosiloxane oligomers may have formula , where R4is as described above, each R3is indep ting of R4and RAld, with the proviso that at least one R3, per molecule, is RAld, and subscript z is 0 to 48. Examples of linear aldehyde-functional polyorganosiloxane oligomers include 1,3-di(propyl- aldehyde)-1,1,3,3-tetramethyldisiloxane; 1,1,1,3,3-pentamethyl-3-(propyl-aldehyde)-disiloxane; and 1,1,1,3,5,5,5-heptamethyl-3-(propyl-aldehyde)-trisiloxane.

[0021] Alternatively, (B2) the aldehyde-functional polyorganosiloxane may comprise an aldehyde-functional polyorganosiloxane resin, such as an aldehyde-functional polyorganosilicate resin and / or an aldehyde-functional silsesquioxane resin. Such resins may be prepared, for example, by hydroformylating an alkenyl-functional polyorganosiloxane resin. The aldehyde- functional polyorganosilicate resin comprises monofunctional units (M’ units) of formula RM’3SiO1 / 2 and tetrafunctional silicate units (Q units) of formula SiO4 / 2, where each RM’may be independently selected from the group consisting of R4and RAldas described above. Alternatively, each RM’may be selected from the group consisting of an alkyl group, an aldehyde-functional group of the formula shown above, and an aryl group. Alternatively, each RM’may be selected from methyl, (propyl-aldehyde) and phenyl. Alternatively, at least one- third, alternatively at least two thirds of the RM’groups are methyl groups. Alternatively, the M’ units may be exemplified by (Me3SiO1 / 2), (Me2PhSiO1 / 2), and (Me2RAldSiO1 / 2). The polyorganosilicate resin is soluble in solvents exemplified by liquid hydrocarbons, such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0022] When prepared, the polyorganosilicate resin comprises the M’ and Q units described above, and the polyorganosiloxane further comprises units with silicon bonded hydroxyl groups, and / or hydrolyzable groups, described by moiety (ZO1 / 2), above, and may comprise neopentamer of formula Si(OSiRM’3)4, where RM’is as described above, e.g., the neopentamer may be tetrakis(trimethylsiloxy)silane.29Si NMR and13C NMR spectroscopies may be used to measure hydroxyl and alkoxy content and molar ratio of M’ and Q units, where said ratio is expressed as {M’(resin)} / {Q(resin)}, excluding M’ and Q units from the neopentamer. M’ / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M’ units) of the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. M’ / Q ratio may be 0.5 / 1 to 1.5 / 1, alternatively 0.6 / 1 to 0.9 / 1.

[0023] The Mn of the polyorganosilicate resin depends on various factors including the types of hydrocarbon groups represented by RM’that are present. The Mn of the polyorganosilicate resin refers to the number average molecular weight measured using GPC, when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resin may be 1,500 Da to 30,000 Da, alternatively 1,500 Da to 15,000 Da; alternatively >3,000 Da to 8,000 Da. Alternatively, Mn of the polyorganosilicate resin may be 3,500 Da to 8,000 Da.

[0024] Alternatively, the polyorganosilicate resin may comprise unit formula (B2-4): (R43SiO1 / 2)mm(R42RAldSiO1 / 2)nn(SiO4 / 2)oo(ZO1 / 2)h, where Z, R4, and RAld, and subscript h are as described above and subscripts mm, nn and oo have average values such that mm ≥ 0, nn > 0, oo > 0, and 0.5 < (mm + nn) / oo < 4. Alternatively, 0.6 < (mm + nn) / oo < 4; alternatively 0.7 < (mm + nn) / oo < 4, and alternatively 0.8 < (mm + nn) / oo < 4.

[0025] Alternatively, (B2) the aldehyde-functional polyorganosiloxane may comprise (B2-5) an aldehyde-functional silsesquioxane resin, i.e., a resin containing trifunctional (T’) units of unit formula: (R43SiO1 / 2)a(R42RAldSiO1 / 2)b(R42SiO2 / 2)c(R4RAldSiO2 / 2)d(R4SiO3 / 2)e(RAldSiO3 / 2)f(ZO1 / 2)h; where R4and RAldare as described above, subscript f > 1, 2 < (e + f) < 10,000; 0 < (a + b) / (e + f) < 3; 0 < (c + d) / (e + f) < 3; and 0 < h / (e + f) < 1.5. Alternatively, the aldehyde-functional silsesquioxane resin may comprise unit formula (B2-19): (R4SiO3 / 2)e(RAldSiO3 / 2)f(ZO1 / 2)h, where R4, RAld, Z, and subscripts h, e and f are as described above. Alternatively, the aldehyde-functional silsesquioxane resin may further comprise difunctional (D’) units of formulae (R42SiO2 / 2)c(R4RAldSiO2 / 2)d in addition to the T units described above, i.e., a D’T’ resin, where subscripts c and d are as described above. Alternatively, the aldehyde-functional silsesquioxane resin may further comprise monofunctional (M’) units of formulae (R43SiO1 / 2)a(R42RAldSiO1 / 2)b, i.e., an M’D’T’ resin, where subscripts a and b are as described above for unit formula (B2-1).

[0026] Suitable aldehyde-functional organosilicon compounds are known in the art and may be prepared by known methods, such as those described in US Patent 4424392 to Petty; US Patent 5021601 to Frances et al.; US Patent 5739246 to Graiver et al.; US Patent 7696294 to Asirvatham; and US Patent 7999053 to Sutton et al.; European Patent Application Publication EP 0392948 A1 to Frances, US Patent Application Publication 20230242711 to Fisk et al., and PCT Patent Application Publications WO2006027074 to Kühnle et al., WO2023200934 to Tulchinsky et al., and WO2023091868 to Han et al. PCT Publications WO2023200934 and WO2023091868 and US Patent Application Publication 20230242711 are hereby incorporated by reference.

[0027] The amounts of (A) the alpha-beta diamino-functional organosilicon compound and(B) the aldehyde-functional organosilicon compound used in the composition depend on various factors including the types and amounts of starting materials (A) and (B), whether starting material (A) and / or starting material (B) has other curable groups (e.g., alkoxy groups), the type and amount of any additional starting materials (described below) that may be added to the composition and the desired properties and end use of the cured product of the composition. However, the amounts of (A) the alpha-beta diamino-functional organosilicon compound and (B) the aldehyde-functional organosilicon compound may be sufficient to provide a molar ratio of reactive amine moieties from starting material (A) to aldehyde moieties of starting material (B) (NH / CHO ratio) of at least 0.19 / 1, alternatively at least 0.2 / 1, alternatively at least 0.3 / 1, alternatively at least 0.37 / 1, alternatively at least 0.4 / 1, alternatively at least 0.45 / 1, alternatively at least 1 / 1, alternatively at least 1.5 / 1, alternatively at least 2 / 1, alternatively at least 2.5 / 1, alternatively at least 3 / 1, alternatively at least 3.5 / 1, alternatively at least 4 / 1, alternatively at least 4.5 / 1, and alternatively at least 4.9 / 1; while at the same time, the NH / CHO ratio may be < 10 / 1, alternatively up to 9.8 / 1, alternatively up to 9.5 / 1, alternatively up to 9 / 1, alternatively up to 8.5 / 1, alternatively up to 8 / 1, alternatively up to 7.5 / 1, alternatively up to 7 / 1, alternatively up to 6.5 / 1, alternatively up to 6 / 1, alternatively up to 5.5 / 1, alternatively up to 5 / 1, and alternatively up to 4.9 / 1. The inventors surprisingly found that if NH / CHO ratio is too high (e.g., > 19 / 1, too much excess amine), or if the NH / CHO ratio is too low (e.g., < 0.1 / 1, too much excess aldehyde) the composition may fail to cure even after 4 days at room temperature. Alternatively, the NH / CHO ratio may be 0.19 / 1 to 9.8 / 1, alternatively 0.37 / 1 to 9 / 1, alternatively 0.45 / 1 to 8 / 1, alternatively 0.5 / 1 to < 4.5 / 1, alternatively 0.5 / 1 to 9.8 / 1, and alternatively 0.5 / 1 to 4.9 / 1. Optional Additional Starting Materials

[0028] The composition described herein may optionally further comprise an additional starting material selected from the group consisting of (C) a crosslinker; (D) a drying agent; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (J) a flame retardant; (K) a surface modifier (e.g., adhesion promoter or release additive); (L) a chain lengthener; (M) an endblocker; (N) a nonreactive binder; (O) an anti-aging additive (e.g., antioxidant); (P) a water release agent; (Q) a colorant (e.g., inorganic pigment or organic dye); (R) a rheological additive; (S) a vehicle (such as a solvent and / or a diluent); (T) a tackifying agent; (U) a corrosion inhibitor; (V) an encapsulating agent; (W) a catalyst; and a combination of two or more thereof. Exemplary additional starting materials are disclosed, for example, in US Patent 9328205 to Brandstadt et al. (C) Crosslinker

[0029] Starting material (C) is a crosslinker that may be added to the composition, forexample, when to increase crosslink density of the reaction product prepared by curing the composition. Generally, starting material (C) is selected with functionality that can vary depending on the degree of crosslinking, modulus, or other properties desired in the reaction product of the composition. Generally, the selection of (C) the crosslinker is made such that the composition remains sufficiently reactive to be useful during storage for several months in a moisture impermeable package. Generally, (C) the crosslinker is selected such that the hydrolyzable substituents on starting material (C) are reactive with the substituents on starting materials (A), (B), or a reaction product thereof. For example, when starting material (A) is an alpha-beta diamino-functional alkoxysilane or (a polyorganosiloxane that has hydrolyzable groups in addition to alpha-beta diamino-functional groups) and / or starting material (B) is an aldehyde-functional alkoxysilane, then (C) the crosslinker may include a hydrolyzable substituent reactive with alkoxy groups, such as an alkoxy group. The exact amount of (C) the crosslinker can vary depending on factors including the type of (A) the alpha-beta diamino- functional organosilicon compound and (B) the aldehyde-functional organosilicon compound selected and the desired crosslink density of the reaction product. However, the amount of crosslinker may range from 0.5 part to 100 parts based on 100 parts by weight of starting materials (A) and (B) combined.

[0030] Starting material (C) may comprise an alkoxysilane (that differs from starting materials (A) and (B)) and may be exemplified by a dialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, such as an alkyltrialkoxysilane; a tetraalkoxysilane; or partial or full hydrolysis products thereof, or another combination thereof. Examples of suitable trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combination thereof, and alternatively methyltrimethoxysilane. Examples of suitable tetraalkoxysilanes include tetraethoxysilane. The amount of the alkoxysilane that is used in the curable silicone composition may range from 0.5 part to 15 parts by weight, per 100 parts by weight of starting material (B). (D) Drying agent

[0031] Starting material (D) is a drying agent that may optionally be added to the composition. The drying agent binds water from various sources. For example, the drying agent may bind by- products of the reaction between the amino-functional groups from starting material (A) and the aldehyde functional groups from starting material (B), where such by-products include water.

[0032] Examples of suitable adsorbents for starting material (D) may be inorganic particulates. The adsorbent may have a particle size of 10 micrometers or less, alternatively 5 micrometers or less. The adsorbent may have average pore size sufficient to adsorb water and alcohols, for example 10 Å (Angstroms) or less, alternatively 5 Å or less, and alternatively 3 Å or less.Examples of adsorbents include zeolites such as chabasite, mordenite, and analcite; molecular sieves such as alkali metal alumino silicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof.

[0033] Examples of commercially available drying agents include dry molecular sieves, such as 3 Å (Angstrom) molecular sieves, which are commercially available from Grace Davidson under the trademark SYLOSIV™ and from Zeochem of Louisville, Kentucky, U.S.A. under the trade name PURMOL, and 4 Å molecular sieves such as Doucil zeolite 4A available from Ineos Silicas of Warrington, England. Other useful molecular sieves include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A, all of which are commercially available from UOP of Illinois, U.S.A.; SILIPORITE NK 30AP and 65xP from Atofina of Philadelphia, Pennsylvania, U.S.A.; and molecular sieves available from W.R. Grace of Maryland, U.S.A.

[0034] Alternatively, the drying agent may bind the water by chemical means. An amount of a silane crosslinker added to the composition (in addition to starting material (C)) may function as a chemical drying agent. Without wishing to be bound by theory, it is thought that the chemical drying agent may be added to a one part composition, or to one or more parts of a multiple part composition, to keep the composition free from atmospheric moisture after the parts of the composition are mixed together. For example, alkoxysilanes suitable as drying agents include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, and a combination thereof; alkenyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and a combination thereof; cyanoalkyltrialkoxysilanes such as cyanoethyltrimethoxysilane, cyanoethyltriethoxysilane, and a combination thereof. Alternatively, starting material (D) may comprise the cyanoalkyltrialkoxysilane such as cyanoethyltrimethoxysilane, cyanoethyltriethoxysilane, or a combination thereof, particularly when the composition is formulated as a one-part composition. The amount of starting material (D) depends on the specific drying agent selected. However, when (D) is a chemical drying agent, the amount may range from 0 parts to 5 parts, alternatively 0.1 parts to 0.5 parts, per 100 parts by weight of the composition. (E) Extender

[0035] Starting material (E) is an extender and / or a plasticizer. An extender comprising a non- functional polyorganosiloxane may be used in the composition. Non-functional polyorganosiloxanes are known in the art and are commercially available. Suitable non- functional polyorganosiloxanes are exemplified by, but not limited to, polydimethylsiloxanes. Such polydimethylsiloxanes include DOWSIL™ 200 Fluids, which are commercially available from Dow Silicones Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 50 cSt to 100,000 cSt, alternatively 50 cSt to 50,000 cSt, alternatively 100 cSt to 50,000cSt, and alternatively 12,500 to 60,000 cSt at 25 °C.

[0036] An organic plasticizer may be used in addition to, or instead of, the non-functional polyorganosiloxane extender described above. Organic plasticizers are known in the art and are commercially available. The organic plasticizer may comprise a phthalate, a carboxylate, a carboxylic acid ester, an adipate or a combination thereof. Alternatively, a polymer plasticizer can be used. Examples of the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, diethylene glycol dibenzoate and pentaerythritol ester; 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; polyethers including polyether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha- methylstyrene; and polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile, and polychloroprene.

[0037] When the organic plasticizer is present, the amount of the organic plasticizer may range from 5 parts to 150 parts by weight based on the combined weights of all starting materials in the composition. The exact amount of starting material (E) used in the composition can depend on various factors including the desired end use of the composition and the cured product thereof. However, the amount of starting material (E) may range from 0.1 % to 10 % based on the combined weights of all starting materials in the composition. (F) Filler

[0038] Starting material (F) is a filler. The filler may comprise a reinforcing filler, an extending filler, a conductive filler, or a combination thereof. For example, the composition may optionally further comprise starting material (f1), a reinforcing filler, which when present may be added in an amount ranging from 0.1% to 95%, alternatively 1% to 60%, based on the weight of the composition. The exact amount of starting material (f1) depends on various factors including the form of the reaction product of the composition and whether any other fillers are added. Examples of suitable reinforcing fillers include reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica. Fumed silicas are known in the art and commercially available; e.g., fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.

[0039] The composition may optionally further comprise starting material (f2) an extending filler in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, and alternatively 1 % to 20 %, based on the weight of the composition. Examples of extending fillers include crushedquartz, aluminum oxide, magnesium oxide, calcium carbonate such as ground or precipitated calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, hollow or plain glass beads, hollow plastics or a combination thereof. Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV. Suitable precipitated calcium carbonates included Winnofil™ SPM from Solvay and Ultrapflex™ and Ultrapflex™ 100 from SMI.

[0040] The composition may optionally further comprise starting material (f3) a conductive filler. Conductive fillers may be thermally conductive, electrically conductive, or both. Conductive fillers are known in the art and are exemplified by metal particulates, metals coated on nonconductive substrates; metal oxides, meltable fillers (e.g., solder), aluminum nitride, aluminum trihydrate, barium titanate, boron nitride, carbon fibers, diamond, graphite, magnesium hydroxide, onyx, silicon carbide, tungsten carbide, and a combination thereof.

[0041] Alternatively, other fillers may be added to the composition, the type and amount depending on factors including the end use of the cured product of the composition. Examples of such other fillers include fibrous fillers such as glass fibers, carbon fibers and organic fibers, magnetic particles such as ferrite; and dielectric particles such as fused glass microspheres, titania, and calcium carbonate. (G) Treating Agent

[0042] The composition may optionally further comprise starting material (G) a treating agent. The amount of (G) the treating agent can vary depending on factors such as the type of treating agent selected and the type and amount of particulates to be treated, and whether the particulates are treated before being added to the composition, or whether the particulates are treated in situ. However, starting material (G) may be used in an amount ranging from 0.01 % to 20 %, alternatively 0.1 % to 15 %, and alternatively 0.5 % to 5 %, based on the weight of the composition. Particulates, such as the filler, the physical drying agent, certain flame retardants, certain pigments, and / or certain water release agents, when present, may optionally be surface treated with starting material (G). Particulates may be treated with starting material (G) before being added to the composition, or in situ. Starting material (G) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid. (H) Biocide

[0043] Starting material (H) is a biocide. The amount of starting material (H) can vary depending on factors including the type of biocide selected and the benefit desired. However, the amount of starting material (H) may range from greater than 0 % to 5 % based on the weightof all starting materials in the composition. Starting material (H) is exemplified by (h1) a fungicide, (h2) an herbicide, (h3) a pesticide, (h4) an antimicrobial, or a combination thereof. (J) Flame Retardant

[0044] Starting material (J) is a flame retardant. Suitable flame retardants may include, for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds. Alternatively, the flame retardant may be a halogen based flame-retardant, a phosphorus based flame-retardant, or a tetraalkyl lead compound. The amount of flame retardant can vary depending on factors such as the flame retardant selected and whether solvent is present. However, the amount of flame retardant in the composition may range from greater than 0 % to 10 % based on the combined weight of all starting materials in the composition. (K) Surface Modifier

[0045] Starting material (K) is a surface modifier. Suitable surface modifiers are exemplified by (k1) an adhesion promoter or (k2) a release agent. Suitable adhesion promoters for starting material (k1) may comprise a transition metal chelate, a hydrocarbonoxysilane such as an alkoxysilane, a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane, or a combination thereof. Adhesion promoters are known in the art and may comprise silanes having the formula R24tR25sSi(OR26)4-(t + s) where each R24is independently a monovalent organic group having at least 3 carbon atoms; R25contains at least one SiC bonded substituent having an adhesion-promoting group, such as amino, epoxy, mercapto or acrylate groups; subscript t has a value ranging from 0 to 2; subscript s is either 1 or 2; and the sum of (t + s) is not greater than 3. Each R26is independently a saturated hydrocarbon group. Saturated hydrocarbon groups for R26may be, for example, an alkyl group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, the adhesion promoter may comprise a partial condensate of the above silane. Alternatively, the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0046] Alternatively, the adhesion promoter may comprise an unsaturated or epoxy-functional compound. The adhesion promoter may comprise an unsaturated or epoxy-functional alkoxysilane. 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-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3-acryloyloxypropyl triethoxysilane, and combinations thereof.

[0047] Alternatively, the adhesion promoter may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the 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 and a reaction product of hydroxy-terminated methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer. Alternatively, the adhesion promoter may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof.

[0048] Starting material (k2) is a release agent. Suitable release agents are exemplified by fluorinated compounds, such as fluoro-functional silicones, or fluoro-functional organic compounds. Alternatively, the surface modifier for starting material (K) may be used to change the appearance of the surface of a reaction product of the composition. For example, surface modifier may be used to increase gloss of the surface of a reaction product of the composition. Such a surface modifier may comprise a polydiorganosiloxane with alkyl and aryl groups. For example, DOWSIL™ 550 Fluid is a trimethylsiloxy-terminated poly(dimethyl / methylphenyl)siloxane with a viscosity of 125 cSt that is commercially available from Dow Silicones Corporation.

[0049] The exact amount of starting material (K) depends on various factors including the type of surface modifier selected as starting material (K) and the end use of the composition and its reaction product. However, starting material (K), when present, may be added to the composition in an amount ranging from 0.01 part to 50 weight parts based on the weight of the composition, alternatively 0.01 part to 10 weight parts, and alternatively 0.01 part to 5 weight parts. (L) Chain Lengthener / Co-crosslinker

[0050] Chain lengtheners may include difunctional silanes and difunctional siloxanes, which extend the length of polyorganosiloxane chains before crosslinking occurs. Chain lengtheners may be used to reduce the modulus of elongation of the cured product. Chain lengtheners and crosslinkers may compete in their reactions with the reactive moieties of starting materials (A) and (B). To achieve noticeable chain extension, the difunctional silane has substantially higherreactivity than the trifunctional crosslinker with which it is used. Suitable chain lengtheners include diamines, such as alkyl, aryl diamines; diamidosilanes such as dialkyldiacetamidosilanes or alkenylalkyldiacetamidosilanes, particularly methylvinyldi(N-methylacetamido)silane, or dimethyldi(N-methylacetamido)silane, diacetoxysilanes such as dialkyldiacetoxysilanes or alkylalkenyldiacetoxysilanes, diaminosilanes such as dialkyldiaminosilanes or alkylalkenyldiaminosilanes, dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane and α-aminoalkyldialkoxyalkylsilanes, polydialkylsiloxanes having a degree of polymerization of from 2 to 25 and having an average per molecule of at least two hydrolyzable groups, such as acetamido or acetoxy or amino or alkoxy or amido or ketoximo substituents, and diketoximinosilanes such as dialkylkdiketoximinosilanes and alkylalkenyldiketoximinosilanes.

[0051] Alternatively, the chain lengthener may be a bis-hydroxyl terminated polydiorganosiloxane. The bis-hydroxyl terminated polydiorganosiloxane may comprise R7R7R7formula: each R7is an independently selectedabove for R5. Alternatively, each R7may be an alkyl group, alternatively methyl. Subscript z ≥ 1, and subscript z has a value sufficient to give the bis-hydroxyl polydiorganosiloxane a viscosity of 250 mPa·s to 1,000 mPa·s at 25 ºC measured by a Modular Compact Rheometer (MCR) 302 from Anton Paar GmbH of Graz, Austria using the most suitable settings and plates for the viscosity concerned, for example using a 25 mm diameter rotational plate with a gap of 0.3 mm at a shear rate of 1 s-1. The bis-hydroxyl terminated polydiorganosiloxane may be used in an amount sufficient to provide a molar ratio of silicon bonded hydroxyl groups (SiOH) in the chain lengthener to alkoxy groups (SiOR) in the other starting materials used to make the composition (SiOH / SiOR) ratio of 1 to 4. (M) Endblocker

[0052] Starting material (M) is an endblocker comprising an M unit, i.e., a siloxane unit of formula R29SiO1 / 2, where each R29independently represents a monovalent organic group unreactive with starting material (B), such as a monovalent hydrocarbon group. Starting material (M) may comprise polyorganosiloxanes endblocked on one terminal end by a triorganosilyl group, e.g., (CH3)3SiO-, and on the other end by a hydroxyl group. Starting material (M) may be a polydiorganosiloxane such as a polydimethylsiloxane. Thepolydiorganosiloxanes having both hydroxyl end groups and triorganosilyl end groups, may have more than 50 %, alternatively more than 75 %, of the total end groups as hydroxyl groups. The amount of triorganosilyl group in the polydimethylsiloxane may be used to regulate the modulus of the reaction product prepared by condensation reaction of the composition. Without wishing to be bound by theory, it is thought that higher concentrations of triorganosilyl end groups may provide a lower modulus in certain cured products. (N) Non-reactive Binder

[0053] Starting material (N) is a non-reactive, elastomeric, organic polymer, i.e., an elastomeric organic polymer that does not react with starting materials (A) and (B). Starting material (N) is compatible, i.e., starting material (N) does not form a two-phase system with starting materials (A) and (B). Starting material (N) may have low gas and moisture permeability. Starting material (N) may comprise a polyisobutylene. Alternatively, starting material (N) may comprise butyl rubber. Alternatively, starting material (N) may comprise a styrene-ethylene / butylene-styrene (SEBS) block copolymer, a styrene-ethylene / propylene- styrene (SEPS) block copolymer, or a combination thereof. The amount of starting material (N) may range from 0 part to 50 parts, alternatively 10 parts to 40 parts, and alternatively 5 parts to 35 parts, based on the weight of the composition. (O) Anti-Aging Additive

[0054] Starting material (O) is an anti-aging additive. The anti-aging additive may comprise an antioxidant, a UV absorber, a UV stabilizer, a heat stabilizer, or a combination thereof. Suitable antioxidants are known in the art and are commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols. Alternatively, the stabilizer may be a sterically hindered amine such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene; octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; butylated hydroxytoluene (BHT); (±)-α-Tocopherol (vitamin E); and IRGANOX™ 1010 from Ciba Specialty Chemicals, U.S.A. IRGANOX™ 1010 comprises pentaerythritol tetrakis(3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate). Examples of UV absorbers include phenol, 2-(2H- benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (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-piperidyl / sebacate; and a combination thereof (TINUVIN™ 272). These and TINUVIN™ additives are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, U.S.A. Other UV and light stabilizers are commercially available, and are exemplified by LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from E. I. du Pont deNemours and Company of Delaware, U.S.A. Oligomeric (higher molecular weight) stabilizers may alternatively be used, for example, to minimize potential for migration of the stabilizer out of the composition or the cured product thereof. An example of an oligomeric antioxidant stabilizer (specifically, hindered amine light stabilizer (HALS)) is Ciba TINUVIN™ 622, which is a dimethylester of butanedioic acid copolymerized with 4-hydroxy-2,2,6,6-tetramethyl-1- piperidine ethanol. Heat stabilizers may include iron oxides and carbon blacks, iron carboxylate salts, cerium hydrate, barium zirconate, cerium and zirconium octoates, and porphyrins.

[0055] The amount of starting material (O) depends on various factors including the specific anti-aging additive selected and the anti-aging benefit desired. However, the amount of starting material (O) may range from 0 to 5%, alternatively 0.1% to 4%, and alternatively 0.5% to 3%, based on the weight of the composition. (P) Water Release Agent

[0056] Starting material (P) is a water release agent that releases water over an application temperature range. Starting material (P) is selected such that starting material (P) contains an amount of water sufficient to partially or fully react the composition and such that starting material (P) releases the sufficient amount of water when exposed for a sufficient amount of time to a use temperature (i.e., a temperature at which the composition is used). However, starting material (P) binds the water sufficiently to prevent too much water from being released during the method for making the composition and during storage of the composition. For example, starting material (P) binds the water sufficiently during compounding of the composition such that sufficient water is available for condensation reaction of the composition during or after the application process in which the composition is used. This “controlled release” property also may provide the benefit of ensuring that not too much water is released too rapidly during the application process, since this may cause bubbling or voiding in the reaction product formed by condensation reaction of the composition. Precipitated calcium carbonate may be used as starting material (P) when the application temperature ranges from 80 °C to 120 °C, alternatively 90 °C to 110 °C, and alternatively 90 °C to 100 °C. However, when the composition is prepared on a continuous (e.g., twin-screw) compounder, the starting materials may be compounded at a temperature 20 °C to 30 °C above the application temperature range for a short amount of time. Therefore, starting material (P) is selected to ensure that not all of the water content is released during compounding; however starting material (P) releases a sufficient amount of water for condensation reaction of the composition when exposed to the application temperature range for a sufficient period of time.

[0057] Examples of suitable water release agents are exemplified by metal salt hydrates, hydrated molecular sieves, and precipitated calcium carbonate, which is available from Solvayunder the trademark WINNOFIL™ SPM. The water release agent selected can depend on various factors including the other starting materials selected for the composition, including catalyst type and amount, if present; and the process conditions during compounding, packaging, and application. In a twin-screw compounder, residence time may be less than a few minutes, typically less than 1 to 2 minutes. The starting materials are heated rapidly because the surface area / volume ratio in the barrels and along the screw is high and heat is induced by shearing the starting materials. How much water is removed from starting material (P) depends on the water binding capabilities, the temperature, the exposure time (duration), and the level of vacuum used to strip the composition passing through the compounder. Without wishing to be bound by theory, it is thought that with a twin screw compounding temperature of 120 °C there would remain enough water on the precipitated CaCO3 to cause the composition to react by condensation reaction over a period of 1 to 2 weeks at room temperature when the composition has been applied at 90 °C.

[0058] The amount of starting material (P) in the composition depends on various factors including the selection of starting materials (A) and (B) and whether any additional starting materials are present, however the amount of starting material (P) may range from 5 parts to 30 parts based on the weight of the composition.

[0059] Without wishing to be bound by theory, it is thought the composition can be heated to an application temperature to allow for the heat to liberate the water, and the water would react with hydrolyzable groups on starting materials (A) and / or (B), e.g., when one or both of starting materials (A) and / or (B) also has alkoxy groups, to further cure the composition. (Q) Colorant

[0060] Starting material (Q) is a colorant, e.g., an inorganic pigment or an organic dye. For purposes of this application, the term ‘colorant’ includes any starting material used to impart color to a reaction product of a composition described herein. The amount of colorant depends on various factors including the type of colorant selected and the desired degree of coloration of the reaction product. For example, the composition may comprise 0 to 20%, alternatively 0.001% to 5%, of a colorant based on the weight of all starting materials in the composition.

[0061] Examples of suitable colorants include indigo, titanium dioxide Stan-Tone 50SP01 Green (which is commercially available from PolyOne) and carbon black, which is available from various sources such as Calgon Carbon Corporation of Pittsburgh, Pennsylvania, USA. (R) Rheological Additive

[0062] The composition may optionally further comprise starting material (R) a rheological additive for modifying rheology of the composition. Rheological additives are known in the art and are commercially available. Examples include polyamides, e.g., Polyvest, which iscommercially available from Evonik, Disparlon from King Industries, Kevlar Fibre Pulp from Du Pont, Rheospan from Nanocor, and Ircogel from Lubrizol. Other suitable rheological additives include microcrystalline waxes, polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof. Without wishing to be bound by theory, it is thought that starting material (R) acts as a process aid that improves flow properties while allowing rapid green strength development (i.e., a strong increase in viscosity, corresponding to increase in the load carrying capability of a seal prepared from the composition, with a temperature drop) upon cooling the composition a few degrees, for example, after the composition is applied to a substrate. The amount of starting material (R) depends on various factors including the specific rheological additive selected and the selections of the other starting materials of the composition. However, the amount of starting material (R) may range from 0 to 20 parts, alternatively 1 part to 15 parts, and alternatively 1 part to 5 parts based on the weight of the composition. (S) Vehicle

[0063] A vehicle (e.g., a solvent and / or diluent) may be used in the composition. The vehicle may facilitate flow of the composition and introduction of certain starting materials, such as silicone resin or catalyst, when used. Vehicles used herein are those that help fluidize the starting materials of the composition but essentially do not react with any of these starting materials. Vehicles may be selected based on solubility the starting materials in the composition and volatility. The solubility refers to the vehicle being sufficient to dissolve and / or disperse starting materials of the composition. Volatility refers to vapor pressure of the vehicle. If the vehicle is too volatile (having too high vapor pressure) bubbles may form in the composition at the application temperature, and the bubbles may cause cracks or otherwise weaken or detrimentally affect properties of the cured product of the composition. However, if the vehicle is not volatile enough (too low vapor pressure) the vehicle may remain as a plasticizer in the reaction product of the composition, or the amount of time for the reaction product to develop physical properties may be longer than desired.

[0064] Suitable vehicles include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as 0.5 to 1.5 cSt XIAMETER™ PMX 200 Fluids and DOWSIL™ OS FLUIDS, which are commercially available from Dow Silicones Corporation of Midland, Michigan, U.S.A.

[0065] Alternatively, the vehicle may be an organic solvent. The organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene,toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n- butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane or methylene chloride; chloroform; dimethyl sulfoxide; dimethyl formamide, acetonitrile; tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methyl pyrrolidone; or a combination thereof. The amount of vehicle depends on various factors including the type of vehicle selected and the amount and type of other starting materials selected for the composition. However, the amount of vehicle may range from 1% to 99%, alternatively 2% to 50%, based on the weight of the composition. (T) Tackifying Agent

[0066] The composition may optionally further comprise starting material (T) a tackifying agent. The tackifying agent may comprise an aliphatic hydrocarbon resin such as a hydrogenated polyolefin having 6 to 20 carbon atoms, a hydrogenated terpene resin, a rosin ester, a hydrogenated rosin glycerol ester, or a combination thereof. Tackifying agents are commercially available. (U) Corrosion Inhibitor

[0067] The composition may optionally further comprise starting material (U), a corrosion inhibitor. Examples of suitable corrosion inhibitors include benzotriazole, mercaptobenzothiazole and commercially available corrosion inhibitors such as 2,5-dimercapto- 1,3,4-thiadiazole derivative (CUVAN™ 826) and alkylthiadiazole (CUVAN™ 484) from R. T. Vanderbilt of Norwalk, Connecticut, U.S.A. When present, the amount of starting material (U) may range from 0.05% to 0.5% based on the weight of the composition. (V) Encapsulating Agent

[0068] Starting material (V) is an optional encapsulating agent that may be used, for example, to encapsulate one or more of the other starting materials so as to prepare a one part composition. For example, one or both of starting materials (A) and (B) may be encapsulated in the encapsulating agent before incorporation into the composition. (W) Condensation Reaction Catalyst

[0069] The composition described herein may optionally further comprise (W) a condensation reaction catalyst. Condensation reaction catalysts include metal and non-metal catalysts. Metal catalysts may include tin, titanium, zirconium, lead, iron, cobalt, antimony, manganese, bismuth and / or zinc compounds. For example, the condensation reaction catalyst may comprise organotin compounds such as organic tin esters and organic tin chelate complexes, organic titanium catalysts such as organic titanate esters and organic titanium chelate complexes. Exemplary organotin compounds include dibutyltin dilaurate, dibutyltin diacetate, dibutyltindimethoxide, tin octoate, dibutyltin oxide, dibutyltin bis-diisooctylphthalate, bistripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, dimethyltin dibutyrate, dimethyltin di-neodecanoate (DMTDN), dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexanoate, and tinbutyrate. Alternatively, non-metal catalysts may include tetramethylguanidylpropyltrimethoxysilane and tetramethylguanidylpropyl- tristrimethylsiloxysilane. Exemplary organotitanium compounds include tetraisopropoxy titanium. Non-metal catalysts are exemplified by phosphonates (e.g., octyl silyl phosphonate) and phosphonic acids. Suitable non-metal catalysts are known in the art and are commercially available. For example, DOWSIL™ 4-6025 INT and DOWSIL™ 4-6085 Octyl Silyl Phosphonate are available from The Dow Chemical Company. The exact amount of catalyst depends on various factors including the type of catalyst selected, and the hydrolyzable group content of the starting materials in the composition, however, the amount of (W) condensation reaction catalyst may be 0.05% to 3%, based on weight of all starting materials in the composition.

[0070] When selecting starting materials for the composition described above, there may be overlap between types of starting materials because certain starting materials described herein may have more than one function. For example, certain alkoxysilanes may be useful as filler treating agents, crosslinkers, drying agents, and / or as adhesion promoters, certain fatty acid esters may be useful as plasticizers and may also be useful as filler treating agents, carbon black may be useful as a pigment, a flame retardant, and / or a filler, and nonreactive polydiorganosiloxanes may be useful as extenders and as solvents.

[0071] One skilled in the art would recognize that the composition described above may be formulated to be cured in the absence of organotin compounds, e.g., as described above for starting material (W). The examples below show that the composition may cure at RT, even in the absence of (W) the condensation reaction catalyst. This is true even if (C) the crosslinker is not present. The starting materials in the composition may be selected by one skilled in the art to increase or decrease cure speed, as desired. Without wishing to be bound by theory, it is thought that the reaction of the amino moiety of (A) (the alpha-beta diamino-functional organosilicon compound) and the aldehyde moiety of starting material (B) produces water as a by-product, which may enhance cure of the composition, such as when one or more of the starting materials, e.g., (A) the alpha-beta diamino-functional organosilicon compound, (B) the aldehyde-functional organosilicon compound and / or an additional starting material with alkoxy groups is used in the composition. Method of Making the Composition

[0072] The composition described above may be prepared as a one-part composition, forexample, by combining all starting materials by any convenient means, such as mixing. For example, a one-part composition may be made by optionally combining (e.g., premixing) one or both of starting materials (A) and (B) with (V) the encapsulating agent and / or (D) the drying agent before combining (A) and (B). One or more of the optional additional starting materials may be added to the composition at any desired stage. A final mixing step may be performed under substantially anhydrous conditions, and the resulting compositions are generally stored under substantially anhydrous conditions, for example in sealed containers, until ready for use.

[0073] Alternatively, the composition may be prepared as a multiple part (e.g., 2 part) composition. In this instance, starting materials (A) and (B) are stored in separate parts, and the parts are combined shortly before use of the composition. For example, a two-part curable composition may be prepared by combining starting materials comprising (A) and one or more of (C) to (W) to form a first part, and combining starting materials comprising (B) and one or more of (C) to (W) to form a second part, by any convenient means such as mixing. The starting materials may be combined at ambient temperature and under ambient or anhydrous conditions. The two parts may be combined by any convenient means, such as mixing, shortly before use. The two parts may be combined in equal amounts, or in an amount of first part to second part of 10:1 to 10:1. The composition will then cure under ambient conditions, e.g. at RT. Exposure to atmospheric moisture may facilitate cure, when one of the starting materials has hydrolyzable groups. The composition may be, for an example, a room temperature vulcanizable (RTV) sealant composition.

[0074] The equipment used for mixing the starting materials is not specifically restricted. Examples of suitable mixing equipment may be selected depending on the type and amount of each starting material selected. For example, agitated batch kettles may be used for relatively low viscosity compositions, such as compositions that would react to form gums or gels. Alternatively, continuous compounding equipment, e.g., extruders such as twin screw extruders, may be used for more viscous compositions and compositions containing relatively high amounts of particulates. Exemplary methods that can be used to prepare the compositions described herein include those disclosed in, for example, US Patent Publications US20090291238 to Scott et al., and US20080300358 to Cook et al. EXAMPLES

[0075] The following examples are provided to illustrate the invention to those skilled in the art and are not to be interpreted as to limit the scope of the invention set forth in the claims. The starting materials used in these examples are summarized below in Table 1. Table 1 – Starting MaterialsStarting Product Name Chemical Description, Source Material Chemical formula, or T Str t r 1 1 1 1 1 1 1 %Starting Product Name Chemical Description, Source Material Chemical formula, or T Str tr alStarting Product Name Chemical Description, Source Material Chemical formula, or T Str t r s e e A-4) N -methylethane-1,2-diamine has structure . Reagent A-5) N -(3-(triethoxysilyl)propyl)ethane-1,2-diamine had . ReagentA-6) 3-Aminopropyltrimethoxysilane had . Reagent A-7) N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine had . Antioxidant 1: Octadecyl 3-(3,5-di-tert-butyl-4-. Antioxidant 3: 2,6-Di-tert-butyl-4-methylphenol has structure ioxidant 4: 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)chroman-6-olald2D180(1.9854 g, 0.15 mmol, 0.30 mmol CHO 1 eq.) and then 3-aminopropyltriethoxysilane (0.0712 g, 0.32 mmol, NH / CHO = 2.1 / 1). After the addition of the 3- aminopropyltriethoxysilane, the mixture became turbid. At this time, the sample was transferred to a pre-heated aluminum block at 100 ºC. The sample was heated (loosely capped) at 100 ºC. After 40 min, the sample became more viscous (difficult to be stirred by the stir bar). After 80 min, the sample was fully cured and had turned bright yellow.

[0078] In this Example 2 (comparative), to a 30 mL vial was added a magnetic stir bar, MPr-ald2D180(1.9945 g, 0.15 mmol, 0.30 mmol CHO 1 eq.) and then 3-aminopropyltrimethoxysilane (0.0551 g, 0.31 mmol, NH / CHO = 2.1 / 1). After the addition of the 3- aminopropyltrimethoxysilane, the mixture became turbid. At this time, the sample was transferred to a pre-heated aluminum block at 100 ºC. The sample was heated (loosely capped) at 100 ºC. After 4 min, the sample became more viscous (difficult to be stirred by the stir bar). After 20 min, the sample was fully cured and had turned bright yellow.

[0079] In this Example 3, to a 30 mL vial was added a magnetic stir bar, MPr-ald2D180(1.981 g, 0.15 mmol, 0.30 mmol CHO 1 eq.) and then N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (0.0705 g, 0.32 mmol, NH / CHO = 3.2 / 1.). After the addition of the N1-(3- (trimethoxysilyl)propyl)ethane-1,2-diamine, the mixture became turbid. The reaction product was analyzed, and the results showed that a cyclic aminal – functional siloxane, shown below, had formed.was heated (loosely capped) at 100 ºC. After 4 min, the sample became more viscous (difficult to be stirred by the stir bar). After 20 min, the sample was fully cured and had not turned bright yellow as the materials in Examples 1 and 2 had.

[0081] In this Example 4, to a 40 mL vial was added a magnetic stir bar, MPr-ald2D180 (8.03 g, 0.61 mmol, 1.21 mmol CHO 1 eq.) and then N1-(3-(triethoxysilyl)propyl)ethane-1,2-diamine (0.34 g, 1.29 mmol, NH / CHO = 3.2 / 1). After the addition of the N1-(3- (triethoxysilyl)propyl)ethane-1,2-diamine, the mixture became turbid. The reaction product was analyzed, and the results showed that a cyclic aminal – functional siloxane, shown below, had formed.followed by 1.01 g of the mixture described in Example 4. The sample was left uncapped open to air. It was checked at 7 min, 13 min, 24 min, 1 h 48 min and 3 h 48 min to determine if it had gelled as indicated by a loss of flow upon inverting the vial. After this time, it was still flowable indicating it had not gelled. The sample was re-checked after 68 h, 97 h, and after 7 d. In all cases, the sample was not gelled.

[0083] In this Example 6, to a 40 mL vial was added a PTFE-coated magnetic stir bar, followed by 1.01 g of the mixture described in Example 4 and then dibutyltin dilaurate (0.014 g, 0.022 mmol, 30 mol% vs. mol of polymer, 1.4 wt% of entire mixture). The sample was left uncapped open to air. It was checked at 7 min, 13 min, 24 min, and 1 h 48 min. At 1 h 48 min, the sample had gelled as indicated by a loss of flow upon inverting the vial. This example showed that cure of the composition may be accelerated by the addition of a catalyst under the conditions tested.

[0084] In this Example 7, to a 30 mL vial was added DOWSIL™ 2-8566 Amino Fluid (2.00 g, 0.095 mmol, 0.59 mmol NH21.05 eq.) and then 3-(trimethoxysilyl)propanal (0.099 g, 0.56 mmol, 1.0 eq., NH / CHO = 3.1 / 1). After the addition of the aldehyde silane to the amine fluid, the mixture manually stirred using a plastic pipette. After 8 seconds, an elastomeric material had formed.mino Fluid (2.00 g, 0.095 mmol, 0.59 mmol NH21.09 eq.) and then 3-(triethoxysilyl)propanal (0.119 g, 0.54 mmol, 1.0 eq., NH / CHO = 3.3 / 1). After the addition of the aldehyde silane to the amine fluid, the mixture manually stirred using a plastic pipette. After 13 seconds, an elastomeric material had formed.the starting materials in amounts (in weight parts) shown below in Table 2. Reagent B-2a), cyanoethyltrimethoxysilane and Reagent A-5) were combined and mixed. Overnight stability was assessed after 16 hours. Then, a condensation reaction catalyst (dioctyl tindiacetylacetonate) was added to samples 9-2, 9-3, and 9-4, and the samples were exposed to ambient air. All of the samples cured into films with good integrity. Table 2 – Model Sealant Compositions Sample 9-1 9-2 9-3 9-4 R t B 2 20 20 20 20

[0087] The data in Table 9 show that a one-part system (with overnight stability of 16 h) can be prepared using cyanoethyltrimethoxysilane under the conditions tested. Cure speed can be selected based on the amount of drying agent used.

[0088] In this Example 10, sealant composition samples were prepared by combining Reagent B-2a), cyanoethyltrimethoxysilane, and Reagent A-5) by mixing to form a premix. A filler and dioctyltindiacetylacetonate were then combined with the premix, in the amounts (weight parts) shown below in Table 3. Overnight stability was evaluated as in Example 9. Overnight +10s @3000 rpm rheology was also evaluated. Durometer (Shore A), tensile strength (psi) and Elongation (%) were also evaluated, and the results are shown below in Table 3. Table 3 – Sealant Compositions Containing Filler Sample 10-1 10-2 10-3 10-4 Reagent B-2a) 20 20 20 20

[0089] In Table 3, Overnight +10s@3000 rpm rheology was evaluated as follows: after sitting overnight, the material was mixed for 10 seconds in a dental mixer at 3000 rpm. Rheology was evaluated by qualitative assessment (eye, spatula). ‘Non Sag’ is a sealant term that means the material does not flow under gravity force but flows when disturbed by force (with a spatula).

[0090] In this Example 11, 2.03 g of Reagent A-1 and 1.74 g of Reagent B-2a (Table 1) were combined. Upon mixing, an elastomeric material formed.

[0091] In this Example 12, 2.06 g of Reagent A-1 and 0.068 g of Reagent B-2a (Table 1) were combined. Upon mixing, the sample remained as a flowable viscous liquid. The sample was checked after 1 h, 2.5 h, 3 h, 22 h, 26 h and 42 h. After 42 h, the sample was no longer flowable and was a soft elastomeric material.

[0092] In this Example 13, 2.02 g of Reagent A-1 and 3.44 g of Reagent B-2a (Table 1) were combined. Upon mixing, an elastomeric material formed.

[0093] In this Example 14, 2.03 g of Reagent A-1 and 6.86 g of Reagent B-2a (Table 1) were combined. Upon mixing, the sample remained as a flowable viscous liquid. The sample waschecked after 1 h, 2.5 h, 3 h, 22 h, 26 h, 42 h, 50 h, and 73 h. After 73 h, the sample was still a viscous flowable liquid and was determined that it would not cure.

[0094] In this Example 15, 2.00 g of Reagent A-1 and 0.17 g of Reagent B-2a (Table 1) were combined. Upon mixing, an elastomeric material formed.

[0095] In this Example 16, 2.00 g of Reagent A-1 and 0.128 g of Reagent B-2a (Table 1) were combined. Upon mixing, the sample remained as a flowable viscous liquid. After 15 min at r.t., an elastomeric material formed.

[0096] In this Example 17, 2.00 g of Reagent A-1 and 0.154 g of Reagent B-2a (Table 1) were combined. Upon mixing, the sample remained as a flowable viscous liquid. After 5 min at r.t., an elastomeric material formed. Table 4 – Impact of NH / CHO ratio on elastomer generation. Sample Mass of Mass of Reagent NH / CHO Mole (A-1) (g) B-2a (g) Ratio Result 73in

[0097] In this Example 18, Reagents B-6 and A-11 or A-12 were pre-dissolved in toluene at 70% solids content prior to mixing. Reagent B-6 was added to reagent A-1 or A-8 while vigorously mixing with a magnetic stir bar. Mixtures almost instantaneously formed a gel. The solvent swollen products were transferred into an open Al dish and placed in a forced air oven set at 120 °C for 30 min followed by 150 °C for 30 min. The result table 5, below shows observations taken after this processing step. Result table 5: Example Amine Aldehyde Amine, g Aldehyde, g Wt% MQResult table 5 Observations: Example Observation 18-A Cured reinforced elastomer. Upon heating to 150 °C under 1 ton pressure noe resin was produced using the method described herein.

[0099] In this Example 19, an amino-functional siloxane and an aldehyde-functional siloxane were dissolved in toluene at 70% solids (30% toluene). The aldehyde-functional siloxane was added to the amino-functional siloxane while vigorously mixing with a magnetic stir bar. Mixtures almost instantaneously cured. The resulting solvent-borne products were each poured into an open Al dish and placed in a forced air oven set at 120 °C for 30 min followed by 150 °C for 30 min. The solids after solvent evaporation were further processed in a hot press at 150 °C set to 1 ton of pressure for 10 min. Table 6 shows the observations taken after this reprocessing test. Table 6 Sample Amino- Aldehyde- Amine Aldehyde Wt% Hot press functional functional reactant reactant MQ reprocessing

[0100] In this Example 20, MPr-ald2D180 and Reagent A-5 were mixed at r.t. in amounts sufficient to provide a NH / CHO mole ratio of 3.1. Samples of MPr-ald2D180with varying amounts of linear and branched isomers (varying N / I ratios) were prepared and used. The Sample, N / I ratio measured by1H NMR and cure time are shown in Table 7, below. Table 7 – Effect of N / I ratio on cure time Sample NH / CHO ratio Reagent B-2, N / I Catalyst 2 Cure Time 4Sample NH / CHO ratio Reagent B-2, N / I Catalyst 2 Cure Time ratio loading (wt% 4Slab Preparation

[0101] A 100-mil draw down is made using either shims and a flat edged putty knife, or a suitable draw down bar (3 mm thick), on standard polyethylene film. Care is taken to ensure a smooth surface, free of imperfections such as air bubbles or drag marks. The slabs are allowed to cure for 7 days in a temperature and humidity-controlled room set to 23 °C and 50% RH. It should be noted that conditions were not always stable in the humidity room, so deviations will be noted, where necessary. Durometer

[0102] Durometer was measured on a digital Zwick Roell 3130 hardness tester (BH04.7206.200) with 12.5 N load weight for Shore A digital durometer head (BH04.3130.000; ASTM C661). A dwell time of 1 second was used to conform to CTM 0099 specifications, which was based on ASTM D2240. Samples were stacked at least 0.25 in. thick, and values reported are an average of three. Tensile Elongation Modulus

[0103] Tensile properties were evaluated according to ASTM D 412. Tensile dog bone specimens were cut out of the slab using a smaller than called for die to cut the dog bones (DIN 53504 S2 Die) to allow room on the tensometer’s (MTS Systems Corporation Alliance RT / 5, serial number 212990043099) frame for the dog bone to pull to break. They were pulled at 20 in / min, using a 22.5 lbf (100 N) load cell. Tensile is calculated using the load given by the load cell divided by the test area of the specimen. %Strain at peak (alternatively, %elongation) is calculated as the distance the crosshead traveled to break, multiplied by 100. Modulus is the value of the stress at a given percentage of elongation. An average of between three and five measurements is reported for each sample. Definitions and Usage of Terms

[0104] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The amounts of all starting materials in a composition total 100% by weight. The SUMMARY and ABSTRACT are hereby incorporated by reference. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated. The transitional phrases “comprising”,“consisting essentially of”, and “consisting of” are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., II., and III. The abbreviations used herein have the definitions in Table 5. Table 5 - Abbreviations Abbreviation Definitions °C degrees Celsius - 2 a

Claims

CLAIMS:

1. An aldehyde – diamine curable polyorganosiloxane composition comprising: (A) an alpha-beta diamino-functional organosilicon compound, and (B) an aldehyde-functional organosilicon compound, with the proviso that at least one of (B) and (A) is a polyorganosiloxane; wherein starting materials (A) and (B) are present in amounts sufficient to provide a NH / CHO mole ratio of 0.19 / 1 to 10 / 1.

2. The composition of claim 1, where (A) the alpha-beta diamino functional organosilicon compound is an alpha-beta diamino functional alkoxysilane, and (B) the aldehyde- functional organosilicon compound is an aldehyde-functional polyorganosiloxane.

3. The composition of claim 1 or claim 2, further comprising an additional starting material selected from the group consisting of selected from the group consisting of (C) a crosslinker; (D) a drying agent; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a nonreactive binder; (O) an anti-aging additive; (P) a water release agent; (Q) a colorant; (R) a rheological additive; (S) a vehicle; (T) a tackifying agent; (U) a corrosion inhibitor; (V) an encapsulating agent; (W) a catalyst; and a combination of two or more thereof.

4. The composition of any one of claims 1 to 3, wherein the composition is free of (W) the catalyst.

5. The compound of any one of claims 1 to 4, wherein (A) the alpha-beta diamino functional organosilicon compound comprises a silane of formula: , wherein G1and G2are each independently selectedy is an integer with a value of 0 or 1; each R2is an independently selected monovalent hydrocarbyl group; and each X has formula -OR2, wherein R2is as described above.

6. The composition of any one of claims 1 to 4, wherein (A) the alpha-beta diamino functional organosilicon compound comprises a polydiorganosiloxane comprising unit formula: (R23SiO1 / 2)a(RNHR22SiO1 / 2)b(R22SiO2 / 2)c(RNHR2SiO2 / 2)d(ZO1 / 2)h, wherein each RNHis an independently selected alpha-beta diaminofunctional group of formula , wherein G1and G2are each independently selected divalenthydrocarbyl groups; each R2is an independently selected monovalent hydrocarbyl group; subscript a is 0, 1, or 2; subscript b is 0, 1, or 2; subscript h is 0, 1, or 2; subscript c ≥ 0; subscript d ≥ 0; with the provisos that a quantity (b + d) ≥ 1, a quantity (a + b + h) = 2, and a quantity (a + b + c + d) ≥ 2.

7. The composition of any one of claims 1 to 6, wherein (B) the aldehyde-functional compound is an aldehyde-functional polyorganosiloxane of unit formula: (R43SiO1 / 2)a(R42RAldSiO1 / 2)b(R42SiO2 / 2)c(R4RAldSiO2 / 2)d(R4SiO3 / 2)e(RAldSiO3 / 2)f(SiO4 / 2)g(ZO1 / 2)h;where each RAld is an independently aldehyde group of , where G is adivalent hydrocarbon group free of aliphatic unsaturationatoms; each R4is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and an hydrocarbonoxy group of 1 to 18 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and R5, where each R5is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms; subscripts a, b, c, d, e, f, and g represent numbers of each unit in the unit formula and have values such that subscript a ≥ 0, subscript b ≥ 0, subscript c ≥ 0, subscript d ≥ 0, subscript e ≥ 0, subscript f ≥ 0, subscript g ≥ 0, with the provisos that a quantity (b + d + f) ≥ 1, and 10,000 ≥ (a + b + c + d + e + f + g) ≥ 2; and subscript h has a value such that 0 ≤ h / (e + f + g) ≤ 1.

5.

8. The composition of claim 7, where (B) the aldehyde-functional organosilicon compound comprises unit formula: (R43SiO1 / 2)a(R42RAldSiO1 / 2)b(R42SiO2 / 2)c(R4RAldSiO2 / 2)d, where each R4is alkyl or aryl; each RAld, the independently selected aldehyde group of formula , has G being a divalent hydrocarbon group free of aliphatic unsaturation thatatoms; subscript a is 0, 1, or 2; subscript b is 0, 1, or 2; a quantity (a + b) has an average value of 2; subscript c is 0 or greater, subscript d is 0 or greater; and a quantity (b + d) is 1 or greater.

9. The composition of claim 7 or claim 8, where each R4is alkyl, each RAldis propyl aldehyde, butyl aldehyde or heptyl aldehyde.

10. The composition of claim 9, where R4is methyl, and each RAldis propyl aldehyde.

11. A method for making the composition of any one of claims 1 to 10 comprising: mixing starting materials comprising (A) the alpha-beta diamino functional organosiliconcompound, and (B) the aldehyde-functional organosilicon compound, so as to make the composition.

12. The method of claim 11, further comprising: adding at least one additional starting material distinct from starting materials (A) and (B), where the at one additional starting material is selected from the group consisting of: (C) a condensation reaction catalyst, (D) a crosslinker; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a nonreactive binder; (O) an anti-aging additive; (P) a water release agent; (Q) a colorant; (R) a rheological additive; (S) a vehicle; (T) a tackifying agent; (U) a corrosion inhibitor; (V) an encapsulating agent; (W) a catalyst; and a combination of two or more thereof.

13. The method of claim 11 or claim 12, wherein the composition is a multiple part composition, and starting material (A) and starting material (B) are stored in separate parts.

14. A method for preparing a cured polyorganosiloxane, wherein the method comprises: mixing the multiple part composition of claim 13 so as to contact starting material (A) and starting material (B) with one another.

15. The cured polyorganosiloxane prepared by the method of claim 14.

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